POLYMER HANDBOOK FOURTH EDITION
Editors
J. BRANDRUP, E. H. IMMERGUT, and E. A. GRULKE Associate Editors
A. ABE D. R. BLOCH
A WILEY-INTERSCIENCE PUBLICATION
JOHNWlLEY & SONS, INC. New York
Chichester
Weinheim
Brisbane
Singapore
Toronto
This book is printed on acid-free paper. @ Copyright © 1999 by John Wiley & Sons, Inc. All rights reserved. Published simultaneously in Canada. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning or otherwise, except as permitted under Sections 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, 222 Rosewood Drive, Danvers, MA 01923, (978) 750-8400, fax (978) 750-4744. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 605 Third Avenue, New York, NY 10158-0012, (212) 850-6011, fax (212) 850-6008, E-Mail: PERMREQ @ WILEY.COM. Library of Congress Cataloging-in-Puhlication Data: Polymer Handbook / Editors: J. Brandrup, E. H. Immergut, and E. A. Grulke; Associate Editors, A. Abe, D. R. Bloch. - 4th ed. p. cm. "A Wiley-Interscience Publication." Includes index. ISBN 0-471-16628-6 (cloth : alk. paper) 1. Polymers—Tables. 2. Polymerization—Tables. I. Brandrup, J. II. Immergut, E. H. III. Grulke, Eric A. QD388.P65 1999 547.7-dc21 98-37261 Printed in the United States of America. 10 9 8 7 6 5 4 3 2
Contributors Abe, A. Tokyo Institute of Polytechnics, Atsugi, Japan Allegra, G. Dipartimento di Chimica del Politecnico, Milano, Italy Andreeva, L. N. Institute of High Molecular Weight Compounds, Russian Academy of Sciences, St. Petersburg, Russian Federation Andrews, R, J. Chemical and Materials Engineering Department, University of Kentucky, Lexington, Kentucky, USA Bai, F. The Maurice Morton Institute of Polymer Science, Univeristy of Akron, Akron, USA Bareiss, R. E. Editorial Office, Macromolecular Chemistry and Physics, Mainz, FR Germany Barrales-Rienda, J. M. Instituto de Ciencia y Tecnologia de Polfmeros, Madrid, Spain Bello, A. Instituto de Ciencia y Tecnologia de Polfmeros, Madrid, Spain Bello, P. Instituto de Ciencia y Tecnologia de Polfmeros, Madrid, Spain Bloch, D. R. Lakeshore Research, Racine, Wisconsin, USA Brandrup, J. Wiesbaden, FR Germany Calhoun, B. H. The Maurice Morton Institute of Polymers Science, University of Akron, Akron USA Casassa, E. F. Department of Chemistry, Carneagfe-Mellon University, Pittsburgh, Pennsylvania, USA Cheng, S. Z. D. The Maurice Morton Institute of Polymer Science, University of Akron, Akron, Ohio, USA Chiu, F.-C. The Maurice Morton Institute of Polymer Science, University of Akron, Akron, Ohio, USA Cho, J. Polymer Science and Engineering Department, Dankook University, Seoul, South Korea Collins, E. A. Avon Lake, Ohio, USA Daniels, C. A. The Geon Company, Avon Lake, Ohio, USA DeLassus, P. T. The Dow Chemical Company, Freeport, Texas, USA Dixon, K. W. Akzo Nobel Chemicals, Inc., Dobbs Ferry, New York, USA
Elias, H.-G. Michigan Molecular Institute, Midland, Michigan, USA Fink, G. Max-Planck-Institut fur Kohlenforschung, Miilheim an der Ruhr, FR Germany Fink, H.-P. Fraunhofer Institut fiir angewandte Polymerforschung, TeltowSeehof, FR Germany Fouassier, J. P. Laboratoire de Photochimie Generate, Ecole Nationale Superieure de Chimie, Mulhouse, France Fu, Q. The Maurice Morton Institute and Department of Polymer Science, University of Akron, Akron, Ohio, USA Furuta, I. Japan Synthetic Rubber Company Ltd., Yokkaichi, Mie, Japan Ganster, J. Fraunhofer Institute for Applied Polymer Research, TeltowSeehof, Germany Greenley, R. Z. Monsanto Corporation (retired), St. Louis, Missouri, USA Grulke, E. A. Chemical and Materials Engineering, University of Kentucky, Lexington, Kentucky, USA Goh, S. H. Department of Chemistry, National University of Singapore, Singapore Guzman G. M. Instituto de Ciencia y Tecnologfa de Polfmeros, Madrid, Spain Hill, D. J. T. Department of Chemistry, University of Queensland, St. Lucia, Australia Hiltner, A. Department of Macromolecular Science, School of Engineering Case Western University, Cleveland, Ohio, USA Inomata, K. Department of Polymer Chemistry, Tokyo Institute of Technology, Ookayama, Meguro-ku, Tokyo, Japan Iwama, M. Japan Synthetic Rubber Company Ltd., Yokkaichi, Mie, Japan Jenkins, A. D. School of Chemistry, Physics and Environmental Science, University of Sussex, Brighton, Sussex, UK Jenkins, J. School of Chemistry, Physics and Environmental Science, University of Sussex, Brighton, Sussex, UK
Johnson, M. Chemistry/Physics Library, University of Kentucky, Lexington, Kentucky, USA Kamachi, M. Department of Applied Physics and Chemistry, Fukui University of Technology, Gakuen, Fukui, Japan Kerbow, D. L. DuPont Fluoroproducts, Wilmington, Delaware, USA Kimura, S.-L Japan Synthetic Rubber Company Ltd., Yokkaichi, Mie, Japan Korte, S. Zentrale Ferschung, Bayer AG, Leverkunsen, FR Germany Krause, S. Department of Chemistry, Rensselaer Polytechnic Institute, Troy, New York, USA Kurata, M. Institute for Chemical Research, Kyoto University, Uji, Kyoto, Japan Lechner, M. D. Physikalische Chemie, Universitat Osnabriick, Osnabriick, FR Germany Leonard, J. Department de Chimie and CERSIM, Universite Laval, Quebec, Canada Li, F. The Maurice Morton Institute of Polymer Science, University of Akron, Akron, Ohio, USA
Muck, K.-F. Ticona GmbH, Kelsterbach, FR Germany Nagai, S. Plastics Technical Association, Osaka, Japan Nordmeier, E. Physikalische Chemie, Universitat Osnabriick, Osnabriick FR Germany Ogo, Y. Research Institute for Solvothermal Technology, Hayashi, Takamatsu, Kagawa, Japan Orwoll, R. A. College of William and Mary, Williamsburg, Virginia, USA Pauly, S. Fachlaboratorium fur Permeationspriifung, Wiesbaden, FR Germany Peebles, L. H., Jr. Chemistry Division, Naval Research Laboratory, Washington, DC, USA Perera, M. C. S. Magnetic Resonance Facility, School of Science, Griffith University, Nathan, Australia Porzio, W. Instituto di Chimica delle Macromolecole del C.N.R., Milano, Italy Pyda, M. Department of Chemistry, University of Tennessee, Knoxville, Tennessee, USA
Liggat, J. Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, Scotland
Quirk, R. P. The Maurice Morton Institute of Polymer Science, University of Akron, Akron, Ohio, USA
Lindemann, M. Greenville, South Carolina, USA Luft, G. Institut fur Chemische Technologie, Technische Hochschule, Darmstadt, FR Germany
Riande, E. Instituto de Ciencia y Tecnologia de Polimeros, Madrid, Spain
Magill, J. H. School of Engineering, University of Pittsburgh, Pittsburgh, Pennsylvania, USA McKenna, T. F. Centre Nationale de Ia Recherche Scientifique, Laboratoire de Chimie et Procedes de Polymerisation/Departement Genie des Procedes, Villeurbanne, France Mehta, R. H. Dupont Nylon, Chattanooga, Tennessee, USA Mettle, S. V. Dipartimento di Chimica del Politecnico, Milano, Italy Metanomski, W. V. Chemical Abstracts Service, Columbus, Ohio, USA Michielsen, S. School of Textile and Fiber Engineering, Georgia Institute of Technology, Atlanta, Georgia, USA Miller, R. L. Michigan Molecular Institute, Midland, Michigan, USA Morita, Y. Japan Atomic Energy Research Institute, Takasaki, Gunma-ken, Japan
Richter, W. J. Max-Planck-Institut fur Kohlenforschung, Miilheim an der Ruhr, FR Germany Rothe, M. University of UIm, UIm, FR Germany Rule, M. Coca Cola Company, Atlanta, Georgia, USA Salort, J. F. Madrid, Spain Salom, C. Escuela Tecnica Superior de Ingenieros Aeronauticos, Universidad Politecnica, Madrid, Spain Sanchez, I. C. Chemical Engineering Department, University of Texas at Austin, Austin, Texas, USA Santos, A. M. Faculdade de Engenharia Quimica de Lorena - FAENQUIL, Lorena, Sao Paulo, Brazil Schoff, C. K. PPG Industries, Allison Park, Pennsylvania, USA Schuld, N. Institut fur Physikalische Chemie, Universitat Mainz, Mainz, FR Germany
Seferis, J. C. Chemical Engineering Department, University of Washington, Seattle, Washington, USA Seguchi, T. Japan Atomic Energy Research Institute, Takasaki, Gunma-ken, Japan
Wagener, K. B. Department of Chemistry and Center for Macromolecular Science and Engineering, University of Florida, Gainesville, Florida, USA Whiteman, N. F. The Dow Chemical Company, Freeport, Texas, USA
Schrader, D. The Dow Chemical Company, Midland, Michigan, USA
Witenhafer, D. E. Dublin, Ohio, USA
Sperati, C. A. Chemical Engineering Department, Ohio University, Athens, Ohio, USA
Wolf, B. A. Institut fur Physikalische Chemie, Universitat Mainz, Mainz, FR Germany
Steinmeier, D. G. Physikalische Chemie, Universitat Osnabriick, Osnabruck, FR Germany
Wu, S. E. I. DuPont de Nemours, Central Research and Development Department, Experimental Station, Wilmington, Delaware
Tsunashima, Y. Institute for Chemical Research, Kyoto University, Uji, Kyoto, Japan
Wunderlich, B. Department of Chemistry, University of Tennessee, Knoxville, Tennessee, USA
Tsvetkov, N. V. Institute of High Molecular Weight Compounds, Russian Academy of Science, St. Petersburg, Russian Federation
Wunderlich, W. ROHM GmbH, Darmstadt, FR Germany
Tsvetkov, V. N. Institute of High Molecular Weight Compounds, Russian Academy of Science, St. Petersburg, Russian Federation
Yamada, B. Department of Applied Chemistry, Faculty of Technology, Osaka City University, Sumiyoshi, Osaka, Japan
Ueda, A. Osaka Municipal Technical Research Institute, Morinomiya, Joto-ku, Osaka, Japan
Zhu, L. The Maurice Morton Institute of Polymer Science, University of Akron, Akron, Ohio, USA
Preface The purpose of the Polymer Handbook is to bring together the data and constants needed in theoretical and experimental polymer research. All polymer researchers have experienced the frustration of searching for data in the everexpanding polymer literature and know the difficulties involved in trying to locate a particular constant that is buried in a long journal article. The contributors to this Handbook have taken on the arduous task of searching the literature and compiling the data and constants that polymer chemists, polymer physicists, and polymer engineers are likely to need. The 520 and odd tables in this Handbook are divided into eight sections. The first lists the IUPAC nomenclature rules for polymers and the International System of Units. Although several naming conventions exist in the technical literature, IUPAC names permit a consistent listing of all polymers. Section II contains data and constants needed for polymer synthesis, kinetic mechanisms, and thermodynamic studies of polymerization and depolymerization reactions. Sections III and IV contain physical constants of monomers, solvents, and oligomers. Section V lists the physical constants of many important commercial polymers. Section VI and VII cover the solid state properties of polymers and the properties of polymer solutions. Section VIII of the Handbook lists the commonly used abbreviations or acronyms for polymers and Chemical Abstract Registry Numbers, and gives suggestions for electronic data searching for polymer information. This section should also be consulted in the few cases where contributors have not used IUPAC nomenclature. As in the previous editions, the Polymer Handbook concentrates on synthetic polymers, poly(saccharides) and derivatives, and oligomers. Few data on biopolymers are included. Spectroscopic data as well as data needed by engineers and designers, such as mechanical and rheological data, are minimized, since many excellent compilations exist elsewhere. Only fundamental constants and parameters that refer to the polymer molecule, that describe the solid state of polymer molecules, or that describe polymer solutions, were compiled. Constants that depend on processing conditions or on sample history were not emphasized, as they can be found in existing plastics handbooks and encyclopedias.
A critical evaluation of the values published in the literature was not attempted, since such a task would have required an inordinate amount of time and a sizable staff. Therefore, the users of this Handbook should consult the original literature for details when in doubt about the validity of any data. (The authors of the individual tables were nevertheless requested to eliminate obviously erroneous data from otherwise complete compilations.) The Fourth Edition revisions have focused on data generated in the ten years since the publication of the Third Edition. Therefore, a completely revised Polymer Handbook has been prepared. We have added new tables and incorporated a large amount of new data into existing tables. As a result, the Fourth Edition contains approximately twenty-five percent more data, and the number of pages has increased from about 1850 in the Third Edition to about 2250. We hope that this new edition will be as useful to the polymer research community as the three earlier editions and that many of the Polymer Handbook's previous users will also obtain the Fourth Edition for their laboratory and library. The publisher plans a CD-ROM for the Polymer Handbook in the near future. We would be grateful if our contributors and users send us any new data they accumulate in the course of their research, and any errors, misprints, omissions and other flaws. We will pass on such data to the publisher, for the polymer database, and for future editions of this Handbook. We would like to thank all of the contributors to the Polymer Handbook for their help and continued patience. The staff at John Wiley, especially Carla Fjerstad, Shirley Thomas, and Jacqueline Kroschwitz, have provided excellent help and support in getting all the work done. We hope that the outstanding efforts of all these people will find due appreciation among the users of this Handbook. July, 1998
J. Brandrup E. H. Immergut E. A. Grulke A. Abe D. R. Bloch
Contents
Contributors .............................................................................................................................
v
Preface ....................................................................................................................................
ix
I.
Nomenclature Rules – Units
Nomenclature ...............................................................................................................................................
I/1
A. Introduction ........................................................................................................................
I/1
B. IUPAC Recommendations .................................................................................................. 1. Source-based Nomenclature .................................................................................. 1.1 Homopolymers ........................................................................................ 1.2 Copolymers ............................................................................................. 1.3 Nonlinear Macromolecules and Macromolecular Assemblies ................ 2. Structure-based Nomenclature ............................................................................... 2.1 Regular Single-strand Organic Polymers ............................................... 2.2 Regular Double-strand Organic Polymers .............................................. 2.3 Regular Single-strand Inorganic and Coordination Polymers ................. 2.4 Regular Quasi-single-strand Coordination Polymers .............................. 2.5 Irregular Single-strand Organic Polymers ...............................................
I/1 I/2 I/2 I/2 I/3 I/3 I/3 I/6 I/6 I/7 I/7
C. Use of Common and Semisystematic Names .....................................................................
I/8
D. Chemical Abstracts (CA) Index Names ...............................................................................
I/8
E. Polymer Class Names ........................................................................................................
I/11
F. References .........................................................................................................................
I/12
Units .............................................................................................................................................................
I/13
A. Introduction ........................................................................................................................
I/13
B. International Units ..............................................................................................................
I/13
C. SI-prefixes ..........................................................................................................................
I/14
D. Conversion Factors ............................................................................................................
I/14
E. Conversion Table for SI vs. English-american Units ...........................................................
I/17
II.
Polymerization and Depolymerization
Decomposition Rates of Organic Free Radical Initiators ............................................................................
II/1
A. Introduction ........................................................................................................................
II/1
B. Tables of Decomposition Rates of Organic Free Radical Initiators ..................................... Table 1. Azonitriles ............................................................................................................... Table 2. Miscellaneous Azo-derivatives ................................................................................
II/2 II/2 II/9
This page has been reformatted by Knovel to provide easier navigation.
xi
xii
Contents Table 3. Table 4. Table 5. Table 6. Table 7.
Alkyl Peroxides ....................................................................................................... Acyl Peroxides ........................................................................................................ Hydroperoxides and Ketone Peroxides .................................................................. Peresters and Peroxycarbonates ............................................................................ Miscellaneous Initiators ...........................................................................................
II/23 II/29 II/43 II/48 II/67
C. Notes ..................................................................................................................................
II/69
D. References .........................................................................................................................
II/70
Propagation and Termination Constants in Free Radical Polymerization ..................................................
II/77
A. Introduction ........................................................................................................................
II/77
B. Tables of Table 1. Table 2. Table 3. Table 4. Table 5. Table 6. Table 7. Table 8. Table 9. Table 10. Table 11. Table 12. Table 13.
Propagation and Termination Constants ............................................................. Dienes ..................................................................................................................... Olefins ..................................................................................................................... Acrylic Derivatives ................................................................................................... Methacrylic Derivatives ........................................................................................... Itaconic Derivatives ................................................................................................. Fumaric Derivatives ................................................................................................ Vinyl Halides ........................................................................................................... Vinyl Esters ............................................................................................................. Vinyl Ethers ............................................................................................................. Styrene Derivatives ................................................................................................. Vinyl Heteroaromatics ............................................................................................. Aldehydes ............................................................................................................... Others .....................................................................................................................
II/79 II/79 II/79 II/80 II/82 II/85 II/87 II/87 II/87 II/88 II/88 II/90 II/90 II/90
C. References .........................................................................................................................
II/91
Transfer Constants to Monomers, Polymers, Catalysts and Initiators, Solvents and Additives, and Sulfur Compounds in Free Radical Polymerization ...........................................................................
II/97
A. Introduction ........................................................................................................................
II/97
B. Tables of Transfer Constants ............................................................................................. Table 1. Transfer Constants to Monomers ........................................................................... Table 2. Transfer Constants to Polymers ............................................................................. Table 3. Transfer Constants to Catalysts and Initiators ........................................................ Table 4. Transfer Constants to Solvents and Additives ........................................................ Table 5. Transfer Constants to Sulfur Compounds ...............................................................
II/98 II/98 II/103 II/106 II/110 II/150
C. Remarks .............................................................................................................................
II/157
D. References .........................................................................................................................
II/159
Photopolymerization Reactions ...................................................................................................................
II/169
A. Introduction ........................................................................................................................
II/169
B. Tables ................................................................................................................................ Table 1. Rate Constants of Cleavage, Electron Transfer and Monomer Quenching in Radical Photoinitiators ............................................................................................ Annex to Table 1. Photoinitiator Compound Chemistries ......................................
II/170
This page has been reformatted by Knovel to provide easier navigation.
II/170 II/173
Contents Table 2. Bimolecular Rate Constants for the Reaction of Phosphonyl Radicals with Various Monomers in Cyclohexane at Room Temperature .................................... Table 3. Bimolecular Rate Constants for the Reaction of Various Radicals with Various Olefinic Monomers at Room Temperature ................................................. Table 4. Bimolecular Rate Constants for the Reaction of Ph2P = O and Ph2P = S with Various Monomers .................................................................................................. Table 5. Electron Transfer Reaction of Radicals with Diphenyliodonium Salts .................... Table 6. Electron Transfer Rate Constants (ke) between Photosensitizers and Cationic Photoinitiators and Quenching Rate Constants (kq) for Cyclohexene Oxide in Methanol (M) and Acetonitrile (AN) .......................................................... Table 7. Excitation Transfer Rate Constants (kT) for Thioxanthones and Photoinitiators ......................................................................................................... Annex to Table 7. Compound Chemistries ............................................................ Table 8. Triplet State Lifetimes (τT) of the Sensitizer (TXI) in Different Media, and Rate Constant (kT) of the Interaction between TXI and TPMK ............................... Table 9. Some Values of the Triplet State Energy Levels of Photoinitiators and Monomers ............................................................................................................... Table 10. Values of τ0T, τT, and kba in Solution ........................................................................ Table 11. Rate Constant of Interaction of Ketones and Light Stabilizers in Solution .............. Annex to Table 11 ...................................................................................................
xiii II/176 II/176 II/176 II/176
II/177 II/178 II/178 II/179 II/179 II/179 II/179 II/179
C. References .........................................................................................................................
II/180
Free Radical Copolymerization Reactivity Ratios .......................................................................................
II/181
A. Introduction ........................................................................................................................
II/181
B. Tables ................................................................................................................................ Table 1. Copolymer Reactivity Ratios ................................................................................... Acenaphthalene to Fumarate, bis(3-chloro-2-butyl) ................................................ Fumarate, di-(2-chloroethyl) to N-N-divinylaniline ................................................... N-vinylimidazole to Styrene, p-2-(2-hydroxypropyl)- ............................................... Styrene, p-4-methoxyphenyl ketone to Vinylbenzoate, p-, sodium ......................... Vinylbenzoic acid, p- to Xanthate, S-methacryloyl O-ethyl ..................................... Table 2. Listing of Quick Basic (Microsoft) Program for Calculating Reactivity Ratios .........
II/182 II/182 II/182 II/212 II/241 II/268 II/285 II/288
C. References .........................................................................................................................
II/290
Q and e Values for Free Radical Copolymerizations of Vinyl Monomers and Telogens ...........................
II/309
A. Introduction ........................................................................................................................
II/309
B. Q and e Table 1. Table 2. Table 3. Table 4.
Values for Free Radical Copolymerizations .......................................................... Monomers ............................................................................................................... Telogens ................................................................................................................. Monomers Arranged by Q Values ........................................................................... Monomers Arranged by e Values ...........................................................................
II/310 II/310 II/314 II/314 II/317
C. References .........................................................................................................................
II/319
Patterns of Reactivity (U,V) Parameters for the Prediction of Monomer Reactivity Ratios and Transfer Constants in Radical Polymerization ...................................................................................
II/321
A. Introduction ........................................................................................................................
II/321
This page has been reformatted by Knovel to provide easier navigation.
xiv
Contents B. Example .............................................................................................................................
II/322
C. Transfer Constants .............................................................................................................
II/322
D. Tables of Parameters ......................................................................................................... Table 1. Monomers ............................................................................................................... Table 2. Transfer Agent ........................................................................................................
II/323 II/323 II/326
E. References .........................................................................................................................
II/327
Copolymerization Parameters of Metallocene-catalyzed Copolymerizations ............................................
II/329
A. Introduction ........................................................................................................................
II/329
B. A Brief Theoretical Outline of Copolymerization Reactions ................................................. 1. First-order Markov Model ........................................................................................ 2. Second-order Markov Model ...................................................................................
II/329 II/330 II/330
C. Calculation of the Copolymerization Parameters ................................................................ 1. First-order Markov Model ........................................................................................ 1.1. Copolymerization Parameters Deduced from the Mayo-lewis Equation .................................................................................................. 1.2. Determination of Copolymerization Parameters from the Sequence Distribution (Triad Distribution) .............................................. 2. Second-order Markov Model ................................................................................... 3. Example ..................................................................................................................
II/331 II/331
D. Table of Copolymerization Parameters ...............................................................................
II/333
E. List of Catalysts/Cocatalysts Used .....................................................................................
II/336
F. References .........................................................................................................................
II/336
Rates of Polymerization and Depolymerization, Average Molecular Weights, and Molecular Weight Distribution of Polymers .........................................................................................................
II/339
A. Introduction ........................................................................................................................
II/339
B. Reference Tables for the Calculation of Rates of Polymerization, Average Molecular Weights, and Molecular Weight Distributions of Polymers for Various Types of Polymerization .................................................................................................................... Table 1. Addition Polymerization with Termination ............................................................... Table 2. Addition Polymerization - "Living" Polymers with Partial Deactivation .................... Table 3. Linear Condensation Polymerization without Ring Formation ................................ Table 4. Equilibrium Polymerization ...................................................................................... Table 5. Nonlinear Polymerization Systems ......................................................................... Table 6. Degradation of Polymers - May Be Accompanied by Crosslinking ......................... Table 7. Influence of Reactor Conditions and Design on the Molecular Weight Distribution ..............................................................................................................
II/340 II/341 II/344 II/346 II/347 II/348 II/350
C. Some Distribution Functions and Their Properties .............................................................. 1. Normal Distribution Function (Gaussian Distribution) ............................................. 2. Logarithmic Normal Distribution Function ............................................................... 3. Generalized Exponential Distribution ...................................................................... 4. Poisson Distribution ................................................................................................
II/352 II/353 II/353 II/354 II/354
This page has been reformatted by Knovel to provide easier navigation.
II/331 II/331 II/332 II/332
II/352
Contents
xv
D. Molecular Weight Distribution in Condensation Polymers: the Stockmayer Distribution Function ...........................................................................................................
II/354
E. References .........................................................................................................................
II/356
Heats and Entropies of Polymerization, Ceiling Temperatures, Equilibrium Monomer Concentrations, and Polymerizability of Heterocyclic Compounds ...................................................
II/363
A. Heats of Polymerization ...................................................................................................... Table 1. Monomers Giving Polymers Containing Carbon Atoms Only in the Main Chain ....................................................................................................................... 1.1 With Acyclic Carbons Only in the Main Chain ........................................
II/365
1.1.1 Dienes ..............................................................................................
II/365
1.1.2 Monomers Giving Polymers with or without Aliphatic Side Chains That Contain Only C, H ........................................................
II/365
1.1.3 Monomers Giving Polymers with Aliphatic Side Chains That Contain Heteroatoms .......................................................................
II/368
1.1.4 Monomers Giving Polymers with Aromatic Side Chains That Contain Only C, H ............................................................................
II/371
1.1.5 Monomers Giving Polymers with Aromatic Side Chains and That Contain Heteroatoms ............................................................... 1.2 With Aromatic or Cyclic Carbons in the Main Chain ............................... Table 2. Monomers Giving Polymers Containing Heteroatoms in the Main Chain ............... 2.1 Monomers Giving Polymers Containing O in the Main Chain, Bonded to Carbon Only ..........................................................................
II/365 II/365
II/371 II/372 II/373 II/373
2.1.1 Ethers and Acetals ...........................................................................
II/373
2.1.2 Cyclic Esters ..................................................................................... 2.2 Monomers Giving Polymers Containing O in the Main Chain, Bonded to Other Heteroatoms (S, Si, P) ................................................ 2.3 Monomers Giving Polymers Containing S in the Main Chain, Bonded in the Chain to Carbon Only ...................................................... 2.4 Monomers Giving Polymers Containing N in the Main Chain, Bonded in the Chain to Carbon Only ...................................................... 2.5 Monomers Giving Polymers Containing N in the Main Chain, Bonded to Other Heteroatoms (P) .......................................................... 2.6 Other Monomers Giving Polymers Not Listed Above ............................. Table 3. Copolymers .............................................................................................................
II/376 II/377 II/378 II/378 II/379 II/379 II/380
B. Entropies of Polymerization ................................................................................................ Table 4. Monomers Giving Polymers Containing Main Chain Carbon Only ......................... 4.1 Main Chain Acyclic Carbon Only ............................................................
II/381 II/382 II/382
4.1.1 Dienes ..............................................................................................
II/382
4.1.2 Monomers Giving Polymers without or with Aliphatic Side Chains That Contain Only C, H ........................................................
II/382
4.1.3 Monomers Giving Polymers with Aliphatic Side Chains That Contain Heteroatoms .......................................................................
II/384
This page has been reformatted by Knovel to provide easier navigation.
xvi
Contents 4.1.4 Monomers Giving Polymers with Aromatic Side Chains That Contain Only C, H ............................................................................
II/385
4.1.5 Monomers Giving Polymers with Aromatic Side Chains That Contain Heteroatoms .......................................................................
II/385
4.1.6 Other Monomers Giving Polymers Not Listed Above ...................... 4.2 With Aromatic or Cyclic Carbons in the Main Chain ............................... Table 5. Monomers Giving Polymers Containing Heteroatoms in the Main Chain ............... 5.1 Monomers Giving Polymers Containing O in the Main Chain, Bonded to Carbon Only ..........................................................................
II/386 II/386 II/387
5.1.1 Ethers and Acetals ...........................................................................
II/387
5.1.2 Cyclic Esters ..................................................................................... 5.2 Monomers Giving Polymers Containing O in the Main Chain, Bonded to Other Heteroatoms (S, Si, P) ................................................ 5.3 Monomers Giving Polymers Containing N in the Main Chain, Bonded in the Chain to Carbon Only ...................................................... 5.4 Other Monomers Giving Polymers Not Listed Above ............................. Table 6. Copolymers .............................................................................................................
II/390
C. Ceiling Temperatures and Equilibrium Monomer Concentrations ....................................... 1. Equilibria Involving Pure Liquid Monomers ............................................................. Table 7. Monomers Giving Polymers Containing Main Chain Acyclic Carbon Only ............................................................................................ Table 8. Monomers Giving Polymers Containing Heteroatoms in the Main Chain ...................................................................................................... 8.1
II/391 II/391 II/392 II/392 II/393 II/394 II/394 II/395
Monomers Giving Polymers Containing O in the Main Chain, Bonded to Carbon Only ....................................................................
II/395
Monomers Giving Polymers Containing O in the Main Chain, Bonded to Other Heteroatoms (S, P, Si) .........................................
II/396
Monomers Giving Polymers Containing S in the Main Chain, Bonded in the Chain to Carbon Only ...............................................
II/396
Monomers Giving Polymers Containing N in the Main Chain, Bonded in the Chain to Carbon Only ...............................................
II/397
8.5 Other Monomers Giving Polymers Not Listed Above ...................... Equilibria Involving Gaseous Monomers ................................................................. Equilibria Involving Monomers in Solution .............................................................. Table 9. Monomers Giving Polymers Containing Main Chain Carbon Only .........
II/397 II/397 II/398 II/398
8.2 8.3 8.4
2. 3.
II/387
9.1
Monomers Giving Polymers Containing Main Chain Acyclic Carbon Only .....................................................................................
II/398
9.2
Monomers Giving Polymers Containing Main Chain Cyclic Carbon .............................................................................................. Table 10. Monomers Giving Polymers Containing Heteroatoms in the Main Chain ......................................................................................................
II/399
10.1 Monomers Giving Polymers Containing O in the Main Chain, Bonded to Carbon Only ....................................................................
II/399
This page has been reformatted by Knovel to provide easier navigation.
II/399
Contents
xvii
10.2 Monomers Giving Polymers Containing O in the Main Chain, Bonded to Other Heteroatoms (Si, P) ..............................................
II/400
10.3 Monomers Giving Polymers Containing S in the Main Chain, Bonded in the Chain to Carbon Only ...............................................
II/400
10.4 Monomers Giving Polymers Containing N in the Main Chain, Bonded in the Chain to Carbon Only ............................................... Table 11. Copolymers .............................................................................................
II/400 II/401
11.1 1:1 Copolymers ................................................................................
II/401
11.2 General Copolymers ........................................................................
II/401
D. Polymerizability of 5-, 6-, and 7-membered Heterocyclic Ring Compounds ........................ Table 12. 5-membered Ring Compounds ............................................................................... Table 13. 6-membered Ring Compounds ............................................................................... Table 14. 7-membered Ring Compounds ............................................................................... Table 15. Comparison of Polymerizability (+ or -)of Unsubstituted 5-, 6- and 7-membered Ring Compounds ...............................................................................
II/401 II/402 II/403 II/404
E. Notes ..................................................................................................................................
II/406
F. References .........................................................................................................................
II/407
Activation Energies of Propagation and Termination in Free Radical Polymerization ...............................
II/415
A. Introduction ........................................................................................................................
II/415
B. Tables ................................................................................................................................ Table 1. Dienes ..................................................................................................................... Table 2. Olefins ..................................................................................................................... Table 3. Acrylic Derivatives ................................................................................................... Table 4. Methacrylic Derivatives ........................................................................................... Table 5. Vinyl Halogens ........................................................................................................ Table 6. Vinyl Ethers and Vinyl Esters .................................................................................. Table 7. Styrene and Derivatives .......................................................................................... Table 8. Vinyl Heteroaromatics ............................................................................................. Table 9. Miscellaneous Compounds .....................................................................................
II/416 II/416 II/416 II/417 II/418 II/420 II/421 II/421 II/422 II/423
C. References .........................................................................................................................
II/424
Activation Volumes of Polymerization Reactions ........................................................................................
II/429
A. Introduction ........................................................................................................................
II/429
3
II/405
B. Activation Volumes (sm /mol) of Some Polymerization Reactions ......................................
II/432
C. Activation Volumes of Initiator Decomposition ....................................................................
II/435
D. Activation Volumes of Chain Propagation ...........................................................................
II/435
E. Activation Volumes of Chain Termination ...........................................................................
II/436
F. Activation Volumes of Chain Transfer Reactions ................................................................
II/436
G. Influence of Pressure on Copolymerization ........................................................................ Table 1. Copolymerization Parameters ................................................................................. Table 2. Reactivity Ratios of Terpolymerization .................................................................... Table 3. Activation Volumes ................................................................................................. Table 4. Q, e Values .............................................................................................................
II/437 II/437 II/438 II/439 II/440
This page has been reformatted by Knovel to provide easier navigation.
xviii
Contents H. References .........................................................................................................................
II/440
Activation Enthalpies and Entropies of Stereocontrol in Free Radical Polymerizations .............................
II/445
A. Introduction ........................................................................................................................
II/445
B. Tables ................................................................................................................................ Table 1. Ratios of Some i-ADS for Different Mechanisms .................................................... Table 2. Ratios of Rate Constants for Markov First Order Mechanisms ............................... Table 3. ∆H++s/i - ∆H++i/s and ∆S++s/i - ∆S++i/s of Free Radical Polymerizations in Different Solvents .................................................................................................... Table 4. Activation Enthalpy Differences (∆H++A - ∆H++B) Calculated from Various Literature Data ........................................................................................................ Table 5. Activation Entropy Differences (∆S++A - ∆S++B) Calculated from Various Literature Data ........................................................................................................ Table 6. Calculated Compensation Temperatures T0 and Compensation Enthalpies ∆∆H++0 for Various Monomers and Modes of Addition, Assuming Markov First Order Trials .....................................................................................................
II/446 II/446 II/446
C. References .........................................................................................................................
II/450
Products of Thermal Degradation of Polymers ...........................................................................................
II/451
A. Introduction ........................................................................................................................
II/451
B. Tables ................................................................................................................................ Table 1. Main-chain Acyclic Carbon Polymers ..................................................................... Table 2. Main-chain Carbocyclic Polymers ........................................................................... Table 3. Main-chain Heteroatom Polymers ........................................................................... Table 4. Main-chain Heterocyclic Polymers .......................................................................... Table 5. Cellulose and Its Derivatives ...................................................................................
II/451 II/451 II/464 II/465 II/473 II/475
C. References .........................................................................................................................
II/475
Radiation Chemical Yields: G Values ..........................................................................................................
II/481
A. Introduction ........................................................................................................................
II/481
B. Tables of G Values ............................................................................................................. Table 1. Homopolymers ........................................................................................................ 1.1 Polydienes .............................................................................................. 1.2 Polyolefins .............................................................................................. 1.3 Polyacrylates .......................................................................................... 1.4 Poly(methacrylates) ................................................................................ 1.5 Poly(styrenes) ......................................................................................... 1.6 Poly(vinyls) .............................................................................................
II/481 II/482 II/482 II/482 II/483 II/484 II/485 II/486
1.6.1 Acrylamides and Nitriles ...................................................................
II/486
1.6.2 Vinyl Monomers ................................................................................ Miscellaneous Polymers .........................................................................
II/486 II/487
1.7.1 Cellulose and Derivatives .................................................................
II/487
1.7.2 Poly(siloxanes) .................................................................................
II/487
1.7.3 Poly(amino Acids) ............................................................................
II/487
1.7.4 Polyesters .........................................................................................
II/488
1.7
This page has been reformatted by Knovel to provide easier navigation.
II/447 II/448 II/449
II/449
Contents
III.
xix
1.7.5 Polysulfones .....................................................................................
II/488
1.7.6 Polyketones ......................................................................................
II/488
1.7.7 Fluoropolymers .................................................................................
II/488
1.7.8 Others ............................................................................................... Table 2. Copolymers ............................................................................................................. 2.1 Copolymers with Ethylene ...................................................................... 2.2 Copolymers with Methyl Methacrylate .................................................... 2.3 Copolymers with Styrene ........................................................................ 2.4 Copolymers with Sulfur Dioxide .............................................................. 2.5 Other Copolymers ................................................................................... Table 3. Polymers Blends ..................................................................................................... Table 4. Composites .............................................................................................................
II/489 II/490 II/490 II/490 II/491 II/491 II/492 II/493 II/493
C. References .........................................................................................................................
II/493
Physical Properties of Monomers and Solvents
Physical Properties of Monomers ................................................................................................................
III/1
A. Introduction ........................................................................................................................
III/1
B. Tables of Table 1. Table 2. Table 3. Table 4.
Table 5.
Table 6.
Table 7. Table 8. Table 9.
Table 10.
Table 11.
Physical Properties ............................................................................................. Acetylenes .............................................................................................................. Acid Dichlorides ...................................................................................................... Acroleins ................................................................................................................. Acrylamides/Methacrylamides ................................................................................ 4.1 Acrylamides ............................................................................................ 4.2 Methacrylamide ...................................................................................... Acrylates/Methacrylates .......................................................................................... 5.1 Acrylate, Acids/Esters ............................................................................. 5.2 Methacrylate, Acids/Esters ..................................................................... Alcohols .................................................................................................................. 6.1 Alkanediols ............................................................................................. 6.2 Ether Diols .............................................................................................. Allyl Functional ........................................................................................................ Amines, Difunctional ............................................................................................... Anhydrides .............................................................................................................. 9.1 Monoanhydrides ..................................................................................... 9.2 Dianhydrides ........................................................................................... Butadienes .............................................................................................................. 10.1 1,2-butadienes ........................................................................................ 10.2 1,3-butadienes ........................................................................................ Butenes ................................................................................................................... 11.1 1-butenes ................................................................................................ 11.2 2-butenes ................................................................................................
This page has been reformatted by Knovel to provide easier navigation.
III/4 III/4 III/4 III/4 III/4 III/4 III/6 III/8 III/8 III/12 III/16 III/16 III/18 III/18 III/20 III/20 III/20 III/24 III/24 III/24 III/24 III/26 III/26 III/26
xx
Contents Table 12. Epoxides ................................................................................................................. 12.1 Monoepoxides ........................................................................................ 12.2 Diepoxides .............................................................................................. Table 13. Ethylene Halides ..................................................................................................... Table 14. Fumaric, Acids/Esters ............................................................................................. Table 15. lsocyanates ............................................................................................................. Table 16. Lactams .................................................................................................................. Table 17. Lactones ................................................................................................................. Table 18. Maleate, Acids/Esters ............................................................................................. Table 19. Propenes ................................................................................................................. Table 20. Styrenes .................................................................................................................. Table 21. Vinyl Functional ....................................................................................................... 21.1 Aryl .......................................................................................................... 21.2 Esters ...................................................................................................... 21.3 Ethers ..................................................................................................... 21.4 N-substituted ........................................................................................... 21.5 Sulfonates ...............................................................................................
III/26 III/26 III/28 III/28 III/30 III/30 III/32 III/32 III/32 III/32 III/34 III/36 III/36 III/36 III/38 III/38 III/40
Isorefractive and Isopycnic Solvent Pairs ....................................................................................................
III/43
A. Introduction ........................................................................................................................
III/43
B. Table of Isorefractive and Isopycnic Solvent Pairs ..............................................................
III/43
Refractive Indices of Common Solvents .....................................................................................................
III/55
A. Introduction ........................................................................................................................
III/55
B. Table of Refractive Indices of Common Solvents ...............................................................
III/55
Physical Constants of the Most Common Solvents for Polymers ...............................................................
III/59
IV.
Physical Data of Oligomers
Physical Data of Oligomers .........................................................................................................................
IV/1
A. Introduction ........................................................................................................................
IV/2
B. Oligomers Containing Main Chain Acyclic Carbon Only ..................................................... Table 1. Oligo(olefins) ........................................................................................................... 1.1. Oligo(methylenes) and Oligo(ethylenes) ................................................ 1.2. Oligo(perfluoromethylenes) and Oligo(perfluoroethylenes) .................... 1.3. Oligo(isobutenes) .................................................................................... 1.4. Oligo(1-alkenylenes) ............................................................................... References .............................................................................................................. Table 2. Oligo(dienes) ........................................................................................................... 2.1. Oligomers of 1,3-butadiene .................................................................... 2.2. Oligomers of lsoprene ............................................................................. 2.3. Oligomers of 1,3-butadiene Derivatives .................................................. 2.4. 1,4-oligo(alkadienes) .............................................................................. 2.5. Oligomers of Cyclopentadiene and 1,3-cyclohexadiene .........................
IV/3 IV/3 IV/3 IV/6 IV/8 IV/9 IV/9 IV/14 IV/14 IV/15 IV/16 IV/16 IV/17
This page has been reformatted by Knovel to provide easier navigation.
Contents
xxi
2.6. Oligomers of Allene ................................................................................ References .............................................................................................................. Table 3. Oligo(acetylenes) .................................................................................................... 3.1. Linear Oligomers of Acetylene ................................................................ 3.2. Polyenyne Oligomers .............................................................................. 3.3. Oligomeric α-ω-diynes ............................................................................ 3.4. Oligo(alkynes) ......................................................................................... 3.5. Cyclic Oligo(alkynes) .............................................................................. 3.6. Pericyclynes ............................................................................................ References .............................................................................................................. Table 4. Oligomers with Aliphatic Side Chains Which in Addition Contain Heteroatoms ........................................................................................................... 4.1. Oligomeric Acrylic Derivatives ................................................................ 4.2. Oligomeric Methacrylic Derivatives ......................................................... 4.3. Oligomers of β-alkyl Substituted Vinyl Derivatives ................................. 4.4. Oligo(vinyl) Derivatives ........................................................................... References .............................................................................................................. Table 5. Oligo(styrenes) ........................................................................................................ References ..............................................................................................................
IV/17 IV/18 IV/19 IV/19 IV/20 IV/20 IV/20 IV/20 IV/21 IV/21
C. Oligomers Contaning Heteroatoms in the Main Chain ........................................................ Table 6. Oligomers Containing O in the Main Chain ............................................................. 6.1. Oligo(ethers) and Oligo(acetals) .............................................................
IV/33 IV/33 IV/33
6.2.
References .................................................................................................. Oligo(carbonates) ...................................................................................
IV/43 IV/47
6.3.
References .................................................................................................. Oligo(esters) ...........................................................................................
IV/47 IV/48
6.4.
References .................................................................................................. Oligo(urethanes) .....................................................................................
IV/56 IV/58
References .................................................................................................. Table 7. Oligo(sulfides) and Oligo(selenides) ....................................................................... 7.1. Cyclic Oligo(thiomethylenes) and Oligo(Selenomethylenes) .................. 7.2. Cyclic Oligo(thioalkylenes) ...................................................................... 7.3. Substituted Cyclic(thioethylenes) ............................................................ 7.4. Cyclic Co-oligomers of Formaldehyde and Thioformaldehyde ............... 7.5. Cyclic Oligo(ether Sulfides) .................................................................... 7.6. Thiacyclophanes ..................................................................................... References .............................................................................................................. Table 8. Oligomers Containing N in the Main Chain ............................................................. 8.1. Oligo(amides) .........................................................................................
IV/61 IV/62 IV/62 IV/62 IV/62 IV/62 IV/63 IV/63 IV/63 IV/64 IV/64
References .................................................................................................. Oligo(peptides) .......................................................................................
IV/70 IV/72
References ..................................................................................................
IV/84
8.2.
This page has been reformatted by Knovel to provide easier navigation.
IV/22 IV/22 IV/24 IV/26 IV/27 IV/28 IV/30 IV/32
xxii
Contents 8.3.
Oligo(imines) ...........................................................................................
IV/88
8.4.
References .................................................................................................. Oligo(ureas) ............................................................................................
IV/89 IV/89
References ..................................................................................................
IV/90
D. Carbon Chain Oligomers Containing Main Chain Cyclic Units ............................................ Table 9. Oligo(cyclopentylenes) ............................................................................................ Table 10. Oligo(spiranes) ........................................................................................................ Table 11. Oligo(xylylenes) ...................................................................................................... 11.1. Linear Oligo(xylenes) .............................................................................. 11.2. Cyclic Oligo(xylylenes) ............................................................................ Table 12. Oligo(stilbenes) ....................................................................................................... Table 13. Oligo(benzyls) ......................................................................................................... Table 14. Oigo(2,5-dimethyl-benzyls) ..................................................................................... Table 15. Oligo(2,3,5,6-tetramethyl-benzyls) .......................................................................... Table 16. Oligo(p-phenylene Oxides) ..................................................................................... Table 17. Oligo(p-phenylene Sulfides) .................................................................................... Table 18. Oligo(p-phenoxyphenylmethanes) .......................................................................... Table 19. Oligo(diphenylmethanes) ........................................................................................ References .............................................................................................................. Table 20. Phenol-formaldehyde and Related Oligomers ........................................................ 20.1. Linear Phenol-formaldehyde Oligomers ................................................. 20.2. Oligomeric Phenol Alcohols .................................................................... 20.3. Cyclic Phenol-formaldehyde Oligomers .................................................. 20.4. Branched Phenol-formaldehyde Oligomers ............................................ 20.5. Hydroquinone Oligomers ........................................................................ References .............................................................................................................. Table 21. Oligo(phenylenes) ................................................................................................... 21.1. o-oligo(phenylenes) ................................................................................ 21.2. m-oligo(phenylenes) ............................................................................... 21.3. p-oligo(phenylenes) ................................................................................ 21.4. Oligo(p-quinones) ................................................................................... References ..............................................................................................................
IV/90 IV/90 IV/90 IV/90 IV/90 IV/90 IV/91 IV/91 IV/91 IV/91 IV/91 IV/91 IV/91 IV/91 IV/91 IV/92 IV/92 IV/93 IV/94 IV/94 IV/95 IV/95 IV/96 IV/96 IV/96 IV/97 IV/98 IV/98
E. Oligomers Containing Heterocyclic Rings in the Main Chain .............................................. Table 22. Heterocyclic Oligomers ........................................................................................... 22.1 Oligo(furan) Derivatives .......................................................................... 22.2. Oligo(thiophene) Derivatives .................................................................. 22.3. Oligo(pyrrole) Derivatives ....................................................................... 22.4. Oligo(pyridine) Derivatives ...................................................................... 22.5. Cyclic Oligo(heterocyclics) ...................................................................... References .............................................................................................................. Table 23. Oligo(saccharides) .................................................................................................. 23.1. Oligomeric Pentoses ...............................................................................
IV/99 IV/99 IV/99 IV/100 IV/100 IV/100 IV/101 IV/101 IV/102 IV/102
This page has been reformatted by Knovel to provide easier navigation.
Contents
xxiii
23.2. Oligomeric Hexoses ................................................................................ IV/102 23.3. Oligomeric Amino Sugars ....................................................................... IV/103 References .............................................................................................................. IV/104
V.
Physical Constants of Some Important Polymers
Physical Constants of Rubbery Polymers ...................................................................................................
V/1
A. Introduction ........................................................................................................................
V/1
B. Tables ................................................................................................................................ Table 1. 1,4-cis(96-98%)Poly(butadiene) ............................................................................. Table 2. Poly(butadiene-co-acrylonitrile) .............................................................................. Table 3. Poly(butadiene-co-styrene) ..................................................................................... Table 4. Poly(chloroprene)(CR Neoprene) ........................................................................... Table 5. Poly(isobutene)-co-isoprene) Butyl Rubber (IIR) .................................................... Table 6. Polyisoprene, Natural Rubber ................................................................................. Table 7. Ethylene-propylene-diene-terpolymer (EPDM) .......................................................
V/1 V/1 V/2 V/3 V/3 V/4 V/5 V/6
C. References .........................................................................................................................
V/6
Physical Constants of Poly(ethylene) ..........................................................................................................
V/9
A. Crystallographic Data and Crystallographic Modifications ..................................................
V/9
B. Molecular Parameters and Solution Properties ...................................................................
V/9
C. Crystallinity, Crystal Size and Crystallization Kinetics .........................................................
V/10
D. Equilibrium Thermodynamic Properties ..............................................................................
V/11
E. Other General Physical Properties .....................................................................................
V/12
F. Effect of Chain Branching (Short) on Physical Properties ...................................................
V/15
G. Properties of a Series of Selected Poly(ethylene) Samples ................................................
V/16
H. Properties of Typical Poly(ethylenes) .................................................................................
V/17
I.
References .........................................................................................................................
V/17
Physical Constants of Poly(propylene) ........................................................................................................
V/21
A. Crystallographic Data and Modifications of Isotactic Polypropylenes ..................................
V/21
B. Crystallographic Data and Modifications of Syndiotactic Polypropylenes ............................
V/21
C. Dimensions of Poly(propylene) Molecules ..........................................................................
V/22
D. Crystallinity and Crystallization Kinetics ..............................................................................
V/22
E. Equilibrium Thermodynamic Properties ..............................................................................
V/23
F. Other General Properties ...................................................................................................
V/24
G. Properties of Typical Mainly Isotactic Poly(propylenes) ......................................................
V/26
H. Properties of Some Commercial Poly(propylene) Grades ...................................................
V/26
I.
Mechanical Properties of Poly(propylene) Homopolymers ..................................................
V/27
J. Mechanical Properties of Poly(propylene) Random Copolymers ........................................
V/28
K. Mechanical Properties of Poly(propylene) Impact Copolymers ...........................................
V/28
L. References .........................................................................................................................
V/28
Physical Constants of Fluoropolymers ........................................................................................................
V/31
A. Introduction ........................................................................................................................
V/31
This page has been reformatted by Knovel to provide easier navigation.
xxiv
Contents B. Physical Constants of Poly(tetrafluoroethylene) ................................................................. Notes ....................................................................................................................................... Infrared Absorption Spectrum of Poly(tetrafluoroethylene) ..................................................... References ..............................................................................................................................
V/31 V/37 V/38 V/39
C. Physical Constants of Melt Processible Fluorocarbon Polymers PFA and FEP .................. Notes ....................................................................................................................................... References ..............................................................................................................................
V/41 V/44 V/45
D. Physical Constants of Modified Poly(ethylene-co-tetrafluoroethylene) ................................ Notes ....................................................................................................................................... References ..............................................................................................................................
V/45 V/48 V/48
E. Physical Constants of Poly(vinylidene Fluoride) ................................................................. Notes ....................................................................................................................................... References ..............................................................................................................................
V/48 V/51 V/52
F. Physical Constants of Amorphous Fluoropolymers ............................................................. Notes ....................................................................................................................................... References ..............................................................................................................................
V/52 V/54 V/54
G. Physical Constants of Poly(chlorotrifluoroethylene) ............................................................ Notes ....................................................................................................................................... References ..............................................................................................................................
V/55 V/57 V/58
Physical Constants of Poly(acrylonitrile) .....................................................................................................
V/59
A. Tables of Table 1. Table 2. Table 3. Table 4. Table 5. Table 6. Table 7. Table 8. Table 9.
Physical Constants ............................................................................................. Crystallinity/Crystallization Behavior ....................................................................... Electric and Electronic Properties ........................................................................... Fiber Properties ...................................................................................................... Further Properties of Acrylic Fibers ........................................................................ Optical Properties ................................................................................................... Polymerization: Kinetic and Thermodynamic Data ................................................. Solubility/Solution Properties .................................................................................. Special Solid State Properties ................................................................................ Thermal and Thermodynamic Data ........................................................................
V/59 V/59 V/60 V/61 V/61 V/61 V/62 V/62 V/63 V/64
B. References .........................................................................................................................
V/64
Physical Constants of Poly(vinyl Chloride) ..................................................................................................
V/67
Physical Constants of Poly(vinyl Acetate) ...................................................................................................
V/77
Physical Constants of Poly(methyl Methacrylate) .......................................................................................
V/87
Physical Constants of Poly(styrene) ............................................................................................................
V/91
Physical Constants of Poly(oxymethylene) .................................................................................................
V/97
Physical Constants of Poly(oxyethylene-oxyterephthaloyl), (Poly(ethylene Terephthalate)) .....................
V/113
Physical Constants of Poly(oxytetramethylene-oxyterephthaloyl) and Copolymers with Tetramethylene Oxide Thermoplastic Elastomers .............................................................................
V/119
Physical Constants of Various Polyamides: Poly[imino(1-oxohexamethylene)], (Polyamide 6) Poly(iminoadipoyl-iminohexamethylene), (Polyamide 66), Poly(iminohexamethyleneiminosebacoyl), (Polyamide 610), Poly[imino(1-oxododecamethylene)], Poly(amide 12) ................
V/121
This page has been reformatted by Knovel to provide easier navigation.
Contents
xxv
Physical Constants of Cellulose ..................................................................................................................
V/135
A. Introduction ........................................................................................................................
V/135
B. Solid State Properties ......................................................................................................... Table 1. Unit Cell Dimensions ............................................................................................... Table 2. Density .................................................................................................................... Table 3. Average Ordered Fraction of Cotton and Linters Measured by Various Techniques ............................................................................................................. Table 4. Average Ordered Fraction Measured by Various Techniques ................................ Table 5. Degree of Crystallinity ............................................................................................. Table 6. Crystallite Sizes ...................................................................................................... Table 7. X-ray Orientation of Cellulose Fibers ...................................................................... Table 8. Heat Capacity ......................................................................................................... Table 9. Thermal Expansion Coefficient ............................................................................... Table 10. Other Thermal Properties ....................................................................................... Table 11. Refractive Index and Birefringence ......................................................................... Table 12. Resistivity ................................................................................................................ Table 13. Dielectric Constant and Loss Factor at 1 kHz ......................................................... Table 14. Other Electrical Properties ...................................................................................... Table 15. Crystal Elastic Modulus E1 in Chain Direction ......................................................... Table 16. Fiber Strength, Elongation and Modulus .................................................................
V/136 V/136 V/136
C. Solution Properties ............................................................................................................. Table 17. Typical Non-aqueous Cellulose Solvents ............................................................... Table 18. Other Solvents ........................................................................................................ Table 19. Viscosity - Molecular Weight Relationships ............................................................ Table 20. Second Virial Coefficients ....................................................................................... Table 21. Sedimentation and Diffusion Coefficients ............................................................... Table 22. Partial Specific Volumes, ν2 .................................................................................... Table 23. Geometrical Chain Characteristics ......................................................................... Table 24. Polymer-solvent Interaction Parameters .................................................................
V/147 V/147 V/148 V/148 V/150 V/150 V/151 V/151 V/152
D. References .........................................................................................................................
V/152
Physical and Mechanical Properties of Some Important Polymers ............................................................
V/159
A. Introduction ........................................................................................................................
V/159
B. Narrative Descriptions ........................................................................................................ 1. Multipurpose Polymers ........................................................................................... 2. Polyolefins and Barrier Polymers ............................................................................ 3. Styrenics and Engineering Thermoplastics ............................................................. 4. Elastomers ..............................................................................................................
V/159 V/159 V/160 V/160 V/161
C. Properties of Commercial Polymers ................................................................................... Table 1. Multipurpose Thermoplastics .................................................................................. Table 2. Polyolefins and Barrier Polymers ............................................................................ Table 3. Styrenics and Engineering Thermoplastics ............................................................. Table 4. Elastomers ..............................................................................................................
V/162 V/162 V/164 V/166 V/168
This page has been reformatted by Knovel to provide easier navigation.
V/136 V/137 V/137 V/138 V/140 V/140 V/141 V/141 V/144 V/144 V/145 V/146 V/146 V/147
xxvi VI.
Contents Solid State Properties
Crystallographic Data and Melting Points for Various Polymers ................................................................
VI/1
A. Introduction ........................................................................................................................ 1. Nomenclature .......................................................................................................... 2. Examples of Polymer Names .................................................................................. 2.1. Polymer Names Based on Source .......................................................... 2.2. Polymer Names Based on Structure ...................................................... References for Introduction .....................................................................................
VI/1 VI/1 VI/2 VI/2 VI/3 VI/5
B. Crystallographic Data for Various Polymers ....................................................................... Table 1. Poly(olefins) ............................................................................................................ Table 2. Poly(vinyls) and Poly(vinylidenes) .......................................................................... Table 3. Poly(aromatics) and Poly(imides) ........................................................................... Table 4. Poly(dienes) and Poly(diynes) ................................................................................ Table 5. Poly(peptides) ......................................................................................................... Table 6. Poly(amides) ........................................................................................................... Table 7. Poly(esters) ............................................................................................................. Table 8. Poly(urethanes) and Poly(ureas) ............................................................................ Table 9. Poly(ethers) ............................................................................................................. Table 10. Poly(oxides) ............................................................................................................ Table 11. Poly(sulfides) and Poly(sulfones) ............................................................................ Table 12. Poly(saccharides) ................................................................................................... Table 13. Other Polymers .......................................................................................................
VI/5 VI/6 VI/13 VI/15 VI/22 VI/26 VI/33 VI/40 VI/49 VI/51 VI/52 VI/57 VI/59 VI/64
C. Melting Points of Polymers ................................................................................................. Cellulose, see Poly (1,4-β-D-glucose) to Poly(4,4'-methylenediphenylene isophthalamide) ....................................................................................................... Poly(4,4'-methylenediphenylene octadecamethylenediurea) to Poly(p-xylylene undecanediamide) ..................................................................................................
VI/71 VI/71 VI/94
D. Appendix: Formula Index to the Tables .............................................................................. VI/113 0 to 4 ....................................................................................................................................... VI/114 5 to 30 ..................................................................................................................................... VI/133 E. References ......................................................................................................................... VI/159 1 to 839 ................................................................................................................................... VI/159 840 to 1946 ............................................................................................................................. VI/174 Glass Transition Temperatures of Polymers ............................................................................................... VI/193 A. Introduction ........................................................................................................................ VI/194 1. Example of a Property Change at Tg ...................................................................... VI/194 2. Tg: a "Non-Equilibrium" Transition ........................................................................... VI/195 B. Tg Measurement Methods .................................................................................................. VI/195 1. Data Interpretation .................................................................................................. VI/195 2. Oscillating Load Methods ........................................................................................ VI/196 C. Other Factors Affecting Tg .................................................................................................. VI/196 1. Structure ................................................................................................................. VI/196
This page has been reformatted by Knovel to provide easier navigation.
2. 3. 4. 5. 6.
Contents
xxvii
Crystallinity/Crosslinking ......................................................................................... Diluents ................................................................................................................... Molecular Weight .................................................................................................... Thermal History ....................................................................................................... Pressure ..................................................................................................................
VI/196 VI/197 VI/197 VI/197 VI/197
D. Estimation Methods for the Glass Transition Temperature ................................................. VI/197 E. Classification, Nomenclature, and Abbreviations ................................................................ VI/197 1. Naming Conventions ............................................................................................... VI/198 2. Abbreviations .......................................................................................................... VI/198 F. Tables of Glass Transition Temperatures of Polymers ....................................................... VI/198 Table 1. Main-chain Acyclic Carbon Polymers ..................................................................... VI/198 1.1 Poly(acrylics) and Poly(methacrylics) ..................................................... VI/198 1.1.1 Poly(acrylic acid) and Poly(acrylic Acid Esters) ............................... VI/198 1.1.2 Poly(acrylamides) ............................................................................. VI/201 1.1.3 Poly(methacrylic Acid) and Poly(methacrylic Acid Esters) .............. VI/201 1.1.4 Poly(methacrylamides) ..................................................................... VI/205 1.1.5 Other α- and β-substituted Poly(acrylics) and Poly(methacrylics) ............................................................................ 1.2 Poly(alkenes) .......................................................................................... 1.3 Poly(dienes) ............................................................................................ 1.4 Poly(styrenes) ......................................................................................... 1.5 Poly(vinyl Alcohol) and Poly(vinyl Ketones) ............................................ 1.6 PoIy(vinyl Esters) .................................................................................... 1.7 Poly(vinyl Ethers) and Poly(vinyl Thioethers) ......................................... 1.8 Poly(vinyl Halides) and Poly(vinyl Nitriles) .............................................. 1.9 Others ..................................................................................................... Table 2. Main-chain Carbocyclic Polymers ........................................................................... 2.1 Poly(phenylenes) .................................................................................... 2.2 Others ..................................................................................................... Table 3. Main-chain Acyclic Heteroatom Polymers .............................................................. 3.1 Main-chain –C–O–C– Polymers .............................................................
VI/205 VI/205 VI/207 VI/209 VI/212 VI/213 VI/214 VI/215 VI/216 VI/218 VI/218 VI/218 VI/219 VI/219
3.1.1 Poly(anhydrides) .............................................................................. VI/219 3.1.2 Poly(carbonates) .............................................................................. VI/219 3.1.3 Poly(esters) ...................................................................................... VI/221 3.1.4 Poly(ether Ketones) ......................................................................... VI/226 3.1.5 Poly(oxides) ...................................................................................... VI/226 3.2
3.1.6 Poly(urethanes) ................................................................................ VI/229 Main-chain O-heteroatom Polymers ....................................................... VI/231 3.2.1 Nitroso-polymers .............................................................................. VI/231 3.2.2 PoIy(siloxanes) ................................................................................. VI/231 3.2.3 Poly(sulfonates) ................................................................................ VI/233
This page has been reformatted by Knovel to provide easier navigation.
xxviii
Contents 3.3
Main-chain –C–(S)n–C- and –C–S–N– Polymers ................................... VI/233 3.3.1 Poly(sulfides) .................................................................................... VI/233 3.3.2 Poly(sulfones) and Poly(sulfonamides) ........................................... VI/234
3.4
3.3.3 Poly(thioesters) ................................................................................ VI/235 Main-chain –C–N–C Polymers ............................................................... VI/235 3.4.1 Poly(amides) .................................................................................... VI/235 3.4.2 Poly(anilines) .................................................................................... VI/241 3.4.3 Poly(imides) ...................................................................................... VI/241 3.4.4 Poly(imines) ...................................................................................... VI/241
3.4.5 Poly(ureas) ....................................................................................... 3.5 Poly(phosphazenes) ............................................................................... 3.6 Poly(silanes) and Poly(silazanes) ........................................................... Table 4. Main-chain Heterocyclic Polymers .......................................................................... 4.1 Carbohydrates ........................................................................................ 4.2 Liquid Crystals ........................................................................................ 4.3 Natural Polymers .................................................................................... 4.4 Poly(acetals) ........................................................................................... 4.5 Poly(anhydrides) ..................................................................................... 4.6 Poly(benzimidazoles) .............................................................................. 4.7 Poly(benzothiazinophenothiazines) ........................................................ 4.8 Poly(benzothiazoles) .............................................................................. 4.9 Poly(benzoxazlnes) ................................................................................ 4.10 Poly(benzoxazoles) ................................................................................ 4.11 Poly(carboranes) .................................................................................... 4.12 Poly(dibenzofurans) ................................................................................ 4.13 Poly(dioxoisoindolines) ........................................................................... 4.14 Poly(fluoresceins) ................................................................................... 4.15 Poly(furan Tetracarboxylic Acid Diimides) .............................................. 4.16 Poly(oxabicyclononanes) ........................................................................ 4.17 Poly(oxadiazoles) ................................................................................... 4.18 Poly(oxindoles) ....................................................................................... 4.19 Poly(oxoisoindolines) .............................................................................. 4.20 Poly(phthalazines) .................................................................................. 4.21 Poly(phthalides) ...................................................................................... 4.22 Poly(piperazines) .................................................................................... 4.23 Poly(piperidines) ..................................................................................... 4.24 Poly(pyrazinoquinoxalines) ..................................................................... 4.25 Poly(pyrazoles) ....................................................................................... 4.26 Poly(pyridazines) .................................................................................... 4.27 Poly(pyridines) ........................................................................................ 4.28 Poly(pyromellitimides) ............................................................................. 4.29 Poly(pyrrolidines) ....................................................................................
This page has been reformatted by Knovel to provide easier navigation.
VI/242 VI/242 VI/243 VI/243 VI/243 VI/244 VI/244 VI/244 VI/244 VI/245 VI/245 VI/245 VI/245 VI/245 VI/245 VI/246 VI/246 VI/247 VI/247 VI/247 VI/248 VI/248 VI/248 VI/248 VI/248 VI/248 VI/249 VI/249 VI/249 VI/249 VI/249 VI/249 VI/250
Contents 4.30 Poly(quinones) ........................................................................................ 4.31 Poly(quinoxalines) .................................................................................. 4.32 Poly(triazines) ......................................................................................... 4.33 Poly(triazoles) ......................................................................................... Table 5. Copolymers .............................................................................................................
xxix VI/250 VI/250 VI/252 VI/252 VI/252
G. References ......................................................................................................................... VI/253 1 to 953 ................................................................................................................................... VI/253 954 to 1560 ............................................................................................................................. VI/268 Rates of Crystallization of Polymers ............................................................................................................ VI/279 A. Introduction ........................................................................................................................ 1. Background ............................................................................................................. 1.1 General Remarks .................................................................................... 1.2 Background ............................................................................................. 1.3 Morphological Outline/Growth Features ................................................. 2. General Principles and Techniques Involved in Crystallization Rate Studies ......... 2.1 Kinetics of Bulk Transformations ............................................................ 2.2 Thermodynamic Crystallization Models .................................................. 2.3 Growth Kinetics of Lamellar Structures: Crystals and Spherulites ......... 3. Other Significant Aspects of Crystallization ............................................................ 3.1 Nonisothermal Crystallization ................................................................. 3.2 Crystallization of Blends ......................................................................... 3.3 Solvent and Pressure-induced Crystallization ........................................ 3.4 Crystallization of Mesophases ................................................................ 3.5 Flow Induced Crystallization ................................................................... 3.6 Epitaxial Crystallization ........................................................................... 3.7 Orientational Crystallization .................................................................... 3.8 Crystallization of Copolymers ................................................................. 3.9 Computer Simulations ............................................................................
VI/280 VI/280 VI/280 VI/280 VI/281 VI/282 VI/282 VI/284 VI/284 VI/286 VI/286 VI/287 VI/288 VI/288 VI/289 VI/289 VI/289 VI/290 VI/290
B. Tables of Rates of Crystallization of Various Polymers ....................................................... VI/291 1. Rates of Crystal Growth .......................................................................................... VI/291 Table 1. Poly(alkenes), Poly(dienes), Poly(vinyls) ................................................ VI/291 1.1
2.
Homopolymer Melts ......................................................................... VI/291
1.2 Solutions ........................................................................................... Table 2. Poly(oxides) ............................................................................................ Rates of Radial Spherulitic Growth ......................................................................... Table 3. Poly(dienes), Poly(alkenes), Poly(vinyls) ................................................ 3.1
VI/296 VI/300 VI/304 VI/304
Homopolymer Melts ......................................................................... VI/304
3.2 Blends ............................................................................................... VI/312 Table 4. Poly(oxides) ............................................................................................ VI/315 4.1
Homopolymer Melts ......................................................................... VI/315
4.2
Complexes ....................................................................................... VI/318
4.3
Blends ............................................................................................... VI/319
This page has been reformatted by Knovel to provide easier navigation.
xxx
Contents Table 5. Poly(carbonates) ..................................................................................... VI/326 Table 6. Poly(esters) ............................................................................................. VI/327 6.1
Homopolymer Melts ......................................................................... VI/327
6.2
Blends ............................................................................................... VI/329
6.3 Copolymers ...................................................................................... VI/331 Table 7. Poly(amides) ........................................................................................... VI/331 Table 8. Poly(siloxanes) ....................................................................................... VI/334 8.1
Homopolymer Melts ......................................................................... VI/334
8.2 Copolymers ...................................................................................... VI/334 Table 9. Others ..................................................................................................... VI/336 9.1 3.
Homopolymers Melts ....................................................................... VI/336
9.2 lonomers ........................................................................................... VI/340 Rates of Bulk Crystallization (Avrami Constants) ................................................... VI/341 Table 10. Poly(dienes), Poly(alkenes), Poly(vinyls) ................................................ VI/341 10.1 Melts and Solutions .......................................................................... VI/341 10.2 Blends and Copolymers ................................................................... VI/353 Table 11. Poly(oxides) ............................................................................................ VI/365 11.1 Homopolymer Melts ......................................................................... VI/365 11.2 Blends ............................................................................................... VI/371 Table 12. Poly(carbonates) ..................................................................................... VI/372 Table 13. Poly(esters) ............................................................................................. VI/373 13.1 Homopolymer melts ......................................................................... VI/373 13.2 Blends and Copolymers ................................................................... VI/377 Table 14. Poly(amides) ........................................................................................... VI/379 14.1 Blends of Poly(amides) .................................................................... VI/382 Table 15. Poly(urethanes) ...................................................................................... VI/383 Table 16. Table 17. Table 18. Table 19.
15.1 Blends of Poly(urethanes) ................................................................ Poly(siloxanes) ....................................................................................... Poly(phosphazenes) ............................................................................... Others ..................................................................................................... Composites .............................................................................................
VI/383 VI/384 VI/384 VI/385 VI/389
19.1 Composites of Blends ...................................................................... VI/390 C. References ......................................................................................................................... VI/391 Isomorphous Polymers Pairs ....................................................................................................................... VI/399 A. Introduction ........................................................................................................................ VI/399 B. Techniques ......................................................................................................................... VI/400 C. Tables of lsomorphous Pairs of Monomer Units ................................................................. Table 1. lsomorphous Units Within the Same Macromolecules (Copolymers) ..................... 1.1 lsomorphous Units with Different Chemical Constitution ........................ 1.2 lsomorphous Units with Different Configurations and/or with Headto-head, Head-to-tail Constitutional Disorder ..........................................
This page has been reformatted by Knovel to provide easier navigation.
VI/401 VI/401 VI/401 VI/405
Contents
xxxi
Table 2. Isomorphism of Macromolecules ............................................................................ VI/405 D. References ......................................................................................................................... VI/406 Miscible Polymers ........................................................................................................................................ VI/409 A. Definition of Miscibility ........................................................................................................ VI/409 B. Data Collection ................................................................................................................... VI/410 C. Arrangement of the Tables ................................................................................................. VI/410 D. Tables ................................................................................................................................ Table 1. Chemically Dissimilar Polymer Pairs Miscible in the Amorphous State at Room Temperature ................................................................................................. Table 2. Polymer Pairs Containing One Monomer in Common, Miscible in the Amorphous State at Room Temperature ................................................................ Table 3. Chemically Dissimilar Polymer Triads (and Tetrads) Miscible in the Amorphous State at Room Temperature ................................................................ Table 4. Polymer Pairs Miscible in the Amorphous State at Room Temperature; Molecular Weight Dependence Investigated .......................................................... Table 5. Polymer Pairs That Appear to Have High Temperature Miscibility Although Immiscible at or Below Room Temperature ............................................................ Table 6. Polymer Pairs Miscible at Room Temperature That Appear to Have a Lower Critical Solution Temperature (LCST) Above Room Temperature ......................... Table 7. Polymer Pairs That Appear to Have Both a Lower Critical Solution Temperature and a Upper Critical Solution Temperature ....................................... Table 8. Polymer Pairs That Cocrystallize ............................................................................
VI/411 VI/411 VI/444 VI/448 VI/450 VI/452 VI/454 VI/458 VI/459
E. References ......................................................................................................................... VI/461 Heat Capacities of High Polymers ............................................................................................................... VI/483 A. Introduction ........................................................................................................................ VI/483 B. Experimental Curves .......................................................................................................... VI/485 C. Data Tables for Solids and Liquids ..................................................................................... Table 1. cis-1,4-Poly(butadiene) (PBDc) .............................................................................. Table 2. trans-1,4-Poly(butadiene) (PBDt) ............................................................................ Table 3. cis-1,4-Poly(2-methylbutadiene) (PMBD) ............................................................... Table 4. Poly(ethylene) (PE) ................................................................................................. Table 5. Poly(propylene) (PP) ............................................................................................... Table 6. PoIy(1-butene) (PB) ................................................................................................ Table 7. PoIy(1-pentene) (PPE) ............................................................................................ Table 8. PoIy(1-hexene) (PHE) ............................................................................................. Table 9. Poly(isobutene) (PIB) .............................................................................................. Table 10. Poly(4-methyl-1-pentene) (P4MPE) ........................................................................ Table 11. Poly(tetrafluoroethylene) (PTFE) ............................................................................ Table 12. Poly(vinyl Fluoride) (PVF) ....................................................................................... Table 13. Poly(vinylidene Fluoride) (PVF2) ............................................................................ Table 14. Poly(trifluoroethylene) (P3FE) ................................................................................. Table 15. Poly(vinyl Chloride) (PVC) ......................................................................................
This page has been reformatted by Knovel to provide easier navigation.
VI/486 VI/486 VI/487 VI/488 VI/488 VI/489 VI/490 VI/490 VI/491 VI/492 VI/492 VI/493 VI/494 VI/494 VI/495 VI/496
xxxii
Contents Table 16. Table 17. Table 18. Table 19. Table 20. Table 21. Table 22. Table 23. Table 24. Table 25. Table 26. Table 27. Table 28. Table 29. Table 30. Table 31. Table 32. Table 33. Table 34. Table 35. Table 36. Table 37. Table 38. Table 39. Table 40. Table 41. Table 42. Table 43. Table 44. Table 45. Table 46. Table 47. Table 48. Table 49. Table 50.
Poly(vinylidene Chloride) (PVC2) ........................................................................... Poly(chlorotrifluoroethylene) (PC3FE) .................................................................... Poly(vinyl Alcohol) (PVA) ........................................................................................ Poly(vinyl Acetate) (PVAc) ...................................................................................... Poly(styrene) (PS) ................................................................................................... Poly(α-methylstyrene) (PMS) .................................................................................. Poly(vinyl Benzoate) (PVBZ) .................................................................................. Poly(methyl Acrylate) (PMA) ................................................................................... Poly(ethyl Acrylate) (PEA) ...................................................................................... Poly(n-butyl Acrylate) (PnBA) ................................................................................. Poly(iso-butyl Acrylate) (PIBA) ................................................................................ Poly(methacrylic Acid) (PMAA) ............................................................................... Poly(methyl Methacrylate) (PMMA) ........................................................................ Poly(ethyl Methacrylate) (PEMA) ............................................................................ Poly(n-butyl Methacrylate) (PnBMA) ....................................................................... Poly(iso-butyl Methacrylate) (PIBMA) ..................................................................... Poly(hexyl Methacrylate) (PHMA) ........................................................................... Poly(acrylonitrile) (PAN) .......................................................................................... Poly(methacrylamide) (PMAM) ............................................................................... Poly(oxy-1-oxoethylene) (PCL) ............................................................................... Poly(oxy-1-oxohexamethylene) (PCL) .................................................................... Poly(oxyethyleneoxyterephthaloyl) (PET) ............................................................... Poly(imino-(1-oxohexamethylene)) (Nylon 6) ......................................................... Poly(iminoadipoyliminohexamethylene) (Nylon 66) ................................................ Poly(iminoadipoyliminododecamethylene) (Nylon 612) .......................................... Poly(oxymethylene) (POM) ..................................................................................... Poly(oxyethylene) ................................................................................................... Poly(oxytrimethylene) (PO3M) ................................................................................ Poly(oxytetramethylene) (PO4M) ............................................................................ Poly(oxypropylene) (POPr) ..................................................................................... Poly(oxy-1,4-phenylene) (POPh) ............................................................................ Poly(oxy-2,6-dimethyl-1,4-phenylene) (PPO) ......................................................... Poly(oxy-2,6-diphenyl-1,4-phenylene) (POPPO) .................................................... Poly(oxycarbonyloxy-1,4-phenylene-isopropylidene- 1,4-phenylene) (PC) ............ Trigonal Selenium (SeT) .........................................................................................
VI/496 VI/497 VI/498 VI/498 VI/499 VI/500 VI/500 VI/501 VI/502 VI/502 VI/503 VI/504 VI/504 VI/505 VI/506 VI/506 VI/507 VI/508 VI/508 VI/509 VI/510 VI/510 VI/511 VI/512 VI/512 VI/513 VI/514 VI/514 VI/515 VI/515 VI/516 VI/517 VI/517 VI/518 VI/519
D. References ......................................................................................................................... VI/519 Surface and Interfacial Tensions of Polymers, Oligomers, Plasticizers, and Organic Pigments ............... VI/521 A. Introduction ........................................................................................................................ 1. Definition ................................................................................................................. 2. Temperature Dependence ...................................................................................... 3. Macleod's Relation .................................................................................................. 4. Molecular Weight Dependence ............................................................................... 5. Effects of Glass and Crystal-melt Transitions ......................................................... This page has been reformatted by Knovel to provide easier navigation.
VI/521 VI/521 VI/522 VI/522 VI/522 VI/522
Contents 6. 7.
xxxiii
Effect of Surface Chemical Constitution ................................................................. VI/523 Dispersion (Nonpolar) and Polar Components ....................................................... VI/523
B. Tables ................................................................................................................................ VI/523 Table 1. Surface Chemical Constitution and Surface Tension ............................. VI/524 1.1
Hydrocarbon Surfaces ..................................................................... VI/524
1.2
Fluorocarbon Surfaces ..................................................................... VI/524
1.3
Chlorocarbon Surfaces .................................................................... VI/524
1.4 Silicane Surfaces .............................................................................. VI/524 Table 2. Surface Tension, Polarity, and Macleod's Exponent for Amorphous Surfaces .............................................................................. VI/524 2.1
Hydrocarbon Polymers ..................................................................... VI/524
2.2
Styrene Polymers ............................................................................. VI/525
2.3
Halogenated Hydrocarbon Polymers ............................................... VI/525
2.4
Vinyl Polymers - Esters .................................................................... VI/526
2.5
Vinyl Polymers - Others ................................................................... VI/526
2.6
Acrylic Polymers - Nonfluorinated .................................................... VI/526
2.7
Acrylic Polymers - Fluorinated ......................................................... VI/527
2.8
Methacrylic Polymers - Nonfluorinated ............................................ VI/527
2.9
Methacrylic Polymers - Fluorinated ................................................. VI/527
2.10 Methacrylic Hydrogels ...................................................................... VI/527 2.11 Poly(ethers) ...................................................................................... VI/528 2.12 Poly(ether) Copolymers ................................................................... VI/529 2.13 Poly(esters) ...................................................................................... VI/529 2.14 Poly(carbonates) .............................................................................. VI/530 2.15 Poly(sulfones) ................................................................................... VI/530 2.16 Phenoxy Resins ............................................................................... VI/530 2.17 Epoxy Resins ................................................................................... VI/530 2.18 Poly(amides) .................................................................................... VI/530 2.19 Poly(imides) ...................................................................................... VI/531 2.20 Poly(imines) ...................................................................................... VI/531 2.21 Poly(urethanes) ................................................................................ VI/531 2.22 Poly(siloxanes) ................................................................................. VI/531 2.23 Organosilanes - Hydrolyzed and Condensed Films ........................ VI/532 2.24 Cellulosics ........................................................................................ VI/533 2.25 Poly(peptides) .................................................................................. VI/533 2.26 Miscellaneous ................................................................................... VI/533 Table 3. lnterfacial Tension for Amorphous Interfaces ......................................... VI/535 3.1
Hydrocarbon Polymers vs. Others ................................................... VI/535
3.2
Styrene Polymers vs. Others ........................................................... VI/537
3.3
Vinyl Polymers vs. Others ................................................................ VI/537
3.4
Acrylic Polymers vs. Others ............................................................. VI/538
This page has been reformatted by Knovel to provide easier navigation.
xxxiv
Contents 3.5
Methacrylic Polymers vs. Others ..................................................... VI/538
3.6
Poly(ethers) vs. Others .................................................................... VI/539
3.7
Poly(esters) vs. Others ..................................................................... VI/539
3.8
Poly(amides) vs. Others ................................................................... VI/539
3.9
Epoxy Resins vs. Others .................................................................. VI/539
3.10 Poly(Siloxanes) vs. Others ............................................................... VI/539 3.11 Miscellaneous ................................................................................... VI/540 C. References ......................................................................................................................... VI/540 Permeability and Diffusion Data .................................................................................................................. VI/543 A. Introduction ........................................................................................................................ VI/543 B. Conversion Factors for Various Units of the Permeability Coefficient ................................. VI/545 C. Tables ................................................................................................................................ Table 1. Permeability Coefficients, Diffusion Coefficients, and Solubility Coefficients of Polymers ............................................................................................................. 1.1 Poly(alkanes) .......................................................................................... 1.2 Poly(styrenes) ......................................................................................... 1.3 Poly(methacrylates) ................................................................................ 1.4 Poly(nitriles) ............................................................................................ 1.5 Poly(vinyls) ............................................................................................. 1.6 Fluorine Containing Polymers ................................................................. 1.7 Poly(dienes) ............................................................................................ 1.8 Poly(xylylenes) ........................................................................................ 1.9 Poly(oxides) ............................................................................................ 1.10 Poly(esters), Poly(carbonates) ............................................................... 1.11 PoIy(siloxanes) ....................................................................................... 1.12 Poly(amides), Poly(imides) ..................................................................... 1.13 Poly(urethanes) ...................................................................................... 1.14 Poly(sulfones) ......................................................................................... 1.15 Poly(aryl Ether Ether Ketone) ................................................................. 1.16 Cellulose and Derivatives ....................................................................... Table 2. Permeability Coefficients of Six Different Fluorinated Hydrocarbons through Polymers ................................................................................................................. Table 3. Permeability Coefficients of Various Organic Compounds through Lowdensity Poly(ethylene) ............................................................................................. Table 4. Permeability Coefficients and Diffusion Coefficients of an Equimolar Mixture of Various Compounds (1.25 M Each) through High-density Poly(ethylene) .......... Table 5. Permeability Coefficients of Various Organic Compounds through Highdensity Poly(ethylene) and Poly(propylene) ........................................................... Table 6. Permeability Coefficients of Various Organic Compounds through Irradiation Crosslinked Low-density Poly(ethylene) ................................................................. Table 7. Permeability Coefficients of Cases through Irradiation Crosslinked Lowdensity Poly(ethylene) .............................................................................................
This page has been reformatted by Knovel to provide easier navigation.
VI/545 VI/545 VI/545 VI/547 VI/548 VI/549 VI/549 VI/552 VI/553 VI/555 VI/555 VI/555 VI/558 VI/559 VI/560 VI/560 VI/561 VI/561 VI/562 VI/562 VI/564 VI/564 VI/564 VI/565
Contents
xxxv
Table 8. Permeability Coefficients of Chemically Crosslinked Poly(oxypropylene) .............. Table 9. Permeability Coefficients of Gases through Various Elastomers ............................ Table 10. Permeability Coefficients of Gases through Various Commercial Elastomers at 35°C. ................................................................................................................... Table 11. Permeability, Diffusion and Solubility Coefficients of Alkanes through Santoprene™ (Blend of Ethylene-propylene Copolymer and lsotactic Poly(propylene)) ...................................................................................................... Table 12. Permeability, Diffusion and Solubility Coefficients of Esters through Poly(epichlorohydrin) (ECO) ...................................................................................
VI/565 VI/566 VI/566
VI/566 VI/567
D. References ......................................................................................................................... VI/568 Refractive Indices of Polymers .................................................................................................................... VI/571 A. Introduction ........................................................................................................................ VI/571 B. Molar Refraction ................................................................................................................. VI/571 C. Refractive Indices of Heterogeneous Polymers .................................................................. VI/572 D. Optical Anisotropy .............................................................................................................. VI/572 E. Applications ........................................................................................................................ Table 1. Intrinsic Optical Properties of Selected Polymers ................................................... Table 2. Average Refractive Indices of Polymers (in Order of Increasing n) ........................ Table 3. Average Refractive Indices of Polymers (in Alphabetical Order) ............................
VI/573 VI/573 VI/574 VI/578
F. References ......................................................................................................................... VI/582 Radiation Resistance of Plastics and Elastomers ....................................................................................... VI/583 A. Introduction ........................................................................................................................ 1. General Comments ................................................................................................. 2. Criterion for Radiation Resistance .......................................................................... 3. Factors of Influence and Their Consideration in Tables ......................................... 3.1 Type of Polymer and Formulation ........................................................... 3.2 Type of Radiation and Dosimetry ........................................................... 3.3 Dose Rate and the Atmosphere ............................................................. 3.4 Temperature ........................................................................................... 3.5 Other Stresses ........................................................................................
VI/583 VI/583 VI/583 VI/583 VI/583 VI/584 VI/584 VI/584 VI/584
B. List of Symbols Used .......................................................................................................... VI/584 C. Tables of Table 1. Table 2. Table 3. Table 4.
Radiation Resistance .......................................................................................... Thermoplastics ........................................................................................................ Elastomers .............................................................................................................. Aromatic Polymers .................................................................................................. Organic Composite Materials ..................................................................................
VI/585 VI/585 VI/586 VI/587 VI/588
D. References ......................................................................................................................... VI/588 PVT Relationships and Equations of State of Polymers ............................................................................. VI/591 A. Introduction ........................................................................................................................ VI/591 B. Isothermal Compressibility Equations ................................................................................. VI/592 C. Empirical or Semiempirical 3-Parameter Equations of State ............................................... VI/593 D. Lattice or Quasi Lattice Models .......................................................................................... VI/593 This page has been reformatted by Knovel to provide easier navigation.
xxxvi
Contents E. Continuum Models .............................................................................................................. VI/594 F. Tables ................................................................................................................................ Table 1. Zero Pressure Volume V0(T) and Bulk Modulus B0(T) ............................................ Table 2. Abbreviations of Polymer Names and the Experimental TemperaturePressure Range for Polymer Liquids ...................................................................... Table 3. PVT Properties of Other Polymers .......................................................................... Table 4. Characteristic Parameters for the Sanchez-cho Equation of State ......................... Table 5. Characteristic Parameters for the Hartmann-haque Equation of State ................... Table 6. Characteristic Parameters for the Simple Cell Model Equation of State ................. Table 7. Characteristic Parameters for the Flory, Orwoll and Vrij Equation of State ............ Table 8. Characteristic Parameters for the Simha-somcynsky Equation of State ................ Table 9. Characteristic Parameters for the Sanchez-lacombe Equation of State ................. Table 10. Characteristic Parameters for the AHS + vdW Equation of State ...........................
VI/595 VI/595 VI/596 VI/597 VI/597 VI/597 VI/598 VI/599 VI/599 VI/600 VI/600
G. References ......................................................................................................................... VI/601
VII. Solution Properties Viscosity – Molecular Weight Relationships and Unperturbed Dimensions of Linear Chain Molecules ............................................................................................................................................
VII/1
A. Introduction ........................................................................................................................ 1. The Viscosity - Molecular Weight Relationship ....................................................... 2. Unperturbed Dimensions of Linear Chain Molecules ..............................................
VII/2 VII/2 VII/4
B. Effect of Molecular Weight Distribution on the Viscosity Constant K ...................................
VII/5
a
C. Tables of Viscosity - Molecular Weight Relationships, [η] = KM ........................................ Table 1. Main-chain Acyclic Carbon Polymers ..................................................................... 1.1 Poly(dienes) ............................................................................................ 1.2 Poly(alkenes), Poly(acetylenes) ............................................................. 1.3 Poly(acrylic Acid) and Derivatives .......................................................... 1.4 Poly(α-substituted Acrylic Acid) and Derivatives .................................... 1.5 Poly(vinyl Ethers) .................................................................................... 1.6 Poly(vinyl Alcohol), Poly(vinyl Halides) ................................................... 1.7 Poly(vinyI Esters) .................................................................................... 1.8 Poly(styrene) and Derivatives ................................................................. 1.9 Other Compounds .................................................................................. 1.10 Copolymers ............................................................................................. Table 2. Main-chain Carbocyclic Polymers ........................................................................... Table 3. Main-chain Heteroatom Polymers ........................................................................... 3.1 Poly(oxides), Poly(ethers) ....................................................................... 3.2 Poly(esters), Poly(carbonates) ............................................................... 3.3 Poly(amides) ........................................................................................... 3.4 Poly(amino Acids) ................................................................................... 3.5 Poly(ureas), Poly(urethanes), Poly(imines) ............................................ 3.6 Poly(sulfides) .......................................................................................... 3.7 Poly(phosphates) .................................................................................... This page has been reformatted by Knovel to provide easier navigation.
VII/5 VII/5 VII/5 VII/7 VII/10 VII/13 VII/17 VII/17 VII/18 VII/19 VII/24 VII/27 VII/31 VII/32 VII/32 VII/34 VII/36 VII/38 VII/39 VII/39 VII/39
Contents
xxxvii
3.8 Poly(siloxanes), Poly(silsesquioxanes) ................................................... 3.9 Poly(heterocyclics) .................................................................................. 3.10 Copolymers (Maleic Anhydride, Sulfones) .............................................. 3.11 Other Compounds .................................................................................. Table 4. Cellulose and Derivatives, Poly(saccharides) ......................................................... Table 5. Miscellaneous .........................................................................................................
VII/40 VII/41 VII/42 VII/42 VII/43 VII/46
D. Calculated Unperturbed Dimensions of Freely Rotating Chains .........................................
VII/46
E. Unperturbed Dimensions of Linear Polymer Molecules ...................................................... Table 6. Main-chain Acyclic Carbon Polymers ..................................................................... 6.1 Poly(dienes) ............................................................................................ 6.2 Poly(alkenes), Poly(acetylenes) ............................................................. 6.3 Poly(acrylic Acid) and Derivatives .......................................................... 6.4 Poly(α-substituted Acrylic Acid) and Derivatives .................................... 6.5 Poly(vinyl Ethers), Poly(vinyl Alcohol), Poly(vinyl Esters), Poly(vinyl Halides) .................................................................................. 6.6 Poly(styrene) and Derivatives ................................................................. 6.7 Other Compounds .................................................................................. 6.8 Copolymers ............................................................................................. Table 7. Main-chain Carbocyclic Polymers ........................................................................... Table 8. Main-chain Heteroatom Polymers ........................................................................... 8.1 Poly(oxides), Poly(ethers) ....................................................................... 8.2 Poly(esters), Poly(carbonates) ............................................................... 8.3 Poly(amides) ........................................................................................... 8.4 Poly(amino Acids) ................................................................................... 8.5 Poly(urethanes) ...................................................................................... 8.6 Poly(sulfides) .......................................................................................... 8.7 Poly(phosphates) .................................................................................... 8.8 Poly(siloxanes), Poly(silsesquioxanes), Poly(silmethylenes) ................. 8.9 Poly(heterocyclics) .................................................................................. 8.10 Copolymers (Maleic Anhydride, Sulfones, Siloxanes) ............................ 8.11 Other Compounds .................................................................................. Table 9. Cellulose and Derivatives, Poly(saccharides) .........................................................
VII/47 VII/47 VII/47 VII/48 VII/49 VII/50
F. References .........................................................................................................................
VII/68
Sedimentation Coefficients, Diffusion Coefficients, Partial Specific Volumes, Frictional Ratios, and Second Virial Coefficients of Polymers in Solution ............................................................................
VII/85
A. Sedimentation Coefficients, Diffusion Coefficients, Partial Specific Volumes, and Frictional Ratios of Polymers in Solution ............................................................................ 1. Introduction ............................................................................................................. 1.1. Sedimentation Coefficient ....................................................................... 1.2. Diffusion Coefficient ................................................................................ 1.3. Molar Mass Averages Determined from Sedimentation and Diffusion Coefficients .............................................................................. 1.4. Partial Specific Volumes ......................................................................... This page has been reformatted by Knovel to provide easier navigation.
VII/53 VII/54 VII/56 VII/58 VII/60 VII/60 VII/60 VII/61 VII/63 VII/63 VII/63 VII/63 VII/64 VII/64 VII/64 VII/65 VII/66 VII/66
VII/86 VII/86 VII/86 VII/87 VII/89 VII/89
xxxviii
Contents 1.5. 1.6. 1.7.
Frictional Ratios ...................................................................................... List of Symbols and Abbreviations .......................................................... Miscellaneous .........................................................................................
B. Tables of Sedimentation Coefficients, Diffusion Coefficients, Partial Specific Volumes, and Frictional Ratios of Polymers in Solution ...................................................... Table 1. Poly(alkenes) .......................................................................................................... Table 2. Poly(dienes) ............................................................................................................ Table 3. Acrylic Polymers ..................................................................................................... Table 4. Vinyl Polymers ........................................................................................................ Table 5. Styrene Polymers .................................................................................................... Table 6. (O, C)-Heterochain Polymers [Poly(ethers), Poly(esters), Poly(carbonates)] ......... Table 7. (N, C)- and (O, N, C)-Heterochain Polymers [Poly(amides), Poly(ureas), Poly(urethanes)] ...................................................................................................... Table 8. Other Synthetic Polymers ....................................................................................... Table 9. Inorganic Polymers ................................................................................................. Table 10. Poly(saccharides) ................................................................................................... Table 11. Other Biopolymers [Proteins, Poly(nucleotides)] ....................................................
VII/89 VII/90 VII/91 VII/92 VII/92 VII/94 VII/96 VII/105 VII/109 VII/134 VII/137 VII/140 VII/141 VII/144 VII/157
C. Second Virial Coefficients of Polymers in Solution .............................................................. 1. Introduction ............................................................................................................. 1.1. Colligative Properties .............................................................................. 1.2. Scattering Methods ................................................................................. 1.3. Sedimentation Velocity ........................................................................... 1.4. Sedimentation Equilibrium ...................................................................... 1.5. p–V–T Measurements ............................................................................ 1.6. Averages of the Second Virial Coefficient .............................................. 1.7. Second Virial Coefficient – Molar Mass Relationship ............................. 1.8. Temperature Dependence, Pressure Dependence ................................ 1.9. Abbreviations .......................................................................................... 1.10. Miscellaneous .........................................................................................
VII/163 VII/163 VII/163 VII/163 VII/163 VII/164 VII/164 VII/164 VII/164 VII/164 VII/164 VII/164
D. Tables of Table 12. Table 13. Table 14. Table 15. Table 16. Table 17. Table 18.
VII/165 VII/165 VII/168 VII/170 VII/177 VII/179 VII/188
Table 19. Table 20. Table 21. Table 22.
Second Virial Coefficients of Polymers in Solution .............................................. Poly(alkenes), Poly(alkynes) ................................................................................... Poly(dienes) ............................................................................................................ Poly(acrylics) ........................................................................................................... Poly(vlnyls) .............................................................................................................. Poly(styrenes) ......................................................................................................... (O, C)-heterochain Polymers [Poly(ethers), Poly(esters), Poly(carbonates)] ......... (N, C)- and (O, N, C)-heterochain Polymers [Poly(amides), Poly(ureas), Poly(urethanes)] ...................................................................................................... Other Synthetic Polymers ....................................................................................... Inorganic Polymers ................................................................................................. Poly(saccharides) ................................................................................................... Other Biopolymers [Proteins, Poly(nucleotides)] ....................................................
VII/191 VII/192 VII/192 VII/194 VII/196
E. References ......................................................................................................................... VII/198 This page has been reformatted by Knovel to provide easier navigation.
Contents
xxxix
Polymolecularity Correction Factors ............................................................................................................ VII/215 A. List of Symbols Used .......................................................................................................... VII/216 B. Introduction ........................................................................................................................ VII/217 Table 1 .................................................................................................................................... VII/223 C. Polymolecularity Correction Factors for Intrinsic Viscosity Versus Molecular Weight Relationship ....................................................................................................................... Table 2 .................................................................................................................................... Table 3 .................................................................................................................................... Table 4 .................................................................................................................................... Table 5 .................................................................................................................................... Table 6 .................................................................................................................................... Table 7 .................................................................................................................................... Table 8 .................................................................................................................................... Table 9 .................................................................................................................................... Table 10 .................................................................................................................................. Table 11 .................................................................................................................................. Table 12 .................................................................................................................................. Table 13 .................................................................................................................................. Table 14 .................................................................................................................................. Table 15 .................................................................................................................................. Table 16 .................................................................................................................................. Table 17 .................................................................................................................................. Table 18 .................................................................................................................................. Table 19 ..................................................................................................................................
VII/223 VII/223 VII/223 VII/223 VII/224 VII/224 VII/224 VII/224 VII/224 VII/225 VII/225 VII/225 VII/225 VII/225 VII/226 VII/226 VII/226 VII/226 VII/226
D. Polymolecularity Correction Factors for Sedimentation Coefficient Versus Molecular Weight Relationship ........................................................................................................... Table 20 .................................................................................................................................. Table 21 .................................................................................................................................. Table 22 .................................................................................................................................. Table 23 .................................................................................................................................. Table 24 .................................................................................................................................. Table 25 .................................................................................................................................. Table 26 .................................................................................................................................. Table 27 ..................................................................................................................................
VII/227 VII/227 VII/227 VII/227 VII/227 VII/228 VII/228 VII/228 VII/229
E. Polymolecularity Correction Factors for Diffusion Coefficient Versus Molecular Weight Relationship ........................................................................................................... Table 28 .................................................................................................................................. Table 29 .................................................................................................................................. Table 30 .................................................................................................................................. Table 31 .................................................................................................................................. Table 32 .................................................................................................................................. Table 33 .................................................................................................................................. Table 34 ..................................................................................................................................
VII/229 VII/229 VII/229 VII/229 VII/230 VII/230 VII/230 VII/230
This page has been reformatted by Knovel to provide easier navigation.
xl
Contents Table 35 Table 36 Table 37 Table 38 Table 39 Table 40 Table 41
.................................................................................................................................. .................................................................................................................................. .................................................................................................................................. .................................................................................................................................. .................................................................................................................................. .................................................................................................................................. ..................................................................................................................................
VII/230 VII/231 VII/231 VII/231 VII/231 VII/232 VII/232
F. Polymolecularity Correction Factors for Mean-Square Radius of Gyration versus Molecular Weight Relationship ........................................................................................... Table 42 .................................................................................................................................. Table 43 .................................................................................................................................. Table 44 .................................................................................................................................. Table 45 .................................................................................................................................. Table 46 .................................................................................................................................. Table 47 ..................................................................................................................................
VII/232 VII/232 VII/233 VII/233 VII/233 VII/234 VII/234
G. Polymolecularity Correction Factors for Second Virial Coefficient Versus Molecular Weight Relationship ........................................................................................................... Table 48 .................................................................................................................................. Table 49 .................................................................................................................................. Table 50 .................................................................................................................................. Table 51 ..................................................................................................................................
VII/234 VII/234 VII/235 VII/235 VII/235
H. Polymolecularity Correction Factors for the Determination of the Dimensions of Macromolecules ................................................................................................................. 1. Fox-flory Relationship ............................................................................................. Table 52 .................................................................................................................. Table 53 .................................................................................................................. Table 54 .................................................................................................................. Table 55 .................................................................................................................. 2. Interconversion of Different Averages of the Mean-square Radius of Gyration .................................................................................................................. Table 56 .................................................................................................................. Table 57 .................................................................................................................. Table 58 .................................................................................................................. Table 59 .................................................................................................................. 3. Interconversion of Different Averages of the Mean-square End-to-end Distance .................................................................................................................. Table 60 .................................................................................................................. Table 61 .................................................................................................................. Table 62 .................................................................................................................. Table 63 .................................................................................................................. Table 64 .................................................................................................................. Table 65 ..................................................................................................................
This page has been reformatted by Knovel to provide easier navigation.
VII/235 VII/235 VII/235 VII/236 VII/236 VII/236 VII/236 VII/236 VII/237 VII/237 VII/238 VII/238 VII/238 VII/238 VII/239 VII/239 VII/239 VII/239
Contents 4.
I.
xli
The Effect of Polymolecularity on the Radius of Gyration of Stiff Polymer Chains ..................................................................................................................... VII/240 Table 66 .................................................................................................................. VII/240 Table 67 .................................................................................................................. VII/240
Polymolecularity Correction Factors for the Determination of Unperturbed Dimensions of Macromolecules .......................................................................................... 1. Burchard-stockmayer-fixman Procedure ................................................................ Table 68 .................................................................................................................. Table 69 .................................................................................................................. Table 70 .................................................................................................................. 2. Cowie-bywater Procedure ....................................................................................... Table 71 .................................................................................................................. Table 72 .................................................................................................................. Table 73 .................................................................................................................. Table 74 .................................................................................................................. 3. Baumann-stockmayer-fixman Procedure ................................................................ Table 75 .................................................................................................................. Table 76 .................................................................................................................. Table 77 .................................................................................................................. Table 78 .................................................................................................................. 4. Baumann-kurata-stockmayer Procedure ................................................................ Table 79 .................................................................................................................. Table 80 .................................................................................................................. Table 81 .................................................................................................................. Table 82 ..................................................................................................................
VII/240 VII/240 VII/240 VII/240 VII/241 VII/241 VII/241 VII/241 VII/241 VII/241 VII/242 VII/242 VII/242 VII/242 VII/242 VII/243 VII/243 VII/243 VII/243 VII/244
J. References ......................................................................................................................... VII/244 Polymer-solvent Interaction Parameters ..................................................................................................... VII/247 A. Introduction ........................................................................................................................ VII/247 B. Concentration Variables ..................................................................................................... VII/247 C. Conversion of Concentration Variables .............................................................................. VII/247 D. Basic Equations .................................................................................................................. VII/247 E. Methods of Determination .................................................................................................. VII/248 F. Temperature Dependence .................................................................................................. VII/249 G. Concentration Dependence ................................................................................................ VII/249 H. Molecular Weight Dependence ........................................................................................... VII/250 I.
Polymer-solvent Interaction Parameters, χ ......................................................................... VII/250
J. References ......................................................................................................................... VII/262 Concentration Dependence of the Viscosity of Dilute Polymer Solutions: Huggins and Schulzblaschke Constants ............................................................................................................................ VII/265 A. Introduction ........................................................................................................................ VII/265 B. Tables ................................................................................................................................ VII/266
This page has been reformatted by Knovel to provide easier navigation.
xlii
Contents Table 1. Huggins Constants ................................................................................................. 1.1 Poly(dienes) and Poly(alkenes) .............................................................. 1.2 Poly(acrylic Acid) and Poly(methacrylic Acid) Derivatives ...................... 1.3 Vinyl Polymers ........................................................................................ 1.4 Poly(oxides) ............................................................................................ 1.5 Poly(esters) ............................................................................................. 1.6 Polyamides ............................................................................................. 1.7 Other Compounds .................................................................................. 1.8 Cellulose, Cellulose Derivatives, and Polysaccharides .......................... Table 2. Schulz-blaschke Constants .....................................................................................
VII/266 VII/266 VII/268 VII/272 VII/277 VII/278 VII/279 VII/280 VII/282 VII/284
C. References ......................................................................................................................... VII/285 Theta Solvents ............................................................................................................................................. VII/291 A. Introduction ........................................................................................................................ 1. Fundamentals ......................................................................................................... 1.1 Thermodynamics .................................................................................... 1.2 Unperturbed Dimensions ........................................................................ 2. Methods to Determine Theta Solvents .................................................................... 2.1 Phase Equilibrium (PE) ........................................................................... 2.2 Second Virial Coefficient (A) ................................................................... 2.3 Cloud Point Titration (CP) ....................................................................... 2.4 Cloud Temperature Titration (CT) ........................................................... 2.5 Unperturbed Dimensions (RGM, VM, DM, SM) ...................................... 2.6 Other Methods ........................................................................................
VII/291 VII/291 VII/291 VII/292 VII/293 VII/293 VII/293 VII/294 VII/294 VII/294 VII/294
B. Tables of Theta Solvents for Polymers ............................................................................... Table 1. Homochain Polymers .............................................................................................. 1.1 Poly(alkanes) .......................................................................................... 1.2 Poly(alkenes) .......................................................................................... 1.3 Poly(styrenes) ......................................................................................... 1.4 Poly(vinyls) ............................................................................................. 1.5 Poly(acrylics) and Related Compounds .................................................. 1.6 Poly(methacrylics) and Related Compounds .......................................... 1.7 Other Carbon Chains .............................................................................. Table 2. Heterochain Polymers ............................................................................................. 2.1 Poly(acetals) and Poly(ethers) ................................................................ 2.2 Poly(esters) ............................................................................................. 2.3 Poly(amides) ........................................................................................... 2.4 Polyureas and Polyurethanes ................................................................. 2.5 Polysaccharides ...................................................................................... 2.6 Carbon-sulfur Chains .............................................................................. 2.7 Silicon-oxygen Chains ............................................................................ 2.8 Phosphorus-oxygen Chains ....................................................................
VII/295 VII/295 VII/295 VII/299 VII/300 VII/305 VII/307 VII/308 VII/312 VII/313 VII/313 VII/315 VII/316 VII/316 VII/316 VII/317 VII/317 VII/318
C. References ......................................................................................................................... VII/318
This page has been reformatted by Knovel to provide easier navigation.
Contents
xliii
Fractionation of Polymers ............................................................................................................................ VII/327 A. Principles of Polymer Fractionation .................................................................................... VII/327 B. Fractionation Methods ........................................................................................................ 1. Fractionation by Solubility ....................................................................................... 2. Fractionation by Chromatography ........................................................................... 3. Cross Fractionation ................................................................................................. 4. Fractionation by Sedimentation .............................................................................. 5. Fractionation by Diffusion ....................................................................................... 6. Fractionation by Ultrafiltration through Porous Membranes .................................... 7. Fractionation by Zone Melting ................................................................................. 8. Electron Microscopic Counting Method ..................................................................
VII/328 VII/328 VII/330 VII/332 VII/333 VII/333 VII/333 VII/333 VII/333
C. Tables of Fractionation Systems for Different Polymers ..................................................... Table 1. Main-chain Acyclic Carbon Polymers ..................................................................... 1.1 Poly(dienes) ............................................................................................ 1.2 Poly(alkenes) .......................................................................................... 1.3 Poly(acrylic Acid) and Derivatives .......................................................... 1.4 Poly(methacrylic Acid) and Derivatives .................................................. 1.5 Other α- and β-Substituted Poly(acrylics) and Poly(methacrylics) ......... 1.6 Poly(vinyl Ethers) .................................................................................... 1.7 Poly(vinyl Alcohol), Poly(vinyl Ketones), Poly(vinyl Halides), Poly(vinyl Nitriles) ................................................................................... 1.8 Poly(vinyl Esters) .................................................................................... 1.9 Poly(styrenes) ......................................................................................... 1.10 Other Compounds .................................................................................. 1.11 Random and Alternating Copolymers ..................................................... 1.12 Block Copolymers ................................................................................... 1.13 Graft Copolymers .................................................................................... 1.14 Mixture of Polymers ................................................................................ Table 2. Main-chain Carbocyclic Polymers ........................................................................... 2.1 Poly(phenylenes) .................................................................................... 2.2 Formaldehyde Resins ............................................................................. Table 3. Main-chain Heteroatom Polymers ........................................................................... 3.1 Poly(oxides) ............................................................................................ 3.2 Poly(carbonates) ..................................................................................... 3.3 Poly(esters) ............................................................................................. 3.4 Poly(urethanes) and Poly(ureas) ............................................................ 3.5 Poly(amides) and Poly(imines) ............................................................... 3.6 Poly(amino Acids) ................................................................................... 3.7 Poly(sulfides), Poly(sulfones), Poly(sulfonamides) ................................. 3.8 Poly(silanes) and Poly(siloxanes) ........................................................... 3.9 Poly(phosphazenes) and Related Polymers ........................................... 3.10 Other Compounds .................................................................................. 3.11 Random Copolymers ..............................................................................
VII/333 VII/333 VII/333 VII/336 VII/344 VII/346 VII/351 VII/353
This page has been reformatted by Knovel to provide easier navigation.
VII/353 VII/355 VII/356 VII/363 VII/366 VII/382 VII/389 VII/395 VII/397 VII/397 VII/397 VII/398 VII/398 VII/404 VII/405 VII/410 VII/411 VII/414 VII/416 VII/418 VII/422 VII/423 VII/425
xliv
Contents 3.12 Block Copolymers ................................................................................... 3.13 Graft Copolymers .................................................................................... Table 4. Poly(saccharides) ................................................................................................... 4.1 Poly(saccharides) ................................................................................... 4.2 Graft Copolymers .................................................................................... 4.3 Mixtures of Polymers ..............................................................................
VII/427 VII/430 VII/431 VII/431 VII/436 VII/438
D. References ......................................................................................................................... 1 to 1188 ................................................................................................................................. 1189 to 2452 ........................................................................................................................... 2453 to 3608 ...........................................................................................................................
VII/438 VII/438 VII/458 VII/478
Solvents and Non Solvents for Polymers .................................................................................................... VII/497 A. Introduction ........................................................................................................................ VII/498 B. Abbreviations ..................................................................................................................... VII/498 C. Tables of Solvents and Nonsolvents ................................................................................... Table 1. Main-chain Acyclic Carbon Polymers ..................................................................... 1.1 Poly(dienes), Poly(acetylenes) ............................................................... 1.2 Poly(alkenes) .......................................................................................... 1.3 Poly(acrylics), Poly(methacrylics) ...........................................................
VII/499 VII/499 VII/499 VII/500 VII/501
1.3.1 Poly(acrylic Acids) ............................................................................ VII/501 1.3.2 Poly(acrylates) .................................................................................. VII/501 1.3.3 Poly(methacrylates) ......................................................................... VII/501 1.3.4 Poly(disubstituted Esters) ................................................................ VII/502 1.3.5 Poly(acrylamides), Poly(methacrylamides) ..................................... 1.4 Poly(vinyl Ethers) .................................................................................... 1.5 Poly(vinyl Alcohols), Poly(acetals), Poly(vinyl Ketones) ......................... 1.6 Poly(vinyl Halides) .................................................................................. 1.7 Poly(vinyl Nitrites) ................................................................................... 1.8 Poly(vinyl Esters) .................................................................................... 1.9 Poly(styrenes) ......................................................................................... 1.10 Other Compounds .................................................................................. Table 2. Main-chain Carbocyclic Polymers ........................................................................... 2.1 Poly(phenylenes) .................................................................................... 2.2 Other Compounds .................................................................................. Table 3. Main-chain Carbonyl Polymers ............................................................................... Table 4. Main-chain Acyclic Heteroatom Polymers .............................................................. 4.1 Main-chain –C–O–C– Polymers .............................................................
VII/503 VII/503 VII/504 VII/505 VII/506 VII/506 VII/507 VII/508 VII/509 VII/509 VII/510 VII/510 VII/511 VII/511
4.1.1 Poly(oxides) ...................................................................................... VII/511 4.1.2 Poly(carbonates) .............................................................................. VII/513 4.1.3 Poly(esters) ...................................................................................... VII/513 4.1.4 Poly(anhydrides) .............................................................................. VII/515 4.1.5 Poly(urethanes) ................................................................................ VII/515
This page has been reformatted by Knovel to provide easier navigation.
Contents 4.2
xlv
Main-chain –O– Heteroatom Polymers ................................................... VII/515 4.2.1 Poly(sulfonates) ................................................................................ VII/515
4.3
4.2.2 Poly(siloxanes) ................................................................................. VII/516 Main-chain –C–S–C– and –C–S–N– Polymers ...................................... VII/516 4.3.1 Poly(sulfides) .................................................................................... VII/516 4.3.2 Poly(sulfones) ................................................................................... VII/517
4.4
4.3.3 Others ............................................................................................... VII/518 Main-chain –C–N–C– Polymers ............................................................. VII/518 4.4.1 Poly(amides) .................................................................................... VII/518 4.4.2 Poly(hydrazides) ............................................................................... VII/520 4.4.3 Poly(ureas) ....................................................................................... VII/521 4.4.4 Poly(carbodiimides) .......................................................................... VII/521
4.4.5 Other Compounds ............................................................................ 4.5 Poly(phosphazenes) and Related Compounds ...................................... 4.6 Poly(silanes), Poly(silazanes) ................................................................. Table 5. Main-chain Heterocyclic Polymers .......................................................................... 5.1 Poly(benzoxazoles), Poly(oxadiazoles), Poly(oxadiazolidines) .............. 5.2 Poly(dithiazoles), Poly(benzothiazoles) .................................................. 5.3 Poly(imides) ............................................................................................
VII/521 VII/522 VII/522 VII/523 VII/523 VII/524 VII/524
5.3.1 Poly(benzimides) .............................................................................. VII/524 5.3.2 Poly(pyromellitides) .......................................................................... VII/525 5.3.3 Others ............................................................................................... 5.4 Poly(quinoxalines) .................................................................................. 5.5 Poly(benzimidazoles) .............................................................................. 5.6 Poly(piperazines) .................................................................................... 5.7 Poly(anhydrides) ..................................................................................... 5.8 Poly(thiophenes) ..................................................................................... 5.9 Others ..................................................................................................... Table 6. Formaldehyde Resins ............................................................................................. Table 7. Natural Polymers and Modified Natural Polymers .................................................. 7.1 Natural Rubber and Derivatives .............................................................. 7.2 Cutta Percha ........................................................................................... 7.3 Cellulose and Derivatives .......................................................................
VII/525 VII/526 VII/526 VII/526 VII/527 VII/527 VII/527 VII/528 VII/528 VII/528 VII/529 VII/529
7.3.1 Cellulose ........................................................................................... VII/529 7.3.2 Cellulose Ethers ............................................................................... VII/529 7.3.3 Cellulose Esters ............................................................................... VII/530 7.3.4 Cellulose Nitrate and Sulfate ........................................................... 7.4 Starch and Derivatives ............................................................................ 7.5 Other Poly(saccharides) ......................................................................... 7.6 Natural Resins ........................................................................................ Table 8. Inorganic Polymers ................................................................................................. Table 9. Poly(electrolytes) .................................................................................................... This page has been reformatted by Knovel to provide easier navigation.
VII/531 VII/531 VII/531 VII/532 VII/532 VII/533
xlvi
Contents Table 10. Block Polymers ....................................................................................................... VII/533 Table 11. Dendrimers ............................................................................................................. VII/534 D. References ......................................................................................................................... VII/536
Specific Refractive Index Increments of Polymers in Dilute Solution ......................................................... VII/547 A. Introduction ........................................................................................................................ VII/547 B. Introduction from the Third Edition ...................................................................................... VII/547 C. Refractometric Calibration Data .......................................................................................... VII/550 D. Tables of Specific Refractive Index Increments of Polymer Solutions ................................. Table 1. Main-chain Acyclic Carbon Polymers ..................................................................... 1.1 Poly(dienes) ............................................................................................ 1.2 Poly(alkenes) .......................................................................................... 1.3 Poly(acrylic Acid) and Derivatives .......................................................... 1.4 Poly(methacrylic Acid) and Derivatives .................................................. 1.5 Other α- or β-Substituted Poly(acrylics) and Poly(methacrylics) ............ 1.6 Poly(styrenes) ......................................................................................... 1.7 Other Compounds .................................................................................. Table 2. Main-chain Cyclic Carbon Polymers ....................................................................... Table 3. Main-chain Heteroatom Polymers ........................................................................... 3.1 C–O–C Polymers (Poly(oxides), Poly(esters), and Others) .................... 3.2 C–S–C Polymers (Poly(sulfones) and Others) ....................................... 3.3 C–N–C Polymers (Poly(amides), Poly(isocyanates), Poly(urethanes), and Others) ................................................................. 3.4 Poly(amino Acids) ................................................................................... 3.5 Poly(silanes) and Poly(silazanes) ........................................................... 3.6 Poly(heterocyclics) and Others ............................................................... Table 4. Cellulose and Derivatives ....................................................................................... Table 5. Poly(saccharides) ...................................................................................................
VII/551 VII/551 VII/551 VII/553 VII/557 VII/561 VII/573 VII/574 VII/588 VII/594 VII/594 VII/594 VII/599 VII/599 VII/604 VII/606 VII/608 VII/609 VII/611
E. References ......................................................................................................................... VII/615 Particle Scattering Factors in Rayleigh Scattering ...................................................................................... VII/629 A. Introduction: General Relations for a Homogeneous Solute ............................................... VII/629 B. Scattering Factors for Various Molecular Models ................................................................ VII/630 C. Effects of Dispersion in Molecular Weight .......................................................................... VII/631 D. Determination of Molecular Weight and Radius of Gyration ................................................ VII/632 E. Calculation of Scattering Factors ........................................................................................ VII/633 F. Particle Scattering Factors and Dissymmetries .................................................................. VII/633 Table 1. Dissymmetries for Monodisperse Systems ............................................................. VII/634 Table 2. Dissymmetries for Monodisperse and Polydisperse Coils ...................................... VII/634 G. References ......................................................................................................................... VII/635 Dipole Moments of Polymers in Solution ..................................................................................................... VII/637 A. Introduction ........................................................................................................................ VII/637 B. Dipole Moments of Polymers In Solution ............................................................................ VII/638 Table 1. Polyoxides (Polyethers) .......................................................................................... VII/638 This page has been reformatted by Knovel to provide easier navigation.
Contents Table 2. Table 3. Table 4. Table 5. Table 6. Table 7. Table 8. Table 9. Table 10. Table 11. Table 12. Table 13.
Polysulfides (Polythioethers) ................................................................................... Hydroxyl Terminated Oxide/Sulfide Copolymers .................................................... Polyesters Derived from Aromatic Diacids .............................................................. Aliphatic and Cycloaliphatic Polyesters .................................................................. Polycarbonates ....................................................................................................... Vinyl Polymers ........................................................................................................ Acrylic Polymers ..................................................................................................... Methacrylic Polymers .............................................................................................. Itaconate Polymers ................................................................................................. Polydienes .............................................................................................................. Silicon Based Polymers .......................................................................................... Styrene Copolymers ...............................................................................................
xlvii VII/639 VII/640 VII/640 VII/641 VII/641 VII/642 VII/643 VII/644 VII/644 VII/644 VII/645 VII/645
C. References ......................................................................................................................... VII/646 Heat, Entropy and Volume Changes for Polymer-liquid Mixtures .............................................................. VII/649 A. Introduction ........................................................................................................................ VII/649 1. Scope of the Table .................................................................................................. VII/649 2. Experimental Methods ............................................................................................ VII/649 B. Key for the Tables .............................................................................................................. VII/650 C. Tables of Literature References for Heat, Entropy, and Volume Changes for Polymer-solvent Mixtures ................................................................................................... Table 1. Main-chain Carbon Polymers .................................................................................. 1.1 Poly(dienes) ............................................................................................ 1.2 Poly(alkenes) .......................................................................................... 1.3 Poly(acrylics) .......................................................................................... 1.4 Vinyl Polymers ........................................................................................ 1.5 Poly(styrenes) ......................................................................................... 1.6 Other Compounds .................................................................................. Table 2. Main-chain Carbon Heteroatom Polymers .............................................................. 2.1 Poly(oxides) and Poly(esters) ................................................................. 2.2 Poly(amides) ........................................................................................... 2.3 Poly(siloxanes) ....................................................................................... 2.4 Derivatives of Cellulose .......................................................................... 2.5 Other Compounds ..................................................................................
VII/650 VII/650 VII/650 VII/651 VII/654 VII/655 VII/657 VII/659 VII/659 VII/659 VII/661 VII/661 VII/662 VII/663
D. References ......................................................................................................................... VII/663 Heats of Solution of Some Common Polymers ........................................................................................... VII/671 A. Introduction ........................................................................................................................ VII/671 B. Table of Heats of Solution .................................................................................................. VII/671 C. References ......................................................................................................................... VII/673 Solubility Parameter Values ......................................................................................................................... VII/675 A. Introduction ........................................................................................................................ VII/675 B. Miscibility of Solvents and Polymers ................................................................................... VII/676 1. Cohesive Energy Density and the Solubility (Hildebrand) Parameter ..................... VII/676 This page has been reformatted by Knovel to provide easier navigation.
xlviii
Contents 2. 3.
Cohesive Energy Parameters for Polar Systems .................................................... VII/677 Relationship Between Solubility Parameters and Other Thermodynamic Parameters ............................................................................................................. VII/677
C. Solubility Parameter Measurements, Calculations, and Correlations .................................. 1. Solvents .................................................................................................................. 2. Polymers ................................................................................................................. 2.1 Indirect Measurements ........................................................................... 2.2 Correlation Methods ............................................................................... Table 1. Selected Solvents for Use in Polymer Solvency Testing ........................................ Table 2. Group Contribution to Cohesive Energy Density .................................................... 2.1 Carbon-containing Groups ...................................................................... 2.2 Oxygen-containing Groups ..................................................................... 2.3 Nitrogen-containing Groups .................................................................... 2.4 Other Groups .......................................................................................... 2.5 Structural Features ................................................................................. Table 3. Contribution to Ecoh and V ....................................................................................... Table 4. Solubility Parameter I: Component Group Contributions ........................................ Table 5. Solubility Parameter II: Component Group Contributions ....................................... Table 6. Equations to be Used for Hoy's System .................................................................
VII/679 VII/679 VII/680 VII/680 VII/682 VII/683 VII/684 VII/684 VII/684 VII/684 VII/684 VII/685 VII/685 VII/686 VII/686 VII/687
D. Solubility Table 7. Table 8. Table 9.
VII/688 VII/688 VII/694 VII/698 VII/698 VII/698 VII/698 VII/699 VII/699 VII/699 VII/699 VII/700 VII/700 VII/700 VII/700 VII/701 VII/701 VII/701 VII/701 VII/702 VII/702 VII/708 VII/709 VII/710
Parameter Tables ................................................................................................ Solubility Parameters of Solvents in Alphabetical Order ......................................... Solubility Parameters of Solvents in Increasing Order of δ ..................................... Hansen Solubility Parameters of Liquids at 25°C ................................................... 9.1 Paraffinic Hydrocarbons ......................................................................... 9.2 Aromatic Hydrocarbons .......................................................................... 9.3 Halohydrocarbons ................................................................................... 9.4 Ethers ..................................................................................................... 9.5 Ketones ................................................................................................... 9.6 Aldehydes ............................................................................................... 9.7 Esters ...................................................................................................... 9.8 Nitrogen-containing Compounds ............................................................ 9.9 Sulfur-containing Compounds ................................................................ 9.10 Acid Halides and Anhydrides .................................................................. 9.11 Alcohols .................................................................................................. 9.12 Acids ....................................................................................................... 9.13 Phenols ................................................................................................... 9.14 Water ...................................................................................................... 9.15 Polyhydric Alcohols ................................................................................. Table 10. Solubility Parameters of Polymers .......................................................................... 10.1 Main Chain Carbon Polymers ................................................................. 10.2 Main Chain C–O Polymers ..................................................................... 10.3 Main Chain C–N Polymers ..................................................................... 10.4 Other Polymers ....................................................................................... This page has been reformatted by Knovel to provide easier navigation.
Contents
xlix
E. References ......................................................................................................................... VII/711 Optically Active Polymers ............................................................................................................................ VII/715 A. Abbreviations Used ............................................................................................................ VII/715 B. Optically Active Polymers from Chiral Monomers ............................................................... Table 1. Main-chain Acyclic Carbon Polymers ..................................................................... 1.1 Poly(alkenes) .......................................................................................... 1.2 Poly(acrylics) and Related Polymers ...................................................... 1.3 Poly(methacrylics) and Related Polymers .............................................. 1.4 Poly(vinyl Ethers), Poly(vinyl Ketones), and Poly(vinyl Esters) .............. 1.5 Poly(styrenes), Poly(carbazoles) ............................................................ 1.6 Poly(dienes) ............................................................................................ 1.7 Poly(isonitriles) ....................................................................................... 1.8 Poly(alkynes) .......................................................................................... 1.9 Poly(maleimides) and Related Polymers ................................................ 1.10 Other Compounds .................................................................................. Table 2. Main-chain Acyclic Heteroatom Polymers .............................................................. 2.1 Poly(oxides) ............................................................................................ 2.2 Poly(esters) ............................................................................................. 2.3 Poly (sulfides), Poly(thioesters) .............................................................. 2.4 Poly(urethanes), Poly(ureas) .................................................................. 2.5 Poly(amides) ........................................................................................... 2.6 Poly(isocyanates) ................................................................................... 2.7 Poly(imines) ............................................................................................ 2.8 Poly(amino Acids) ................................................................................... Table 3. Poly(saccharides) ...................................................................................................
VII/716 VII/716 VII/716 VII/716 VII/717 VII/718 VII/719 VII/720 VII/720 VII/721 VII/722 VII/723 VII/723 VII/723 VII/724 VII/725 VII/725 VII/726 VII/728 VII/728 VII/729 VII/732
C. Optically Active Polymers from Achiral Monomers .............................................................. Table 4. Main-chain Acyclic Carbon Polymers ..................................................................... 4.1 Poly(acrylics) and Related Polymers ...................................................... 4.2 Poly(methacrylics) and Related Polymers .............................................. 4.3 Poly(vinyl Ethers) .................................................................................... 4.4 Poly(styrenes) ......................................................................................... 4.5 Poly(dienes) ............................................................................................ 4.6 Poly(isonitriles) ....................................................................................... 4.7 Poly(maleimides) .................................................................................... 4.8 Other Compounds .................................................................................. Table 5. Main-chain Acyclic Heteroatom Polymers .............................................................. 5.1 Poly(oxides) and Poly(sulfides) .............................................................. 5.2 Poly(isocyanates) ...................................................................................
VII/733 VII/733 VII/733 VII/734 VII/735 VII/735 VII/735 VII/736 VII/736 VII/737 VII/737 VII/737 VII/738
D. References ......................................................................................................................... VII/739 Anisotropy of Segments and Monomer Units of Polymer Molecules ......................................................... VII/745 A. Introduction ........................................................................................................................ VII/745
This page has been reformatted by Knovel to provide easier navigation.
l
Contents B. Tables of Anisotropy of Segments and Monomer Units of Polymer Molecules ................... Table 1. Main-chain Acyclic Carbon Polymers ..................................................................... 1.1 Poly(dienes) ............................................................................................ 1.2 Poly(alkenes) .......................................................................................... 1.3 Poly(acrylic Acid) and Derivatives .......................................................... 1.4 Poly(methacrylic Acid) and Derivatives .................................................. 1.5 Poly(acrylic Acid) Derivatives with Mesogenic Side Groups ................... 1.6 Poly(methacrylic Acid) Derivatives with Mesogenic Side Groups ........... 1.7 Vinyl Polymers ........................................................................................ 1.8 Poly(vinyl) Derivatives with Mesogenic Side Groups .............................. 1.9 Copolymers, Graft and Block Copolymers .............................................. Table 2. Main-chain Carbocyclic Polymers ........................................................................... Table 3. Main-chain Heteroatom Polymers ........................................................................... 3.1 Poly(oxides) ............................................................................................ 3.2 Poly(esters) ............................................................................................. 3.3 Poly(amides) ........................................................................................... 3.4 Poly(peptides) and Nucleic Acids ........................................................... 3.5 Poly(phosphazenes) ............................................................................... 3.6 Poly(siloxanes) ....................................................................................... Table 4. Main-chain Heterocyclic Polymers .......................................................................... 4.1 Poly(imides) ............................................................................................ 4.2 Poly(pyrromellitimides) ........................................................................... 4.3 Poly(quinoxalines) .................................................................................. 4.4 Poly(benzimidazoles), Poly(benzoxazoles) ............................................ 4.5 Poly(saccharides) ...................................................................................
VII/746 VII/746 VII/746 VII/747 VII/747 VII/748 VII/748 VII/749 VII/750 VII/751 VII/751 VII/752 VII/752 VII/752 VII/752 VII/755 VII/755 VII/755 VII/756 VII/756 VII/756 VII/756 VII/757 VII/757 VII/758
C. References ......................................................................................................................... VII/760 Gelation Properties of Polymer Solutions .................................................................................................... VII/765
VIII. Abbreviations of Polymer Names and Chemical Abstract Numbers Abbreviations for Thermoplastics, Thermosets, Fibers, Elastomers and Additives ...................................
VIII/1
A. Introduction ........................................................................................................................
VIII/1
B. Abbreviations in Alphabetical Order ....................................................................................
VIII/2
C. Abbreviations and Acronyms Based on Poly(monomer) Names ......................................... VIII/15 D. Abbreviations for Polymers Named after a Characteristic Polymer Croup .......................... VIII/17 E. Abbreviations for Polymers Produced by Chemical Transformation of Other Polymers ............................................................................................................................ VIII/18 F. Abbreviations for Blends, Reinforced Polymers, etc. .......................................................... VIII/19 G. ISO Codes for Thermoplastic Materials .............................................................................. 1. Codes for ISO Data Blocks 1-5 ............................................................................... 1.1 ISO and DIN Codes for Data Block 1 ..................................................... 1.2 ISO Codes for Items in Data Block 2 ...................................................... 1.3 ISO Codes for Items in Data Block 3 ......................................................
This page has been reformatted by Knovel to provide easier navigation.
VIII/19 VIII/19 VIII/19 VIII/20 VIII/20
Contents 1.4 1.5
li
ISO Codes for Extending and Reinforcing Fillers (Data Block 4) ........... VIII/20 ISO Codes for Data Block 5 .................................................................... VIII/21
H. SPI Codes for the Recycling of Plastics .............................................................................. VIII/21 I.
Recommended Abbreviations and Acronyms for Names of Elastomers ............................. VIII/21
J. Abbreviations for Textile Fibers .......................................................................................... VIII/22 Chemical Abstract Registry Numbers and Online Database Searching for Polymer Literature ................ VIII/25 A. Nomenclature ..................................................................................................................... VIII/25 B. CAS Registry Numbers ...................................................................................................... VIII/25 C. Indexing and CAS Registry Number Assignment ................................................................ VIII/26 D. Example Searches ............................................................................................................. 1. Example of a Search Using the Polymer CAS Registry Number ............................ 2. Example of a Search Using the Monomer CAS Registry Number .......................... 3. Example of a Combined Search ............................................................................. 4. Example of a Copolymer Search ............................................................................ 5. Example of an Engineering Database Search ........................................................ 6. Example of a Search with Punctuation in the Polymer Name ................................. 7. Example of an Engineering Materials Abstracts Search ......................................... 8. Example of a Polymer Trademark Search ..............................................................
VIII/26 VIII/26 VIII/26 VIII/26 VIII/28 VIII/29 VIII/29 VIII/29 VIII/29
E. List of CAS Regisry Numbers of Common Polymers .......................................................... VIII/32
Index .......................................................................................................................................
This page has been reformatted by Knovel to provide easier navigation.
IX/1
S E C T I O N
N
O
M
E
N
C
L
A
T
U
R
E
I
R U L E S
—
U
N
I
T
S
N o m e n c l a t u r e
W . V. Metanomski Chemical Abstracts Service, Columbus, Ohio, USA
A. Introduction B. IUPAC Recommendations 1. Source-Based Nomenclature 1.1. Homopolymers 1.2. Copolymers 1.3. Nonlinear Macromolecules & Macromolecular Assemblies 2. Structure-Based Nomenclature 2.1. Regular Single-Strand Organic Polymers 2.2. Regular Double-Strand Organic Polymers 2.3. Regular Single-Strand Inorganic and Coordination Polymers 2.4. Regular Quasi-Single-Strand Coordination Polymers 2.5. Irregular Single-Strand Organic Polymers C. Use of Common and Semisystematic Names D. Chemical Abstracts (CA) Index Names E. Polymer Class Names F. References A.
1-1 1-1 I-2 I-2 I-2 I-3 I-3 I-6 I-6 I-7 I-7 I-8 I-8 1-11 1-12
INTRODUCTION
Macromolecular (polymer) nomenclature has an almost 50-year history. As early as 1949 there existed a Subcommission on Nomenclature within the International Union of Pure and Applied Chemistry (IUPAC) under the chairmanship of Maurice L. Huggins. The Subcommission was part of the IUPAC Commission on Macromolecules, chaired then by Herman F. Mark. Other notable pioneers in polymer science, Jan Joseph Hermans, Otto Kratky, Harry W. Melville, and George J. Smets, were members of the Commission. The Subcommission produced its first official report in 1952. It recognized then, what is just as true today, that the practice in the field of small molecules of providing rigorous definitions is impractical for polymers. The latter consist of molecules not necessarily exactly of the same size, chemical composition, or structure. The differences result from the presence of end groups, branches, variation in orientation of monomeric units, and irregularity in the sequence of different types of units. The American Chemical Society (ACS) Division of Polymer Chemistry established its Nomenclature Commit-
tee in 1963 to try to unify earlier attempts to name polymers in some coherent way. Their first major project resulted in a structure-based nomenclature for regular linear polymers, first published in ACS Polymer Preprints in 1967, adopted by Chemical Abstracts in 1968, and incorporated in IUPAC recommendations in 1975 [I]. When the IUPAC Commission on Macromolecules was elevated to become the IUPAC Division of Macromolecular Chemistry, the latter in turn established its Commission on Macromolecular Nomenclature in 1968. The Commission in the course of its nearly 30 years of existence produced a series of major documents that have shaped modern nomenclature and terminology of polymer science. The recommendations are being published in the IUPAC official journal, Pure and Applied Chemistry, and occasionally are republished in the form of a "Compendium" which groups all the currently valid documents in a single volume. The Commission published its "Compendium of Macromolecular Nomenclature" in 1991 [2]. The book, which IUPAC has designated the "Purple Book", in analogy to other IUPAC books ("Blue" - organic, "Red" - inorganic, "Orange" - analytical, "Green"- physical, and "Gold" - overall chemistry), has the two most basic macromolecular nomenclature recommendations: "nomenclature of regular single-strand organic polymers" and "source-based nomenclature for copolymers". In more recent years, the Commission extended that basic nomenclature to double-strand (ladder and spiro) organic polymers, irregular and crosslinked polymers, and polymer blends and interpenetrating networks. In this article, the basic structure-based and source-based nomenclature of polymers is explained and illustrated in some detail. The continuing use of common and semisystematic nomenclature with reference to specific tables in this Handbook is highlighted. The current Chemical Abstracts (CA) index names [3] are compared and contrasted with the IUPAC practice and typical names employed in the polymer journals and textbooks. B.
IUPAC RECOMMENDATIONS
Since polymers, unlike low-molecular-weight compounds, have no uniform structure and are mixtures of macromolecules of different length and different structural
arrangement, their graphical representation and their names require a special approach. Often enough, the structure of the polymer has not been sufficiently characterized and the researcher cannot draw its chemical structure. Consequently, no name of the polymer reflecting its structure is possible. A polymerization reaction for a polymer formed from a monomer such as vinyl chloride can schematically be represented by
polybutadiene polyethylene poly(methyl methacrylate) poly(methyl vinyl ether) polystyrene poly(tetrafluoroethylene) poly(vinyl alcohol) poly(vinyl acetate) poly(vinyl chloride) poly(vinylidene dichloride)
That shows an idealized product. In fact, however, the polymer consists of long-chains of various lengths. The repeating units, - C H 2 - C H C l - , are not necessarily all uniquely oriented and joined in a regular fashion as shown in the idealized structure above. In addition to "head-totail" links
Parentheses are used when the name of the monomer consists of two or more words, and when the monomer has substituents. These are all olefinic type reactants, from which two carbon atoms originally linked by a double bond form a bivalent group:
other links such as "head-to-head"
where R and R [ represent a hydrogen atom or a substituent group. Many of these are joined, in turn, to each other but their exact orientation or sequence is seldom known. On the other hand, different polymers derived from a single monomer and having identical constitutional units can still be differentiated by additional information, such as average molecular weight and other chemical and physical characteristics.
and "tail-to-tail"
can occur, and the exact sequence of all these repeating units usually is not known. This becomes even more complicated when a copolymer is derived from more than one monomer, such as styrene and methyl acrylate, which contribute two constitutional or monomeric units:
They can combine into a polymeric chain, resulting in many types such as unspecified, statistical, random, alternating, periodic, block, or graft copolymers. Because the exact structure of the polymer is not always known, two systems of naming polymers exist: source-based nomenclature, structure-based nomenclature. 1.
Source-Based Nomenclature
1.1. Homopolymers Homopolymers are derived from only one species of monomer, which may be the actual starting reactant (or source), or be a hypothetical monomer if the homopolymer is formed by a modification of another homopolymer. The name of the polymer is formed by attaching the prefix "poly" to the name of the actual or assumed monomer, or the starting reactant (source), from which the polymer is derived. Examples: poly (acrylic acid) polyacrylonitrile
1.2. Copolymers For copolymers, the names of monomers are cited after the prefix "poly". In addition, an italicized connective (infix) is placed between the names of monomers to denote the kind of sequential arrangement by which the constitutional (monomeric) units, derived from each monomer, are related in the structure [4]. Seven types of sequence arrangements are listed with their corresponding connectives:
Type
Connective
unknown or unspecified statistical (obeying known statistical laws) random (obeying Bernoullian distribution) alternating (for two monomeric units) periodic (ordered sequence of more than two) block (linear arrangement of blocks) graft (side blocks chains connected to main chain)
Examples:
-co-stat-raft-alt-per-block-graft-
poly[styrene-C(?-(methyl methacrylate)! poly^tyrene-statf-acrylonitrile-statf-butadiene) poly[ethylene-ran-(vinyl acetate)] poly[(ethylene glycol)-tf/r-(terephthalic acid)] poly[formaldehyde-/?er-(ethylene oxide)-per(ethylene oxide)] polystyrene-&/oc&-polybutadiene polybutadiene-gra/f-polystyrene
The names of the monomers are those common or semisystematic names that are encountered most often in the literature of polymer science. The order of citation of monomers in copolymer names is arbitrary. An equally acceptable alternative scheme for naming copolymers utilizes the prefix "copoly", followed by citation of the names of the monomers, separated by an oblique stroke (a solidus). Parentheses are not needed to enclose monomer names consisting of two or more words. Examples:
the constituent macromolecules with an italicized connective between them. Examples:
copoly(styrene/methyl methacrylate) j"tatf-copoly(styrene/acrylonitrile/butadiene) ran-copoly(ethylene/vinyl acetate) a/f-copoly(ethylene glycol/terephthalic acid) per-copoly(formaldehyde/ethyleneoxide/ethylene oxide) Wtfc/:-copoly(styrene-butadiene) gra/£-copoly(butadiene-styrene)
1.3. Nonlinear Macromolecules and Macromolecular Assemblies Most recently, the source-based nomenclature has been extended for non-linear macromolecules and macromolecular assemblies [5], The non-linear macromolecules comprise branched, graft, comb, star, cyclic, and network macromolecules. The macromolecular assemblies comprise polymer blends, interpenetrating polymer networks, and polymer-polymer complexes. The following italicized qualifiers can be used as both prefixes (e.g., blend-, net-) and infixes (connectives) (e.g., -blend-, -net-) to designate the skeletal structure of nonlinear macromolecules or macromolecular assemblies:
Type cyclic branched, unspecified short-chain-branched long-chain-branched branched with branch point of functionality / comb star star with / arms network crosslink polymer blend interpenetrating polymer network semi-interpenetrating polymer network polymer-polymer complex
Connective cyclo branch sh-branch l-branch f-branch comb star f-star net t (Greek iota) blend ipn sipn compl
2.
poly styrene-com£>-poly aery lonitrile com&-poly(styrene~statf-acrylonitrile) poly styrene-comZ?- [poly acrylonitrile; poly(methyl methacrylate)] 4-sfar-polystyrene star-(po\yA-block-polyB-block-polyC) star-(polyA; polyB; polyC) star-(polyacrylonitrile; polystyrene) (M1 100000:20000) fte£-polystyrene-£-divinylbenzene n^-poly[styrene-<3/Kmaleic anhydride)]^-(ethylene glycol) polystyrene-Weftd-poly(2,6-dimethylphenol) poly(methyl methacrylate)-We?i(i-poly(tt-butyl acrylate) (net-polystyrene)-sipn-poly(vinyl chloride) [net-poly(styrenQ-stat-butSidiene]-ipn-[netpoly(ethyl acrylate)
Structure-Based Nomenclature
2.1. Regular Single-Strand Organic Polymers For regular organic polymers which have only one species of constitutional repeating unit (CRU) in a single sequential arrangement and consist of single strands only, the name is poly(constitutional repeating unit), wherein the repeating group is named as a bivalent organic group according to the IUPAC nomenclature rules for organic compounds [I]. Each such repeating group can consists of simple or substituted subunits such as: methylene ethylene vinylene hexane-l,6-diyl 1-chloroethylene 1 -oxopropane-1,3-diyl adipoyl 1,4-phenylene cyclohexane-1,4-diyl oxy thio sulfonyl imino methylimino hydrazo piperidine-1,4-diyl
In naming non-linear homopolymer molecules, the italicized prefix for the skeletal structure of the macromolecule is placed before the source-based name of the constituent linear chain. Assemblies of macromolecules held together by noncovalent bonds are named by a combination of the names of
silanediyl dimethylsilanediyl Before the total constitutional repeating unit (CRU) can be given a unique name, a single preferred CRU must be selected. References page 1-12
For instance, in a polymer such as
it is immediately evident that a three-atom group (oxygen, chlorine-substituted methylene group, and methylene group) are being regularly repeated. Yet, the CRU can be identified in at least three ways
d. for carbon-only acyclic chains, seniority is determined first by length, then by the number of substituents, by the ascending order of locants, and, finally, by the alphabetical order of the names of the substituent groups.
c. carbocycles, e.g., 1,4-phenylene:
In all cases, the basic seniority rules apply only to those atoms or groups of atoms that are in the main chain. The kinds of substituents on the main chain (whether acyclic carbon-only groups, or hetero-atom-containing groups, or any ring systems) do not affect the selection of the CRU, unless identical basic subunits in the chain have to be further differentiated by the number of substituents and their alphabetical order, but not by the type of the substituent. If completely identical subunits are separated by other subunits, the direction of citation is determined by the shorter part between them. The preferred CRU is the one beginning with the subunit of highest seniority. To establish direction, one proceeds from this subunit to the neighboring subunit of the same or next in seniority. In the example of a poly(chloroethylene oxide), shown above, where a regularly repeating structure has been assumed, the subunit of the highest seniority is the oxygen atom and the subunit next in seniority is a substituted - C H 2 - C H 2 - . The substituted subunit, - C H C l - C H 2 - , is oriented in such a way that the substituent, chlorine atom, is assigned the lowest locant (1 rather than 2). The CRU is written to read from left to right. Thus, the preferred CRU is
cyclobutane-1,3-diyl: d. carbon-containing acyclic groups, e.g., 1-chloroethylene: - C H C l - C H 2 propane-1,3-diyl: - C H 2 - C H 2 - C H 2 -
and the polymer
To obtain a unique name based on a preferred CRU, several rules have to be applied. Rules have been developed to specify both seniority among subunits, that is, the point at which to begin writing the CRU, and also the direction in which to move along the chain from left to right to reach the end of the chain. The order of seniority among the types of bivalent groups that are parts of the chain of a single-strand polymer is a.
heterocycles, e.g., piperidine-l,4-diyl: thiophene-2,5-diyl:
b. heteroatomic acyclic groups, e.g., oxy: - O - , sulfonyl: - S O 2 - , imino: - N H -
Within each structural type, the seniority is established by further criteria: a.
for heterocycles, a ring system containing nitrogen is senior to a system containing a hetero atom other than nitrogen, with further descending order of seniority governed by the greatest number of rings in the ring system, the largest individual ring in the ring system, the largest number of hetero atoms, and the greatest variety of hetero atoms; b. for heteroatomic acyclic chains, oxygen is senior to sulfur, sulfur to nitrogen, nitrogen to phosphorus, phosphorus to silicon, silicon to germanium, etc.; c. for carbocycles, a three-ring system is senior to a two-ring system, a two-ring system containing two 6-membered rings is senior to one containing a 5and a 6-membered rings, a fused two-ring system (two atoms common to both rings) is senior to a spiro two-ring system (one atom in common), and an unsaturated ring is senior to a saturated ring of the same size;
is named poly [oxy (1 -chloroethylene)] The second example:
poly [(methylimino)methyleneimino-1,3-phenylene] illustrates a polymer whose CRU starts with a substituted nitrogen atom and proceeds through the shortest path to the unsubstituted nitrogen atom and then through a carbocycle. The chemical structure of the CRU is enclosed in parentheses or brackets. While dashes representing chemical bonds may be omitted within the formula unless necessary for clarity, at the ends of the CRU, dashes must be shown. They are drawn across the enclosing marks.
symbol a denoting the left-hand end group and the symbol co denoting the other end group.
The third example:
Example: poly(pyridine-3,5-diylcarbonyloxymethylene) shows a polymer, whose CRU starts with a heterocycle and then proceeds through a substituted carbon atom to a hetero atom. If the end groups of the chain are known, they may be specified by adding prefixes to the polymer name, with the
Structure
a-(trichloromethyl)-co-chloropoly (1,4-phenylenemethylene) The following table compares and contrasts structurebased and source-based names of some common polymers.
Structure-based name
Source-based or trivial name
Poly(methylene) Poly(propylene)
Polyethylene Polypropene
Poly (1,1 -dimethylethylene) Poly (1 -methyl-1 -butenylene)
Polyisobutylene Polyisoprene
Poly (1 -phenylethylene)
Polystyrene
PoIy(I -chloroethylene)
Poly(vinyl chloride)
Poly (1 -cyanoethylene)
Poly aery lonitrile
PoIy(I-acetoxyethylene)
Poly(vinyl acetate)
PoIy(1,1-difluoroethylene) Poly(difluoromethylene)
Poly(vinylidene fluoride) Polytetrafluoroethylene
Poly[(2-propyl-1,3-dioxane-4,6-diyl)methylene]
Poly(vinyl butyral)
Poly[ 1 -(methoxycarbonyl)-1 -methylethylene]
Poly(methyl methacrylate)
Poly(oxyethylene)
Poly(ethylene oxide)
Poly(oxy-1,4-phenylene)
Poly(phenylene oxide)
Poly[imino(l-oxohexane-1,6-diyl)]
Poly(e-caprolactam)
Poly(oxyethyleneoxyterephthaloyl)
Poly(ethylene terephthalate)
Poly(iminoadipoyliminohexamethylene)
Poly(hexamethylenediamine-a/?-adipic acid) or poly(hexamethylene adipamide) Poly(maleic anhydride-a/r-styrene)
Poly[(2,5-dioxotetrahydrofuran-3,4-diyl)( 1 -phenylethylene)]
References page 1-12
2.2. Regular Double-Strand Organic Polymers In a double-strand polymer, the macromolecules consist of an uninterrupted sequence of rings with adjacent rings having two or more atoms in common (a ladder polymer) or one atom in common (a spiro polymer). As for a single-strand polymer, a single preferred constitutional repeating unit (CRU) must be selected in order to obtain a unique name [6]. The CRU is usually a tetravalent group denoting attachment to four atoms and is named according to the usual rules of organic nomenclature. Again, the name of the polymer is in the form of
common at each junction:
the name based on the preferred CRU is
poly(constitutional repeating unit) Since the polymer has a sequence of rings, in order to identify a preferred CRU, the rings must be broken by observing the following criteria in decreasing order of priority: a. minimize the number of free valences in the CRU, b. maximize the number of most preferred hetero atoms in the ring system, c. retain the most preferred ring system, and d. choose the longest chain for acyclic CRU. Further decisions are based on the seniority of ring systems (indicated in the preceding section), on the orientation of the CRU to give the lowest free valence locant at the lower left of the structural diagram, and on placing the acyclic subunits, if any, on the right side of the ring system within the CRU. For a polymer consisting of adjacent 6-membered saturated carbon rings:
the name of the preferred CRU, which in this case is an acyclic chain of four carbon atoms with four free valences at each atom (the lowest at the lower left), is
poly (butane-1,4: 3,2-tetrayl)
poly(l,4-dithiin-2,3:5,6-tetrayl-5,6-dicarbonyl) Here, by applying the seniority of the rings system, the heterocycle was left intact, but the carbocycle was broken. That left two bivalent acyclic subunits (carbonyl groups), which according to the rule, have been placed on the right side of the cyclic subunit, with attachments as in the original polymer. Another, still more complex ladder polymer, derived from the polycondensation of 1,4,5,8-naphthalenetetracarboxylic dianhydride with 1,2,4,5-benzenetetramine:
poly[(7-oxo-7//,10//-benz[
the preferred CRU and the name are:
The free valence locants are always placed just in front of the corresponding ending of the tetravalent unit and are cited in the order lower-left, upper-left: upper-right, lower-right that is, in a clockwise direction, the left locants being separated from the right locants by a colon. For a more complex ladder polymer consisting of an alternating sequence of 6-membered sulfur-containing rings and keto-group containing carbocycles, with two atoms in
poly(2,4,8,10-tetraoxaspiro[5.5]undecane-3,3:9,9-tetrayl-9,9-diethylene)
2.3. Regular Single-Strand Inorganic and Coordination Polymers The names of inorganic and coordination polymers are based on the fundamentals developed for organic polymers [7]. As in the nomenclature of organic polymers, these rules apply to structural representations
which may at times be idealized and do not take into account irregularities, chain imperfections, or random branching. A constitutional repeating unit (CRU) is selected and named. However, because of the basic difference between the organic and inorganic nomenclature, the subunits of the CRU are not named as bivalent groups, but as inorganic or coordination groups indicating covalent and/or coordinate bonding. The name of the polymer is the name of the CRU prefixed by the term "poly", "catena", or other structural indicator. In order to arrive at the preferred CRU, seniorities of the constitutent subunits are considered as well as the preferred direction for the sequential citation. The constituent subunit of the highest seniority must contain one or more central atoms; bridging groups between central atoms in the backbone of the polymer are of lower seniority. This is consistent with the principle of coordination nomenclature which puts the emphasis on the coordination center. Examples of homoatomic backbones are
catena-poly [dimethyltin]
caterca-poly[(difluorosilicon) (dimethylsilicon)]
More common coordination polymers consist of a mononuclear central atom with a bridging ligand. The CRU of such a polymer cites the central atom first, which is prefixed by its associated non-bridging ligands, followed in turn by the name of the bridging ligand prefixed by the Greek letter \i:
2.4. Regular Quasi-Single-Strand Coordination Polymers In a regular quasi-single-strand coordination polymer, the preferred CRU has one terminal constituent subunit connected through a single atom to the next CRU [7]. Such polymers are named as single-strand coordination polymers:
catena-poly [palladiumdi-u-chloro]
catena-polyfsilicondi-u-thio]
catena-poly[platinum(ubromo-u-chloro)]
catena-poly [titaniumtri-u-chloro]
2.5. Irregular Single-Strand Organic Polymers Irregular polymers are named by placing the prefix "poly" before the structure-based names of the constitutional units, collectively enclosed in parentheses or brackets, with the individual constitutional units separated by an oblique stroke (a solidus) [8]. The stroke indicates the irregular or unknown sequential arrangement of these units. The dashes at each end of the formula are drawn fully inside the enclosing marks to denote that these are not necessarily terminal bonds of the macromolecule. For instance, a partially hydrolyzed poly(vinyl acetate) containing units:
is represented graphically and named:
catena-poly [(amminechlorozinc)-u-chloro]
catena-pory[(dihydroboron)-ju-(dimethylamido)] poly( 1 -acetoxyethylene/1 -hydroxyethylene)
Multiple bridging ligands between the pair of central atoms are cited in alphabetic order. Italicized element symbols indicating the coordinating atoms in bridging ligands are cited in the order of direction of the CRU and are separated by a colon:
A copolymer of vinyl chloride and styrene joined head-totail is
poly (1 -chloroethy lene/1 -pheny lethylene) A chlorinated polyethylene consisting of units
catena-poly [copper-[|i-chloro-bis-u-(diethyl S')] -copper- u-chloro]
disulfide-S: References page 1-12
is shown and named as
poly(chloromethylene/dichloromethylene/methylene) C.
USE OF COMMON AND SEMISYSTEMATIC NAMES
The main purpose of chemical nomenclature is to identify a chemical species by means of written or spoken words for a useful communication among chemists. A systematic nomenclature arose from the need to provide a relationship between the structure and the name. In other words, the reader should be able to deduce and identify the structure from the name. Traditional names, however, not necessarily based on structures, have been widely used for many common compounds. These are the so-called common, trivial, or semisystematic names, which are satisfactory for communication within a given special chemical field. It was earlier stated that in the macromolecular nomenclature IUPAC is recommending the use of common and semisystematic names for monomers in the sourcebased polymer names. The structure-based names, on the other hand, are more related to the structural characteristic of the polymers. But even there, IUPAC allows for a limited number of common names for such substituent groups as "allyl" and "vinyl", and for bivalent groups such as "adipoyl" and "terephthaloyl". The authors in this Handbook for the most part are using the IUPAC-recommended names, or very close variants thereof. On the other hand, in some compilations such as "Crystallographic Data for Various Polymers" (in Section VI), the author provides an excellent introduction and explanation of the names used. For some structure-based names, reflecting constitutional repeating units (CRU), especially for those with a center of symmetry, the naming of linking bivalent groups begins with the central subunit and proceeds in both directions. The IUPAC method selects the most senior bivalent group and proceeds naming from left to right.
In no case, there is any misunderstanding in either case as to which structure is associated with each name. Abbreviations and acronyms are also extensively used in the chemical literature for monomers, polymers, as well as for additives, modifiers, and fillers. Their extensive list is provided in Section VIII of this Handbook. As is clearly stated there, the same abbreviation is often used for different monomers and polymers, and the same polymer may have different abbreviations or acronyms. Examples: 1. DPP 2. PVA 3. trioctyl phosphate 4. polyacrylonitrile
diphenyl phthalate dipropyl phthalate poly(vinyl alcohol) poly(vinyl acetate) TOF TOP PAC PAN
The IUPAC policy [9] on the use of abbreviations in the chemical literature states that there are great advantages in defining all abbreviations in a single conspicuous place in each paper, preferably near the beginning of the paper in a single list. An alternative is to define each abbreviation fully the first time it appears in the text. No abbreviations should be used in the titles of publications. A chapter of this Handbook contains a set of abbreviations recognized by international organizations. D.
CHEMICAL ABSTRACTS (CA) INDEX NAMES
Chemical Abstracts Service (CAS), the publisher of printed Chemical Abstracts (CA) and corresponding products and services in microform, online databases, CD-ROM, and World Wide Web also names the polymers, selected for inclusion in the CAS Chemical Registry System and in the CA Chemical Substance Indexes, in two ways: a.
Examples:
Handbook name: poly(4,4'-sulfonyldiphenylene carbonate) IUPAC name: poly(oxycarbonyloxy-l,4-phenylenesulfonyl-1,4-phenylene) 2.
Handbook name: poly (oxy die thy lene succinate) IUPAC name: poly(oxyethyleneoxyethyleneoxysuccinyl)
in terms of the component monomer(s) from which they are prepared b. in terms of the final structure of the resulting polymer. There are definitive rules that govern when each type of structure is recorded and named [3], The primary, comprehensive representation of polymers by CAS is by citation of the component monomer(s) because, in many cases, the structure of the final polymer is either not known or is not described in sufficient detail by the author. When the polymer structure is well documented by the author or can be confidently assumed, because one and only one structure is chemically possible, then a supplementary representation with a corresponding systematic name is added to the CAS Registry System and included in the printed indexes and online files.
The chemical nomenclature used by CAS has developed in parallel, and generally in accordance, with the rules and recommendations published by IUPAC. However, their rules of systematic nomenclature do not necessarily lead to a unique name for each compound, but do lead to an unambiguous one. This causes no difficulty in normal scientific communication, but is unacceptable in a formal, rigidly controlled, alphabetic listing such as the CA Chemical Substance Index. The CA index names must not only be unambiguous, unique, and totally reproducible, but also selected so as to bring the names of structurally related substances into juxtaposition in the alphabetic index. CAS has always recognized that, while a unique name is needed for an index and for substance identification, the use of such invariant name in scientific papers is neither practicable nor desirable. In this section, it is intended to highlight the characteristics of the CA index names for polymers and compare them with some of the typical names used in the scientific community. a. b.
c. d.
e.
IUPAC rules have been adapted to the specific needs of a highly ordered alphabetical index. Most common names were eliminated and exceptional treatment for various classes of substances was discontinued. A single preferred name is determined for each identifiable substance. A strict order of precedence of chemical functions and compound classes is followed to determine the preferred "index heading parent". A total name is "inverted" by citing first the index heading parent (usually, basic skeleton name with a locant and suffix denoting the principal function), followed by the comma of inversion, the substituents, and the modification (derivative of the principal function), e.g., 2-propenoic acid, 2-methyl-, methyl ester
As mentioned above, most common names, including those still sanctioned by IUPAC, have been replaced by fully systematic names. The following is a short list of most common monomers with both common names and CA Index names: Common acrylamide acrylic acid acrylonitrile adipic acid 8-caprolactam 8-caprolactone ethylene glycol ethylene oxide fumaric acid
CA Index names (inverted form) 2-propenamide 2-propenoic acid 2-propenamide hexanedioic acid 2//-azepin-2-one, hexahydro2-oxepanone 1,2-ethanediol oxirane 2-butenedioic acid, (E)-
glycolic acid hydroquinone isophthalic acid lactic acid maleic acid maleic anhydride melamine methacrylic acid methyl acrylate phthalic anhydride propylene oxide styrene terephthalic acid vinyl alcohol vinyl chloride vinylidene chloride
acetic acid, hydroxy1,4-benzenediol 1,3-benzenedicarboxylic acid propanoic acid, 2-hydroxy2-butenedioic acid, (Z)2,5-furandione 1,3,5-triazine-2,4,6-triamine 2-propenoic acid, 2-methyl2-propenoic acid, methyl ester 1,3-isobenzofurandione oxirane, methylbenzene, ethenyl1,4-benzenedicarboxylic acid ethenol ethene, chloroethene, 1,1-dichloro-
Similarly, commonly named substituent and multiplying groups have their systematic equivalents in CA Indexes: adipoyl allyl tert-butyl ethylene hexamethylene isopropyl succinyl vinyl vinylene
1,6-dioxo-1,6-hexanediyl 2-propenyl 1,1 -dimethylethyl 1,2-ethanediyl 1,6-hexanediyl 1-methylethyl 1,4-dioxo-1,4-butanediyl ethenyl 1,2-ethenediyl
Homopolymers are described by the term "homopolymer" cited in the modification under the monomer name in the index. In the structural diagram derived from the CAS Registry System records, the structure of the monomer is enclosed in parentheses followed by a subscript "x". The corresponding empirical formula is also expressed in a similar way. Examples: 1. Poly (methacrylic acid): (CH 2 =CH-COOH) x CH3 (C 4 H 6 O 2 ), CA name: 2-Propenoic acid, 2-methyl-, homopolymer 2. Polystyrene: (CH2=CH)x C6H5 (C 8 H 8 ), CA name: Benzene, ethenyl-, homopolymer 3. PoIy(11-aminoundecanoic acid): (H 2 N-(CH 2 )Io-COOH), (C 11 H 23 NO 2 ), CA name: Undecanoic acid, 11-amino-, homopolymer References page 1-12
4. Poly (lac tic acid): (CH3-CH-COOH)x OH (C3H6O3)* CA name: Propanoic acid, 2-hydroxy-, homopolymer Copolymers formed from two or more monomers are described by the term "polymer with" (followed by the other monomers in alphabetical order) cited in the modification under each monomer name. In the structural diagram derived from the CAS Registry System records, the structures of monomers, separated by a period or periods, are enclosed in parentheses followed by a subscript ' V . The corresponding empirical formulas are similarly expressed. The descriptors alternating, block, and graft are cited whenever applicable. Examples: 1. Butadiene-vinyl ethyl ether copolymer: (CH2=CH-CH=CH2•CH2=CH-O-CH2CH3)X (C4H8OC4H6)Jt (in Formula Index order) CA names: 1,3-Butadiene, polymer with ethoxyethene Ethene, ethoxy-, polymer with 1,3butadiene 2. Isophthalic acid-terephthalic acid-ethylene glycol polyester: (HOOC-m-C6H4-COOHHOOC-p-C6H4-COOHOH-(CH2)2-OH)X (C 8 H 6 O 4 C 8 H 6 O 4 C 2 H 6 O 2 ), CA names: 1,3-Benzenedicarboxylic acid, polymer with 1,4-benzenedicarboxylic acid and 1,2-ethanediol 1,4-Benzenedicarboxylic acid, polymer with 1,3-benzenedicarboxylic acid and 1,2-ethanediol 1,2-Ethanediol, polymer with 1,3-benzenedicarboxylic acid and 1,4-benzenedicarboxylic acid Telomers are named as copolymers with the term "telomer with" cited in the modification under both the monomer (taxogen) and the chain-transfer agent (telogen). In the structural representation, the monomer is enclosed in parentheses with a subscript "*", followed by the telogen structure. The corresponding empirical formula is expressed in the same way. Examples: 1. Vinylpyrrolidone homopolymer terminated with mercaptopropionic acid:
CA names: 2-Pyrrolidinone, 1-ethenyl-, telomer with 3-mercaptopropanoic acid Propanoic acid, 3-mercapto-, telomer with l-ethenyl-2-pyrrolidinone 2. Acrylic acid-vinyl choride copolymer terminated with carbon tetrachloride: (CH 2 =CH-COOH-CI-CH=CH 2 )X-CCI 4
(C3H4O2C2H3Cl)xCCl4 CA names: 2-Propenoic acid, telomer with chloroethene and tetrachloromethane Ethene, chloro-, telomer with 2-propenoic acid and tetrachloromethane Methane, tetrachloro-, telomer with chloroethene and 2-propenoic acid Structural repeating units (SRU), equivalent to IUPAC constitutional repeating units (CRU), are selected and named for polymers that have well documented regular structure, or can confidently be assumed. Assumptions are made for a. polyamides formed from a dibasic acid (ester or halide) and a diamine; from an amino acid (ester or halide); from a lactam; b. polyesters formed from a dibasic acid (anhydride, ester, or halide) and a dihydric alcohol (phenol); from a hydroxy acid (ester, halide); from a lactone; c. polycarbonates formed from carbonic acid (ester, dihalide) and a dihydric alcohol (phenol); d. polyurethanes formed from a diisocyanate and a dihydric alcohol (phenol). The structural repeating unit is named by citation of one or more multivalent radicals of regular substitutive nomenclature. The selection of the preferred SRU, its orientation, and the construction of the name, proceeding from left to right, follows the same rules as those in the IUPAC recommendations for the CRU. In CA names, however, the names of the radicals are fully systematic, as explained and contrasted above. The empirical formula is enclosed in parentheses followed by a subscript "n". Examples: 1. Nylon 11:
CA name: Poly[imino(l-oxo-l,ll-undecanediyl)] 2. Poly(ethylene adipate):
CA name: Poly[oxy-1,2-ethanediyloxy(1,6-dioxo1,6-hexanediyl)]
3. Poly (ether ether ketone) (PEEK):
CA name: Poly(oxy-1,4-phenyleneoxy-1,4-phenylenecarbonyl-1,4-phenylene) Poly(alkylene glycols) and their ethers and esters are indexed in CA as structural repeating units with the specified end groups, if aplicable. Examples: 1. Poly(ethylene glycol): HfO-CH 2 -CH 2 ^ n OH CA name: Poly(oxy-l,2-ethanediyl), a-hydroco-hydroxy2. Poly(trimethylene glycol) dimethyl ether: CH3 4 0 - C H 2 - C H 2 - C H 2 ^ O - C H 3 CA name: Poly(oxy-1, 3-propanediyl), a-methylco-methoxy3. Poly(tetramethylene glycol) diacrylate: CH2=CH-C(O) 40-CH 2 -CH 2 -CH 2 -CH 2 ^ n 0-C(O)-CH=CH 2 CA name: Poly(oxy-1, 4-butanediyl), a-(l-oxo2-propenyl)-co- [(1 -oxo-2-propenyl)oxy ] E. POLYMER CLASS NAMES In most textbooks, handbooks, encyclopedias, and indexes to polymer nomenclature, information on polymer is grouped under polymer class names. The following is a list of such terms extracted from these sources. Acrylic Polymers Alkyd resins Aminoplasts Coumarone-indene-resins Epoxy resins Fluoropolymers Phenolic resins Polyacetals Polyacetylenes Polyacrylics Polyalkylenes Polyalkenylenes Polyalkynylenes Polyamic acids Polyamides Polyamines Polyanhydrides Polyarylenealkenylenes Polyarylenealkylenes Polyarylenes Polyazomethines
Polybenzimidazoles Polybenzothiazoles Polybenzoxazinones Polybenzoxazoles Polybenzyls Polycarbodiimides Polycarbonates Polycarboranes Polycarbosilanes Polycyanurates Polydienes Polyester-polyurethanes Polyesters Polyetheretherketones Polyether-polyurethanes Polyethers Polyhydrazides Polyimidazoles Polyimides Polyimines Polyisocyanurates Polyketones Polyolefins Polyoxadiazoles Polyoxides Polyoxyalkylenes Polyoxyarylenes Polyoxymethylenes Polyoxyphenylenes Polyphenyls Polyphosphazenes Polypyrroles Polypyrrones Polyquinolines Polyquinoxalines Polysilanes Polysilazanes Polysiloxanes Polysilsesquioxanes Polysulfides Polysulfonamides Polysulfones Polythiazoles Polythioalkylenes Polythioarylenes Polythioethers Polythiomethylenes Polythiophenylenes Polyureas Polyurethanes Polyvinyl acetals Polyvinyl butyrals Polyvinyl formals Vinyl polymers
These classes are not mutually exclusive, some are relatively generic and some more specific. Some of them References page 1-12
could be grouped and arranged in a hierarchy, e.g., Polyacetals Polyvinyl acetals polyvinyl butyrals polyvinyl formals Polyesters polycarbonates
Polyethers epoxy resins polyetheretherketones polyoxyalkylenes polyoxymethylenes polyoxyarylenes polyoxyphenylenes
Some are synonymous or near synonymous, e.g., polyalkenylenes and polydienes, polyalkynylenes and polyacetylenes, polyethers and polyoxides, polythioethers and polysulfides. F. REFERENCES 1. IUPAC, "Nomenclature of Regular Single-Strand Organic Polymers (Recommendations 1975)", Pure Appl. Chem. 48, 373 (1976). Reprinted as Chapter 5 in Ref. 2. 2. IUPAC, "Compendium of Macromolecular Nomenclature". W. V. Metanomski, (Ed.), Blackwell Scientific, Oxford, 1991.
3. Chemical Abstracts Service, "CA Index Guide 1997", Appendix IV, "Chemical Substance Index Names", Chemical Abstracts Service, Columbus, Ohio, 1997. 4. IUPAC, "Source-Based Nomenclature for Copolymers (Recommendations 1985)", Pure Appl. Chem. 57, 1427 (1985). Reprinted as Chapter 7 in Ref. 2. 5. IUPAC, "Source-Based Nomenclature for Non-Linear Macromolecules and Macromolecular Assemblies (Recommendations 1997)", Pure Appl. Chem. 69, 2511 (1997). 6. IUPAC, "Nomenclature of Regular Double-Strand (Ladder and Spiro) Organic Polymers (Recommendations 1993)", Pure Appl. Chem. 65, 1561 (1993). 7. IUPAC, "Nomenclature for Regular Single-Strand and Quasi-Single-Strand Inorganic and Coordination Polymers (Recommendations 1984)", Pure Appl. Chem. 57, 149 (1985). Reprinted as Chapter 6 in Ref. 2. 8. IUPAC, "Structure-Based Nomenclature for Irregular Single-Strand Polymers (Recommendations 1994)", Pure Appl. Chem. 66, 873 (1994). 9. IUPAC, "Use of Abbreviations in the Chemical Literature (Recommendations 1979)", Pure Appl. Chem. 52, 2229 (1980).
U n i t s J. Brandrup Wiesbaden, FR Germany
A. B. C. D. E.
A.
Introduction International Units Si-Prefixes Conversion Factors Conversion Table for SI vs. English-American Units
1-13 1-13 1-14 1-14 1-17
INTRODUCTION
The International System of Units (1) is used in this Handbook as far as possible, since this system has become obligatory in many European countries and since it is supported by the National Bureau of Standards (2) and the American Society for Testing and Materials (3). Only
cursory information is given here for units needed in this Handbook. Detailed information may be found in the following References: 1. "Si-units and recommendations for the use of their multiples and of certain other units'', ISO 1000-1973. 2. "The International System of Units (SI)", Eds. C. H. Page, P. Vigoreux, Natl. Bur. Std. Spec. Publ., 1981, 330. 3. "Standard Metric Practice Guide", ASTM E-380-85. 4. Manual of Symbols and Terminology for Physicochemical Quantities and Units; Pergamon Press, Oxford 1979 (Pure Appl. Chem., 51, 1 (1979). 5. F. S. Conant, using the SI units, Polym. Eng. ScL, 17, 222 (1977) (further references).
B. INTERNATIONAL UNITS Selection of multiples of the Si-unit
Quantity
Si-unit
Length Area Volume Time Frequency Mass Density Force
m (metre) m2 m3 s (second) Hz (hertz) kg (kilogram) kg/m3 N (newton)
km, cm, mm, jum, nm km2, dm2, cm2, mm2 dm3, cm3, mm3 ks, ms, us, ns THz, GHz, MHz, kHz Mg, g, mg, jag mg/m3; kg/dm3; g/cm3 MN, kN, mN, uN
Pressure
Pa (pascal) or N/m2
GPa, MPa, kPa, mPa, uPa
Stress Viscosity (dynamic) Viscosity (kinematic) Surface tension Energy, work, heat
Pa or N/m2 Pas m2/s N/m J (joule)
Power Temperature Thermal conductivity Heat capacity Specific heat Entropy Amount of substance Electrical resistance Electrical conductivity
W (watt) K (kelvin), 0C W/mK J/K J/(kgK) J/K mol (mole) ft S (I/ft)
GPa; MPa or N/mm2; kPa mPas mm2/s mN/m TJ, GJ, MJ, kJ, mJ GW, MW, kW, mW, uW
Accepted units used with SI
Units accepted temporarily 1A = 10 ~10 m
Non SI units that should not be used 1 JJ. = 10 ~6 m
litre (1, L) (1 1= 1 dm3) d, h, min Iy= 10 ~9 kg
t t/m3; kg/1 1 bar = 105 Pa 1 atm = 101325 Pa
Electronvolt (eV) IeV«1.602 x 10" 19 J
1 dyn = 10 ~5 N; pond, kilopond 101325 1 Torr = Pa /OU = 133.32Pa poise; 1P = 0.1 Pas stokes; 1 St= 1 cm2/s dyn/cm lerg=10~ 7 J lcal = 4.1868J I0K=IK 0.86kcal/(mhgrd)
kJ/K kJ/(kgK) kJ/K Mole
1/13
C
SI-PREFIXES
Factor
Prefix
Symbol
Factor
Prefix
Symbol
10 18 10 15 10 12 10 9 10 6 10 3 10 2 10 l
exa peta tera giga mega kilo hecto deca
E P T G M k h da
10 ~l 10 ~2 10 ~3 10 " 6 10 ~9 10 " 1 2 10 ~15 10 ~18
deci centi milli micro nano pico femto atto
d c m \i n p f a
in
ft
yd
thou or mil
3.281 8.333 x 10~2 1 3 8.334 xlO~ 5
1.094 2.778 x 10~2 3.333XlO" 1 1 2.778 x 10" 5
3.937 x 104 1.0 x l O 3 1.2 x 104 3.6 x 104 1
D.
CONVERSION FACTORS
Length
m
Im in ft yd thou or mil
1 2.540 xlO~ 2 3.048XlO- 1 9.144X10" 1 2.540 xlO~ 5
Area
m2
Im2 sq. in sq. ft sq. yd ar
1 6.452 x 10 ~4 9.29OxIO" 2 8.361 x KT 1 1.0 x l O 2
Volume
m3
1 m3 1 (lit) cu. in cu. ft cu. yd gal (US) gal (UK)
Mass lkg lbm ton (metric) ton (UK) cwt (UK) ton (US) ounce grain Density lkg/m 3 Mg/m 3 =g/cm 3 lbm/cu. ft lbm/cu. in lbm/gal (UK) lbm/gal (US)
3.937XlO 1 1 12 36 1.0 x l O " 3 sq. in 1.55OxIO3 1 1.44OxIO2 1.296 x 103 1.55OxIO5 1 (lit)
1 10~3 1.639 x 10 ~5 2.832 x 10~2 7.646XlO" 1 3.785 x 10~3 4.546 xlO~ 3
sq. ft
103 1 1.639 x 10 ~2 2.832 x 101 7.645 x 102 3.785 4.546
kg
lbm
1 4.536 x 10" 1 1 x 103 1.016 x l O 3 5.080 x 101 9.072 x 102 2.835 x 10~2 6.480 x 10 " 5
2.205 1 2.205 x 103 2.24OxIO 3 1.120 x 102 2.0 x 103 6.250 x 10~2 1.429 x 10 ~8
kg/m3 1 1.OxIO3 1.602 x 101 2.768 x 104 9.978XlO 1 1.198 x 102
1.076XlO1 6.994 x 10 ~3 1 9 1.076 x 103
sq. yd
ar
1.196 7.716 x 10 ~4 1.111 x 10" 1 1 1.196 x l O 2
l.OxlO" 2 6.452 x 10 ~6 9.29OxIO" 4 8.361 x 10" 3 1
cu. in
cu. ft
cu. yd
gal (US)
gal (UK)
6.102 x 104 6.102 x 101 1 1.728 x 103 4.666 x 104 2.31OxIO2 2.774 x 102
3.531 x 10l 3.531 x 10~2 5.787 x 10 ~4 1 2JxIO1 1.337 xlO" 1 1.605 x 10 - 1
1.308 1.308 x 10~3 2.143 x 10~5 3.703 x 10" 2 1 4.951 x 10~3 5.946 x 10~3
2.642 x 102 2.642 x 10" 1 4.329 x 10 ~3 7.481 2.02OxIO2 1 1.201
2.20 x 102 2.20 x 10" 1 3.605 x 10~3 6.229 1.682 xlO 2 8.327 x 10"1 1
ton (UK) (long ton) 9.842xlO~ 4 4.464 x 10~4 9.842XlO" 1 1 5.0 x 10~2 8.929 x 10" 1 2.790 x 10~5 6.378 x 10 ~8
Mg/m3 = g/cm3 1.0 XlO" 3 1 1.602 x 10" 2 2.768 x 101 9.978 x 10~2 1.198 x 10" 1
cwt (UK) (long cwt)
ton (US) (short ton)
ounce
grain
1.968xlO~ 2 8.929 x 10~3 19.68 2.OxIO 1 1 1.786 x 101 5.580 x 10" 4 1.276 x 10 ~6
1.102xl0~ 3 5.0 x 10~4 1.102 1.120 5.600 x 10" 2 1 3.125 x 10~5 7.143 x 10 ~8
3.527XlO 1 1.6 x 101 3.527 x 104 3.584 x 104 1.792 x 103 3.2 x 104 1 2.286 x 10 " 3
1.543 x 104 7.0 x 103 1.543 x 107 1.568 x 107 7.840 x 105 1.4 x 107 4.375 x 102 1
lbm/cu.ft 6.243 XlO" 2 6.243XlO 1 1 1.728 x 103 6.229 7.480
lbm/cu.in
lbm/gal (UK)
lbm/gal (US)
3.613 x 10" 5 3.613xlO~ 2 5.789 x 10~4 1 3.605 x 10~3 4.329 x 10~3
1.002 x 10~2 1.002XlO1 1.605 x 10" 1 2.774 x 102 1 1.201
8.345 x 10" 3 8.345 1.337 x 10" 1 2.310 x 102 8.327XlO" 1 1
Force IN kp lbf dyn tonf (UK) tonf (US)
N (kg m/s2)
kgf, kp
lbf
dyn
tonf (UK) (long ton)
tonf (US) (short ton)
1 9.807 4.448 1.0 x IO"5 9.964 x 103 8.896 x 103
1.02OxIO-1 1 4.536 x 10~! 1.020 x 10~6 1.016 x 103 9.072 x 102
2.248 x HT 1 2.205 1 2.248 x 10~6 2.240 x 103 2.0 x 103
1.0 xlO 5 9.807 x 105 4.448 x 105 1 9.964 x 108 8.896 x 108
1.004 x 10~4 9.842 x 10~4 4.464 x 10~4 1.004 x 10~9 1 8.929 x 10"1
1.124 x 10" 4 1.102 x 10~3 5.0 x 10~4 1.124 x 10~9 1.120 1
Pressure lPa(=lN/m2) IkPa 1 MPa (=1 N/mm2 1 bar ( = 0.1 MPa) lp/cm 2 t lkp/m 2 t lat^lkp/cm2)+ 1 atm( = 760Torr)t lTorr(= 1/760atm)f Psi (lbf/sq. in) f
Pa
MPa (N/mm 2 )
kPa
1 103 106 105 9.8IxIO 1 9.81 9.8IxIO 4 1.01325 x 105 1.33 x 102 6.895 x 103
10~3 1 103 102 9.8IxIO" 2 9.8IxIO" 3 9.8IxIO 1 1.01325 xlO 2 1.33XlO"1 6.895
10- 6 10" 3 1 10"1 9.8IxIO" 5 9.8IxIO" 6 9.81 x 10~2 1.01325XlO"1 1.33 x 10" 4 6.895 x 10" 3
bar
p/cm 2
kp/m 2
at+
atm*
Torrt
Psi (lbf/sq. in)t
10" 5 10" 2 10 ! 1 9.81 x 10"4 9.8IxIO" 5 9.8IxIO" 1 1.013 1.33 x 10" 3 6.895 xlO" 2
1.02 x 10" 2 1.02x10' 1.02 xlO 4 1.02 xlO 3 1 10" ! 103 1.033 x 103 1.36 7.03IxIO" 5
1.02XlO-1 1.02 xlO 2 1.02 x 105 1.02 xlO 4 10] 1 104 1.033 x 104 1.36XlO1 7.03IxIO" 6
1.02 x 10~5 1.02 xlO" 2 1.02x10" 1.02 10" 3 10~4 1 1.033 1.36 x 10" 3 7.031 x 10~2
9.87 x 10" 6 9.87 x 10" 3 9.87 9.87 xlO" 1 9.68 x 10 " 4 9.68 x 10" 5 9.68 xlO" 1 1 1.32 x 10" 3 6.805 xlO" 2
7.50xl0~ 6 7.50 7.5OxIO3 7.5OxIO2 7.36x10"' 7.36 x 10"2 7.36 xlO 2 7.6OxIO2 1 5.17IxIO" 1
1.450xl0~ 4 1.45OxIO-1 1.45OxIO2 1.45OxIO1 1.422 x 10 ~2 1.422 x 10~3 1.422XlO1 1.47OxIO1 1.934 x 10"2 1
Non SI units.
Stress l P a ( = lN/m 2 ) lN/mm 2 (= IMPa) lkp/cm2 ( = 1 at)t lkp/mm 2 t Psi lbf/sq. in
Pa
N/mm2
kp/cm 2t
kp/mm2t
Psi (lbf/sq. in)1
1 106 9.8IxIO 4 9.8IxIO 6 6.895 x 103
10" 6 1 9.8IxIO- 2 9.81 6.895 x 10~3
1.02 XlO" 5 1.02XlO1 1 102 7.031 x 10~2
1.02 xlO" 7 1.02XlO-1 10~2 1 7.031 x 10~4
1.45OxIO-4 1.45OxIO2 1.422XlO1 1.422 xlO 3 1
Non SI units.
Viscosity (dynamic) lPas mPas cP kps/m2 kph/m2 lbm/(fts) lbm/(fth) lbf s/sq. ft
Viscosity (kinematic) Im2Zs mm2/s m2/h cSt sq. ft/s sq. ft/h
Pas (Ns/rcm2) (kg/(sm)) 1 1.0 x 10- 3 1.0 xlO" 3 9.807 3.530 x 104 1.488 4.134 x 10~4 4.788XlO 1
mPas (mNs/m2)
cP
1.0 xlO 3 1.0 xlO 3 1 1 1 1 9.807 x 103 9.807 x 103 3.530 x 107 3.530 x 107 1.488 x 103 1.488 x 103 1 4.134 x 10" 4.134 x 10" 1 4.788 x 104 4.788 x 104
m2/s 1 1.0 x 10" 6 2.778 x 10~4 1.0 x IO' 6 9.290 x 10~2 2.581 x 10" 5
mm2/s 1.0 xlO 6 1 2.778 x 102 1.0 9.290 x 104 2.581 x 10" 1
kps/m 2
kph/m2
lbm/(fts)
1.02OxIO-1 1.020 x 10" 4 1.02OxIO-4 1 3.60 x 103 1.518 x 10"1 4.215 x 10~5 4.882
2.833 x 10 ~5 2.833 x 10~8 2.833 xlO~ 8 2.778 x 10" 4 1 4.215 x 10" 5 1.171 x IO"8 1.356 x l O " 3
6.720 x KT 1 6.720 x 10~4 6.72OxIO- 4 6.590 2.372 x 104 1 2.778 x 10" 4 3.2HxIO 1
m2/h 3.6OxIO3 3.60 x 10" 3 1 3.60 x 10- 3 3.345 x 102 9.290 x 10~2
cSt 1.0 x 106 1.0 2.778 x 102 1 9.290 x 104 2.581 x IO1
lbm/(fth) 2.419 x 103 2.419 2.419 2.372 x 104 8.540 x 107 3.60 x 103 1 1.158 x 105
sq. ft/s 1.076 x 10l 1.076 x 10~5 2.990 x 10"3 1.076 x 10~5 1 2.778 x 10~4
lbf s/sq. ft 2.089XlO" 2 2.089 x 10~5 2.089 x 10~5 2.048XlO- 1 7.373 x 102 3.103 x 10~2 8.634 x 10" 6 1
sq. ft/h 3.875 x 104 3.875 x 10~2 1.076 x 101 3.875 x 10" 2 3.60 x IO3 1
N/m (kg/s2)
Surface tension lN/m mN/m kp/m dyn/cm
Energy IJ kWh kpm PSh lbfft erg HPh kcal BTU a
J(Nm) (kgm 2 /s 2 ) 1 3.6OxIO6 9.807 2.648 x 106 1.356 1.0 x 10" 7 2.685 x 106 4.187 xlO 3 1.055 x 103
dyn/cm
1.02OxIO-1 1.020 xlO~ 4 1 1.020 x 10 ~4
1.0 xlO 3 1.0 9.807 x 103 1
kgfm kpm
Psh
lbfft
erg
HPh
kcal
BTUa
1.02OxIO-1 3.67IxIO 5 1 2.70 x 105 1.363 x 10"1 1.020 x 10 " 8 2.737 x 105 4.269 X^ 102 1.076 x 102
3.777xlO~ 7 1.360 3.704 xlO~ 6 1 5.120 x 10"7 3.777 x 10~14 1.014 1.581 x 10" 3 3.985 x 10" 4
7.376X10" 1 2.655 x 106 7.233 1.953 x 106 1 7.375 x 10" 8 1.980 x 106 3.088 x 103 7.782 x 102
1.OxIO7 3.6OxIO13 9.807 x 107 2.648 x 1013 1.356 x 107 1 2.685 x 1013 4.187 xlO 1 0 1.055 x 1010
3.725xlO~ 7 1.341 3.653 x 10~6 9.863 x 10"1 5.051 x 10~7 3.725 x 10~14 1 1.560 xlO~ 3 3.930 x 10~4
2.388xlO~ 4 8.598 x 102 2.342 x 10~3 6.324 x 102 3.238 x 10~4 2.388 x IO' 11 6.412 x 102 1 2.520 x 10"1
9.478xlO~ 4 3.412 x 103 9.295 x 10~3 2.510 x 103 1.285 x 10~3 9.478 x 10"11 2.544 x 103 3.968 1
kWh 2.778xlO~ 7 1 2.724 xlO" 6 7.355 x 10"1 3.766 x 10~7 2.778 x 10"14 7.457 x 10"1 1.163 xlO~ 3 2.931 x 10" 4
kgf/m (kp/m)
1.0 xlO 3 1 9.807 x 103 1.0
1 1.0 xlO~ 3 9.807 1.0 x 10 ~3
British thennal unit.
J (Nm) (kgm 2 /s 2 )
Heat 1J kcal BTU CHU Wh a
mN/m
kca! 2.388 x 10" 4 1 2.520 x 10" 1 4.539XlO" 1 8.598XlO" 1
1 4.187 xlO 3 1.055 x 103 1.90OxIO3 3.6OxIO3
BTU
CHU°
9.478 x 10~A 3.968 1 1.80 3.412
5.262 x 10" 4 2.203 5.552 x 10" 1 1 1.894
Centigrade heat unit.
Power
W (J/s) (kgm 2 /s 3 )
kgf m/s kpm/s
1W kpm/s PS HP erg/s ft lbf/s kcal/h BTU/h
1 1.020 x IO"1 9.807 1 7.355 x IO2 7.5 x IO1 7.457 x IO2 7.604 x 10l 1.0 x 10" 7 1.020 x 10~8 1.356 1.383 x 10" 1 1.163 1.186 x 10"1 2.931 x 10" 1 2.988 x 10~2
PS HP (metr) 1.360 x 10" 3 1.333 x 10~2 1 1.014 1.360 x IO"10 1.843 x 10" 3 1.581 x 10" 3 3.985 x 10" 4
HP 1.341 x 1.315 x 9.863 x 1 1.341 x 1.818 x 1.560 x 3.930 x
erg/s 10~3 10" 2 10" 1 10" 10 10" 3 10" 3 10" 4
1.0 x 107 9.807 x 107 7.355 x 109 7.457 x IO9 1 x 10~8 1.356 x IO7 1.163 x IO7 2.931 x IO6
ft lbffs 7.376 x 10"1 7.233 5.425 x IO2 5.50 x IO2 7.375 1 8.578 x 10" 1 2.162 x 10" 1
kcal/h
BTU/h
8.598 x 10" 1 8.432 6.324 x 102 6.412 x IO2 8.598 x 10~8 1.166 1 2.520 x 10" 1
3.412 3.346XlO1 2.510 x IO3 2.544 x IO3 3.412 x 10" 7 4.626 3.968 1
Thermal conductivity
W/mK (kgm/(s3K))
kcal/(mh°C)
BTU/(fth°F)
BTU/(inh°F)
BTU in/ (sq.fth°F)
1 W/(mK) kcal/(mh°C) BTU/(fth°F) BTU/(inh°F) BTU in/(sq. fth°F)
1 1.163 1.731 2.077 x IO1 1.442 x 10" 1
8.598 x 10~! 1 1.488 1.786 x IO1 1.24 x 10" 1
5.778 x 10~J 6.72OxIO" 1 1 1.2 x IO1 8.333 x 10~2
4.815 x 10~2 5.6OxIO" 2 8.333 x 10" 2 1 6.944 x 10~3
6.933 8.064 1.2XlO1 1.44 x IO2 1
Specific heat, heat capacity
J/kgK (m2Z(S2K))
kJ/(kgK)
kcal/(kg°C)
BTU/(lbm°F)
1 J/(kgK) kJ/(kgK) kcal/(kg°C) BTU/(lbm°F) Wh/(kgK)
1 1.0 x IO3 4.187 xlO 3 4.187 x IO3 3.6OxIO3
1.0 x 10 ~3 1 4.187 4.187 3.60
2.389 x 10 " 4 2.389 x 10" 1 1 1.0 8.598XlO" 1
2.389 x 10 ~4 2.389 x 10"1 1.0 1 0.8598
E.
C O N V E R S I O N TABLE FOR SI vs. E N G L I S H - A M E R I C A N U N I T S
SI to English-American unit
English-American unit to SI
Length I m = 1.0936 yd = 3.28 ft = 39.37 in 1 mm = 0.03937 in
lyd = 3 ft = 0.9144m l f t = 12 in = 0.3048 m Im = 25.4 mm
lkg = 2.20461b
lib = 0.45359 kg
1 N = l(kgm)/s 2 = 2.248 x 10" 1 lbf
I M = 4.448 N
1 Pa = 1 N/m 2 = 1.450 x 1O-4 lbf/in2
1 lbf /in 2 = 1 psi = 6.89475 x 103 Pa
Mass, weight
Force
Pressure 4
= 6.89475 x 10 ~2 bar
= 2.953 x 10 ~ in Hg = 4.015 x 10~ 3 inH 2 O
HnHg = 3.38638 x 103Pa = 3.38638 x 10"2 bar
1 bar = 105 Pa = 1.450 x 10l lbf /in 2 = 2.953 x 101UiHg
ImH 2 O = 2.49089 x 102Pa
2
= 4.015 x 10 HiH 2 O
= 2.49089 x 10 " 3 bar
Tension, stress lN/mm 2 = 1.450 x 10 2 lbf/in 2
1 lbf/in2 = 6.89475 x 10 " 3 N/mm 2
Dynamic viscosity IPas = (Ns)/m 2 = 2.089 x 10~2 (lbf s)/ft2 1
= lkg/(ms) = 6.72x 10" lbf/(ft s)
1 (lbf s)/ft2 = 4.78802 x 101 Pas llb/(fts) = 1.488 Pa s
Kinematic viscosity I m 2 / s = 1.076 x 101 ft 2 /s
Ift 2 /s = 9.29x 10~ 2 m 2 /s
U = I W s = INm = 7.376 x 10"1 ftlbf
1 ft lbf = 1.35582 J
Energy, quantity of heat
1
IkJ = 9.478 x 10- BTU
IBTU= 1.05506 kJ
Power, heat flow rate I W = I Nm/s = 7.367 x 10 - 1 (ftlbf)/s 1
= 1 J/s = 4.425 x 10 (ftlbf)/min = 3.412 BTU/h
l(ftlbf)/s= 1.35582 W 1 (ftlbf)/min = 2.25969 x 10~2 W 1 BTU/h = 2.93072 x 10" 1 W
Specific heat capacity 1 J/(kg K) = 2.388 x 10~ 4 BTU/(lb/ 0 F) 3
5
1 J/(m K) = 1.491 x 10~ BTU/(ft
3 0
F)
IBTU/(Ib 0F) =4.1868 x 10 3 J/(kgK) IBTU/(ft 3 0F) =6.71 x 10 4 J/(m 3 K)
Thermal conductivity 1 W/(mK) = 6.933 (BTUin)/(ft 2 h °F) = 5.778 x 10~ 1 BTU/(fth°F) = 4.815 x 10 " 2 BTU/(inh 0F)
1 (BTUin)/(ft2h °F) = 1.442 x 10^1 W/(mK) lBTU/(fth°F) = 1.7307 W/(m K) 1 BTU/(in h °F) = 2.07689 x 101 W/(mK)
English-American unit to SI
SI to English-American unit Heat flux density
lBTU/(ft 2 h) = 3.1546 W/m 2
l W / m 2 = 3.17x 10- 1 BTU/(ft 2 h)
1BTU/(in2 h) =4.54263 x 10 2 W/m 2
= 2.201 x Kr 3 BTU/(in 2 h) Heat transfer coefficient lW/(m 2 K) = 1.761 x 10- 1 BTU/(ft 2 h°F)
1 BTU/(ft2 h °F) = 5.678 W/(m 2 K)
1 (m2 K)/W = 5.678 (ft2 h °F)/BTU
1 (ft2h °F)/BTU = 1.761 x 10- 1 (m 2 /K)/W
I K = I 0 C = 1.8 0 F
1 0F = 5.555 x 10" 1 K = 5.555 x 10" 1 0C
Thermal resistance
Temperature
Conversion: Tc= ^(rF-32)
r F = | r c + 32
7 K = ^ Tp+ 255.372
TF = I (TK- 255.372)
TQ - Temperature in Celsius ( 0 C); T? - Temperature in fahrenheit (0F); TK -
Temperature in kelvin (K).
S E C T I O N
P
O
L
Y
M
E
R
I
D
E
P
O
L
Y
M
Z E
A R
T I
Il
I Z
O A
N T
A I
O
N N
D
D e c o m p o s i t i o n F r e e
R a t e s
R a d i c a l
o f
O r g a n i c
I n i t i a t o r s
K. W . D i x o n Akzo Nobel Chemicals Inc., Dobbs Ferry, NY, USA A. Introduction 11-1 B. Tables of Decomposition Rates of Organic Free Radical Initiators II-2 Table 1. Azonitriles II-2 Table 2. Miscellaneous AzoDerivatives M-9 Table 3. Alkyl Peroxides II-23 Table 4. Acyl Peroxides II-29 Table 5. Hydroperoxides and Ketone Peroxides II-43 Table 6. Peresters and Peroxy Carbonates II-48 Table 7. Miscellaneous Initiators II-68 C. Notes II-69 D. References II-70 A.
INTRODUCTION
The decomposition of most organic free radical initiators follows first order kinetics. With certain peroxides, however, higher order decompositions are observed. Generally, the higher order reaction is caused by a reaction of radicals with the initiator (induced decomposition). The value of the rate for unimolecular decomposition may be determined either by extrapolation of the rate back to zero initiator concentration or by use of a monomer or other radical "trap". Some of the peroxides may also decompose by non-radical routes. Acids, bases, and polar solvents favor ionic intermediates. Koenig (296) presents an excellent discussion of azo and peroxide decomposition pathways. Decomposition rate (kd) data in these tables are reported for first order kinetics:
where / is the initiator concentration (mol/1) and t is the time (s). The decomposition rate constant k^ is related to half-life (t ^ 2 ) by the following equation:
Fig. 1 relates kd in s" 1 to half-life for the range of k^ found in the tables. For some of the initiators listed, the enthalpy (AH *) is given (Note h) rather than the Arrhenius activation energy
(E2). The two quantities are related by the equation £ a = AH* +RT, where R is the gas constant (in kJ/moldeg.) and T is the absolute temperature (94). Assuming that k& is linear with respect to \/T and that the activation energy, £ a , and the decomposition rate constant, kd, for one temperature are known, kd for any temperature can be calculated from the following expression:
Where given by the author, the overall equation for kd in terms of the frequency factor (A) and activation energy (£ a ) has been included. Thus for any temperature (converted to K) the kd may be calculated:
Although a wide range of initiators is reported in the tables, the author admits that the compilation is far from complete. There are several purposeful omissions: (a) azo compounds, where the azo group is part of a ring structure - these recombine almost exclusively; (b) compounds that decompose at appreciable rates only above 200 degrees. Neither class would be expected to be useful initiators. The data have been arranged into seven tables. Within each table the individual initiators are listed according to the following criteria: 1. Initiators: (a) according to increasing number of carbon atoms; (b) alphabetically (neglecting trivial prefixes), for compounds containing equal number of carbons; (c) miscellaneous initiators are listed alphabetically in Table 7. 2. For each initiator, solvents are listed alphabetically. 3. For a given solvent, all measurements reported by one investigator are listed in a series, with the activation energy listed opposite the lowest temperature. Abbreviations: DMSO - dimethyl sulfoxide; DMAC dimethylacetamide; DMF - dimethylformamide; THF tetrahydrofuran; DCB - 1,2-dichlorobenzene.
20hrs. 100 days
120 min.
12 min.
10 days
100 sec. 200 min.
10 sec.
1 sec. 0.12 sec.
20 min.
40hrs. 200 days _200 sec.
60 min.
1 year 50 days
100 hrs.
10 hrs.
40 sec.
0.5 sec.
5 sec.
10 min. Rate constant (*d)
Figure 1. Relationship of half life to rate constant (k^) (half lives are to the right of each vertical line)
B.
TABLES O F D E C O M P O S I T I O N RATES O F O R G A N I C FREE R A D I C A L I N I T I A T O R S
TABLE 1. AZONITRILES Number of C atoms 5
Initiator
Solvent
N-Acetyl N'-oc-cyanoethyl diimide
Toluene
2-Cyano-2-propyl-azo-formamide
Chlorobenzene Toluene
Xylene
8
2-(Carbamoylazo)isobutyronitrile N-Acetyl N'-ot-cyanocyclopentyldiimide
Toluene Toluene
2,2/-Azo-bis-isobutyronitrile (2,2'-azo-bis-2-methylpropionitrile)
Acetic acid
Acetonitrile tert-Amyl alcohol Aniline Benzene
T( 0 C) 60.8 68.6 82.0 100 100 110 104 100 120 104 65.7 76.8 91.5 79.9 79.9 79.9 80 82 82 79.9 79.9 80.2 80.2 40.0 45.2 50.0 55.0 60.5 69.5
^d(S"1) 2.46 x 10 " 5 5.45 x l 0 ~ 5 2.49 xlO~ 4 1.5 x 10 " 5 2.1 x 10 ~5 6.8 x l O " 5 1.9 XlO" 5 2.IxIO-5 2.4xlO-4 1.93 x 10 ~5 1.82 x l O " 5 7.29 x 10 ~5 3.65 x l O " 4 1.43 x 10 ~4 1.48 x 10 ~4 1.62 XlO" 4 1.52 x l O - 4 1.50xl0" 4 1.49 XlO" 4 1.25 x 10 " 4 1.24 xlO~ 4 1.40 x 10~4 1.68 x l O " 4 5.44 x l O " 7 1.12 XlO" 6 2.64 XlO" 6 5.19 x l O " 6 1.16 x l O " 5 3.78 x l 0 ~ 5
Ea (kj/mol)
Notes
110.2
144.3 a 144.3 a 120.3
V2 V3 a a a v2
128.4
a,t2 a,t2 a,t2 a,t2 a,t2 a,t2
Refs. 322 322 322 93 93 93 339 93 93 340 322 322 322 146 146 146 62 2 175 146 146 61 61 69 69 69 69 69 69
TABLE 1. cont'd Number of C atoms S (cont'd)
Initiator 2,2'-Azo-bis-isobutyronitrile
Solvent Benzene
Benzene or Toluene
H-Butanol Isobutanol Di-n-butyl phthalate
Carbon tetrachloride
Chlorobenzene
Cyclohexanone Dichloroethane Dichloroethane: propionitrile (1:1) Diethylene glycol monobutylether DMF DMF DMF/methyl methacrylate (9/1) (8/2) (7/3) (6/4) (5/5) (4/6) (3/7) (2/8) (1/9) N,iV-Dimethylaniline
Dioxane/Water (80/20) pH7.0
Dioxane/Water (80/20) pH 10.7 Dodecanethiol
T( 0 C) 40 50 60 70 78 37 43 50 60 100 T (K) 82 82 82 80.2 80 90 100 110 120 127 137 145 80 90 100 110 120 40 60 77 64 82 101 T (K) 82 70
^d(S"1)
Ea (kj/mol)
4.83 x 10~7 2.085 XlO" 6 8.45 xlO~ 6 3.166 XlO" 5 8.023 x l O " 5 2.83 x 10 ~7 7.35 x l O - 7 2.16 x l O " 6 9.15 x l O - 6 1.52 x l O - 3 1.58 x 1015 1.54 x 10~4 1.55 XlO" 4 1.66 x 10~4 (1.67-1.76) x 10~4 2.64 x 10 ~4 6.47 x l O - 4 1.78 XlO" 3 4.88 x l O - 3 1.43 XlO" 2 2.48 x l O " 2 5.43 XlO" 2 1.24XlO- 1 2.22 x l O " 4 4.23 XlO" 4 1.99 x l O - 3 5.3 x l O " 3 1.48 x l O - 2 2.15XlO" 7 4.0OxIO- 6 1.2IxIO- 4 1.93 x 10 ~5 1.93 x l O - 4 1.93 x l O - 3 2.89 x 1015 1.43 x 10 ~4 2.0IxIO- 5 1.64 x l O - 5
123.4
Notes
128.9
exp[- 128.9/#7] a a a 122.2
y4 y4 y4 y4 y4 y 16 y 16 y 32
128.4
a,t2 a,t2 a
exp[- 130.23//?7] a m8
Refs. 66 66 66 66 66 39 39 39 19 39 39 175 2 2,175 61 236 236 236 236 236 236 236 236 375 375 375 375 375 69 69 62 344 344 344 344 2,175 293 293
1.94 x 10~5 2.442 x 10 ~5
293 26
6.2096 x l O - 5 6.45 x l O - 4
294 355
60 60 60 60 60 60 60 60 60 66.82 72.27 80 65.3 70.0 75.0 80.0
5.55 x 10~4 5.1OxIO- 4 5.1OxIO- 4 5.3OxIO- 4 5.65 x 10 ~A 5.35 x l O - 4 5.65 x l O - 4 6.25 x l O - 4 6.5OxIO- 4 3.483 x 10~5 6.914 XlO" 5 1.83 x l O - 4 2.53 x 10 " 5 3.20xl0~ 5 8.5 x l O - 5 1.62 x l O - 4
355 355 355 355 355 355 355 355 355 26 26 62 186 186 186 186
75.0 80
1.72 x l O " 4 1.46 x 10 ~4
70 66.82 71.2 60
a 141.0
a
186 62
Notes page 11-69; References page 11-70
TABLE 1. cont'd Number of C atoms S (cont'd)
Initiator 2,2'-Azo-bis-isobutyronitrile
Solvent Ethyl acetate Ethyl acetate/ SnCl4 (1:1) Glycerol/DMF 95/5, (v/v) Maleimide (solid state) Methyl methacrylate
Nitrobenzene 1-Nitrobutane Propionitrile/SnCl4 (1:1) Propylene carbonate Styrene
Toluene
Toluene/SnCl4 (1:1) Xylene
o-Xylene
3,6-Dicyano-3,6-dimethyl1,2-diazacyclohexene-l
Water Dichloromethane
2,2/-Azo-bis[2-(hydroxymethyl)propionitrile
Methyl cellosolve
9
N-Acetyl W-a-cyanocyclohexyldiimide
Toluene
10
N-Acetyl N'-oc-cyanocycloheptyldiimide
Toluene
4,4/-Azo-bis-(4-cyanopentanol) 4,4/-Azo-bis-(4-cyanovaleric acid) l,r-Azo-bis-l-cyclobutanenitrile
Acetone Acetone Mesitylene
2,2'-Azo-bis-2-methylbutyronitrile
Xylene Toluene Xylene
T( 0 C) 40 60 T (K) 71.2 65 72 50 50 60 70 70 80 100 82 T (K) 72.27 50 70 T (K) 68.4 60.00 60 65 70 80.4 90.0 100.0 105.0 69.8 80.2 80.3 60 50 77 82 80 80 82 85 95 105 T(K) 50 -6.06 0.03 2.52 77
82.0 92.8 100.6 59.4 66.1 79.6 70 70 130.4 141.6 120.4 69.8 80.2 80
kA (s^1) 4.7 x l O " 7 9.36 XlO- 6 8.56 x 1015 2.6054 x 10~5 4.97 x 10 ~5 2.07 x l O - 4 9.7 x 10 ~7 7.5 x l O - 6 7.2OxIO- 4 3.1 x 10" 5 1.27 x l O - 4 1.98 x l O " 4 2.24 x l O - 3 1.45 x l O " 4 9.10 x 1015 5.821 x 10 ~5 2.97 x 10~6 4.72 x l O - 5 1.29 x 1015 3.8 x l O - 5 9.03 x 10~6 9.8 x l O " 6 1.9 x l O - 5 4.OxIO- 5 1.55 x l O - 4 4.86 x 10- 4 1.6OxIO- 3 2.61 x 10 - 3 3.8 x l O - 5 (1.72-1.60) x 10- 4 1.3OxIO- 4 4.0 x 10" 5 2.OxIO- 6 9.46 x l O - 5 1.44 x l O - 4 1.53 xlO~ 4 1.5OxIO- 4 1.45 x l O " 5 2.75IxIO- 4 9.58IxIO- 4 2.782 x l O - 3 3.16xl0 1 5 1.56 x 10 ~6 4.6OxIO- 4 1.14 x l O " 3 1.64 x l O - 3 1.93 x 10 ~5
5.2IxIO- 5 1.7OxIO- 4 3.74 XlO" 4 4.44 x 10 ~5 9.82 x 10 ~5 4.51 x 10- 4 4.26 x 10~5 4.58 x 10 ~5 5.20xl0"5 1.6OxIO- 4 2.05 x 10 ~5 2.3 x IO"5 8.4-9.OxIO- 5 9.97 x 10~5
Ea (kj/mol)
Notes
128.5
a,t2 a,t2
exp[- 121 A/RT]
a a a a,v20
132.2
V4 a a a
exp[- 121.0/RT] 127.6
a a
exp[- 127.6/RT] c,m3 a 121.3
142.3 m2
131.0
a a a a a,t4 a
131.8
exp[-131.8//?7] 88.8
h
a
114.8
112.0
m7 ni7 134.3
129.7 123.0
a
Refs. 69 69 290 294 185 185 289 289 355 216 216 226 226 2,175 290 26 132 132 132 234 291 290 339 47 47 47 47 47 61 61 234 290 175 175 175 62 62 2 332 332 332 332 285 252 252 252 339
322 322 322 322 322 322 305 305 101 101 101 61 61 62
TABLE 1. cont'd Number of C atoms
Initiator
10 (cont'd)
2,2'-Azo-bis-2-ethylpropionitrile
Nitrobenzene
2,2'-Azo-bis-2-methylbutyronitrile
Cyclohexanone
Solvent
Chlorobenzene
Ethanol
Ethylbenzene
N-benzoyl iV'-a-cyanoethyldiimide
4-Bromophenyl-azo-2-methyl2-propionitrile 4-Bromophenyl-azo-(methylpropanedinitrile)
DCB
4-Nitrophenyl-azo-2-methyl2-propionitrile 4-Nitrophenyl-azo-2-(methylpropanedinitrile)
DCB
Phenyl-azo-2-methyl-2propionitrile Phenyl-azo-2-(methylpropanedinitrile)
11
Toluene Toluene
DCB
DCB
DCB DMF 1,2,4-Trimethylbenzene DCB
Phenyl-azo-2-(methylpropanedinitrile)
DCB
4-Bromophenyl-azo-2-(ethylpropanedinitrile)
DCB
4-Methoxyphenylazo-2(methylpropanedinitrile)
Butanol Chlorobenzene DCB Decane DMSO Heptane Hexanol Octane Octanol Propanol Toluene Chlorobenzene
4-Methoxyphenyl-azo2-(methylpropanedinitrile)
DCB
T( 0 C) 80 100 79.9 90.0 100.1 66 84 104 T (K) 80.0 90.0 100.0 80.0 90.0 100.0 67 69.2 83.2 90.0 160 80 85 90 T (K) 160 80 85 90 T(K) 160 160 160 80 85 90 T (K) 80 85 90 T (K) 80 85 90 T (K) 85 85 85 85 85 85 85 85 85 85 85 78.1 85.3 90.2 75.0 85.1 95.1 104.9
kd (s"1) 8.3 x 10~5 1.08 x l O - 3 1.06 x l O " 4 3.7IxIO-4 1.27xlO- 3 1.93 x 10 ~5 1.93 x l O - 4 1.93 XlO" 3 1.38 x 1015 1.05 x 10 " 4 3.23 x l O - 4 9.87 x l O - 4 8.22 x l O " 5 2.94 x l O - 4 1.02 x l 0 ~ 3 1.9 x l O " 5 1.31 x 10 ~5 7.96 x l O - 5 1.744 xlO~ 4 2.85 x 10 ~5 2.4xlO" 5 4.8xlO-5 9.4 x 10 ~5 7.23 xlO 1 6 2.3 x 10 " 5 3.1 x 10~5 6.0xl0"5 1.14 x l O - 4 1.35 xlO 1 6 5.65 x 10~5 6.9xlO" 5 5.35 x 10 ~5 4.45 x 10 ~5 8.0xl0"5 1.42 x l O - 4 8.48 x 1013 2.4xlO~ 5 4.8xlO" 5 9.4 x l O - 5 7.23 x 1016 1.85 x 10 " 5 3.65 x 10 ~5 7.05 x l O - 5 3.00 x 1016 2.9xlO" 4 9.5 x 10" 5 8.35 x l 0 ~ 5 3.8xl0"5 4.87 XlO" 4 5.15 x l 0 ~ 5 1.6 x l O " 4 4.4xlO~ 5 1.5xlO~ 4 3.1 x 10~4 6.75 x l 0 ~ 5 5.76 x 10 ~5 9.52 x 10 ~5 1.307 xlO~ 4 2.73 x l 0 ~ 5 8.35 x l 0 ~ 5 2.236 xlO~ 4 6.397 xlO~ 4
Ea (kj/mol)
Notes
143.1 131.6
a a h
exp[- 129.93//?7] 119.8
h
134.9
h
a 127.9
145.0
exp[-U5.0/RT]
139.1
exp[-139.1 /RT]
123.2
exp[- 123.2/RT] 145.0
exp[- 145.0/RT] 142.9
exp[- 142.9/RT] 110 71 115 142 114 136 102 140 112 103 137 71.5
116
Refs. 226 226 336 336 336 344 344 344 344 336 336 336 336 336 336 339 322 322 322 329 329 329 329 329 329 329 329 329 329 329 329 329 329 329 329 329 329 329 329 329 329 329 329 329 331 331 331 331 331 331 331 331 331 331 331 330 330 330 330 330 330 330
Notes page 11-69; References page 11-70
TABLE 1. confd Number of C atoms 11 {confd)
Initiator 4-Methoxyphenyl-azo2-(methylpropanedinitrile)
DCB
Phenyl-azo-2-(2-methylbutyronitrile)
DCB DMF 1,2,4-Trimethylbenzene DCB
4-Tolyl-azo-2-(methylpropanedinitrile)
12
13
14
Solvent
4,4/-Azo-bis-(l-bromo4-cyanopentane) 4,4/-Azo-bis-4-cyanopentanoic acid 4,4'-Azo-bis-(4-cyanopentanol)
Toluene
U'-Azo-bis-l-cyclopentanenitrile
Toluene
2,2'-Azo-bis-2-cyclopropylpropionitrile (mp 64-65)
Toluene
2,2'-Azo-bis-2-cyclopropylpropionitrile (mp 76-77)
Toluene
2,2'-Azo-bis-2,3dimethylbutyronitrile 2,2/-Azo-bis-2-methylvaleronitrile 4-Bromophenyl-azo-2(isopropylpropanedinitrile)
Toluene
T(K) 80 85 90 T (K) 160 160 160 80 85 90 T(K) T(K)
kd (s"1) 5.67 x 1012 4.7xlO~ 5 8.1 x 10 " 5 1.38 x l O " 4 2.94 x 1012 5.OxIO" 5 5.2xl0~ 5 5.05 x 10 " 5 4.5xlO" 5 7.9xl0~5 1.365 XlO" 5 1.21 x 1013 1.OxIO11 1.9 x l O " 5 8.97 x 10 " 5 2.55 x 10 " 4 7.99 XlO" 4 2.81 x 10" 3 8.99 x l O " 3 2.6xlO-2 5.2 XlO" 2 7.45 x l O " 5 2.43 x 10 " 4 5.18 xlO~ 4 3.50 x 10~5 7.53 x 10 ~5 2.68 XlO" 4 3.90 x 10 ~5 8.17 x 10 " 5 2.46 XlO" 4 2.6 x l O " 5 1.02 x 10 " 4 4.2xlO~ 5 (1.65-1.74) x 10" 4 1.4xl0~ 5 2.80xl0"5 5.4 XlO" 5 1.73 xlO 1 6 3.06 x 10 " 5 1.177 x 10 ~A 4.594 XlO" 4 7.320xl0" 4 2.06 xlO 1 7 1.62 x l O " 5 3.17 x 10 " 5 2.252 XlO" 4 1.12 x l O " 4 2.21 x 10 " 4 4.26 XlO" 4 1.19 xlO 1 7 4.85 x 10 " 5
£ a (kj/mol)
Notes
exp[- U6/RT] 114.8
Refs. 330 329 329 329 329 329 329 329 329 329 329 329 307
exp[- 114.S/RT]
117.7
exp[- UlJ/RT] exp[-104.7 /RT]
2,6-Dimethylphenyl-azo2-methylpropanedinitrile
DCB
N-Benzoyl W-a-cyanocyclopentyl diimide
Toluene
4-Bromophenyl-azoisobutylpropanedinitrile
DCB
4-Bromophenyl-azo-2(2-terf-butylpropionitrile) 4-Nitrophenyl-azo-2(2-terf-butylpropionitrile) Phenyl-azo-2-(2-terf-butylpropionitrile)
DCB
69 80 80 90 100 110 120 130 80.3 89.2 95.1 44.2 49.5 59.2 44.2 49.5 59.3 69.8 80.2 69.8 80.2 80 85 90 T(K) 60.1 70.0 80.6 84.5 T(K) 76.7 82.0 98.4 80 85 90 T(K) 160
DCB
160
1.8 x l O " 5
329
DCB 1,2,4-Trimethylbenzene Hexamethylphosphoramide Toluene
160 160 160
9.35 x 10 " 5 9.65 x 10 ~5 9.5xl0~5
329 329 329
2,2'-Azo-bis-2-cyclobutylpropionitrile (mp 38-42) 2,2'-AzO-Ws^-CyClObUIyIpropionitrile (mp 81.5-82.5)
Water
T( 0 C)
Di-w-butyl phthalate
Toluene DCB
Toluene
142.3
a a
141.4
117.2
108.8
w w w w w w
133.9 138.1 142.0
exp[- 142.0/RT] 130.5
exp[-130.5//?7] 131.9
141.6
exp[-141.6kJ//?7]
339 62 375 375 375 375 375 375 101 101 101 57 57 57 57 57 57 61 61 61 61 329 329 329 329 330 330 330 330 330 322 322 322 329 329 329 329 329
80.5
1.51 x 10 " 4
w
104
80.5
1.51 x 10 " 4
w
104
TABLE 1. cont'd Number of C atoms
Initiator
Solvent
14 {cont'd)
U'-Azo-bis-l-cyclohexanenitrile
Chlorobenzene DMSO
Nitrobenzene Toluene
2,2'-Azo-bis-2,4-dimethylvaleronitrile
Dimethyl-4,4'-azo-bis-cyanopentanoate (meso)
Xylene Toluene
Xylene DMAC
(no+)
(nD_)
4,4'-Azo-bis-4-cyano-l-methylpiperidine
DMSO
2,2'-Azo-bis-2-propylbutyronitrile
Nitrobenzene
2,2/-Azo-bis-2,3,3-trimethylbutyronitrile(mp 114-116) 2,2'-Azo-bis-2,3,3-trimethylbutyronitrile (mp 116-118) 2,2/-Azo-bis-2-methylhexylnitrile 2,2'-Azo-bis-2,4-dimethylvaleronitrile
Toluene
2,2/-Azo-bis-2,4-dimethylvaleronitrile (mp 56-57) 2,2/-Azo-bis-2,4-dimethylvaleronitrile (mp 74-76) 2,2/-Azo-bis-2-isopropylbutyronitrile AH4-Chlorobenzoyl) N'-OLcyanocyclohexyl diimide AHl-Cyanocyclohexyl)pentamethyleneketenimine
Toluene Toluene Toluene Toluene Toluene Toluene Toluene
Chlorobenzene Cumene Toluene terf-Butylbenzene
15
2-Phenyl-azo-2,4-dimethyl4-methoxyvaleronitrile JV-Benzoyl N'-ot-cyanocycloheptyl diimide
Xylene Toluene
T( 0 C) 79.97 100.12 80 85 90 95 100 80.3 95.2 102.4 88 77 51 68 T(K) 77 77.9 85.0 90.2 99.7 77.6 85.9 90.0 99.2 77.9 85.4 90.2 99.0 80 85 90 95 80 100 79.9 89.0 79.9 88.9 80.2 69.8 80.2 59.7 69.9 69.8 80.2 80.5 79.1 86.4 99.7 100 100 100 100 100 100 100 100 122 74.6 82.8 89.2
A^(S"1) 8.42 x l O " 6 1.107 XlO" 4 1.01 x l O " 5 2.01 x 10 " 5 3.89 x l O " 5 6.83 x l O " 5 1.14 x l O " 4 6.5 x 10" 6 5.44 x l O " 5 1.26 x l O " 4 1.9 XlO" 5 5.31 x 10 ~6 1.9 x l O " 5 1.9xlO" 4 6.98 xlO 1 4 5.77 x 10 ~4 1.43 x l O " 4 3.76 x 10 " 4 6.8OxIO" 4 2.05 XlO" 3 1.46 x l O " 4 4.03 x l O " 4 6.9OxIO" 4 2.04X10- 3 1.49 XlO" 4 3.90 x 10 ~4 6.95 x l O " 4 1.97xl0- 3 9.7xlO~ 6 1.75 x 10 " 5 3.64 x l O " 5 6.47 XlO" 5 2.55 x 10" 4 2.72 XlO" 5 7.42 x 10 " 5 2.59 x l O " 4 1.05 x 10 " 4 3.09 x 10" 4 1.58 x l O " 4 1.98 xlO~ 4 7.1 x 10 " 4 8.05 x 10 ~5 2.89 x 10 " 4 1.98 x l O " 4 7.IxIO"4 1.01 x 10" 4 8.6 x l O " 6 2.01 x 10 ~5 1.044 x l O - 4 3.85 x 10 " 5 2.07 x 10 " 5 3.93 x 10~5 1.42 x 10 " 5 3.10x 10" 5 1.83 x l O " 5 2.39 x 10 " 5 1.22 x 10- 5 1.9 x 10~5 6.43 x 10 " 5 1.781 x 10" 4 3.519 x l O " 4
E* (kj/mol)
Notes
140.2 135.6
h
121.3
121
a a a a
exp[-121//?7] 133.9
133.5
133.5
136.4
128.9 146.4 125.5
a a a a a a a a a a a a a h
a a w w w w
121.3 121.3 121.3
w w w w
132.7
p,z (1) p,z (3950) p,z (1) p,z (3950) p,z (1) p,z(3950) p,z (1) p,z (3950)
122.8
Refs. 179 179 135 135 135 135 226 101 101 101 339 175 343 343 343 175 205 205 205 205 205 205 205 205 205 205 205 205 135 135 135 135 226 226 57 57 57 57 61 61 61 57 57 57 57 50 322 322 322 299 299 299 299 299 299 299 299 339 322 322 322
Notes page 11-69; References page II - 70
TABLE 1. cont'd Number of C atoms 15 (cont'd)
16
Initiator
Solvent
N-(4-Methoxybenzoyl) N'-OLcyanocyclohexyldiimide
Toluene
JV-(4-Methylbenzoyl) jy'-otcyanocyclohexyl diimide
Toluene
iV-Phenylacetyl W-a-cyanocyclohexyl diimide
Toluene
4-Cyano-l-methylpiperidine-4,4'-azo4'-cyano-l,l'-dimethylpiperidinium nitrate
DMSO
4,4'-Azo-bis-4-cyano-1,1'-dimethylpiperidinium nitrate
DMSO
4,4/-Azo-bis(4-cyanopentanoyl)bis2-aminoethanol
DMF
Toluene
2,2/-Azo-bis-2-methylheptylonitrile
Toluene Xylene Toluene Xylene
80
Toluene
80.5
Toluene
80.5
Toluene
40 1.175 50 4.45 40 6.95 50 2.89 80.5 (1.325±0.35)
l,l'-Azo-bis-l-(2-methylcyclohexane)nitrile l,l'-Azo-bis-l-cyclohexanecarbonitrile 2,2/-Azo-bis-cyclopentylpropionitrile (mp 72.2-74.5) 2,2'-Azo-bis-2-cyclopentylpropionitrile (mp 96.3-97.6) 2,2/-Azo-bis-2,4,4-trimethylvaleronitrile (mp 67.5-69) 2,2'-Azo-bis-2,4,4-trimethylvaleronitrile (mp 94.5-95.5) 2,2'-Azo-bis-2-isopropyl-3-methylbutyronitrile U'-Azo-bis-l-cyano-^' dimethyl cyclohexane
Acetic acid Toluene
Toluene Toluene
133.9
132.6
h
124.7
h
115.1
a a exp[- 115/RT]
a
62
1.31 x 1O -4
w
104
1.30 x 10 ~4
w
104
w w w w
50 50 50 50 50
h
135 135 135 135 61 104 101 101 101 357 357 357 357
x x x x x
10~4 10~4 10~5 10~4 10~4
Toluene
69 74 80
2.83 x l O - 5 4.65 x l O - 5 1.16 x l O " 4
DMF
134.1
322 322 322 322 322 322 322 322 322 135 135 135 135 135 135 135 135 357 357 357 357 357 357 101 101 101 101 343 343 343 50 62 101
166.9
4.7 x l O " 6
DMAC
4,4'-Azo-bis(4-cyanopentanoyl)bis2-(2-aminoethoxy)ethanol
Toluene
142.8
Refs.
a
1.5IxIO- 5 2.79XlO" 5 5.4OxIO- 5 9.77 XlO" 5 8.3 x 10 ~6 2.27 x 10 ~4 5.35 x 10~5 1.45 x l O - 4 2.6OxIO- 4 1.77 x 10~5 2.9OxIO- 5 4.9OxIO- 5 1.74 x l 0 ~ 5
Toluene
Notes
126.4
80 85 90 95 80.3 80.5 36.6 45.4 49.7 65 69 74 65
DMSO
2,2'-AzO-Ms^-CyClOhCXyIpropionitrile l,l'-Azo-bis-l-cyclooctanenitrile
2,2'-Azo-bis-2-benzylpropionitrile
£ a (kj/mol)
7.1 x 1(T6 1.71 x 10 ~5 9.73 XlO- 5 1.06 x l O " 5 2.20 x 10 ~5 1.255 xlO~ 4 3.08 x 10 ~5 9.76 x 10 - 5 2.77xlO- 4 1.76 x 10~5 3.31 x 10~5 6.23 x 10 ~5 1.156xlO- 4 2.84 x l 0 ~ 5 5.1IxIO-5 9.87 x l 0 ~ 5 1.626xlO- 4 1.76 x 10 ~5 2.85 x 10 ~5 4.66 x l 0 ~ 5 1.73 x l O " 5 2.73 x l O - 5 4.53 x l O - 5 3.28 x 10~4 2.69 x l O " 5 9.72 x l O - 5 2.69X10- 4 1.9xlO" 5 1.9 x l O " 4 1.03 x 1015 1.63 x 10 ~4 1.78 x 10~4 7.43 x 10~6
2,2'-Azo-bis-(4-methoxy-2,4dimethylvaleronitrile)
l,r-Azo-bis-l-cycloheptane-nitrile
20
A:d (s"1)
80.8 87.9 101.2 81.4 87.3 101.9 74.3 82.9 91.2 80 85 90 95 80 85 90 95 65 69 74 65 69 74 69.5 48.9 58.9 67.3 30 47 T(K) 80.0 80.0 80.2
DMAC
18
T( 0 C)
113.5 121.3
132.2
108.4
357 357 54
TABLE 1. cont'd Number of C atoms 20 (cont'd)
22
34
Initiator /
2,2 -Azo-bis-2-isobutyl-4-methylvaleronitrile 2,2'-Azo-bis-2-(4-chlorobenzyl)propionitrile / 2,2 -Azo-bis-2-(4-nitrobenzyl)propionitrile l,l'-Azo-bis-l-cyclodecanenitrile
4,4'-Azo-bis-(4-cyanopentanyl)bis(heptadecafluorododecanoate)
Solvent Toluene
0
T( C)
1
kd (s" )
E* (kj/mol)
Notes
4
Refs.
Toluene
60.1 80.5 80
3.78 xlO~ 3 5.28 x 10 " 5 8.8xl0~
50 50 54
Toluene
80
1.00 x 10 ~
4
54
Toluene
50.8 60.2 69.5 90 100 110 120 130
5.4OxIO" 4 1.7OxIO4 5.69xlO4 9.86 x 10 " 3 2.11 x 10 ~ 3 4.4 x l 0 ~ 2 1.1 x 10~ 2 1.42 XlO"
Di-n-butyl phthalate
5
101 101 101 375 375 375 375 375
TABLE 2. MISCELLANEOUS AZO-DERIVATIVES Number of C atoms 2
Initiator l,l'-Azo-bis-formamide
Solvent DMF
DMSO
Formamide
4
Methyl-azo-3-propene
Hexamethylphosphoramide Vapor
5
2,3-Diazobicyclo[2,2,l]hept-2-ene
Isooctane
6
2,2'-AzO-Ws-PrOPaHe
Toluene Vapor
3,3'-Azo-bis-l-propene
Vapor
2,2'-Dichloro-2,2'-azo-bis-propane
Diphenyl ether
Siliconeoil
Methyl-azo-l,l-dimethyl-2-propene (cw) (trans)
Perfluoroazo-2-propane
Acetone
p-DiisopropylBenzene Vapor
T( 0 C)
*d (s" 1 )
86.0 100.3 115.3 86.0 100.3 115.3 86.0 115.3 115.3
1.56 x 10 " 5 5.73 XlO" 5 1.14x10-4 5.48 XlO" 6 2.72 x l O - 5 1.01 XlO" 4 9.25 x 10 ~5 -2.0 x l O " 3 3.83 x 10~5
163.3 169.8 182.8 T (K) 131.5 142.3 164.1 180.8 164.1 250 260 270 280 290 142.65 152.68 167.12 158.5 167.9 178.5 185 199 221 -13.89 -5.04 4.00 114.55 123.83 133.33 T(K)
5.88 x 10 ~4 1.110 x l 0 ~ 3 3.36 XlO" 3 3.2 x 10 1 4 5.44 x 10~6 1.82 XlO" 5 1.66xlO- 4 8.35 x l O " 4 1.64 x l O " 4 7.67 x 10 " 3 1.67xlO- 2 3.35X10- 2 6.52X10- 2 1.28XlO-1 3.88 x l O " 4 1.10 x l O - 3 4.45 x l O - 3 1.03 x 10~4 4.54 x l O - 4 8.08 X l O " 4 4.8xlO"4 2.1 x 10" 3 1.6xlO- 2 3.62 x 10~5 1.7OxIO- 4 6.82 x l O - 4 1.02 x l O " 4 2.68 x l O " 4 8.44 XlO" 4 5.0IxIO16
Ea (kj/mol)
148
Notes C2 C2 C2 c c c
268 268 268 268 268 268 268 268 268
h
298 298 298 298 180 180 180 180 180 110 110 110 110 110 319 319 319 297 297 297 240 240 240 252 252 252 252 252 252 360
exp[- №/RT] 157.7
171.1
a a a a a
151.3
138.3
h,u 4 U4 U4
96.8
h
147.9
h
exp[-189.0//?7]
Refs.
Notes page 11-69; References page 11-70
TABLE 2. cont'd Number of C atoms 6 (cont'd)
Initiator
Solvent
l-Propyl-azo-3'-propene
Vapor
Triazobenzene
Nitrobenzene
Tetralin
7
8
terf-Butyl-azo-3-propene
2,2/-Azo-isobutyramide Azo-bis-isobutyramidine
Azo-bis-isobutyramidine 2HCl (AIBA)
Vapor
Water Water Chloroform DMSO Methanol Water (pH 1.9) Water (pH 5.8) Water (pH 9.5) Water
AIBA
Water
AIBA-kaolin adduct
Water
AIBA-bentonite adduct
Water
Azo-bis(2-amidinopropane) 2HCl 2,2'-Azo-bis(2-amidinopropane) 2HCl Azo-bis-isobutyramidine 2HNO3
Methanol Water Water DMSO-cumene
2,2'-Azo-bis-isobutane
Vapor
2,2'-Azo-bis-isobutane
Diphenyl ether/isoquinoline (90/10)
J( 0 C) 101.32 114.10 126.02 T (K) 105 115 130 145 105 115 130 145 80.88 90.90 106.81 T (K) 88 60 60 60 70 60 50 60 50 60 50 60 60.0 70.0 75.0 80.0 40.15 50.05 60.20 70.10 100.10 70 50.0 60.0 70.0 80.0 50.0 55.0 65.0 70.0 80.0 50 50 56 60 70 160 180 190 210 174.8 188.3 188.8 165 175 185 190
kd (s'1) 1.10 x 10~ 6 5.60 x l O ~ 6 2.11 x l O ~ 5 6.3 x 10 1 4 3.5 x 10~ 7 1.20 x l O ~ 6 6.25 x l O ~ 6 2.5OxIO-5 4.0xl0~7 1.34 x 10~6 6.01 x 10 ~6 2.47 x l 0 ~ 5 2.13 x l O ~ 6 7.27 x l O ~ 6 3.89 x l O ~ 5 5.4 x 10 12 1.9xl0~ 5 3.15 x 10~5 2.80xl0~ 5 7.1 x 10~6 3.68 xlO~ 6 1.45 x 10 ~6 8.3 x 10 ~6 3.42 x 10 ~5 8.0xl0~ 6 3.22 x l 0 ~ 5 4.7 x 10 ~6 2.53 x l 0 ~ 5 3.70 x 10 ~5 1.33 xlO~ 4 2.58 xlO~ 4 5.13 xlO~ 4 2.49 xlO~ 6 9.79 xlO~ 6 4.03 x l 0 ~ 5 1.52 xlO~ 4 4.96 x l 0 ~ 3 1.52 xlO~ 4 1.37 x l 0 ~ 5 6.16 xlO~ 5 2.28 xlO~ 4 9.53 xlO~ 4 1.8OxIO- 5 3.97 xlO~ 5 1.53 xlO~ 4 3.21 x 10~4 1.04 XlO- 3 1.45 x 10 ~5 8.1x 10 ~6 1.93 x 10 ~5 4.86 x l 0 ~ 5 1.53 xlO~ 4 1.9xlO~ 5 5.01 x l 0 ~ 5 1.53 xlO~ 4 1.05 x l 0 ~ 3 6.8 x l 0 ~ 5 1.75 xlO~ 4 1.14 xlO~ 4 2.782 x l 0 ~ 5 8.74 x l 0 ~ 5 2.513 x l O ~ 4 4.143 XlO" 4
Ea (kj/mol)
Notes
149.2
v2i V2I V2I
e x p [ - 149.2/RT] 140.2
136.0
124.9
exp[- 124.9/RT]
v2i V21 V2I v2i a q2 q3
126.5 124.4 151.7 128.9
h
122.6
h
133.9
h
126.4
h
a
a m4 m4 m4
176.6
m4 h
Refs. 298 298 298 298 45 45 45 45 45 45 45 45 298 298 298 298 342 288 288 184 21 184 341 341 341 341 341 341 233 233 233 233 237 237 237 237 237 21 233 233 233 233 233 233 233 233 233 356 356 340 21 21 339 221 221 221 243 243 243 171 171 171 171
TABLE 2. cont'd Number of C atoms 8 (cont'd)
Initiator 2,2'-Azo-bis-isobutane 2,2'-Dimethoxy-2,2'-azopropane
10
Diphenyl ether/isoquinoline (90/10) Diphenyl ether
2,2/-Dimethylmercapto-2,2/azopropane
Diphenyl ether
Isopropyl-azo-l,l-dimethyl-2propene (cis)
Acetone
(trans)
9
Solvent
Diisopropylbenzene
2,2/-Azo-bis(2-methylpropane) 2-(4-Bromophenyl-azo)-2nitropropane
Vapor DCB
rm-Butyl-azo-U-dimethyl2-propene (trans)
Diisopropylbenzene
2-(4-Nitrophenylazo)-2-nitropropane
DCB
oc-Phenylethyl-azo-methane
Diphenyl ether
2,2'-Diacetylthio-2,2'-azopropane
Hexadecane Diphenyl ether
2,2 '-Diacetoxy-2,2 '-azopropane
Diphenyl ether
Siliconeoil Azo-bis( 1,1 -dimethyl-2-propene) (trans)
Xylene
Azo-bis-(l,l-dimethyl)-2-propyne (trans)
Xylene
2,2/-Azo-bis-2-methylbutane
Ethylbenzene
Isoamyl alcohol
2,2'-Azo-bis-2-methylbut-3-ene
n-Decane
2,2'-Azo-bis-2-(methylcarboxy)propane 2,2'-Azo-bis-methyl-2-methylpropionate
Water
2,2'-Azo-bis-methyl-2-methylpropionate
Collidine 1,2-Dichlorobenzene Diethyl oxalate Ethylene glycol Nitrobenzene Undecane Xylene
T( 0 C)
A;d (s *)
195 200 150.1 159.9 174.6 125.0 135.0 145.0 -25.09 -16.65 -8.20 97.41 106.06 115.06 160 130 135 140 T(K) 73.72 80.31 87.08 130 140 145 T(K) 151 161 171 161 130.0 140.0 149.4 190.0 200.1 210.3 258
6.73IxIO- 4 1.093 x 10~3 4.02 x l O " 5 1.50xl0~ 4 6.67 XlO" 4 3.40xl0~ 4 7.10 xlO~ 4 1.15 x l 0 ~ 3 6.30x 10" 5 2.87 x 10 " 4 1.10 x l O - 3 1.15 x 10~4 3.19 x l O - 4 9.22 x l O - 4 1.93 x 10 " 5 1.62 x 10~4 2.59 x 10 ~4 4.3OxIO- 4 1.1 xlO 1 3 8.69 x 10 ~5 1.83 x 10~4 3.80xl0~ 4 LOOx 10~4 2.44 x 10 ~4 4.06 x l O - 4 1.1 x 1013 4.35 x 10 ~5 1.16 x l O - 4 3.48 XlO" 4 1.2OxIO- 4 1.33 x 10~4 4.4OxIO" 4 1.19 x l O - 5 8.23 x 10 ~5 2.6IxIO-4 6.38 x l O " 4 1.46 x 10 ~2
42.03 49.98 57.39 41.32 48.20 57.19 180.0 190.0 200.0 180.0 190.0 200.0 44.90 55.44 63.74 50
5.95 x 10~5 1.73 x l O - 4 4.54 x l O - 4 5.37 x l 0 ~ 5 1.3OxIO- 4 4.39 x l O - 4 1.36 x KT 4 3.89 x l O - 4 1.03 x l O - 3 1.14xlO- 4 3.5IxIO-4 9.26 xlO~ 4 6.73 x 10 ~5 2.631 x 10 ~4 7.045 x l O " 4 3.51 x 10~6
80 80 80 80 80 100 80 80
1.67 x 10 ~A 1.44 x 10 " 4 1.52 x 10 ~4 1.24 x 10 " 4 1.6IxIO- 4 1.73 x 10- 3 1.04 x 10 ~4 1.09 x 10 ~4
Ea (kj/mol)
Notes
171.8
84.6
91.3
h,u5 U5 U5 h
137.8
h
a 130
exp[- 130/RT] 112.3
h
134
exp[- 134/RT] 161.5
151.3
h
171.4
h
109.4
h
111.9
h
176.4
h
176.0
h
107.3
h
129.3
149.8
a a a a a a a a
Refs. 171 171 297 297 297 297 297 297 252 252 252 252 252 252 340 325 325 325 325 252 252 252 325 325 325 325 149 149 149 149 297 297 297 297 297 297 240 252 252 252 252 252 252 336 336 336 336 336 336 278 278 278 285 226 226 226 226 226 226 226 62
Notes page 11-69; References page 11-70
TABLE 2. cont'd Number of C atoms 10 (cont'd)
Initiator
Solvent
N,Af'-Azo-piperidine
Silicone oil
2-(4-Methoxyphenylazo)2-nitropropane
DCB
Dimethyl 2,2'-azo-isobutyrate
Acetic acid
Acetonitrile
Benzene
Cyclohexane
Dimethyl-2,2'-azo-isobutyrate
Methanol
Methanol/SnCl4
Methanol/ZnCl2 Paraffin Toluene
11
2,3,7,8-Tetraazahexacyclo[7.4.1.04'12.0611.01013]tetradeca2,7-diene 2-(2,6-Dimethylphenylazo)2-nitropropane
a-Phenylethyl-azo-2-propane
12
Toluene/SnCl4 Acetonitrile-d3
DCB
Diphenyl ether/ benzoquinone Diphenyl ether
Azo-bis-isobutanoldiacetate
Cyclohexane
Azo-bis-(l-carbomethoxy-3-methylpropane)
Benzene
Carbon tetrachloride
4,4'-Azo-bis-(4-cyanopentanoic acid) (meso)
DMAC
T( 0 C)
kA (s" 1 )
181 228 135 140 150 T(K) 40 50 60 70 40 50 60 70 50 60 70 40 50 60 80 40 50 60 40 50 60 60 99.2 60 60 66 70 80 60 215 230 250 135 140 150 T(K) 143.2
1.7 x l O " 3 4.3 XlO- 2 7.4xlO" 5 1.30 x 10 ~4 3.67 XlO" 4 2.5 XlO 15 8.61 x 10 ~7 3.16 xlO~ 6 1.56 XlO" 5 5.49 x l O " 5 5.44 x 10~7 2.68 XlO" 6 1.01 x 10 " 5 3.57 XlO- 5 2.22 x 10 " 6 8.85 XlO" 6 3.27 x l O " 5 2.89 x 10 " 7 1.38 x l O " 6 5.85 XlO" 6 2.22 x l O - 5 6.86 x 10 " 7 3.12 XlO" 6 1.44 XlO" 5 1.20 x 10 " 6 4.46 x l O " 6 1.98 XlO" 5 1.51 x 10 ~5 1.02 x 10 " 3 8.9xlO- 6 8.11xlO" 6 1.93 x l 0 ~ 5 3.17 x l O " 5 1.19xlO- 4 1.63 x 10 ~4 1.18 x l 0 ~ 5 6.65 x l O " 5 3.4OxIO" 4 9.OxIO" 5 1.44 x 10 ~4 3.86 x l O " 4 4.8 xlO 1 3 1.5OxIO"4
143.0 152.0 165.5 170.0 180.0 189.0 199.0 36 45 55 65 45 55 65 77.6 85.3 90.9 99.8
1.54 x 10 ~4 4.24 xlO~ 4 1.57Ox 10" 3 4.86 x 10 " 5 1.27 XlO" 4 3.47 x l O " 4 1.01 x 10" 3 3.05 x 10 ~7 1.31 x 10 " 6 4.54 x l O " 6 1.82 x l O - 5 7.18 x 10 " 7 3.79 xlO~ 6 1.02 x l O " 5 1.33 x 10 ~4 3.7OxIO" 4 7.17 XlO" 4 2.02 x l O " 3
£ a (kj/mol)
Notes
153
exp[-153//CT] a a a a a a a a a a a a a a a a a a a a a
131.6 a
188.7
Xi X1 Xi
exp[- 13S/RT]
113 ti 3 ti3
133.5
a a a a
Refs. 240 240 325 325 325 325 326 326 326 326 326 326 326 326 326 326 326 326 326 326 326 326 326 326 326 326 326 326 240 290 340 340 340 340 290 174 174 174 325 325 325 325 220 310 310 310 189 189 189 189 68 68 68 68 68 68 68 205 205 205 205
TABLE 2. cont'd Number of C atoms 12 (cont'd)
Initiator
Solvent
4,4'-Azo-bis-(4-cyanopentanoic acid) (nD±)
Azo-bis-(AyV'-dimethylene isobutyramidine) 2HCl Azo-bis-(W-dimethyleneisobutyramidine)
tert-Butyl(2,2,4-trimethyl2-pentyl)diazene
60 70 75 70 60 44
2.06 x 10 " 4 6.64 x 10~4 1.08 XlO" 3 6.97 x 10 ~4 2.13 x 10 ~4 1.9xlO" 5
80 75 80 85 60 61 155 165.7 180.0 120.0 135.0 143.0 145.0 150.0 155.0 160.0 165.0 170.0 60 70 80 60 70 80 60 70 80 58
1.79 x 10~4 8.04 x 10 ~5 1.39 x l O - 4 2.6 x l O " 4 1.09 x 10~5 1.9xl0~ 5 1.6IxIO- 4 4.75 x 10 " 4 1.98 x l O - 3 1.06 x 10 ~4 5.94 x l O - 4 1.42IxIO- 3 7.56 xlO~ 5 1.273 xlO~ 4 2.147 x l O " 4 3.771 x 10~4 6.07 x l O - 4 1.033 x l O - 3 1.6IxIO- 5 5.88 x 10 ~5 2.02 XlO" 4 1.53xl0- 5 5.62 x l O - 5 2.OxIO- 4 1.62 x l O " 5 5.83 x l O - 5 2.066 XlO" 4 1.93 x 10 " 5
Methanol Water
50 50
4.83 x 10 ~5 4.02 x 10 ~5
Methanol «-Decane
50 39.21 50.71 58.95
Chlorobenzene Nitrobenzene Water DMSO
DMSO-cumene DMSO-tetralin Water DMSO DMSO-cumene
DMSO-tetralin Methanol Diphenyl ether
oc-Cumyl-azo-isopropane
Diphenyl ether
2,2/-Dicyclopropyl-2,2/-azopropane
Diphenyl ether/ ^ isoquinoline (90/10)
Di-(2-hydroxyethyl)-2,2'-azobis-isobutyrate
Dioxane
DMF
Toluene
14
2,2/-Azo-bis[AK2-hydroxyethyl)2-methylpropionamidine] 2HCl 2,2'-Azo-bis[2-(imidazoline-2-yl)propane 2HCl 2,2'-Azo-bis[2-(irnidazoline-2-yl)propane 2,2'-Azo-bis-(2-cyclobut1-enylpropane)
(s" 1 )
1.53 x l O - 4 4.1IxIO-4 7.0OxIO- 4 2.09 x l O - 3 1.55 x l O - 4 4.05 x l O " 4 6.98 x l O - 4 2.0OxIO- 3 1.51 x 10" 4 4.34 x l O - 4 7.33 xlO~ 4 2.24 x l O - 3 4.13 x l O " 5 5.93 x 10 ~4 1.56 x 10~4 1.9xl0" 5
(nD_)
2,2-Azo-bis-[2-methyl-J/V(2-hydroxyethyl) propionamide] Azo-bis-(AyV'-dimethyleneisobutyramidine) 2HNO3
fcd
77.9 85.8 90.1 99.1 78.0 85.4 90.0 99.0 77.7 86.0 90.5 99.7 70 92.6 80 86
(n D + )
2,2-Azo-bis-(ethyl-2-methylpropionate)
T( 0 C)
Water
4.7xlO~ 6 1.286 x l O " 4 5.678 x 10 ~4 1.762 XlO" 3
Ea (kj/mol)
Notes
134.3
a a a a a a a a a a a a a a a a
205 205 205 205 205 205 205 205 205 205 205 205 139 139 226 342
a
21 21 21 21 21 339
134.3
134.3
123.0
159.6
a h
158.2
h
125.7
129.9
129.9
a
Refs.
21 21 21 21 21 339 314 314 314 310 310 310 171 171 171 171 171 171 292 292 292 292 292 292 292 292 292 339 356 356
112.3
h
356 278 278 278
Notes page 11-69; References page II - 70
TABLE 2. cont'd Number of C atoms
Initiator
U (cont'd)
2,2'-Azo-bis-(2-methylhex-3-ene)
n-Decane
Di-(2-chloroethyl)-2,2'-azo-bisisobutyrate
Dioxane
Solvent
DMF Di-(2-chloroethyl)-2,2'-azo-bisisobutyrate
Toluene
l,l'-bis-(4-Chlorophenyl) azomethane
Diphenyl ether
Di-(2-hydroxypropyl)2,2/-azo-bis-isobutyrate
Dioxane DMF Toluene
15 16
2,2/,3,3,3',3/-Hexamethyl2,2'-azo-butane
Diphenyl ether
U'-Diphenyl-azo-methane
Diphenyl ether
2,2'-Azo-bis[2-methyl-N-(phenylWater methyl)propionamidine] 2HCl 2,2'- Azo-bis[2-(4-methylimidazoline-2-yl)-propane Methanol 2,2'-Azo-bis[2-(4-methylimidazolineMethanol 2-yl)-propane 2HCl Water 2,2'-Azo-bis[2-(3,4,5-trihydroMethanol pyrimidine-2-yl)propane 2,2'-Azo-bis[2-(3,4,5-trihydroMethanol pyrimidine-2-yl)propane 2HCl Water 1-Methylcyclopentyl-azoterf-Butyl benzene a-cumene l,r-Azo-bis-l-chloro1-phenylethane
Acetophenone Benzophenone Paraffin
Toluene
!,r-Azo-bis-1-chloro-l(3-bromophenyl)ethane l,r-Azo-bis-l-chloro-l(4-bromophenyl)ethane
Toluene Toluene
J(0C)
* d (s" 1 )
39.25 49.52 58.95 60 70 80 60 70 80 60 70 80 145.56 155.56 165.56 175.56 60 70 80 60 70 80 60 70 80 170.0 180.0 190.0 145.0 155.0 165.0 175.0 53
5.33 xlO~ 5 2.256 xlO~ 4 7.584 XlO" 4 1.56 x 10~5 5.55 x 10 " 5 1.9672 x l O - 4 1.25 x l O " 5 4.902 x l O - 5 1.9125 x 10" 4 1.666 x 10 " 5 5.018 x l O - 5 1.99 x l O " 4 2.3OxIO- 4 7.6OxIO" 4 1.49 XlO" 3 4.4OxIO" 3 1.80 x 10 " 5 7.6xlO~ 5 2.22 XlO" 4 1.97 x l O - 5 6.55 x l O " 5 2.3OxIO- 4 1.9Ox 10" 5 7.72 x l O " 5 2.365 x l O - 4 2.37 xlO" 4 5.29 x l O " 4 1.00 x l 0 ~ 3 1.72 x l O " 4 4.93 x l O - 4 1.12 x l O " 3 2.34 x l O - 3 1.93 x 10 " 5
50 50 50 50 50 50 88.3 107.3 117.6 74.8 83 67.8 86.2 98.2 94.5 112.3 120.5 129.3 137 64 74 64 74 59 69 59 69
Ea (kj/mol)
Notes
115.2
h
129.9 134.1 129.9 146.6
h
121.5 121.5 121.5 156.7
h
119.0
h
a
Refs. 278 278 278 292 292 292 292 292 292 292 292 292 297 297 297 297 292 292 292 292 292 292 292 292 292 297 297 297 297 297 297 297 339
10 ~5 10 " 5 10 " 5 10 ~6
356 356 356 356
7.8xlO~ 6 5.9xlO~ 6 5.00xl0" 5 4.95 x 10 " 4 1.43 x l O " 3 8.6xlO~ 4 1.95 x 10 " 3 2.8xlO" 4 3.3 x l O " 3 1.40xl0" 2 2.4xlO" 3 5.2 x l O - 2 1.03XlO"1 1.6XlO" 1 5.OxIO" 1 1.8 x 10 " 4 7.2 x l O " 4 1.79 xlO" 4 7.2OxIO" 4 1.64 x 10~4 6.64 x 10 ~4 1.77 xlO" 4 6.75 x 10 ~4
356 356 327 327 327 240 240 240 240 240 240 240 240 240 240 240 240 239 239 239 239 239 239
1.23 x 7.48 x 6.73 x 1.1 x
132.0
h
135.1
a a a a a a
131.8 127.2
TABLE 2. cont'd Number of C atoms 16 (cont'd)
Initiator U'-Azo-bis-l-chloro-l(4-chlorophenyl)ethane 2,2/-Azo-bis-(2-cyclopent-lenylpropane)
Solvent Toluene n-Decane
l,l'-Azo-bis-l,l-dicyclopropylethane
Diphenyl ether/ isoquinoline (90/10)
2,2/-Azo-bis-{2-methyk/V-[U(bis-hydroxymethyl)-2-hydroxyethyl] propionamide} 2,2/-Azo-bis-{2-methyl-iV-[l,l(bis-hydroxymethyl)ethyl] propionamide} 2,2'-Azo-bis[2-(4, 4-dimethylimidazoline-2-yl) propane 2,2'-Azo-bis[2-(4,4-dimethylimidazoline-2-yl)propane 2HCl 2,2 '-Azo-bis[2-(4,5-dimethylimidazoline-2-yl)propane 2HCl
Water
2,2'-Azo-bis[2-(4,5,6,7-tetrahydrolH-l,3-diazepine-2-yl)propane 2HCl 2,2/-Azo-bis-(2,2,4-trimethylpentane) U'-Azo-bis-l-phenylethane l,r-Azo-bis-l-phenylethane
l,l'-Di-(3-chlorophenyl)-l,razo-ethane l,l'-Di-(4-chlorophenyl)-l,l'azo-ethane
1.97 x 10~4 6.93 x 10 " 4 9.98 x l O " 5 4.593 x 10 " 4 1.528 x l O - 3 6.33 x l O " 5 2.03 x 10 ~4 6.07 XlO" 4 1.695 x l O " 3 1.9 x 10~5
Ea (kj/mol)
Notes
118.8 116.9
a a h
149.0
h
Refs.
a
239 239 278 278 278 171 171 171 171 342
a
342
82
1.9 x l O " 5
Methanol
50
9.3xlO" 6
356
Methanol Water
50 50
9.55 x 10 ~5 9.30xl0"5
356 356
Methanol Water Methanol Water
50 50 50 50
9.21 8.94 1.23 1.04
x 10 " 5 x 10 " 5 x 10~5 xlO"5
356 356 356 356
1.9 x 10~5
Diphenyl ether
110
Dodecane Ethylbenzene Toluene Ethylbenzene
97.3 3.175 x l 0 ~ 5 100.4 (5.45 ± 0.05) x 10~5 110.3 (1.69 ± 0.01) x 10 ~4 105.02 8.473 x 10 " 5 105.28 9.02 x l O - 5 105.28 7.62 x l O " 5 105.02 7.623 x l O " 5 97.3 4.135 x 10 ~5 97.3 3.688 x 10 " 5 97.3 3.995 x 10 " 5 97.3 3.294 x 10 ~5 140.0 1.93 x l O " 4 150.1 5.29 x 10~4 164.8 2.18 x l O " 3 95 4.13 x l O " 5 105 1.218 x l O " 4 85 1.45 x 10~5 95 4.82 x l O " 5 105 1.650xl0~ 4 120.05 7.8xlO-5 130.0 2.63 xlO~ 4 139.0 7.38 XlO" 4 147.0 1.906 x l O - 3 105 1.121 x 10~4
N-Methyl-N-benzyl aniline N-Methyl propionamide Diphenylmethane Propylene carbonate Diphenyl ether
p-Cymene p-Cymene
a,oc-Diethylbenzyl-azo-3-pentane
Diphenyl ether
l,l'-Di-(3-fluorophenyl)1,1'-azo-ethane l,r-Di-(4-fluorophenyl)1,1'-azo-ethane
p-Cymene
Di-(3-hydroxybutyl)-2,2'-azo-bisisobutyrate
59 69 39.21 49.52 58.95 120 130 140 150 80
^d(S" 1 )
Water
(l,l'-d 2 ) (l,l,U',r,l'-d6)
terr-Butyl-(2,2,4,6,6-pentamethyl-4-heptyl)-diazine
T( 0 C)
/?-Cymene
Dioxane
DMF
85 95 105 60 70 80 60 70 80
5.5 x l O " 6 2.35 x 10 " 5 7.85 x l O - 5 2.22 x 10" 5 7.84 x 10 ~5 2.413 x l O " 4 1.83 x l O " 5 7.69 x l O " 5 2.424 XlO" 4
a
136.4
141.6
h
122.3
h
134.1
h
147.0
h
117.3
121.5
339 26 107,98 107,98 152 183 183 152 26 26 26 26 314 314 314 266,313 266,313 266.313 266,313 266,313 310 310 310 310 266,313 266,313 266,313 266,313 292 292 292 292 292 292
Notes page 11-69; References page II - 70
TABLE 2. cont'd Number of C atoms 16 (cont'd)
Initiator
Solvent
Di-(3-hydroxybutyl)-2,2'-azo-bisisobutyrate
Toluene
Di-(4-hydroxybutyl)-azo-bisisobutyrate
Dioxane
DMF
Toluene
l,r-Bis-(4-methoxyphenyl)azo-methane
Diphenyl ether
2,2',4,4,4',4'-Hexamethyl2,2'-azo-pentane
Diphenyl ether
1-Methylcyclohexyl-azo-a-cumene
17
18
terf-Butylbenzene
1,1 '-Diphenyl-l,l'-azo-ethane
p-Cymene
2-(Phenylazo)-2-propyl perbenzoate
Chlorobenzene
(l-Phenylethyl)-azo-diphenylmethane l,l'-Bis(p-tolyl)-azo-methane
Chloroform-d Chlorotoluene Ethylbenzene Diphenyl ether
3,7-Diphenyl-l,2-diaza-l-cycloheptene
l,l'-Azo-bis-cumene
Xylene
Benzene terr-Butylbenzene
Chlorobenzene
Cumene
Dodecane «-Octane
Toluene
T( 0 C) 60 70 80 60 70 80 60 70 80 60 70 80 145.0 155.0 165.0 175.0 130.2 140.0 150.0 102.2 113.1 122.0 95 105 10 35 10 10 58 145.0 155.0 165.0 175.0 61.0 70.0 80.0 89.3 100.2 80 100.2 58.91 60 60 60 55 55 55 55 55 55 60 60 60 60.23 60 60 60 40.04 49.52 59.42 69.23 41.0 44.8 58.5
fcd
(s" 1 ) 2.43 x 10 ~5 8.18 x 10 ~5 2.461xlO~ 4 2.12 x 10 ~5 6.57 x 10 ~5 2.539 x l 0 ~ 4 1.97 x l 0 ~ 5 6.19xlO- 5 2.50xl0~ 4 2.59 x l 0 ~ 5 6.66 XlO- 5 2.628 xlO~ 4 2.23 x 10~A 5.67 x 10 ~4 1.61 x 10~3 3.79 x l 0 ~ 3 1.82 xlO~ 4 4.51 x 10 ~4 1.28 x l 0 ~ 3 2.58 x 10 ~4 9.81xlO~ 4 2.2OxIO- 3 2.74 x l 0 ~ 5 8.21xl0~ 5 4.5 x 10~4 1.9 x l 0 ~ 3 5.IxIO-. 4 6.4xlO~ 4 1.9XlO" 5 2.00 x 10~4 4.69 xlO~ 4 1.22 x l O - 3 3.45 x l 0 ~ 3 3.80xl0~ 5 1.34 xlO~ 4 4.27 XlO" 4 1.59 x l O - 3 4.04 x 10 ~3 4.26 xlO~ 4 3.94 XlO" 3 1.94 xlO~ 4 1.03 x 10 ~4 4.03 x l 0 ~ 5 4.44 x l O - 6 8.50 x 10 " 5 6.88 x l 0 ~ 5 4.42 x l O - 5 8.1OxIO- 5 6.75 x l O " 5 3.83 x l O - 5 1.16 x l O - 4 4.73 x l 0 ~ 5 7.23X10- 6 1.47 x 10~4 1.14 x 10~4 4.44 x l 0 ~ 5 8.32xl0-6 9.46 x 10 ~6 4.33 x l O - 5 1.62 xlO~ 4 5.80xl0~ 4 9.6x10-6 1.98 xlO~ 5 1.28OxIO-4
E* (kj/mol)
Notes
117.3
125.7
125.7
121.5
145.0
h
132.8
h
131.1
h
124.0
h
145.4
a h
a a V5 z (1256) z (3890) z (1013) z (4154) z (1013) z (4154) z (1256) z (3890)
z (1256) z (3890) h
122.8
Refs. 292 292 292 292 292 292 292 292 292 292 292 292 297 297 297 297 297 297 297 327 327 327 266,313 266,313 372 372 372 372 339 297 297 297 297 138 138 138 138 138 44 44 217 333 333 333 280 280 280 280 280 280 333 333 333 217 333 333 333 217 217 217 217 309 309 309
TABLE 2. cont'd Number of C atoms IS (cont'd)
Initiator
Solvent
l,l'-Azo-bis-4-bromocumene
Toluene
lJ'-Azo-bis-S-chlorocumene
Toluene
1,1'- Azo-bis-4-chlorocumene
Toluene
l,r-Azo-bis-l-chloro-l-(4-tolyl)ethane
Acetophenone
Paraffin
Toluene
2,2'-Azo-bis[2-(4-ethyl-4-methylimidazoline-2-yl)propane 2HCl 2,2/-Azo-bis[2-(4-ethyl-5-methylimidazoline-2-yl)propane 2HCl 2,2'-Azo-bis[2-(5,5-dimethyl-3,4,5-trihydropyrimidine-2-yl)propane 2,2/-Azo-bis[2-(5,5-dimethyl-3,4,5-trihydropyrimidine-2-yl)propane2HCl l,l'-Azo-bis-4-fluorocumene
Methanol Water Methanol Water Methanol
l,l'-Di-3-trifluoromethylphenyl)-l,l'-azo-ethane l,l/-Azo-bis-(2-methoxyphenyl)ethane
p-Cymene
Methanol Water Toluene
p-Cymene
l,l'-Azo-bis-(2-methoxyphenyl)ethane
Ethylbenzene
l,l/-Azo-bis-(3-methoxyphenyl)ethane l,r-Azo-bis-(4-methoxyphenyl)ethane l,r-Azo-bis-l-(4-methoxyphenyl)ethane l,r-Azo-bis-l-phenylpropane
p-Cymene
2,2/-Azo-bis-2-phenyl-hexafluoropropane
Toluene
p-Cymene Ethylbenzene Ethylbenzene
U'-Dimethyl-azo-cyclooctane
Benzene
!,l'-Diphenyl-azo-cyclopropane
Benzene
Ethylbenzene
T( 0 C) 42.8 48.6 58.0 36.0 42.8 48.2 61.1 36.0 42.8 48.2 74.8 79.5 86 105 109.5 126 135.5 59 69 59 69 50 50 50 50 50
kd ( s 1 ) 2.72 xlO~ 5 6.28 x l O " 5 2.189 x l O - 4 8.8 x 10~6 2.46 XlO" 5 5.55 x l 0 ~ 5 2.796xlO- 4 1.11 x 10 ~~5 2.9OxIO- 5 6.52 x l 0 ~ 5 2.1 x 10~3 3.OxIO" 3 7.4 x l O - 3 1.66 x l O " 3 2.5 x l O - 2 6.4 x l O - 2 UxlO"1 1.03 x 10 ~4 4.OxIO" 4 1.03 x l O - 4 3.93 XlO" 4 6.8OxIO" 5 7.38 x 10 " 5 9.48 x 10 " 5 1.1 x 10 " 4 9xlO"7
50 8.OxIO- 6 50 7.9xlO" 6 36.0 5.7xlO-6 42.8 1.31 x 10 ~5 48.2 2.94 XlO" 5 61.1 1.880xl0~ 4 95 4.13 x IO" 5 105 1.357 x 10~4 84.6 1.69 x 10~5 95 6.1IxIO-5 105 1.975 x l O - 4 106.06 2.29 x l O " 5 113.81 5.52 x 10~5 133.66 4.87 XlO" 4 95 1.53 x IO" 5 105 6.91 x 10 ~5 95 3.56 x l O " 5 105 1.09OxIO- 4 100.4 (7.15 ±0.1) x 10~5 110.3 (2.48 ± 0.02) x 10 ~4 100.4 (2.35 ±0.1) x 10~5 110.3 (7.2 ±0.2) x 10- 5 45.0 8.36 x l O " 6 50.0 2.16 x l O " 5 55.0 4.92 x l O - 5 60.0 8.81xl0"5 67.0 2.46 x l O - 4 43.8 6.3 x l O - 5 53.8 2.4 x l O - 4 130.0 1.09 x l O " 4 140.0 3.05 x l O - 4 150.0 8.96 x l O " 4 165.0 9.6xlO" 5 175.0 2.2IxIO" 4 185.0 5.09 x l O - 4 170.0 1.67 x 10 ~4 180.0 3.48 x l O " 4
Ea (kj/mol)
Notes
117.7
115.9
112.5
126.8
a
115.9
134.9
h
135.6
h
171.8
a a a h
126.5
h
149.8 135.1 137.2
h
115.5 145.8
h
135.3
h
Refs. 309 309 309 200 200 200 200 200 200 200 240 240 240 240 240 240 240 240 240 239 239 356 356 356 356 356 356 356 200 200 200 200 266,313 266,313 266 266,313 266,313 300 300 300 266,313 266,313 266,313 266,313 98 98 98 98 173 173 173 173 173 42 42 327 327 327 323 323 323 323 323
Notes page 11-69; References page 11-70
TABLE 2. cont'd Number of C atoms IS (cont'd)
19
20
Initiator
Solvent
3,8-Diphenyl-l,2-diaza-lcyclooctene
Tetralin
U'-Di-O-tolyO-U'-azo-ethane l,l'-Di-(4-tolyl)-l,r-azo-ethane
/?-Cymene p-Cymene
Phenyl-azo-diphenylmethane
Decalin
2-(2-Phenyl-4-methylpentyl)azo-2-(4-methylpentane)
Diphenyl ether
l,l'-Azo-bis-l-acetoxy1-phenylethane
Paraffin
U'-Azo-bis-U-dicyclopropylbutane
Diphenyl ether/ isoquinoline (90/10)
9-Azo-bis-decalin (cis)
Ethylbenzene
(trans)
oc,a'-Azo-bis(a-methylbenzyl) diacetate
Dichlorobenzene
Azo-bis-4-methylcumene
Cumene
Toluene
2,2'-Azo-bis[2-(4-ethyl-5-isopropylimidazoline-2-yl)propane 2HCl 2,2'-Azo-bis-2-(4-tolyl)-propane
Methanol Water Toluene
l,r-Azo-bis-l,l,l-tricyclopropylmethane
Diphenyl ether/ isoquinoline (90/10)
l,r~Di-(4-ethylphenyl)1,1-azo-ethane l,l'-Diphenyl-azo-butane
l,l'-Diphenyl-azo-cyclobutane
Decalin/ isoquinoline (90/10) Isoquinoline Cumene/ isoquinoline (90/10) p-Cymene Ethylbenzene
Ethylbenzene
T( 0 C)
^d(S"1)
143 151 165 173 105 95 105 124.5 144.5 103.0 110.0 120.0 130.0 131 142 149.5 120.0 125.0 130.0 135.0 140.0 147.0 180.0 190.0 200.0 180.0 190.0 200.0 65 70 80 90 55 55 55 41.0 49.5 58.5 50 50 36.0 42.8 61.1 105.0 110.0 115.0 120.0 125.0 130.0 135.0
9.52 x 10~5 2.09 x l O " 4 8.77 XlO" 4 1.82 xlO~ 3 8.17 x l O " 5 3.06 x 10~5 9.35 x l O - 5 3.44 x 10 " 5 2.69 x l O - 4 1.17 x l O " 4 2.52 x 10 ~4 8.51 x 10- 4 2.611 x l O " 3 3.2 x l O " 2 4.3 x 10~2 8.OxIO- 2 4.26 x l O " 5 7.94 x l O " 5 1.49 x l O " 4 2.697 x l O - 4 4.774 x l O " 4 1.055 XlO" 3 1.41 x 10" 4 3.95 x l O " 4 1.05 XlO" 3 1.9Ox 10" 4 5.35 XlO" 4 1.41xlO" 3 1.86 x 10 ~5 4.0OxIO" 5 1.592 x l O " 4 5.525 x l O " 4 8.86 x 10 " 5 7.54 XlO" 5 4.47 x 10- 5 1.33 x 10~5 5.02 XlO" 5 1.690xl0" 4 7.72 x 10~5 1.01 x 10 ~4 8.4xlO~ 6 1.62 x l O - 5 2.08 x l O " 4 7.89 x l O " 5 1.374 x l O " 4 2.36 XlO" 4 4.58 x l O " 4 7.76 xlO~ 4 1.38 x l O " 3 2.39 x l O " 3
118.5 118.5
3.60 x 10 " 4 3.30 x l O " 4
118.5 95 105 93.88 105.68 119.55 63.2 73.8 79.1 87.7
445xlO" 4 3.02 x l O " 5 9.14 x l O " 5 1.67 x 10~5 6.96 XlO" 5 3.39 x l O " 4 8.2xlO~ 6 3.5 XlO" 5 6.9 x l O " 5 1.69 XlO" 4
Ea (kj/mol)
Notes
153.6
126.5
h
142.3
159.0
h
175.1
h
175.1
h
z (1013) z (4154) 120.7
110.0
143.5
h
Refs. 137 137 137 137 266,313 266,313 266,313 46 46 310 310 310 310 240 240 240 171 171 171 171 171 171 335 335 335 335 335 335 366 366 366 366 280,333 280,333 280,333 309 309 309 356 356 200 200 200 171 171 171 171 171 171 171 171 171
h 125.3 a a a h 122.3
b,h
171 266,313 266,313 300 300 300 323 323 323 323
TABLE 2. cont'd Number of C atoms 20 (cont'd)
22
24
25
Initiator (-HJ)-I,l'-Diphenyl-lmethyl-azo-methane 2,2'-Azo-bis(2-methyl-A^-phenylpropionamidine) 2HCl 2,2/-Azo-bis[A^-(4-chlorophenyl)2-methylpropionamidine] 2HCl 2,2'-Azo-bis[Af-(4-hydroxyphenyl)2-methylpropionamidine] 2HCl l,r-Azo-bis-l-phenyl-3methylbutane 1,1'-Azo-bis-4-ethylcumene
Solvent
T( 0 C)
^d(S1)
Water
106.0 127.9 45
8.26 x l O " 6 1.18 x l O " 4 1.93 x 10 ~5
Water
45.5
Water
Cumene
Ethylbenzene Toluene
l,r-Azo-bis-4-isopropylcumene
Toluene
U'-Diisopropyl-U'diphenyl-azo-ethane l,l'-Diphenyl-azocyclopentane
Ethylbenzene
2,2'-Azo-bis[2-methyl-N-(phenylmethyl)propionamidine] 2HCl 2,2'-Azo-bis[2-(4-methyl-4-isobutylimidazoline-2-yl)propane 2HCl 2,2'-Azo-bis[2-(4-methyl-5-isobutylimidazoline-2-yl)propane 2HCl 2,2/-Azo-bis[2-(4-ethyl-5-propylimidazoline-2-yl)propane 2HCl U'-Azo-bis-4-terf-butylcumene
Water
oc,a'-Azo-bis(a-methylbenzyl)dimethacrylate
Dichlorobenzene
Bis(2,2,4,6,6-pentamethyl4-heptyl)diazine
Diphenyl ether
l,r-Diphenyl-azo-cyclohexane
Benzene
3-Bromophenyl-azo-triphenylmethane 4-Bromophenyl-azo-triphenylmethane 4-Hydroxyphenyl-azo-triphenylmethane
Toluene
Benzene
Methanol Water Methanol Water Methanol Water Toluene
Toluene Acetic acid Pyridine Toluene
2-Nitrophenyl-azo-9-phenylfluorene
Toluene
4-Nitrophenyl-azo-9-phenylfluorene
Toluene
2,4-Dinitrophenyl-azo-9-phenylfluorene 2-Nitrophenyl-azo-triphenylmethane
Toluene Toluene
3-Nitrophenyl-azo-triphenylmethane
Toluene Benzene terf-Butylbenzene
Ea (kj/mol)
Notes
149.2
b
Refs.
a
318 318 339
1.93 x 10 ~5
a
339
47.5
1.93 x 10~5
a
339
100.4 110.3 42.8 48.6 58.0 42.8 51.2 58.0 50
7.6xl0"5 2.42 x 10 " 4 1.29 x l O " 5 3.29 x l O " 5 1.24Ox 10~4 1.13 x l O " 5 4.26 x l 0 ~ 5 1.078 xlO~ 4 3.52 x l O ' 5
h
98 98 309 309 309 309 309 309 324
a
323 323 323 339
29.5 40.0 50.0 52 50 50 50 50 50 50 42.8 48.6 58.0 65 70 80 90 100.1 109.2 125.0 45.5 54.0 69.7 53.8 64.0 53.35 64.30 54.00 64.00 54.00 64.00 54.00 64.00 45.45 55.55 45.45 55.55 55.55 64.94 64.94 75.06 53.8 64.0 60 60
3.16 1.24 4.68 1.93
x 10~4 x 10 " 3 XlO" 3 x 10 ~5
5.54 x 10 " 5 7.08 x 10 ~5 7.72 x 10 ~5 9.78 x 10 ~5 1.06 x 10 " 4 1.41 x 10~4 1.16 x l 0 ~ 5 2.58 x l 0 ~ 5 1.080xl0" 4 3.65 x 10~5 7.98 x 10 ~5 2.313 xlO~ 4 1.344 XlO" 3 3.03 x 10 ~4 7.62 x l O " 4 3.90xl0~ 3 2.52 x 10~5 8.74 x l O - 5 7.12 xlO~ 4 1.14 x 10 " 4 4.58 x 10 " 4 1.05 x 10 " 4 4.28 x 10 " 4 1.42 x 10~4 6.2xlO~ 4 1.52 x l O " 4 6.7 XlO" 4 1.70 x 10~4 6.4 x l O " 4 1.01 x 10~4 3.71 x 10" 4 2.06 x 10 " 4 7.53 XlO" 4 2.06 x 10 " 4 6.92 x 10 ~4 1.46 x 10 ~4 5.26 XlO" 4 5.8 x 10 ~5 1.99 x l O " 4 9.92 x 10 ~5 9.18 x 10 ~5
139.3 108.9
124.4
113.6 103.1
123.6 h
125.7 h 125.7
125.1 117.2 133.9 133.9 121.3 119.7 111.7 119.2 123.8 110.9
356 356 356 356 356 356 309 309 309 366 366 366 366 314 314 314 323 323 323 42 42 52 52 52 52 52 52 52 52 75 75 75 75 75 75 75 75 42 42 263 263
Notes page 11-69; References page 11-70
TABLE 2. cont'd Number of C atoms 25 (cont'd)
Initiator
Solvent
3-Nitrophenyl-azo-triphenylmethane
Cumene Ethylbenzene Octane Toluene
4-Nitrophenyl-azo-triphenylmethane
Benzene tert-Butylbenzene
Chlorobenzene
Cumene
Decane
1-Decene Dodecane
1-Eicosene Heptane
Hexadecane
1-Hexadecene Hexane 1-Hexene Nonane
Octadecane 1-Octadecene Octane
1-Octene Pentane Tetradecane
4-Nitrophenyl-azo-triphenylmethane
2,4-Dinitrophenyl-azo-triphenylmethane Phenyl-azo-triphenylmethane
1-Tetradecene Toluene
Toluene Acetic acid Anisole
T( 0 C)
A^(S"1)
60 60 60 45 60 60 60 60 60 55 55 55 55 55 55 60 60 60 50 60 70 77.5 60 50 60 70 60 50 60 70 50 60 70 77.5 60 50 60 60 50 60 70
1.04 x 10~4 1.10 x 10~ 4 1.01 x 10~4 1.25 x 10 " 5 1.22 x l O ~ 4 1.09 x 10 " 4 9.7xlO~ 5 4.03 x l O - 5 4.44 x 10 " 6 8.50xl0~ 5 6.88 x l O " 5 4.42 x l O - 5 8.1OxIO- 5 6.75 XlO" 5 2.62 x l O - 5 1.15 x l O " 4 4.73 x l O " 5 7.23 XlO" 6 2.017 x l O " 5 9.988 x l O " 4 3.35OxIO- 4 1.16 XlO" 3 1.038 x l O " 4 1.933 x 10 ~5 9.166 x l O " 5 3.25OxIO- 4 7.6OxIO- 5 2.716 x l O " 5 1.043 x l O - 4 3.900xl0"4 1.716 x l O " 5 8.133 x l O " 5 2.966 x l O - 4 1.09xl0-3 8.25 x 10 ~5 2.75OxIO- 5 1.195 x l O ~ 4 1.143 x 10 ~4 2.20OxIO- 5 9.900 x l O " 5 3.71OxIO- 4
60 70 60 60 70 77.5 60 50 60 50 60 70 60 64.94 75.06 53.35 64.30 75.06 84.98 43.30 64.00 25.0
7.78OxIO- 5 2.783 x l O - 4 7.58 x 10 ~5 1.015 x 10~4 3.65OxIO- 4 1.78 x l O - 3 1.123 x l O ~ 4 3.600xl0"5 1.28OxIO- 4 1.866 x l O " 5 8.80OxIO- 5 3.116 x l O ~ 4 9.02 x 10 " 5 2.58 x 10~4 9.19 x l O - 4 5.7 x l O - 5 2.25 XlO" 4 1.9OxIO- 4 6.13 x 10~4 5.7 x 10~5 8.4 x l O - 4 2.58 x l O " 6
Ea (kj/mol)
Notes
z (1256) z (3890) z (1013) z (4154) z (1013) z (6180) z (1256) z (3890)
123.0 113.0 122.6 117.2 120.5
b,h
Refs. 263 263 263 263 263 263 263 263 263 333 333 333 333 333 333 263 263 263 168,263 168,263 168 168 168 168,263 168,263 168 168 168 168,263 168 168,263 168,263 168 168 168 168,263 168,263 168 168,263 168,263 168 168,263 168 168 168,263 168 168 168 168,263 168,263 168,263 168,263 168 168 75 75 52 52 75 75 52 52 103
TABLE 2. Number of C atoms 25 (cont'd)
cont'd
Initiator Phenyl-azo-triphenylmethane
Solvent Anisole
Benzene
Benzonitrile
/m-Butylbenzene
Chlorobenzene
Cumene
Cyclohexane
Decane Dodecane Diethyl malonate
Ethylbenzene Heptane Hexadecane Hexane Nitrobenzene
Octane
Pyridine Tetradecane Toluene
26
2,2/-Azo-bis[2-(4-ethyl-5-propylimidazoline-2-yl)propane 2HCl Azo-bis-diphenylmethane
Methanol Water Toluene
1,1'-Bis-biphenyl-azo-methane
Diphenyl ether
l,l'-Azo-bis-l-(4-tolyl)-cyclohexane
Toluene
T( 0 C) 50.2 74.7 25.0 74.5 80.1 85.9 25.0 49.6 74.7 50 25.0 50.3 74.7 50 50 50 25.0 49.6 74.7 50 50 50 25.0 49.6 74.7 60 60 25.1 74.5 80.1 85.9 50 60 60 60 25.0 74.5 80.1 85.9 50 50 50 60 53.35 64.00 60 43.8 53.8 45 50 45.45 55.55 43.30 53.35 53.3 50 50 54.0 64.0 135.0 145.0 155.0 165.0 36.0
^d(S1) 1.31 x 10~4 3.03 x l O ~ 3 3.0xl0~6 2.9 x l O ~ 3 6.8 x l 0 ~ 3 1.1 x l O ~ 2 4.29 x l O ~ 6 1.24 x l O - 4 3.12 x l 0 ~ 3 1.37 x l O ~ 4 2.62 x l O ~ 6 1.56 x l O ~ 4 3.14 x l 0 ~ 3 1.33 x 10 ~4 3.83 x l 0 ~ 5 9.53 x l O ~ 6 3.77 x l O ~ 6 1.67 x l O ~ 4 3.93 x l 0 ~ 3 1.50 x 10 ~4 6.82 x l 0 ~ 5 7.65 x l O ~ 6 4.22 x l O ~ 6 9.90 x l 0 ~ 5 1.75 x l 0 ~ 3 5.72 x 10~4 5.35 x 10 ~4 3.1 x 10~6 2.8 x 10 ~3 5.9 x l O " 3 1.0 x l 0 ~ 2 1.58 x 10 ~4 6.60xl0~4 4.76 x 10 ~4 7.60xl0~4 2.6xlO~ 6 3.0xl0~3 5.8 x l 0 ~ 3 9.8 x l 0 ~ 3 1.59 x 10 ~4 7.53 x l O ~ 5 1.17 x l 0 ~ 5 6.41 x l O ~ 4 1.74 x l 0 ~ 4 8.OxIO" 4 4.99 x 10 ~4 6.3 x 10" 5 2.4 x l O - 4 9.23 x l 0 ~ 5 1.73 x l O - 4 8.48 x l 0 ~ 5 3.5IxIO-4 6.0xl0~5 2.25 XlO" 4 2.25 x l O - 4 9.75 x 10 ~5 1.33 x 10 ~4 1.01 x 10 ~4 3.4OxIO- 4 1.23 x 10~4 3.58 x l O " 4 7.76 XlO" 4 2.09 x l O - 3 8.7xlO~ 6
E a (kj/mol)
Notes
Refs.
b b
118.3
112.1
121.3
118.4
102.5
116.6
118.7
129.7
115.5
122.6 113.0 113.0
111.3 134.1
107.1
103 103 114 114 114 114 b,h 103 103 b 103 263 b,h 103 b 103 103 263 z (1140) 263 z (4265) 263 b,h 103 b 103 b 103 263 z (1140) 263 z (4265) 263 h 103 b 103 b 103 263 263 114 114 114 114 263 263 263 263 114 114 114 114 263 z (1140) 263 z (4265) 263 263 52 52 263 42 42 263 263 75 75 52 52 46 356 356 107,312 46,107,312 h 297 297 297 297 200
Notes page 11-69; References page 11-70
TABLE 2. cont'd Number of C atoms 26 (cont'd)
Initiator l,l'-Azo-bis-l-(4-tolyl)-cyclohexane
Toluene
l,r-Diisopropyl-2,2'-dimethyl1,1 '-Diphenyl-azo-propane
Ethylbenzene
4-Methoxyphenyl-azo-triphenylmethane l,r-Diphenyl-azo-cycloheptane
Toluene
3-Tolyl-azo-triphenylmethane
Benzene terf-Butylbenzene Cumene Ethylbenzene Octane Toluene
4-Tolyl-azo-triphenylmethane
27 28
Solvent
4-Acetaminophenyl-azo-triphenylmethane U'-Azo-bis-l,2-diphenylethane (meso)
Benzene
Benzene tert-Butylbenzene Cumene Ethylbenzene Octane Toluene
Toluene Ethylbenzene
(D,L)
30
l,l'-Dibutyl-l,l'-diphenylazo-pentane
Ethylbenzene
34
l,r-Azo-bis-(l,3-diphenylpentane) 3,10,13,20-Tetraphenyl-l,2,ll,12-tetraaza-Ul-cycloeicosadiene
Bromobenzene Xylene Xylene
3,12,15,24-Tetraphenyl-l,2,13,14-tetraaza-l,13-cyclotetracosadiene
Ethylbenzene Xylene
40
44
Poly[oxyethylenexoxy(l-oxo-2,2-dimethylethylene)azo-(2-oxo-1,1 -dimethylethylene)
o-Xylene
T( 0 C) 42.8 61.1 50.0 60.0 70.0 54.00 64.00 16.2 24.8 33.4 41.1 50 50 50 50 45 43.8 53.8 45 50 50 50 50 50 45 43.30 53.35 45 50 54.00 64.00 96.56 106.47 115.28 96.56 106.47 115.28 50.0 60.0 70.0 89.7 118.8 110 120 130 112.95 110.8 119.8 110 120 130 85 95 105 T(K)
* d (s" 1 ) 2.0IxIO" 5 2.009 x l O " 4 6.24 x l O " 5 2.49 x 10 " 4 7.77 XlO" 4 2.13 x l O " 4 7.6xlO" 4 1.65 x 10 " 4 5.52 xlO~ 4 1.66 x l 0 ~ 3 4.52 XlO" 3 1.3OxIO"4 1.3OxIO"4 1.51 x 10 " 4 1.72 x 10 " 4 8.9xl0"5 7.4 x l O " 5 2.77 XlO" 4 9.74 XlO" 5 1.81 x 10" 4 1.26 x 10 ~4 1.35 x 10 ~4 1.4OxIO"4 1.62 x 10 ~4 8.6xl0"5 6.9xlO" 5 2.25 XlO" 4 9.3 x l O " 5 1.52 x l O " 4 1.46 x 10" 4 5.9xlO" 4 2.75 x l O " 5 9.03 x 10" 5 2.42 XlO" 4 3.22 x l O " 5 1.04 XlO" 4 2.84 XlO" 4 5.05 x l O " 5 2.03 x 10~4 6.24 x l O " 4 1.5 x 10" 5 5.6 x 10 " 4 7.2OxIO" 5 2.3OxIO" 4 6.9OxIO" 4 8.76IxIO" 5 8.9 x 10"5 2.2 XlO" 4 7.63 xlO" 5 2.46 x 10"4 7.12 xlO" 4 2.106 x 10"4 7.312 x 10~4 1.995 x 10"3 1.99 x 1014
Ea (kj/mol)
Notes
117.2
113.8
100.4
125.5 138.5
138.9
108.9
145.6
126.4 143.9
124.0
exp[-124.0//?7]
a,h a a a,h a a h
Refs. 200 200 324 324 324 52 52 323 323 323 323 263 263 263 263 263 42 42 263 263 263 263 263 263 263 52 52 263 263 52 52 162 162 162 162 162 162 324 324 324 311 311 38 38 38 158 48 48 38 38 38 332 332 332 332
TABLE 3. ALKYL PEROXIDES Number of C atoms
Initiator
2
Methyl peroxide
4
Ethyl peroxide
Solvent Vapor Methanol Styrene Vapor
Vapor (toluene)
5
2,4-Pentanedione peroxide
Triethyl phosphate
6
Propyl peroxide
Vapor
7
Isopropyl peroxide Allyl tert-butylperoxide
Styrene Toluene
Dimethylaminomethyl peroxide
ter/-butyl
8
tert-Butyl
peroxide
Acetic acid
Acetonitrile
Benzene
Benzhydrol terf-Butanol
2-Butanol n-Butyl mercaptan Tri-n-butylamine
T( 0 C) T(K) T(K) 60 140.2 147.8 160.0 176.5 184.5 145.9 145.9 200 210 218 226 234 245 100 115 125 146.5 155.3 166.8 175.4 60 130 140 150 160 110 120 130 115 120 125 130 95 125 115 120 125 130 80 130 100 100 115 130 120 120 120 120 120 125 130 135 125 120 125 130 135 125 125 125 135
^a(S1)
Ea (kj/mol)
1.6xlO 15 4.IxIO15 1.2xlO" 9 1.75 x 10 ~4 3.6OxIO- 4 1.08 x l O " 3 3.78 x l 0 ~ 3 7.16 x l O " 3 6.69 x l O - 4 5.02 x l O " 4 3.58 x 10 ~2 6.76xlO- 2 1.47XlO- 1 2.23XlO- 1 3.86XlO" 1 6.43XlO- 1 1.9X10" 6 6.IxIO"6 1.4 x l O " 5 2.50xl0~ 4 6.0OxIO- 4 1.95 x l O " 3 4.1OxIO- 3 6. xlO" 1 0 5.76 x l O " 5 1.785 XlO" 4 4.800xl0~ 4 1.27OxIO-3 5.5xl0~ 5 1.9 x l O " 4 4.76 x l O " 4 1.2 x l O " 5 2.19 x l O " 5 2.98 x l O " 5 6.29 x l O - 5 9.53 x 10 " 7 3.89 x l O - 5 1.19 x l O " 5 2.21 x 10~5 3.47 x l O - 5 5.63 x l O " 5 7.81xl0"8 (2.48-3.04) x 10~5 8.8 x l O " 7 8.75 XlO" 7 5.66 x l O " 6 3.0OxIO- 5 1.39 x l O - 5 7.6 x l O - 6 7.5 x l O - 6 3.7 XlO" 6 1.10 x l O - 5 1.99 x l O - 5 3.22 XlO" 5 6.19 x l O " 5 8.7xl0"5 1.41 x 10 ~5 2.49 x l O " 5 4.3OxIO- 5 7.32 x l 0 ~ 5 4.8xlO-5 1.5 x 10 ~5 (1.7±0.3) x 10" 5 (4.2 ±0.4) x 10 " 5
exp[- Ul.l/RT] exp[-153.9//?7] 147.3 131.8
Notes
a a a a a t8
132.6
92
132.2
154.8 139.1
a a a a a a a h,m6
134.5
139.7
h
129.7
d h
142.3 146.9
m 2 ,u 2 m 2 ,u 2 a
147.7
a a z (0.98) z (864) z (1620) z (3480) h
143.5
h
Refs. 72 225 92 127 127 127 127 127 187 187 87 87 87 87 87 87 337 337 337 128 128 128 128 92 321 321 321 321 303 303 303 192 192 192 192 208 208 192 192 192 192 129 129 126,337 197 126,337 126,337 33 33 33 33 192 192 192 192 140 192 192 192 192 140 140 64 64
Notes page II - 69; References page II - 70
TABLE 3. cont'd Number of C atoms 8 (cont'd)
Initiator terf-Butyl
peroxide
Solvent Tri-n-butylamine tert-Butylbenzene
Carbon tetrachloride
Chlorobenzene
Cumene
Cyclohexane
Cyclohexanol Cyclohexene
Cyclohexylamine Decane
Dodecane
Dimethylaniline
Ethyl benzoate
Af-Ethylcyclohexyl amine Heptane Hexadecane
Hexane
T( 0 C) 145 T (K) 125 135 145 T (K) 125 125 125 120 120 120 120 125 150 121 141 164 T (K) 125 135 145 T (K) 95 120 125 130 135 125 120 125 130 135 120 120 120 120 125 80 110 130 115 130 140 80 110 130 120 125 130 135 120 125 130 135 125 80 110 80 110 130 80 110
kd (s~l) (1.60±0.21) x 10~4 2.8 x 1 0 u (1.5 ±0.2) x 10~5 (5.0±0.3)xl0-5 (1.51 ±0.22) xlO~ 4 2.8 x 1014 2.1OxIO- 6 2.49 x l O - 6 2.03 xlO~ 6 9xlO"6 2.4 x l O - 6 2.3 x l O - 6 8.6 x l 0 ~ 7 1.4OxIO- 6 4.45 x 104 1.93 x l 0 ~ 5 1.93 x l O - 4 1.93 XlO" 3 4.20 x 1015 (1.6±0.1) x 10~5 (5.2 ±0.3) x 10- 5 (1.56±0.13)x 10~4 2.8 x 1014 2.48 x 10 ~7 6.3 x l O - 6 1.52 x l O - 5 2.59 XlO" 5 4.64 x l 0 ~ 5 2.4 x l O " 5 7.6 x 10~6 1.38 x l O - 5 2.81 x 10- 5 4.4IxIO-5 8.3 XlO" 6 6.2 XlO" 6 3.77 x l O " 6 2.65 XlO" 6 5.50xl0~ 5 1.39 x 10 ~8 2.0IxIO-6 2.48 XlO" 5 3.00xl0~ 6 2.16 xlO~ 5 6.66 x l 0 ~ 5 1.29 x 10 ~8 1.87 xlO~ 6 2.44 x l 0 ~ 5 9.6xlO~ 6 1.89 x l 0 ~ 5 3.41 x l 0 ~ 5 5.84 x l 0 ~ 5 1.07 x l 0 ~ 5 1.92 x l 0 ~ 5 3.39 x l 0 ~ 5 5.90xl0~ 5 4.01 x 10 ~5 1.44 x 10 ~8 2.19 xlO~ 6 1.07 x 10 ~8 1.82 xlO~ 6 2.33 xlO~ 5 1.64 x 10 ~8 2.17 xlO~ 6
EB (kj/mol)
Notes
exp[- U6A/RT\
exp[- 146A/RT] U1 s s,t6 z (0.98) z (1930) z (2890) z (5525) ui,t 6
exp[- 153.46/RT]
exp[- H6A/RT] 170.7
h
156.1
h
157.3
z (0.98) z (1275) z (2890) z (5725) h
163
a a a
148.5
h
Refs. 64 123 64 64 64 123 301 301 301 33 33 33 33 301 346 344 344 344 344 64 64 64 123 208 192 192 192 192 140 192 192 192 192 33 33 33 33 143 270 270 270 337 337 337 270 270 270 192 192 192 192 192 192 192 192 143 270 270 270 270 270 270 270
TABLE 3. cont'd Number of C atoms S (cont'd)
Initiator terf-Butyl
peroxide
Solvent 2-Methyl-2-butanol
Methyl methacrylate AT-Methylpipendine Mineral oil Nonane
Norbornanol Nujol Octane 2-Octanol Piperidine 1-Propanol Styrene Tetradecane
Tetrahydrofuran
Toluene
Triethylamine
Vapor (acetone)
Vapor (carbon tetrachloride) Vapor (chloroform) Vapor (dichlorodifluoromethane) Vapor (trichloro ethylene) Vapor (methylene chloride) Vapor (3-pentanone) Vapor (silicon tetrafluoride) Vapor (toluene) Vapor
T( 0 C)
^d(S"1)
Ea (kj/mol)
Notes
149.4
h
Refs.
120 125 130 135 T (K) 125 T (K) 80 110 130 125 125 80 110 125 125 125 T(K) 80 110 130 120 125 130 135 125 100 120 120 120 120 125 125 T(K) 120 125 130 135 127.5 131 146 151.5 162 167 145 T (K) 150
1.26 xlO" 5 2.34 XlO" 5 4.47 xlO" 5 6.8OxIO"5 2.8 x 10 14 1.54 xlO" 5 1.31 x 1015 1.36 x 10 ~8 2.0IxIO" 6 2.54 x 10 ~5 4.4xlO" 5 7.8 XlO" 7 1.48 x 10 "8 2.19 xlO" 6 5.5xl0"5 3.49 x 10 ~5 2.8xl0"5 2.8xlO 1 4 1.12 xlO" 8 1.82 xlO" 6 2.38 xlO" 5 9.7xlO" 6 1.84 XlO" 5 3.39 xlO" 5 5.76 xlO" 5 1.5 x l 0 ~ 5 6.82 x 10 ~7 1.34 XlO" 5 9.5 xlO" 6 8.OxIO- 6 5.7 xlO" 6 1.6 xlO" 5 1.62 xlO" 5 1.3OxIO16 7.9xlO~ 6 1.69 xlO" 5 3.15 xlO" 5 5.55 XlO" 5 7.4 xlO" 6 1.13 XlO" 5 6.OxIO" 5 1.03 xlO" 4 3.6 xlO~ 4 5.2 xlO" 4 1.3 xlO" 4 5.9 x 10 16 8.58 x 10 "4
150 150
1.167 xlO" 3 >(2.00 x 10 ~4)
1
130 130
150
2.35 x 10"3
1
130
150
1.017 x 10 ~3
1
130
145 T (K) 160 160 160 148 158 103.2 111.9
1.5 x 10~ 4 6.8 x 10 16 1.05 xlO" 3 1.25 x l 0 ~ 3 1.27 xlO" 3 9.OxIO- 5 2.5 xlO" 4 5.6xlO" 7 2.03 XlO" 6
exp[- U6A/RT] exp[- 154.6/RT]
u
exp[-146.4//?7]
155.2
h
z (0.98) z (2000) z (2850) z (5170)
exp[- 15S3/RT] 169.9
h
165.3 exp[- 1653/RT] 1
165.3 exp[- 1653/RT] 113.0
a,i(2.6) a,i(33) a,i(100)
192 192 192 192 123 143 376 270 270 270 140 301 270 270 140 143 140 123 270 270 270 192 192 192 192 140 197 33 33 33 33 140 143 376 192 192 192 192 238 238 238 238 238 238 125 125 130
125 125 117 117 117 88 88 227 227
Notes page 11-69; References page II - 70
TABLE 3. cont'd Number of C atoms S (cont'd)
Initiator tert-Butyl peroxide
Solvent Vapor
Vapor (He)
KBr pellets
terf-Butyl 2-chloro-l,l-dimethylethylperoxide
Cumene
sec-Butyl peroxide
Toluene Vapor Decane Dodecane Heptane Hexadecane Octane Styrene Tetradecane Chlorobenzene Chlorobenzene Chlorobenzene Chlorobenzene
Butyl peroxide
Bromo-terf-butyl peroxide Chloro-terf-butyl peroxide Bis(chloro-tert-butyl) peroxide 2-terf-Butyl peroxy-2-methyl1-propanol
T( 0 C) 120.2 129.5 138.5 145.4 125 135 145 129.6 141.0 152.5 166.8 130 140 150 160 170 129 138 149 152 139.7 147.2 154.6 159.8 T (K) 145 T(K) 149.5 160 160 160 130 140 150 160 280 290 300 310 320 330 340 350 109 127 149 120 130 140 150 100 100 80 80 80 80 80 60 80 150 150 150 150
A^(S" 1 ) 6.39 x 10 " 6 1.98 XlO- 5 6.0OxIO- 5 1.24 x l O ~ 4 1.1 x K r 5 3.6 XlO- 5 1.15 x l O - 4 1.64 x l 0 ~ 5 6.28 XlO" 5 2.25 x l O - 4 8.92 x l O - 4 1.82 x l O - 5 5.75 x l O " 5 1.75 x l O - 4 4.88 x l O " 4 1.35 x l O - 3 1.97 x l O - 5 4.3 x l O - 5 1.30 x l O ~ 4 1.62 XlO" 4 6.OxIO- 5 1.43 x l O - 4 3.22 x l O - 4 5.53 x l O - 4 3.2 x 10 16 1.3 x l O - 4 1.9xlO 1 6 1.79 XlO" 4 4.0OxIO- 4 4.53 XlO" 4 4.83 x l O - 4 1.91 x 10" 5 5.95 x l 0 ~ 5 1.78 x l O " 4 4.96 x l 0 ~ 4 7.7 1.5IxIO 1 2.77X10 1 4.87XlO 1 8.34XlO 1 1.38 x l O 2 2.13 x l O 2 3.22 x l O 2 3.8 x 10" 7 2.96 x l O - 5 4.4 x l O " 4 8.82 x 10~6 2.8OxIO- 5 9.26 x l 0 ~ 5 2.78 x l O - 4 2.7 x 10 ~6 1.5 x 10" 6 1.43 x 10 " 8 1.17 x l O " 8 2.04 x 10~8 8.8 x 10 ~9 1.58 x l O " 8 3.3 x 10 ~9 9.6xlO-9 3.63 x 10 " 4 4.15 x 10 ~A 3.11 x 10 ~4 1.16 x 10 " 3
Ea (kj/mol)
159.0
Notes
a a a a a
163.6
exp[- 163.6/RT] 161.5 exp[-161.5//?7] 156.5 i(37-132) 154.8 a,i(2.6) a,i(33) a,i(100) 156.7 U3 U3 U3 U3 154.8 i(10) i(10) i(10) i(10) i(10) KlO) i(lO) i(lO) 159.0 h
t6 t6 t6 t6 t6 142.3 t6
Refs. 227 227 227 227 64 64 64 86 86 86 86 96 96 96 96 96 88 88 88 88 63 63 63 63 63 125 175,125 83 117 117 117 277 277 277 277 111 111 111 111 111 111 111 111 241 241 241 363 363 363 363 197 197 270 270 270 270 270 92 270 346 346 346 346
TABLE 3. cont'd Number of C atoms
J(0C)
Initiator
Solvent
2-tert-Buty\ peroxy-2-methyl1-propanol-di l-Hydroxybutyl-«-butyi peroxide
Chlorobenzene
150
a-Methylstyrene
1-Hydroxyisobutyl-isobutyl peroxide
a-Methylstyrene
1-Hydroxyisobutyl-l-di-isobutyll,l-d 2 peroxide
a-Methylstyrene
Dimethylaminomethylterf-amyl peroxide
Styrene
Diethylaminomethylterf-butyl peroxide
Styrene
N-Piperidinomethyltert-buty\ peroxide
Styrene
9
tert-Butyl tert-amyl peroxide
Cumene
10
tert-Amyl peroxide
Bulk
79.4 99.4 109.9 79.4 99.4 109.9 99.5 109.8 122.0 110 120 130 110 120 130 110 120 130 110 120 130 140 125 132.2 108 128 150 T (K) 125 125 125 132.2 136.7 142.2 149.2 136.7 142.2 149.7 110 120 130 140 110 120 130 140 150 127.5 130 132.5 135 137.5 140 142.5 145 147.5 150 80 85 100 115
8 (cont'd)
Chlorobenzene
Decalin Octane Triethylamine Vapor
11 12
tert-Butyl 1,1-dimethylbutyl peroxide
Cumene
ter/-Butyl 1,1,2-trimethylpropyl peroxide
Cumene
2-Methyl-2-tert-butyl-peroxyacetate Ethyl 2-terf-butylperoxymethylpropenoate
Chlorobenzene Triisopropylbenzene
Apocamphane-1-formyl peroxide 2,2-Bis(tert-butylperoxybutane)
Benzene Benzene
A:d (s" 1 )
Ea (kj/mol)
Notes
1.23 x 10" 3 1.7 x 10~5 1.06 x l O - 4 2.9 x l O - 4 3.7 x 10" 5 2.OxIO" 4 4.8 x l O - 4 6.9xlO~ 5 1.8 x 10~4 4.2 x l O - 4 4.9xlO"5 1.19 x 10" 4 3.76 x l O " 4 4.IxIO-5 1.35 x 10~4 3.25 x l O - 4 5.5 x 10" 5 2.66 x 10 ~4 4.16 x l O - 4 3.86 x 10" 6 1.287 x l O - 5 4.3OxIO- 5 1.406 x l O - 4 5.7xlO- 5 1.15 XlO" 4 1.93 x 10 ~5 1.93 x l O " 4 1.93 x 10- 3 4.02 xlO 1 5 2.8xl0-5 3.0xl0"5 3.5 x 10 ~5 7.2 x 10~5 1.15 XlO" 4 2.16 xlO~ 4 4.8 x l O " 4 1.34 x l O - 4 2.4IxIO- 4 5.61 x 10" 4 4.38 x l O " 6 1.537 x l O " 5 4.99 x l 0 ~ 5 1.544 x l O - 4 7.07 x 10 " 6 2.374 x 10 ~5 7.62 x l 0 ~ 5 2.308 xlO~ 4 4.12 x 10 " 4 1.63 x 10~4 1.95 x l O " 4 2.16 x l O " 4 2.56 x l O - 4 3.47 XlO" 4 3.92 x l O - 4 4.68 x l O - 4 5.37 x l O - 4 6.3OxIO- 4 7.76 x l O ~ 4 2.3 x 10 ~4 3.OxIO- 6 1.9 x l 0 ~ 5 9.36 x l 0 ~ 5
Refs. 346
102.9
83.7
c c c
89.5
130.7
132.4
130.7
tn tn tn tn tn tn tn tn tn
exp[- US35/RT]
154.8-171.5
i(200-225) i(200-225) i(200-225) i(100-200) i(440-610) i(440-610) i(440-610)
C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 151
a a a
32 32 32 32 32 32 25 25 25 303 303 303 303 303 303 303 303 303 363 363 363 363 202 202 344 344 344 344 202 202 202 63 63 63 63 63 63 63 363 363 363 363 363 363 363 363 346 353 353 353 353 353 353 353 353 353 353 244 337 337 337
Notes page 11-69; References page II - 70
TABLE 3. cont'd Number of C atoms 12 (cont'd)
13
Initiator
Solvent
tert-Butyl 1,1,3,3-tetramethylbutyl peroxide
Cumene
1-Hydroxy-l-hydroperoxydicyclohexyl peroxide
Benzene
Di-(I -hydroxycyclohexyl)peroxide Diisopropylaminomethyltert-amyl peroxide
Chlorobenzene
1-Phenylethyl terf-butyl peroxide terf-Butyla-cumyl peroxide
Chlorobenzene terf-Butylbenzene
Styrene
Chlorobenzene
Cumene
Dodecane
14
15 16
terf-Butyl />-chlorocumyl peroxide tert-Butyl p-nitrocumyl peroxide tert-Butyl l,l-dimethyl-2-phenylethyl peroxide
Cumene Cumene Cumene
U-Di-(terf-butylperoxy)cyclohexane Ethyl-3,3-di-tert-butylperoxy)-butyrate l-[4-(Dimethylamino)phenyl]ethyl tert-butyl peroxide
Benzene Benzene Chlorobenzene
tert-Butyl /?-methoxycumyl peroxide tert-Butyl p-methylcumyl peroxide terf-Butyl m-methoxycumyl peroxide Bis(l, 1,2,2-tetramethylpropyl) peroxide 2-[4-(Dimethylamino)phenyl]propyl tert-buty\ peroxide l,l-Di-(terf-amylperoxy)cyclohexane tert-Butyl 3-isopropenylcumyl peroxide
Cumene Cumene Cumene Cumene Chlorobenzene
2,5-Dimethyl-2,5-di(tert-butylperoxy)-hexane
Benzene
Benzene Chlorobenzene
Chlorobenzene
2,5-Dimethyl-2,5-di(terr-butylperoxy)-3-hexyne
Benzene
T( 0 C)
kd (s" 1 )
110 120 130 140 85 100 115 130 105 120 110 120 130 129.2 138 158 115 136 159 T(K) 138 158 125 128 138 148 158 125 125 110 120 130 140 93
1.085 x 10~5 3.73 x 10 ~5 1.141 x 10~4 3.40xl0~ 4 9.6xlO~ 6 5.1 x 10 ~5 1.9 xlO~ 4 5.2 x l O - 4 ~1.9xl0~5 ~1.9xlO~4 3.9xl0"5 1.21 x 10~4 3.OxIO" 4 3.09 x 10~5 1.48 xlO~ 4 9.62 XlO" 4 1.93 x 10 ~5 1.93 xlO~ 4 1.93 x l 0 ~ 3 1.17 xlO 1 5 1.44 xlO~ 4 8.88 xlO~ 4 3.04 x l 0 ~ 5 4.44 x 10 ~5 1.39 xlO~ 4 3.21 x 10 ~4 8.88 xlO~ 4 2.42 x 10 ~5 2.20 x 10 ~5 4.35 x 10 ~6 1.458 x 10~5 4.70xl0~ 5 1.463 xlO~ 4 1.9xlO~ 5
111 100.4 110.8 120.9 129.2 129.2 125 125 125 125 129.2
1.9xl0" 5 1.82 xlO~ 6 6.97 x 10 ~6 2.18 x l 0 ~ 5 6.18 x l 0 ~ 5 5.22 x l 0 ~ 5 3.72 x 10 ~5 3.22 x 10 ~5 2.84 x 10 ~5 4.84 xlO~ 4 1.51 x 10~4
90 104 126 152 T(K) 115 130 145 115 134 156 T (K) 115 130 145 160
1.9xl0~ 5 1.93 x 10 ~5 1.93 x 10 ~4 1.93x10-3 1.161xl0 13 1.15 x l 0 ~ 5 6.86 x 10 ~5 4.75 xlO~ 4 1.93 x l 0 ~ 5 1.93 xlO~ 4 1.93 x l 0 ~ 3 1.68 x 1016 3.91 x 10 ~6 2.35 x 10 ~5 1.14 xlO~ 4 6.17 xlO~ 4
Ea (kj/mol)
Notes
a,c2 a,c2 a,c2 a,c2
132.4
tn tn tn a a
exp[-146.98//?7] a a 146.4
a a a a
a a 151.7
m2
m2
a
exp[-128.33/#7] 166.9
exp[- 155.49/RT] 156.9
a a a
a a a a
Refs. 363 363 363 363 337 337 337 337 344 344 303 303 303 282 80 80 344 344 344 344 80 80 352 80 80 80 80 352 352 363 363 363 363 338 338 282 282 282 282 282 352 352 352 352 282
338 344 344 344 344 126,337 126,337 126,337 344 344 344 344 126,337 126,337 126,337 126,337
TABLE 3. cont'd Number of C atoms 16 (cont'd)
17
18
Initiator 2,5-Dimethyl-2,5-di(terf-butylperoxy)-3-hexyne
rc-Butyl-4,4-bis(terf-butylperoxy)valerate
Solvent Chlorobenzene
Dodecane
1,1 -Bis-(terr-butylperoxy)3,3,5-trimethylcyclohexane
Benzene
Cumyl peroxide
Benzene
terr-Butylbenzene Chlorobenzene
Cumene
Dodecane
Diisopropylcarbinol Neat
Bicyclo[2.2.2]octane1-formyl peroxide
20
a,a'-Bis(tert-butyrperoxy)diisopropyl benzene
Carbon tetrachloride
Chlorobenzene Cyclohexane Isooctane Toluene Benzene
Chlorobenzene
Neat
24
TABLE 4. Number of C atoms 4
2,5-Dimethyl-2,5-di-(2-ethylhexanoylperoxy) hexane
Benzene
T( 0 C)
^d(S" 1 )
Ea (kj/mol)
Notes
Refs.
120
1.93 x 10~5
344
141 164 T (K) 100 115 130
1.93 xlO~ 4 1.93 x l O - 3 1.90 x 1015 5.83 x 10" 6 3.53 x 10 ~5 2.9IxIO-4
344 344 344 8 8 8
85 100 115 115 130 145 158 112 132 154 T (K) T (K) 138 158 128 138 148 158 138 150 155 160 165 30
6.9xlO~ 6 138 5.05 x l O - 5 2.7IxIO-4 2.05 x 10 ~5 159 1.05 x l O - 4 6.86 x l O - 4 1.72 x 10 ~3 1.93 x IO" 5 1.93 xlO~ 4 1.93 x l O - 3 9.24 x 1015 exp[- 152.61/RT] 4.31 x 1014 exp[- 1443/RT] 2.57 x l O - 4 1.52 x l O - 3 8.75XlO" 5 2.31 x 10- 4 5.37 xlO~ 4 1.83 x l O - 3 3.16 x 10~4 3.98 x 10~3 4.81 x 10- 3 9.63 x l O - 3 1.16 x l O - 2 1.71 x 10 " 4 1.73 x 10 " 3 1.68 x l O - 4 6.2OxIO" 4 6.IxIO-5 5.OxIO- 5 3.66 x 10 " 4 1.9 x l O " 5 147 4.91 x 10 ~5 9.61 x 10- 5 1.93 x 10~5 1.93 x l O - 4 1.93 x l O - 3 7.65 xlO 1 5 exp[- 152.69 kJ/RT] 3.61 x 10~3 4.44 x l O " 3 4.62 x l O - 3 1.9xlO- 5
30 30 30 30 115 125 130 114 134 156 T(K) 155 160 165 68
exp[- 150.61/RT] a a a a a a a a a a
a a a a a a a a a a a n vi
a a a
a a a a
337 337 337 337 126,337 126,337 80 344 344 344 344 67 80 80 80 80 80 80 80 371 371 371 371 244 244 244 244 244 244 244 337 337 337 344 344 344 344 371 371 371 338
ACYL PEROXIDES
Initiator Acetyl peroxide
Solvent Acetic acid
T( 0 C) 55.2 64.9 75.2 85.2 73.2
kd (s"1) 2.8 x 10~6 9.9xlO~ 6 3.75 x l O - 5 1.3OxIO- 4 2.62 x l O - 5
£ a (kj/mol)
Notes
126.4
d,e d,e d,e d,e a
Refs. 106,176 106,176 106,176 106,176 100
Notes page 11-69; References page II - 70
Table 4. cont'd Number of C atoms 4 (cont'd)
Initiator Acetyl peroxide
Solvent Benzene
H-Butanol seoButanol tert-Butanol Carbon tetrachloride
Chloroform Cyclohexane
Cyclohexene
Cyclopentene
Cumene Decane n-Dodecane Ethanol Heptane Hexadecane «-Hexane 1-Hexene
2-Methyl-l-pentene
rc-Octadecane n-Octane Isooctane
1-Pentene
Propionic acid
J( 0 C) 35 55 65 50 70 85 70 60.3 80 55.2 64.9 75.2 85.2 60.3 60.3 60.3 80.3 26 46 65 80 80.3 55.2 64.9 75.2 85.2 60 70 80 90 100 70 80 90 100 80 80 60 80 60.3 80.3 80 80 60 70 80 90 100 80 90 100 60 60 80 60 55.2 64.9 75.2 85.2 70 80 90 64.9 85.2
A^(S"1) 9.5 x 10 ~7 3.14 XlO" 6 1.27 x l O - 5 1.1 x l O " 6 2.39X10" 5 1.73 x l O " 4 2.38 XlO" 5 5.OxIO" 6 8.7xl0-5 2.6 XlO" 6 1.07x10-5 4.65x10-5 1.62 XlO" 4 3.4xlO" 5 3xl0~5 3.1xl0"6 4.9x10-5 1.08 x 10 " 7 4.84 XlO" 7 2.11 x l O " 6 5.5x10-5 ~5 2.1 x 10"6 8.3 XlO" 6 3.6OxIO- 5 1.27 XlO" 4 4.5xlO~ 6 1.77x10-5 7.0x10-5 2.28 xlO" 4 7.61X10" 4 1.6OxIO-5 7.0x10-5 2.55 XlO" 4 7.25 xlO" 4 7.6xl0-5 6.85 x l 0 ~ 5 2.3xlO" 6 6.15x10-5 1.01 x 10 " 4 1.4OxIO-3 7.72 x 10 " 5 5.39 x l O " 5 3.4xlO~ 6 2.35 x 10" 5 8.7x10-5 3.05 XlO" 4 9.83 x l O " 4 9.OxIO" 5 3.12 XlO" 4 9.81 x 10 " 4 1.9xlO" 6 2.9xlO" 6 7.34x10-5 2.9xlO~ 6 2.35 x l O " 6 9.4 XlO" 6 4.03x10-5 1.49 XlO" 4 2.45 x 10 " 5 9.4 x 10"5 3.22 XlO" 4 1.4 x l O " 5 1.66 XlO" 4
Ea (kj/mol)
Notes
134
a a a a
135.1
c,e c,e c,e c,e
133.9
131.4
c,e c,e c,e c,e
133.5
137.2
129.7
132.6
126.8
134.7
c,e c,e c,e c,e
d,e
Refs. 68 68 68 337 126,337 126,337 16 4 20 106,176 106,176 106,176 106,176 4 4 4 4 68 68 68 20 4 106,176 106,176 106,176 106,176 20 20 20 20 20 20 20 20 20 20 168 70 168 4 4 168 168 70 20 20 20 20 20 20 20 70 70 168 70 106,176 106,176 106,176 106,176 20 20 20 106,176 106,176
Table 4. cont'd Number of C atoms 4 (cont'd)
Initiator Acetyl peroxide
Solvent n-Tetradecane Toluene
Vapor (toluene)
6
Propionyl peroxide
Acetic acid Acetic anhydride Benzene
Benzonitrile Dioxane n-Hexane Isooctane Nitrobenzene Toluene Vapor
2-Iodopropionyl peroxide
Perfluoropropionyl peroxide
8
2,2,3,3-Tetrafluoropropionyl peroxide tert-Butyl permaleic acid Butyryl peroxide
Acetone Benzene
H-Butyl vinyl ether Cyclohexene 95%Ethanol Freon 113
Isooctane Freon 113 Acetone Acetic acid Acetic anhydride
J( 0 C) 60 80 60.3 55.2 64.9 75.2 85.2 73.2 85.5 90 88.0 134.7 150.7 161.7 170.7 184.2 65.0 85.0 65.0 85.0 65.0 85.0 50 70 85 65.0 85.0 65.0 85.0 65.0 85.0 65.0 86.5 65.0 85.0 65.0 85.0 65.0 85.0 99.4 134.4 152.2 176.4 190.9 T (K) 56 62.5 62.5 62.5 62.5 62.5 62.5 20 30 40 T (K) T(K) 25 35 87 65.0 85.0 65.0 85.0
^d(S1) 2.OxIO" 6 5.9OxIO" 5 5xlO"6 2.7 xlO~ 6 1.14 x l O " 5 4.70xl0~ 5 1.59 xlO~ 4 3.06 XlO" 5 1.72 XlO" 4 7.33 x l O " 5 3.12 x l O " 4 3.1 x 10" 2 1.18XlO"1 2.77XlO" 1 6.10X10" 1 1.76 3.8xlO~ 5 4.3 XlO" 4 3.5 x l O " 5 4.5 x l O " 4 1.88 x KT 5 2.4OxIO" 4 2.72 x l O " 6 4.3OxIO" 5 2.89 XlO" 4 3.9xl0"5 5.IxIO"4 4.5 x 10~5 4.5 x l O " 4 1.50x 10" 5 1.72 x l O " 4 9.8 x l O " 6 1.44 x l O " 4 3.7xl0"5 4.1 x 10 " 4 1.87 x l O " 5 2.54 x l O " 4 1.0 x l O " 5 1.6 xlO~ 4 8 xlO"4 2.6 XlO" 2 1.22XlO- 1 8.OxIO" 1 2.33 2.5 x 10 " 4 2.19 x 10 ~4 (2.40-2.81) x 10 ~4 7.12 XlO" 4 (2.36 ±0.07) x 10 ~4 2.47 x 10" 4 2.7xlO" 4 4.OxIO" 4 2.19 x 10 " 5 8.5OxIO- 5 3.26 XlO" 4 1.8 x 109 1.5xlO 17 2.26 x 10 " 4 7.17 x 10 " 4 1.9xlO~ 5 4.7 x 10" 5 5.6 x l O " 4 4.3 x 10 " 5 5.5 x l O " 4
Ea (kj/mol)
129.7 133.9
138.1 129.7 123.4
123.0 128.9 129.3 127.6
130.5 116.7
Notes
c,e c,e c,e c,e a a a
c,e c,e d,e c,e c,e c,e a a a d,e d,e c,e c,e
123.8 130.5 120.9
c,e c,e c,e
130.1 125.5 125.5
exp[- 125.5/RT]
100.1
s s n,s p s s s h
exp[- 83.8//?7] exp[- 121.5/RT} 86.3
h
108.8
125.1
a c,e c,e c,e
Refs. 70 168 4 106,176 106,176 106,176 106,176 100 100 113 105 105 105 105 105 105 51 51 51 51 51 51 126,337 126,337 126,337 51 51 51 51 51 51 51 51 51 51 51 51 51 51 85 85 85 85 85 85 77 77 77 77 77 77 77 283 283 283 304 304 283 283 338 51 51 51 51
Notes page II - 69; References page II - 70
Table 4. cont'd Number of C atoms 8 (cont'd)
Initiator Butyryl peroxide
Solvent Benzene Benzonitrile Dioxane Hexane Isooctane Toluene Vapor
Isobutyryl peroxide
Acetonitrile Benzene
Benzonitrile tert-Butanol Carbon tetrachloride
Chlorobenzene
Chloroform Cyclohexane Fluorobenzene Isooctane
Cyclopropane formyl peroxide
Isopropanol Nitrobenzene Nujol Tetralin Toluene Vapor p-Xylene Carbon tetrachloride
Diacetyl succinoyl diperoxide
Styrene
Succinoyl peroxide
Acetone
T( 0 C) 65.0 85.0 65.0 85.0 65.0 85.0 65.0 85.0 65.0 85.0 65.0 85.0 65.0 85.0 96.7 127.4 158.9 178.9 T(K) 40 20 30 40 40 40 40 40 40 45 50 55 60 40 23 39 57 T (K) 40 40 40 40 25 35 45 55 T (K) 40 40 40 40 40 40 40 40 64.5 70.4 77.8 60 73.5 85 70 85 100
^a(S1) 2.24 x 10~5 3.02 x l O - 4 4.3 x 10~5 5.8 x l O - 4 4.6xlO~ 5 4.6 x l O - 4 1.14 x 10~5 1.53 x l O - 4 1.11 x 10~5 1.56 x l O " 4 2.14 x l O " 5 2.87 x l O - 4 1.6 x l O " 5 2.OxIO- 4 8.6 x l O " 4 1.5 XlO" 2 3.OxIO" 1 1.27 1.9 xlO~ 4 6.81 x 10 " 4 1.6 x l O " 5 6.75 x l O - 5 2.59 x l O - 4 2.38 XlO" 4 2.4OxIO- 4 4.2xlO~ 4 2.5IxIO" 4 7.8xl0"5 1.58 XlO" 4 3.05 x l O - 4 5.61 x 10~4 7.67 xlO~ 4 1.73 x 10 " 4 1.93 x l O - 5 1.93 x l O - 4 1.93 XlO" 3 3.37 xlO 1 4 7.5 x 10 ~5 4.5 x 10 ~5 4.7OxIO- 5 1.23 x 10 " 4 3.35 x 10 ~6 1.54 XlO" 5 6.14 x l O - 5 2.26 x l O - 4 2.8 x 1014 3.2 x l O " 5 3.05 x 10~4 5.8OxIO- 4 4.63 XlO" 5 1.75 x 10 ~4 1.43 x 10 ~4 -1 x 10 ~5 1.4OxIO- 4 4.4xlO" 6 9.3 x 10 ~6 2.31 x 10- 5 5.2xlO~~6 2.3 x l O - 5 9.3 x 10- 5 2.8OxIO- 5 1.21 x 10- 4 4.36 x l O - 4
Ea (kj/mol)
Notes
131.4
d,e c,e d,e
131.4 116.3 131.4 133.5 130.5
c,e c,e c,e c,e c,e c,e d,e c,e
123.8 123.8
exp[-123.8//?7] 109
1113 a a a In3
exp[- 109.06//?7]
114.2
exp[- 1H2/RT]
125.5
99.6
a a a
Refs. 51 51 51 51 51 51 51 51 51 51 51 51 51 51 85 85 85 85 85 167 337 337 337 167 148,244 148 148 148 148 148 148 148 148 344 344 344 344 148 148 167 148 84 84 84 84 84 148 148 148 167 148 148 167 148 34 34 34 215 215 215 126,337 126,337 126,337
Table 4. cont'd Number of C atoms 9
10
11
Initiator Acetyl benzoyl peroxide
T( 0 C)
Chlorobenzene
70 96 96 75 75 75 41 41 65 70 75 14 25 44.5 56.5 44.5 60 73.5 85 50 60 70
5-Bromo-2-thenoyl peroxide 4-Bromo-2-thenoyl peroxide 5-Chloro-2-thenoyl peroxide a-Chloropropionyl m-chlorobenzoylperoxide Cyclobutane formyl peroxide
Carbon tetrachloride Carbon tetrachloride Carbon tetrachloride Acetonitrile Cyclohexane Carbon tetrachloride
Cyclopropane acetyl peroxide
Carbon tetrachloride
Diacetyladipoyl diperoxide
Styrene
Difuroyl peroxide
styrene
2,2,3,3,4,4,5,5-Octafluoropentanoyl peroxide
Freon 113
Perfluoro-2-(2-ethoxysulfinic acid) propionyl peroxide Pivaloyl peroxide 2-Thenoyl peroxide 3-Thenoyl peroxide Benzoyl isobutyryl peroxide
m-Chlorobenzoyl isobutyryl peroxide
12
Solvent
Freon 113 Carbon tetrachloride Carbon tetrachloride Carbon tetrachloride Acetonitrile Cyclohexane
Acetonitrile Cyclohexane
p-Chlorobenzoyl isobutyryl peroxide
Cyclohexane
p-Fluorobenzoyl isobutyryl peroxide
Cyclohexane
5-Methyl-bis-2-thenoyl peroxide p-Nitrobenzoyl isobutyryl peroxide
Carbon tetrachloride Cyclohexane
P-Allyloxypropionyl peroxide
Toluene
p-Xylene
m-Chlorobenzoyl 2-methylbutanoyl peroxide
Acetic acid Acetonitrile
kd (s"1) 2xl0~5 5.12 x l O " 4 4.08 XlO" 4 1.53 x 10 " 5 1.14 x 10 ~5 1.58 x 10 ~5 3.05 x 10 ~5 1.51xl0~ 5 5.15 x 10 " 5 8.95,6.63 x l O " 5 1.41 x 10" 4 9.45 x 10 ~5 9.75,10.57 x 10" 4 5.01 x 10 " 5 2.64 XlO" 4 6.5-8.OxIO" 4 6.6xlO" 6 4.73 XlO" 5 1.84 x l O " 4 7.0xl0"7 2.9 xlO~ 6 1.03 XlO" 5
20 30 40 T(K)
3.29 x 10 " 5 1.27 XlO" 4 5.01 x 10 " 4 2.8xlO 1 4
10 75 75 41 41 70 40 50 60 70 41 40 50 41 50 55 60 65 55 60 65 70 75 40 45 50 55 60 70 80 90 70 80 90 40 40
1.9xlO~ 4 2.21 x 10 ~~5 2.14 x 10 " 5 4.06 x 10 " 4 1.63 x l O " 5 3.05 xlO~ 4 1.45 x l O - 5 5.398 XlO" 5 1.924 x l O " 4 6.872 x l O " 4 1.03 x 10 ~3 3.486 x 10 " 5 1.362 x l O " 4 4.4OxIO- 5 1.029 x 10 ~4 1.651 x 10- 4 3.21 x 10- 4 5.638 x l O - 4 1.117 x 10 " 4 2.038 XlO" 4 4.893 x l O - 4 9.603 x l O " 4 2.92 x 10 " 5 8.1xl0"5 1.336 x l O " 4 2.889 x l O - 4 4.725 X l O ' 4 8.921 x 10 ~4 2.0IxIO" 5 8.62 x l O " 5 2.53 x l O " 4 2.32 x l O " 5 8.88 x l O " 5 2.95 x l O " 4 1.60 x 10 ~3 1.72 x 10 " 3
Ea (kj/mol)
Notes
z(25),vi3 z(19),vi3 a,mi a,mi a,mi ni3 ni3
101.7 n
125.7
h
100.6
h
exp[-95.1//?7]
a,mi a,mi
112.5
h,j j j j
111.3
h,j j j
a
a a a a a a
Refs. 155 284 284 232 232 232 167 167 34 34 34 34 34 24 24 24 215 215 215 287 287 287 283 283 283 304 244 232 232 167 167 167 164 164 164 164 167 164 164 167 164 164 164 164 164 164 164 164 232 164 164 164 164 164 191 191 191 191 191 191 256 256
Notes page II - 69; References page II - 70
Table 4. cont'd Number of C atoms 12 (cont'd)
14
Initiator m-Chlorobenzoyl 2-methylbutanoyl peroxide
Solvent
Cyclobutane acetyl peroxide
2-Butanol Carbon tetrachloride Cyclohexane Carbon tetrachloride
Cyclopentane formyl peroxide
Carbon tetrachloride
Hexanoyl peroxide 5-Hexenoyl peroxide
Toluene Toluene
4-Methoxybenzoyl isobutyrylperoxide
Cyclohexane
4-Methylbenzoyl isobutyrylperoxide
Cyclohexane
4-Methyl-2-thenoyl peroxide 5-Methyl-2-thenoyl peroxide Perfluoro-2-furnanacetyl peroxide Perfluoro-2-propoxypropionylperoxide Perfluoro-2-n-propoxypropionylperoxide
Carbon tetrachloride Carbon tetrachloride Freon 113 Freon 113 perF-ether mix. Freon 113
Perfluoro-2-iso-propoxypropionylperoxide
Freon 113
2-Azidobenzoyl peroxide
Benzene
Benzoyl peroxide
Acetic acid Acetone
Acetonitrile Acetophenone
Allyl alcohol Anisole Benzaldehyde Benzene
T( 0 C) 40 40 40 65 70 75 40 45 50 55 77 60.1 70.4 76.4 85.0 55 60 65 70 40 50 60 70 75 75 T (K) T(K) T (K) 20 30 40 20 30 40 50 80 75 50 70 85 100 70 70 80 94.5 80 30 80 90 25 30 55 60 60 80 70 78 78 79.8 80 66 72.5 78 70
kd (s"1) 9.0xl0~4 1.32 x 10 ~4 6.OxIO" 5 1.37 x 10 ~5 2.13,3.08 x 10- 5 3.83 x l O - 5 1.50 x 10 ~5 2.55 XlO" 5 4.96 XlO" 5 8.17,7.85 x 10" 5 1.186 x 10 ~4 1.06 x 10 " 5 4.15 XlO" 5 8.59 x l O " 5 2.668 x l O - 4 5.465 x 10 ~5 1.024 x l O " 4 1.876 XlO" 4 3.208 XlO" 4 9.6IxIO" 6 3.619 x l 0 ~ 5 1.305 XlO" 4 4.772 x l O " 4 2.92 x 10 " 5 4.21 x 10 ~5 1.2 x 1011 4.4xlO 1 4 8.9 x 1016 4.81 x 10 ~5 1.96 x 10 ~4 7.16 XlO" 4 8.32 x 10 ~5 3.43 x 10 ~4 1.34 x l 0 ~ 3 2.5 x 10~5 9.4 XlO" 4 7.53 x 10 " 5 2.25 x 10 ~6 2.63X10- 5 1.34 xlO~ 4 5.83 xlO~ 4 1.76 x 10 ~5 1.15 x 10~5 4.32xlO- 5 2.30xl0~ 4 3.80 x 10 ~4 1.42 x 10 ~7 5.50xl0~ 5 1.71 x 10- 4 6.4xlO~ 5 4.80 xlO~ 8 1.14 xlO~ 6 2.76 xlO~ 6 2.0xl0~6 2.5xlO-5 1.38x10-5 2.3OxIO- 5 1.67x10-5 3.48x10-5 4.8x10-5 7.72 x 10 ~6 1.87x10-5 3.77x10-5 1.17x10-5
Ea (kj/mol)
129.3
Notes
c c c c
j j j j a,mi ^m1 exp[- 11A/RT] exp[- 9Z.5/RT] exp[-110.2/RT] 100.1
h
102.7
h
111.3
126.4
116.3
124.3
129.7
133.9
d2 d2 a,r a a a a tj a a a a,r a a,r a,r p2 a a,r a,r m2 m2 a c X9
a a a a
Refs. 256 256 256 34 34 34 34 34 34 34 209 209 209 209 209 164 164 164 164 164 164 164 164 232 232 304 304 304 283 283 283 283 283 283 161 161 74 126 126 126 126 124 5 5 5 74 109 74 74 279 109 74 74 14 14 213 230 230 170 20 131 131 131 73
Table 4. cont'd Number of C atoms 14 (cont'd)
Initiator Benzoyl peroxide
Solvent Benzene
Benzyl alcohol Bromobenzene
Butanol Butanone Di-n-butyl phthalate
Carbon tetrachloride Chlorobenzene
Chloroform Cumene
Cyclohexane Decane Decalin Dioxane
J( 0 C) 75 80 80 50.8 54.9 60.9 65.6 71.0 75.8 70 85 100 70 70 75 75 85 85 100 100 79 80 80 80.2
80 80 117 127 137 147 75 79 70 80 80.2 80.2 80.2 80.2 71 91 113 T (K) 30 80 85 90 30 45 60 80 T (K) 100 80 80 80 70 80 80 80
kd (s"1) 2.62 x 10 " 5 4.39 XlO" 5 3.27 XlO" 5 4.28 XlO" 7 8.53 x l O - 7 1.66 x l O - 6 3.22 XlO" 6 5.94 x l O - 6 1.19 XlO" 5 1.27 XlO" 5 8.94 x l O - 5 4.96 x l O - 4 1.03 x l O - 5 1.18 XlO" 5 1.48 x l O - 5 1.66 x l O - 5 4.7 x l O - 5 5.5 XlO" 5 2.28 x l O - 4 2.56 x l O " 4 2.58 x l O - 5 3.35 x l O " 5 4.44 x 10 " 4 8.15 x l O " 5 2.19 x l O " 5 3.84 x l O - 5 3.55 x l 0 ~ 5 4.34 x l O - 5 6.06 x 10 " 4 4.64 x 10 " 5 2.78 x 10 ~3 7.44 X l O " 3 1.72 x l O - 2 3.89 X l O " 2 1.07 x 10 " 5 1.69 X l O " 5 1.35 x 10 ~5 4.64 x l O - 5 2.85 x l O " 5 2.36 x l O - 5 3.52 x l 0 ~ 5 2.62 X l O " 5 1.93 x l O - 5 1.93 x l O " 4 1.93 XlO" 3 6.94 x l O 1 3 5.47 x 10 ~8 3.69 x 10 ~5 6.39 XlO" 5 1.19 x l O - 4 7.3OxIO- 8 1.85 x l O 7 1.45 x l O - 6 1.70 XlO" 5 1.20 x 10 13 2.5 XlO" 4 7.72 x 10 ~5 2.53 x 10 " 5 2.26 x 10 " 4 1.30 x 10 " 5 6.72 x l O - 4 4.2OxIO- 4 4.18 x l 0 ~ 5
Ea (kj/mol)
123.8
130
128.0 124.3
Notes a a a,b 2 a,t2 a,t2 a,t2 a,t2 a,t2 a,t2 a a a a,m2 t2 m3 m3 m3 a,t6 a a,r t9
Hi1 m3 m5
120.1
a,r a,r yi6
a,r t 6 ,a I1 a,r t9 Cm 1 c,m 3
exp[- 12235/RT] a a,r a,r a,r a 120.5
exp[- 120.5/RT] a,t7 a,r a,r ti a,r a,r a,m!
Refs. 73 73 347 69 69 69 69 69 69 337 126,337 126,337 16 124 12 12 12 12 12 12 120 7 74 231 231 231 231 231 74 74 236 236 236 236 74 121 124 74 231 231 231 231 344 344 344 344 109 74 74 74 109 67 67 67 67 122 74 270 74 74 74 6 232
Notes page 11-69; References page 11-70
Table 4. cont'd Number of C atoms 14 (cont'd)
Initiator Benzoyl peroxide
Solvent Ethanol
Ethylbenzene
90% Formic acid H-Heptane
Hexadecane Hexane Isooctane Isopropylbenzene Methyl acetate Methylcyclohexane 4-Methyl-2pentanone a-Methylstyrene Mineral oil Neat Nitrobenzene PEG 400
90% aq. PEG 400
80% aq. PEG 400
70% aq. PEG 400
rt-Pentanol Phenol Propionic acid Propylene glycol
Styrene
T( 0 C) 25 40 50 30 75 80 85 90 80 80 80 80 130 135 140 145 145 145 145 150 155 160 80 80 80 80 80 49.2 53.9 80 80 70 80 105 80 30 25 40 50 70 25 40 50 70 25 40 50 70 25 40 50 70 80 80 80 25 40 50 34.8 49.4 61.0 74.8 100.0
^d(S1) 3.02 x l O ~ 8 2.77 x l O " 7 4.72 x l O - 7 3.61 x 10 " 8 1.8IxIO- 5 3.33 XlO" 5 5.56 XlO" 5 1.01 x 10- 4 3.15 x l 0 ~ 5 6.94 x 10 " 4 3.11 x 10 ~5 2.7IxIO-5 5.73 XlO" 3 1.02 x l O " 2 1.54 x l O - 2 2.25 XlO" 2 2.22xlO-2 2.21 x 10~2 2.12 x l O - 2 3.47 x l O " 2 5.21 x 10- 2 7.87 x l O - 2 2.51 x 10 " 5 2.85 x 10 ~5 2.79 x 10 ~5 2.7OxIO" 5 3.34 x 10~5 6.28 x 10 ~7 1.0 XlO" 6 5.25 x 10 ~5 4.28 x 10 ~5 3.02 x 10 " 5 2.89 x 10~5 7.22 x 10 ~3 4.58 x 10 ~5 6.6IxIO-8 5.0IxIO-7 5.73 x l O - 6 1.15 x l 0 ~ 5 1.15 XlO" 4 3.65 x 10~7 5.35 x l O " 6 1.15 x l O - 5 1.15 x l O " 4 2.77 x 10 ~7 3.09 x l O " 6 7.29 x l O - 6 1.15 x l O - 4 1.71 x 10 ~7 2.1IxIO-6 5.01 x 10- 6 1.15 x l O " 4 1.48 x 10 ~4 6.25 x 10 " 4 3.19 x 10~5 3.25 x 10 ~8 1.51 x l O ~ 7 3.16 x l O - 7 3.89 x 10 ~8 5.28 XlO" 7 2.58 x l O - 6 1.83 x l 0 ~ 5 4.58 x l O " 4
£ a (kj/mol)
Notes a a a a a,r a,r a,r a,r c a,r a,r z (1500) z (1500) z (1500) z (500) z (1000) z (1500) z (2000) z (1500) z (1500) z (1500)
123.8
117.6
m2 c a,t2 a,t2 a,r a,r a m2 a a,r a a a a a a a a a a a a a a a a a a,r a,r a,r a a a a a a a a
Refs. 351 351 351 109 74 74 74 74 239 74 74 270 377 377 377 377 377 377 377 377 377 377 270 270 270 308 229 69 69 74 74 213 308 371 74 109 351 351 351 351 351 351 351 351 351 351 351 352 351 351 351 351 74 74 74 351 351 351 10 10 10 10 10
Table 4. cont'd Number of C atoms 14 (cont'd)
Initiator Benzoyl peroxide
Solvent Poly(styrene)
Tetradecane Tetralin Toluene
Poly(vinylchloride)
Styrene
3-Bromobenzoyl peroxide
4-Bromobenzoyl peroxide 4-terr-Butylbenzoyl peroxide 2-Chlorobenzoyl peroxide 3-Chlorobenzoyl peroxide 4-Chlorobenzoyl peroxide
p-Xylene Benzene
Dioxane Dioxane Dioxane Acetophenone Benzene Acetophenone Dioxane Acetophenone Benzene
Dioxane Styrene
Cyclohexane formyl peroxide
Benzene
Carbon tetrachloride
Cyclopentane acetyl peroxide
Carbon tetrachloride
Diacetylsebacoyl diperoxide
Carbon tetrachloride
T( 0 C) 56.4 64.6 76.7 83.4 98.5 70.9 80.1 89.5 80 80 30 49.0 55.1 60.2 65.1 70.3 60.00 64.6 76.7 83.4 98.5 50 60 70 80 60 80 80 80 80 80 80 80 80 80 80 80 50 85 100 80 34.8 49.4 61.0 74.8 100.0 30 35 40 45 50 35 45 50 60 35 40 45 65 70 75 60 73.5 85
^d(S"1) 3.8 x 10~7 1.47 x l O - 6 9.27 x l O " 6 2.5OxIO- 5 1.41 x l O " 4 2.86 x l O - 6 1.11 x l O - 5 3.33 x l O - 5 2.64 x 10 ~5 3.72 x 10 " 5 4.94 x l O " 8 6.OxIO- 7 1.31 x 10- 6 2.83 x l O - 6 5.69 x l O - 6 1.10 x l O - 5 2.24 x l O " 6 6.3xlO" 7 5.11 XlO" 6 1.44 x l O - 5 9.33 x l O " 5 7 x IO" 7 7.7 x l O - 6 9.9 x l O " 6 3.1OxIO- 5 1.1 x 10 " 6 1.22 x l O - 5 2.6OxIO- 5 2.57 x 10 ~5 3.23 x 10 ~5 6.06 x 10 ~5 3.88 x 10 " 4 3.12 x 10 " 4 2.85 x 10 ~5 2.63 x 10 ~5 3.83 x 10 " 5 2.17 x 10 ~5 6.2 x l O " 7 6.64 x l O - 5 3.86 x l O - 4 3.62 x 10 " 5 8.3xl0-8 8.3 x l O " 7 3.33 x l O - 6 2.22 x l O - 5 4.17 x l O - 4 9.64 x 10 ~5 1.46 x l O " 4 3.1OxIO- 4 5.11xlO" 4 7.77 x l O - 4 6.6xlO~~5 2.1IxIO-4 4.45 xlO~ 4 1.3OxlO" 3 2.87 x l O - 5 5.22,5.29 x 10 " 5 9.67 x l O - 5 1.48 x 10" 5 3.2OxIO" 5 4.97 x l O - 5 1.04 x 10 ~5 5.20xl0~5 2.3OxIO- 4
E a (kj/mol)
120.5 123.8
Notes
Refs.
a a a a a a a a
17 17 17 17 17 15 15 15 270 74 109 69 69 69 69 69 291 17 17 17 17 287 287 287 229 116 116 7 6,232 6,232 232 5 7 5 6 5 7 126 126 126 6 10 10 10 10 10 219 219 219 219 219 148 148 148 148 34 34 34 34 34 34 215 215 215
a,r a a,t2 a,t2 a,t2 a,t2 a,t2 e,m3 a a a a
125.7
c
123.0 128.4 127.2 128.9
84.5
a a,mi a,mi a,m a a a a,mi a a a a a ^m1 a a a a a a,h
Xi X1 xi
Notes page 11-69; References page II - 70
Table 4. cont'd Number of C atoms 14 (cont'd)
Initiator 2,4-Dichlorobenzoyl peroxide
Solvent Benzene
Styrene
2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoroheptanoyl peroxide Heptanoyl peroxide 6-Heptenoyl peroxide
2-Iodobenzoyl peroxide 2-Iodobenzoyl 4-nitrobenzoyl peroxide
3-Methylbenzoyl peroxide 4-Methylbenzoyl peroxide 2-Nitrobenzoyl peroxide
Freon 113 Toluene Toluene
Chloroform Acetone Acetonitrile Benzene Carbon tetrachloride Chloroform Nitrobenzene Dioxane Dioxane Acetophenone Methyl iodide
15
16
3-Nitrobenzoyl peroxide 4-Nitrobenzoyl peroxide 3,5-Dinitrobenzoyl peroxide Perfluoroheptanoyl peroxide
Acetophenone Acetophenone Acetophenone Freon 113
Benzoyl phenylacetyl peroxide
Benzene
4-terf-Butylbenzoyl isobutyryl peroxide
Cyclohexane
3-Cyanobenzoyl benzoyl peroxide 3-Methoxybenzoyl benzoyl peroxide 4-Methoxybenzoyl benzoyl peroxide 4-Methoxybenzoyl 3-bromobenzoyl peroxide 4-Methoxybenzoyl-3,5-dinitrobenzoyl peroxide
Dioxane Dioxane Dioxane Dioxane Benzene Nitrobenzene
J( 0 C) 70 70 50 70 85 34.8 49.4 61.0 74.8 100.0 30 40 77 70 70 77 85 22 25 25 25 25 25 25 80 80 59.3 80 24.95 45.05 80 80 80 20 30 40 20 25 25 25 30 35 55 60 65 70 80 80 80 80
^d(S" 1 ) 9.7OxIO" 5 1.24 xlO~ 4 1.08 xlO~ 5 1.37 xlO~ 4 7.69 XlO" 4 3.88 x 10 " 6 2.39 x l 0 ~ 5 7.78 xlO~ 5 2.78 xlO~ 4 4.17 x l 0 ~ 3 1.14 x 10~4 4.06 x 10 ~4 1.24 x 10 ~4 5.33 x 10 ~5 5.01 x 10 ~5 1.07 xlO~ 4 2.88 xlO~ 4 1.86 x 10 ~3 3.0xl0~4 2.1x 10 ~4 5.7xl0~5 3.4xl0~5 2.8xlO~ 4 6.2xlO~ 4 4.38 x 10 ~5 6.11 x 10 ~5 5.80xl0~ 5 1.34 x l 0 ~ 3 1.78 xlO~ 5 1.50xl0~ 4 3.80xl0"5 4.33 x 10 " 5 1.87 x l 0 ~ 5 3.01 x 10 ~5 1.11 xlO~ 4 4.20xl0~4 1.10 x 10~4 2.05 xlO~ 4 3.15 xlO~ 4 6.38 xlO~ 4 3.88 xlO~ 4 6.67 xlO~ 4 6.543 x 10 ~5 1.171 x 10~4 2.663 xlO~ 4 5.016 xlO~ 4 2.73 x 10 ~2 4.82 x 10 ~2 7.57 x 10 ~5 4.43 x 10 ~2
£ a (kj/mol)
117.6
100.6
Notes a,j a,k a a a a a a a a h a a,k a,j a,j a,k
119.7 81.2 126.4 126.8 130.5 98.0
a,mi a,mi a a h a a a
90.8 vi n
ti 0 tio t 10 tio a,m\ a,mi a,mi a,mi
Refs. 16 16 126,337 126,337 126,337 10 10 10 10 10 283 283 19 19 19 19 19 82 78 78 78 78 78 78 232 232 5 5 82 82 5 5 5 283 283 283 222 222 222 222 222 222 164 164 164 164 6 6 6 6
51 51 51
1.02 x 10 ~5 9.61 x 10 ~4 1.67 XlO" 3
t5
108 108 108
a a
89 89
a a a
95 116 116 126 126 126
4-Methoxybenzoyl 4-nitrobenzoyl peroxide
Benzene
70 70
2.08 x 10 ~5 8.03 x l 0 ~ 5
3,5-Dibromo-4-methoxybenzoyl peroxide
Benzene
Caprylyl peroxide
Benzene
60 60 80 50 70 85
9.5 x 10 ~7 6.1 xlO~ 7 9.4 x 10 ~6 3.44 x 10 ~6 5.78 x l 0 ~ 5 3.78 xlO~ 4
128.9
Table 4. cont'd Number of C atoms 16 (cont'd)
Initiator
Solvent
Caprylyl peroxide /7-(Chloromethyl)benzoyl peroxide
Mineral oil Acetone
3-Cyanobenzoyl peroxide 4-Cyanobenzoyl peroxide Cycloheptane formyl peroxide
THF Toluene Dioxane Acetophenone Dioxane Carbon tetrachloride
Cyclohexane acetyl peroxide
Carbon tetrachloride
2-Ethyl-4-methyl-2-pentenoyl peroxide 2-Ethylhexanoyl peroxide 2-Ethyl-2-hexenoyl peroxide 2-Iodophenylacetyl peroxide
2-Methoxybenzoyl peroxide 3-Methoxybenzoyl peroxide 4-Methoxybenzoyl peroxide 2-Methylbenzoyl peroxide 3-Methylbenzoyl peroxide 4-Methylbenzoyl peroxide Endo-norbornane-2-carbonylperoxide
Mineral oil Mineral oil Mineral oil Acetone Chloroform Toluene Acetophenone Acetophenone Dioxane Acetophenone Dioxane Acetophenone Acetophenone Dioxane Acetophenone Dioxane Carbon tetrachloride
Exo-norbornane-2-carbonylperoxide
Carbon tetrachloride
Endo-norbornene-5-carbonylperoxide
Carbon tetrachloride
Exo-norbornene-5-carbonylperoxide
Carbon tetrachloride
Dioctanoyl peroxide
w-Heptane
T( 0 C) T (K) 70 70 70 70 80 80 80 35 40 45 65 70 75 54.4 64.3 71.8 T(K) T(K) T (K) 0 0 0 50 80 80 80 80 80 70 80 80 80 80
A^(S"1)
Ea (kj/mol)
9.8 x 1015 2.07 x 10 ~5 1.82 x l O " 5 1.15 XlO" 5 8.8xl0"6 1.70 x 10 ~2 2.43 x 10 ~5 2.03 x 10 " 5 7.85 x 10 ~5 1.63,1.34XlO"5 2.02 XlO" 4 1.27 x 10 " 5 2.76 XlO" 5 3.61 x 10 " 5 3.1 x 10 " 6 1.19 x l O " 5 2.95 XlO" 5
exp[- UOA/RT]
7.IxIO16 1.2xlO 14 1.6 x 1016 2.6OxIO" 5 3.98 x 10 ~5 1.3xlO" 5 6.0xl0"5 2.15 XlO" 3 6.42 x 10 " 5 5.75 x 10 ~5 1.56 x 10 " 4 1.18 x 10 ~A 9.02 x 10 " 5 4.7OxIO" 5 4.4OxIO" 5 5.92 x 10 " 5 6.13 x 10~5
exp[-138.4//?7] exp[- 106A/RT] exp[-136.3//?7]
Notes
m7
a,mi a a,mi
113.8 120.9 120.1 126.4 126.4 125.1
Refs. 1 307 307 307 307 6 5 6 34 34 34 34 34 34 24 24 24
c,e,q q a a a a,mi a a,mi a a a,mi a a,mi
1 1 1 79 79 79 5 5 5 6 5 6 5 5 6 5 6
44.5 53.9 65.9
6.IxIO"6 2.83 XlO" 5 1.25 XlO" 4
j j j
23 23 23
44.5 53.9 65.9 44.5 53.9 65.9 44.5 53.9 65.9 44.5 53.9 65.9 445 53.9 65.9 44.5 53.9 65.9 44.5 53.9 65.9 70 80 80
9.1 x 10" 6 4.33 x l O " 5 1.28 x l O " 4 4.68 x 10 " 5 2.05 x 10 " 4 8.18 xlO~ 4 7.2 XlO" 5 1.6OxIO"4 8.48 XlO" 4 6.30xl0~ 5 1.2IxIO" 4 7.18 x l O " 4 2.22 x l O " 5 4.52 XlO" 5 2.37 x l O " 4 6.58 x 10 " 5 1.2IxIO- 4 8.42 XlO" 4 2.58 xlO~ 5 1.2OxIO"4 7.1OxIO- 4 1.70xl0" 5 7.0IxIO-5 6.8OxIO- 5
j,m 2 j , m2 j,m 2 j j j j , m2 j,m 2 j , m2 j j j j,m 2 j,m 2 j,m 2 j j j j,m 2 j,m 2 j,m 2 z (1500) z (500) z (1000)
23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 377 377 377
Notes page 11-69; References page 11-70
Table 4. Number of C atoms 16 (cont'd)
18
cont'd
Initiator
Solvent
T( 0 C)
^d(S1)
Ea (kj/mol)
Notes
Refs.
80 80 80 90 95 100 63 80 100 T (K) 20 20 20 20 0 0 18 80 80 80
6.27 x 10~5 6.01 x l 0 ~ 5 5.77xlO-5 2.13 x l O ~ 4 3.8OxIO- 4 6.79 x l O ~ 4 1.93 x 10 ~5 1.93 x l O - 4 1.93 x l O - 3 2.30 x 10 15 1.02 x 10 ~3 4.76 x 10 ~4 1.86 x 10 ~4 1.6OxIO- 4 7.8xl0~5 2.5OxIO- 5 3.34 XlO" 4 1.42 x 10 ~4 1.4 x l O ~ 4 2.3 x 10 ~4
Acetonitrile 2-Butanol Carbon tetrachloride Cyclohexane
40 40 40 40
5.9xl0~3 4.4xlO~ 3 6.7 x 10 ~4 4.4xlO~ 4
256 256 256 256
5-terf-Butylthenoyl peroxide Cinnamoyl peroxide
Acetonitrile 2-Butanol Carbon tetrachloride Cyclohexane Carbon tetrachloride Styrene
Dibenzoyl succinoyl diperoxide
Unknown
Nonanoyl peroxide Isononanoyl peroxide (3,5,5trimethylhexanoyl peroxide)
Mineral oil
40 40 40 40 75 50 70 70 75 85 T(K)
4.2xlO~ 3 2.8 x 10 ~3 6.5 x 10 ~4 3.9xlO~ 4 4.03 x 10 ~5 1.2OxIO- 5 1.67 x l O - 4 7.7 x 10 ~6 1.42 x l O - 5 5.4 x l O - 5 8.4xlO 1 4
256 256 256 256 232 316 316 214 214 214 1
50 70 85 60 59 77 96 T (K) 60 70 80 80 80 80 80 80 90 100 120 125 130 135 140 145 150 T (K)
6.IxIO-6 8.02 x l 0 ~ 5 5.3OxIO- 4 1.9 x l O - 5 1.93 x 10 ~5 1.93 XlO" 4 1.93 x l O - 3 2.84 x 1015 5.28 x 10 ~6 2.06 x l 0 ~ 5 9.53 x l O - 5 9.1OxIO- 5 8.62 x l O - 5 8.24 x l O - 5 7.86 x l O - 5 7.46 x l O - 5 2.52 x l O - 4 8.8IxIO-4 6.98 x l O - 3 1.27xl0- 2 2.15 XlO" 2 2.6OxIO- 2 5.7IxIO- 2 8.62xl0-2 1.17XlO- 1 1.6 x 1015
Dioctanoyl peroxide
^-Heptane
Dioctanoyl peroxydicarbonate
Chlorobenzene
Phenylacetyl peroxide
Acetonitrile Benzene Carbon tetrachloride Cyclohexane Styrene Toluene
Triptoyl peroxide
Benzene
Apocamphoyl peroxide ds-5-rm-Butylcyclohexylformylm-chlorobenzoyl peroxide
Benzene
fra«5-4-^rf-Butylcyclohexylformylm-chlorobenzoyl peroxide
Benzene
Chlorobenzene
n-Heptane
2-Nonenoyl peroxide
Mineral oil
z z z z z z
(1500) (2000) (2500) (1500) (1500) (1500)
exp[- 129.05/RT]
96.2
f,u2 f,uj
a,mi
125.5
X1 xi xi
exp[-121A/RT] 126
a a a a
exp[- 128.34/^7] z (1500) z (1500) z(l) z (500) z (1000) z (1500) z (2000) z (2500) z (1500) z (1500) z (1500) z (1500) z (1500) z (1500) z (1500) z (1500) z (1500) exp[-128.8//?7]
377 377 377 377 377 377 344 344 344 344 167 167 167 167 316 59 59 102 244 102
337 337 337 338 344 344 344 344 377 377 377 377 377 377 377 377 377 377 377 377 377 377 377 377 377 1
Table 4. cont'd Number of C atoms
Initiator
18 (cont'd)
3-Nonenoyl peroxide 2-Phenylpropionyl peroxide
19
Dibenzoyl itaconyl diperoxide
Solvent Mineral oil Cyclohexane On silica Styrene Unknown
J(0C) T (K) 55.8 49.4 70 70 75 85
Dibenzoyl a-methylsuccinoyldiperoxide
Unknown
70 75 85
20
Decanoyl peroxide
Benzene
Chlorobenzene
Dioctanoyl a-bromosuccinoyldiperoxide
Mineral oil Unknown
60 70 85 63 80 100 T (K) T(K) 70 75 85
Dioctanoyl a-chlorosuccinoyldiperoxide
Unknown
70 75 85
21
Dioctanoyl a-chlorosuccinoyldiperoxide 4-Ethyl-2-octenoyl peroxide Dioctanoyl itaconoyl diperoxide
Chlorobenzene
70
Chlorobenzene THF Chlorobenzene
70 70 70
1.18 x 10 " 4 6.2xl0"5 1.54 x 10 " 5
Chlorobenzene
35 70 35 50 55 65 T(K) 55
9.42 x 10 " 5 3.02 x 10" 3 9.77 x 10" 4 7.92 x l O " 5 1.45 x l O " 4 4.13 x l O " 4 1.07 x l O 1 2 1.38 x l O " 4
85 T (K) 70
85 Unknown
70 75 85
22
Benzoyl 2-[mms-2-(3-nitrophenyl)vinyljbenzoyl peroxide Benzoyl 2- [frans-2-(4-nitrophenyI)vinyl]benzoyl peroxide Benzoyl 2-[fra«s-2-(4-nitrophenyI)vinyl]-4-nitrobenzoyl peroxide Benzoyl 2-[frans-2-(phenyl)vinyl]benzoyl peroxide 4-Benzylidenebutyryl peroxide
3.7 x 10 14 6.8xlO~ 6 7.5 x 10 " 5 5.5 x 10" 5 5.63 x 10~ 4 1.87 XlO" 5 8.63xlO- 4 3.62 xl0~ 5 1.69 X l O " 3 1.00 X l O - 4 2.74 x 10 " 4 1.26 x l O " 5 4.26 X l O " 4 2.40xl0~5 9.6OxIO"4 8.7 x l O " 5 1.53 x 10~5 5.67 XlO" 5 3.8OxIO- 4 1.93 x 10 " 5 1.93 x l O - 4 1.93 x l 0 ~ 3 3.64 x 10 15 2.7xl015 1.52 x 10 ~~4 1.82 x l O " 5 2.74 XlO" 4 3.83 xlO- 5 6.97 x l O " 4 1.15 X l O " 4 2.02 x 10 ~A 2.42 x l O " 5 3.23 x l O " 4 4.83 xlO~ 5 8.5OxIO-4 1.58 x 10~ 4 8.2 x 10 1 4 3.23 x 10 ~4 2.8OxIO-5 5.47 x l O " 4 5.6OxIO"5 1.28 x l O " 3 1.92 X l O " 4 5.48 x 10 ~4 5.88 x l 0 ~ 5 9.58 x l O " 4 1.06 x l O " 4 2.61xl0"3 3.84 x l O " 4 1.87 x 10~4
Unknown Mineral oil Unknown
75
Dioctanoyl a-methyl succinoyldiperoxide
* d (s" 1 )
Methanol Acetophenone
E31 (kj/mol)
Notes
exp[- 10S.0/RT]
83.7 115.1
82.8 116.3
127.2
exp[- 130.48//?7] exp[- 131.9/K7] 96.2 126.4
95.4 126.4
X2 X2 X2 X2 X2 X2 X2 X2 X2 X2 X2 x2 a a a
X2 X2 X2 X2 x2 X2 X2 X2 X2 X2 X2 X2
e x p [ - 121A/RT] 92.9 127.6
96.2 131.0
84.5
1 258 258 316 214 214 214 214 214 214 214 214 214 214 214 214 126,337 126,337 126,337 344 344 344 344 1 214 214 214 214 214 214 214 214 214 214 214
X2 X2 X2 X2 X2 X2 X2 x2 X2 x2 x2 x2 t9
214 1 214 214 214 214 214 214 214 214 214 214 214 214 175
t9 t9 t9
175 175 175
h,t 9 t9 t9
175 175 175 133 133 133 133 133
99.6
exp[-99.6//?7] 98.7
Refs.
m2
Notes page II - 69; References page II - 70
Table 4. cont'd Number of C atoms 22 (cont'd)
Initiator 4-Benzylidenebutyryl peroxide
Solvent Acetophenone Benzene
Carbon tetrachloride
Nitrobenzene Propylene carbonate
4-ter/-Butylbenzoyl peroxide cis-4-tert-Butylcyclohexane formylperoxide
Toluene Dioxane Butane Carbon tetrachloride
frarcs-4-te7t-Butylcyclohexane formylperoxide
Carbon tetrachloride
fra«s-4-(4-Chlorobenzylidene)butyryl peroxide
Benzene
Propylene carbonate
frarcs-4-(4-Fluorobenzylidene)butyryl peroxide
Benzene
Propylene carbonate
1-Naphthoyl peroxide
Benzene
4-Nitrobenzoyl-2-[rra«5-2-(4-nitrophenyl)vinyl] benzoyl peroxide 2-Phenylisovaleryl peroxide
Chlorobenzene
5-Phenylpenta-2,4-dienoyl-peroxide 5-Phenylpentanoyl peroxide
Acetonitrile Cyclohexane On silica Styrene Acetophenone Benzene Carbon tetrachloride
Propylene carbonate 24
Dibenzoyl 2-bromosebacoyldiperoxide
Unknown
J( 0 C) 65 T(K) 50 60 70 60 70 T(K) 60 40 50 T (K) 50 40 50 60 70 80 40 40 40.0 45.45 50.7 40.0 44.7 48.9 50 60 70 40 50 60 50 60 70 40 50 60 54.6 59.9 64.5 70 55.0 55.0 50 70 77 77 70 77 85 T(K) 60 60 70 75 85
Dioctanoyl 2-bromosebacoyldiperoxide
Unknown
70 75
A^(S"1) 4.02 x 10 " 4 7.14xlOn 2.40xl0~ 5 6.8OxIO- 5 1.845 x l O - 4 3.47 x 10~5 1.06 XlO" 4 1.42xlO 13 3.38 x 10~4 7.36 x 10~5 2.13 XlO- 4 5.93 x 1010 2.08 XlO" 4 7.23 x l O - 5 2.093 x l O " 4 5.117 x l O - 4 1.64 x 10~4 6.08 x 10 ~2 1.25 x 10 ~5 1.69 x l O " 5 (8.65 ± 0.35) x 10 ~5 (1.32 ±0.04) x 10- 4 (2.35 ±0.05) x 10- 4 (4.25 ±0.23) x 10~5 (7.10 ± 0.38) x 10 ~5 (1.14±0.04)x 10~4 2.10xl0"5 6.56 x 10 ~5 1.75 x l O " 4 5.33 x 10 ~5 1.448 x 10~4 2.791 x 10~4 2.67 x 10 " 5 8.44 x 10 ~5 2.119 x l O - 4 6.53 x 10 ~5 1.685 x l O - 4 4.54OxIO- 4 1.01 x 10~4 1.86 x l O - 4 3.OxIO" 4 6.06 x 10~5 2.27 x 10 " 5 6.4xlO-6 2.56 x 10 ~4 2.18 x l O " 4 2.37 x 10 ~4 1.054 x l O " 5 2.76 x l O " 5 7.19 x l O - 5 1.87 x l O - 4 1.76xlO 15 4.41 x 10 ~5 2.8Ox 10" 5 4.80xl0~4 3.87 x 10~5 7.64 x l O - 4 7.22 XlO" 5 2.0OxIO" 3 2.02 x l O - 4 6.46 x 10 ~4 5.23 x 10~5 1.17IxIO- 3
Ea (kj/mol)
Notes
exp[- 98.1/RT] 91.2
m2 m2 h
112.5 exp[-112.5 /RT]
m2 m2 m2
89.5 exp[- 89.5/RT] 82.0
m2 h
76.1
a,mi z (0.98) z (1010) h
81.6
h
95.0
h
94.1
h
t9
n2
127.6 130.1
exp[-130.1/i?7]
87.9 110.8
99.6 129.7
h,m2 m2 m2 m2 m2 m2 X2 X2 x2 X2 x2 X2 X2 X2 x2
Refs. 133 133 194 194 194 133 133 133 133 133 133 133 133 194 194 194 133 6 145 145 35 35 35 35 35 35 194 194 194 194 194 194 194 194 194 194 194 194 170 170 170 175 258 258 258 316 133 194 133 133 133 133 133 133 214 214 214 214 214 214 214 214 214
Next Page
Table 4. cont'd Number of C atoms 24 (cont'd)
Initiator
Solvent
Dioctanoyl 2-bromosebacoyldiperoxide
Unknown
Lauroyl peroxide
Benzene
Chlorobenzene
Ethyl acetate
Ethyl ether Mineral oil Styrene
26 28 36 x
TABLE 5. Number of C atoms 4
2-Phenoxybenzoyl peroxide Myristoyl peroxide Menthylphthaloyl peroxide Aliphatic polymeric diacyl peroxide
kd(s'1)
Benzene Benzene
Acetophenone Benzene Dioxane Chlorobenzene
Ea (kj/mol)
30 40 50 60 70 60 70 85 70 40 50 60 70 61 79 99 T (K) 40 50 61 70 30 T (K) 34.8 49.4 61.0 74.8 100.0 50 60 65 70 50
1.08 x 10 " 4 3.0OxIO" 3 3.72 x l 0 ~ 4 2.56 x 10 " 7 4.91 x 10~7 2.19 x l O - 6 9.17 xlO~ 6 2.86 x l O - 5 1.51 x 10~5 5.58 x l 0 ~ 5 3.75 x l O - 4 4.33 x l O - 5 2.91 x 10 ~7 1.15 XlO" 6 4.75 x l O - 6 1.87 xlO~ 5 1.93 x 10 ~5 1.93 x l O - 4 1.93 XlO" 3 3.92 xlO 1 4 6.03 x 10 ~7 2.7OxIO- 6 1.05 x l 0 ~ 5 3.99 x l 0 ~ 5 1.97 x 10 " 6 2.2 x 1016 2.06 x 10 ~7 2.25 x l O " 6 1.42 x l 0 ~ 5 1.00 x l O - 4 2.39 x l O - 3 3.1 x 10" 6 1.2OxIO- 5 2.22 x l O - 5 4.32 x l O - 5 2.03 x 10 ~4
50 60 70 65 70 55 75 75 80
6.58 x 10 ~5 1.815 x 10 ~4 4.729 x l O " 4 8.18x10 ~5 3.38 x 10 ~5 1.15 x 10~4 9.04 x 10 ~5 9.00 x 10 " 5 1.720xl0" 4
85
Carbon tetrachloride
rraw5-4-(4-Methoxybenzylidene)butyryl peroxide frarcs-4-(4-Methylbenzylidene)butyryl peroxide
T( 0 C)
Notes X2 X2 X2 a
127.2
a a a a,j
exp[- 12337/RT]
a exp[- 137.9/RT] a a a a a 121.1
90.4
121.3
c,h c c a a Vu Vi5 V 15
Refs. 214 214 214 99 68 68 68 68 126,337 126,337 126,337 16 68 68 68 68 344 344 344 344 68 68 68 68 99 1 10 10 10 10 10 287 287 287 287 194 194 194 194 5 16 65 302 302 302
HYDROPEROXIDES AND KETONE PEROXIDES
Initiator
Solvent
sec-Butyl hydroperoxide
Toluene
ter/-Butyl hydroperoxide
Benzene
T( 0 C) 172.0 182.3 130 145 160 154.5 161.7 169.3 174.6
fcd
(s"1) 2.65 x 10 ~5 4.9 XlO" 5 3 x 10 ~7 1.6 XlO" 6 6.6 x l O - 6 4.29 XlO" 6 9.27 x l O - 6 2.OxIO- 5 4.OxIO- 5
Ea (kj/mol)
138
170.7
Notes
a a a h
Refs. 199 199 337 337 337 76 76 76 76
Notes page 11-69; References page II - 70
Previous Page
Table 4. cont'd Number of C atoms 24 (cont'd)
Initiator
Solvent
Dioctanoyl 2-bromosebacoyldiperoxide
Unknown
Lauroyl peroxide
Benzene
Chlorobenzene
Ethyl acetate
Ethyl ether Mineral oil Styrene
26 28 36 x
TABLE 5. Number of C atoms 4
2-Phenoxybenzoyl peroxide Myristoyl peroxide Menthylphthaloyl peroxide Aliphatic polymeric diacyl peroxide
kd(s'1)
Benzene Benzene
Acetophenone Benzene Dioxane Chlorobenzene
Ea (kj/mol)
30 40 50 60 70 60 70 85 70 40 50 60 70 61 79 99 T (K) 40 50 61 70 30 T (K) 34.8 49.4 61.0 74.8 100.0 50 60 65 70 50
1.08 x 10 " 4 3.0OxIO" 3 3.72 x l 0 ~ 4 2.56 x 10 " 7 4.91 x 10~7 2.19 x l O - 6 9.17 xlO~ 6 2.86 x l O - 5 1.51 x 10~5 5.58 x l 0 ~ 5 3.75 x l O - 4 4.33 x l O - 5 2.91 x 10 ~7 1.15 XlO" 6 4.75 x l O - 6 1.87 xlO~ 5 1.93 x 10 ~5 1.93 x l O - 4 1.93 XlO" 3 3.92 xlO 1 4 6.03 x 10 ~7 2.7OxIO- 6 1.05 x l 0 ~ 5 3.99 x l 0 ~ 5 1.97 x 10 " 6 2.2 x 1016 2.06 x 10 ~7 2.25 x l O " 6 1.42 x l 0 ~ 5 1.00 x l O - 4 2.39 x l O - 3 3.1 x 10" 6 1.2OxIO- 5 2.22 x l O - 5 4.32 x l O - 5 2.03 x 10 ~4
50 60 70 65 70 55 75 75 80
6.58 x 10 ~5 1.815 x 10 ~4 4.729 x l O " 4 8.18x10 ~5 3.38 x 10 ~5 1.15 x 10~4 9.04 x 10 ~5 9.00 x 10 " 5 1.720xl0" 4
85
Carbon tetrachloride
rraw5-4-(4-Methoxybenzylidene)butyryl peroxide frarcs-4-(4-Methylbenzylidene)butyryl peroxide
T( 0 C)
Notes X2 X2 X2 a
127.2
a a a a,j
exp[- 12337/RT]
a exp[- 137.9/RT] a a a a a 121.1
90.4
121.3
c,h c c a a Vu Vi5 V 15
Refs. 214 214 214 99 68 68 68 68 126,337 126,337 126,337 16 68 68 68 68 344 344 344 344 68 68 68 68 99 1 10 10 10 10 10 287 287 287 287 194 194 194 194 5 16 65 302 302 302
HYDROPEROXIDES AND KETONE PEROXIDES
Initiator
Solvent
sec-Butyl hydroperoxide
Toluene
ter/-Butyl hydroperoxide
Benzene
T( 0 C) 172.0 182.3 130 145 160 154.5 161.7 169.3 174.6
fcd
(s"1) 2.65 x 10 ~5 4.9 XlO" 5 3 x 10 ~7 1.6 XlO" 6 6.6 x l O - 6 4.29 XlO" 6 9.27 x l O - 6 2.OxIO- 5 4.OxIO- 5
Ea (kj/mol)
138
170.7
Notes
a a a h
Refs. 199 199 337 337 337 76 76 76 76
Notes page 11-69; References page II - 70
TABLE 5. cont'd Number of C atoms 4 (cont'd)
Initiator tert-Butyl hydroperoxide
Solvent Benzene Chlorobenzene
Cumene Cyclohexane Dodecane Heptane w-Octane
Toluene
Vapor
tert-Butyl hydroperoxide/cobalt 2-Ethyl hexanoate
Chlorohenzene
tert-Butyl hydroperoxide/cobalt stearate Methyl ethyl ketone peroxides
Benzene
5
tert-Amyl hydroperoxide
Ethyl acetate Chlorobenzene
6
Acetone cyclic diperoxide
Benzene
3,3,6,6-Tetramethyl-1,2,4,5tetroxane
Toluene Benzene
Toluene Vapor
Cyclohexyl hydroperoxide
Benzene Benzene/styrene (50/50) Cyclohexane
T( 0 C) 172.3 182.6 171 199 231 182.6 100 172 86.1 98.5 172 149.8 159.9 169.6 179.6 100 172.5 181.5 192.6 204.5 214.9 570 670 773 873 973 0 0 0 25 25 45 45 100 115 130 70 153 190 228 135.5 145.5 165.0 165.0 135.5 140.5 145.5 150.5 165.0 165.0 130.1 150.1 170.1 177.1 185.1 194.1 207.1 215.1 250.1 70 70 130 140 150
#d ( s 1 ) 1.09 x l O " 5 3.1 x 10~5 1.93 x 10~5 1.93 x l O " 4 1.93 x l O " 3 8.1 x 10" 5 1.2xlO- ? 1.4IxIO- 4 1.32 xlO~ 6 5.55 x l O - 6 1.41 x 10" 4 8xlO"6 2.5 XlO" 5 6.9 x l 0 ~ 5 1.82 x l 0 ~ 5 5.7xl0"8 9.2 x l O " 6 2.69 XlO" 5 8.3 x l O " 5 1.52 XlO" 4 3.24 xlO~ 4 3.4XlO 1 4.95 8.4XlO 1 5.66 x 102 2.58 x 103 1.01 x 10" 3 8.29 x 10 ~5 5.4OxIO" 4 2.3 XlO" 3 1.1 x l O " 3 1.4xlO" 3 l.OxlO" 3 1.3 x 10 " 5 4.80xl0"5 1.60xl0" 4 1.28 x 10~6 1.93 x 10 " 5 1.93 x l O " 4 1.93 x l O " 3 6.25 x l O " 7 2.09xl0-6 1.41 x 10" 5 1.37 x l O " 5 6.25 x l O " 7 1.19 x 10~6 2.09 x l O " 6 2.83 XlO" 6 1.41 x 10" 5 1.37 x l O " 5 1.8 x l O " 6 3.4xlO- 6 3.5xl0-6 4.6x10-6 1.3 x l 0 ~ 5 2.4 x l O - 5 8.5 x l O " 5 1.66 x l O " 4 4.88 x l O - 4 0 1.27 x 10~3 2.38 x l 0 ~ 3 1.16 x l O - 2 3.20xl0" 2
Ea (kj/mol)
Notes
c
128.4
163.2
c b b f f f
c
Vi0 V7 V1
101
147.1
Vi a a a
h
a a a a a
Refs. 199 199 344 344 344 199 199 199 41 41 199 118 118 118 118 199 199 199 199 199 199 188 188 188 188 188 190 190 190 198 198 198 198 337 337 337 13 344 344 344 286 286 286 286 373 373 373 373 373 373 365 365 365 365 365 365 365 365 365 91 91 91 91 91
TABLE 5. cont'd Number of C atoms 6 (cont'd)
Initiator Cyclohexyl hydroperoxide
Solvent Benzene
80
Cyclohexane
80
Cyclohexene
80
Dimethylheptadiene
80
1-Octene
80
7
Benzyl hydroperoxide
Styrene
8
1,4-Dimethylcyclohexanehydroperoxide 1,1,3,3-Tetramethylbutylhydroperoxide
1,4-Dimethylcyclohexane
Benzene
Chlorobenzene
2,5-Dimethyl-2,5-di(hydroperoxy)hexane
(S)x
9
Benzene
n-Octyl hydroperoxide 2,4,4-Trimethylpentyl2-hydroperoxide Poly(phenyleneethyl hydroperoxide)/manganese resinate
White oil White oil
Cumene hydroperoxide
Benzene
Chlorobenzene
Chlorobenzene
Cumene
Mesitylene Styrene Toluene
Cumyl hydroperoxide
10
p-Cymene hydroperoxide
T( 0 C)
White oil Acetone-d6
/?-Cymene
^d(S" 1 )
60 60 120
Reaction order varies from 1.5 to 2.0 Reaction order varies from 1.5 to 2.0 Reaction order varies from 1.5 to 2.0 Reaction order varies from 1.5 to 2.0 Reaction order varies from 1.5 to 2.0 9xlO~6 1.8 x l O - 5 1.4xlO" 5
130 145 160 135 153 173
1.7xlO~ 5 7.41 x 10- 5 2.83 XlO" 4 1.93 x 10 ~5 1.93xlO- 4 1.93 x l O - 3
130 145 160 150 150
2.7xlO~ 6 1.0 x l O - 5 3.16 x l O - 5 9.29 x 10 ~5 9.29 x 10 " 5
26 30 35 115 130 145 159 193 253 110 120 132 T(K)
2.0OxIO- 4 2.75 x 10" 4 3.67 XlO" 4 4xlO"7 1.7 x l O - 6 6.6 x l O ~ 6 1.93 x 10 ~5 1.93 x l O " 4 1.93xl0-3 2.742 x 10 ~6 5.194 x l O - 6 9.305 x l O - 6 2.1OxIO 11
125 139 182.3 150 -33.0 -23.0 -12.0 -18.0 -8.0
9xlO~6 3 xlO-5 6.45 x l O " 5 1.34 x 10~4 7.0xl0~5 2.28 XlO" 4 1.2IxIO- 3 8.3 x l O - 5 4.23 x l O - 4
-3.0 110 120 132 T(K)
1.65xlO- 3 5.50OxIO" 6 1.20OxIO- 5 2.089 XlO" 5 1.23 x l O 1 2
Ea (kj/mol)
Notes
Refs. 119
119
119
119
119
C3 C4 c
276 276 224
134
a a a
337 337 337 344 344 344
113
a a a a a
337 337 337 177 177
t3 t3 t3 a a a
212 212 212 337 337 337 344 344 344 367 367 367 367 58 58 199 199 199 177 264 264 264 264 264
137.2
112.5 112.5 46.0
122
exp[- S0.0/RT] 98.7 101.3
121.3 62.0
a
110.2
tu tM tu
exp[-85.48//?71
264 367 367 367 367
Notes page 11-69; References page II - 70
TABLE 5. cont'd Number of C atoms 10 (cont'd)
Initiator Decalin hydroperoxide
Solvent
Pinane hydroperoxide
Acetic acid Chlorobenzene Decalin 1,2-Dichlorobenzene Ethylene glycol Nitrobenzene Pyridine Benzene
2-Phenylbutyl 2-hydroperoxide
sec-Butylbenzene
l-Phenyl-2-methylpropylhydroperoxide
Benzene
l-Phenyl-2-methylpropyl-2hydroperoxide
Benzene
Tetralin hydroperoxide
Poly(butene) n-Butyl stearate 2-Ethyl-l-hexene 1-Hexadecene Mineral oil
/i-Octadecane Isooctane Octyl ether Poly(propylene) «-Tetradecane Tetralin 2,2,4-Trimethyl-l-pentene white oil Toluene
(1O)n
Poly(cumyleneethylhydroperoxide) (MWIlOO)
11
2,2-Bis(terf-butyldioxy)propane
Cumene
l-Methoxy-l-(terf-butylperoxy) cyclohexane
Cumene
s£c-Butyltoluene hydroperoxide
^c-Butyl toluene
2,2-Di-(tert-butylperoxy)butane
Chlorobenzene
2,2-Bis(ter/-butyldioxy)butane Diisopropylbenzene monohydroperoxide
Cumene Chlorobenzene
l-Methoxy-l-(terr-amylperoxy) cyclohexane
Cumene
12
T( 0 C) 130 130 130 130 130 130 130 130 145 160 110 120 132 T(K) 133.8 143.9 153.9 163.7 174 144.2 154.5 165.6 176.0 170 170 130 170 170 135.6 150.6 170 170 170 170 170 170 T(K) 170 150 130 140 150 90 100 110 120 80 90 100 110 100 110 120 T(K) 98 116 136 T(K) 100 150 182 218 80 90
^d(S"1) 5.5xl0~4 10% in 3 h 1.4IxIO- 5 4.48 x l O " 5 1.65 x 10 ~4 4.73 x 10 ~5 (2.31-2.89) x 10 ~4 7.08 x 10 " 6 2.72 x l 0 ~ 5 9.17 x l O - 5 2.944 x 10 ~6 6.61IxIO- 6 1.089 XlO" 5 4.06 xlO 1 2 3.18 x l O " 6 8.95 x 10 " 6 2.OxIO" 5 4.03 XlO" 5 9.77 x l O " 5 5.04 x 10 " 6 1.21 x IO"5 2.92 x l O " 5 6.97 XlO" 5 2.17 x l O " 3 1.47 x l O " 4 1.08 x l O " 4 1.26 x l O " 3 7.92 x l O " 4 4.2 x l O " 5 1.00 XlO" 4 4.82 x l O - 4 2.54 x 10~4 1 31 x 10" 4 1.45 x l 0 ~ 3 2.5OxIO" 3 2.32 x 10~4 2.27 x 109 1.67 x 10~3 1.34 x 10~4 2.79 x 10" 5 4.OxIO- 5 5.78 XlO" 5 2.16 x 10~6 9.14 x l O " 6 2.97 XlO" 5 9.56 x l O " 5 4.79 x 10 ~6 1.898 x 10 ~5 6.57 x l 0 ~ 5 2.139 x l O - 4 4.11IxIO- 6 8.194 XlO" 6 1.9555 x l O - 5 1.02 xlO 1 6 1.93 x 10 ~5 1.93 x l O - 4 1.93 xlO" 3 9.3OxIO 16 1.84 x 10 ~5 1.93XlO" 5 1.93 x 10 ~4 1.93 x l O - 3 7.82 xlO~ 6 3.07 x 10 " 5
£ a (kj/mol)
Notes
124.3 176.4 117.2
123.8
a a a
exp[-87.15//?7] 122.2
h
125.5
h
78.2 125.5 82.8
t3 t3 e,t3 t3 t3 t3 e,t3 t3 t3 t3 t3 t3 t3
117.2 131.4
119.2 121.3
exp[-102.1 /RT] t3 121.3
txp[-\W2/RT]
exp[-154.08/^7]
Refs. 228 228 228 228 228 228 228 18 18 18 367 367 367 367 76 76 76 76 76 76 76 76 76 71 71 71 71 71 71 71 71 71 71 71 71 71 112 71 177 210 210 210 361 361 361 361 348 348 348 348 367 367 367 367 344 344 344 344 361 344 344 344 348 348
TABLE 5. cont'd Number of C atoms 12 (cont'd) 13
14
Initiator
Solvent
l-Methoxy-l-(te/Y-amylperoxy) cyclohexane l-Methoxy-l-(terf-hexylperoxy) cyclohexane
Cumene
U-Bis(tert-butylperoxy)cyclopentane
Cumene
2,2-Bis(terf-butyldioxy)-3-methylbutane
Diphenylmethane
U-Bis(terf-butylperoxy)cyclohexane
Cumene
Cumene Cumene
Chlorobenzene
l,l-Bis(terr-butylperoxy)-2-methylcyclopentane
15
16
17
w-Dodecane n-Hexadecane H-Hexane n-Nonane Cumene
1,1-Diphenylethyl hydroperoxide
Chlorobenzene
l-Methoxy-l-(rm-octylperoxy)cyclohexane
Cumene
U-Bis(^-butylperoxy)-2-methylcyclohexane
Cumene
U-Bis(terf-amylperoxy)cyclohexane
Cumene
l,l-Bis(terf-butylperoxy)cyclooctane
Cumene
l,l-Bis(^rr-butylperoxy)-2-n-propylcyclohexane
Cumene
l,l-Bis(terf-butylperoxy)2-isopropylcyclohexane
Cumene
l,l-Bis(ferf-butylperoxy)3,3,5-trimethylcyclohexane
Cumene
T( 0 C) 100 110 80 90 100 110 80 90 100 110 90 100 110 120 100 80 90 100 110 94 113 134 T (K) 100 100 100 100 80 90 100 110 90 110 130 150 T (K) 70 80 90 100 80 90 100 110 80 90 100 110 90 100 110 120 80 90 100 70 80 90 100 80 90 100 110
A:d (s"1) 1.058 xlO~ 4 3.450 x 10 " 4 8.34 x 10~6 3.17 x l O " 5 1.12Ox 10" 4 3.653 x l O - 4 4.98 x l O " 6 1.80xl0~ 5 6.67 x l O " 5 2.17 XlO" 4 1.08 x 10 ~5 3.75 x 10 ~5 1.29 XlO" 4 4.1IxIO-4 3.17 x l O " 5 3.47 x 10~6 1.45 x 10 ~5 5.06 x l O " 5 1.62 XlO" 4 1.93 x 10 " 5 1.93 x l O " 4 1.93 x l 0 ~ 3 3.47 x 1015 3.51 x 10 ~5 3.15 x l O " 5 3.82 x 10 " 5 3.62 x 10 ~5 1.55 x 10~5 5.82 x 10~5 1.85 x l O " 4 6.0OxIO" 4 2.OxIO" 9 1.007 XlO" 6 1.034 XlO" 6 1.223 XlO" 6 1.38 x 108 5.9xlO~ 6 2.3OxIO" 5 8.18 x l O " 5 2.84OxIO" 4 1.29 x 10~5 4.51 x 10 " 5 1.43 XlO" 4 4.58 x l O " 4 5.34 x l O " 6 2.02 x 10 " 5 7.32 x l O " 5 2.44 XlO" 4 1.11 x 10 " 5 4.15 x 10~5 1.36 x l O - 4 4.24 xlO~ 4 1.2OxIO- 5 4.19 x 10 " 5 1.38 XlO" 4 2.59 x 10" 5 4.86 x 10 ~5 1.98 x l O " 4 7.46 XlO" 4 3.82 x 10~6 1.50 x 10 " 5 5.31 x 10 " 5 1.75 XlO" 4
Ea (kj/mol)
exp[- 142A/RT]
exp[- 105A/RT]
Notes
Refs. 348 348 348 348 348 348 349,364 349,364 349,364 349,364 358 358 358 358 361 349,350 349,350 349,350 348,349,350 344 344 344 344 364 364 364 364 349 349 349 349 374 374 374 374 374 348 348 348 348 349 349 349 349 348 348 348 348 364 364 364 364 349 349 349 349 349 349 349 349,364 349,364 349,364 349,364
Notes page 11-69; References page 11-70
TABLE 5. cont'd Number of C atoms Il (cont'd)
Initiator
Solvent
U-Bis(tert-butylperoxy)3,3,5-trimethylcyclohexane
Chlorobenzene
rc-Butyl 4,4-di-(terf-butylperoxy) valerate
Chlorobenzene
18
l,l-Bis(terr-hexylperoxy)cyclohexane
Cumene
20
U-Bis(tert-butylperoxy)cyclododecane
Cumene
22
U-Bis(tert-octylperoxy)cyclohexane
Cumene
31
2,2-Bis[4,4-di-(tert-butylperoxycyclohexyl)propane
Chlorobenzene
TABLE 6. Number of C atoms 4 5
85 105 128 T (K) 102 121 143 T(K) 80 90 100 110 90 100 110 80 90 100 110 87 106 128 T(K)
kd (s"1) 1.93 x ICT5 1.93 x 10 ~4 1.93 X l O - 3 7.59 x 10 13 1.93 x 10 " 5 1.93 x 10 ~4 1.93 XlO- 3 1.91 x 1015 5.38 x 10~6 2.06 x 10 ~5 7.48 XlO" 5 2.48 XlO- 4 8.14 x l O " 6 3.22 x 10~5 9.93 XlO" 5 1.513 x 10~5 5.62 x 10 ~5 1.983 X l O - 4 6.26 x l O - 4 1.93 x 10 ~5 1.93 x 10 ~4 1.93 x l O - 3 8.79 x l O 1 4
Ea (kj/mol)
Notes
Refs. 344 344 344 344 344 344 344 344 348 348 348 348 364 364 364 348 348 348 348 344 344 344 344
exp[- 127.52/RT]
exp[- 143.51/RT]
exp[-135.56//?7]
PERESTERS AND PEROXYCARBONATES
Initiator Dimethyl peroxalate tert-Butyl percarbamate tert-Butyl performate
Solvent
J( 0 C)
Pentane Chlorobenzene Chlorobenzene
25 90 130.8 140.8 140.6 140 140 140.6 140 140.6 140 79.5 88.4 92.8 64 64 64 64 79.6 87.8 92.6 88.2 92.8 99.4 75 85 85 100 115 130 75
4-Chlorotoluene Cumene 6
J( 0 C)
Isobutyl peracetate
a-Methylstyrene
tt-Butyl peracetate
a-Methylstyrene
sec-Butyl peracetate
terr-Butyl peracetate
a-Methylstyrene
terf-Amyl
alcohol Benzene
n-Butanol
A^(S"1) 1.7xlO~ 5 6.6xlO" 6 5.43 x 10 ~5 1.7OxIO- 4 1.8OxIO- 4 2.12 XlO" 3 5.06 x l O - 4 1.61 x 10~4 1.62 x l O - 3 1.77 x 10~4 1.02 XlO" 3 1.36 x l O " 5 3.61xl0" 5 5.58 x l O - 5 ~9.6xl0~3 8.2 x l O - 3 6.5 x l O - 4 1.2 x l O - 3 1.57 x l O - 5 3.27 x l O - 5 5.38 x l O - 5 1.79XlO"5 3.19 x l O - 5 5.37 x l O - 5 2.8 x 10 " 6 1.2xlO~ 6 2.18 x l O - 6 1.54 x 10- 5 1.02 XlO" 4 5.69 x l O - 4 2.65 x 10 ~5
Ea (kj/mol)
Notes
159.0
h
64.0
m2 V8 V1 v8 b b,v6
115.2
g2,vi6 g2,vi7 g2,vi8 g2,vi9 101.0
104.3
151.9
a a a a
Refs. 203 141 218 218 218 218 218 218 218 218 218 253 253 253 253 253 253 253 253 253 253 253 253 253 193 193 126,337 126,337 126,337 126,337 193
TABLE 6. cont'd Number of C atoms 6 (cont'd)
Initiator rm-Butyl peracetate
Solvent 2-Butanol
Chlorobenzene
Decane
rm-Butyl trichloroperacetate
Diethyl peroxydicarbonate
Dodecane Hexadecane Hexane Octane Paraffin Tetradecane Chlorobenzene
terr-Butanol 2,2'-Oxydiethylene bis(allyl carbonate)
7
Diethyl peroxalate ten-Amyl peracetate
Pentane Chlorobenzene
tert-Butyl methoxyperacetate
Ethylbenzene
terf-Butyl peracrylate
Benzene
terr-Butylperoxy isopropyl
Chlorobenzene
terr-Butyl perpropionate carborate
Benzene Decane Dodecane Hexadecane a-Methylstyrene
8
rm-Butyl 2-acetoxyperacetate tert-Buty\ cyclopropanepercarboxylate
Octane Tetradecane Ethylbenzene «-Dodecane rc-Hexadecane 2,2,4-Trimethylpentane
ferf-Butyl ethoxyperacetate
Ethylbenzene
T (0C)
£ d (s" 1 )
75 75 75 60 100 119 139 T (K) 100 115 125 100 100 100 130.1 100 130.1 100 60 66.8 77.0 45 55 40 50 60 25 90 108 129 T(K) 40.0 39.6 50.2 60.1 90 100 110 98 117 137 T(K) 80 90 100 100 100 70 90 100 100 91.8
1.13 x 10" 4 5.3 XlO" 5 4 xlO-7 2.3IxIO"8 1.93 XlO" 5 1.93 XlO" 4 1.93 x l O " 3 1.57 x 10 16 1.5 x IO" 5 7.9IxIO-5 2.45 XlO" 4 1.95 x 10- 5 1.78 x 10 ~5 1.55 x 10 " 5 5.08 x 10~4 2.07 x 10 ~5 3.13 x 10~4 1.55 x 10 ~5 1.19 x 10 " 5 2.75 x l O - 5 1.00 XlO" 4 1.25 x 10 " 5 5.7 x l 0 ~ 5 6.94 x l O " 6 2.86 x 10 " 5 1.28 x l O - 4 2.6xlO"5 1.93 x 10 " 5 1.93 x l O " 4 1.93xl0- 3 4.13 x l O 1 5 2.2xlO"4 1.94 x l O - 4 8.24 x l O - 4 2.35 x l O - 3 1.12 x l O " 5 1.5IxIO- 5 4.85 x l O - 5 1.93 x 10 " 5 1.93 XlO" 4 1.93 x l O - 3 2.49 x l O 1 6 1.53 x 10~6 6.04 x 10 " 6 1.82 x 10 ~5 1.78 x IO" 5 1.58 x 10 ~5 3.02 x 10~7 4.85 x l O " 6 2.03 x 10 ~5 1.68 x 10 ~5 2.73 x 10 ~5
113.0 102.6 113.0 102.6 113.0 120.4 40.0 40.6 46.0 55.6
5.48 x 10 ~5 1.28XlO" 5 4.92 x l O - 5 1.7IxIO- 5 6.19 x 10~5 1.505 XlO" 4 2.96 x 10 ~4 2.89 x l O - 4 5.58 x l O - 4 1.94 XlO" 3
E31 (kj/mol)
Notes
159.0
c t7 m3 a,h
exp[- 149.36/RT] 134
125.9 126.8
a,h h
133.9-138.1
c c a a a
127.2
exp[-141.1/#n 104.7 103.9
86.2
a,h h
a a a
exp[-150.15//?7] a a
a a
b
153.8
h
146.2
h
105 102.7
a m 2 ,h
Refs. 193 193 193 81 344 344 344 344 337 337 337 270 270 270 169 270 169 270 81 28 28 18 18 90 90 90 203 344 344 344 344 315 328 328 328 211 211 211 344 344 344 344 213 213 270 270 270 213 213 270 270 328 255 255 255 255 255 255 315 328 328 328
Notes page 11-69; References page 11-70
TABLE 6. cont'd Number of C atoms 8 (cont'd)
Initiator tert-Butyl heptafluoroperoxybutyrate
Solvent Benzene
Methanol
Methoxybenzene
Nitrobenzene
Octane
Pyridine
Toluene
terf-Butyl methoxyperpropionate terr-Butyl perisobutyrate
Ethylbenzene Benzene
Bulk Chlorobenzene
Cumene
Decane
terf-Butyl percrotonate
Dodecane Hexadecane Iso-octane Nujol Octane Tetradecane Benzene
T( 0 C) 65.0 70.0 75.0 80.0 60.0 65.0 70.0 75.0 80.0 60.0 65.0 70.0 75.0 10.0 15.0 19.6 30.0 55.0 60.2 65.0 70.0 40.0 45.0 50.0 85.0 90.0 95.0 100.0 30.0 40.0 50.0 65.0 75.0 80.0 85.0 40.3 78 70 85 100 70 90.6 100.7 110.0 79 98 118 T(K) 90.6 100.7 110.0 70 85 100 100 100 100 103.4 103.4 100 100 100 115 130
^d(S"1) 1.56 x 10 " 5 3.09 x 10 ~5 5.27 XlO" 5 9.08 x l O " 5 9.5 x l O " 6 1.61 x 10~5 2.7OxIO- 5 5.23xl0-5 9.18 x l 0 ~ 5 9.6 XlO" 6 1.93 x l O - 5 3.57 XlO" 5 6.35 x l 0 ~ 5 7.19 x 10~5 9.37 x l 0 ~ 5 1.304 x l O - 4 2.604 x l O - 4 5.01 x 10 ~5 8.56 x l O " 5 1.378 x l O - 4 2.444 XlO" 4 3.26 x 10 ~5 6.36 x l O " 5 9.31 x 10 " 5 5.1 x 10 ~6 9.5 xlO~ 6 1.75 x l O - 5 3.41 x 10 " 5 2.74 x 10 " 5 7.66 x l O " 5 1.868 x l O " 4 1.88 x 10 " 5 4.66 XlO" 5 7.06 x l O " 5 1.203 x l O " 4 4.30xl0~ 3 3.77 x 10~5 6.69 x l O " 5 5.33 x l O - 5 3.5OxIO- 4 4.12 XlO" 5 8.13 x 10" 5 2.75 x l O " 4 8.92 x l O " 4 1.93 xlO~ 5 1.93 x l O - 4 1.93 x l O " 3 2.07 xlO 1 5 6.9 x l O " 5 2.35 x l O " 4 6.57 x l O " 4 4.7 x l O " 6 2.6 x l O - 5 1.55 x l O " 4 1.46 x l O " 4 1.56 x 10 " 4 1.47 x 10 " 4 2.16 xlO~ 4 2.23 x l O " 4 1.59 x 10 ~4 1.52 x 10 " 4 2.5xlO" 5 1.5OxIO- 4 7.39 x l O - 4
Ea (kj/mol)
Notes v 24 V24 V24 V24 V25 V25 V25 V25 V25 V26 V26 V26 V26
140.6
a a a a a h
exp[-135.16/,RrI 133.1
h
140.6
122
a a a
138
a a a
Refs. 370 370 370 370 370 370 370 370 370 370 370 370 370 369 369 369 369 370 370 370 370 370 370 370 370 370 370 370 370 370 370 369 369 369 369 328 37 126,337 126,337 126,337 37 136 136 136 344 344 344 344 136 136 136 337 337 337 270 270 270 251 251 270 270 337 337 337
TABLE 6. cont'd Number of C atoms 8 (cont'd)
Initiator
Solvent
tert-Butyl permaleic acid
Acetone
tert-Butyl permethacrylate
Benzene
tert-Butyl peroxyisopropyl carbonate
Benzene
Cyclohexyl peracetate
a-Methylstyrene
Diisopropyl peroxalate Diisopropyl peroxydicarbonate
Pentane Benzene Di-rc-butyl phthalate
Decane
Ethylbenzene Mineral spirits
2,2/-Oxydiethylenebis(allyl carbonate)
9
Ethyl tert-butyl peroxalate
Toluene Benzene
tert-Butyl 2-acetoxyperpropionate ter/-Butyl 5-bromo-2-perthenoate
Ethylbenzene Carbon tetrachloride
tert-Butyl 5-chloro-2-perthenoate
Carbon tetrachloride
tert-Butyl cyclobutanepercarboxylate
n-Hexadecane 2,2,4-Trimethylpentane
T( 0 C)
^d(S"1)
70 85 101 90 100 110 90 100 110 88.6 93.0 99.3 25 54.0 77 87 97 107 117 35 45 60 54.3 54.3 30 45 60 75 40 50 60 50 45 55 65 91.4 99.2 112.0 124.5 99.2 112.0 124.5
2.7xlO~ 6 1.6 x l O " 5 6.77 x l O " 5 1.92 x l O ' 5 7.66 XlO- 5 1.92 x l O " 4 6.64 x 10 " 6 2.21 x 10~5 6.87xl0-5 1.63 x l O " 5 2.30xl0"5 4.75 XlO" 5 6.0xl0~ 5 5.0xl0"5 1.39 x 10 ~3 4.09 x l O " 3 1.25 x l O " 2 3.54xl0-2 7.98 x l O " 2 6.3 x l O " 6 2.7xlO-5 1.85 x l O " 4 4.5 x 10 " 5 5.2x10-5 2xlO"6 1.8xl0-5 1.28 XlO" 4 7.55 x l O " 4 6.39 x 10~6 2.28 x 10 " 5 9.44xlO- 5 3.03 x 10 " 5 4.48 x 10~5 1.63 x l O " 4 5.93 x l O " 4 3.6OxIO" 4 2.24 x 10 " 6 1.18x10-5 4.30x10-5 2.29 x 10 " 6 9.56 XlO" 6 4.42x10-5
102.6 92.9 102.6 113.0
4.33 x 10~5 1.2IxIO- 5 4.84 x 10 " 5 1.668 XlO" 4
E2, (kj/mol)
Notes
113
a a a a a a a a a
137.0
109.4
113
113
117.6
112.5
143.5
143.5
ni2 yi 6 yi 6 y 16 yi6 y!6 a a a m2 a a a a a a a a c,h
a a a a a a
150.4
h
Refs. 337 337 337 211 211 211 9 9 9 253 253 253 203 60 236 236 236 236 236 337 337 337 60 60 337 337 337 337 90 90 90 90 31 31 31 328 176 176 176 176 176 176 255 255 255 255
ter/-Butyl 2,2-dimethyl3-bromoperpropionate
Cyclohexane
55 65 75
9.50xl0~ 6 3.58xl0-5 1.23 x l O " 4
118.2
h,t6 t6 t6
320 320 320
tert-Butyl 2,2-dimethyl3-chloroperpropionate
Cyclohexane
55 65 75
3.55 x 10" 6 1.48x10-5 5.65x10-5
128.6
h,t6 t6 t6
320 320 320
tert-Butyl 2,2-dimethyl3-iodoperpropionate
Cyclohexane Ethylbenzene
2.91 x 10" 5 3.76 x l O - 4 4.8 x 10~4 4.22 x l O - 4 1.39 x 10 " 3 2.68 x l O " 3
116.9
tert-Butyl isopropoxyperacetate
55 75 40.0 39.9 49.9 55.3
h,t6 t6 a,h h,m2
320 320 315 328 328 328
100.6 98.9
Notes page 11-69; References page 11-70
TABLE 6. cont'd Number of C atoms 9 (cont'd)
Initiator tert-Butyl 1-methylcyclopropylpercarboxylate Di-(tert-butylperoxy)-carbonate
terf-Butylperoxy isopropyl carbonate terf-Butyl perpivalate
Solvent 2,2,4-Trimethylpentane Chlorobenzene
1,2-Dichlorobenzene Cumene Isopropyl ether Benzene
Benzene
Chlorobenzene
Cumene
Cyclohexane
Decane
Dioxane/water (90/10) Dodecane Hexadecane Hexane
Heptane Isooctane Mineral spirits
tert-Buty\ perpivalate-d6
Octane Tetradecane Chlorobenzene
T(0C) 102.6 113.0 99.95 110.1 120.1 120.1 99.95 99.95 85 100 115 50 70 85 50 55 60 65 70 48.9 58.6 64.3 57 75 94 T(K) 74.8 60 60.6 74 45 55 60 65 64.6 75.6 84.6 70.3 55 65 75 50 70 80 60.6 80 80 55 60 65 70 80 60.6 73.9 55 60 65 70 75 T (K) 80 80 60.6 74.0
* d (s"1) 2.30 x 10 " 5 7.47 x l O " 5 6.72 x 10~5 2.13 xlO~ 4 6.05X10- 4 5.98 x 10 ~4 6.72 x 10 " 5 2.76 x 10 ~4 3.3xlO" 6 2.2xlO" 5 1.36xlO- 4 9.77 x 10 " 6 1.24X10- 4 7.64X10- 4 1.03 XlO" 5 1.94 XlO" 5 3.92 x l 0 ~ 5 7.31 x 10~5 1.30x10-4 8.4xlO" 6 3.35xlO- 5 7.0IxIO- 5 1.93 x l 0 ~ 5 1.93xlO- 4 1.93 x l O " 3 7.09 XlO 14 2.79xlO- 4 3.85 XlO" 5 4.0OxIO- 5 1.93X10- 4 3.53 x 10 ~6 1.73 x l O " 5 2.95 XlO" 5 4.53 x l O - 5 5.8IxIO- 5 2.1OxIO- 4 5.94 x l O " 4 1.11 x l O - 4 1.03 x 10 ~5 4.02 x l O - 5 1.45 x l O - 4 4.IxIO"6 5.52 XlO" 5 2.18 x l O - 4 6.26 x 10~5 2.38 x 10 ~4 2.39 x 10 " 4 8.42 x 10 '6 1.59 XlO" 5 3.39 x l O - 5 6.19 XlO" 5 2.33 x 10 ~4 1.97 x 10 ~5 8.82 x l O " 5 1.01 x 10 ~5 2.15 x l 0 ~ 5 4.14 x l O - 5 7.58 XlO" 5 1.47X10- 4 3.56 x 1014 2.34 x 10 ~4 2.27 x 10 ~A 3.24 x 10~5 1.57 xlO~ 4
£ a (kJ/mol)
Notes
Refs.
133.7
h
255 255 27 27 27 27 27 27 337 337 337 126,337 126,337 126,337 359 359 359 359 359 249 28 28 344 344 344 344 28 81 156 156 160 160 362 160 159 159 159 267 320 320 320 337 337 270 156 270 270 359 359 359 358 270 165 165 359 359 359 359 359 376 270 270 156 156
133.1
138
119.7
125.5
a a a a a a
k h
exp[- 123.59/RT] 128.0
106.7
a,h t9 t9 h
115.5
122.8
h
117
a a t9
t9 t9
exp[- 123/RT]
t9 t9
TABLE 6. cont'd Number of C atoms 9 (cont'd)
Initiator tert-Butyl
perpivalate-d6
tert-Butyl 2-perthenoate
tert-Butyl 1-pyrollidinepercarboxylate tert-Butyl Af-succinimidopercarboxylate
10
tert-Amyl
perpivalate
Solvent
(s"1) 5.05 x 10" 5 1.62 x 10~5 8.82 x l O - 5 3.3 x 10 " 6 1.66 x l 0 ~ 5 6.87 x l O - 5
Chlorobenzene
90
7.59 x 10 ~5
Acetonitrile Benzene Chlorobenzene
100 100 90 100 90 100 100 100 90 100 51 55 72 91 T (K) 50 60 70 80 35 45 60 47 63 82 T(K) 30 40 60 49 65 83 T (K) 74.7 80.7 90.8 40.3 99.8 116.6 129.9
9.9xlO~ 4 3.79 x 10~5 1.32 x 10 ~5 4.9IxIO-5 3.3xl0-6 1.10 x 10~5 9.OxIO- 6 6.00xl0"3 9.24 x 10 ~5 3.4IxIO-4 1.9XlO" 5 1.93 x 10 ~5 1.93 x l O - 4 1.93 x l O - 3 4.12 x 1015 1.05 x 10 ~5 3.5IxIO-5 1.309 XlO" 4 4.239 XlO" 4 6.9xlO~ 6 2.6xlO" 5 1.8OxIO- 4 1.93 x 10 ~5 1.93 XlO" 4 1.93 XlO" 3 3.19 xlO 1 5 2xlO"6 1.0 x l O - 5 1.34 x l O - 4 1.93 x 10 " 5 1.93 x l O - 4 1.93 XlO" 3 7.00 x 1015 1.98 xlO~ 4 4.37 x 10 " 4 1.25 x l O - 3 2.91 x 10 " 4 1.65 x 10 ~5 1.38 x 10~4 6.83 x l O - 4
113.0 92.9 102.6 113.0 75 93 113 T (K) 42.42 50.30 57.95 44.85 50.10 60.20
3.02 x 10 ~4 2.47 x 10 ~5 8.87 x 10 " 5 2.89 x l O - 4 1.93 x 10 " 5 1.93 x l O - 4 1.93 x l 0 ~ 3 2.45 x 1015 9.04 x 10 ~5 2.349 x l 0 ~ 5 5.66OxIO- 5 1.874 x 10 ~5 3.609 x l O - 5 1.306 x l O - 4
Carbon tetrachloride
Cumene Cyclohexane Cyclohexene Methanol Methylene chloride Nitrobenzene Benzene Chlorobenzene
Decane
Chlorobenzene
Mineral spirits
Di-w-butyl peroxydicarbonate
Chlorobenzene
tert-Butyl 2-acetoxy-2methyl perpropionate
Ethylbenzene
tert-Butyl tert-butoxyperacetate tert-Butyl 4-carbomethoxyperbutyrate
Ethylbenzene Cumene
tert-Butyl cyclopentylpercarboxylate
fcd
60.6 60.6 73.9 99.2 112.0 124.5
Dioxane/water (90/10) Isooctane
Cumene
Di-(sec-butyl)peroxydicarbonate
T( 0 C)
n-Hexadecane 2,2,4-Trimethylpentane
tert-Butyl peroxydiethyl acetate
Chlorobenzene
tert-Butyl 2,2-dimethylperbutenoate
Cumene
tert-Butyl 2,2-dimethylperbutyrate
Cumene
Ea (kj/mol)
147.3
Notes t9 t9 t9 m2 m2 m2
Refs. 156 165 165 176 176 176 141
113.4
h,m2 m2 t9
m2 a
exp[- 121J6/RT]
113
exp[-123.85//?7] 113
a a a
a a a
exp[- 126.65/RT] m2
151.3
h
140.8
h
exp[- 134.00/RT] 100.7
h
142 142 141 142 141 142 142 142 141 142 338 344 344 344 344 362 362 362 362 337 337 337 344 344 344 344 337 337 337 344 344 344 344 328 328 328 328 257 257 257 255 255 255 255 344 344 344 344 274 274 274 274 274 274
Notes page 11-69; References page II - 70
TABLE 6. cont'd Number of C atoms 10 (cont'd)
Initiator Di(tert-butylperoxy)-oxalate
Solvent Benzene
tert-Butanol Decane Dodecane Octane n-Pentane Tetradecane Styrene
11
tert-Butyl 5-methyl-7-perthenoate
Carbon tetrachloride
P-Methyl-P-phenyl-P-peroxypropiolactone
Carbon tetrachloride
Bis(2-nitro-2-methylpropyl)-peroxydicarbonate 1-Phenylethylperacetate tert-Butyl 4-chloroperbenzoate
tert-Butyl-JV-(2-chlorophenylperoxy)carbamate
Toluene Benzene Phenyl ether
Carbon tetrachloride Toluene
tert-Butyl-AK3-chlorophenylperoxy> carbamate
Toluene
tert-Butyl-AH4-chlorophenylperoxy)carbamate
Toluene
tert-Butyl cyclohexylperoxycarboxylate
«-Hexadecane 2,2,4-Trimethylpentane
tert-Butyl-iV-(2,5-dichlorophenylperoxy) carbamate
Toluene
tert-Butyl 2,2-dimethylperpentanoate
Cyclohexane
Cumene tert-Butyl 5-ethyl-2-perthenoate
Carbon tetrachloride
tert-Butyl 2-iodoperbenzoate
Chlorobenzene
tert-butyl 4-nitroperbenzoate
Phenyl ether
tert-Butyl 3,5-dinitroperbenzoate
Carbon tetrachloride Carbon tetrachloride
T( 0 C)
kd (s"1)
Ea (kj/mol)
Notes c,h c c
35.0 45.0 55.0 25.0 41 41 41 37.8 41 35 45 55 99.2 112.0 124.5 106.8 126 134 50
6.77 x 10" 5 2.6IxIO" 4 9.3 XlO" 4 1.83 x l O " 5 1.75 x 10 " 4 1.81 x 10" 4 1.79 x 10 " 4 1.01 x 10" 4 1.71 x 10~4 5.5xl0"5 1.71 x 10" 4 6.0IxIO" 4 4.6xlO~ 6 1.94 x l 0 ~ 5 7.95 XlO" 5 5.65 x 10 " 6 4.59 x 10 " 5 9.71 x 10" 5 2.22 x 10 ~5
106.7
100 100.0 110.1 120.2 130.9 80 87.0 95.5 103.3 78.0 87.0 96.6 102.7 73.0 78.5 87.0 92.5 92.9 102.6 82.2 92.9 102.6 113.0 88.0 95.0 103.3 114.5 55 65 75 45 55 99.2 112.0 124.5 85.0 102.4 118.8 110.1 120.2 130.9 141.5 80 80
1.14 x l O " 4 3.89 x 10 ~6 1.85 x l 0 ~ 5 6.39 XlO" 5 2.42 xlO~ 4 4.2xlO~ 7 3.5xl0"5 1.48 x 10 ~4 3.3 XlO" 4 2.6 x l O " 5 7.8xl0"5 2.03 xlO~ 4 4.62 XlO" 4 5.57 x 10 ~5 1.42 x 10 ~4 2.75 xlO~ 4 5.37 x l O " 4 6.70xl0~ 5 2.046 x 10 ~4 1.57 x l O " 5 6.13 x l 0 ~ 5 2.046 xlO~ 4 6.58 x l O " 4 2.75 x 10 ~5 5.58 x 10 ~5 1.48 xlO~ 4 4.82 xlO~ 4 1.66 x 10 ~5 6.31 x 10~5 2.23 xlO~ 4 6.2xlO~ 6 2.15 x l 0 ~ 5 5.39 x 10 ~6 2.12 x l 0 ~ 5 7.91 x 10~5 4.02 x 10 ~5 2.58 xlO~ 4 1.32 xlO~ 3 7.56 x 10 " 6 3.19 x l 0 ~ 5 1.11 xlO~ 4 3.92 xlO~ 4 2.9xlO~ 7 1.1 x 10 ~7
138.7 164.4
h a a a a
157.3
h
115.5
h
119.7
h
136.6
h
135.8
h
128.9
h
120.7
h
105.4
h
75.3
137.7
131.8
a,m2 a,m2 a,m2 h,v 9 c,v9 a
130.5
172.8
Refs. 30 30 30 197 270 270 270 197 270 215 215 215 176 176 176 195 195 195 90 259 53 53 53 53 354 36 36 36 36 36 36 36 36 36 36 36 255 255 255 255 255 255 36 36 36 36 320 320 320 160 160 176 176 176 134 134 134 53 53 53 53 354 354
TABLE 6. cont'd Number of C atoms W (cont'd)
Initiator
Solvent
/m-Butyl-AH3-nitrophenylperoxy)carbamate
Toluene
fm-Butyl-AK4-nitrophenylperoxy)carbamate
Toluene
terf-Butyl perbenzoate
Acetic acid Benzene
Bromobenzene rc-Butanol «-Butyl acetate
tert-Butylbenzene w-Butyl ether Carbon tetrachloride Chlorobenzene
4-Chlorotoluene
Cumene
Decane
Dodecane Ethylbenzene Heptane Hexadecane Methyl benzoate Octane Phenyl ether
Tetradecane Trimethylbenzene Xylene
T( 0 C) 78.0 88.7 98.0 106.0 73.0 87.0 98.0 106.0 100.0 110.0 100 115 130 110.0 119.4 130.0 119.4 90.0 100.0 110.0 119.4 110.0 1194 119.4 100.0 110.0 80 110.0 119.4 120 135 150 103 122 142 T(K) 110.0 119.4 130.0 60 79.6 85.0 99.3 115.0 130.2 100 115 130 115 115 119.4 115 115 119.4 115 100.0 110.1 120.2 130.9 115 T (K) 119.4 130.0
A:d (s"1) 8.4 x l O " 6 2.43 x 10 " 5 1.01 x 10- 4 2.36 x l O " 4 6.4xlO~ 6 3.11 x 10~5 8.75 x l O " 5 2.38 xlO~ 4 3.83 x 10 ~5 1.14 x 10~4 1.07 x KT 5 6.22 x l 0 ~ 5 3.5OxIO- 4 3.50xl0" 5 1.04 XlO" 4 3.30xl0~ 4 1.37 x 10 ~4 9.27 x 10 " 5 2.7OxIO- 4 1.06 x 10~4 2.67 x l O " 4 3.6IxIO- 5 1.10 xlO~ 4 1.03 x 10 ~4 7.8OxIO- 5 1.80 XlO" 4 8.8xl0"7 3.83 x 10~5 1.11 x l O " 4 1.3IxIO- 4 6.74 x l O - 4 3.12 x l O - 3 1.93 XlO" 5 1.93 x l O - 4 1.93 x l O " 3 2.23 xlO 1 6 3.25 x 10 " 5 9.80xl0"5 3.06 x l O - 4 3.85 XlO" 7 7.21 x 10 ~5 1.320xl0" 6 9.37 x l O - 6 5.8IxIO- 5 3.24 x l O " 4 1.4xlO- 5 8.05 XlO" 5 3.56 x l O - 4 6.77 XlO" 5 6.44 x KT 5 1.07 x 10~4 7.21 x 10~5 5.97 x 10 ~5 7.8OxIO" 5 7.06 x 10 " 5 6.94 x 10 ~6 2.28 x l O " 5 9.0OxIO- 5 2.92 x l O " 4 6.03 x 10 ~5 2.62 x 1016 1.09 x 10~4 3.42 x l O - 4
E2, (kj/mol)
Notes
133.1
h
113.8
h
130.1
a a a a a a a a a a a a a a,m2 a,m2 a a a
145.2
144.3
120.5 123.4 148.5
99.2
141.8
exp[- 151.59/RT\ 144.3
140.2
134
a a m2 m2 m2
c c c a,h
a a a
a
a 156.9
exp[-152.0/RT] 141.4
a a a a
a a
Refs. 36 36 36 36 36 36 36 36 56 56 126,337 126,337 126,337 56 56 56 56 56 56 56 56 56 56 56 56 56 354 56 56 22 22 22 344 344 344 344 55 55 55 81 272 345 345 345 345 337 337 337 270 270 56 270 270 56 270 53 53 53 53 270 376 56 56
Notes page 11-69; References page II - 70
TABLE 6. cont'd Number of C atoms 11 (cont'd)
Initiator
Solvent
terf-Butyl-AK4-bromophenylperoxy)carbamate
Toluene
tert-Butyl percarboxycyclohexane
Chlorobenzene
Cumene
12
tert-Butyl per-2-methylphenylacetate
Isooctane
tert-Butyl-N-(phenylperoxy) carbamate
Toluene
tert-Hexyl peroxypivalate
Chlorobenzene Cumene
1,1,2-Trimethylpropyl perpivalate
Cumene
Cumyl peracetate tert-Amyl peroxybenzoate
Carbon tetrachloride Toluene Chlorobenzene
4-Bromocumyl perpropionate
Benzene
oc-Methylstyrene
tert-Butyl bicyclo[2.2.1]lheptane2-percarboxylate
terf-Butyl endo-bicyclo[2.2.1]heptane percarboxylate
Cumene
Chlorobenzene
Cumene
terf-Butylexo-bicyclo[2.2.11]heptane-2-percarboxylate
Chlorobenzene
T( 0 C) 70.8 79.8 84.0 96.0 100.1 111.4 120.0 79.6 79.6 79.6 60.6 73.9 51.2 67.7 77.7 90.7 T(K) 40 50 60 70 80 40 50 60 70 100 100 99 118 139 T (K) 70 80 90 70 80 90 85 100 110 110 120 130 94.0 101.9 109.6 120.5 94.5 101.9 111.9 100.1 111.4 120.0 94.0 101.9 109.6 120.3 94.5 101.9 111.9 94.5 101.9 112.1
A^(S"1) 3.32 x 10 " 5 1.04 x 10 ~4 1.75 x l O - 4 7.70xl0~ 4 2.75 x 10 ~4 9.65 XlO- 4 2.39 XlO- 3 1.86 x l O " 5 1.42 x l 0 ~ 5 1.15xl0- 5 6.60 x 10 ~5 3.233 x l O - 4 3.4xlO-6 2.31 x 10 " 5 1.15 x l O - 4 6.41 x 10 ~4 1.51 x 1016 2.39 x 10 ~6 8.83 x l O - 6 3.37xl0-5 1.226 x l O - 4 4.166 x l O - 4 3.6xlO" 6 1.59x10-5 5.14x10-5 1.921 x 10- 4 4.68 x 10 " 5 3.43 x 10 ~5 1.93 x 10 ~5 1.93 x 10~4 1.93 x l O - 3 8.38 x 1015 1.48 x 10 " 6 5.73 x l O - 6 1.8IxIO- 5 1.99 x 10~6 4.93 x l O - 6 1.55x10-5 1.16 x 10~6 1.02 x 10 ~5 3.76xlO- 5 4.6x10-5 1.56 XlO" 4 4.99 x l O " 4 1.75XlO" 5 6.20xl0"5 1.7 x l O - 4 5.72 x l O - 4 9.69x10-5 1.96xlO- 5 6.53x10-5 4.6IxIO-5 1.96 xlO~ 4 5.4OxIO- 4 1.87 x l O " 5 5.3OxIO- 5 1.10 x l O " 4 4.3 x l O - 4 5.27xl0-5 1.12 x l O - 4 3.57 x l O - 4 8.86 x 10 ~5 2.28 x 10 ~4 8.85 x l O - 4
Ea (kj/mol)
Notes
177.6
h
131.0
h
139.7
z (1) z (2030) z (4050) ni2 m2 h
exp[- 136.0/RT]
c p
exp[- 147.02/RTl 129.7
121.3
a a a a a
155.2 160
h
150.2
h
137.2
h
149.0
h
154.0
h
130.1
h
Refs. 36 36 36 36 181 181 181 163 163 163 165 165 36 36 36 36 40 362 362 362 362 362 362 362 362 362 271 271 344 344 344 344 213 213 213 213 213 213 160 160 223 223 223 147 147 147 147 147 182 182 181 181 181 147 147 147 147 182 182 182 182 182 182
TABLE 6. Number of C atoms
cont'd
Initiator
Solvent
12 (cont'd)
Cumene
tert-Butyl endo-bicyclo[2.2.1]-hept5-ene-2-percarboxylate
Cumene
tert-Butyl exo-bicyclo[2.2.1]-hept5-ene-2-percarboxylate
Chlorobenzene
Cumene
tert-Butyl 4-bromophenoxyperacetate tert-Butyl 4-chlorophenoxyperacetate tert-Butyl 3-chlorophenylperacetate
Ethylbenzene Ethylbenzene Chlorobenzene
Cumene tert-Butyl 4-chlorophenyl peracetate
Chlorobenzene
Cumene tert-Butylcycloheptyl percarboxylate
rc-Hexadecane 2,2,4-Trimethylpentane
tert-Butyl 2,4-dichlorophenoxyperacetate tert-Butyl 2,2-diethyl perbutyrate
Ethylbenzene Cumene
tert-Butyl per-2-ethylhexanoate
Benzene Chlorobenzene
tert-Butyl 2-methoxy-2-methylperpropionate
Chlorobenzene
tert-Butyl 4-methoxyperbenzoate
Phenyl ether
tert-Butyl peroxy-2-methylbenzoate
Chlorobenzene
tert-Butyl 4-methoxyperbenzoate tert-Butyl 4-methylperbenzoate
Carbon tetrachloride Phenyl ether
T( 0 C)
£ d (s"1)
96.0 100.1 111.4 120.0 84.4 94.7 100.1 108.6 113.5 94.5 101.9 112.1 94.5 101.9 112.0 94.5 101.9 112.1 94.5 101.9 112.1 70.5 70.5 79.6 90.7 100.5 79.6 79.6 79.6 90.7 100.5 79.6 79.6 92.9 102.6 92.9 102.6 70.5
1.33 x 10"4 1.90xl0" 4 6.79 xlO" 4 1.64 xlO" 3 2.19 xlO" 5 7.29 x l 0 ~ 5 1.37 xlO~ 4 3.6 XlO" 4 6.19 XlO" 4 6.05 x l O " 5 1.53 x l O " 4 4.72 XlO" 4 3.11 x l O " 5 7.35 x 10 ~5 2.48 x l O " 4 5.59 x l O " 5 1 25 x 10" 4 5.0OxIO" 4 4.48 x l O " 5 1.18 x l O - 4 3.97 x l O " 4 2.6xlO~ 4 2.9xlO~ 4 4.05 x 10 ~5 1.44 x l O - 4 4.38 x l O " 4 2.98 x 10 " 5 1.99 x l O " 5 8.44 x 10 " 5 2.95 x l O - 4 8.19 x l O " 4 6.54 x 10 " 5 4.45 x 10 " 5 1.801 x 10 " 4 5.17 x l O " 4 1.703 x 10 " 4 5.07 x l O " 4 9.4xlO" 5
45 55 65 72 72 91 113 T(K) -14.0 -7.0 -1.0 15.0 100.0 110.1 120.2 130.9 96 115 136 T (K) 80 100.0 110.1 120.2
1.23 x 10 " 5 4.92 x l O " 5 1.46 x l O - 4 1.9xlO" 5 1.93 x 10 ~5 1.93 x l O " 4 1.93xl0- 3 1.54 xlO 1 4 2.05 x 10 " 5 6.73 x 10" 5 1.67 XlO" 4 1.28 XlO" 3 1.07 x 10 " 5 4.17 x l O " 5 1.28 x l O - 4 4.28 x l O " 4 1.93 x 10 " 5 1.93 x 10 " 4 1.93 x l O " 3 8.56 x 1015 l.OxlO" 6 9.42 x 10 " 6 3.19 XlO" 5 1.06 XlO" 4
Ea (kj/mol)
Notes
129.3
h
129.3
h
131.4
h
136.4
h
138.1
h
123.0
a a h
117.2
z (0.98) z (6090) h
121.5
z (0.98) z (6090) h
125.7
h a
100.3
h
a
exp[- 124.90/RT] 86.3
149.8
m2 m2 m2 m2 a a a a
expr[- 145.97/RT] 151.0
a a a
Refs. 147 181 181 181 147 147 147 147 147 182 182 182 182 182 182 182 182 182 182 182 182 315 315 178 178 178 207 207 178 178 178 207 207 255 255 255 255 315 160 160 160 338 344 344 344 344 275 275 275 275 53 53 53 53 344 344 344 344 354 53 53 53
Notes page 11-69; References page II - 70
TABLE 6. cont'd Number of C atoms 12 {cont'd)
Initiator terr-Butyl 4-methylperbenzoate rm-Butyl 2-methyl-2-terfbutylperoxyperpropionate
Solvent Phenyl ether Benzene
terf-Butyl 2-methylsulfonyl perbenzoate
Chlorobenzene
tert-Butyl 2-(methylthio)perbenzoate
Chlorobenzene
tert-Butyl 4-(methylthio)perbenzoate terf-Butyl 4-nitrophenoxyperacetate /m-Butyl 4-nitrophenylperacetate
Chlorobenzene Ethylbenzene Chlorobenzene
terf-Butyl 4-nitrophenylperacetate
Decane Dodecane Hexadecane Octane
Di-terf-butyl per-2-chlorosuccinoate
Tetradecane Unknown
T( 0 C) 130.9 9.0 19.0 30.0 42.0 105 120 135 150.6 60 39.4 50.1 50.2 69.8 120.4 70.5 79.6 90.7 100.5 80 77.5 77.5 100 77.5 77.5 100 77.5 105 115 125
tert-Butyl peroctoate
Benzene
Decane
Di-rm-butyl persuccinoate
Styrene
/m-Butyl phenoxyperacetate rm-Butyl phenylperacetate
Ethylbenzene Chlorobenzene
Cumene
Decane Dodecane Hexadecane Isooctane
70 85 100 70 85 100 105 115 125 70.5 60 77.0 88.6 79.6 90.7 100.5 79.6 79.6 79.6 79.6 85.0 79.6 79.6 79.6 79.6 79.61 77.5 77.5 77.5 85.0 95.2
^d(S"1) 3.25 x 10~A 6.66 xlO~ 5 1.99 x 10 ~4 6.94 xlO~ 4 2.43 x l 0 ~ 3 6.68 x 10 ~6 5.57 x 10~5 2.76 xlO~ 4 2.05 x l 0 ~ 3 8.08 x 10~A 2.59 x l O - 5 2.42 XlO- 4 1.88 x l O - 4 1.96 XlO" 3 1.75 x 10 ~4 6.7xlO" 5 2.5xlO" 5 8.9 XlO" 5 2.83 xlO~ 4 3.77 XlO" 5 6.3OxIO- 6 5.8IxIO" 6 1.3IxIO- 4 5.11 x 10" 6 6.42 x 10 " 6 1.6OxIO- 4 5.56 x 10 " 6 2.74 x 10 " 4 1.22 x l O - 5 5.9OxIO" 4 3.83 x l O - 5 1.52 XlO" 3 1.00 x l O - 4 1.4xlO" 5 8.55 x l O - 5 4.55 x l O - 4 6.9xlO~ 6 4.39 x l O - 5 2.64 x l O - 4 1.93 x 10 " 5 6.7 x l O - 5 2.53 XlO" 4 4.4xlO" 4 6.79 x 10~6 6.85 x l O - 5 2.45 x l O - 4 1.05 x l O - 4 3.53 XlO" 4 1.003 XlO" 3 1.07 x l O - 4 9.1 x 10 " 5 1.02 XlO" 4 9.0 x 10- 4 1.945 XlO" 4 6.6xlO- 5 5.6 xlO~ 5 6.78 x l O - 5 4.73 x l O - 5 1.1 x l 0 ~ 5 3.0OxIO- 5 2.75 x l 0 ~ 5 2.6OxIO- 5 1.08 x l O " 4 3.527 x l O - 4
E2, (kj/mol)
Notes
78.8
a m2
95.0
a,h b c m2
129.9 124.7
a,h h
102.9 143.5
X2 X2 X2 x2 X2 x2 a a a a a a Xi X1 X1 a,h a,h h m2 h
130
130
154.8
113.1 120.1 117.6 116.7
z (0.98) z (4050) z (0.98) z (4050) m2 z (0.98) z (4050) z (0.98) z (6090)
Refs. 53 275 275 275 275 22 22 22 22 97 134 134 134 134 134 315 178 178 178 169 168 168 168 168 168 168 168 214 214 214 214 214 214 337 337 337 337 337 337 215 215 215 315 81 28 28 178 178 178 157 157 163 163 165 157 157 163,207 163,207 274 168 168 168 165 165
TABLE 6. cont'd Number of C atoms 12 (cont'd)
Initiator tert-Butyl phenylperacetate
tert-Buty\ 2-propylperpenten-2-oate (cw)
(trans)
Solvent Octane Paraffin oil Tetradecane Cumene
Cumene
tert-Butyl 2,2,3,3-tetramethylperpropionate
Cumene
tert-Butyl thiophenylperacetate tert-Butyl per-o-toluate ferf-Butyl per-paratoluate
Ethylbenzene Benzene Cumene
tert-Butyl-AH3-tolylperoxy)carbamate
Toluene
tert-Butyl 2,4,5-trichlorophenoxyperacetate 4-Chlorocumyl perpropionate
Ethylbenzene Benzene
a-Methylstyrene
Cumyl perpropionate
Benzene
a-Methylstyrene
4-Iodocumyl perpropionate
Benzene
a-Methylstyrene
4-Nitrocumyl perpropionate
Benzene
a-Methylstyrene
13
1,1,3-Trimethylbutyl perpivalate
Cumene
tert-Amyl per-2-ethylhexanoate
Benzene Chlorobenzene
Benzyl(ter?-butylperoxy)oxalate
Benzene
T( 0 C) 77.5 85.0 77.3 94.9 100.1 100.1 100.1 110.1 94.9 100.1 100.1 100.1 110.1 42.2 54.9 70.3 70.5 97 84.0 99.3 115.0 64.0 70.7 78.0 88.5 70.5 70 80 90 70 80 90 70 80 90 70 80 90 70 80 90 70 80 90 70 80 90 70 80 90 40 50 60 70 70 73 91 111 T(K) 45 55 65
A^(S"1) 3.1IxIO"5 1.150 x 10~4 2.66 x 10 ~5 2.78 x 10 ~5 5.4 XlO" 5 4.26 x l 0 ~ 5 2.31 x 10~5 1.72 x l O - 4 2.47 x 10 ~5 4.7 x l O - 5 3.13 x l O - 5 1.42 x-K) - 5 1.64 x l O - 4 8.76 x l O " 6 5.84 x 10 ~5 3.36 x l O - 4 3.8 x 10 ~4 1.9xl0"5 1.660 x 10 ~6 1.139 x l O - 5 6.77 XlO" 5 4.58 x 10 " 5 9.17 x l O " 5 2.03 x l O - 4 5.78 x l O - 4 5.8 x l O " 5 1.46 x 10 " 6 5.68 x l O - 6 1.79 x l O " 5 1.50x 10" 6 4.54 x l O - 6 1.47 x l O - 5 2.6OxIO- 6 6.15 x l O - 6 1.90 x l O " 5 6.31 x 10 ~6 1.7IxIO- 5 4.94 x l O " 5 1.37 x 10~6 5.76 x l O - 6 1.79 x l O - 5 1.54 x 10~6 4.96 x l O - 6 1.62 x l O - 5 1.36 x 10 " 6 5.32 x l O " 6 1.78 x l O - 5 1.35 x 10~6 4.07 x l O - 6 1.43 x l O - 5 4.8OxIO- 6 1.77 x l O - 5 6.18 x l O " 5 2.344 x l O - 4 1.9xl0-5 1.93 x 10 ~5 1.93 x l O - 4 1.93 x l O - 3 1.77 x l O 1 5 3.65 x 10 " 5 1.33 x l O - 4 4.69 x l O - 4
Ea (kj/mol)
Notes
137.2
h z (0.98) z (1100) z (4000)
143.9
h z (0.98) z(llOO) z (3830)
114
h
a a
102.9
h
a 129.3
118.8
101.7
106.7
133.1
125.5
133.5
124.7
a a a a a a a a a a a a a a a a a a a a a a a a
a
exp[- 132.1 l/RT] 111.3
c,h c c
Refs. 168 165 168 172 172 172 172 172 172 172 172 172 172 267 267 267 315 338 345 345 345 36 36 36 36 315 213 213 213 213 213 213 213 213 213 213 213 213 213 213 213 213 213 213 213 213 213 213 213 213 362 362 362 362 338 344 344 344 344 31 31 31
Notes page 11-69; References page 11-70
TABLE 6. cont'd Number of C atoms 13 (cont'd)
Initiator
Solvent
tert-Butyl benzyloxyperacetate
Ethylbenzene
tert-Butyl benzylthioperacetate
Ethylbenzene
tert-Butyl bicyclo[2.2.2]octane1-percarboxylate
Cumene
ter/-Butyl endo-bicyclo[2.2.1j-2methylheptane-2-percarboxylate
Cumene
tert-Butyl exo-bicyclo[2.2.1]2-methylheptane-2-percarboxylate
Cumene
tert-Butyl 1,4-dimethylcyclohexane1-percarboxylate (cis)
Cumene
(trans)
Cumene
tert-Butyl 3-methoxyphenylperacetate
Chlorobenzene
terf-Butyl 4- methoxyphenylperacetate
Chlorobenzene
Cumene
tert-Butyl 4-methylphenyl peracetate
Decane Dodecane Ethylbenzene Isooctane Octane Paraffin oil Tetradecane Chlorobenzene
Cumene
Di-terr-butyl perglutarate
terf-Butylperoxy 2-ethylhexylcarbonate
Decane Dodecane Ethylbenzene Hexadecane Octane Tetradecane Styrene
Chlorobenzene
T( 0 C) 40.0 40.0 51.0 60.7 40.0 60.0 70.0 65 75 85 80 90 100 75 80 85 90 95 60 65 70 75 80 60.0 70.0 80.0 60.0 70.0 80.0 79.6 90.7 100.5 56.0 60.3 70.2 79.3 48.9 60 60 79.6 77.5 77.5 70.5 60.5 77.5 60.5 77.5 70.4 79.6 90.7 79.6 79.6 77.5 77.5 70.5 77.5 77.5 77.5 105 115 125 99 117 137
A:d (s"1) 1.3 x 10" 4 1.45 x l O - 4 5.03 XlO" 4 1.62 x l O - 3 2.60xl0~~5 3.31 x 10- 4 1.14 XlO" 3 7.5 x 10 ~6 2.82 x l O " 5 8.47 x l O " 5 5.IxIO"5 1.67 x l O - 4 4.86 XlO" 4 7.35 x 10 ~5 1.39 x 10 " 4 2.64 x l O - 4 4.81 x 10 " 4 8.41 x 10- 4 7.78 x 10 " 5 1.44 x 10 " 4 2.75 x l O " 4 4.89 XlO" 4 8.93 XlO" 4 7.52 x l O " 5 2.66 x 10 " 4 8.49 xlO~ 4 6.93 x 10 ~5 2.52 x l O " 4 7.79 x l 0 ~ 4 9.9xl0~5 3.45 x 10 ~4 1.051 x 10" 3 4.57 x 10 ~5 9.9xlO~ 5 3.06 x l O " 4 7.99 xlO~ 4 1.93 XlO" 5 6.85 x 10 ~5 5.31 x 10 ~5 5.942 x l O - 4 2.52 x 10 ~4 2.60xl0~ 4 1.4xlO~ 3 4.72 x 10 ~5 2.53 x 10 ~4 4.20 x l 0 ~ 5 2.68 x 10 ~4 8.67 x 10 ~5 2.37 xlO~ 4 7.95 xlO~ 4 1.649 x 10 ~4 1.180xl0~ 4 9.08 x 10 ~5 8.57 x l 0 ~ 5 7.2xlO~ 4 1.032 x 10 ~4 8.83 x 10 ~5 7.75 x 10 ~5 2.65 x 10 ~5 1.06 xlO~ 4 3.0OxIO- 4 1.93 x 10 ~5 1.93 x 10 ~4 1.93 x l 0 ~ 3
Ea (kj/mol)
Notes
100.6 101.8
a,h h,m2
108.1
h,m2
119.2
h
120.1
h
126.8
h
116.7
h
115.2
c h
116.3
c c,h c
122.2
h
105.4
h
k z (0.98) z (4050)
Refs. 315 328 328 328 328 328 328 160 160 160 223 223 223 206 206 206 206 206 206 206 206 206 206 206 206 206 206 206 206 178 178 178 178 178 178 178 249 207 207
207
104.8
a,h
110.9
h
z (0.98) z (6080)
a
Xi X1
168 168 315 169 168 169 168 178 178 178 207 207 168 168 315 168 168 168 215 215 215 344 344 344
TABLE 6.
cont'd
Number of C atoms 13 (cont'd)
14
Initiator terf-Butylperoxy 2-ethylhexylcarbonate terr-Butyl 2-phenylperpropionate
Solvent
T(K)
4.07 xlO 1 6
Cumene
40.7 60.1 80.1 40.8 54.7 70.7 40.0 95 114 135 T(K) 45 55 65 95 113 134 T (K) 54.7 70.2 85.4 70.8 85.4 101.0 40.0
7.88 x 10 " 6 8.44 x l O - 5 8.1OxIO- 4 6.15 x 10~6 3.82 x 10 ~5 2.73xlO- 4 2.62 x 10 " 5 1.93 x 10 " 5 1.93XlO" 4 1.93 x l O - 3 1.94 xlO 1 5 1.3OxIO" 5 4.89 x 10 " 5 1.89 x l O - 4 1.93 x 10 ~5 1.93 x l O " 4 1.93 x l O " 3 2.22 x 1016 4.38 x 1O -6 3.56 x l O - 5 2.44 x l O - 4 1.48 x 10 " 5 8.07 x 10" 5 4.38 x l O " 4 7.2xlO-4
50.0 50.0 50.0 60.0 67.0 50.0 60.0 67.0 50.0 60.0 67.0 99.6 109.8 99.6 109.8 34.1 39.7 47 46 64 84 T (K) 50.0 50.0 50.0 60.0 67.0 67.0 84.0 99.3 115.0 113.0 120.0 130.0 140.0
2.55 x 10 " 4 2.03 x 10 " 4 7.98 x 10~5 2.68 x l O - 4 6.36 x l O - 4 8.0OxIO- 5 2.56 x l O " 4 5.96 x l O - 4 8.1OxIO- 5 2.65 x l O - 4 5.95 x l O " 4 1.23 x 10 " 4 3.7OxIO- 4 3.5 x 10~5 1.03 x l O - 4 3.26 x 10 ~5 5.63 x 10" 5 1.9xlO- 5 1.93 x 10 " 5 1.93 x l O " 4 1.93 x l O " 3 1.52 x 1014 7.5OxIO- 5 6.4OxIO" 5 2.63 x 10- 5 9.27 x l O - 5 2.03 x l O " 4 1.98 x 10 - 4 1.464 x 10 " 5 9.94 XlO" 5 6.7 x l O - 5 8.67 x l O " 5 2.49 x 10 ~4 7.49 x l O " 4 2.22 x l O - 3
Cumene
terf-Butylthiobenzylperacetate tert-Butyl peroxy-3,5,5-trimethylhexanoate
Ethylbenzene Chlorobenzene
4-Nitrobenzyl(terf-butylperoxy)oxalate
Benzene
2-ethylhexyl-
Chlorobenzene
tert-Butyl di-terf-butylperacetate
Cumene
terf-Butyl 2-carbomethoxyphenylperacetate
Cumene
terf-Butyl 2-(4-chlorophenoxy)2-methylperpropionate tert-Butyl 2-(4-chlorophenyl)2-methylperpropionate
Ethylbenzene Acetonitrile Benzene Dodecane
Hexadecane
Octane
tert-Butyl a-methylpercinnamate (cis) (trans)
kd (s'1)
Chlorobenzene
tert-Butyl 2,2,4,4-tetramethylperbutyrate
terf-Amylperoxy carbonate
T(0C)
Cumene Cumene
tert-Butyl 2-methyl-2-phenylperpropionate tert-Butyl perneodecanoate
Chlorobenzene Cumene Benzene Chlorobenzene
tert-Butyl 2-(4-nitrophenyl)2-methylperpropionate
Acetonitrile Benzene Dodecane
tert-Butyl permesitoate
Octane Cumene
tert-Butyl 1-phenylcyclopropylpercarboxylate
rc-Dodecane Ethylbenzene
Ea (kj/mol)
Notes
exp[-151.72/RT]
344
111
h
100.6
a,h
exp[- 140.78/K7] 116.7
c,h c c
exp[- 148.41/#7] 125.3
h
116.9
h
a
108.1
h
128.0
f,h f f,h f
125.5
exp[- 115 A7/RT] 105.2
147.5
Refs.
h
h,t i ti ti
273 273 273 267 267 267 315 344 344 344 344 31 31 31 344 344 344 344 245 245 245 257 257 257 315 265 265 265 265 265 265 265 265 265 265 265 150 150 150 150 249 249 338 344 344 344 344 265 265 265 265 265 265 345 345 345 255 323 323 323
Notes page 11-69; References page 11-70
TABLE 6. cont'd Number of C atoms 14 (cont'd)
Initiator tert-Butyl 1-phenylcyclopropylpercarboxylate
Solvent 2,2,4-Trimethyl pentane
tert-Butyl phenyldimethylperacetate
Chlorobenzene Isooctane
tert-Butyl 2-phenyl-3-perbutenoate tert-Butyl 4-phenyl-3-perbutenoate tert-Butyl 2-phenyl-2-methylperpropionate
Chlorohenzene Chlorobenzene Acetonitrile Benzene Benzophenone Benzyl benzoate Butyl phthalate Chlorobenzene Cumene Dodecane
tert-Butyl 4-vinylphenylperacetate
Hexadecane Methyl benzoate Octyl phthalate Toluene Cumene
Dibenzyl peroxalate Di-tert-butyl adipate
Pentane Styrene
Dicyclohexyl peroxydicarbonate
Benzene Chlorobenzene
a-Methylstyrene Mineral spirits
15
4-Methoxybenzyl (tert-butylperoxy)oxalate
Benzene
1-Methyl-1-phenylethyl 2,2-dimethylperoxyporpionate
Cumene
tert-Amy\ perneodecanoate
Benzene Chlorobenzene
Dibenzoyl monopercarbonate tert-Butyl 1-adamantylpercarboxylate
Benzene Cumene
T( 0 C) 102.6 113.0 120.4 60 40.6 60.6 60.6 60 60 50.0 50.0 60 60 60 60 60 50.0 60.0 67.0 60 60 60 60 60 70.9 85.4 100.3 25 105 115 125 50 44 60 77 T (K) 50 45 50 60 45 55 65 40 50 60 70 45 43 61 81 T (K) 60.00 45 55 65 64.6 74.6 84.6 60 70 80
^d(S" 1 ) 2.53 x 10 ~5 8.96 x 10 ~5 2.04 xlO~ 4 9.6xlO~ 4 2.95 x 10 ~5 3.059 xlO~ 4 4.064 xlO~ 4 2.9xlO~ 3 1.15 x 10 ~4 3.08 x 10 " 4 2.18 xlO~ 4 7.73 x 10 ~A 7.92 x 10 ~4 6.5 x 10 ~4 7.00xl0~ 4 5.25 x 10 ~4 8.77 x 10 ~5 3.00xl0~ 4 7.13 xlO~ 4 2.88 xlO~ 4 3.53 x 10 ~4 7.55 x 10 ~4 5.70xl0~ 4 5.66 x 10 ~4 5.54 x 10 " 5 3.00xl0~ 4 1.48 x l 0 ~ 3 6.7 x 10 ~5 3.50xl0~ 5 1.23 xlO~ 4 3.05 xlO~ 4 5.4xlO~ 5 1.93 x 10 ~5 1.93 x l 0 ~ 4 1.93 x l 0 ~ 3 3.3 x 1016 5.9xlO~ 5 2.78 x 10 ~5 5.58 xlO~ 4 2.07 xlO~ 4 6.69 x 10 ~5 2.48 x 10 ~A 8.27 xlO~ 4 6.91 x 10 ~6 2.80 x 10 ~5 1.032 xlO~ 4 3.57 x l O - 4 1.9xl0~ 5 1.93 x 10 ~5 1.93 xlO~ 4 1.93 x l O - 3 1.47 x 1014 8.05 x 10 ~5 5.15 x 10 ~5 2.05 x 10 ~5 7.4OxIO- 5 6.87xl0-5 2.44 xlO~ 4 7.78 x l O - 4 5.4 x l O - 5 2.12 x l O - 4 7.20xl0~ 4
Ea (kj/mol)
Notes
141.2
h
109.2
96.2 98.3
c,h t9 t9 m2 c,h c,h,g
109.3
h
t 12
116.5
h,k k
151.0
X2 X1 X1 c
exp[- 129.0/RT] 117
109.6
a a a c,h c c
a
exp[- 114.38/K7] 116.5 115.5
h h
116.7
h
124.7
h
Refs. 255 255 255 81 165 165 165 81 81 265 265 334 334 334 334 334 265 265 265 334 334 334 334 334 254 254 254 203 215 215 215 201 344 344 344 344 201 337 337 337 31 31 31 368 368 368 368 338 344 344 344 344 280 160 160 160 159 159 159 223 223 223
TABLE 6. Number of C atoms 15 (cont'd)
cont'd
Initiator tert-Butyl 4-(carboethoxy)phenoxyperacetate tert-Butyl a,p-dimethylpercinnamate (cis)
Solvent Ethylbenzene
(trans)
tert-Butyl 1-pernaphthoate tert-Butyl 2,2-dimethyl3-phenylthio perpropionate
Chlorobenzene Cyclohexane
tert-Butyl 2-(4-methoxyphenyl)2-methylperpropionate
Acetonitrile Benzene Dodecane
tert-Butyl 1-phenylcyclo-n-Dodecane butylpercarboxylate
tert-Butyl 4-tert-butylperbenzoate
Chlorobenzene
Di-tert-butyl perpimelate
Styrene
tert-Butyl 2-(4-tolyl)2-methylperpropionate
Acetonitrile Benzene Dodecane
tert-Butyl triisopropylperacetate
16
Octane 52.3 Ethylbenzene n-Hexadecane 2,2,4-trimethyl pentane
Octane Cumene
l,l-Dimethyl-2-phenylethylperpivalate
Cumene
1-Phenylethyl 4-methoxyperacetate 1-Phenylethyl 3-nitroperbenzoate 1-Phenylethyl 4-nitroperbenzoate 1-Phenylethyl perbenzoate Dibenzyl peroxydicarbonate
Benzene Benzene Benzene Benzene Benzene
Di-tert-butyl2-iodoperisophthalate
Chlorobenzene
Di-tert-butyl perphthalate
Benzene
Di-n-butyl phthalate
Chlorobenzene
T( 0 C) 70.5 95.0 103.2 110.1 85.1 95.0 103.7 110.0 110.0 110.1 55 65 75 50 50 40 50 57 50 7.89 x 10 ~5 60.0 52.3 52.3 61.6 100.1 119.8 135.9 105 115 125 50.0 50.0 50.0 60.0 67.0 60.0 24.8 41.6 55.2 40 50 60 70 99.7 100 100 100 40 50 60 68.4 85.4 101.6 100 115 130 100 115 130 107 125 146 T(K)
A^(S"1)
Ea (kj/mol)
1.6xlO~ 4 1.02 xlO~ 4 2.29 x 10 ~4 5.15xlO- 4 3.9xl0~5 1.17xlO- 4 2.84xlO~4 6.05xl0-4 7.9OxIO- 4 8.69 x l 0 ~ 5 1.63 x 10 ~5 1.61 x 10 ~5 1.98xlO- 4 1.675 x 10 ~3 9.96 x 10 ~A 1.49 x l O " 4 4.21 x IO- 4 1.028 XlO" 3 4.18 xlO~ 4 3.62 x 10 " 4 8.80xl0~ 5 7.69 x 10 ~5 2.46x10-4 3.81 x 10 ~5 4.5OxIO- 4 2.38 x l 0 ~ 3 4.45 x 10 ~5 1.05x10-4 5.06x10-4 6.0OxIO" 4 3.85 x 10 " 4 1.9OxIO- 4 5.58 xlO~ 4 1.32OxlO" 3 5.43 x 10 " 4 5.32 x 10~6 6.84 x l O - 5 3.78 XlO" 4 4.56 x 10~6 1.833 x 10~5 6.1 x 10 ~5 2.5IxIO-4 3.50xl0"4 5.97 x 10 ~4 4.10xl0~4 4.03 x 10 ~4 2.0xl0"5 6.25 x l O - 5 2.67 x l O - 4 8.24 x 10~5 4.45 x l O - 4 1.68 x l O " 3 1.1 x 10 ~5 7.8IxIO-5 4.8IxIO"4 1.08 x 10 " 5 7.8 x l O " 5 4.8 XlO" 4 1.93 x 10 ~5 1.93 x l O - 4 1.93 x l O - 3 9.39 xlO 1 6
118.8
122.6
116.9
Notes a
315
a,h a a a,h a a a a,v6
151 151 151 151 151 151 151 151 154 320 320 320 265 265 265 265 265 265
h,t6 t6
93.0
h
255 ti 110.6
h
150.6
Xi X1 X1
100.6
h
111.5
h
134.1 136.2 146.2 123.6 117
h h h h a a a h
93.9
159
155.0
exp[-157.85/^7]
Refs.
a a a h
323 255 255 255 134 134 134 215 215 215 265 265 265 265 265 265 267 267 267 362 362 362 362 259 259 259 259 337 337 337 248 248 248 337 337 337 269 269 269 344 344 344 344
Notes page 11-69; References page 11-70
TABLE 6. cont'd Number of C atoms 16 (cont'd)
Initiator Di-tert-butyl perphthalate
Cumene
terr-Butyl 1-phenyl-l-cyclopentane percarboxylate terf-Butyl 2,3-dimethyl2-phenylperbutyrate Cumyl 7V-phenylperoxy carbamate Dibenzyl peroxydicarbonate Di-terr-butyl perphthalate
Di-tert-bxxty\ persuberate
17
Solvent
^d(S1) 6
Ethylbenzene
99.9 115.0 130.1 60.0
8.34 x 10" 4.68 XlO- 5 2.6OxIO- 4 1.52 x 10 ~3
Ethylbenzene
50
4.3OxIO- 5
T(K) 50 100 115 130 115 125 43.5 52.3 60 70 80 10 35 10 10 100
1.26 x l O 1 4 2.92 x 10 " 5 1.08 x 10 " 5 7.83 x l O - 5 4.8OxIO- 4 7.86 x 10 ~5 2.8IxIO-4 1.184 x l O " 4 3.51 x 10 ~4 1.9xlO~ 5 5.3OxIO- 5 1.38 x l O " 4 4.5 x 10~4 1.9 x l O - 3 6.4X10" 4 5.IxIO"4 2.16 x l O " 3
79.6 70.6 80.3 100.5 60.0 43.5 52.3 61.6 25 40 25 40 25 40 39.3 53.8 53.8 70.0 25 40 25 40 25 40 25 40 25 40 25 40 105 119.4 135.1 105 115 125 98 116 137 T (K)
2.38 x 10 " 5 9.44 x 10 ~6 2.8OxIO- 5 3.09 x l O - 4 1.9OxIO- 3 1.27 x 10 ~4 3.91 x 10 ~4 1.218 x l O - 3 1.89 x 10 ~5 1.22 x l O - 4 1.01 x 10 ~4 5.44 XlO" 4 5.26 x 10~5 3.24 x l O - 4 4.98 x 10 ~5 5.23 x l O ~ 4 4.58 x l O - 4 2.62 x l O " 3 1.76 XlO" 5 1.03 x l O - 4 9.8X10" 7 6.9 x l O - 6 1.11 x l O ~ 4 6.02 x 10 " 4 2.31 x 10~4 1.65 x l O " 3 1.33 x 10" 4 7.25 XlO" 4 8.21 x 10~4 4.75 x l O " 3 2.79 x 10 ~5 1.29 x 10 " 4 6.07 x l O - 4 5.13 x 10~5 1.2OxIO- 4 5.1OxIO- 4 1.93 x 10 ~5 1.93 x l O - 4 1.93 x l O - 3 1.35 x 10 16
Xylene Toluene Benzene
Styrene
tert-Butyl 1-phenylcyclopentylpercarboxylate 1,1,3,3-Tetramethylbutylper-2-ethylhexanoate
2,2,4-Trimethylpentane Benzene
2-Phenylazo-2-propylperbenzoate
Chlorobenzene
1-Phenylethyl 4-dimethylaminoperbenzoate Di-terf-butylperhomoterephthalate
J( 0 C)
/7-Chlorotoluene Chloroform-di Benzene Cumene Toluene
tert-Butyl 1-phenylcyclohexanepercarboxylate
Ethylbenzene 2,2,4-Trimethylpentane
tert-Butyl 2-(phenylthio)perbenzoate
Acetone Acetonitrile terf-Butanol Chlorobenzene
Cyclohexane DMSO Ethanol Isopropanol Methanol terf-Butyldibenzothiophene-4-percarboxylate
Chlorobenzene
Di-tert-butyl perazelate
Styrene
Chlorobenzene
E* (kj/mol)
Notes
140.8
h
ti
Refs. 269 269 269 323 324
exp[- U1.6/RT] 157.7
159.0 103.5
a a a a Xi Xi h
101
a a a
111.5
h
122.3
h
107.7
h
m2 ITi2 m2 m2 m2 m2 b m2
128.0
154.8
exp[- 141.95/RT]
m2 m2 m2 m2 m2 m2 m2 m2 m2 m2 m2 m2 h
40 90 126 126 126 215 215 255 255 337 337 337 260 260 260 260 259 272 272 272 272 323 255 255 255 22 22 22 22 22 22 134 134 134 134 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 215 215 215 344 344 344 344
TABLE 6. cont'd Number of C atoms 18
Initiator tert-Butyl 4-benzoylperbenzoate terf-Butyl diphenylperacetate
2,4,4-Trimethylpentyl2-perneodecanoate
a,co-Di-0,O-ter?-butyl-(bispersuccinyl)ethylene glycol
tert-Buty\ 1-phenyl-l-cycloheptanepercarboxylate Di-tert-buty\ /?-phenylenediperacetate
tert-Buty\ 2-(phenylthiomethyl)perbenzoate tert-Buty\ thioxanthone-4-percarboxylate Di-tert-butyl persebacate
Di-(2-ethylhexyl)peroxydicarbonate
Solvent Benzene Chlorobenzene Chlorobenzene Cumene
Decane Dodecane Hexadecane Octane tetradecane Chlorobenzene
Ethylbenzene
Ethylbenzene Cumene
Chlorobenzene Chlorobenzene Styrene
Benzene Chlorobenzene
Decane
Mineral spirits
19
Di-«-heptyl persuccinate
Styrene
tert-BxAy\ diphenylmethylperacetate terr-Butyl diphenylperglycidate (cis)
Chlorobenzene Cumene
(trans)
tert-Buty\ 2,2-diphenylperpropionate tert-Butyl 4-hydroxy-3,5-di(tert-butyl)perbenzoate tert-Butyl 4-(4-methylbenzoyl)perbenzoate
Cumene
Chlorobenzene Benzene Carbon tetrachloride Benzene Chlorobenzene
T( 0 C)
kd (s"1)
Ea (kj/mol)
25 110 60 40.3 49.6 59.9 70.4 77.5 77.5 77.5 77.5 77.5 40 57 76 T (K)
1.84 x 10 ~4 2.88 x 10 ~5 4.44 x 10 ~4 2.75 x 10 " 5 9.81xl0"5 3.10xl0"4 1.04 XlO- 3 1.66 x l O " 3 1.688 x l O " 3 1.632 x 10~3 1.651 x 10" 3 1.627 x 10 ~3 1.93 x 10 ~5 1.93 x 10 " 4 1.93 XlO" 3 3.97 x 1014
95 105 115
2.68 x 10 " 6 9.10xl0"6 2.97 XlO" 5
60.0
2.75 x 10 ~3
70.9 85.4 100.3 98.7 120.1 120 135 105 115 125
3.69 x 10 ~5 2.08 XlO" 4 8.83 x l O " 4 4.64 x 10 " 5 4.2OxIO" 4 1.89 x 10 " 4 1.15 x l O " 3 5.10xl0~ 5 1.2Ox 10" 4 5.0OxIO" 4
40 47 64 83 T (K) 30 45 60 40 50 60 60 73.5 85
1.9xlO~ 5 1.93 x 10 " 5 1.93 XlO" 4 1.93 XlO" 3 1.83 x 1015 5.3xl0"6 3.31xl0~ 5 2.32 XlO- 4 1.3xl0" 5 6.14 xlO" 5 2.3IxIO- 4 6.IxIO"" 6 3.85xl0- 5 1.70 XlO" 4
60 60.0 70.0 80.0 60.0 70.0 80.0 34.1 100 100 25 110
1.9xl0" 3 2.8xl0"5 5.5 x l 0 ~ 5 1.68 x l O " 4 1.6 x l O " 5 3.9 XlO" 5 1.20 XlO" 4 7.76 x 10 ~5 3.18 x 3.60 x 1.45 x 3.03 x
10 ~5 10 ~5 10 " 4 10 ~5
Notes p2
101.7 104.6
a,h h
exp[- 115.19/RT\ 147.5
Refs. 279 279 81 136 136 136 136 168 168 168 168 168 344 344 344 344 306 306 306 323
112.7
134.7 156.5 154.8
h,k k k h h,m2 m2 Xi Xi Xi a
exp[- 122.45//?7] 105
126
131.0
a a a a a a Xi X1 X1
103.3 112.1
a,h h
117.2
h
c,e c,e p2
254 254 254 154 154 22 22 215 215 215 338 344 344 344 344 337 337 337 337 337 337 215 215 215 81 204 204 204 204 204 204 249 246 246 279 279
Notes page 11-69; References page 11-70
TABLE 6. cont'd Number of C atoms 19 (cont'd)
20
21
22
23
Initiator ten-Butyl a-phenylpercinnamate (cw) (trans)
Cumene Cumene
Cumyl perneodecanoate
Benzene Chlorobenzene
Di-rc-heptyl peradipate
Styrene
tert-Butyl 2-carbobenzoxyphenylperacetate
Cumene
tert-Butyl 2-methyl-2-phenylperhexanoate oc,co-Di-0,O-tert-butyl-(bispersuccinyl)diethylene glycol
Ethylbenzene Ethylbenzene
tert-Butyl 8-(phenylthio)1-pernaphthoate
Chlorobenzene
tert-Butyl 4-(2,4,6-trimethylbenzoyl)perbenzoate tert-Butyl 2,2-diphenyl3,3-dimethylperbutanoate
Benzene Chlorobenzene Toluene (?)
Di-tert-butyl 2-thiophenylperisophthalate
Chlorobenzene
2,5-Dimethylhexyl 2,5-di(peroxybenzoate)
Benzene
Di-(4-tert-butylcyclohexyl)peroxydicarbonate
Chlorobenzene
tert-Butyl 2,6-di(phenylthio)perbenzoate tert-Butylperoxy stearyl carbonate
Chlorobenzene
tert-Butyl 2,4,6-tri-tert-butylperbenzoate
24
Solvent
tert-Butyl
triphenylperacetate
Chlorobenzene
Cumene
Chlorobenzene Cumene
Di-tert-butyl 2,3-diphenylpersuccinate
Cumene
Di-rc-heptyl persebacate
Styrene
2,5-Dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane
Benzene
Chlorobenzene
T( 0 C)
A:d (s"1)
Ea (kj/mol)
Notes
136.8
h
133.9
h
99.6 109.8 99.6 109.8 39 39 56 75 T(K) 60 73.5 85 71.0 85.4 102.4 50
1.52 x 10~4 4.4IxIO"4 8.2 x 10~5 2.59 x 10 ~4 1.9xl0~ 5 1.93 x 10 " 5 1.93 xlO~ 4 1.93 x l 0 ~ 3 3.12 xlO 1 4 1.02 x 10 ~5 6.57 x l O " 5 2.98 x l O - 4 8.84 x 10" 6 5.46 x 10 ~5 4.23 x l O - 4 5.01 x 10 " 5
95 105 115 50 70 70 80 25 110 30 39.7 50 12.1 25.0 40.0 100 115 130 48 64 82 T (K) 40.1
2.34 x 10 ~6 155.0 8.88 x 10 ~6 3.27 x l O - 5 3.83 x 10 ~5 99.2 3.44 x 10~4 3.12 x l O " 4 9.82 x l O - 4 1.34 x 10 ~4 1.8OxIO- 5 2.76 x 10 ~5 • 114.8 1.15 x 10 ~4 5.45 x l O - 4 1.68 x l O " 4 73.7 6.45 x 10 ~4 3.09 x l O - 3 1.87 x l 0 ~ 5 154.0 1.25 x 10 ~4 7.14 xlO~ 4 1.93 x 10 ~5 1.93 x 10 ~4 1.93 XlO" 3 7.44 x 1015 exp[- 12639/RT] 7.07 x l O " 5
98 117 137 T (K) 70.4 84.0 99.3 115.0 34.9 25.7 34.9 45.5 70.1 79.9 90.0 60 73.5 85 60 70 80 68 86
1.93XlO" 5 1.93 x l O - 4 1.93 XlO" 3 3.94 x 1016 5.84 x 10 " 6 3.54 x 10 " 5 2.67 x l O - 4 1.656 x l O " 3 7.8xlO" 4 1.7 x l O " 4 5.8 XlO" 4 2.3 XlO" 3 9.83 x 10 ~5 3.29 x 10 " 4 1.20 x l O " 3 1.17xlO" 5 7.13 x l O - 5 3.03 xlO~ 5 6.7xlO~ 6 2.92 x 10 " 5 1.14 XlO" 4 1.93 x 10 " 5 1.93 x l O " 4
a
exp[-114.59//?7] 133.1
129.5
Xi Xi X1 h
h
h,m2 m2 m2 p2 J2 J2 k h
a a a
exp[- 151.59/RT]
100.8
h
125.5
c,h c c xi Xi X1 a a a
131.0
142
Refs. 150 150 150 150 338 344 344 344 344 215 215 215 257 257 257 324 306 306 306 154 154 154 154 279 279 250 250 250 248 248 248 126,337 126,337 126,337 344 344 344 344 154 344 344 344 344 345 345 345 345 153 153 153 153 196 196 196 215 215 215 337 337 337 344 344
TABLE 6. cont'd Number of C atoms 24 (cont'd) 25
Initiator
Solvent
2,5-Dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane tert-Butyl 2-(2,2-diphenylvinyl)perbenzoate
Chlorobenzene Chlorobenzene
Cyclohexane Methanol tert-Butyl 2-percarboxybenzalfluorene 26
30
oc,co-Di-0,0-caprylyl-(bis succinyl)ethylene glycol
Chlorobenzene Methanol Ethylbenzene
oc,co-Di-0,O-caprylyl-(bispersuccinyl)triethylene glycol
Ethylbenzene
Dimyristyl peroxydicarbonate
Chlorobenzene
34
Dicetyl peroxydicarbonate
Chlorobenzene
36
oc,0)-Di-0,0-heptanoyl-(bisperphthaloyl)triethylene glycol
Ethylbenzene
42
oc,co-Di-0,0-caprylyl-(bispersuccinyl)nonaethylene glycol
Ethylbenzene
46
a,oo-Di-0,0-heptanoyl-(bisperphthaloyl)tridecaethylene glycol a,ca-Di-O,O-caprylyl-(bispersuccinyl)tridecaethylene glycol
Ethylbenzene
50
TABLE 7.
Ethylbenzene
T( 0 C) 106 T(K) 90.0 90.3 100.0 105.5 119.3 90.0 90.4
*d (s" 1 ) 1.93 2.19 1.32 7.45 3.27 4.64 1.54 3.5 2.3
x 10 ~3 x 1015 x 10~4 x 10~5 xlO"4 XlO" 4 xlO-3 x 10 ~5 x 10~3
90 90
3.75 x 10 ~4 2.47 x 10 ~3
65 75 85 95 65 75 85 95 48 65 84 T (K) 48 65 84 T (K) 65 75 85 95 65 75 85 95 75 85 95 65 75 85
1.48 x 10~5 4.10xl0"5 2.19 x l O - 4 6.92 x l O - 4 2.74 x 10 ~5 8.47 x 10 " 5 2.95 x l O - 4 8.92 x l O - 4 1.93 x 10 " 5 1.93 x l O - 4 1.93 x l O " 3 2.82 x 10 15 1.93 x 10 ~5 1.93 x l O - 4 1.93 x l O - 3 3.02 x 1015 5.02 x IO ~5 1.420 x 10 ~4 5.19 x l O - 4 1.410 x l O " 3 1.66 x 1O~5 6.57 x 10 " 5 1.78 XlO" 4 9.72 x l O - 4 1.13OxIO- 4 3.5OxIO" 4 8.80xl0~ 4 1.28 x l 0 ~ 5 4.46 x 10 ~5 1.91 x l O ~ 4
Ea (kj/mol)
Notes
Refs. 344 344 175 175 175 175 175 175 175
exp[- 130.SS/RT] t9 t9 t9 t9
175 175 120.7
h
306 306 306 306 306 306 306 306 344 344 344 344 344 344 344 344 306 306 306 306 306 306 306 306 306 306 306 306 306 306
116.9
exp[- 124.10/RT]
exp[- 124.30/RT] 124.4
116.9
122.3
128.2
MISCELLANEOUS INITIATORS
Initiator
Solvent
Acetyl cyclohexyl sulfonyl peroxide
Benzene
AH1-Cyanocyclohexyl)pentamethylene keteneimine
Chlorobenzene
Dibenzyl hyponitrite
Paraffin
T ( 0 C) 30 40 45 80.0 89.2 100.1 61.5 68.5 75.5 80.5 132
^d(S1) 1.4XlO" 5 9.42 x l 0 ~ 5 2.10xl0~4 3.25 x 10 ~6 1.007 x l 0 ~ 5 4.025 XlO" 5 6.5 x 10~4 3.7 x l 0 ~ 3 8.3 x l O - 3 1.45 x l O ~ 2 8.7XlO- 1
£ a (kj/mol)
Notes
147
a a a
Refs. 337 337 337 179 179 179 240 240 240 240 240
Notes page 11-69; References page 11-70
TABLE 7. cont'd Initiator Di-terf-butyl hyponitrite
Peroxybenzoylnitrate
Solvent tert-Butanol rc-Butyl ether Ethanol(95%) Isooctane
Nujol Vapor
Vapor + NO
Vapor + NO
2,3-Dimethyl-2,3-diphenylbutane
Chlorobenzene
3,4-Dimethyl-3,4-diphenylhexane
Chlorobenzene
l,4-Dimethyl-l,4-diphenyl-tetrazene-2
Benzophenone Cumene Paraffin
Siliconeoil Potassium persulfate
0.1 M NaOH
Water (pH 3) Water
1-Pentanesulfonylazide 1,4-Butanedisulfonyl azide 1,6-Hexanedisulfonyl azide 1,9-Nonanedisulfonyl azide
Diphenyl ether Diphenyl ether Diphenyl ether Diphenyl ether
1,10-Decanedisulfonyl azide l,4-Dimethylcyclohexane-a,a'-disulfonyl azide
Diphenyl ether Diphenyl ether
T( 0 C) 65 65 65 45 55 65 75 65 7.6 19.9 30.4 40.6 50.1 60.5 T(K) 18.1 30.4 40.6 T (K) 30.4 50.2 68.5 T(K) 237 259 284 T(K) 201 226 254 T(K) 121 149 120 130 140 164.2 174.3 186 194 126 139 50 60 70 80 90 50 80 80 40 50 60 50 60 70 50 166 163 163 150 160 170 163 163
kd (s" 1 )
Ea (kj/mol)
4.68 x 10 " 4 4.50 x 10 " 4 3.93 x 10 ~4 2.72 xlO~ 5 116.9 1.07 x l O - 4 4.0OxIO" 4 1.33OxIO-3 5.17 x 10~4 2.79 x 10 ~6 69.1 1.05 x l O - 5 2.02 XlO" 5 3.64 x l O - 5 1.21 x 10- 4 2.74 XlO" 4 1 x 107 exp[-69.1//?7] 8.18 xlO" 5 108.5 3.62 XlO" 4 1.42 x l O - 3 1.6 x 1015 exp[- 108.5/RT] 1.34 x l 0 ~ 5 79.2 7.22 x l O - 5 3.41 x 10" 4 6.3 x l O - 8 exp[-79.2/i?n 1.93 x 10 ~5 1.93 x l O " 4 1.93 x l O - 3 7.34 xlO 1 8 exp[-230.19//?n 1.93 x 10 ~5 1.93 x l O - 4 1.93 x l 0 ~ 3 1.45 xlO 1 5 exp[- IS032/RT] 3.3xl0"4 3.45 x l 0 ~ 3 2.3xlO" 4 6.5 x l O - 4 1.67 XlO" 3 2.6xlO- 2 5.6 x l O - 2 1.43XlO"1 2.5XlO- 1 3.7xlO" 4 1.92 x l O - 3 9.5 x 10 ~7 140.2 3.16 xlO~ 6 2.33 x l O - 5 9.16 XlO" 5 3.5 x l O - 4 1.66 x 10 ~6 6.89 x 10~5 5.78 x l O - 5 1.65 xlO" 2 83.4 4.02 x l O " 2 1.08XlO"1 3.78 XlO" 3 121.5 2.18 x l O - 2 5.01xl0~ 2 1.1 x 10- 6 4.46 x 10 " 4 5.02 x 10 " 4 5.02 x 10 ~4 8.84 x 10 " 5 2.25 xlO" 4 4.45 x l O - 4 4.45 x 10 ~4 4.82 x 10" 4
Notes
h
h
h
h
a a a a a a a,vn a,v u d 3 ,v 22 d 3 ,v 22 d 3 ,v 22 d 3 ,v 23 d 3 ,v 23 d 3 ,v 23
Refs. 317 317 317 317 317 317 317 317 261 261 261 261 261 261 261 261 261 261 261 261 261 261 261 344 344 344 344 344 344 344 344 240 240 240 240 240 240 240 240 240 240 240 242 242 242 242 242 242 115 115 262 262 262 262 262 262 262 166 166 166 166 166 166 166 166
ro-Xylene-a,a'-disulfonyl azide p-Xylene-o^oc'-disulfonyl azide Benzenesulfonyl azide
Diphenyl ether Diphenyl ether Naphthalene
/7-Bromobenzenesulfonyl azide p-Chlorobenzenesulfonyl azide p-Methoxybenzenesulfonylazide p-Nitrobenzenesulfonyl azide p-Toluenesulfonyl azide
Naphthalene Naphthalene Naphthalene Naphthalene 1,4-Dichlorobutane Dimethyl terephthalate Diphenyl ether
p-Toluenesulfonyl-p-tolylsulfone
Hexanoic acid Naphthalene Nitrobenzene 1-Octanol Tetradecane Acetonitrile
Dioxane
163 163 110 120 125 130 175 120 120 120 120 145 155 130 145 155 155 120 155 155 155 29.3 39.1 49.3 29.3 39.5 49.3
6.09 x 10 ~4 5.78 x 10 ~4 3.6xlO" 6 1.07 x l O - 5 1.97xlO- 5 3.41xl0"5 6.08 x l O - 5 1.36 x 10 ~5 1.15 x 10 " 5 1.31 x 10 ~5 1.6OxIO" 5 1.7OxIO- 4 3.23 x 10 ~4 3.30 x 10~5 1.44 XlO" 4 3.43 x l O " 4 2.97 x 10 ~4 1.12 x l O " 5 3.97 x 10 ~4 3.63 x 10" 4 3.80 x 10 ~4 3.9xl0-5 1.45 x l O - 4 5.4 XlO" 4 2.IxIO-5 1.01 x l O - 4 3.9 x 10 ~4
152.3
103.8
h
115.5
h
166 166 235 235 235 235 235 235 235 235 235 166 166 166 166 166 166 235 166 166 166 144 144 144 144 144 144
C. NOTES a /cd converted to s" 1 from author's units b kd values for several concentrations averaged t)2 analyzed from nonisothermal conditions c kd increases with increasing initiator concentration c 2 rate non-linear c3 hydroperoxide concentration 7.83 x 10~ 3 mol/1 C4 hydroperoxide concentration 2.50 x 10~ 3 mol/1 d kd decreases with increasing initiator concentration d2 after 1st half life; rate slower initially d3 rate is second order: units are 1/mol sec. e fcd listed is for lowest initiator concentration f &d is extrapolated value for zero initiator concentration g kd ^ has been corrected for induced decomposition g2 corrected for uncatalysed reaction (7 x 10 ~5 s" 1 ) h AH (not E2) i pressure (number gives mbar) j iodometric analysis j 2 manometer measurement k infrared analysis 1 kd is limiting value with respect to additive concentration mi 3,4-dichlorostyrene added to minimize induced decomposition m2 styrene added to minimize induced decomposition ni3 methyl methacrylate added to minimize induced decomposition ni4 isobutene added to minimize induced decomposition m5 acenaphthalene added to minimize induced decomposition m 6 1 mol/1 oc-methylstyrene added to minimize induced
decomposition mj butadiene added to minimize induced decomposition mg acrylonitrile added to minimize induced decomposition n trichloroacetic acid added n2 3.2wt.% or about 0.1 monolayer o addition of trichloroacetic acid did not affect kd p degassed p 2 photochemical benzophenone added: 6.56 x 10 17 quants/min @ 366 nm q addition of trichloroacetic acid increased kd several fold q 2 pH 2.90 q 3 pH 7.05 r not inhibited, but initiator concentration low enough (0.01-0.09 M) so that higher order decomposition is unimportant s solvent not degassed 11 2,6-di-terr-butylphenol added to inhibit induced decomposition t2 oc,a-diphenyl-P-picrylhydrazyl added to inhibit induced decomposition t3 phenyl-oc-naphthylamine added to inhibit induced decomposition t4 tetrachloroquinone added to inhibit induced decomposition t5 1,3,5-trinitrobenzene added to inhibit induced decomposition t6 12 added to inhibit induced decomposition tj O 2 added to inhibit induced decomposition t8 5-20% NO 2 added to inhibit decomposition References page II - 70
t9 tio
vi V2 V3 V4 V5 v6 v7 Vg v9
galvanoxyl added to inhibit induced decomposition a,y-bisdiphenylene-p-phenylallyl added to inhibit induced decomposition oc-naphthylamine added to minimize induced decomposition 2,3 / ,5 / ,6 / -tetra-te7t-butyl indophenoxy added benzoquinone added 2,6-di-teJt-butyl-4-methylphenol added in absence of oxygen from initiation data in multisurface reaction vessel rate reduced when nujol layer used to exclude Hg vapor rate increased when nujol layer used to exclude Hg vapor acetic acid added CuCl 2 added CuCl added 0.1 mol AgClO 4 /mol AIBN added 3.9 mol thiophenol added tert-bxxtyl mercaptan added 2.5 mol cyclohexane added ~ 4 x l O ~ 2 mol pyridine added 2 x 10~ 2 mol pyridine added
D.
REFERENCES
tn ti2 ti3 114 ui u2 u3 U4 U5
1. J. E. Guillet, T. R. Walker, M. F. Meyer, J. R Hawk, E. B. Towne, Ind. Eng. Chem., Prod. Res. Develop., 3, 257 (1964). 2. L. M. Arnett, J. Am. Chem. S o c , 74, 2027 (1952). 3. L. M. Arnett, J. H. Peterson, J. Am. Chem. Soc, 74, 2031 (1952). 4. W. M. Thomas, M. T. O'Shaughnessy, J. Polym. Sci., 11,455 (1953). 5. A. T. Blomquist, A. J. Buselli, J. Am. Chem. S o c , 73, 3883 (1951). 6. C. G. Swain, J. T. Parke, W. H. Stockmeyer, J. Am. Chem. Soc, 72, 5426 (1950). 7. D. J. Brown, J. Am. Chem. Soc, 70, 1208 (1948). 8. S. W. Butaka, L. L. Zabrocki, M. F. McLaughlin, J. R. Kolcznski, O. L. Mageli, Ind. Env. Chem. Prod. Res. Develop., 3, 261 (1964). 9. W. A. Strong, Ind. Eng. Chem. Prod. Res. Develop., 3, 264 (1964). 10. L. E. Redington, J. Polym. Sci., 3, 503 (1948). 11. B. Baysal, A. V. Tobolsky, J. Polym. Sci., 8, 529 (1952). 12. A. Conix, G. Smets, J. Polym. Sci., 10, 525 (1953). 13. M. R. Gopalan, M. Santhappa, J. Polym. Sci., 25,333 (1957). 14. J. C. Bevington, J. Toole, J. Polym. Sci., 28, 413 (1958). 15. H. C. Haas, J. Polym. Sci., 39, 493 (1959). 16. A. I. Lowell, J. R. Price, J. Polym. Sci., 43, 1 (1960). 17. H. C. Haas, J. Polym. Sci., 55, 33 (1961). 18. D. F. Doehnert, O. L. Mageli, Mod. Plastics., 36, (6), 142 (1959). 19. R. C. Lamb, P W. Ayers, M. K. Toney, J. Am. Chem. Soc, 85, 3483 (1963).
v 10 Vn v 12 v 13 v 14 v 15 v 16 v 17 v is v 19 V 20 v2i V 22 v23 v24 v25 v 26 w x1 x2 y z
2.5 mol cumene added buffered with sodium pyrophosphate saturated with ethyl acetate 3.11 mol CCl4 present peroxide in P(MMA) peroxide in P(sty.) 0.26 mol piperidine 0.24 mol triethylamine 0.21 mol AT,Af-diethylaniline 0.22 mol pyridine 0.9 mol Z n C l 2 in presence of 1 5 N O 0.12 mol 18 crown 6 added 0.24 mol diglyme added 0.02 M pyridine added 0.10 M pyridine added 0.10 M 2,6-lutidine added stereoisomers actual rate divided by 2 because of two identical peroxide groups each peroxide group has different k^ measured in differential scanning calorimeter: subscript is heating rate in deg/min pressure (in bar)
20. H. J. Shine, J. A. Waters, D. M. Hoffman, J. Am. Chem. S o c , 85, 3613 (1963). 21. G. S. Hammond, R. C. Neuman, Jr., J. Am. Chem. Soc, 85, 1501 (1963). 22. D. L. Tuleen, W. G. Bentrude, J. C. Martin, J. Am. Chem. Soc, 85, 1938 (1963). 23. H. Hart, F. J. Chloupek, J. Am. Chem. Soc, 85,1155 (1963). 24. H. Hart, R. A. Cipriani, J. Am. Chem. Soc, 84, 3697 (1962). 25. L. J. Durham, H. S. Mosher, J. Am. Chem. Soc, 84, 2811 (1962). 26. R. C. Petersen, J. H. Markgraf, S. D. Ross, J. Am. Chem. Soc, 83, 3819 (1961). 27. M. M. Martin, J. Am. Chem. Soc, 83, 2869 (1961). 28. R D. Bartlett, D. M. Simons, J. Am. Chem. Soc, 82, 1753 (1960). 30. R D. Bartlett, E. P Benzing, R. E. Pincock, J. Am. Chem. Soc, 82, 1762 (1960). 31. R D . Bartlett, R. E. Pincock, J. Am. Chem. Soc, 82, 1769 (1960). 32. L. J. Durham, H. S. Mosher, J. Am. Chem. S o c , 82, 4537 (1960). 33. C. Walling, G. Metzger, J. Am. Chem. Soc, 81,5365 (1959). 34. H. Hart, D. P. Woman, J. Am. Chem. Soc, 81, 4891 (1959). 35. H. H. Lau, H. Hart, J. Am. Chem. Soc, 81, 4897 (1959). 36. E. L. O'Brien, F. M. Bennger, R. B. Mesrobian, J. Am. Chem. S o c , 81, 1506 (1959). 37. N. A. Milas, A. Golubovic, J. Am. Chem. S o c , 80, 5994 (1958). 38. C. G. Overberger, I. Tashlick, M. Vernstein, R. G. Hiskey, J. Am. Chem. S o c , 80, 6556 (1958).
39. J. P. Van Hook, A. V. Tobolsky, J. Am. Chem. Soc, 80, 779 (1958). 40. E. L. O'Brien, F. M. Beringer, R. B. Mesrobian, J. Am. Chem. Soc, 79, 6238 (1957). 41. B. K. Morse, J. Am. Chem. Soc, 79, 3375 (1957). 42. S. Solomon, C. H. Wang, S. G. Cohen, J. Am. Chem. Soc, 79, 4104 (1957). 43. C. Walling, J. Pellon, J. Am. Chem. Soc, 79, 4786 (1957). 44. C. G. Overberger, J. G. Lombardino, I. Tashlich, R. G. Hiskey, J. Am. Chem. Soc, 79, 2662 (1957). 45. K. E. Russel, J. Am. Chem. Soc, 77, 3487 (1955). 46. S. G. Cohen, C. H. Wang, J. Am. Chem. Soc, 77, 3628 (1955). 47. M. Talat-Erben, S. Bywater, J. Am. Chem. Soc, 77, 3712 (1955). 48. C. G. Overberger, M. Lapkin, J. Am. Chem. Soc, 77, 4651 (1955). 49. G. S. Hammond, J. N. Sen, C. E. Boozer, J. Am. Chem. Soc, 77, 3244 (1955). 50. C. G. Overberger, W. F. Hale, M. B. Berenbaum, A. B. Finestone, J. Am. Chem. Soc, 76, 6185 (1954). 51. J. Smid, A. Rembaum, M. Szwarc, J. Am. Chem. Soc, 78, 3315 (1956). 52. S. G. Cohen, C. H. Wang, J. Am. Chem. Soc, 75, 5504 (1953). 53. A. T. Blomquist, I. A. Berstein, J. Am. Chem. Soc, 73, 5546 (1951). 54. C. G. Overberger, H. Biletch, J. Am. Chem. Soc, 73, 4880 (1951). 55. A. T. Blomquist, A. F. Ferris, J. Am. Chem. Soc, 73, 3408 (1951). 56. A. T. Blomquist, A. F. Ferris, J. Am. Chem. Soc, 73, 3412 (1951). 57. C. G. Overberger, M. B. Berenbaum, J. Am. Chem. Soc, 73, 2618 (1951). 58. V. Stannett, R. B. Mesrobian, J. Am. Chem. Soc, 72, 4125 (1950). 59. P. D. Bartlett, J. E. Leffler, J. Am. Chem. Soc, 72, 3030 (1950). 60. S. G. Cohen, D. B. Sparrow, J. Am. Chem. Soc, 72, 611 (1950). 61. C. G. Overberger, M. T. O'Shaughnessy, H. Shalit, J. Am. Chem. Soc, 71, 2661 (1949). 62. F. M. Lewis, M. S. Matheson, J. Am. Chem. Soc, 71, 747 (1949). 63. J. H. Raley, F. F. Rust, W. E. Vaughan, J. Am. Chem. Soc, 70, 88 (1948). 64. J. H. Raley, F. F. Rust, W. E. Vaughan, J. Am. Chem. Soc, 70, 1336 (1948). 65. C. S. Marvel, R. L. Frank, E. Prill, J. Am. Chem. Soc, 65, 1647 (1943). 66. C. E. H. Bawn, D. Verdin, Trans. Faraday Soc, 56, 815 (1960). 67. H. C. Bailey, G. W. Godin, Trans. Faraday Soc, 52, 68 (1956). 68. C. E. H. Bawn, R. G. Halford, Trans. Faraday Soc, 51, 780 (1955).
69. C. E. H. Bawn, S. F. Mellish, Trans. Faraday Soc, 47, 1216 (1951). 70. W. Braun, L. Rajbenbach, F. R. Eirich, J. Phys. Chem., 66, 1591 (1962). 71. J. R. Thomas, O. L. Harle, J. Phys. Chem., 63, 1027 (1959). 72. P. L. Hanst, J. G. Calvert, J. Phys. Chem,. 63, 104 (1959). 73. B. Barnett, W. E. Vaughan, J. Phys. Chem., 51, 926 (1947). 74. B. Barnett, W. E. Vaughan, J. Phys. Chem., 51, 942 (1947). 75. S. G. Cohen, F. Cohen, C. H. Wang, J. Org. Chem., 28,1479 (1963). 76. R. R. Hiatt, W. M. J. Strachan, J. Org. Chem., 28, 1893 (1963). 77. J. E. Leffler, J. S. West, J. Org. Chem., 27, 4191 (1962). 78. W. Honsberg, J. E. Leffler, J. Org. Chem., 26, 733 (1961). 79. J. E. Leffler, A. E Wilson, J. Org. Chem., 25, 424 (1960). 80. M. S. Kharasch, A. Fono, W. Nudenberg, J. Org. Chem., 16, 105 (1951). 81. R D . Bartlett, R. R. Hiatt, J. Am. Chem. Soc, 80, 1398 (1958). 82. J. E. Leffler, R. D. Faulkner, C. C. Petropoulos, J. Am. Chem. Soc, 80, 5435 (1958). 83. L. Batt, S. W. Benson, J. Chem. Phys., 36, 895 (1962). 84. J. Smid, M. Szwarc, J. Chem. Phys., 29, 432 (1958). 85. A. Rembaum, M. Szwarc, J. Chem. Phys., 23, 909 (1955). 86. R. K. Brinton, D. H. Volman, J. Chem. Phys., 20, 25 (1952). 87. R. E. Rebbert, K. J. Laidler, J. Chem. Phys., 20, 574 (1952). 88. J. Murawski, J. S. Roberts, M. Szwarc, J. Chem. Phys., 19, 698 (1951). 89. J. E. Leffler, J. Am. Chem. Soc, 72, 67 (1950). 90. E Strain, W. E. Bissinger, W. R. Dial, H. Rudolf, B. J. DeWitt, H. C. Stevens, J. H. Langston, J. Am. Chem. Soc, 72, 1254 (1950). 91. A. Farkas, E. Passaglia, J. Am. Chem. Soc, 72, 3333 (1950). 92. W. A. Pryor, D. M. Huston, T. R. Fiske, T. L. Pickering, E. Ciuffarin, J. Am. Chem. Soc, 86, 4237 (1964). 93. J. C. Bevington, A. Wahid, Polymer, 4, 129 (1963). 94. A. A. Frost, R. G. Pearson, "Kinetics and Mechanism," Wiley, New York, 1953, p. 97. 95. J. C. Bevington, T. D. Levis, Polymer, 1, 1 (1960). 96. F. W. Birss, C. J. Danby, C. Hinshelwood, Proc Roy Soc. (London). A, 239, 154 (1957). 97. J. C. Martin, W. G. Bentrude, Chem. Ind. (London), 192 (1959). 98. S. G. Cohen, S. J. Groszos, D. B. Sparrow, J. Am. Chem. Soc, 72, 3947 (1950). 99. W. E. Cass, J. Am. Chem. Soc, 72, 4915 (1950). 100. S. D. Ross, M. A. Fineman, J. Am. Chem. Soc, 73, 2176 (1951). 101. CG. Overberger, H. Biletch, A B. Finestone, J. Lilker, J. Herbert, J. Am. Chem. Soc, 75, 2078 (1953). 102. P. D. Bartlett, F. D. Greene, J. Am. Chem. Soc, 76, 1088 (1954). 103. M. G. Alder, J. E. Leffler, J. Am. Chem. Soc, 76., 1425 (1954).
104. C. G. Overberger, A. Lebovits, J. Am. Chem. Soc, 76, 2722 (1954). 105. A. Rembaum, M. Szwarc, J. Am. Chem. Soc, 76, 5975 (1954). 106. M. Levy, M. Steinberg, M. Szwarc, J. Am. Chem. Soc, 76, 5978 (1954). 107. S. G. Cohen, C. H. Wang, J. Am. Chem. Soc, 77, 2457 (1955). 108. J. E. Leffler, C. C. Petropoulos, J. Am. Chem. Soc, 79, 3068 (1957). 109. W. E. Cass, J. Am. Chem. Soc, 68, 1976 (1946). 110. H. C. Ramsperger, J. Am. Chem. Soc, 50, 714 (1928). 111. RR Lossing, A. W. Tickner, J. Chem. Phys., 20, 907 (1952). 112. A. Robertson, W. A. Waters, J. Chem. Soc, 1578 (1948). 113. O. J. Walker, G. L. E. Wild, J. Chem. Soc, 1132 (1937). 114. J. E. Leffler, R. A. Hubbard, II, J. Org. Chem., 19, 1089 (1954). 115. P. D. Bartlett, K. Nozaki, J. Polym. ScL, 3, 216 (1948). 116. J. C. Bevington, J. Toole, L. Trossarelli, Makromol. Chem., 32, 57 (1959). 117. A. N. Bose, C. Hinshelwood, Proc Roy. Soc, (London) A, 249, 173 (1959). 118. E. R. Bell, J. H. Raley, F. F. Rust, F. H. Seubold, W. E. Vaughan, Disc. Faraday Soc, 10, 242 (1951). 119. L. Bateman, H. Hughes, A. L. Morns, Disc. Faraday Soc, 14, 190 (1953). 120. G. S. Hammond, J. Am. Chem. Soc, 72, 3737 (1950). 121. G. S. Hammond, L. M. Softer, J. Am. Chem. Soc, 72, 4711 (1950). 122. G. A. Russell, J. Am. Chem. Soc, 78, 1044 (1956). 123. J. A. Offenbach, A. V. Tobolsky, J. Am. Chem. Soc, 79, 278(1957). 124. G. S. Hammond, U. S. Nandi, J. Am. Chem. Soc, 83, 1213 (1961). 125. G. O. Pritchard, H. O. Pritchard, A. F. Trotman-Dickenson, J. Chem. Soc, 1425 (1954). 126. O. L. Mageli, S. D. Butaka, D. J. Bolton, Wallace and Tiernan, Lucidol Division, Bulletin 30.30, "Evaluation of Organic Peroxides from Half-Life Data". 127. E. J. Harris, A. C. Egenon, Proc Roy. Soc, (London) A, 168, 1 (1938). 128. E. J. Harry, Proc Roy. Soc, (London) A, 173, 126 (1939). 129. J. K. Allen, J. C. Bevington, Proc Roy. Soc, (London) A, 262, 271 (1961). 130. G. Archer, C. Hinshelwood, Proc Roy. Soc, (London) A, 261, 293 (1961). 131. J. H. McClure, R. E. Robertson, A. C. Cuthbertson, Can. J. Res. B, 20, 103 (1942). 132. J. W. Breitenbach, A. Schindler, Monatsh. Chem., 83, 724 (1952). 133. R. C. Lamb, F. F. Rogers, G D. Dean, F. W Voight, J. Am. Chem. Soc, 84, 2635 (1962). 134. W. G. Bentrude, J. C. Martin, J. Am. Chem,. 84,1561 (1962). 135. R. C. Neuman, R. P. Pankratz, J. Org. Chem., 36, 4046 (1971). 136. R D. Bartlett, L. B. Gonler, J. Am. Chem. Soc, 85, 1864 (1963).
137. C. G. Overberger, I. Tashlick, J. Am. Chem. Soc, 81, 217 (1959). 138. C. G. Overberger, J. G. Lambardino, J. Am. Chem. Soc, 80, 2317 (1958). 139. G. S. Hammond, J. R. Fox, J. Am. Chem. Soc, 86, 1918 (1964). 140. E. S. Huyser, C. J. Bredeweg, J. Am. Chem. Soc, 84, 2401 (1964). 141. E. Hedaya, R. L. Hinman, L. M. Kibler, S. Theodoropulos, J. Am. Chem. Soc, 86, 2727 (1964). 142. T. Koenig, W. Brewer, J. Am. Chem. Soc, 86, 2728 (1964). 143. E. S. Huyser, C. J. Bredeweg, R. M. Van Scoy, J. Am. Chem. Soc, 86, 4148 (1964). 144. J. L. Kice, N. E. Pawlowski, J. Am. Chem. Soc, 86, 4898 (1964). 145. C. Walling, H. N. Moulden, J. H. Waters, R. C. Newman, J. Am. Chem. Soc, 87, 518 (1965). 146. J. K. Kochi, D. M. Mog, J. Am. Chem. Soc, 87, 522 (1965). 147. P. D. Bartlett, M. McBride, J. Am. Chem. Soc, 87, 1727 (1965). 148. R. C. Lamb, J. G. Pacifici, P. W. Ayers, J. Am. Chem. Soc, 87, 3928 (1965). 149. S. Seltzer, F. T. Dunne, J. Am. Chem. Soc, 87, 2628 (1965). 150. L. A. Singer, N. R Kong, J. Am. Chem. Soc, 88, 5213 (1966). 151. R. M. Fantazier, J. A. Kampmeier, J. Am. Chem. Soc, 88, 5219 (1966). 152. S. Seltzer, E. J. Hamilton, Jr., J. Am. Chem. Soc, 88, 3775 (1966). 153. J. P. Lorand, P. D. Bartlett, J. Am. Chem. Soc, 88, 3294 (1966). 154. T. H. Fischer, J. C. Martin, J. Am. Chem. Soc, 88, 3382 (1966). 155. C. Walling, Z. Cekovic, J. Am. Chem. Soc, 89, 6681 (1967). 156. T. Koenig, R. Wolf, J. Am. Chem. Soc, 89, 2948 (1967). 157. R. C. Neuman, J. V. Behar, J. Am. Chem. Soc, 89, 4549 (1967). 158. S. G. Mylonakis, S. Seltzer, J. Am. Chem. Soc, 90, 5487 (1968). 159. J. P Lorand, S. D. Cnodroff, R. W. Wallace, J. Am. Chem. Soc, 90, 5266 (1968). 160. R. C. Fort Jr., R. E. Franklin, J. Am. Chem. Soc, 90, 5267 (1968). 161. J. E. Leffler, H. H. Gibson. Jr., J. Am. Chem. Soc, 90, 4117 (1968). 162. S. E. Scheppelle, S. Seltzer, J. Am. Chem. Soc, 90, 358 (1968). 163. R. C. Neuman, J. V. Behar, J. Am. Chem. Soc, 91, 6024 (1969). 164. R. C. Lamb, J. R. Sanderson, J. Am. Chem. Soc, 91, 5034 (1969). 165. T. Koenig, R. Wolf, J. Am. Chem. Soc, 91, 2574 (1969). 166. D. S. Breslow, M. F. Sloan, N. R. Newburg, W. B. Renfrow, J. Am. Chem. Soc, 91, 2273 (1969). 167. C. Walling, H. P. Warts, J. Milovanovic, C. G. Pappiaonnou, J. Am. Chem. Soc, 92, 4927 (1970).
168. W. A. Pryor, K. Smith, J. Am. Chem. Soc.,.92, 5403 (1970). 169. T. Koenig, J. Huntington, R. Cruthoff, J. Am. Chem. Soc, 92, 5413 (1970). 170. J. E. Leffler, R. G. Zepp, J. Am. Chem. Soc, 92, 3713 (1970). 171. J. C. Martin, J. W. Timberlake, J. Am. Chem. Soc, 92, 978 (1970). 172. R. C. Newman Jr., G. D. Holmes, J. Am. Chem. Soc, 93, 4242 (1971). 173. J. B. Levy, E. J. Lehmann, J. Am. Chem. Soc, 93, 5790 (1971). 174. K. Shen, J. Am. Chem. Soc, 93, 3064 (1971). 175. T. W. Koenig, J. C. Martin, J. Org. Chem., 29, 1520 (1964). 176. R. D. Schuetz, J. L. Shea, J. Org. Chem., 30, 844 (1965). 177. J. R. Thomas, J. Am. Chem. Soc, 77, 246 (1955). 178. P. D. Bartlett, C. Ruchardt, J. Am. Chem. Soc, 82, 1756 (1960). 179. C. S. Wu, G. S. Hammond, J. M. Wright, J. Am. Chem. Soc, 82, 5386 (1960). 180. S. G. Cohen, R. Zand, C. Steel, J. Am. Chem. Soc, 83, 2895 (1961). 181. RD. Bartlett, R. E. Pincock, J. Am. Chem. Soc, 84, 2445 (1962). 182. M. M. Martin, D. C. De Jongh, J. Am. Chem. Soc, 84, 3526 (1962). 183. S. Selzer, J. Am. Chem. Soc, 83, 2625 (1961). 184. S. N. Gupta, U. S. Nandi, J. Polym. Sci. A-1,8, 3019 (1970). 185. T. Kagiya, M. Izu, S. Kauai, K. Fukni, J. Polym. Sci. A-I, 6, 1719 (1968). 186. K-P. S. Kwei, J. Polym. Sci. A, 3, 2387 (1965). 187. C. Leggett, J. C. J. Thynne, Trans. Faraday Soc, 63, 2504 (1967). 188. S. W. Benson, G. N. Spokes, J. Phys. Chem., 72, 1182 (1968). 189. G. A. Mortimer, J. Org. Chem., 30, 1632 (1965). 190. W. H. Richardson, J. Org. Chem., 30, 2804 (1965). 191. R. C. Lamb, J. G. Pacifici, P. W. Ayers, J. Org. Chem., 30, 3099 (1965). 192. E. S. Huyser, R. M. Van Scoy, J. Org. Chem., 33, 3524 (1968). 193. C. Walling, J. C. Azar, J. Org. Chem., 33, 3888 (1968). 194. R. C. Lamb, L. R Spadafino, R. G. Webb, E. B. Smith, W. E. McNew, J. G. Pacifici, J Org. Chem., 31, 147 (1966). 195. F. D. Greene, W. Adam, G. A. Knudsen Jr., J. Org. Chem., 31, 2087 (1966). 196. L. M. Bobroff, L. B. Gortler, D. J. Sahn, H. Wiland, J. Org. Chem., 31, 2678 (1966). 197. R. Hiatt, T. Mill, K. C. Irwin, J. K. Castleman, J. Org. Chem., 33, 1421 (1968). 198. R. Hiatt, K. C. Irwin, C. W. Gould, J. Org. Chem., 33, 1430 (1968). 199. R. Hiatt, K. C. Irwin, J. Org. Chem., 33, 1436 (1968). 200. P. Kovacic, R. R. Flynn, J. F. Gormish, A. H. Kappelman, J. R. Shelton, J. Org. Chem., 34, 3312 (1969). 201. D. E. Van Sickle, J. Org. Chem., 34, 3446 (1969). 202. E. S. Huyser, K. J. Jankauskas, J. Org. Chem., 35, 3196 (1970).
203. R. A. Sheldon, J. K. Kochi, J. Org. Chem., 35, 1223 (1970). 204. A. Padwa, N. C. Das, J. Org. Chem., 34, 816 (1969). 205. C. G. Overberger, D. A. Labianca, J. Org. Chem., 35, 1762 (1970). 206. W. G. Schindel, R. E. Pincock, J. Org. Chem., 35, 1789 (1970). 207. R. C. Newman Jr., J. V Behar, J. Org. Chem., 36,654 (1971). 208. C. Walling, D. Bristol, J. Org. Chem., 36, 733 (1971). 209. R. C. Lamb, W. E. McNew Jr., J. R. Sanderson, D. C. Lunney, J. Org. Chem., 36, 174 (1971). 210. G. S. Kolesnikov, A. Y. Chuchin, Polym. Sci. USSR, 7,1931 (1965). 211. G. A. Nosayev, O. N. Romanlsova, Polym. Sci. USSR, 8, 14 (1966). 212. Y. A. Chuchin, V. A. Lazarev, M. B. Fromberg, Polym. Sci. USSR, 10, 2968 (1968). 213. L. M. Aparovich, T. I. Yurzhenko, Polym. Sci. USSR, 10, 1313 (1968). 214. A. I. Prisyazhnyuk, S. S. Ivanchev, Polym. Sci. USSR, 12, 514 (1970). 215. S. G. Yerigova, S. S. Ivanchev. Polym. Sci. USSR, 11, 2377 (1969). 216. C. H. Bamford, R. Denyer, J. Hobbs, Polymer, 8, 493 (1967). 217. S. F. Nelsen, P. D. Bartlett, J. Am. Chem. Soc, 88, 137 (1966). 218. R. E. Pincock, J. Am. Chem. Soc, 86, 1820 (1964). 219. R. C. Lamb, J. G. Pacifici, J. Am. Chem. Soc, 86, 914 (1964). 220. S. Seltzer, J. Am. Chem. Soc, 85, 14 (1963). 221. J. B. Levy, B. K. W. Copeland, J. Am. Chem. Soc, 82, 5314 (1960). 222. T. Suchiro, H. Tsuruta, S. Hibino, Bull. Chem. Soc Japan, 40, 674 (1967). 223. L. B. Humphrey, B. Hodgson, R. E. Pincock, Can. J. Chem., 46, 3099 (1968). 224. V. Stannett, R. B. Mesrobian, Disc. Faraday Soc, 14, 242 (1953). 225. Y. Takezaki, C. Takeuchi, J. Chem. Phys., 22, 1527 (1954). 226. K. Ziegler, W. Deparade, W. Meye, Annalen, 567, 141 (1950). 227. A. R. Blake, K. O. Kutschke, Can. J. Chem., 37, 1462 (1959). 228. C. F. H. Tipper, J. Chem. Soc, 1675 (1953). 229. W. R. Foster, G. H. Williams, J. Chem. Soc, 2862 (1962). 230. G. B. Gill, G. H. Williams, J. Chem. Soc, 995 (1965). 231. G. B. Gill, G. H. Williams, J. Chem. Soc, 7127 (1965). 232. R. D. Schuetz, D. M. Teller, J. Org. Chem., 27, 110 (1962). 233. H. G. G. Dekking, J. Appl. Polym. Sci., 9, 1641 (1965). 234. C. G. Overberger, P. Fram, T. Alfrey Jr., J. Polym. Sci., 6,539 (1951). 235. K. Takemoto, R. Fujita, M. Imoto, Makromol. Chem., 112, 116(1968). 236. K. E. J. Barrett, J. Appl. Polym. Sci., 11, 1617 (1967). 237. T. J. Dougherty, J. Am. Chem. Soc, 83, 4849 (1961).
238. M. T. Jaquiss, J. S. Roberts, M. Szwarc, J. Am. Chem. Soc, 74, 6005 (1952). 239. S. Goldschmidt, B. Acksteiner, Annalen, 618, 173 (1958). 240. J. C. McGowen, T. Powell, Rec. Trav. Chim., 81, 1061 (1962). 241. H. A. Bent, B. Crawford Jr., J. Am. Chem. Soc, 79, 1793 (1957). 242. I. M. Kolthoff, I. K. Miller, J. Am. Chem. Soc, 73, 3055 (1951). 243. D. F. McMillen, D. M. Golden, S. W. Benson, J. Am. Chem. Soc, 94, 4403 (1972). 244. J. E. Leffler, A. A. More, J. Am. Chem. Soc, 94, 2483 (1972). 245. G. J. Abruscato, T. T. Tidwell, J. Am. Chem. Soc, 94, 672 (1972). 246. A. M. Hucek, J. T. Barbas, J. E. Leffler, J. Am. Chem. Soc, 95, 4698 (1973). 247. E. L. Allred, K. J. Voorhees, J. Am. Chem. Soc, 95, 620 (1973). 248. J. C. Martin, M. M. Chau, J. Am. Chem. Soc, 96, 3319 (1974). 249. J. P. Lorand, J. Am. Chem. Soc, 96, 2867 (1974). 250. J. P. Lorand, R. W. Wallace, J. Am. Chem. Soc, 96, 1402 (1974). 251. T. Koenig, J. G. Huntington, J. Am. Chem. Soc, 96, 592 (1974). 252. P. S. Engel, D. J. Bishop, J. Am. Chem. Soc, 97, 6754 (1975). 253. R. R. Hiatt, L. C. Glover, H. S. Mosher, J. Am. Chem. Soc, 97, 1556 (1975). 254. L-F. Lai, T. T. Tidwell, J. Am. Chem. Soc, 99, 1465 (1977). 255. R. A. Wolf, M. J. Migliore, P. H. Fuery, P. R. Gagnier, I. C. Saheta, R. J. Trocino, J. Am. Chem. Soc, 100, 7967 (1978). 256. C. Walling, J. P. Sloan, J. Am. Chem. Soc, 101,7679 (1979). 257. C. M. Rynard, C. Thankachan, T. T. Tidwell, J. Am. Chem. Soc, 101, 1196(1979). 258. J. E. Lefller, J. T. Barbas, J. Am. Chem. Soc, 103, 768 (1981). 259. B. G. Dixon, G. B. Schuster, J. Am. Chem. Soc, 103, 3068 (1981). 260. A. S. Nazran, J. Warkentin, J. Am. Chem. Soc, 104, 6405 (1982). 261. R. A. Kenley, D. G. Hendry, J. Am. Chem. Soc, 104, 220 (1982). 262. J. K. Rasmussen, S. M. Heilmann, P. E. Toren, A. V. Pocius, T. A. Kotnour, J. Am. Chem. Soc, 105, 6845 (1983). 263. R. C. Neuman, G. D. Lockyer, J. Am. Chem. Soc, 105, 3982 (1983). 264. W. A. Pryor, N. Ohto, D. F. Church, J. Am. Chem. Soc, 105, 3614 (1983). 265. J. R Engstrom, J. C. DuBose, J. Org. Chem., 38,3817 (1973). 266. J. R. Shelton, C. K. Liang, J. Org. Chem., 38, 2301 (1973). 267. J. A. Ernst, C. Thankachan, T. T. Tidwell, J. Org. Chem., 39, 3614 (1974). 268. J. E. Herweh, R. M. Fantazier, J. Org. Chem., 39, 786 (1974).
269. D. A. Cable, J. A. Ernst, T. T. Tidwell, J. Org. Chem., 37, 3420 (1972). 270. W. A. Pryor, E. H. Morkved, H. T. Bickley, J. Org. Chem., 37, 1999 (1972). 271. J. E. Leffler, F. E. Scrivener, J. Org. Chem., 37, 1794 (1972). 272. A. I. Dalton, T. T. Tidwell, J. Org. Chem., 37, 1504 (1972) 273. J. P Engstrom, F D. Greene, J. Org. Chem., 37, 968 (1972). 274. P. S. Engel, A. I. Dalton, L. Shen, J. Org. Chem., 39, 384 (1974). 275. W. B. Richardson, W. C. Koskinen, J. Org. Chem., 41, 3182 (1976). 276. W. A. Pryor, D. Graham, J. Org. Chem., 43, 770 (1978). 277. L. Batt, S. W. Benson, J. Chem. Phys., 36, 895 (1962). 278. P. S. Engel, R. L. Allgren, W. K. Chae, R. A. Leckonby, N. A. Marron, J. Org. Chem., 44, 4233 (1979). 279. L. Thijs, S. N. Gupta, D. C. Neckers, J. Org. Chem., 44,4123 (1979). 280. R. C. Neuman, M. J. Amrich, J. Org. Chem., 45, 4629 (1980). 281. J. R. Hurst, G. B. Shuster, J. Org. Chem., 45, 1053 (1980). 282. W. H. Richardson, S. A. Thomson, J. Org. Chem., 47, 4515 (1982). 283. Z. Chengxue, Z. Renmo, P. Hegi, J. Xiangshan, Q. Yangling, W. Chengjiu, J. Xikui, J. Org. Chem., 47, 2009 (1982). 284. E. M. Shulman, A. E. Merbach, W. J. Ie Noble, J. Org. Chem., 47, 431 (1982). 285. A. Pohlman, T. Mill, J. Org. Chem., 48, 2133 (1983). 286. L. F. R. CaRerata, G. N. Eyler, M. V. Mirifico, J. Org. Chem., 49, 2107 (1984). 287. S. Molnar, J. Polym. Sci. A-I, 10, 2245 (1972). 288. K. Ito, J. Polym. Sci., Polym. Chem. Ed., 11, 1673 (1973). 289. M. B. Lachinov, V P. Zubov, V. A. Kabanov, J. Polym. Sci., Polym. Chem. Ed., 15, 1777 (1977). 290. B. Yamada, H. Kamei, T. Otsu, J. Polym. Sci., Polym. Chem. Ed., 18, 1917 (1980). 291. S. G. Ng, K. K. Che, J. Polym. Sci., Polym. Chem. Ed., 20, 409 (1982). 292. B. B. Idage, S. P Vernckar, N. D. Ghatge, J. Polym. Sci., Polym. Chem. Ed., 21, 2145 (1983). 293. B. L. Funt, G. Pawel Chak, J. Polym. Sci., Lett. Ed., 13, 451 (1975). 294. M. G. Kulkarni, R. A. Mashelkar, L. K. Doraiswam, J. Polym. Sci., Lett. Ed., 17, 713 (1979). 295. R S. Engel, Chem. Rev., 80, 99 (1980). 296. T. Koenig, in: "Free Radicals", Wiley, New York, 1973, p. 113. 297. B. K. Bandlish, A. W. Garner, M. L. Hodges, J. W. Timberlake, J. Am. Chem. Soc, 97, 5856 (1975). 298. R. J. Crawford, K. Takagi, J. Am. Chem. Soc, 94, 7406 (1972). 299. R. C. Neuman., J. J. Amrich, J. Am. Chem. Soc, 94, 2730 (1972). 300. S. E. Scheppele, W. H. Rapp, D. W. Miller, D. Wright, T. Marriott, J. Am. Chem. Soc, 94, 539 (1972). 301. C. Walling, H. P. Waits, J. Phys. Chem., 71, 2361 (1967). 302. Y. L. Zherebin, S. S, Ivanchev, N. M. Domareva, Polym. Sci., USSR, 16, 1033 (1974).
303. R. V. Kucher, A. A. Turovskii, N. V. Dzumedzei, V. A. Tamko, Polym. ScL, USSR, 16, 1216 (1974). 304. V. A. Novikov, V. P. Sass, S. L. Ivanova, L. F. Sokolov, S. V. Sokolov, Polym. ScL, USSR, 17, 1414 (1975). 305. V. P. Kartavykh, V. A. Drach, Y. N. Barantsevich, Y. L. Abramenko, Polym. ScL, USSR, 19, 1413 (1977). 306. V. I. Galibei. L. V. Dudnik, T. A. Tolpygina, A. B. Petrova, V. I. Sokolova, Polym. ScL, USSR, 19, 1519 (1977). 307. B. N. Pronin, Y. N. Barantsevich, L. V. Shumnyi, S. S. Ivanchev, Polym. ScL, USSR, 19, 1850 (1977). 308. J. C. Martin, J. H. Hargis, J. Am. Chem. Soc, 91, 5399 (1969). 309. J. R. Shelton, C. K. Liang, P. Kovacic, J. Am. Chem. Soc, 90, 354 (1968). 310. C. G. Overberger. A. V. DiGiulio, J. Am. Chem. Soc, 81, 2154 (1959). 311. C. G. Overberger, A. B. Finestone, J. Am. Chem. Soc, 78, 1638 (1956). 312. S. G. Cohen, C. H. Wang, J. Am. Chem. Soc, 77, 2457 (1955). 313. J. R. Shelton, C. K. Liang. J. Org. Chem., 38, 2301 (1973). 314. J. W. Timberlake. A. W. Garner, J. Org. Chem., 41, 1666 (1976). 315. C. Ruchardt, H. Bock, I. Ruthardt, Angew. Chem. Int. Ed., 5, 253 (1966). 316. W. Cooper, J. Chem. Soc, 2408 (1952). 317. H. Kiefer, T. G. Traylor, Tetrahedron Lett., 6163 (1966). 318. K. R. Kopecky, T. Gillan, Can. J. Chem., 47, 2371 (1969). 319. B. H. Al-Sader, R. J. Crawford, Can. J. Chem., 48, 2745 (1970). 320. D. D. Tanner, H. Yabuuchi, H, Lutzer, Can. J. Chem., 55,612 (1977). 321. R. Hiatt, V. G. K. Nair, Can. J. Chem., 58, 450 (1980). 322. T. R. Lynch, F. N. MacLachlan, J. L. Suschitzky, Can. J. Chem., 51, 1378 (1973). 323. J. Bonnekessel, C. Ruchardt, Chem. Ber., 106, 2890 (1973). 324. W. Duismann, C. Ruchardt, Chem. Ber., 106, 1083 (1973). 325. R. Kerber, O. Nuyken, L, Weithmann, Chem. Ber., 108,1533 (1975). 326. T. Otsu, B. Yamada, J. Macromol. Sci.-Chem., A3, 187 (1969). 327. I. Hinz, C. Ruchardt, Ann. Chem., 765, 94 (1972). 328. C. Ruchardt, I. Mayer-Ruthardt, Chem. Ber., 104, 593 (1971). 329. R. Kerber, O. Nuyken, Makromol. Chem., 164, 183 (1973). 330. R. Kerber, O. Nuyken, V. Pasupathy, Makromol. Chem., 170, 155 (1973). 331. R. Kerber, O. Nuyken, R. Steinhausen, Makromol. Chem., 175, 3225 (1974). 332. R. WaIz, B. Bomer, W. Heitz, Makromol. Chem., 178, 2527 (1977). 333. R. C. Neuman, G. D. Lockyer, M. J. Amrich, Tetrahedron Lett, 1221 (1972). 334. F. E. Herkes, J. Friedman, P. D. Bartlett, Int. J. Chem. Kinet., 1, 193 (1969). 335. N.-T.-Giac, C. Ruchardt, Chem. Ber., 110, 1095 (1977).
336. W. Duismann, C. Ruchardt, Chem. Ber., Ill, 596 (1978). 337. Anon., "Evaluation of Organic Peroxides from Half-Life Data," Technical Bulletin, Lucidol Division, Pennwalt (no date). 338. Anon., Product Guide US Peroxygen Division, Witco, 1984. 339. Anon., "Azo Polymerization Initiators", Wako Chemicals, USA, 1983. 340. Anon., Product Bulletin "V-601", Wako Chemicals, USA (no date). 341. Anon., Product Bulletin " V-50", Wako Chemicals, USA, 1985. 342. Anon., "Azo Amide Compounds", Wako Chemicals, USA (no date). 343. Anon., Product Bulletin "V-65" Wako Chemicals, USA, 1985. 344. Anon., "Initiators for Polymer Production", Akzo Nobel Chemicals Inc., pp. 94-116. 345. S. IcIi, K. A. Kandil, C. Thankachan, T. T. Tidwell, Can. J. Chem., 53, 979 (1975). 346. W. H. Richardson, M. B. Yelvington, A. H. Andrist, E. W. Ertley, R. S. Smith, T. D. Johnson, J. Org. Chem., 38, 4219 (1973). 347. D. J. Robbins, A. J. Almquist, D. C. Timm, J. I. Brand, R. E. Gilbert, Macromol., 28, 8729 (1995). 348. K. Matsuyama, T. Sugiura, Y. Minoshima, J. Org. Chem., 60, 5520 (1995). 349. S. Suyama, H. Ishigaki, T. Nakamura, Y. Sugihara, H. Kumura, Y. Watanabe, Polym. J., 26, 273 (1994). 350. Y. Sugihara, Y. Watanabe, H. Kumura, T. Nakamura, S. Suyama, Y. Sawaki, Bull. Chem. Soc. Japan, 65, 664 (1992). 351. E. M. Chellquist, W. G. Gorman, Pharmaceutical Research, 9, 1341 (1992). 352. W. H. Hendrickson, C. C. Nguyen, J. T. Nguyen, K. T. Simons, Tetrahedron Lett., 36, 7217 (1995). 353. C. Navarro, B. Maillard, Thermochimica Acta, 220, 103 (1993). 354. W. A. Pryor, W. H. Hendrickson Jr., J. Am. Chem. Soc, 105, 7114(1983). 355. J. Szafko, W. Feist, J. Polym. ScL, Polym. Chem., 33, 1637 (1995). 356. H. Fujie, K. Shiraki, T. Miyagawa, N. Minamii, J. Macromol. ScL, Pure Appl. Chem. A, 29, 741 (1992). 357. S. Idage, B. Idage, S. Vernekar, J. Appl. Polym. ScL, 45, 931 (1992). 358. T. Komai, S. Suyama, Bull. Chem. Soc. Japan, 58, 3045 (1985). 359. T. Komai, H. Ishigaki, K. Matsuyama, Bull. Chem. Soc. Japan, 58, 2431 (1985). 360. K. V. Scherer Jr., L. Batt, P. H. Stewart, Int. J. Chem. Kinet., 26, 73 (1994). 361. S. Suyama, Y. Watanabe, Y. Sawaki, Bull. Chem. Soc. Japan, 63, 716 (1990). 362. T. Komai, K. Matsuyama, M. Matsushima, Bull. Chem. Soc. Japan, 61, 1641 (1988). 363. K. Matsuyama, Y. Higuchi, Bull. Chem. Soc. Japan, 64, 259 (1991). 364. K. Matsuyama, H. Kumura, J. Org. Chem., 58, 1766 (1993).
365. L. F. R. Cafferata, J. D. Lombardo, Int. J. Chem. Kinet., 26, 503 (1994). 366. B. Yamada, T. Otsu, Makromol. Chem., 190, 915 (1989). 367. U. Shanker, G. N. Kulsrestha, J. S. Sharma, B. S. Pathania, Indian J. Tech., 23, 318 (1985). 368. T. Komai, K. Kato, K. Matsuyama, Bull. Chem. Soc. Japan, 61, 2641 (1988). 369. H. Sawada, H. Hagii, K. Aoshima, T. Arai, Bull. Chem. Soc. Japan, 57, 1161 (1984). 370. H. Sawada, H. Hagii, K. Aoshima, M. Yoshida, M. Kobayashi, Bull. Chem. Soc. Japan., 58, 3448 (1985). 371. F. Severini, R. Gallo, J. Thermal Anal., 30, 841 (1985).
372. A. S. Nazran, J. Warkentin, J. Am. Chem. Soc, 104, 6405 (1982). 373. L. F. R. Cafferata, G. N. Eyler, M. V. Mirifico, J. Org. Chem., 49, 2107 (1984). 374. A. F. Shushunova, L. Y. Prokhorova, J. Chrom., 283, 365 (1984). 375. J. M. Bessiere, B. Boutevin, O. Loubet, Polym. Bull., 30,545 (1993). 376. J. C. M. Torfs, L. Deij, A. J. Dorrepaal, J. C. Heijens, Anal. Chem., 56, 2863 (1984). 377. M. Buback, C. Hinton, Zeit. Phys. Chem., 193, 61 (1996).
P r o p a g a t i o n i n
F r e e
a n d
T e r m i n a t i o n
R a d i c a l
C o n s t a n t s
P o l y m e r i z a t i o n
M. Kamachi Department of Applied Physics and Chemistry, Fukui University of Technology, Gakuen, Fukui, Japan B. Y a m a d a Department of Applied Chemistry, Faculty of Technology Osaka City University, Sumiyoshi, Osaka, Japan A. Introduction B. Tables of Propagation and Termination Constants Table 1. Dienes Table 2. Olefins Table 3. Acrylic Derivatives Table 4. Methacrylic Derivatives Table 5. ltaconic Derivatives Table 6. Fumaric Derivatives Table 7. Vinyl Halides Table 8. Vinyl Esters Table 9. Vinyl Ethers Table 10. Styrene Derivatives Table 11. Vinyl Heteroaromatics Table 12. Aldehydes Table 13. Others C. References
11-77 11-79 II-79 II-79 II-80 II-82 II-85 U-87 II-87 II-87 II-88 II-88 II-90 II-90 II-90 11-91
The rate constants kv and kt have usually been assumed to be independent of chain length. In this chapter termination constants depending on the length of the polymer radicals are also reported. In American literature the right hand side of (A4) is written as 2£t[P#] . In this chapter the definition given in Eq. (A4) has been used. Simultaneous determination of absolute values of both kv and kt from a single experiment has not been reported. In practice, the ratio k^/kt is determined from measurements of molecular weight as a function of rate of polymerization for a low conversion polymerization or from measurements of initiation rate and polymerization rate in a low conversion. The ratio kp/kt is determined from nonsteady-state measurements of the average lifetime, r, of the growing polymer chain in a photochemically initiated polymerization. This lifetime may be defined by noting that the concentration of chains present must be related to their average lifetime and rate of disappearance by (A6)
A.
INTRODUCTION
In free radical polymerization the propagation and termination rate constants describe the reactions
which, from (A3) and (A4), yields (A7)
(Al) dead polymer
(A2)
where P^ is a propagating chain of any length n and M is the monomer. The rate constants are defined by the following equations:
By combining the separately determined ratios, k^/kt and kp/kt, the individual propagation and termination rate constants may be calculated. Alternatively, the rate of initiation, R[, may be measured as the rate of initiator disappearance and equated to R1. This gives (from (A6) and (A3))
(A3) (A4) where (A5)
(A8) There is a large degree of imprecision inherent in measuring r and in combining data from different experiments, which helps to explain the scatter in the data tabulated here.
/Ct(XiO"6)
kp
/C1(XiO-6)
Figure 1. Arrhenius plots of all bulk polymerization data for styrene for kp (•) and /ct (+). Solid lines are least squares obtained by assuming all points to be of equal value.
The two monomers styrene and methyl methacrylate have been so extensively studied that their data are presented as Arrhenius plots (Figs. 1 and 2). Because of the influence of solvents on the rates, only data of bulk polymerizations are shown. It remains a wide scatter, which should serve as a warning against casual acceptance of any single number. Solid lines are the least squares that have been calculated assuming all points to be of equal value. For the termination rate of methyl methacrylate the leastsquares line results in a positive slope and is not shown. In this case a temperature-independent kt could be a better representation of the experiments. The pulse laser polymerization (PLP) method has been developed as a new method of obtaining kp. In the PLP method, the value of kp can be estimated from the degree of polymerization of polymer formed, vp, a knowledge of the monomer concentration, [M], and tf the time between pulses: (A9) The reproducibility of the PLP method has been recognized by an IUPAC Working Party on Modeling of Kinetic and Process of Polymerization, which is establishing a critical review of the literature values of kp.
K9
1000 T Figure 2. Arrhenius plots of all bulk polymerization data for methyl methacrylate for /cp (•) and /ct(+). Solid lines are least squares obtained by assuming all points to be of equal value. The line for kx is not shown since a horizontal line for a temperature independent kt could be a better representation. Classification of the methods for the determination of rate constants The tabulated data refer to seven different methods. Method A uses the following four methods for the measurement of the lifetime r: Al -rotating sector or a "flashing" laser A2 - flow through a tube with spatially separated light and dark sections A3 - spacial intermittent polymerization (SIP) A4 - intermittent illumination method Method B effectively measures only a single decrease (increase), in the radical concentration by the following methods: B l - dilatometry B 2 - dielectric constant B 3 - interferomety B4 - temperature change B5 - viscosity B6 - light scattering B7 - monomer pressure
B 8 - cathetometer B9-inhibitor BlO-scavenger
Method F uses pulse laser photopolymerization (PLP) method
Method C uses electron spin resonance (ESR) for the determination of the radical concentration Method D refers to values obtained in emulsion polymerization by application of the Smith-Ewart theory
Fl - PLP F2 - PLP-GPC (MWD) F3 - PLP-MALDI TOF (-GPC) Method G refers to the method of measuring molecular weight (MW) and molecular weight distribution (MWD) by Gl - gel permeation chromatography (GPC) G2 - high performance liquid chromatography (HPLC)
Method E refers to recalculated values
B. TABLES OF PROPAGATION AND TERMINATION CONSTANTS TABLE 1. DIENES Monomer 1-Acetoxybutadiene Butadiene
k9 (1/mol/s)
M x I O " 6 ) (l/mol/s)
Temp. (0C)
Method
18.0 &p = 1 . 2 x l 0 8 x exp(- 39000/RT) 150 ± 4 0
281
25 10
Al D
152 23
kt = 1.13 x l O 4 xexp(-711/r)
5 45-60
C Gl
223 202
50
Fl
221
-
50
Fl F2
Solvent: chlorobenzene Solvent: chlorobenzene
-
40
D D
Quoted in Ref. 86
l n * p = l n (3.873 x 1010) - 53400/RT 111.6 kp = 8.05 x 107 xexp(-35710//?7) Chloroprene 220 fcp = 2 . 9 x l 0 9 x exp(-41000/^7) *p = 1.95 x l O 7 x exp(- 26630/RT) 2,3-Dimethyl-l,3-butadiene &p = 8 . 9 x l 0 7 x exp(- 38000//?7) Ethyl 4-ethoxy-2,4-pentadienoate 9.9 Ethyl 4-methyl-2,4-pentadienoate 29.7 Ethyl pentadienoate 30.9 1,3-Hexadiene 20 ± 1 0 2,4-Hexadiene 16 ± 1 2 Isoprene 2.8
2-Methyl-l,3-pentadiene
Remarks
Refs.
221 187 59 84
Fl
198
D
71 152 152 152 223 223 24
9.3 23 19 -
25 25 25 5 5 5
Al Al Al C C D
125 ± 3 0 35 ± 10
-
5 5
C C
k p (1/mol/s)
M x I O 6 ) (1/mol/s)
Temp. (° C)
Method
1050 ± 5 0 455 ± 5 0 200
83 -20.01 130
Al Al Al
3.9 (7.8) x 102 1.99 x 102 -
130 190 230
Al C Fl
3.2 x 103
190
Fl
Calalyst system: diisopropylbenzene, monohydroperoxidetetraethylenepentamine
223 223
TABLE 2. OLEFINS Monomer Ethylene
Propylene
470 ± 3 0 18.6 ± 2 5400 £ p = 4.8x 107 x exp[(- 4450 + 3.Ix 10~6p)/T] 1.2 x 104 1.09 x 104 3.08 x 104
&p = 2 x l 0 6 x exp(- 32000/RT)
50-150
Remarks Solvent: benzene Pressure 1.8 x 10 8 Pa Pressure (5-17.5) x 10 7 Pa, using results of Ref. 141 Pressure 1.9 x 108 Pa Initial pressure 2.27 x 108 Pa Pressure 2.55 x 108 Pa, at low or moderate conversion Pressure 2.50 x 108 Pa, at conversion 0 Radical telomerization
Refs. 53 66 139 142 135 151 167 167 129
References page 11-15
TABLE 3. ACRYLIC DERIVATIVES Monomer
kp (1/mol/s)
kt (xlO~ 6 ) (1/mol/s)
Acrylamide
6000 ± 1000 18000 ±1500 8200 220 (7.9 ±0.5) x 10 4 (4.3 ±0.2) x 104 (3.3 ±0.2) x 104 (2.3 ±0.1) x 10 4 fcp=7xl06 x exp[(- 21000 ± 2000)/RT]
3.3 ±0.6 14.5 ±2.0 5.5 1.0 660 ± 4 0 350 ± 2 0 230 ± 2 0 160 ± 1 0
650
2.6
3150
2.6
Temp. (0C)
25 19 26 30 30
Method Al, Bl Al A A Al Al Al Al Fl
Remarks Solvent: water, pH 5.5 Solvent: water Solvent: water Solvent: DMSO Solvent: water 0.38M H 2 O : DMSO (90:10) H 2 O:dioxane (90:10) H 2 O : THF (92:8)
Refs. 79 41 89 89 126 119 119 119 197
Acrylic acid
-,butyl ester
- , cyclohexyl ester -,ethyl ester
6600 2.7 13 0.018 2100 330 1977 3.84 679±66 6.4±0.6 log 10 fcp = 6.0123-748.4/7 ln[(*t[p]/(1.00 + OMp)] = l n * t [I]-0.6Op 1360 1.28 963 1.18 1320 1.07 360 0.36 2722 ±248 3.2 ±0.3 800 1.76 12.39 x 10 3 139.2
- , 2-ethylhexyl ester - , methyl ester
23
Al Al
30 25-80 30
Al Al B4 Al Al Fl B5
30
Al
30 50 50
Al Al Al
25 25
155 1300
0.233 75
50 15
Al Al
880
260
15
Al
25 25
Al Bl Al
1580 580 fcp = 1 . 0 x l 0 8 x exp(- 30000/RT) 1000 11680 21300 (1.5 ±0.2) x 10 4 (3.7 ±0.6) x 104 6.3 x 104 (1.4 ±0.2) x 104
55 6.5 fct = 2.8xl0n x exp(- 22000/RT) 3.5550 194 -
60
Al Al Al G2
-
60 60 60
G2 G2 G2
- , 2-(acetoacetoxy-methyl)-, ethyl ester - , 2-cyano-, ethyl ester
300 1622 1610 1613 1607
1.0 411 404 411 404
60 30 30 30 30
C Al Al Al Al
- , 2-chloro-, ethyl ester
1660 1408 1120 978 350
333 244 4.8 x 102 435 2.1
30 30 30 30 60
Al Al Al Al C
- , 2-fluoro-, ethyl ester - , 2-acetoxymethyl-, methyl ester
Solvent: Water, pH 7.9, (with 1.2MNaOH) Solvent: water, pH 7.9 (with 1.5NNaCl) Solvent: water, pH 11
Pressure 5.0 x 107 Pa Solvent: benzene 1.76M kt \p\; kt for pressure p (bar), kt [l] = 3.5x 106 Solvent: anisole 2.00M Solvent: benzene 2.00M Solvent: chlorobenzene 2.00M Solvent: benzonitrile 2.00 M Solvent: benzene 1.76M Solvent: toluene 1.84 M Solvent: benzene x\ molar fractions of monomer, x = 0.401, kp and kt also given by other [M] Solvent: toluene 1.94M From unpublished results of Ross and Melville From unpublished results of Matheson
99 99 99 10 57 107 137 201 122 138 138 138 138 137 108 171
108 22 22 19 48 21
Solvent: benzene 2.69 M Primary propagating step (jfcpl), Ph-MA* PhCO 2 -MA' tert-BuO-MAm Secondary propagating step (kp2), Ph-MA-MA*, PhCO 2 -MA-MA', tert-BuO-MA-MA* Solvent: benseme AcOH 7 wt.% 1,3-propanesulfone 0.5 wt.% Optimum value, solvent: AcOH Optimum value Solvent: propanesulfone AIBN 4.88 x 10" 2 M Optimum value Optimum value Solvent: benzene LOOM, MAIB 0.050 M
50 144 144 190 190 190
170 143 143 123 123 140 123 146 123 225
TABLE 3. cont'd Monomer
fep
(1/mol/s)
fct(x..l0-6)
(l/mol/s)
Temp. ( 0 C)
Method
- , 2-acetyloxy-, methyl ester
430
-
60
C
- , 2-benzoyloxy-, ethyl ester - , 2-(benzyloxymethyl)-, methyl ester
990 182
2.9 1.6
60 60
C C
- , 2-[2,2-bis(carbomethoxy) ethyl], methyl ester
4.0
0.038
60
C
- , 2-butoxy-, methyl ester
298 184
8 -
60 60
C C
- , 2-butyroxymethyl-, methyl ester
360
1.4
60
C
19
0.51
60
C
8.6 1.6 300
21 1.8 1.1
60 60 60
C C C
11
0.08
50
C
0.57
0.11
60
C
0.76
1.4
60
C
- , 3-methyl, dimethyladamantyl ester
0.41 0.71
0.081 1.1
60 60
C C
- , 3-methyl, terf-butyl ester
0.90 LO
2.3 4.7
60 60
C C
- , 2-naphthoyloxymethyl-, ethyl ester
320
0.37
60
C
- , 2-pivaroxymethyl-, methyl ester
230
0.59
60
C
- , trans-2-vinyl-, methyl ester
125
-
60
C
3000-5000 127 52 51 20000 24
12.2 5 1.8
OD 25 25 25 40 50
B4 B4 B4 D
1960 15400 28000 1910 382 ±230 3300 ± 300 3200 ±400 3000 ± 600 (6.5 ± 1.3) x 103 28.2
782 2700 3700 290 47.6 ± 2 2 1200 ± 170 300 ± 5 0 240 ± 70 4700± 1300 0.20
60 25 25 25 25 50 50 50 50 60
Al Al Al Al Al Al Al Al Al C
273 273 8267
17.9 11.9 2200
30 30 30
Al Al Al
- , 2-(2-carbomethoxy)- ethyl-, methyl ester - , 2-ethyl-, methyl ester - , 2-ethyl-, cyclohexyl ester - , 2-isobutyroxymethyl-, methyl ester -,-2-(methoxycarbonylmethyl)-, phenetyl ester - , 3-methyl, adamantyl ester
Acrylonitrile
Ar-Acryloyl-2,2-dimethyl5 (R)-phenyl-l,3-dioxazoline 7V-Acryloylpiperidine N-Acryloylpyrrolidine
23
Remarks Solvent: 1,1,2-trichloroethane 2.0M 2,2'-azobis (4-methoxy-2,4dimethylvaleronitrile) 0.030 M, kp also given by other temp. Solvent: benzene 1.56M Solvent: benzene 2.0M, AIBN 5 ^ x IQ^ 3 M Bulk AVN 0.05 M, Ic p and kt also given by other temp. Solvent: benzene 2 M Solvent: 1,1,2-trichloroethane 2.0M 2,2'-azobis (4-methoxy-2,4dimethylvaleronitrile) 0.030 M, kp also given by other temp. Solvent: benzene LOOM, MAIB 0.050 M Bulk MAIB 0.05 M, kp and kt also given by other temp. Bulk AIBN 0.10M Bulk AIBN 0.10M Solvent: benzene LOOM, MAIB 0.050 M Solvent: benzene 2.22 M, kp and kt also given by other temp. and [M] Bulk 4.8 M MAIB 0.05 M Solvent: benzene 2.4 M, MAIB 0.05 M, kp also given by other [M] Bulk 4.0 M, MAIB 0.05 M Solvent: benzene 2.0M, MAIB 0.05 M Bulk 5.9 M, MAIB 0.05 M Solvent: benzene 2.0M, MAIB 0.05 M Solvent: benzene LOOM, MAIB 0.01 M Solvent: benzene LOOM, MAIB 0.005 M Solvent: benzene LOM, AIBN 0.25 M
Solvent: DMF
Refs. 224
172 206 228
176 224
225 229 230 230 225 157
232 232
232 232 232 232 226 225 227 42 49 63 75 42 35
Primary radical termination in a precipitating medium Solvent: DMF 43 Solvent: water 54 Solvent: water 55 Solvent: DMSO 70 Solvent: DMF 68 Solvent: DMF 3.8 M 88 Solvent: DMSO 3.8 M 88 Solvent: Ethylene carbonate 3.8 M 88 Solvent: Mg (C1O4)2 • 12H2O 3.04M 88 Solvent: benzene 1.08 M, 231 MAIB 0.05 M, kp and kt also given by other temp. 145 Optimum value 123 Optimum value 123
References page 11-15
TABLE 3. cont'd Monomer
kp (1/mol/s)
ifetCxlO"6) (1/mol/s)
Temp. (0C)
Method
JVW'-Dimethylacrylamide
11000 27200 29198 15 x 10 3 2330 ±230
38 3540 4080 0.540 ±0.053
50 30 30 25 30
Al Al Al Fl A4
2760 ±342
0.452 ±0.056
30
9.9 x 10 3
-
25
Fl
kp (1/mol/s)
kt (x 10 ~6) (1/mol/s)
Temp. (0C)
Method
79.6 ±5.6 1.1 x 10 3 ~21 26
16.5 ± 1 . 4 ~27 21
25 25 30 25
Al Fl Al
670
2.1
23
Al
1950 1410 110 895 1250 510
2.25 41.9 80 40 41.9 2.87
30 32.5 32.5 30 20
Al Al C C Al Al
- , bornyl ester
580
3.3
60
C
- , n-butyl ester
369 573 360 lnfcp = 6 . 1 3 + 6.33 x 10 ~9 p lnfcp = 15.8-2751/7
10.2 18.0 10
30 30 30 30 12-93 70 30
Al Al Al F2 F2 B5 B5
10-90
Fl Fl A3 Al
3-Dimethyl-(acryloyloxyethyl)ammonium propane sulfonate
N-Methylacrylamide
Remarks
Optimum value Solvent: water, pH 1.4 Solvent: formamide: 1,4-dioxane (3:1 (v/v)) Solvent: formamide: 1,4-dioxane (3:1 (v/v)), NaCl 0.1 M Solvent: water, pH 1.9
Refs. 74 121 123 197 192 192 197
TABLE 4. METHACRYLIC DERIVATIVES Monomer Methacrylamide Methacrylonitrile £p
Remarks Solvent: water Solvent: water, pH 1
Refs. 69 197 26 39
106.43±0.26
=
xexp[(-29700±1500)//?n Methacrylic acid
- , benzyl ester
- , terf-butyl ester
2.6 In [(kt\p]/(\M + 0.0lp)] = InJt1[I] - 0.73/7 ln*p = (14.41 ±0.09) - (2472±29)/T jfcp = 3.44 x 10 6 exp(- 23300/RT) 1576 9.74 350 14 £p
=
1O7.4±o.4
30 25 9
_66
Solvent: water, pH 8.0 (with 0.22MNaOH) pH=13.6
kp and kt also given as a function of viscosity Solvent: benzene 1.0 M, AIBN 0.05 M Pressure: 5.0 x 10 7 Pa
Pressure 1.0 x 10 8 Pa 77=1.92cp kt \p]\ kt for pressure p (bar), kt[l] = 13.4 x 10 6
99 99 101 153 153 87 103 193 27 106 109 216 216 212 122 219 169 225 52 203
F 1
xexp[-(27.7±2.5)x IO3/RT] - , trans-4-tert-buty\cyclohexyl ester
- , cetyl ester - , p-Ip-(cetyloxy)benzoyloxy]phenyl ester - , 2-chloroethyl ester - , 2-cyclohexylethyl ester - , cyclohexyl ester - , 2-decahydronaphthyl ester
550
1.9
60
C
510 570 ± 1 0 300 ± 9 0 300
1.9 0.5-2.3 0.16 ±0.04 0.25
60 60 30 50
C C Al Al
170 254 1190
0.30 6.71 32.8
50 30 30
Al Al Al
510
5.4
60
C
570
3.1
60
C
Solvent: benzene LOM, AIBN 0.05 M, trans 100% trans 28.9% Solvent: benzene Solvent: dioxane 0.2 M
Solvent: toluene 0.2M
Solvent: benzene LOM, AIBN 0.05 M Solvent: benzene LOM, AIBN 0.05 M
194 194 210 109 97
97 87 87 193 193
TABLE 4. cont'd Monomer - , 2,6-dimethylphenyl ester - , dodecyl ester -,ethyl ester
- , hexadecyl ester - , isobornyl ester - , isobutyl ester - , isopropyl ester - , lauryl ester
- , 2-methoxyethyl ester - , methyl ester
kp (1/mol/s)
M x l O " 6 ) (1/mol/s)
Temp. (0C)
Method
68
2.1
30
Al
72 126
2.4 0.6 7.35 10
30 70 30 70
Al B5 Al B5 Fl
0.16 3.5
10-90 70 60
Fl B5 C
10-90 30 30
Fl Al Al Fl
219 87 109 169
30 23.6
Al Al Al
87 9 7
32.5 40 50 -30 20
C Bl E Bl Al
* p = 1.50 XlO 6 x exp(- 20460/RT) ln* p = (15.11±0.17)-(2753±55)/r 390
lnfcp = (14.72±0.13)-(2590±42)/7 121 4.52 460 ±140 0.6 ±0.2 kp = 2.93 x l O 5 x exp(- 16190/RT) 249 9.30 310 ± 2 0 66 ± 4 fcp = 5 . 1 3 x l 0 6 kt = 1.36 x l O 3 x exp(- 26400/RT) x exp(- 11900/flT) 187 72.1 404 17.6 410 24 13.2 0.488 390 517 527 28 260 270 280 285 310 330 340 240 335 270 330 250 240 280 320 390 ± 4 0 410 ± 40 410 ± 4 0 180±50
37 23 4.4 21 21 19.5 17.5 17 17 17 11.5 9 22 16 29 25 14 28 42 ± 4 29 ± 3 26 ± 3 20 ± 6
10 10 10 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 20
Bl Bl Bl Al Al Al Al Al Al B5 B5 B5 B5 B5 B5 B5 B5 B5 Al Al Al E
500 ±250 41.6 62 200 128 364
63 ± 3 2 2.69 8.44 41.8
20 0 5 20 22 22.5
B6 B5 D B6 Bl B4
512.6 410
46.6 42.7
25 25
Al Al
248 141 106 140
22.7 11.6 5.7 -
30 30 32 40
Al A B4 D
Remarks
Refs. 120
Optimum value r? = 3.96cp
123 212 87 212 169
7^ = 0.91 cp
rj = 7.52cp Solvent: benzene 1.0 M, AIBN 0.05 M
Solvent: ethyl acetate Using results of Ref. 7 Solvent: ethyl acetate kp also given as a function of temp. and of viscosity for other solvents Solvent: methanol Solvent: pyridine Solvent: DMF Solvent: benzene 4.69 M Solvent: fluorobenzene 4.69 M Solvent: chlorobenzene 4.69 M Solvent: anisole 4.69 M Solvent: bromobenzene 4.69M Solvent: benzonitrile 4.69 M Solvent: methyl benzoate 4.69 M Solvent: methylphenyl acetate 4.69 M Solvent: dimethyl phthalate 4.69 M Solvent: dimethyl carbonate 4.69 M Solvent: diethyl oxalate 4.69 M Solvent: methyl formate 4.69 M Solvent: methyl propionate 4.69 M Solvent: diethyl succinate 4.69 M Solvent: acetonitrile 4.69 M Solvent: methanol 50% by vol. Solvent: n-octane 5% by vol. Solvent: «-nonane 20% by vol. DP = (2-8) x 10 3 using results of Ref. 86 DP = ( 3 - 5 ) x l 0 4 Assuming biradical initiation Jfcp found as a linear function of Mw Rate of initiation; 1.20 x 10 " 8 (moles/1/s) kp and kt also given as a function of viscosity for other solvents
219 212 193
153 51 62 72 92 94 94 94 85 85 85 85 85 85 90 90 90 90 90 90 90 90 90 104 104 104 96 96 11 65 91 29 60 30 93 14 87 58 65
References page 11-15
TABLE 4. cont'd Monomer
A:p (1/mol/s)
M x l O ~ 6 ) (1/mol/s)
Temp. (0C)
Method
0.224 573
2.0
45 60
D E
573
11.9
60
E
995 ± 83 506 ±48 450 ± 3 3 456±29 448 ±47 498 ± 39 614±43 427 ±38 290 1020 530 550
43.6 ± 4.9 35.6 ±3.9 42.0 ±3.0 43.8±2.0 47.2 ±6.6 42.9 ± 4.7 39.9±3.3 30.9 ±3.7 21 292 55 68
80 30
kp= 4.92 XlO 5 x exp(- U210/RT) 315
kt = 9S x exp(- 2930/RT) 33.9
15-30
A2
25
A2
336 ± 9 0 441 fcp = 2 . 5 x l 0 6 x exp[(- 23000 ± 2500)/RT] kp=k® (0.33 < Wp < 0.84) = ££exp[-29.8(Wp-0.84)] (0.84 < w p < 0.99)
28 ± 12 19.7 720
25 30 25-60
Al Al C
50
C
w p (weight fraction of polymer)
150
At high conversions ( ~ 65%) Special evaluation from steady-state and Mn Solvent: toluene
148 134
30 60
Al Al Al Al Al Al Al Al Al Al Al
Remarks
Refs.
Termination by combinat. using results of Refs. 7 and 31 Termination by disprop. using results of Refs. 7 and 31 Solvent: benzene 4.7 M Solvent: anisole 2.0M Solvent: benzene 2.0M Solvent: C 6 D 6 2.0M Solvent: fluorobenzene 2.0M Solvent: chlorobenzene 2.0 M Solvent: benzonitrile 2.0M Solvent: benzene 1.0 M Addition of 1 x 10 " 3 mol pyridine Addition of 1 x 10" 3 mol acetone Addition of 1 x 10 " 3 mol triethanolamine P n = IO4 kp and kt also given as a function of P n Pressure 5.0 x 106 Pa Pressure 5.0 x 10 7 Pa
67 33 33 111 133 133 133 133 133 133 133 118 118 118 118 114 110 127 105 45
(*J= 790 ±300) 130 705.6
20.7 ±1.0 25
0 60
Al
170 306 292
-
0.2 25 25
F3 Fl Fl
60 20-90
C Fl
30
B5
670 ± 3 0 22 InATp = 14.69-2670/7+ 0.201/7x(1.0x 1 0 " 5 P - I ) \nkt[p] = InA:t[l] -0.57/7 26.6
1.4
5
BlO
5.8
0.017
5
BlO
kt(m,n) = 1.22 x W2(n x m)~ 0075
25
A3
21
70
B5
0.034
50
D
0.16
50
D
- 1 to - 70 60
Fl C
- 8 30
F3 Fl
fcp = 106 694 exp(- 23940/RT) lnJfcp (VmoVmin) = ln*p,<>-(3.86 [AIBME]0 + 0.8) x (l-(f>m)- 1.6 (l-cj)m)60
131 680- 820
-
690-810
-
Fl
222 196
Solvent: ethanol (50%) 4.67 M, kv also given by other [M] and solvents 175 207 kt\p\\ kt for pressure/? (bar), fct[l] = 15.4x 106 Scavenger DPPH, solvent: DMF, blank polymn. Scavenger DPPH, solvent: DMF, template polymn., template; it-MMA n: n-mer; m: m-mer, coupling with rt-mer and m-mer 77 = 0.53 cP No addition of chain-transfer agent, Time 7.5-20.5 min. Addition of 2% CBr4, Time 7.5-20.5 min. AIBME (dimethyl 2,2'azodiisobutyrate) 0.0434M, >m; monomer volume fraction £pX) = 700(l/mol/min) Benzoin 7 x 10 " 4 M Solvent: toluene, pressure 1.0 x 108 Pa, k p also given by other pressures Solvent/2-butanone, pressure 1.OxIO 8 Pa
122 115 115
147 212 149 149 217 158
199 208
208
TABLE 4. cont'd Monomer
kp (1/mol/s)
M x l O " 6 ) (1/mol/s)
Temp. (0C)
Method
313±8.1 794.0 815.0 957.0
39±4 62.4 51.6 38.2 25(±3)
25 60
Fl B5
60
C
21 ± 2 45 50
60 25 40
C Al
191 160 160
-
25 50
Fl Fl C
198 220 184
510 ±100 299 431 )tp = 2.39 x 106 x exp(- 22000/#D 359 12
135 292 200 135 ± 5 0 170
-, octyl ester
35 2960 *p = 1.9068 x 106 xexp(-21181.07//?D kp = 1.2169 x 106 x exp(- 25203.59//?D kp = 3.0598 x 107 x exp(-28008.18/RT) 35 1710 240 ± 8 0
0 25 28 0 50
29.1
50 30
Al Fl Bl Al C
Values from Chem. Abstr.
159 164 83 165 155
30% MMA in benzyl alcohol
227
Fl
30% MMA in NMP
227
p.s. 500 nm Pressure 5.0 x 10 7 Pa
155 113 109 122
30 30 30 60
Al Al Al Al Al Al Al Al Al Al C
26 1470 ±170
0.301 0.499 ±0.058
32.5 30
C A4
2760 ±342
0.452 ±0.056
30
185
0.034
20
B8
230
0.053
20
B8
kp (1/mol/s)
£ t ( x l 0 ~ 6 ) (1/mol/s)
Temp. (0C)
Method
1.7 3.9
2.5 x 10" 3 3.4xl0~3
60 60
C C
Polyhydroxytetramethylene-a, co-methacrylate of MW = 700
particle size 260 nm, kp also given by other particle sizes kp; average value
Fl
411 230 ± 1 5 176±8 180±9 223 ±11 235 ± 8 273 ± 8 228 149 467 590
30 30
Emulsion polymn.,
161 204 204 204 166
A3 Fl
50 30 30
Solvent: benzene 3 M Solvent: chlorobenzene 3 M Solvent: benzonitrile 3 M
Refs.
Emulsion polymn., n-butyl aery late: MMA: methacrylic acid (8:91:1), particle size (p.s.) 50 nm, kp also given by other temp, and particle sizes p.s. 500 nm 155 225 227
62.6 2.6 ±0.9 ln[(fct[p]/(1.00- 0.19)] = \nkt[l]-l.01p 11.9 2.02 ±0.22 2.06±0.21 2.16±0.19 2.26 ± 0.22 1.72 ±0.11 1.96 ±0.12 1.88 0.813 45.1 2.6
-, phenyl ester
- , 2-phenylethyl ester - , 3-phenylpropyl ester - , rc-propyl ester - , 3-tetracyclo-[4.4.02'5.l7'10]dodecyl ester -, triphenylmethyl ester 3-Dimethyl-(methacryloyloxy-ethyl) ammonium propane sulfonate
25.6 -
Remarks
Al Al B5
kt[p]\ kt for pressure p (bar), ikt[l] =40.0 x 106 Solvent: Solvent: Solvent: Solvent: Solvent: Solvent:
anisole 2.00M benzene 2.00M fluorobenzene 2.00M chlorobenzene 2.00M bromobenzene 2.00M benzonitrile 2.00M
Solvent: benzene 1.0M, AIBN 0.05 M
87 116 116 116 116 116 116 87 87 28 193
153 Solvent: formamide: 192 1,4-dioxane (3 :1 (v/v)) Solvent: formamide: 192 1,4-dioxane (3 : 1 (v/v)), NaCl 0.1 M Calcd. from nonstationary 125 state kinetics Calcd. from stationary state kinetics 125
TABLE 5. ITACONIC DERIVATIVES Monomer Itaconic acid - , bis (4-terf-butyl-cyclohexyl) ester - , bis (cyclohexyl-methyl) ester
Remarks
Solvent: benzene 0.5M Solvent: benzene 1.5M, MAIB 0.02 M
Refs.
213 182
References page 11-15
TABLE 5. cont'd kp (1/mol/s)
M x l O " 6 ) (1/mol/s)
Temp. (0C)
Method
- , bis (3,5-dimethyl-l-adamantyl) ester - , bis (2-ethylhexyl) ester
0.92 6.8 3.4 2.0 2.1 2.2 2.1 2.1 1.4 3.0
0.32 x 10~3 0.001
60 50 50 50 50 50 50 50 50 50
C C C C C C C C C C
- , diadamantyl ester
0.56
0.30 x 10~3
60
C
- , di-n-butyl ester
3.5
1.59 x l O " 2
60
C
13
0.11
50
C
11 6.8 9.4 6.7 3.4 3.2
0.13 0.07 0.11 0.083 0.068 0.13 1.0 x l O " 3
50 50 50 50 50 50 50
C
5.3
8.5 x l O " 2
50
C
5.9
0.053
50
C
- , di-sec-butyl ester
0.6
4.0 x 10 ~3
60
C
- , di-terf-butyl ester
0.2
5.6 x 10~3
60
C
- , dicyclohexyl ester
2.3
1.4xlO" 3
60
C
- , diethyl ester
7.7
0.24
50
C
3.7
6.41 x l 0 ~ 2
60
C
- , diisobutyl ester
2.7
1.56 x 10~2
60
C
- , diisopropyl ester
1.1
5.0xl0~~ 3
60
C
- , dimethyl ester
5.2
0.36
60
C
10
0.59
50
C
- , a-ethyl-P-hexarluoropropyl ester
5.0
0.28
60
C
- , a-methyl-P-isopropyl ester - , a-methyl-P-tert-butyl ester - , a-isopropyl-P-methyl ester - , a-fm-butyl-P-methyl ester AT(2,6-dimethylphenyl)itaconimide
3.4 4.2 1.9 0.91 26
0.06 0.051 0.07 0.056 0.082
60 60 60 60 50
C C C C C
15
0.29
60
C
Monomer
Methyl N-phenyl-itaconamate
Remarks Solvent: benzene 1.5 M Solvent: hexane 1.03 M Solvent: cyclohexane 1.03 M Solvent: toluene 1.03 M Solvent: benzene 1.03 M Solvent: chlorobenzene 1.03 M Solvent: ethyl acetate 1.03 M Solvent: THF 1.03 M Solvent: acetone 1.03 M Solvent: benzene 2.0M, MAIB 0.05 M Solvent: benzene 1.5 M, kp and kt also given by other [M] Solvent: benzene 1.5M, MAIB 0.02 M Solvent: cyclohexane 1.33 M, MAIB 5.00 x 10~2 M, kp and kt also given by other temp. Solvent: n-hexane 1.33 M Solvent: chlorobenzene 1.33 M Solvent: methyl benzoate 1.33 M Solvent: benzene 1.33 M Solvent: acetone 1.33 M Solvent: acetonitrile 1.33 M Solvent: benzene 0.794M, AIBN 0.05 M kt also given by other [M] Solvent: benzene 0.794M, MAIB 0.05 M Solvent: benzene 2.0M, MAIB 0.05 M Solvent: benzene 1.5 M, MAIB 0.02 M Solvent: benzene 1.5M, MAIB 0.02 M Solvent: benzene 1.5 M, MAIB 0.02 M Solvent: benzene 2.0M, MAIB 0.05 M Solvent: benzene 1.5M, MAIB 0.02 M Solvent: benzene 1.5M, MAIB 0.02 M Solvent: benzene 1.5M, MAIB 0.02 M Solvent: benzene 1.5 M, MAIB 0.02 M Solvent: benzene 2.0M, MAIB 0.05 M Solvent: benzene 2.0M, MAIB 0.05 M, kp and kt also given by other [M] and temp.
Solvent: THF 0.44 M, AIBN 0.05 M, J^p andfct also given by other [M] Solvent: DMF 1.4 M, AIBN 0.05 M, jfcp andfct also given by other [M] and temp.
Refs. 213 185 185 185 185 185 185 185 185 177 213 182 162
162 162 162 162 162 162 154
154 177 182 182 182 177 182 182 182 195 177 233
195 195 195 195 234
235
TABLE 6. FUMARIC DERIVATIVES Monomer Fumaric acid - , bis (2-methoxy-ethyl) ester - , bis (2-chloro-ethyl) ester - , tert-butyl methyl ester - , tert-buty\ isopropyl ester
- , di-terf-butyl ester - , dicyclohexyl ester - , diethyl ester
- , diisopropyl ester
- , dimethyl ester - , dineopentyl ester Ethyl o-formylphenyl fumarate
TABLE 7.
M x l O " 6 ) (1/mol/s)
Temp. (0C)
Method
0.19 0.26 0.23 0.51 0.35 0.39 0.61 0.60 0.21 0.015
330 x 10~6 320 x 10~6 150xl0~6 26xlO"6
60 60 60 60 60
C C C C C
1.75 x l O - 5 30 x 10~6 40 x 10~6 (510-560) x 10" 6 1.64 x l O - 4
60 60 60 30
C C C Al
0.029 ±0.003
8 xlO-6
30
BlO
0.46 0.31 ±0.07
(80-100) x 10~6 0.84 x l O - 6
60 30
C BlO
0.058 0.028 4.0
430 x 10~6 44xlO~6 1.4
60 60 60
C C C
k p (1/mol/s)
M x I O " 6 ) (1/mol/s)
Temp. (0C)
Method
7400
7.4xlO"5
40
22.7 570 kp = 3.3 x 106 x exp(- 15000/RT) 11000 3130 8.6 kp = 10 9 x exp(- 4540/7)
92 385 kt = 1.3 x 106 x exp(- 4200/RT) 2100 2300 0.175 kt = 106 x exp(- 2670/7)
-30 20
kp (1/mol/s) 4600 795 556-586 670-770 700 559 1100 1000 895 kp = 2.43 x l O 8 x exp(- 30600/RT) 9500-19000 (15-26) x 102
Remarks
Solvent: benzene l.OM Solvent: benzene l.OM Solvent: benzene l.OM Solvent: benzene l.OM AIBN MAIB Solvent: benzene l.OM Solvent: benzene l.OM Solvent: benzene l.OM AVN (2,2'-azobis-2,4dimethylvaleronitrile), ACN (l.l'-azobiscyclo-hexane1 -carbonitrile) ACN, scavenger TPV (1,3,5-triphenylverdazyl), sovent: benzene Solvent: benzene l.OM ACN, scavenger TPV, solvent: benzene Solvent: benzene l.OM Solvent: benzene l.OM Solvent: benzene 1.16 M, MAIB 0.100 M, kp and ^ t also given by other [M]
Refs.
211 211 211 211 181 181 211 211 211 173
179
211 180 211 211 236
VINYL HALIDES
Monomer Tetrafluoroethylene
Vinyl bromide Vinyl chloride
Vinylidene chloride
TABLE 8.
kp (1/mol/s)
Remarks Large active chain end concentration measured by addition of inhibitor in aqueous solution polymn.
Al
Refs. 81
Al
80 44 32
25 25 25 22-75
Al Al Al Al
56 77 18 117
M x I O " 6 ) (1/mol/s)
Temp. (0C)
Method
220 46 2860-3040 2500-3100 2600 51.8 80 59 24 kt =4.16 x 105 x exp(- 21900/RT) 380-760 25
25 15 15.9 15.9 15.9 20 25 25 25
B5 Bl Al Al Al B4 Al Al B4 Al
60 50
E Al
Quoted in Ref. 80
Solvent: N-methylpyrrolidone 2.0M
VINYL ESTERS
Monomer Vinyl acetate
Remarks
Solvent: «-hexane
At 4% conversion
Using results of Refs. 8 and 15
Refs. 13 47 1 3 4 37 2 15 36 8 64 128
References page 11-15
TABLE 8. cont'd Monomer
Vinyl benzoate
TABLE 9.
kv (1/mol/s)
£ t (xIO~ 6 ) (1/mol/s)
Temp. (0C)
Method
Remarks
117zb 12 113±10 48 ± 5 97 ± 10 61 ± 9 37 ± 5 8± 1 637 ± 101 78 #
319±61 351±54 239 ± 4 5 311 d= 59 266 ± 7 5 412 ± 104 258 ± 76 94.2 ± 23.7 -
30
Al Al Al Al Al Al Al Al
32.5 32.5 32.5 32.5 30 15-60
Al C C C Al C
Solvent: benzene 2.00M Solvent: C 6 D 6 2.00M Solvent: anisole 2.00M Solvent: fluorobenzene 2.00M Solvent: chlorobenzene 2.00M Solvent: ethyl benzoate 2.00M Solvent: benzonitrile 2.00M Solvent: ethyl acetate 2.00M Solvent: ethyl acetate: ethyl benzoate (1:1 (v/v)) Solvent: benzene Solvent: benzene 5.41 M Solvent: ethyl acetate 5.43 M
120 310 530 630 1900 280 1400 4435 64.4 £ p = 2.0 XlO 6 27.5 x exp[(- 19000 ± 2900)/RT] Jcp = 2 . 1 x l O 8 x exp(- 27820//?7) ln[(*t|>]/(1.00-0.07/?)] = lnJfct[l]-0.50p 106 ± 1 4 253 ± 6 3 185 ± 8 402 ± 3 2 245 ± 13 522 ± 48 168 ± 18 383 ± 76 69 ± 13 257 ± 72 33 ± 3 299 ± 4 4 267±33 451 ± 6 5
Monovinyl ether of ethylene glycol Monovinyl ether of diethylene glycol
Monomer Styrene
Pressure 5.0 x 10 7 Pa
Fl 30
B5
30
Al Al Al Al Al Al Al
130 130 130 130 130 130 130 130 130 153 153 153 153 112 45 209
kt\p]; kt for pressure p (bar) £ t [l] = 52.0x 106 Solvent: anisole 1.01 M Solvent: benzene 1.01 M Solvent: fluorobenzene 1.01 M Solvent: chlorobenzene 1.01 M Solvent: ethyl benzoate 1.01 M Solvent: benzonitrile 1.01 M Solvent: ethyl acetate 1.01 M
122 116 116 116 116 116 116 116
VINYL ETHERS
Monomer
TABLE 10.
Refs.
k p (1/mol/s)
kt (x 10 6 ) (1/mol/s)
5.0 ±1.0 3.0 ± 0.8
1.5 ±0.3 1.4 ± 0.3
Temp. ( C )
Method
50 50
Al Al
Refs. 136 136
STYRENE DERIVATIVES k p (1/mol/s)
kt (x 10 ~6) (1/mol/s)
Temp. (0C)
Method
40 ± 20 24
80 ± 40 14
15 20
Al Al
51.9 108 106 102 390 209 18.7 39.5 £p = 2 . 1 6 x l 0 7 x exp(- 32500/RT) 22
10.5 32.5 108 -
30 30 30 40 50 50 25 25
Al Al Al D D E B5 Bl Al
5
D
40 50 50
D D D
139 223 206
115 2.79 5.96 2£t = 2 . 5 9 x l 0 3 x exp(- 9920/RT) -
Remarks Dimension of kp and kt: kg/mol/s From copolymn. data with sulfur dioxide
Quoted in Ref. 86 Using results of Ref. 20
Catalyst: cumene hydroperoxidetriethylenetetramine Catalyst: persulfate
Refs. 46 25 16 38 78 59 5 61 6 17 20 24 24 40 67
TABLE 10. cont'd Monomer
kp (1/mol/s)
M x l O " 6 ) (l/mol/s)
Temp. (0C)
* p = 2.24 XlO 14 xexp(-73510//?r) 50 80 64 370 915 25 ± 3 9 ± 1.5 35 ± 7 19 ± 4 35 ± 5 19 ± 3 29 ± 7 15 ± 4 23±8 11 ± 2 27 ± 4 31 ± 0.4 *p = 1.09 XlO 7 * t = 1.703 x l O 3 x exp(- 31380/K7) x exp(- 9489/RT) 66.6 22.4 66.5 £ p = 2.4 XlO 8 x exp(- 38000 ± 11OO)/RT 187.1 29.4
84
-,p-bromo-,/?-chloro-,/7-cyano-,p-fluoro-,/7-methoxy-
25 60
D Al
25 25 25 25 25 25 15-30
Al Al Al Al Al Al A2
65 118 Addition of 1 x 10 " 3 mol pyridine 118 Solvent: dodecane 40% by vol 104 100 Solvent: bromobenzene 20% by vol 100 Solvent: diethyl malonate 20% by vol 100 Solvent: diethyl phthalate 20% by vol 100 Solvent: dinonyl phthalate 60% by vol 100 DP = 2500 114
30 25 50-90
Al C
60 F2 Fl
25 25 40 70
Fl Fl Fl C
16.6-17.0
100
C
190 -
50 25
C Gl
kt (m,/i) = 1.97 x 102 (n x m) " ° 1 2
30
A3
5 30-90
C Fl F2
25 25 60
Fl Fl B5
91.2 25 30 25 25 28
Gl Al Fl Fl Fl Bl Fl
180 ± 1 0 £ p = 1.99xl0 7 exp(-30780//?D In kp = 17.14-1.873 x 10" 9 p - 3748/r + 2.02 x 10 " 6 p/T 77 ±4.1 79 ±5.1 187.0 201.0 167.0 641 ±48 89 107 92 78 23 In kp = 16.09-28950//?r (overall) = 16.47-3003/KT (chain length > 4) * p = 107-1±0-5 xexp[-(29±3)xlO3/*r] fcp = 1.8861 x 107 x exp(- 30737.52//?r) kp = 4.2060 x l O 8 x exp(- 37468.93/RT) kp = 4.2458 x 108 xexp(-39014.90//?7) 186 150 219 112 2.92 71
-
78 ± 1 2 96 ± 9 63.2 51.1 37.9 132 0.6
46 77 35 127 1.06 33
Refs. 73
-
256 107
Remarks
Bl
kp = 107-630 x exp(- 32510/RT) - 1 2 - 93 25
76 70 380 ±110 480 ± 1 0
Method
30 30 30 30 0 30
Pressure 5.0 x 10 7 Pa
102 98 98
Special evaluation from steady-state kinetics and Mn
134
215 kp also given by other [M] and 196 solvents Solvent/ethanol(25%)6.52M 196 Solvent: methanol (25%) 6.52 M 196 Pressure 2.0 x 108 Pa 186 Over a range of degree of polymn. 188 of the polymer radical from 40 to 410 Conversion 0-20% 174 TBP (terf-butyl peroxide) kp and kt also given by other temp. 189 Laser-flash-initiated polymn. by 156 benzoin n: n-mer, m: m-mer, 147 coupling with n-mer and m-mer 223 169 Pressure 1 x 10 5 -2.8 x 108 Pa 214
Solvent: Solvent: Solvent: Solvent: Solvent:
toluene 50% (v/v) benzene 3 M chlorobenzene 3 M benzonitrile 3 M toluene
kp also given by other temp.
Solvent: benzene 4.33 M
161 161 204 204 204 178 160 198 220 164 83 200
Bl
131
Fl
227
Fl
30% styrene in benzylalcohol
227
Fl
30% styrene in NMP
227
Al Al Al Al B5 Al
Solvent: dimethylacetamide
78 78 78 78 12 78
References page 11-15
TABLE 10. cont'd Monomer
kv (l/mol/s) kp = 1.67 x 1 0 n x exp(- 58240/RT) 84 kp = 2.27 XlO 7 x exp(- 32060/RT) kp = 10 5 7 7 x exp(- 23.0/RT) &p = 3 . 6 3 x l 0 7 x exp(- 31500/RT)
- , o-methyl- , p-methyl-
Styrene-d8
TABLE 11.
A: t (xl0~ 6 ) (l/mol/s)
66
Temp. (0C)
Method Bl
73
30
Al Bl
78 73
24-55
Fl
£t = 2 . 5 5 x l 0 4 x exp(- 14200/7?7)
Solvent: toluene 2M
Al
kp (l/mol/s)
Ict (x 10~ 6 ) (l/mol/s)
Temp. (0C)
Method
6.0 186 96.6 12 47 122
0.306 33 8.9 3 3.5 66
10 25 25 25 25 20
Al Al B4 B5 B4 Bl
209 17.3 953 22000 ± 4000
43 1.2 65 600 db 200
20 20 20 25
Bl Bl B4 Al
k p (l/mol/s)
M x 10 ~6) (l/mol/s)
Temp. (0C)
Method
-
(7-10) x 10 ~3
—190
B4
kp (l/mol/s)
kt(x 10~ 6 ) (l/mol/s)
Temp. (0C)
Method
Maleimide - , N-tert-amyl- , N-tert-butyl-
69 100
0.048a,0.017b 0.021 a ,0.023 b
60 60
C C
-, -, -, -,
120 23 120 49
0.20a 0.027 a ,0.015 b 0.15 a ,0.23 b 0.054
60 60 60 50
C C C C
55
0.069
W-Vinylcarbazole 2-Vinylpyridine 4-Vinylpyridine 5-Vinylpyridine - , 2-methyl-
Af-Vinylpyrrolidone
226 168
Remarks
Refs. 80 76 76 34 75 94
Solvent: methanol 1.95 M, kp also given as a function of [M] Solvent: 50% (molar) aqueous methanol 94 Solvent: acetic acid 94 82 Solvent: water 132
ALDEHYDES
Monomer Formaldehyde
TABLE 13.
Refs.
VINYLHETEROAROMATICS
Monomer
TABLE 12.
Remarks
Remarks Solid monomer, gamma irradiation
Refs. 95
OTHERS
Monomer
A^m-butyl-dimethylsilylN-tert-octylN-trimethylsilylN-cyclohexyl-
Remarks
Solvent: benzene 1M (a) Determined from steady-state equation kt = (2kdf[l])/[P']2, AIBN 0.005 M; (b) determined from second order plot of the decay curve of the radical concentration, ATMP (2,2 '-azobis-(2,4,4-trimethylpentane)) 0.02 M, for tert-BMl, ATMP 0.01 M
Solvent: benzene 0.559 M, AIBN 1.39 x 10" 2 M Solvent: benzene 0.698 M, AIBN 1.00 x 10~2 M, kp and kt also given by other [M] and [I]
Refs.
205 205
205 205 205 163 163
TABLE 13. cont'd A: p (1/mol/s)
Jt t (xl0" 6 ) (1/mol/s)
Temp. (0C)
- , AH2,6-diethylphenyl-
2.0
0.0078
60
C
- , Af-(2,6-dimethylphenyl)-
14
0.034
60
C
- , AH4-ethylphenyl)-
1200
3.9
60
C
- , #-(2-methylphenyl)-
190
0.59
60
C
- , Af-(2-carboethoxyphenyl)- , N-dodecyl-
96 54 104 175 80 128 149
0.10 0.12 0.45 1.0 0.40 0.064 0.17
60 50 50 50 50 50 50
C C C C C C C
386 250 235 196
0.55 -
50 50 50 50
C C C C
33
0.10
50
C
400
0.07
50
B9
Monomer
- , iV-octadecylOligotetramethylene glycol dimethacrylic ester (MW 600)
Method
Remarks Solvent: benzene 1M, AIBN 5 x 10- 3 M Solvent: benzene 1M, AIBN 5 x 10- 3 M Solvent: benzene 1M, AIBN 5 x 10- 3 M Solvent: benzene 1M, AIBN 5 x 10- 3 M Solvent: benzene MAIB 0.005 M Solvent: benzene MAIB 0.01 M Solvent: toluene MAIB 0.01 M Solvent: anisole MAIB 0.01 M Solvent: chlorobenzene MAIB 0.01 M Solvent: bromobenzene MAIB 0.01 M Solvent: methyl benzoate MAIB 0.01 M Solvent: THF, MAIB 0.01 M Solvent: dioxane, MAIB 0.01 M Solvent: ethyl acetate MAIB 0.01 M Solvent: methyl ethyl ketone MAIB 0.01 M Solvent: benzene AIBN 0.20M, kp and k[ also given by other [I]
Refs. 183 183 183 183 237 238 238 238 238 238 238 238 238 238 238 239 124
C. REFERENCES 1. G. M. Burnett, H. W. Melville, Nature, 156, 661 (1945). 2. C. G. Swain, P. D. Bartlett, J. Am. Chem. Soc, 68, 2381 (1946). 3. G. M. Burnett, H. W. Melville, Proc. R. Soc. London, Ser. A, 189, 456 (1947). 4. G. M. Burnett, H. W. Melville, Proc. R. Soc. London, Ser. A, 189, 494 (1947). 5. W. V. Smith, J. Am. Chem. Soc, 70, 3695 (1948). 6. C. H. Bamford, M. J. S. Dewar, Proc. R. Soc. London, Ser. A, 192, 308 (1948). 7. M. S. Matheson, E. E. Auer, E. B. Bevilacque, E. J. Hart, J. Am. Chem. Soc, 71, 497 (1949). 8. M. S. Matheson, E. E. Auer, E. B. Bevilacque, E. J. Hart, J. Am. Chem. Soc, 71, 2610 (1949). 9. M. H. Mackay, H. W. Melville, Trans Faraday Soc, 45, 323 (1949). 10. H. W. Melville, A. F. Bickel, Trans. Faraday Soc, 45, 1049 (1949). 11. C H . Bamford, M. J. S. Dewar, Proc R. Soc London, Ser. A, 197, 356 (1949). 12. D. W. E. Axford, Proc. R. Soc. London, Ser. A, 197, 374 (1949). 13. G. Dixon-Lewis, Proc R. Soc. London, Ser. A, 198, 510 (1949). 14. L. Valentine, Thesis, Aberdeen (1949). 15. H. Kwart, H. S. Broadbent, P. D. Bartlett, J. Am. Chem. Soc, 72, 1060 (1950). 16. H. W. Melville, L. Valentine, Trans. Faraday Soc, 46, 210 (1950).
17. G. M. Burnett, Trans. Faraday Soc, 46, 772 (1950). 18. J. D. Burnett, H. W. Melville, Trans. Faraday Soc, 46, 976 (1950). 19. Ross, Thesis, Aberdeen (1950). 20. M. S. Matheson, E. E. Auer, E. B. Bevilacqua, E. J. Hart, J. Am. Chem. Soc, 73, 1700 (1951). 21. M. S. Matheson, E. E. Auer, E. B. Bevilacqua, E. J. Hart, J. Am. Chem. Soc, 73, 5395 (1951). 22. T. G. Majury, H. W. Melville, Proc R. Soc London, Ser. A, 205, 496 (1951). 23. M. Morton, P. P. Salatiello, H. Landfield, J. Polym. Sci., 8, 215 (1952). 24. M. Morton, P. P. Salatiello, H. Landfield, J. Polym. Sci., 8, 279 (1952). 25. W. G. Barb, Proc. R. Soc London, Ser. A., 212, 177 (1952). 26. P. J. Flory, in: P. J. Flory (Ed.), "Principles of Polymer Chemistry", Cornell University Press, New York, 1953, p. 158. 27. G. M. Burnett, P. Evans, H. W. Melville, Trans. Faraday Soc, 49, 1096 (1953). 28. G. M. Burnett, P. Evans, H. W. Melville, Trans. Faraday Soc, 49, 1105 (1953). 29. G. M. Burnett, in: G. M. Burnett (Ed.), "Mechanism of Polymer Reactions", Interscience, New York, 1954, p. 230, p. 233. 30. B. R. Chinmayanandam, H. W. Melville, Trans. Faraday Soc, 50, 73 (1954). 31. J. C. Bevington, H. W. Melville, R. P. Taylor, J. Polym. Sci., 14, 463 (1954).
32. G. M. Burnett, W. W. Wright, Proc. R. Soc. London, Ser. A, 211, 41 (1954). 33. J. L. O'Brien, F. Gormick, J. Am. Chem. Soc, 77, 4757 (1955). 34. R F. Onyon, Trans. Faraday Soc, 51, 400 (1955). 35. J. Dump, M. Magat, J. Polym. ScL, 18, 586 (1955). 36. W. J. Bengough, H. W. Melville, Proc R. Soc London, Ser. A, 230, 429 (1955). 37. H. Miyama, Bull. Chem. Soc. Japan, 29, 720 (1956); ibid. 30, 10 (1957). 38. E. A. Nicholson, R. G. W. Norrish, Disc. Faraday Soc, 22, 104 (1956). 39. N. Grassie, E. Vance, Trans. Faraday Soc, 52, 727 (1956). 40. E. Bartholome, H. Gerrens, R. Herbeck, H. Weitz, Z. Elektrochem., 60, 334 (1956). 41. F. S. Dainton, M. Tordoff, Trans. Faraday Soc, 53, 499 (1957). 42. W. M. Thomas, R. L. Webb, J. Polym. ScL, 25, 124 (1957). 43. C. H. Bamford, A. D. Jenkins, R. Johnston, Proc R. Soc. London, Ser. A, 241, 364 (1957). 44. M. Kryszewski, Roczniki Chemii, 31, 893 (1957). 45. S. E. Bresler, E. N. Kasbezov, V. N. Shandrin, Vysokomol. Soedin., Ser. A, 17, 507 (1957). 46. K. Ueberreiter, G. Sorge, Z. Phys. Chem. (Frankfurt), 13, 158 (1957). 47. W. J. Bengough, Trans. Faraday Soc, 54, 868 (1958). 48. W. J. Bengough, A. C. K. Smith, Trans. Faraday Soc, 54, 1553 (1958). 49. W. J. Bengough, J. Polym. ScL, 28, 475 (1958). 50. Z. A. Sinitsyna, Kh. S. Bagdasaryan, Zh. Fiz. Khim., 32, 1319 (1958). 51. S. W. Benson, A. M. North, J. Am. Chem. Soc, 81, 1339 (1959). 52. D. H. Grant, N. Grassie, Trans. Faraday Soc, 55, 1042 (1959). 53. Z. Litia, Z. Machacek, J. Polym. ScL, 38, 459 (1959). 54. F. S. Dainton, D. G. L. James, J. Polym. ScL, 39, 299 (1959). 55. F. S. Dainton, R. S. Eaton, J. Polym. ScL, 39, 313 (1959). 56. W. J. Bengough, S. A. Mclntosh, R. A. M. Thomson, Nature, 184, 266 (1959). 57. W. J. Bengough, H. W. Melville, Proc R. Soc London, Ser. A, 249, 445 (1959). 58. W. J. Bengough, H. W. Melville, Proc R. Soc London, Ser. A, 249, 455 (1959). 59. Z. Manasek, A. Rezabek, Int. Symp. Macromol. Chem. (Moscow), Section 2 (Russian version) (1960). 60. R Hayden, H. W. Melville, J. Polym. ScL, 43, 201 (1960). 61. G. Henrici-Olive, S. Olive, Makromol. Chem., 37, 71 (1960). 62. G. V. Shulz, G. Henrici-Olive, S. Olive, Z. Phys. Chem. (Frankfurt), 27, 1 (1960). 63. W. J. Bengough, Proc R. Soc. London, Ser. A, 260, 205 (1961). 64. G. V. Schulz, D. J. Stein, Makromol. Chem., 52, 1 (1962). 65. R E. M. Allen, G. M. Burnett, J. M. Downer, J. R. Majer, Makromol. Chem., 58, 169 (1962).
66. W. Rabel, K. Ueberreiter, Ber. Bunsenges. Phys. Chem., 67, 710 (1963). 67. H. Gerrens, Ber. Bunsenges. Phys. Chem., 67, 741 (1963). 68. N. Coleboume, E. Collinson, D. J. Currie, F. S. Dainton, Trans. Faraday Soc, 59, 1357 (1963). 69. F S. Dainton, W. D. Sisley, Trans. Faraday Soc, 59, 1369 (1963). 70. E. F. T. White, M. J. Zissell, J. Polym. ScL, Part A: Gen. Pap., 1, 2189 (1963). 71. M. Morton, W. E. Gibbs, J. Polym. ScL, Part A: Gen. Pap., 1, 2679 (1963). 72. J. Hughes, A. M. North, Trans. Faraday Soc, 60, 960 (1964). 73. K. R Paoletti, Jr. F. W. Billmeyer, J. Polym. ScL, Part A: Gen. Pap., 2, 2049 (1964). 74. A. M. North, A. M. Scallan, Polymer, 5, 447 (1964). 75. A. F. Revzin, Kh. S. Bagdasaryan, Zh. Fiz. Khim., 38, 1020 (1964). 76. W. I. Bengough, W. Henderson, Trans. Faraday Soc, 61,141 (1965). 77. W. I. Bengough, R. A. M. Thomson, Trans. Faraday Soc, 61, 1735 (1965). 78. M. Imoto, M. Kinoshita, M. Nishigaki, Makromol. Chem., 86, 217 (1965). 79. D. J. Currie, F. S. Dainton, W. S. Watt, Polymer, 6, 451 (1965). 80. J. Hughes, A. M. North, Trans. Faraday Soc, 62, 1866 (1966). 81. A. N. Plyusnin, N. M. Chirkor, Teor. Eksp. Khimiya, 2, 777 (1966). 82. V. A. Agasandyan, E. A. Trosman, Kh. S. Bagdasaryan, A. D. Litmonovich, V. Ya. Shtern, Vysokomol. Soedin., 8, 1580 (1966). 83. K. M. Gibov, G. R Gladyshev, Izv. Akad. Nauk Kaz. SSR, Ser. Khim., 17, 53 (1967). 84. F. Hrabak, M. Bezdek, V. Hynkova, Z. Pelzbauer, J. Polym. ScL, Part C: Polym. Symp., 16, 1345 (1967). 85. C. H. Bamford, S. Brumby, Makromol. Chem., 105, 122 (1967). 86. Kh. S., in: Kh. S. Bagdasaryan (Ed.), "Bagdasaryan Theory of Free Radical Polymerization", translated from the Russian Second Edition (1966) by J. Schmorak, Israel Program for Scientific Translations, 1968. 87. K. Yokota, M. Kani, Y. Ishii, J. Polym. ScL, Part A-I: Polym. Chem., 6, 1325 (1968). 88. J. Ulbricht, J. Polym. ScL, Part C: Polym. Symp., 16, 3747 (1968). 89. W. F. Gromov, R M. Chomikovski, A. D. Abkin, N. A. Rosanova, Vysokomol. Soedin., Ser. B, 10, 754 (1968). 90. C. H. Bamford, S. Brumby, Chem. Ind., 1020 (1969). 91. G. N. Kornienko, A. Chervenka, I. M. Belugovskii, N. S. Yenikolopyan, Vysokomol. Soedin., Ser. A, 11, 2703 (1969). 92. J. R Fischer, G. V. Schulz, Ber. Bunsenges. Phys. Chem., 74, 1077 (1970). 93. G. M. Burnett, G. G. Cameron, M. M. Zafar, Eur. Polym. J., 6, 823 (1970).
94. A. V. Angelova, Yu. L. Spirin, R. Ye. Koval'chuk, Vysokomol. Soedin., Ser. A, 12, 2703 (1970). 95. D. R Kiryukin, A. M. Kaplan, I. M. Barkalov, V. I. Gol'danskii, Dokl. Akad. Nauk SSSR, 199, 857 (1971). 96. S. V. Koslov, I. M. Bulugovskii, N. S. Enikolopyan, Vy sokomol. Soedin., Ser. B, 13, 46 (1971). 97. A. A. Baturin, Yu. B. Amerik, B. A. Krentsel, V. N. Tsvetkov, I. N. Shtennikova, E. I. Ryumtsev, Dokl. Akad. Nauk SSSR, 202, 586 (1972). 98. S. B. Bresler, E. N. Kasbekov, V. N. Formichev, V. N. Shadrin, Makromol. Chem., 157, 167 (1972). 99. T. M. Karaputadse, A. I. Kurilova, D. A. Topchiev, V. A. Kabanov, Vysokomol. Soedin., Ser. B, 14, 323 (1972). 100. G. M. Burnett, G. G. Cameron, S. N. Joiner, J. Chem. Soc, Faraday Trans. I, 69, 322 (1973). 101. K. Yokota, A. Konda, Makromol. Chem., 171, 113 (1973). 102. Y. Ogo, M. Yokawa, T. Imoto, Makromol. Chem., 171, 123 (1973). 103. G. Mayer, G. V. Schulz, Makromol. Chem., 173,101 (1973). 104. G. G. Cameron, J. Cameron, Polymer, 14, 107 (1973). 105. M. Yokawa, Y. Ogo, T. Imoto, Makromol. Chem., 175, 179 (1974). 106. M. Yokawa, Y. Ogo, T. Imoto, Makromol. Chem., 175, 2903 (1974). 107. M. Yokawa, Y. Ogo, T. Imoto, Makromol. Chem., 175, 2913 (1974). 108. M. Ratzsch, J. Zschach, Plaste und Kautschuk, 21, 245 (1974). 109. N. A. Plate, A. G. Ponomarenko, Polym. Sci. USSR (Engl. Transl.), 16, 3067 (1974). 110. K. F. O'Driscoll, H. K. Mahabadi, J. Polym. Sci., Polym. Chem. Ed., 14, 869 (1976). 111. P. Penchev, Makromol. Chem., 177, 413 (1976). 112. M. Yokawa, Y Ogo, Makromol. Chem., 177, 429 (1976). 113. M. Yokawa, Y. Ogo, T. Imoto, Makromol. Chem., 178, 443 (1976). 114. H. K. Mahabadi, K. F. O'Driscoll, J. Macromol. Sci. A: Chem., 11, 967 (1977). 115. J. Gons, E. J. Vorenkamp, G. Challa, J. Polym. Sci., Polym. Chem. Ed., 15, 3031 (1977). 116. M. Kamachi, J. Satoh, D. J. Liaw, S. Nozakura, Macromolecules, 10, 501 (1977). 117. K. Matsuo, G. W. NeIb, W. H. Stockmayer, Macromolecules, 10, 654 (1977). 118. B. M. Soghomonyan, N. M. Beilerian, Armen. Chim. Zh., 31, 567 (1978). 119. T. O. Osmanov, V. F. Gromov, P. M. Khomikovskii, A. D. Abkin, Dokl. Akad. Nauk SSSR, 240, 910 (1978). 120. T. Otsu, B. Yamada, S. Sugiyama, Kobunshi Ronbunsyu, 35, 705 (1978). 121. B. Yamada, M. Yoshioka, T. Otsu, Kobunshi Ronbunsyu, 35, 795 (1978). 122. Y. Ogo, T. Kyotani, Makromol. Chem., 179, 2407 (1978). 123. B. Yamada, H. Ohnishi, T. Otsu, Mem. Fac. Eng., Osaka City Univ., 19, 189 (1978). 124. N. N. Tvorogov, A. G. Kondrat'eva, Vysokomol. Soedin., Ser. A, 20, 230 (1978).
125. N. N. Tvorogov, A. G. Kondrat'eva, Vysokomol. Soedin., Ser. A, 20, 1550 (1978). 126. R M. Komikovskii, A. D. Abin, Vysokomol. Soedin., Ser. B, 20, 263 (1978). 127. N. N. Bashenova, B. A. Egorov, Yu. D. Semchikov, Dokl. Akad. Nauk SSSR, 245, 621 (1979). 128. H. A. Bruk, S. A. Pavlov, A. D. Abkin, Dokl. Akad. Nauk SSSR, 245, 626 (1979). 129. A. G. Shostenko, V. E. Myshkin, Kinet. Katal., 20, 781 (1979). 130. M. Kamachi, D. J. Liaw, S. Nozakura, Polym. J., 11, 921 (1979). 131. S. W. Lansdowne, R. G. Gilbert, D. H. Napper, J. Chem. Soc, Faraday Trans. I, 76, 1344 (1980). 132. E. V. Shtamm, Yu. I. Skurlatav, I. M. Karaputadse, Yu. E. Kirsh, A. P. Purmal, Vysokomol. Soedin., Ser. B, 22, 420 (1980). 133. M. Kamachi, D. J. Liaw, S. Nozakura, Polym. J., 13, 41 (1981). 134. K. Jen-Feng, C. Chu-Yung, Polym. J., 13, 453 (1981). 135. T. Takahashi, R Ehrlich, Polym. Prepr., 22, 203 (1981). 136. Z. S. Nurkeeva, E. M. Shaidutinov, A. S. Seitov, Izv. Akad. Nauk Kaz. SSR, Ser. Khim., 1982, 47 (1982). 137. D. J. Liaw, K. C. Chung, J. Chinese Inst. Chem. Eng., 13,145 (1982). 138. M. Kamachi, M. Fujii, S. Nozakura, J. Polym. Sci., Polym. Chem. Ed., 20, 1489 (1982). 139. T. Takahashi, P. Ehrlich, Macromolecules, 15, 714 (1982). 140. B. Yamada, T. Hayashi, T. Otsu, J. Macromol. Sci. A: Chem., 19, 1023 (1983). 141. P. C. Lim, G. Luft, Makromol. Chem., 184, 207 (1983). 142. P. C. Lim, G. Luft, Makromol. Chem., 184, 849 (1983). 143. B. Yamada, M. Yoshioka, T. Otsu, Makromol. Chem., 184, 1025 (1983). 144. A. Nagy, T. Foldes-Beresznich, T. Tudos, Eur. Polym. J., 20, 25 (1984). 145. B. Yamada, M. Yoshioka, T. Otsu, J. Polym. Sci., Polym. Chem. Ed., 22, 463 (1984). 146. B. Yamada, T. Kontani, M. Yoshioka, T. Otsu, J. Polym. Sci., Polym. Chem. Ed., 22, 2381 (1984). 147. H. K. Mahabadi, Macromolecules, 18, 1319 (1985). 148. G. Meyerhoff, R. Sack, M. Kouloumbris, Polym. Prepr., 26 (1), 293 (1985). 149. M. J. Ballard, D. H. Napper, R. G. Gilbert, D. F. Sangster, J. Polym. Sci., Part A: Polym. Chem., 24, 1027 (1986). 150. M. J. Ballard, R. G. Gilbert, D. H. Napper, P. J. Pomery, P. W. O'Sullivan, J. H. O'Donnell, Macromolecules, 19, 1303 (1986). 151. M. Buback, H. Hippler, J. Schweer, H. -P. Vogele, Makromol. Chem., Rapid Commun., 7, 261 (1986). 152. M. Kamachi, H. Umetani, S. Nozakura, Polym. J., 18, 211 (1986). 153. M. Kamachi, Adv. Polym. Sci., 82, 209 (1987). 154. T. Sato, S. Inui, H. Tanaka, T. Ota, M. Kamachi, K. Tanaka, J. Polym. Sci., Part A: Polym. Chem., 25, 637 (1987). 155. W. Lau, D. G. Westmoreland, R. W. Novak, Macromolecules, 20, 457 (1987).
156. O. F. Olaj, I. Schnoll-Bitai, F. Hinkelmann, Makromol. Chem., 188, 1689 (1987). 157. T. Sato, K. Morino, H. Tanaka, T. Ota, Makromol. Chem., 188, 2951 (1987). 158. J. Shen, Y. Tian, Y. Zeng, Z. Qiu, Makromol. Chem., Rapid Commun., 8, 615 (1987). 159. R. Sack, G. V. Schulz, G. Meyerhoff, Macromolecules, 21 3345 (1988). 160. O. F. Olaj, P. Kremminger, I. Schnoll-Bitai, Makromol. Chem., Rapid Commun., 9, 771 (1988). 161. O. F. Olaj, I. Schnoll-Bitai, Eur. Polym. J., 25, 635 (1989). 162. T. Sato, N. Morita, H. Tanaka, T. Ota, J. Polym. Sci., Part A: Polym. Chem., 27, 2497 (1989). 163. T. Sato, K. Arimoto, H. Tanaka, T. Ota, K. Kato, K. Doiuchi, Macromolecules, 22, 2219 (1989). 164. T. P. Davis, K. F. O'Driscoll, M. C. Piton, M. A. Winnik, Macromolecules, 22, 2785 (1989). 165. R. Sack-Kouloumbris, G. Meyerhoff, Makromol. Chem., 190, 1133 (1989). 166. R. W. Garrett, D. J. T. Hill, J. H. O'Donnell, P. J. Pomery, C. L. Winzor, Polym. Bull., 22, 611 (1989). 167. M. Buback, J. Schweer, Z. Phys. Chem. (Munich), 161, 153 (1989). 168. G. Clouet, P. Chaffanjon, J. Macromol. Sci. A: Chem., 27, 193 (1990). 169. T. P. Davis, K. F. O'Driscoll, M. C. Piton, M. A. Winnik, Macromolecules, 23, 2113 (1990). 170. T. Sato, N. Morita, H. Tanaka, T. Ota, Makromol. Chem., 191, 2559 (1990). 171. F. Tudos, A. Nagy, T. Foldes-Berezsnich, Angew. Makromol. Chem., 185/186, 303 (1991). 172. T. Sato, I. Kamiya, H. Tanaka, T. Ota, Eur. Polym. J., 27, 1087 (1991). 173. T. Otsu, B. Yamada, T. Ishikawa, Macromolecules, 24, 415 (1991). 174. B. Yamada, M. Kageoka, T. Otsu, Macromolecules, 24,5234 (1991). 175. J. Shen, Y Tian, G. Wang, M. Yang, Makromol. Chem., 192, 2669 (1991). 176. B. Yamada, M. Satake, T. Otsu, Makromol. Chem., 192, 2713 (1991). 177. T. Sato, Y Takahashi, M. Seno, H. Nakamura, H. Tanaka, T. Ota, Makromol. Chem., 192, 2909 (1991). 178. O. F. Olaj, I. Schnoll-Bitai, Makromol. Chem., Rapid Commun., 12, 373 (1991). 179. B. Yamada, E. Yoshikawa, H. Miura, T. Otsu, Polym. Bull., 26, 543 (1991). 180. B. Yamada, E. Yoshikawa, K. Shiraishi, H. Miura, T. Otsu, Polymer, 32, 1892 (1991). 181. M. Yoshioka, T. Otsu, Macromolecules, 25, 559 (1992). 182. T. Otsu, K. Yamagishi, M. Yoshioka, Macromolecules, 25, 2713 (1992). 183. A. Matsumoto, Y Oki, T. Otsu, Eur. Polym. J., 29, 1225 (1993). 184. W. Lau, D. G. Westmoreland, Macromolecules, 25, 4448 (1992).
185. T. Sato, T. Shimizu, M. Seno, H. Tanaka, T. Ota, Makromol. Chem., 193, 1439 (1992). 186. M. Buback, B. Huckestein, B. Lugwig, Makromol. Chem., Rapid Commun., 13, 1 (1992). 187. S. Deibert, F. Bandermann, J. Schweer, J. Sarnecki, Makromol. Chem., Rapid Commun., 13, 351 (1992). 188. B. Yamada, M. Kageoka, T. Otsu, Polym. Bull., 28, 75 (1992). 189. B. Yamada, M. Kageoka, T. Otsu, Polym. Bull., 29, 385 (1992). 190. G. Moad, E. Rizzardo, D. H. Solomon, A. L. J. Beckwith, Polym. Bull., 29, 647 (1992). 191. T. G. Carswell, D. J. T. Hill, D. I. Londero, J. H. O'Donnell, P. J. Pomery, C. L. Winzor, Polymer, 33, 137 (1992). 192. D. J. Liaw, J. R. Lin, K. C. Chung, J. Macromol. Sci. A: Pure Appl. Chem., 30, 51 (1993). 193. A. Matsumoto, K. Mizuta, T. Otsu, J. Polym. Sci., Part A: Polym. Chem., 31, 2531 (1993). 194. A. Matsumoto, K. Mizuta, T. Otsu, Macromolecules, 26, 1659 (1993). 195. T. Otsu, K. Yamagishi, A. Matsumoto, M. Yoshioka, H. Watanabe, Macromolecules, 26, 3026 (1993). 196. B. R. Morrison, M. C. Piton, M. A. Winnik, R. G. Gilbert, D. H. Napper, Macromolecules, 26, 4368 (1993). 197. P. Pascal, M. A. Winnik, D. H. Napper, R. G. Gilbert, Macromolecules, 26, 4572 (1993). 198. R. A. Hutchinson, M. T. Aronson, J. R. Richards, Macromolecules, 26, 6410 (1993). 199. P. O. Danis, D. E. Karr, D. G. Westmoreland, M. C. Piton, D. I. Christie, P. A. Clay, S. H. Kable, R. G. Gilbert, Macromolecules, 26, 6684 (1993). 200. M. Deady, A. W. H. Mau, G. Moad, T. H. Spurling, Makromol. Chem., 194, 1691 (1993). 201. M. Buback, B. Degener, Makromol. Chem., 194, 2875 (1993). 202. S. Deibert, F. Bandermann, Makromol. Chem., 194, 3287 (1993). 203. P. Pascal, M. A. Winnik, D. H. Napper, R. G. Gilbert, Makromol. Chem., Rapid Commun., 14, 213 (1993). 204. E. L. Madruga, Makromol. Chem., Rapid Commun., 14,581 (1993). 205. A. Matsumoto, Y. Oki, T. Otsu, Polym. J., 25, 237 (1993). 206. B. Yamada, S. Kobatake, S. Aoki, Macromol. Chem. Phys., 195, 933 (1994). 207. S. Beuermann, M. Buback, G. T. Russell, Macromol. Rapid Commun., 15, 351 (1994). 208. S. Beuermann, M. Buback, G. T. Russell, Macromol. Rapid Commun., 15, 647 (1994). 209. R. A. Hutchinson, J. R. Richards, M. T. Aronson, Macromolecules, 27, 4530 (1994). 210. A. Matsumoto, K. Mizuta, Macromolecules, 27, 5863 (1994). 211. A. Matsumoto, T. Otsu, Proc. Jpn. Acad., Ser. B, 70, 43 (1994). 212. V. P. Budtov, B. V. Revnov, Vysokomol. Soedin., Ser. A Ser. B, 36, 1061 (1994). 213. A. Matsumoto, K. Yamagishi, T. Otsu, Eur. Polym. J., 31, 121 (1995).
214. M. Buback, F. D. Kuchta, Macromol. Chem. Phys., 196, 1887 (1995). 215. M. Buback, R. G. Gilbert, R. A. Hutchison, B. Klumperman, F. Kuchta, B. G. Manders, K. F. O'Driscoll, G. T. Russell, J. Schweer, Macromol. Chem. Phys., 196, 3267 (1995). 216. U. Bergert, M. Buback, Macromol. Rapid Commun., 16,275 (1995). 217. U. Bergert, S. Beuermann, M. Buback, C. H. Kurz, G. T. Russell, C. Schmaltz, Macromol. Rapid Commun., 16, 425 (1995). 218. D. A. Shipp, T. A. Smith, D. H. Solomon, H. David, G. Moad, Macromol. Rapid Commun., 16, 837 (1995). 219. R. A. Hutchinson, D. A. Paquet, J. H. McMinn, R. E. Fuller, Macromolecules, 28, 4023 (1995). 220. J. Sarnecki, J. Schweer, Macromolecules, 28, 4080 (1995). 221. F. Bandrmann, C. Guenther, J. Schweer, Macromol. Chem. Phys., 197, 1055 (1996). 222. M. D. Zammit, T. P. Davis, D. M. Haddleton, Macromolecules, 29, 492 (1996). 223. M. Kamachi, A. Kajiwara, Macromolecules, 29, 2378 (1996). 224. H. Tanaka, S. Yoshida, Macromolecules, 28, 8117 (1995). 225. S. Kobatake, B. Yamada, S. Aoki, Polymer, 36, 413 (1995). 226. T. Sato, I. Kamiya, M. Seno, H. Tanaka, J. Macromol. Sci. A: Pure Appl. Chem., 32, 415 (1995).
227. M. Ueda, S. Shimada, T. Ogata, K. Ookawa, H. Ito, B. Yamada, J. Polym. Sci., Part A: Polym. Chem., 33, 1059 (1995). 228. S. Kobatake, B. Yamada, Macromolecules, 28,4047 (1995). 229. S. Kobatake, B. Yamada, J. Polym. Sci., Part A: Polym. Chem., 34, 95 (1996). 230. S. Kobatake, B. Yamada, Polym. J., 28, 535 (1996). 231. M. Seno, T. Takikawa, H. Tanaka, T. Sato, Macromolecules, 28, 4795 (1995). 232. A. Matsumoto, K. Shimizu, K. Mizuta, T. Otsu, J. Polym. Sci., Part A: Polym. Chem., 32, 1957 (1994). 233. T. Sato, Y. Hirose, M. Seno, H. Tanaka, J. Polym. Sci., Part A: Polym. Chem., 33, 797 (1995). 234. T. Sato, A. Takarada, H. Tanaka, T. Ota, Makromol. Chem., 192, 2231 (1991). 235. T. Sato, M. Okazaki, M. Seno, H. Tanaka, Makromol. Chem., 194, 637 (1993). 236. T. Sato, S. Shimooka, M. Seno, H. Tanaka, J. Polym. Sci., Part A: Polym. Chem., 33, 2865 (1995). 237. A. Matsumoto, T. Kimura, J. Macromol. Sci. A: Pure Appl. Chem., 33, 1049 (1996). 238. T. Sato, K. Masaki, M. Seno, H. Tanaka, Polym. Bull., 35, 345 (1995). 239. T. Sato, K. Masaki, M. Seno, H. Tanaka, Makromol Chem., 194, 849 (1993).
T r a n s f e r
C o n s t a n t s
P o l y m e r s ,
C a t a l y s t s
S o l v e n t s S u l f u r
a n d
t o a n d
I n i t i a t o r s ,
A d d i t i v e s ,
C o m p o u n d s
R a d i c a l
M o n o m e r s ,
i n
a n d F r e e
P o l y m e r i z a t i o n
A. Ueda Osaka Municipal Technical Research Institute, Osaka, Japan S. Nagai Plastics Technical Association, Osaka, Japan
A. Introduction B. Tables Table 1. Transfer Constants Table 2. Transfer Constants Table 3. Transfer Constants Initiators Table 4. Transfer Constants Additives Table 5. Transfer Constants Compounds C. Remarks D. References A.
to Monomers to Polymers to Catalysts and
11-97 11-98 II-98 11-103 11-106
to Solvents and 11-110 to Sulfur 11-150 11-157 11-159
INTRODUCTION
The transfer reaction in radical polymerization describes a process in which the polymer radical reacts with another molecule (monomer, polymer, catalyst, solvent, modifier, etc.) forming a dead polymer and new radical. This new radical can continue the kinetic chain:
If it is assumed that (a) all new radicals X# react only by formation of growing polymer radicals; (b) all polymer radicals have equal reactivities independent of their size; (c) all rate constants are independent of solvent; (d) the consumption of monomer by initiation and transfer is negligible compared with propagation; (e) a steady-state concentration of polymer radicals is quickly established (d[P#]/dr = 0). The application of these assumptions to the common reaction scheme results in the following relationship of ideal kinetics (Ref. 145):
P n , p n 0 = number-average degree of polymerization obtained in the presence or absence, respectively, of transfer agent X. [M], [X] = concentration of monomer or transfer agent, respectively.
The dimensionless transfer constant is defined by the ratio
where kv is the rate constant of propagation. Based on the tables in the third edition, by K. C. Berger and G. Brandrup.
The left-hand side of this equation is obtained by measuring the number average molecular weight of polymer at different concentrations of the transfer agent X, all other variables being kept constant. In many cases the degree of polymerization was determined by measurement of viscosity (Remark R). It should be noted that the ratio of
viscosimetric to number average molecular weight shows a considerable dependence on the molecular weight distribution. The first term P n 0 of the right-hand side of this equation is the number average molecular weight measured in the absence of transfer agent X. This is limited to cases where the transfer agent is a modifier. In all other cases, Pno is calculated by combination of several kinetic expressions and used with its numerical value:
This decrease of the transfer agent concentration with increasing monomer conversion is important in practice because very reactive transfer agents are used up preferentially, giving a broad molecular weight distribution if they cannot be replenished. In analogy to quickly decomposing initiators with their criterion of "half-life", one can define, in addition to the transfer constant Cx, a "half-conversion" U\/2 as that monomer conversion where the transfer agent is half consumed:
Initiation Termination Propagation Number-average molecular weight where ku fct,d, and k^c are the rate constants of termination, termination by disproportionation, and termination by combination, respectively.
The second term of the right-hand side of the above equation is given by the following expression:
where Cp is the constant of chain transfer with added polymer before starting polymerization. The transfer constant of very reactive molecules can be determined from the rate of disappearance of both transfer agent and monomer:
The following table demonstrates (with some examples for a calibration curve) that the "half-conversion" IZ1^2 decreases with increasing transfer constant Cx: The "Half-Conversion" of Transfer Agents Cx
U1/2(%)
Cx
Ul/2(%)
0.1 0.2 0.5 1 2
99.9 96.8 75.0 50.0 29.3
5 10 20 50 100
13.0 6.7 3.4 1.4 0.7
The transfer agent must be replenished at this monomer conversion at the latest, if polymerization is to proceed, still yielding a narrow molecular weight distribution. Numerous examples are known of polymerization systems that possibly do not satisfy basic assumptions: retardation (Remark J), induced decomposition and primary radical termination by peroxide or hydroperoxide initiation (Remarks C and B), diffusion control of termination (Remark X), electron donor/acceptor complexes (Remarks JJ), etc. Corresponding data in this table have to be used with caution.
B. TABLES OF TRANSFER CONSTANTS TABLE 1. TRANSFER CONSTANTS TO MONOMERS Monomer
T( 0 C)
Acetic acid, allyl ester
80
Acrylamide
25
Acrylamide, AT,iV-dimethylAcrylic acid, benzyl ester
50 60 60 50 55 60 60 60
- , butyl ester
C M (xlO 4 ) 170 700 0.12 0.16 0.2 0.2 0.558 0.651 0.6 1.5 0.883 0.905 0.333 1.05
Remarks
D E C2, F13, LL C2, F13, LL E
Cl, H, KK Cl, H, KK
Refs. 29 27 92 74 75 103 560 560 103 272 291 291 561 561
TABLE 1. cont'd Monomer Acetic acid, butyl ester (cont'd) -,ethyl ester
T( 0 C) 60 65 50 60 65 70
- , - 2 ethylhexyl ester - , methyl ester
70 80 50 55 60 65
70
75 -, tetrahydrofurfuryl ester -, 2-chloro-, ethyl ester - , thio-, methyl ester Acrylonitrile
40 60 60 20 25 30 40 50 60
Allyl bromide Ammonium chloride, A^-diallyl-MJV-diethyl- , Ar,Ar-diallyl-AW-dimethylAnisole, p-\iny\ Anthranilic acid, vinyl ester Benzoic acid, vinyl ester
1,3-Butadiene, 2-chloro- , 1,1,2-trichloro1-Butene 2-Butene, cis- , trans3-Butene-2-one, 3-methyl-
60 60 60 60 60 60 0 60 70 60 80 95 50 25 40 50 60 40 50 60 40 50 60 80
C M (xlO 4 )
Remarks
1.25 0.955 0.193 0.90 0.41 0.579 0.332 0.351 0.789 6.28 3.79 0.80 0.275 0.036 0.325 0.10 0.11 0.11 0.37 0.01 0.072 0.16 0.18 0.405 0.224 0.25 0.25 4.0 3.0 560 0.18 0.105 1.5 0.17 0.050 0.27 8.2 0.26 0.3 0.333 0.57 1.02 30 18 7 0.198 0.74 80 6.0 7.0 2.0 4.0 2.32 16 3.1 5.1 7.3 3.2 4.9 11.2 3.0 5.2 10.8 4.00
Cl, H, KK
F7 C, F17, R C, F17, R C, F17, R C, F17, R C, F17, R F7 C,AA B, AA C, AA C,AA CFlO CAA C, AA CFlO B, AA CAA C AA C, AA CAA C, FlO C AA C, F2 E F8 F18 F17 F16 Cl, H, KK Cl, H, KK Cl, H, KK C, R, HH Cl, F30 Cl, F30
F2 E
C
Refs. 561 291 306 510 512 512 306 306 512 512 512 510 221 221 221 221 123 221 221 322 221 221 221 221 221 123 221 319 342 140 299 284 196 284 410 376 362 95 23 561 561 561 505 538 538 13 53 139 321,393 26 321 213 153 230 334 334 334 334 334 334 334 334 334 84
Remarks page 11-157; References page 11-159
TABLE 1. cont '6 Monomer Butyric acid, vinyl ester Carbamic acid, vinyl-, ethyl ester Carbazole, A^-vinyl-7H-benzo(2)Decanoic acid, vinyl ester Ethylene
T( 0 C) 50 80 60 70 50 60
70
26.7 22.3 0.25 11 45.5 0.4 1.4 4.2 5.0 5.32 1.1 3.5 9.0 0.0 1.6 4.7 11.2 5 3.2 3.2 7.0 6.25 19.4 50 6.4 7.8 8.5 11 13.5 10.8 12.3 12.8 23.8
60
42
83 110
130
- , chloro-
50-70 20 25 30 40 50
60
Glutaramic acid, MA^-diisobutyl-, vinyl ester - , AW-diisopentyl-, vinyl ester
Hexanoic acid, vinyl ester 5-Hexen-3-yn-2-ol, 2-methylIsobutyric acid, vinyl ester Laurie acid, vinyl ester Maleic anyhydride Maleic anhydride/methyl methacrylate Maleimide, A^-(3-dimethylamino-6-methyl-phenyl) Methacrylamide Methacrylic acid, bornyl ester - , butyl ester
-, -, -, -, -, -,
tert-butyl ester o-r-butylphenyl ester /?-?-butylphenyl ester n-dodecyl ester 2,3-epoxypropyl ester ethyl ester
-, -, -, -, -,
0-ethylphenyl ester p-ethylphenyl ester glycidyl ester hexadecyl ester isobornyl ester
C M (xlO 4 )
60 70 80 80 60 80 50 75 60 50 60 60 50 60 70 60 60 60 60 45 60 80 90 60 60 60 70 60
51 51 51 36 5.0 46 45.5 750 100 720 10 x 105 2.85 0.54 120 x 105 0.14 0.35 30.41 2.01 80xl05 0.59 0.248 0.259 0.456 0.442 3.63 1.36 45 x 105 0.14 1.85
Remarks
Refs.
F4 Y
71 200 117 522 71 102 102 102 204 205 102 102 102 259 102 102 102 218 94 315 425 58 463 246 379 379 379 392 58 379 379 379 58
C, FlO
106
C, FlO C, FlO CFlO
107 107 107 200 226 200 71 175 367 542 515 162 233 515 264 9 550 550 515 198 193 193 193 193 550 550 515 138 162
R, F2 W5 W4, W5 W4 D, W D, W W4, W5 W4, W5 W4 C, F21,W5 W4, W5 W4, W5 W4 W3
Y F5 F3 F4 C, F26 Y F3
C F2 JJl
JJl
C C JJl CC CC CC CC C C JJl
TABLE 1. cont'd Monomer Methacrylic acid, isobutyl ester
- , n-nonyl ester - , phenyl ester - , o-tolyl ester - , p-tolyl ester Methacrylonitrile
Methyl methacrylate
J( 0 C) 35 50 60 80 100 60 27 60 60 60 25 60 70 80 0 30
40 50
60
65 70
75
80
Naphthalene, 1-vinyl1,4-Pentadiene, 1,1,2,3,3,4,5,5-octafluoroPhernol, o-vinyl2-Picoline, 5-vinyl1-Propene, 2-chloro-, 2-methylPropionic acid, vinyl ester
90 100 120 50 60 70 110 70 70 80 40 50 60 50
C M (xlO 4 ) 0.189 0.179 0.14 0.165 0.224 0.301 0.382 105 x 105 400 0.61 1.13 1.06 2.08 5.81 8.00 10.05 0.128 0.148 0.117 0.260 0.15 30 x 105 242 x 105 0.10 0.15 0.477 241 x 105 0.85 0.07 0.10 0.103 0.18 240 x 105 0.20 0.17 0.20 0.23 0.265 0.29 0.30 0.45 0.807 1.37 240 x 105 0.27 0.33 0.60 0.70 0.25 0.40 0.10 0.38 0.58 290 310 300 500 130 6.7 1600 2.5 4.4 6.9 3.6 48.9
Remarks DD DD F2 DD DD DD JJl R C C C Z Z Z Z
D JJ2 JJl F2 D JJl
C JJO CFlO
C, F17 D JJl CFlO C CFIl C, F2
WlO
Refs. 193 193 264 264 193 193 193 515 534 550 550 550 125 125 125 125 69 18 69 224 508 525 528 147,327 145 224 528 69 274 34,290,317 316 145 556 123 123 267 145 440 123 123 104 224 459 528 123 123 123 123 145 123 147 145 145 216 216 216 68 186 11 27 334 334 334 158 71
Remarks page II-157; References page II-159
TABLE 1. cont'd Monomer Pyridine, 2-vinyl- , 4-vinyl2-Pyrrolidinone, 1-vinylStearic acid, vinyl ester Styrene
T( 0 C) 15-35 25 20 50 O 25 27 30 45 50
60
67.8 70
75
80 80.3 90
99 100
110 117 132
Styrene, p-boromo-, o-chloro-
50 30 50
C M (xlO 4 ) O 6.7 4.0 69.8 O
Remarks D
BB 0.108 0.279 0.358 0.31 0.2 0.32 0.3 0.35 0.40 0.50 0.6 0.62 0.65 0.78 0.07 0.6 0.6 0.6 0.75 0.79 0.85 0.92 1.1 1.37 20 x 10 5 1.0 O 0.6 0.6 0.8 0.96 1.16 1.35 2.0 O 1.6 5.0 5.00 0.7 0.75 1.00 4.0 0.85 1.25 1.47 1.79 1.5 1.72 1.8 1.83 2.80 1.40 2.45 3.0 3.4 5.33 23 0.25 0.25 0.28
A BB BB H F2 C, H C A, K B, C, H A C C BB A A, F
C JJl CFlO BB B, H A A C, F2 C,F10 C C, F2 CFIl BB BB CF A A A A, F A A A A, F A A
C C, H
Refs. 38 283 59 71 360 17,69 69,245 17 145 318,360 245 360 354,355 318,327 388 145 145 388 146 467 34,171,223 145,240 318,360 467 145 145 447 53 234 515 34 123 104 360 388 67 145 145 123 123 123 123 123 98 360 318 34 360 145 145 145 98 145 145 145 145 318 145 145 145 145 192 62 60 60
TABLE 1. cont'd Monomer Styrene, p-iodoSuccinimide, JV-vinylValeric acid, 4-methyl-, vinyl ester Vinyl acetate
T( 0 C) 50 55 80 -60 -40 -20 -20 O 20 25
40 45 50
60
65 70 Vinylidene chloride
50 60
C M (xlO 4 )
Remarks
Refs.
1.9 0.55 24.8 1.9 0.40 0.60 0.70 0.30 0.50 0.90 0.96 0.94 0.90 1.3 1.45 2.4 10.7 1.29 1.32 2.0 0.25 0.41 0.54 0.61 1.29 2 4.55 20 1.75 1.8 1.9 1.91 1.93 2.0 2.1 2.4 2.5 2.5 2.6 2.8 2.1 2.4 2.9 22 38
Fl C
113 R R
56 93 200 158 464 464 464 241 241 86 464 328 241 86 86 202 69 12 328 51 466 265 265 265 12 552 71 225 12 466 124 328 348 231 145 294 86 167 167 80 466 403 86 541 541
C P (xlO 4 )
Remarks
Refs.
D D D D D 14 D D 17 17 D
W14 W15 C
112 C
C C
TABLE 2. TRANSFER CONSTANTS TO POLYMERS Polymer Acrylamide, N,N-dimethylPoIy(N, Af-dimethylacrylamide) Acrylic acid, ethyl ester Poly(methyl methacrylate) - , methyl ester Poly(isoprene) - , chlorinated Poly (methyl acrylate) Poly (methyl methacrylate) Acrylonitrile Cellulose
T( 0 C) 50
0.61
272
60
12800
M6
120
75 60
12.6 0.5 1.0 18000
C, F2 L L M6
308 212 105 120
1.0 11 20
L, N L, M4 L, M5
361 361 361
60 60
Remarks page 11-157; References page 11-159
TABLE 2. cont'd Polymer Acrylonitrile, (cont'd) Poly(acrylonitrile) Poly(methyl methacrylate)
Poly(sarcosine) 1,3-Butadiene PoIy(1,3-butadiene) Ethylene
-, chloro Poly(vinyl chloride) Hexanoic acid, vinyl ester Poly(oxyethylene), dodecyl ether Methacrylic acid, butyl ester Poly(methyl methacrylate) -, dodecyl ester Poly (methyl methacrylate) -, ethyl ester Poly(isoprene), chlorinated Poly (vinyl chloride) Methyl methacrylate Poly(ethylene) Poly(isoprene), chlorinated Poly(methyl methacrylate)
T(0C)
50 60 60
60
Poly(vinyl chloride) Poly(vinyl urethane) Rubber, natural 2-Pyrrolidinone, 1-vinyl-dextran Dextran
376 135 25 25 25 25 23
C, C, C, C, C, C, C, C, C, C,
50
5
L
60
780
60
7700
M6
120
60
12800
M6
120
C, F2 C, F28
308 308
70 70
18.3 21.0
50 80 40
0.6 23.4 1.5 360 0.22 1.5 1.5 360 360 1000 0.1 1.5 2.1 360 2.48 0.22 1000 0.04 1.0 0.42 0.75 2.20 2.95 2.0 2.8 11 10.0 17 10.9 11.0
80 90
Poly(vinyl acetate)
F14 L N M2 M3 M
Refs.
11 108.40 150.70 194.81 214.46 337.31 256.85 195.81 199.89 155.78 348.46
60
Poly(styrene)
4.7 3.5 0.2 240 900 1270 400
Remarks
50 174.8 201.6 215.0 231.2 230.3 229.2 230.3 230.4 230.5 256.0
50
Poly(propylene)
C P (xlO 4 )
50 130 50 60 80 60 80 70 50 50 50
5 5.87
W20, F32 W20, F32 W20, F32 W20, F32 W22, F32 W21, F32 W20, F32 W19, F32 W18, F32 W20, F32
142 540 540 540 540 540 540 540 540 540 540 211 278
C, F17 N M N N M M N M N M N M C
C, F28 C, F8 C
209 307 326 326 147 326 327 326 327 147 105 326 262 326 262 147 147 292 209 292 148 262 262 263 263 250 308 157 258 258 333 203
TABLE 2. cont'd Polymer Styrene Poly(oxyadipoyloxy-2,2-dibromomethyl trimethylene) Poly(oxyethylene) - , dodecyl ether Poly(oxythexamethyleneoxy sebacoyl) Poly(methyl methacrylate)
T( 0 C)
60 70 70 60 80 50
60
Poly(propylene)
Poly(styrene)
80 100 60 66 130 50
55 60
73.5 85 90 100 110
Poly(vinyl acetate) Poly(vinyl chloride) Poly(2-vinylpyridine) Vinyl acetate Poly(oxyethylene) - , dodecyl ether Poly (methyl methacrylate) Poly(styrene) Poly(vinyl acetate)
130 154 100 130 50 60 60 60 75 40 60 75 -15 0 11 21 31 40 50
C P (xlO 4 ) 4.05 19 14 20 13 0.4 <0.3 1110 1140 16.4 17.5 5.7 x 104 32 x 104 3.74 6.04 0.025 26 0.3 0.30 1.9 4.5 14.0 16.6 15 0.8 1.9 3.1 15.4 15.8 16.6 1.0 1.4 5.8 2.0 9.2 10.8 1.8 1.5 6.6 9.2 160 8-10 17 40 10 40 750 21 26 12 15 19 0.36 0.5 1.7 2 4 16 11.2 30.9 32.0 0.06
Remarks
L MlO MlO C, N N M N M Ml Ml M7 M6 C
L
Ml Ml C C N
N M M8 M9
O O O
W15
Refs.
325 562 562 278 394 327 326 326 327 64 64 120 120 262 262 292 486 292 207 144,148 327 327 176 177 105 73 105 64 64 176 8 8 327 276 177 176 43 43 263 263 250 279 277 277 277 277 271 263 263 263 263 263 97 97 350 145 145 145 12 43 263 265
Remarks page 11-157; References page 11-159
TABLE 2. cont'd T( 0 C)
Polymer Vinyl acetate {cont'd) Poly (vinyl acetate) (cont 'd)
60
60-70 70 Poly(vinyl acetate-co-vinyl chloride)
TABLE 3.
60
C P (xlO 4 )
Remarks
0.11 0.15 3 10.2 1.2 1.4 1.8 1.9 2.5 3.0 4.0 6.8 8.0 47.0 3.5 2 4 0.21 3.0
W14
P O VCL-Part VOAC-Part
Refs.
265 265 43 12 124 168,169 348 328 329 165 105 12 105 263 350 403 403 166 166
TRANSFER CONSTANTS TO CATALYSTS AND INITIATORS
Catalyst/Initiator Acrylamide Bisulfite ion Hydrogen peroxide Potassium persulfate Acrylic acid, benzyl ester Isobutyronitrile, 2,2'-azobis-
- , ethyl ester Isobutyronitrile, 2,2'-azobis- , methyl ester Benzoyl peroxide
2-Butanone, peroxide
T(0C)
tert-Butyl peroxide
Chloroform/CuCl2 Acrylonitrile Isobutyronitrile, 2,2'-azobis-
Azodiphenylmethane, benzyl-
-, cyclohexyl-
Remarks
0.17 0.0005 0.0258 0.028
55 60 65
0 0 0
291 291 291
65
0
306
55 60 65 70 65
60 70 65 70 75 120
0.0143 0.0246 0.0375 0.01 0.05 0.05 0.05 0.077 0.113 0.113 0.01 0.0266 0.00047 0.00082 0.00111 600
F13 D F13, LL F13, LL
Refs.
75 25 50 60
70 75 tert-Butyl hydroperoxide
Ci
C, FlO FlO
FlO
Q(5-19), Fl
352 92 560 560
221 221 221 322 221 123 221 221 123 221 221 221 221 221 221 551
50 60
0 0
F16
362 95
50 60 80 50 60 80
0.07 0.07 0.07 0.02 0.04 0.05
R R R R R R
536 536 536 536 536 536
TABLE 3. cont'd Catalyst/Initiator Azodiphenylmethane (cont'd) - , 1-phenylethyl-
- , 2-propyl-
Benzoic acid, vinyl ester Benzoyl peroxide Isobutyronitrile, 2,2'-azobis3-Buten-2-one, 3-methylBenzoyl peroxide Ethylene Azoethane, 1,1 '-dimethylEthylene, chloroValeronitrile, 2,2'-azobis[2,4,4-trimethylMaleic anhydride Benzoyl peroxide Methacrylonitrile Isobutyronitrile, 2,2'-azobisMethyl methacrylate Acetophenone, 2-diazo-2-phenyl/7-Anisoyl peroxide Benzoyl peroxide
2-Butanone peroxide
T (0C)
Remarks
0.1 0.1 0.1 0.02 0.04 0.05
80 80
0.0527 0
26 26
80
0.0509
84
83
0.5 0.51
25
0.85
425
75
2.63
175
60
0
125
70 60 50 60
0.0 0.037 0.01 0 0.02 0.0025 0.00698
459 316 145 34 145 123 123
65
75
80 tert-Buty\ hydroperoxide terf-Butyl peroxide Butyronitrile, 2-ethyl-,2,2'-azobis- , 2-methyl-, 2,2'-azobis- , 2,3,3-trimethyl-, 2,2'-azobisCinnamoyl peroxide Cobalt, [bis-[ja-[(2,3-butane-dionedioximato)(2-)-O,O;]] tetrafluorodiborato(2-)-A^',vV",;V'']-
60 20 60 60 60 60
Cyclohexanecarbonitrile, l,l'-azodiCyclopropanecarboxylic acid, 1-methyl2-(9/-anthryl)-, methyl ester Hydrogen peroxide Hydroperoxide, a,oc-dimethylbenzyl Isobutyronitrile, 2,2'-azobis-
60
Methane, diazodiphenylPalmitoyl peroxide
70 60 60 50 60 70 60
Peroxide, bis(ra-chlorobenzoyl) - , bis(o-chlorobenzoyl)
60 60
60 60
0.0033 0.0033 0.0040 0.0092 0.00553 0.00667 0.0071 0.0089 0.0111 0.0128 1.27 x [cat] < 0.0001 0 0 0 0.009 36000 2500 0 0.002 0.046 0.33 0 0 0.0 0 0.16 0.003 0.019 0.35 0.8 0.009 0.012
R R R R R R
Refs.
50 60 80 50 60 80
70
- , bis(p-chlorobenzoyl) - , bis(m-nitrobenzoyl)
C1
D, W D, W
12 F2
F17 FlO FIl FIl F2 FlO F17
C, D
536 536 536 536 536 536
204 205
123 123 123 123 123 123 123 123 123 123 34 35 317 317
317 316 563 F17 317 440 FIl F2 FlO
111
FlO 110
563
290 34 327 34,290,317 267 316 145 316 316 290 145 316 316
Remarks page 11-157; References page 11-159
TABLE 3.
cont'd
Catalyst/Initiator Methyl methacrylate (cont'd) - , bis(p-nitrobenzoyl) - , bis(m-phenylazobenzoyl) 2-Tetrazene, 1,1,4,4-tetramethyl0-Toluoyl peroxide Valeronitrile, 2-methyl, 2,2'-azobisStyrene Acetyl peroxide p-Anisoyl peroxide Benzoyl peroxide
J(0C)
Ci
60 50 30 60
0.144 0.00001 0.038 0.046 0.06 0
60 70 70 22 50 60 70
80 Cobalt, [Bis-[^-[(2,3-butane-dionedioximato)(2-)-O,O/]] tetrafluorodiborato(2-)-N,iV/,A^//,N//]Di-3-phenylazo benzoyl peroxide 2-Butanone, peroxide
50 70 90 50 70 75
tert-Butyl hydroperoxide
Butyl peroxide sec-Butyl peroxide tert-Buty\ peroxide
60 70
80 60 80 60 80 60
70 80 Butyryl peroxide Cinnamoyl peroxide Crotonyl peroxide Cyclohexanone peroxide Ethyl peroxide Formamide, 2-cyano-2-propylazoFuroyl peroxide Hexanoyl peroxide Hydroperoxide, a,a-dimethylbenzyl
70 70 70 60 60 80 100 70 70 40
0 0.074 0.1 0.13 0.048 0.055 0.101 0 0.075 0.12 0.18 0.13 0.813 1500 6.7 5.5 4.8 0.46 0.0667 0.1250 0.1670 0.1250 0.1670 0.2000 0.243 0.035 0.051 0.060 0.063 0.064 0.066 0.003 0.00076 0.00092 0.0029 0.0004 0.0021 0.00023 0.0003 0.0006 0.00086 0.0013 0.039 0.0022 0.0033 0.018 1.10 0.146 0.062 0.00066 0.0024 0.17 0.23 0.166 0.052
Remarks
C D 111
D
C
F17 R R R H F2 FlO FIl F2 FlO FIl H F6 F2, F5 F9 F2 F9 F2 F2 F9 F2, F12 F2 F2
F2 F2
H
Refs.
316 282 483 316 145 317 87,217 87 65 58 171 240 234 217 87 67 58,65 58,65 530 563 527 527 527 388 123 123 123 123 123 123 123 171 388 399 400 400 400 385 302 302 302 301 301 303 303 303 300 304 400 303 385 87 87 87 33 301 301 47 87 87 388
TABLE 3. cont'd T( 0 C)
Catalyst/Initiator Styrene (cont'd) Hydroperoxide, a,a-dimethylbenzyl (cont'd)
-, a,a-dimethylbenzyl, /?-isopropylIsobutyronitrile,2,2'-azobis-
50 60 70 70 50 60
Isopropyl peroxide Lauroyl peroxide
60 80 70
p-Menth-8-yl hydroperoxide Myristoyl peroxide
84 50 70
2-Naphthoyl peroxide Nickel peroxide Octanoyl peroxide
70 60 70
Oleoyl peroxide Palmitoyl peroxide Peroxide, bis(p-acetoxybenzoyl) -, bis(ra-bromobenzoyl) -, bis(o-[bromobenzoyl)
70 70 70 70 50 70 70 70 70 22 70 70 70 60 70 50 70 70 70 50 70 70 70 70 70 90 70 50 70 70 70 80 90 80 90 80 90 80 90 70
-, bis(/?-bromobenzoyl) - , bis(p-ter£-butylbenzoyl) -, bis(m-chlorobenzoyl) Peroxide, bis(o-chlorobenzoyl) - , bis(p-chlorobenzoyl) - , bis(/7-cyanobenzoyl) - , bis(2,4-dichlorobenzoyl) -, -, -, -, -, -, -, -, -, -,
bis(oc,a-dimethylbenzyl) bis(m-fluorobenzoyl) bisO-fluorobenzoyl) bis(p-fluorobenzoyl) bis(hydroxyheptyl) bis(m-iodobenzoyl) bis(/?-methoxycarbonyloxy-benzoyl) bis(m-nitrobenzoyl) bis(/?-nitrobenzoyl) bis(m-phenylazobenzoyl)
- , bis(5-phenyl-2,4-pentadienoyl) - , bis(2-thiophenecarbonyl) -, -, -, butylidenebis[rm-butyl
tert-butoxymaleoyl tert-butoxyphthaloyl
-, sec-butylidenebis[terf-butyl -, isobutylidenebis[terr-butyl - , isopropylidenebis[tert-butyl Pinanyl hydroperoxide
Ci 0.069 0.063 0.082 0.10 0.033 0 0 0 0 0.012 0.16 0.0003 0.0015 0 0.024 0 0.048 0 0.116 0.178 0.00265 0 0.098 0.154 0.142 0.187 0.465 1.0 2.17 0.193 0 0.346 2.0 1.91 0.216 0.804 2.9 2.6 0.01 0.246 0.40 0.219 < 0.005 0.262 0.208 6.2 7.4 5.5 4.8 5.24 0.23 0.38 1.52 0.018 0.00077 0.00140 0.00072 0.00115 0.00083 0.00155 0.00040 0.00105 0.026
Remarks H H H F2 H
F2 F2
H
C, F2
D
H
H
C C
C C C C C C C C H
Refs. 388 171 388 399 388 327 388 171 318 468 447 301 301 217 87 217 388 217 87 87 266 217 87 87 87 87 87 58,65 87 87 87 87 65 87 217 87 217 217 388 87 87 87 388 87 87 87 87 281 281 87 65 65 87 87 411 411 411 411 411 411 411 411 388
Remarks page II-157; References page II-159
TABLE 3. cont'd Catalyst/Initiator Styrene (cont'd) Pivalonitrile Propylene, oxidized Propyl peroxide Sorboyl peroxide Stearoyl peroxide Succinonitrile, tetramethyl2-Tetrazene, 1,1,4,4-tetramethylo-Toluoyl peroxide /7-Toluoyl peroxide 9-Undecenoyl peroxide Valeronitrile, 2,2/-azobis[2,44-trimethylVinyl acetate Benzoyl peroxide
T( 0 C)
60 60 70 60 70 70 60 30 70 50 70 70 25 60
Lauroyl peroxide Palmitoyl peroxide
65 50 60 60 60
Peroxide, bis(m-bromobenzoyl)
60
- , bis(o-bromobenzoyl)
60
- , bis(/?-bromobenzoyl) - , bis(o-chlorobenzoyl)
60 60
Isobutyronitrile, 2,2/-azobis-
Ci
0.000038 1.01 1.14 0.00084 1.19 0.154 0.000037 0.038 0.175 0.17 0.003 0.19 0.065 0.59 0.032 0.09 0.15 0.040 0.025 0.055 0.10 0.10 0.17 0.24 0.6 0.25 3.5 0.17 0.17
Remarks
D
13 13 13 13
Refs.
468 396 396 305 87 87 468 483 87 65 87 65 87 426 465 231 80 466 466 466 80 80 145 80 145 80 145 80 145
TABLE 4. TRANSFER CONSTANTS TO SOLVENTS AND ADDITIVES Solvent/Additive Acetic acid, allyl ester Benzene /7-Benzoquinone -, 2,3,5,6-tetrachloro- , 2,3,5,6-tetramethyl- , 2,3,5-trichloroCarbon tetrachloride Phosphorus trichloride Acrylamide Acetonitrile tris(2-Carbamoylethyl)amine Iron(III) chloride Isopropyl alcohol Methanol Propionamide
Water Acrylic acid, butyl ester Aniline, MN-dimethylEthanol Methanol Propanol Iso-propanol
J( 0 C)
C s (xlO 4 )
Remarks
80 80 80 80 80 100 40
21.0 5.2 x 105 16 x 105 4.14 x l O 4 5.5 x 105 2.0 x 104 1.0 x 104
J J J J C C, D
25 50 80 30 25 60
5.5 85 4.26 x 104 19 7.2 0.13 220 64
25 40 50 80 80 80 80
0.204 5.8 380 4.28 0.47 3.78 14.12
F13 Fl 3
Refs.
273 27 27 27 27 210 214
F13 F13, S C, F13 E E
564 564 75 353 353 130 103 103
C, F13 F13
437 444
A, R F31, A, R A, R A, R
161 548 548 548 548
TABLE 4. cont'd Solvent/Additive Acrylic acid, ethyl ester Acetic acid Acetone
Acetonitrile
Aniline, A^-dimethylBenzene
-, bromo- , chloro- , ethyl-
2-Butanone
Butyl alcohol
sec-Butyl alcohol
terf-Butyl alcohol
Butyric acid Carbon tetrachloride
Chloroform
Cumene
Cyclohexane
T( 0 C)
50 80 100 40 60 80 100 50 60 80 100 50 50 60 80 100 60 80 100 40 80 100 40 60 80 100 50 60 80 90 40 60 80 100 45 63 80 100 40 60 80 100 80 40 60 70 80 100 40 60 70 80 100 50 60 80 90 50 60
C 8 (xlO 4 )
0.176 0.537 1.05 0.207 0.27 1.10 2.30 0.158 0.245 0.55 1.43 2300 0.016 0.22 0.27 0.45 0.525 2.2 0.163 0.685 3.34 0.054 0.37 1.68 0.668 11.6 16.80 28.7 1.44 0.151 1.92 3.29 4.45 1.28 2.91 5.85 12.6 10.6 18.5 22.20 31.5 0.068 0.17 0.712 1.64 0.855 0.332 0.90 3.2 1.13 1.55 2.80 0.195 0.89 1.57 1.49 4.74 11.7 13.8 22.2 26.0 28.9 0.48 0.61
Remarks
A A C A A A A F16 C C A A A A A A A A C A A A A A A A A A
C A A C C A A A A C
Refs.
472 471 472 472 134 471 472 472 472 471 472 228 472 472 133 134 471 472 472 471 472 472 471 472 472 472 471 472 472 134 472 471 472 472 472 471 472 472 472 471 472 472 472 471 472 471 472 472 416 134 471 472 472 134 134 471 472 472 472 471 472 472 472 134
Remarks page II-157; References page II-159
TABLE 4. cont'd Solvent/Additive Acrylic acid, ethyl ester (cont'd) cyclohexane (cont'd) Dimethylformamide Ethanol Ethyl acetate
T( 0 C)
C s (xlO 4 )
Remarks
80 100 50 80 50 60
1.22 3.08 0.1 4.38 0.298 0.448 0.69 0.89 1.82 0.046 0.524 0.593 0.97 1.46 2.1 3.31 4.65 8.06 21 28.70 0.32 1.70 0.36
A A F7 A, R
80 100 80 50 60 80 100 45 63 80 100
Formic acid Heaxane
Isobutyl alcohol
Isopropyl alcohol 80 60
Methanol
80
Propanol Toluene
80 40 50 60 70 80 100
- , 2-ethylhexylester Toluene - , methyl ester Acetone
70 80
28.70 2.13
60 80
0.23 0.622 1.1 <2.5 480 <1.0 60 42.1 26.7 72.7 1000 0.326 0.45 0.52 0.986 0.71 309 6.056 46.4 2040 107 <1.0 600 1890 1000 3.92 400 1200 33.1 1600
Acetophenone Aluminum, triethyl Aniline -,MTV-dimethyl- , m-nitro-,p-nitroAnisole, m-nitroAnthracene Benzene
50 60 50 50 50 50 50 50 80
- , chloro-
80
- , 0-dichloro-, -,ethyl- , nitro- , 1,3,5-trinitroBenzoic acid, /?-nitroBenzonitrile Copper(II) chloride Phosphine, tributylPhosphorus trichloride Propanol Silane, dimethyphenyl- , methyldichloro- , tetraethyl- , trichloro-
ra-dinitro-
4.73 0.88 0.611 0.929 1.37 1.84 2.60 6.80
80 50 80 50 50 50 50 120 60 40 80 60 60 60 60
C A A A
A A
A A C A, R C 4 A, R
A,R
Refs.
471 472 510 548 472 472 134 471 472 471 472 472 471 472 472 472 471 472 445 548 134 472 548
C, F17, R C, F17, R C, F17, R C A A
548 472 512 512 512 134 471 471
C, F17, R C, F17, R
512 512
C
470 332 111 15 156 15 228 15 15 15 15 332 111 111 332 111 15 332 15 15 15 15 565 156 214 548 539 539 156 539
C F2, S F16
C C C
F34 F2 C, D A, R A, R A, R F2 A, R
TABLE 4.
cont'd
Solvent/Additive Acrylic acid, methyl ester(cont'd) - , triethyl- , triphenylStearic acid, methyl ester Toluene - , m-nitro-,/7-nitroTriethylamine Tripropylamine - , tetrahydrofurfuryl ester Carbon tetrachloride Acrylonitrile Acetaldehyde Acetamide, AW-dimethylAcetic acid Acetone Acetonitrile Acrolein, bis(2-ethoxyethyl)acetal - , bis(2-butoxyethyl)acetal Aluminum, hydrodiisobutyl -,triethyl - , triisobutyl Aniline
- , N,N-diethy\-
T( 0 C)
Remarks
Refs.
A, R A, R
50 50 60 60
300 800 0.751 2.7 1.775 2.7 41.2 48.6 400 470
539 539 441 21,24 332 111 15 15 24 156
40
1.0
C, F2
60 60 60 60 80
50 50 50 50 60 50 60 60 60 60 60 100 100 40 50 60 40 50 60
Aniline, AW-dimethyl-
40 50
60 Anthracene Arabinose Benzene - , bromo- , tert-butyl- , chloro-,ethyl- , iodoBenzoic acid, vinyl ester /7-Benzoquinone Borane, tributyl 2-Butanone - , 3-methyll-Buten-3-yne Butyl alcohol sec-Butyl alcohol tert-Butyl alcohol
C s (xlO 4 )
50 60 60 60 60 60 60 60 65 50 60 60 60 50 60 60 60
14 47 4.945 5.05 0.81 1.7 1.13 0.7 2.0 120 90.5 3940 590 17.0 x 104 28.0 x 104 32.0 44.0 9600 1.22 xlO 4 215 5.8IxIO 4 359 9.38 x 104 547 14.3 x 104 605 1.19 xlO 4 708 1040 1.5 x 104 1.54 xlO 4 870 964 2.18 xlO 4 1.8 x 104 13.0 2.46 1.36 1.93 0.79 35.73 5.19 1400 1.3 x 104 6470 6.43 21.08 3800 15.42 97.55 0.44
C
F2
F F7 F14 F14 F F14 Fl 5 F7 F7 F7 F7 F7 F7 F2, G F2, J F16, G, J F16, G, J F2, J F16, G, J F2, J F16, G, J F2, J F16, G, J F2, J F16, G, J F2, J F16, J F16, G, J J F2, J F16, G, J F8 G G, S G G, S G G, S F7 G G F7 G G G
319 436 377 375 197 377 377 95 377 86 499 156 156 156 247 247 229 229 227,229 229 229 229 229 227,229 229 229 229 229 229 161 228 227,229 24 229 229 15 361 95 95 95 95 95 95 136 15 156 95 95 377 95 95 95
Remarks page 11-157; References page 11-159
TABLE 4. cont'd Solvent/Additive Acrylonitrile (cont'd) Butyric acid, 4-hydroxy-y-lactone Cadmium, dibutyl Carbonic acid, cyclic ethylene ester
Carbon tetrabromide Carbon tetrachloride
T( 0 C) 50 60 50
60 50 60
Copper(II) chloride
60 80 60 80 35
Copper(II) sulfate
60 35
Chloroform
Crotonaldehyde Crotononitrile, transCumene Cyclohexane -,methylDimethylamine m-Dioxane, 5,5-dimethyl-2-vinylm-Dioxane, 5,5-dimethyl-2-vinyl- , 4-methyl-2-vinyl- , 2-vinyl1,3,-Dioxolane, 2-vinyll,3-Dioxolane-4-methanol, 2-vinylDiphenylamine-T Erythritol Ethane, 1,2-dichloro- , 1,1,2,2-tetrachloro- , 1,1,1-trichloro- , 1,1,2-trichloroEthanol, 2,2MmInOdI- , 2,2',2"-nitrilotriEther, dodecyl vinyl Ethyl acetate Formamide, N,N-dimethyl-
50 50 60 60 60 50 60 60 60 60 60 60 60 60 60 60 60 30 30 50 60 20 25 40 50
60
C s (xlO 4 ) 0.658 0.74 5.5 x 104 0.073 0.33 0.39 0.474 0.5 0.511 1.0 0.128 400 500 1900 0.85 1.13 5.64 5.90 1.8 x 105 1.9 xlO 5 3.2 xlO 5 10 x 105 1900 2800 3000 1.07 x 104 1.35 xlO 4 3.93 x 104 13.6 x 104 21.OxIO 4 47 19 41.41 2.06 2.31 175 2.20 4.40 2.71 16.60 2.40 700 12.8 1.47 3.11 1.25 1.68 10.1 76.0 4.95 2.54 1.4 4.97 3.24 1.0 2.70 2.78 2.8 2.83 10 2.412 4.494 5.0
Remarks
F7
E
F7, J G C G C U(0.01) U(0.1) U(l.O) F7 F13, J J, V(0.0001) J, U(0.01) J, V(0.001) J, U(0.1) J, V(O.Ol) J, U(LO) J, V(0.1) F7 F7 G G G F7 F7 F7 F7 F7 F7 F7 F8 G G G G F13 F13 C G C, J, F7 D, J E
F7
F15
Refs. 375 374 156 293 197 374 375 404 458 356 293 493 20 24 96 336 95 336 402 402 402 37 402 402 402 402 402 402 402 402 377 377 95 95 95 377 498 498 498 498 498 61 361 95 95 95 95 476 476 4 95 248 91 458 347 374 197 377 375 356 347 22 86
TABLE 4. cont'd Solvent/Additive Acrylonitrile (cont'd) Formamide, A^N-dimethyl- (cont'd) -, Af-methylFormic acid Glucose ot,D-Glucoside, methyl- , -, 6-deoxy-6-iodo- , - , 6-deoxy-6-mercapto- , - , 6-deoxy-6-phthalimido- , -, 2,3-di-O-benzyl- , -, 2,3,4,6-tetra-O-acetyl- , -, 6,-O-(/?-toluenesulfonyl)- , - , 6-O-triphenylmethylP,D-Glucoside, methyl- , - , 6-deoxy-6-dipropylaminoGlutaronitrile, 2,4-dimethylGlyceraldehyde Glycerol 2,4,6-Heptanetricarbonitrile 1-Heptanol, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluorol,5-Hexadien-3-yne Hydrocyanic acid
T( 0 C)
50 50 60 60 60 60 60 60 60 60 60 60 60 50 60 60 50 60 50 50
Indium, triethyl Iron(III) chloride Isobutyl alcohol Isobutylene Isobutyronitrile
60 60 60 60 50 60
Lactonitrile Lead, tetraethyl Magnesium perchlorate Mercury, diethyl Methane, dichloro- , nitroMethanol Methylamine 2,6-Octadiene, 2,6-dimethylOxime, acrolein -, crotonaldehyde-, ethylisopropenylketone-, methacrolein-, methylacrolein-, methylvinylketone-, methylisopropenylketone-, methylisobutenylketone1-Pentanol, 2,2,3,3,4,4,5,5-octa-fluoro1-Pentanol, 4-methylPiperidine, 1-ethyl- , 1-methyl1-Propanol, 2,2,3,3-tetrafluoroSilane, tetraethyl Sorbitol Stibine, tributyl Succinonitrile Sulfur dioxide Tin, tetrabutyl Toluene
50 60 50 60 60 60 50 50 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 50 60 50 60
o-Toluidine, MN-dimethyl-
40 50
C s (xlO 4 )
1.8 0.5 6.9 20 50 1300 60 90 30 10 80 20 1100 0.6 32.1 23.5 1.0 1.9 1.17 x 104 0.81 6.2 2220 3.33 x 104 24.06 70 1.3 1.8 3.5 4.0 1 243 < 0.05 72.2 3.06 6.0 0.5 175 450 6.26 x 105 2.05 x 104 1.03 x 104 9.41 x 104 5.35 x 104 1.2 x 104 1.71 x 104 2.65 x 104 1.9 11.79 3300 2300 1.5 21.0 6.1 11.1 x 104 0.6 0 80.8 1.153 2.632 3.2 5.83 272 334
Remarks
Refs.
F14 F14 F8 F7 F7 F7 F7 F7 F7 F7 F7 F7 F7 F14 F8 F8 F14 F2 F7 F14 F F7 F7 G
377 377 361 220 220 220 220 220 220 220 220 220 220 376 361 361 376 442 377 377 436 156 19 95 553 376 376 135 86 377 156 376 156 95 86 377 377 6 555 555 555 555 555 555 555 555 442 95 24 24 442 156 361 156 86 362 156 347 347 21 24,95 229 229
F14 16 F15 F14 F7 F7 G F15 F14 F7
F2 G J J F2 F7 F8 F7 F7 G G G F2, J F2, J
Remarks page 11-157; References page II-159
TABLE 4. cont'd Solvent/Additive
T( 0 C)
Acrylonitrile (cont'd) 0-Toluidine, ^//-dimethyl- (confd) Tributylamine Triethylamine
Trimethylamine Tripropylamine Zinc, diethyl Zinc chloride Acrylonitrile/styrene (38.5-61.5 mol%) Methanol Anisole, /?-vinylAnisole, /?-isopropylBenzonitrile,/7-isopropylCumene -,/7-bromo-,/7-tert-butyl-,/?-chloroBenzoic acid, vinyl ester Benzene Benzoic acid, isopropyl ester 2-Butanone Carbon tetrachloride Chloroform Cyclohexane 1,3-Butadiene, 2-chloro1-Butene, 3-chloro-3-methyl2-Butene, l-chloro-3-methyl2,6-Octadiene, 2,7-dichloro3-Buten-2-one, 3-methylBenzene -,ethylCyclohexane, methylToluene Butyraldehyde, divinyl acetal Aniline, N,TV-dimethylBenzene Butyl alcohol tert-Butyl alcohol 1,3-Dioxolane, 2-propylButyric acid, vinyl ester Benzene Carbamic acid, vinyl-, ethyl ester Acetone Benzene Chloroprene 3-Chloro-(methyl-14C)l-butene(4-14C) 3-Cfcloro-2-pentene-(2,4-14C) /?-Dioxin, 2,3-dihydro-/maleic anhydride Benzene Carbon tetrabromide Carbon tetrachloride Chloroform /7-Dioxane Toluene m-Xylene
60 60 60
50 60 60 60 50
C s (xlO 4 )
30200 463 6700 1700 1900 3800 5900 6600 175 790 4820 1.05 x l O 4 1.06 x l O 4 0.006
Remarks
Refs.
F16, G, J F2, J J T
227,229 229 24 20 20 22 24 24 377 24 156 24 156 410
F7, J J F7 J F7 J F7 F13
65
1.4
116
60 60 60 60 60 60
3.40 40.9 4.28 11.8 3.64 8.52
407 407 407 407 407 407
60 80 60 80 80 80 80
1.5 0.4 1.0 29.0 730 105 2.3
393 26 393 26 26 26 26
50 50 50
5.47 4.57 5.24
Fl F2 F2
80 80 80 80
2.489 6.934 0.500 3.282
C C C C
50 50 50 50 50
1060 27.7 3500 37.2 708
152 152 152 84 84 84 84 430 430 430 430 430
80
3.28
201
60 60
8.5 1.25
117 117
50 50
5.37 3.94
60 60 60 60 60 60 60
11500 100 x 105 1.7 x 105 3.6 x 104 1.07 x 104 6.OxIO 4 9.9 x 104
F2 F2
509 509
R R R R R R R
169 169 169 169 169 169 169
TABLE 4. cont'd Solvent/Additive Ethylene Acetamide, AW-diethyl- , AW-diisopropyl- , Ar,A7-dimethyl- , N-ethyl-,TV-methylAcetic acid, butyl ester - , tert-buty\ ester - , methyl ester Acetic acid, chloro- , - , methyl ester
T( 0 C)
C s (xlO 4 )
Remarks
130 130 130 130 130 130 130 130
125 57 182 115 61 89 40 40
C, W5 C, W5 C, W5 C, W5 C, W5 C, W5 C, W5 C, W5
454 454 454 454 454 454 454 454
90
130
610 1210 2170 2150 2580 630 1160 1880 1990 2090 1120
C, Ql C, Q2 C, Q3 C, Q4 C, Q5 CQl C, Q2 C, Q3 C, Q4 C, Q5 C, W5
434 434 434 434 434 434 434 434 434 434 454
130
6700
C, W5
454
55
1800 7900 11100 13000 1900 6900 9400 10500 2000 5900 8100 11100
C, Ql C, Q2 C, Q3 C CQl C, Q2 C, Q3 C C, Ql C, Q2 C Q3 C
435 435 435 435 435 435 435 435 435 435 435 435
700 16100 27500 38000 65700 1000 17000 27700 39000 65200 1200 15400 23600 33000 54100 130 160 165 168 282 100 1970 0.629 20 21 9.4 18
C, Ql C, Q2 C, Q3 C, Q4 C CQl C, Q2 C, Q3 C, Q4 C CQl C, Q2 C, Q3 C Q4 C C, W5 C, W17 C, F21, W5 C, W5 C,W5 C, F21, W5 C, W5 E, W D D, W C,W5 W3
484 484 484 484 484 484 484 484 484 484 484 484 484 484 484 454 456 259 456 455 159 457 143 204 205 260 218
120
Acetic acid, cyano- , - , methyl ester Acetic acid, dichloro- , -, methyl ester
90
120
Acetic acid, trichloro- , - , methyl ester
55
90
120
Acetic anhydride Acetone
130 130
Acetonitrile Benzaldehyde Benzene
200 130 130 20 83 130 50-70
Refs.
Remarks page 11-157; References page 11-159
TABLE 4. cont'd Solvent/Additive
T( 0 C)
Ethylene (cont'd) -,ethyl-
130
Benzene-D6 Benzoic acid, butyl ester -,ethyl ester - , methyl ester Butane
200 130 130 130 130 130
- , 1-iodo-
100
2-Butanone
130
- , 3-methyl1-Butene
200 130 130
- , 2-methyl-
189 200 130
-,3-methyl2-Butene
130 130
- , 1,4-dichloro-,2-methyl tert-Buty\ alcohol
130 130 30 130 130 130 130 130 20 50 70
Butylamine Butyraldehyde Butyric acid, methyl ester Butyronitrile Carbon tetrachloride
90
95
130
140
C s (xlO 4 )
Remarks
Refs.
430 480 520 560 500 5.6 140 55 53 40 45 9.45 x 104 11.3 xlO 4 12.6 x 104 550 600 750 840 330 470 560 900 570 210 530 1200 250 380 4100 470 0 2 220 3250 220 520 215 772 974 7000 32000 740 1210 20200 32500 34000 1250 ±200 22000 ± 1000 43000 ± 4000 1130 ±700 2000 ±1000 37000 ± 3000 9800
C, W17 C, W5 C, W5 C, W5 C, W5 C, W5 C, W5 C, W5 C, W5 C, F21, W5 C, W17 Ql, W14 Q2, W14 Q3, W14 C, W17 C, F21, W5 C, W5 C, F21, W5 C, W5 C, W5 C, F21, W5 B, W5 C, W5 C, F21, W5 C, F21, W5 C, F21, W5 C, F21, W5 C, W5 C, W5 C, F21, W5 E, W4 C, F21,W5 C-W5 C, W5 C, W5 C, F21, W5 E, W CQl, C, Ql C, W4 C Ql, W12 CQl Q2, W12 Q3, W12 W12 W23, Q(I) W23, Q(2) W23, Q(3) W20, Q(I) W20, Q(2) W20, Q(3) C,F21,W5
456 52 454 52 455 260 454 454 454 259 456 187 187 187 456 259 455 259 52 52 259 443 455 259 259 259 259 454 454 259 482 259 454 457 454 259 143 391 391 215 210 453 391 453 453 453 518 518 518 518 518 518 259
1600 1700 1800 2200 22000 23000 30000 36000 38000 39000 60000
CQl C, Ql, F19 C, Ql, W13 C, Ql, F20 C, Q2 C, Q2, F19 C, Ql, Wl C Q3 C Q2, F20 C Q3, F19 C,Q2, W13
170 170 170 170 170 170 170 170 170 170 170
TABLE 4. cont'd Solvent/Additive Ethylene (cont'd) Carbon tetrachloride (cont'd)
Chloroacetic acid, methyl ester Chloroform
Cumene Cyclohexane
-,methylCyclopentane Cyclopropane Decane 1-Decene Dibutylamine Dichloroacetic acid, methyl ester Dimethylamine p-Dioxane Ethane - , U-bis(dimethylamino)- , l-bromo-2-chloro- , chloro- , 1,2-dibromo- , 1,1-dichloro-
T( 0 C)
C s (xlO 4 )
60000 61000 70000 90000 100000 110000 130000 140000 180000 90 590, 550, 1200 1680, 2240, 2340 28 2100 13000 15000 70 8000 30000 80 2470 15500 24900 31200 43900 95 2000±120 10000 ±500 16000 ± 3000 1150±50 5000 ±300 8000 ±1000 101 1500 4500 5400 103 2890 15400 23800 29800 41100 130 2900 140 3210 15200 22200 28000 37600 130 500 130 80 90 91 200 190 130 110 130 109 127 200 22& 130 0 130 120 189 425 189 1090 130 1070 901900, 6900, 9400 130 1900 130 320 130 6 130 1070 130 390 70 120 130 1250 70 1500
Remarks C, Q3 C, Q3, F20 C, Q4, F20 C, Q4, F20 C, Q2, Wl C, Q3, Wl C, Q3, W13 C, Q4, Wl C C, Q(I), Q(2), Q(3) C, Q(4), Q(5), Q(6) E, Ql, W E, Q2, W E, Q3, W C, W4 C C, Ql, W12 C, Q2, W12 C, Q3, W12 C, Q4, W12 C, W12 W23, Q(I) W23, Q(2) W23, Q(3) W20, Q(I) W20, Q(3) W20, Q(3) E, Ql, W E, Q3, W E, Q2, W C, Q1,W12 C, Q2, W12 C, Q3, W12 C, Q4, W12 C, W12 C, F21,W5 C, Ql, W12 C, Q2, W12 C, Q3, W12 C, Q4, W12 C, W12 C, F21, W5 C, F21, W5 C, W17 C, F21, W5 C, W5 C, F21, W5 C, W17 C, F21, W5 C, W5 C, F21, W5 C, F21, W5 B, W5 B, W5 C, W5 C, Q(I), Q(2), Q(3) C, F21, W5 C, F21, W5 C, F21, W5 C, W5 C, W5 C, W4 C, W5 C, W4
Refs. 170 170 170 170 170 170 170 170 170 557 557 244 244 244 215 210 101 101 101 101 101 518 518 518 518 518 518 224 244 244 101 101 101 101 101 259 101 101 101 101 101 259 259 456 259 455 259 456 259 455 259 259 443 443 454 558 259 259 259 457 454 215 454 215
Remarks page 11-157; References page 11-159
TABLE 4. cont'd Solvent/Additive
T( 0 C)
Ethylene (cont'd) Ethane, 1,2-dichloro- , iodo-
130 65 100
- , 1,1,1-trichloroEthanol
Ethyl acetate Ethylene oxide Formaldehyde Fomamide, W,TV-dimethylFormic acid, methyl ester Furan, tetrahydroHeptaldehyde Heptane Hexane 1-Hexene - , 2-ethylHydrogen Isobutyronitrile Isocyanic acid, butyl ester Isopropanol
Isothiocyanic acid, butyl ester Methane - , bromochloro-
70 20 30 60 100 125 130 125-135 150 180 200 130 200 130 130 130 130 130 200 130 200 50-70 130 130 189 189 130 130 200 130 130 30 60 100 125 130 125-135 150 180 200 130 130 100
130 140
C s (xlO 4 )
110 1.51 x 105 1.59 x l O 5 1.65 x 105 1.1 x 105 1.36 x l O 5 1.43 x l O 5 1.48 x l O 5 1.49 x 105 500 5.71 110,210, 270 76,240, 280 89,270, 340 100,310, 320 68 69 75 190 92,260 73,350 135 45 121 7 560 260 42 288 289 401 2600 3900 4800 90 80 68 225 900 3300 159 160 400 1070 212 96,410, 520 65,310, 380 65,300, 350 75,380, 380 130 140 144 570 98,470, 460 86,440, 500 234 0 0 1600 4500 7500 8000 10000 16.OxIO 5
Remarks
C, F21, W5 Ql Q2 Q3 Ql Q1,W14 Q2, W14 Q3, W14 Q3 C, W4 E, W E, Q(I), Q(3), Q(5) E, Q(I), Q(3), Q(5) E, Q(I), Q(3), Q(5) E, Q(I), Q(3), Q(5) C, W17 C, F21, W5 C, W5 C, W2 E, Q(I), Q(3) E, Q(I), Q(3) C, W5 C, W5 C, W17 C, F21, W5 C, W5 C, F21, W5 C, W5 C, W5 C, F21, W5 C, W5 C, W17 C, W5 C, W5 W3 C, F21,W5 C, F21, W5 B, W5 B, W5 C, F21, W5 C, W5 C, F21, W5 C, W5 C, F21, W5 C, W5 E, Q(I), Q(3), Q(5) E, Q(I), Q(3), Q(5) E, Q(I), Q(3), Q(5) E, Q(I), Q(3), Q(5) C, W17 C, F21, W5 C, W5 C, Wl E, Q(I), Q(3), Q(5) E, Q(I), Q(3), Q(5) C, W5 C, W5 C, W5 C, Ql, WIl C, Q2, WIl C, Q3, WIl C, Q4, WIl C, W5 Ql, WIl, II
Refs.
259 189 189 189 452 188 188 188 452 215 143 523 523 523 523 456 259 454 381 523 523 455 454 455 259 457 259 454 454 259 455 457 457 457 218 259 259 443 443 259 454 259 455 259 454 523 523 523 523 456 259 454 381 523 523 455 454 259 2 2 2 2 454 1
TABLE 4. cont'd Solvent/additive Ethylene (cont'd) Methane, bromochloro- (cont'd) - , chloro- , dichloro- , dimethoxy- , iodo-
T( 0 C)
70 70 130 130 65 100
Methanol
Methylamine 1-Octene
30 60 100 125 130 150 180 130 130
Pentane, 2,2,4-trimethylPentene - , 4,4-dimethyl- , 4-methylPhosphine - , dibutyl - , tributyl - , triphenyl Phosphorous acid, dimethyl ester Propane
130 189 130 130 130 130 130 130 130 130
- , 2-chloroPropane, 2-chloro-2-methyl-, 2,2-dimethyl- , 2-iodo-
200 70 70 130 65 100
- , 2-methyl-
130
- , 1,1,1,2,2,3,3,3-octafluoro1-Propene
200 130 130
Propionaldehyde
200 130
Propionic acid, methyl ester
200 90
120
C 8 (xlO 4 ) 47.0 x 105 4 700 360 73 41000 45000 45000 41000 45000 45000 36, 84, 100 46, 100, 140 34, 90, 120 56, 100, 140 21 53, 120, 160 37, 120, 160 53 360 360 64 900 175 310 207000 36000 4500 50 5100 27 27.6 31 65.2 250 40 8 5.7 x 105 5.9 x 105 6.07 xlO 5 4.55 x 105 4.70 x 105 4.83 x 105 50 72 136 4 110 122 150 200 2300 3300 2830 63000 92000
1.08 xlO 5 630, 420, 780 890, 1030, 1230 78000 1.12 xlO 5 1.39 xlO 5 780, 430, 1060 1220, 1300, 1410
Remarks
Refs.
Q2, WIl, II C, W4 C, W4 C, F21,W5 C, W5 Ql Q2 Q3 Ql Q2 Q3 E, Q(I), Q(2), Q(3) E, Q(I), Q(2), Q(3) E, Q(I), Q(2), Q(3) E, Q(I), Q(2), Q(3) C, F21, W5 E, Q(I), Q(2), Q(3) E, Q(I), Q(2), Q(3) C, W5 C, W5 C, F21, W5 C, F21, W5 B, W5 C, W5 C, W5 C, W5 C, W5 C, W5 C, W5 C, F21, W5 C, F21, W5 C, W17 C, F21, W5 C, W5 C, W4 C, W4 C, F21, W5 Ql Q2 Q3 Ql Q2 Q3 C, F21, W5 C, W5 C, W5 C, F21, W5 C, W5 C, W5 C, W5 C, W5 C, W17 C, W5 C, W5 C, Ql C, Q3
1 215 215 259 454 189 189 189 189 189 189 523 523 523 523 259 523 523 454 52 259 259 443 454 454 457 454 454 454 259 259 456 259 455 215 215 259 189 189 189 189 189 189 259 454 455 259 52 454 52 455 457 457 457 485 485
C, Q5 C, Q(I), Q(2), Q(3) C, Q(4), Q(5), Q(6) CQl
485 516 516 485
C, Q3 C, Q5 C, Q(I), Q(2), Q(3) C, Q(4), Q(5), Q(6)
485 485 516 516
Remarks page II-157; References page II-159
TABLE 4. cont'd Solvent/Additive
T( 0 C)
Ethylene (cont'd) -, 3-cyano-, methyl ester Silane, tetramethyl Tetradecane 1-Tetradecene Toluene
130 130 189 189 130
Tributylamine Trichloroacetic acid, methyl ester Tridecane Trimethylamine
200 130 90 130 130
Water /?-Xylene
20 130 200
Ethylene, bromoCarbon tetrachloride Ethylene, chloroAcetaldehyde Aniline, A^-dimethylBenzene Butyraldehyde
Carbon tetrabromide
60 50 50 35 50
50 60
Cyclohexane, 1,2-epoxy-4- vinylEthane, 1,2-dichloroEther, dodecyl vinyl Furan, tetrahydroHeptane, 2,4,6-trichloroOxalic acid, diethyl ester Pentane, 2,4-dichloroEthylene, 1,1 -dichloroPhosphorus trichloride Ethylene, tetrafluoroEthanol
25 50 50 25 40 50 50 25 25 50
790 0 580 1760 130 154 180 220 820 1000, 1700, 2770 140 180 330 1.71 300 317 400 434
110 2700 1500 350 420 500 580 4.7 x 104 50.0 x 104 3300 1.85 xlO 4 7.45 x 104 12.15 xlO 4 264 4.0 4.5 156 16 30 24 5 1.4 9.0 5 14
100
800 820 860 880 1540 1660 1700 350 390
100
Methanol
100 80 140 125-135 30-35
Remarks
C, W5 C, F21, W5 B, W5 B, W5 C, W5 C, W5 C, W17 C, W5 C, W5 C, Q(I), Q(2), Q(3) C, F21, W5 C, F21, W5 C, W5 E, W C, F21, W5 C, W5 C, W17 C, W5
50
60
Isopropanol
Hexanoic acid, vinyl ester Benzene 1-Hexene Carbon tetrachloride Cyclohexanol Ethyl alcohol
C s (xlO 4 )
454 259 443 443 52 454 456 455 454 559 259 259 454 143 259 454 456 455 417
W8 W7 W15 F26 Ql Q2 Q3 Q4 C, F26
G D C, Q5, W2 C, Q6, W2 C, Q4, W2 C, Q3, W2 C, Q3, W2 C, Q4, W2 C, Q5, W2 C, Q3, W2 C, Q4, W2
4.9 4.1 x 104 390 170
Refs.
164 161 219 500 500 500 500 492 66 418 418 418 418 428 425 392 4 425 246 164 211 315 315 211 214 3 3 3 3 3 3 3 3 3 201
C, Ql, F19 C D
170 381 381
TABLE 4. cont'd Solvent/Additive
T( 0 C)
Isobutene Carbon tetrachloride
100
Isobutyric acid, vinyl ester Benzene Maleic acid, diethyl ester Stearamide, iV-allylMaleic anhydride/methyl methacrylate Acetone Maleic anhydride/styrene Aniline, A^-dimethylCarbon tetrachloride Methacrylic acid Bromotrichloromethane - , butyl ester Benzene -, 2-(diethylamino)ethyl ester/styrene Carbon tetrachloride Toluene -, ethyl ester Acetic acid Acetone Acetophenone Benzene -, chloro- , ethyl2-Butanone Butyl alcohol sec-Butyl alcohol tert-Butyl alcohol Carbon tetrachloride
80
Remarks
E, Q(I) E, Q(2)
4.49 22.4
60
Refs.
537 201
J
173
1.6
HH
367
60 70
930 1.04
HH
489 365
70
300
60 80 80 80 80 80 80 80 80 80 80 80 80 80
566
0.158
264
23.6 13.3
335 335
80 80 80 80 80 80 80 80
0.095 0.102 0.281 0.081 0.436 1.428 0.252 0.454 1.604 0.417 0.901 5.640 0.703 2.360 2.067 0.928 1.821 0.311 1.820 0.536 0.919 0.429 0.865 0.702 0.445 0.236 0.436
70 70
0.983 2.05
-
137 137
60 80 80 80 80
0.165 1.971 1.110 0.510 0.510
C C C C
264 183 183 183 183
100 120 60 60 60
900 1000 30800 0.001 0.996
80
Cumene Cyclohexane Ethane, 1,2-dichloroEthane, 1,1,2,2-tetrachloro-
80 80 80 80
Iron(III) chloride Isobutyraldehyde Toluene Methyl methacrylate Acetaldehyde Acetic acid
(7.1 ±0.2) x 104 (8.1 ±0.5) xlO 5
90
Chloroform
-, 1,1,1-trichloroEthyl acetate Ethyl alcohol Heptane 2-Heptanone Isobutyl alcohol 2,4-Pentanedione Toluene - , hexadecyl ester Carbon tetrachloride Cumene - , isobutyl ester Benzene Carbon tetrachloride Chloroform Ethane, 1,2-dichloro- , 1,1,2,2-tetrachloroMethacrylonitrile Carbon tetrabromide
C s (xlO 4 )
60 80
6.5 0.24
S
C C C C
A, F7 A, F7 F7
A
83 83 83 83 83 83 83 83 83 83 83 183 83 183 83 83 183 83 183 83 83 83 83 83 83 83 83
109 109 19 70 21 86 31
Remarks page II-157; References page 11-159
TABLE 4.
cont'd
Solvent/Additive
T (°)
Methyl methacrylate (cont'd) Acetic acid, monochloro- , dichloro- , l,l-dimethyl-2,2,2-trinitroethyl ester - , trichloroAcetone
60 60 45 60 60 80
Acetonitrile, (m-bromophenyl)- , (p-bromophenyl)- , (m-chlorophenyl)- , (p-chlorophenyl)- , (p-methoxyphenyl)- , phenyl- , m-tolyl-,/?-tolylAcetylene,/7-bromophenyl-,/?-chlorophenyl- , /MiitrophenylAluminum, hydrodiisobutyl - , triethyl
60 60 60 60 60 60 60 60 60 60 60 60 50 60 60 80 100 30 50
Aniline - , MN-dimethyl-
60 70 80 100 60 60 80 100 60 25 60 60 60 50 50 60
- , AW-divinyl- , Af-methylp-Anisaldehyde Anisole - , />-ethynyl-,/j-isopropyl-,p-methylAnthracene Azobenzene Benzaldehyde -,/j-bromo-, m-chloro-,p-chloro-,/?-cyanoBenzene
60 60 60 60 25 30 50 52 60 75 80
- , allyl- , bromo-,
tert-butyl-
90 60 25 80
C 8 (xlO 4 ) 0.64 0.80 520 1.10 0.195 0.225 0.275 3.89 2.78 4.28 3.21 19.0 5.18 5.75 7.83 41.3 38.9 127.5 3600 1550 1240 4.2 6.3 9.0 2.45 18 30.4 430 11.3 10.8 17.0 20.0 340 7.0 10.0 13.3 1.11 0 40.3 3.46 0.57 0 100 2.5 0.86 1.43 0.96 1.03 2.06 0 0.01 0.036 0.027 0.040 0.83 0.33 0.075 0.080 0.24 0.036 400 0 0.260
Remarks R R R A
K K K S R, F2 F2 F2 F2 F16 H A, F2 A, F2 A, F2 F2 F2 F2 D K
C
D
C C A Il D A
Refs. 529 529 110 529 81 31 81 462 461 462 461 461 461 462 461 151 151 151 156 547 156 424 424 424 508 228 409 161 424 270 424 424 82 424 424 424 495 16 151 406 496 15 282 86 495 495 495 495 495 16 508 147,327 81 81 181 123 31 81 145 147 502 16 31
TABLE 4. cont'd J( 0 C)
Solvent/Additive Methyl methacrylate (cont'd) -, chloro-
-,/7-diisopropyl-, - , ethyl-
25 60 80 ra-dinitro-
- , ethynyl-, Benzene sulfonylchloride -,/7-chloro-,/7-dimethylBenzonitrile -,p-hydroxy- , p-isopropylp-Benzoquinone - , 2,3,5,6-tetrachloroBenzothiazolethion, 3-allylBenzyl ether Bibenzyl Biphenyl, 2,2-methyleneBorane, tributylBromoform Butane, 1-chloro-, 1,1,1-trinitro1,4-Butanediol 2-Butanone
1-Butene - , 3,4-epoxy-2-methyl2-Butene, cis- , trans3-Buten-2-ol, l-chloro-3-methylButyl alcohol sec-Butyl alcohol tert-Butyl alcohol
60 50 52 60 80 60
fluoro-
25 60 60 60 25 60 50 60 44.1 50 60 44.1 60 25 60 50 60 60 60 77 80 45 60 80 60 70 75 80 40 50 80 40 50 40 50 80 60 80 60 80 60 80
Butylamine, N-nitroButyl ether 1-Butyne, 1-phenylButyraldehyde
45 60 60 50
Carbon tetrabromide
30
C s (xlO 4 )
0 0.074 0.200 0.207 5.72 52 0.501 0.766 1.311 1.350 2.1 21.9 22.3 0 5.16 8.56 4.06 0 0.162 6.0 4.99 5.5 x 104 5.7 x 104 4.5 x 104 2600 153 10.4 8.0 0.0 41.8 53.5 7.45 23 1.20 8300 0.61 1.07 0.45 0.56 0.83 0.70 3.1 5.1 29.6 3.2 4.9 3.0 5.2 18.8 0.394 0.25 0.259 0.85 0.085 0.100 0.152 0 0.8 10.8 1.47 2.25 3.40 2800 ±600 1000 ±100
Remarks
Refs.
D
16 81 31 81 406 15 81 81 81 31 145 151 150 16 543 543 543 16 150 479 406 194 15 42 194 502 368 368 354 567 567 156 506 31 110 421 421 290 123 123 31 287 287 269 287 287 287 287 269 479 31 479 31 81 31 81 110 86 150 500 500 500 521 521
A
A Il K J D R R R D
D F2
D, C, R A F24 F24 C C C A
A A A
W8 W7 D, R, JJ3a D, R, JJ3b
Remarks page 11-157; References page 11-159
TABLE 4. cont'd Solvent/Additive
T( 0 C)
Methyl methacrylate (cont'd) Carbon tetrabromide (cont'd)
Carbon tetrachloride
60 60 60 80 100 20 30 50 60
70 80
Chloroform
60 80
Copper(II) chloride Cumene
60 60 80
-,p-bromo-
60
-, p-tert-butyl-,/7-chloroCyclohexane
60 60 60 80 80 60 60 50 79.5 80 44.1 60 79.5 79.5 60 60 60 80 45 60 80
-,methyl- , trans-lA-, diacetate - , cis/trans-1,4-, dicarboxylic acid dimethylester Cyclotetrasiloxane, octamethylp-Dioxane Diphenylamine Diphenylamine-T Disiloxane, l,l-dimethoxy-3,3,3-trimethyl-l-phenyl- , hexamethylEpibromohydrin Epichlorohydrin Ethane, 1,2-dichloro- , nitro- , 1,1,2,2-tetrachloro- , 1,1,1-trichloro- , 1,1,1-trinitroEthyl acetate
80 45 60
C s (xlO 4 ) 1000 ±500 50Od= 200 2700 1500 1900 3300 4600 0.2 20 0.20 0.82 0.925 2.40 5 20.11 18.52 0.42 0.5 1.74 2.393 2.421 3.3 24.4 0.454 1.77 1.129 1.400 1.9 1.9 105 x 105 1.9 2.56 1.9 2.4
Remarks
Refs.
D, R, JJ3c D, R, JJ3d F2
521 521 109 568 568 109 109 35 451 514 514 81 181 86 529 529 568 568 514 31 81 145 427 81 181 81 31 145 427 36 7 406 31 145
F2 F2 C, D D, F2
C R R, H R R, H A Il D C A Il D F7 A Il
3.71
2.74 3.07 12 0.10 0.195 8.46 1.16 2.5 0.080 0.222 0 0.3 0.032 0.104 16.53 9.3 0.35 0.756 2.0 0.155 0.200 0.235 0.600 1400 0.100 0.13 0.132 0.134 0.155
406
A A C C C A F2 R R
A A C A C
406 406 86 31 31 569 569 450 474 31 194 46 474 474 529 529 81 81 110 81 31 81 31 110 316 290,316 216 290 290
TABLE 4. cont'd Solvent/Additive
T( 0 C)
Methyl methacrylate (cont'd) Ethyl acetate (cont'd)
Ethyl alcohol Ethylene glycol Germane, diethylchloro- , ethyldichloro- , triethyl- , triphenylGlycerol Heptane 1-Heptanol, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroHydrazyl, 2,2-diphenyl-l-picryl Hydroquinone Indium, triethylIsobutyl alcohol
70 75 80 60 80 100 60 80 60 60 60 60 60 50 60 44.1 45 131 60 60 80
Isobutyric acid - , methyl ester Isopropyl alcohol
80 60 60 80 100 130
Lead, tetraethyl Malononitrile, furfurylideneMercury, diethyl Methane, bromotrichloro- , bromotrinitroMethane, dichloro- , nitro- , trinitro- , triphenylMethanol 1-Naphthol 2,6-Octadiene, 2,6-dimethylOleic acid, methyl ester Oxime, acrolein- , crotonaldehyde-, ethylisopropenylketone- , methacrolein- , methylacrolein-, methylisobutenylketone-, methylisopropenylketone- , methylvinylketoneOxolane, c/s-3,4-diacetoxyPentane, 2,2,4-trimethyl1-Pentanol, 2,2,3,3,4,4,5,5-octa-fluoro2-Pentanone, 4,4-dimethyl-5,5,5-trinitro-
60 44.1 60 30 45 60 80 60 45 60 60 80 100 45 60 60 60 60 60 60 60 60 60 60 60 50 60 45
C s (xlO 4 )
0.156 0.46 0.55 0.83 0.240 0.40 0.625 0.80 0.28 0.60 22000 39300 5800 18500 0.152 1.8 2.8 20OxIO 5 7.0 100 332 0.10 0.505 0.229 0.250 0.900 0.26 0.583 1.907 3.00 8 43 45 3.14 1.2 x 104 0.898 830 1.2 xlO 4 4.5 xlO 4 1.0 x 104 0.100 0.217 2.0 5400 4.0 0.2 0.33 0.45 <5.0 6.7 1.68 8.0 25500 500 3000 17000 5200 4700 2900 1300 1.39 1.2 2.36 400
Remarks
C 110 C C A A, F2 A, F2 A F24 F24 A, R A, R A, R A, R F2 A
A A
A C C C S D, Q3 D D, Q4
A, F2 A, F2 A
C F2
Refs.
290 146 123 123 31 423 423 49 421 421 539 539 539 539 479 206 442 194 30 398 156 81 479 81 31 31 275 81 81 49 337 337 480 156 194 156 311 311 311 110 81 81 86 110 44 423 423 49 30 324 441 7 555 555 555 555 555 555 555 555 569 206 442 110
Remarks page II-157; References page II-159
TABLE 4. cont'd Solvent/Additive Methyl methacrylate (cont'd) - , 4-methyl3-Pentanone
Pentasiloxane, dodecamethylPhenol - , 0-bromo-,/7-bromo- , o-chloro- , o-ethyl-,/?-ethyl- , 0-isopropyl- , /?-isopropyl-,/7-methoxy- , 2,3,4,6-tetramethylPhenyl ether Phosphine, octyl-,phenyl- , tributylPhthalic acid, dimethylester Piperidine, 1-nitrosoPropane, 1,2-dichloro- , 1,1-dinitro- , 2,2-dinitro- , 1-nitro1,2-Propanediol 1-Propanol, 2,2,3,3-tetrafluoroPropene, 1,3-diphenyl1-Propene, 2-methylPropionic acid, 2,2,2-trinitroethyl ester Propionitrile, 3-phosphino- , 3,3/-phosphinylidenediPropyl alcohol
Pyridine Pyrocatechol - , p-tert-buty\Pyrogallol Silane, (oc-bromotolyl)trimethoxy- , bromomethylphenyltrimethoxy- , chlorotrimethyl- , dichlorodimethyl- , dichloromethyl- , diethylchloro- , dimethoxymethylphenyl- , dimethylphenyl- , hexamethoxy-^^'-thiodipropyDbis- , methyldichloro- , (3-mercaptopropyl)trimethoxy- , tetraethyl- , tetramethyl- , trichloro - , trichloromethyl-
J(0C)
80 60 80
79.5 50 50 50 50 50 50 50 50 45 45 25 60 60 60 60 30 45 80 45 45 45 60 80 60 60 40 50 45 60 60 60 80 100 70 45 45 45 79.5 79.5 30 50 30 50 79.5 60 79.5 60 79.5 79.5 60 79.5 60 30 50 60 30 50
C s (xlO 4 )
0.700 0.833 1.729 1.775 2.7 0.145 2.5 5.0 5.0 3.5 7.2 7.5 13.3 13.3 <5.0 11.0 6.42 9.13 2.3 x 104 16.IxIO4 30.6 0.2 8.2 0.675 68 15 5 0.48 0.86 1.86 15.6 2.5 4.4 3000 1.4 x l O 4 1.3 x 104 0.69 0.84 1.25 0.176 <5 9 26 29.8 29.8 144 2.2 175 2.45 15.2 1700 0.20 0.2 300 25.8 15.2 3100 6930 5.75 5.0 1.3 5000 185 2.7
Remarks
A
A Il
D
S
A
F24 F24 F2
A, F2 A, F2 A
R D, F2 D, F2
A, R R A, R R R A, R R D, F2 A, R D, F2
Refs.
31 81 81 31 145 474 479 479 479 479 479 479 479 479 30 30 368 368 295 295 156 508 110 31 110 110 110 421 421 442 567 287 287 110 295 295 423 423 49 514 30 30 30 474 554 451 249 451 249 474 539 474 554 539 554 554 539 554 156 451 249 539 451 249
TABLE 4. cont'd T( 0 C)
Solvent/Additive Methyl methacrylate (cont'd) - , triethyl - , triisopropoxymethyl-
60 79.5
- , trimethoxymethyl-
79.5
- , trimethoxyphenyl-
79.5
- , triphenylSilicon chloride
60 30 50 79.5 79.5 79.5 79.5 79.5 79.5 79.5 79.5 79.5 79.5
Siloxane, l,l-dimethoxy-trimethyl-l-phenyl-di-3,3,3- , dodecamethyl penta- , l,l,l,3,5,5,5-heptamethyl-3-phenyltri- , 1,1,1,3,5,5,5-heptamethyl-tri- , 1,1,1,3,5,5,5-heptamethyl-tri- , l,l,l,3,5,5,5-heptamethyl-3-(3,3,3,3-tri-fluoropropyl)-tri- , hexamethyl-di- , hexamethyl-phenyl-tri- , l,l,l,5,5,5-bexamethyl-3-(2-phenylpropyl)-tri- , 3-(3-mercaptopropyl)1,1,1,3,5,5,5-heptamethyl-tri- , octamethyl cyclotetra- , octamethyl triSorbit-2,5-diacetate, 1,4:3, 6-, dianhydroStearamide, JV-allylStearic acid, methyl ester Stibine, tributyl Tin, tetrabutyl Toluene
79.5 79.5 60 90 60 60 60 20 52 60
70 80
-, p-bromo-, -,p-chloro-, a-chloro - , p-ethynyl-,p-nitro-, 2,4,6-trinitrom-Tolunitrile, a-cyanop-Tolunitrile -, a-cyanoTributylamine Triethylamine
ra-chloro-
Tripropylamine Trisiloxane, 1,1,1,3,5,5,5-heptamethyl- , - , 3-(p-methylphenethyl)- , - , 3-phenyl- , - , 3-propyl- , - , 3-(3,3,3-trifluoropropyl)-
60 60 60 60 60 44.1 44.1 60 60 60 70 20 60 60 79.5 79.5 79.5 79.5 79.5
C s (xlO 4 )
200 0.697 0.697 0.331 0.331 0.053 0.053 1200 256 3.0 0.032 0.145 0.232 0.284 0.189 0.205 0.104 1.84 2.08 1284.5 0.08 0.0316 29 3.01 0.282 <1.0 1.32 0.04 0.084 0.170 0.190 0.202 0.250 0.26 0.400 0.45 0.567 0.292 0.303 0.52 0.525 0.91 0.58 0.48 0.49 4.17 64.4 0 500 4.55 0.73 1.74 25.7 1.5 8.3 1900 14.6 0.284 2.08 0.232 0.189 0.205
Remarks
A, R
Refs.
R R R R R R R R R R
539 474 554 474 554 474 554 539 451 249 554 554 554 554 554 554 554 554 554 554
R R C
554 554 569
R R R A, R D, F2
C, J
C, D C C C C C C Il A C
C K
C, D J
173 441 156 156 35 81 21,81 316 32,316,317 316 275 316 496 123 32 81 145 31 123 496 496 496 181 151 194 194 462 496 461 270 35 24 25 156 474 474 474 474 474
Remarks page 11-157; References page 11-159
TABLE 4. cont'd Solvent/Additive Methyl methacrylate {cont'd) - , l,l,l,5,5,5-hexamethyl-3-phenyl- , octamethylUrea, thioWater
m-Xylene p-Xylene 2,4-Xylenol Naphthalene, 1-vinylNaphthalene Nonanoic acid, vinyl ester Toluene 1-Octene Butyl alcohol sec-Butyl alcohol Ethyl alcohol Isopropyl alcohol Methanol Phthalimide, N-vinylChloroform Ethane, 1,2-dichloroMethane, dichloro2-Picoline, 5-vinylAllyl ether 1-Propene Carbon tetrachloride Chloroform 1-Propene, 3-chloroCarbon tetrachloride Hydrochloric acid 1-Propene, 2-methylCarbon tetrachloride - , 3,3,3-trifluoroCarbon tetrabromide Propionic acid, vinyl ester Toluene Propylene Bromoethane
J( 0 C) 79.5 79.5 42 60 80.5 60 60 50
30-50
50 60 70
11.1 13.9 15.2
117-118 117-118 115-118 30-35 120-125 116-120 55 55 55 70 100 100
Styrene Acetaldehyde
270 520 230 630 520 110
Remarks
A, R F7, F24
4800 1.8 x 104 5.4 xlO 4
100
17.0 x 104 640000
474 474 503 268 479 529 48 496 496 479
R R R
357 357 357
C C C D C C
381 381 381 381 381 381 313 313 313
21.4 (5-10) x 104 1.03 x 104
Refs.
216
3.4 0.35 0.97
100 80
11 C C
210 210
C Ql Q2
210 238 238
C
210
C, Q(I-3)
570
-
1.4
50 75
1200 1400 1500 1800 1700 1900 1800 2200 2100 2700 17200 ±1100 33000 ± 15000 17000 ±800 299000 ± 8000
Q(I-4) Q(I) Q(2) Q(3-4) Q(I) Q(2) Q(3-4) Q(l-2) Q(3-4) Q(l-4) W23, Q(I) W23, Q(2) W24, Q(I) W24, Q(2)
517 517 517 517 517 517 517 517 517 517 518 518 518 518
13800 ±800 266000 ± 10000
W20, Q(I) W20, Q(2)
518 518
125
Stearic acid, vinyl ester Toluene
1.84 0.032 1.21 0 0.002 0.03 0 0.43 0.50 6.5
60
100
Chloroform
C s (xlO 4 )
150 95
50 70
20.7 21.6
60
8.5
158
R R
357 357 86
TABLE 4. cont'd Solvent/Additive Styrene (cont'd) Acetamide, N,Af-dimethylAcetic acid - , methyl ester - , bromo- , chloro- , - , methyl ester - , dibromo-, ethyl ester - , monochloro- , dichloro-, -, -, -, -,
dichloro-, ethyl ester iodophenyl- , ethyl ester tribromo-
- , -, ethyl ester - , trichloro-
-, - , ethyl ester
T( 0 C)
50 60 40 100 60 68 68 60 100 90 60 60 60 68 60 100 90 90 60
Acetic anhydride Acetoacetic acid, ethyl ester - , 2-acetyl, ethyl ester Acetone
60 90 100 60 100 100 60
- , oxime Acetonitrile - , m-bromophenylAcetonitrile, p-bromophenyl-, m-chlorophenyl-,/7-chlorophenyl-,/?-methoxyphenyl-,phenyl-, m-tolyl-,/7-tolylAcetyl bromide Acetyl chloride, chloroAcetylene, p-bromophenyl- , p-chlorophenyl-,/7-nitrophenylAdipic acid, diallyl ester - , di-(3,3,5,5-tetramethyl-4-nitrosocyclohexyl) ester Allyl alcohol Aluminum, hydrodiisobutyl
60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 100
- , triethoxy- , triethyl
100 100
-, triisobutyoxy- , triisobutyl Aniline
100 110 50 60 50
- , MN-dimethyl- , AW-divinyl-
60
C s (xlO 4 )
0.743 4.6 2.22 0.33 430 300 200 0.3 0.75 2700 28.6 0.76 35.0 1.0 1.3 8000 6.0 8.8 3.0 x 104 2.4 xlO 4 10.5 x 104 270 66.0 100 3.75 65.0 90.0 145.0 0.7 1.3 3.0 4.1 <0.5 0.32 2.2 0.44 66.7 68.5 65.2 66.0 51.0 45.1 48.5 49.2 8600 3300 188.5 161 3130 6.0 1.1 x 104 1.5 26.9 x 104 28.OxIO 4 <0.1 8.05 x 104 17.OxIO4 <1.0 28.5 x 104 20 2.0 12 53 130
Remarks
C
A A C R R, H R R, H A A C C A R R, H A C A A C A A A A
S K K K F9, J A A A A A A F2 A F2
Refs.
375 113 385 72 112 149 149 128 128 64 529 529 529 529 128 149 128 72 178 64 64 178 128 529 529 128 64 128 128 72 72 182 128 501 128 128 462 461 462 461 461 461 462 461 112 112 151 151 151 446 314 128 156 155 155,156 156 155 155 155 154 128 154 161 82
Remarks page 11-157; References page 11-159
TABLE 4. cont'd Solvent/Additive
T (°)
C s (xlO 4 )
Styrene (cont'd) Aniline, N-methyl- , 2,4,6-trinitro/7-Anisaldehyde Anisole,/7-ethynyl- , m-isopropyl- , p-isopropyl- , p-methyl-,2,4,6-trinitroAnthracene - , dihydro2H-Azepin-2-one, hexahydroAzobenzene Benzaldehyde
50 50 60 60 60 60 60 50 44.1 50 130 70 60
13 11.8 x 104 2.86 60.0 5.23 3.23 0.78 20.3 x 104 2.OxIO 4 610 0.61 750 4.54 5.5 2.6 12.2 13.7 8.63 5.6 76.7 3.9 5.8 0.01 0.018 0.023 0.028 0.04 1.92 5.50 6.67 0.061 0.121 0.156 0.184 0.23 0.31 0.42 0.81 0.89 1.5 36 1.78 3 6.22 0.04 0.06 0.193 0.55 0.133 1.50 0.235 0.874 0.54 0.6 58.5 x 104 1950 7.02 10.70
-,/7-bromo-, m-chloro-,/7-chloro-,p-cyanoBenzene
100 60 60 60 100 60 35 40 50 60
70 75 80
100
132
-, allyl-, bromo- , sec-butyl- , tert-bx\ly\-
100 60 155 60 60
- , chloro-
80 100 60 80
- , - , 2,4,6-trinitro- , 1,2-dibromoethyl-,/?-dibutyl - , /?-di-seobutyl- , p-<\i-tert-bu\y\-
100 140 50 60 60 60 60
0.87
- , m-dichloro-
140
- , o-dichloro-,/7-dichloro-
60 60
0.2 1.4 3.4 2.6
Remarks F2
Refs.
H H
154 370,372 495 151 405 406 496 370,372 159 271 108 281 495 86 298 495 495 495 298 495 119 119 327 127 79 255 145 415 123 123 185 255 273 127 145 235 235 235 127 145 524 182 237 415 145 127 185 127 255 182 255 185 235 58 370,372 112 415 415
H
415
C C
58 67 182 182
K
J D C, I C A
A F2 F2 A C A, 15 H C C 15 C A A, 15 A A A A A, 15 A, R C A H A, 15 A 15 A C C C 15 A
TABLE 4. cont'd Solvent/Additive
T( 0 C)
C s (xlO 4 )
Remarks
Styrene (cont'd) Benzene, diethyl-, (mixture)
100
A A A
-, ethynyl-
60
-, -, -, -,
60 60 60 40 50 60 44.1
3.35 6.33 5.13 3.30 6.60 0.67 0.70 0.710 0.83 2.7 1.07 1.113 1.38 1.62 2.2 2.33 2.31 2.9 4.9 96.3 98.3 12.76 9.43 13.30 9.48 x 105 6.43 x 105 3.51 x 105 1.3 x 105
70 50 60 60 60 44.1 60 80 45 80 80 80 80 80 25 60 60 60 80 60 60 100 100 60 100 60 100 60 100 60 60 100 60 80 100
700 5.72 x 105 40 5.3 18.6 1.4 x 105 22.7 x 105 56.6 x l O 5 53.2 x 105 4.3 x 105 21.OxIO 5 95.0 x 105 6700 2.6 x 105 71.6 62.4 3020 1.12 x 104 1.2 x l O 4 142 97.9 <0.1 34.8 0.06 0.35 0.04 0.37 1.2 0.3 0.43 1.85 5.5 3.2 5.6 9.3
-,/?-diisopropyl-,ethyl-
132 60 60
80 100
132
sec-hexylsec-pentyltri-sec-butyl1,3,5-trinitro-
Benzo[B] chrysene Benzoic acid -, m-(phenylazo)-, methyl ester - , 2,4,6-trinitro-, ethyl ester Benzoin Benzonitrile -,/7-isopropyl Benzo[A]pyrene p-Benzoquinone /7-Benzoquinone, 2-anilino- , 2,5-dimethyl- , 2-methyl- , 2,3,5,6-tetrachloro- , 2,3,5,6-tetramethyl- , 2,3,5-trimethylBenzyl ether Bibenzyl, ococ'-dibromoBicyclohexyl, 3,3,3',3',5,5,5',5'-octamethyl-4,4'-dinitrosoBiphenyl, 2,2 '-methyleneBorane, tributoxy- , tributyl Butane, 1-bromo- , 1-chloro-, 2-chloro- , 2,2-dimethyl- , 1-iodo1,4-Butanediol
A C A, 15 C 15 C A A A, 15 A A A A, 15 K J H H H
J C A J J J J J J J J D F9, J F9, J
A A A A A, S A A A F24 F24 F24
Refs. 235 235 235 497 406 127 79 255 145 363 185 255 235 127 145 235 235 127 145 151 150 415 415 415 372 370,372,373 372 159 281 370,372 128 150 406 159 42 27 199 27 27 27 27 27 368 368 112 314 314 567 567 156 156 128 128 128 128 128 128 304 128 128 422 422 422
Remarks page II-157; References page 11-159
TABLE 4. cont'd Solvent/Additive Styrene (cont'd) 2-Butanone
T( 0 C)
1-Butene - , 3,3-dimethyl-2-phenyl- , 2,4-diphenyl- , 3,4-epoxy-2-methyl- , 2-methyl- , 3-methyl-
60 70 75 100 110 110 80 100 100
2-Butene - , 1,4-dichloro- , 2,3-dimethyl-
100 80 100
-,2-methyl3-Buten-2-ol, l-chloro-3-methylButyl alcohol
100 80 40 50 60
sec-Butyl alcohol terf-Butyl alcohol
Butylamine terf-Butyl ether tert-Buty\ isocyanide 1-Butyne, 1-phenylButyraldehyde
60 50 60 80 100 130 60 60 80 100 60 50
- , diallyl acetal Butyric acid, 4-hydroxy-, y-lactone Cadmium, dibutyl Carobonic acid, cyclic ethylene ester - , diallyl ester - , di-(3,3,5,5-tetramethyl-4-nitrosocyclohexyl) ester Carbon tetrabromide
60 100 60 50 100 50 60 60 80 40 60
60 60 70 80 90 100
C s (xlO 4 ) 4.98 8.60 12.00 2.6 10 70 17.4 3.1 6.9 6.1 2.0 51 5.4 5.1 2.9 8.2 11.2 6.5 0.06 1.6 0.562 6.6 0.22 6.65 0.345 0.55 1.0 0.5 2.6 1.0 33.0 34.3 2.7 14.3 2.7 3.7 4.0 4.7 8.0 8.0 11.7 14.3 5.7 11.0 20.2 0.409 1170 0.235 6.2 1.3 x 104 1.4 x l O 4 1.8 x 104 1.78 x l O 4
2.2 x 10 4 2.5 x 10 4 13.6 x 10 4 4.2 x 10 4 (5.09 ±0.18) xlO 5 88300 40600 1.8 x 10 4 2.3 xlO 4 2.51 x 10 4 2.35 x 10 4
Remarks C C C A A A A A A, R A C A A, R A F24 A A, C
A A A A C, F2 C, F2 W8 F29, W8 F29, W16 F2, W7 F29, W7 F2, W15 F29, W15 F2 F29 A A
E F27, J F9, J F2 C
F2 Fl A 112
F2 C A
Refs. 182 123 123 358 433 433 269 358 358 524 358 112 358 524 358 269 119 430 128 323,385 479 430 422 385 422 261 261 128 301 301 4,75 150 412 412 414 414 413 414 413 414 413 414 128 128 446 375 156 458 446 314 314 109 64
109 109 128 487 520 568 568 61 109 64 128
TABLE 4. cont'd Solvent/Additive
F( 0 C)
C s (xlO 4 )
Remarks
80 100 17 248 69 84 87 90 92 98 100 109 110 120 122 144.1 130.9 148 92 110 18 117 133 34.1 148 186 185 304 300 0.41 0.5 0.566 3.40 4.0 0.50 0.916 3.3 11 33 43 22.1 39 <5 0.8 0.82 1.04 3.88 1.31 2.00 2.90 8.29 7.57 3.46 6.90 0.024 0.031 0.04 0.063 8.5 0.066 0.083 0.156 0.16 0.23
W8
Refs.
Styrene (cont'd)
Carbon tetrachloride
50 60
60 60 76 80 85 95
Chloroform
100 132 140 60
68 80 Chloroform/acetone m-Cresol 0-Cresol p-Cresol - , a-phenylCumene
60 50 50 60 50 60 60 60
80 100 - , m-bromo-,/7-bromo- , p-tert-butyl-,p-chloroCyclohexane
60 60 60 60 60
80 100
Q36 C, W8 C C, W7 A C Q142 A, X R R, H X C A 15 Q38 Q142 A A A A C C 15 C
A A, 15 15 A A, 15
A A, 15 C F23 15 C A A, 15
412 412 513 513 63 401 113,183 401 128,129,210 401 366 63 223 416 114 529 529 115 568 568 236 236 185 163 63 63 128,129 129 58 501 128,210 255 182 149 185 255 501 247,248 247,248 121 247,248 121 121 7 127 145 406 185 127 145 405 406 406 406 127 79 145 255 119 185 255 273 127 145
Remarks page 11-157; References page 11-159
TABLE 4.
cont'd
Solvent/Additive
T( 0 C)
Styrene (cont'd) Cyclohexane (cont'd) 132 Cyclohexanone •-, trans-lA-, diacetate - , cis/trans-1,4-, dicarboxylic acid dimethylester Cyclopentanone 1-Cyclopentene- 1-carboxylic acid, 3,3,5,5-tetramethyl-4-nitroso-, diester with pyrocatechol Cyclotetrasiloxane, octamethyl1,2,3,4-Dibenzpyrene 1,2,7,8-Dibenztetracene 1,2,9,10-Dibenztetracene p-Dioxane
Diphenylamine-T Disiloxane, hexamethylEpibromohydrine Epichlorohydrine Ethane, 1,2-dibromo-,1,2-dichloro-
60 60 60 60 60 80 50 44.4 44.4 44.4 60 100 60 79.5 60 60 60 80 60 70 80
- , pentaphenyl- , 1,1,2,2-tetrachloro- , l,l,2,2-tetrachloro-l,2-difluoro- , l,l,2-trichloro-l,2,2-trifluoroEthanehexacarboxylic acid, hexaethyl ester 1,1,2-Ethanetricarboxyic acid Ether, benzyl methyl -, p-bromobenzyl methyl - , p-chlorobenzyl methyl -, /7-cyanobenzyl methyl - , dodecyl vinyl Ethyl acetate
Ethyl alcohol Ethylene, 1,1-diphenylEthylene glycol - , bis(m-phenylazobenzoate) Ethyl ether Fluorene Formamide, N,AT-dimethyl-
100 60 100 90 90 50 100 68 68 68 68 60 60 70 75 100 60 80 110 60 80 100 70 60 60 100 40 50 60 100
C 8 (xlO 4 )
Remarks
0.31 12.3 0.81 0.87 1.5 7.90 16.9 4.2 3.30
A A, R A A A, 15 C C C C
235 524 235 127 145 182 569 569 182
1.3 x 104 1.0 x l O 4 4.0 6.0 x 104 13.OxIO 4 13.OxIO 4 0 2.28 2.75 0.8 0.9 0.387 67.48 37.87 0.988 1.914 0.333 4.12 1.1 1.137 9.8 3.84 20000 10.8 1.13 0.84 <50 0.94 6.0 6.0 4.0 20.0 3.32 4.11 15.5 5.5 6.67 0.39 1.32 1.611 2.60 450 1.36 2.70 4.70 900 5.64 75.0 124.0 1.09 0.869 4.0 1.08
F27, J F9, J C J J J A, S C C
314 314 450 159 159 159 128 4 182 220 46 474 529 529 255 255 255 182 67 255 112 235 127 235 14 14 89 72 149 149 149 149 4 4 119 123 123 72 423 479 423 432 422 422 422 281 4 127 127 458 375 113 256
F2 R R C C C C C C A A A A A
C C FlO C C F2 F2 A F24 F24 F24 C C A A E
Refs.
TABLE 4. cont'd Solvent/Additive
T( 0 C)
C s (xlO 4 )
Remarks
Refs.
Styrene (cont'd)
Furan, tetrahydroa, D-Glucoside, methyl- , - , 6-deoxy-6-mercapto- , - , 2,3-di-O-benzyl- , - , 2,3,4,6-tetra-O-acejyl- , -,6-0-(p-toluenesulfbnyl)- , - , 2,3,4-tri-0-acetyl-6-deoxy-6-iodo- , - , 6-0-triphenylmethylP, D-Glucoside, methyl- , - , 6-deoxy-6-dipropylaminoGermane, ethyldichloro- , diethylchloro- , triethyl- , dimethylchloro- , triphenylHeptane
50
0.50
100 100 100 100 100 100
55000 62 2.0 2.0 50 21
1-Heptanol, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro1-Heptene 2-Heptene Hexane 1-Hexene
100 60 60 60 60 60 60 100 60 100 100 100 100
2-Hexene Hydrochloric acid Hydroquinone Hydroxylamine, MW-dibenzyl- , N-benzyl-N-phenyl- , iV,AT-diethylene- , W-ethyl-W-phenylIndium triethyl Iron(III) chloride Isobutyl alcohol
100 100 60 60 60 60 60 100 60 60
Isobutyl alcohol-D
100 130
22 56900 31600 2400 33500 23000 0.42 0.95 13.33 2.7 3.2 0.9 2.5 2.5 3.6 0 3.6 5000 3.8 x 104 2.5 x 104 20.5 x 104 1.760OxIO4 536.0 x 104 0.17 0.497 2.9 7.8 8.2 21.0 2.5 4.6 2.7 3.5 3.5 3.05 4.00 1.7 6.0 2.7 1.6 0.78 1.24 5.2 0.47 0.46 0.42 1.2 700 1200 0.82 1.2 x 104 30.0 62.0 0.88 0.72
Isobutyraldehyde Isobutyric acid
60
Isobutyronitrile
100 130 60 60 80 100
Isophthalic acid, diallyl ester Isopropyl alcohol
Isopropyl alcohol-D Isopropyl-1-D alcohol-D Lead, tetraethyl Malonic acid, diallyl ester - , diethyl ester - , dimethyl ester - , acetyl-, diethyl ester - , bromo-, diethyl ester - , butyl-, diethyl ester - , dibromo-, diethyl ester - , dichloro-, diethyl ester - , diethyl-, diethyl ester - , ethyl-, diethyl ester
130 100 100 100 60 60 100 100 100 60 100 100 60 60 100 100 100
C
449 220 220 220 220 220 220
A, R A, R A, R A, R A, R A A F2 A A A A A, R A A R R R R A A A W8 C A A A F2 F2 A F2 A A A A
A A A A A
220 539 539 539 539 539 127 127 442 358 358 358 358 524 358 238 128 533 533 533 533 156 19 385 479 261 261 412 412 385 385 261 261 446 423 423 261 423 261 261 261 156 446 128 72 72 72 128 128 72 128 128 128 72 72
Remarks page 11-157; References page 11-159
TABLE 4. cont'd Solvent/Addition
J( 0 C)
Styrene (cont'd) Malonic acid, phenyl-, diethyl ester Mercury, diethyl Methane, bis(2-chloroethoxy)- , bromotrichloro-
100 100 80 80
60-80 - , dibromo- , dichloro- , diiodo- , diphenyl- , nitro- , triphenyl-
80 60 60 80 100 60 60 100
Methanetricarboxylic acid Methanol
60 60 80 100 100 60
- , (4-biphenylyl)phenyl(p-vinyl-phenyl)- , bis(4-biphenylyl)(/?-vinyl-phenyl)Naphthalene - , decahydro- , 2-isopropenyl-
80 100 50 50 60 60 80 99
- , 2-methoxy- , 1,2,3,9-tetahydro-l-phenyl1-Naphthol - , 2,4-dichloro1-Naphthol-D 2-Naphthol Naphtho[2,3-a]pyrene 2,6-Octadiene, 2,6-dimethyl2-Octene Oleic acid, methyl ester
60 60 60 60 60 60 44.4 60 100 60
Oxalic acid, diallyl ester - , diethyl ester Oxetane, 3,3-bis(chloromethyl)Oxime, acrolein - , crotonaldehyde- , ethylisopropenylketone- , methacrolein- , methylacrolein- , methylisobutylketone-,methylisopropenylketone-, methylvinylketoneOxolane, ds-3,4-diacetoxyPentane, 1-chloro- , 2,2,4-trimethyl2,4-Pentanedione
70 90 60 60 50 60 60 60 60 60 60 60 60 60 60 100 100
C s (xlO 4 )
3.5 0.335 6.0 7.6 x 104 7.7 x 104 2.4 xlO 6 2.78 x 106 6.5 x 105 (6.5 ±0.4) xlO 5 9450 110 0.15 9.5 11.8 710 2.3 4.2 35 10 3.5 6.0 8.0 0.91 0.296 0.74 1.10 1.22 3.5 3.5 11 0.4 56 70 69 86 <5.0 10000 480 490 75 77 24.0 x 105 2.0 2.8 3.15 3.52 455 420 6.64 4.2 13.5 8.0 10800 1500 4300 13000 400 2300 1100 2700 1.89 0.49 < 10 2.0
Remarks
C D, Q2 D, Q2 D, Q3 D, Q3 15 A C A A A A, R A A F2 F2 F2
A
C J J J C A C C A F22 C
C A A
Refs.
72 156 112 312 195 312 195 439 504 185 112 128 112 128 112 127 127 524 86 127 44 127 72 479 423 423 423 57 57 216 127 98 98 98 98 121 467 50,121 121 50,121 122 159 324 358 441 441 239 141 441 446 119 449 555 555 555 555 555 555 555 555 569 128 155 72
TABLE 4. cont'd Solvent/Additive Styrene (cont'd) 1-Pentanol, 2,2,3,3,4,4,5,5-octa-fluoro3-Pentanone Pentasiloxane, dodecamethyl1-Pentene - , 4,4-dimethyl-2-phenyl- , 2,4-diphenyl- , 4-methyl-2,4-diphenyl- , 4-methyl-2-phenyl- , 2,4,4-triphenyl2-Pentene - , 2-methyl- , 4-methylPhenol -,/7-benzyloxy - , p-tert-buty\- , 0-chloro-,p-chloro- , 2,6-di-terf-butyl- , 2,6-diisopropyl-,p-fluoro-, m-methoxy-, o-methoxy-,/7-methoxy- , 0-phenyl- , 2,3,4,6-tetramethyl- , 2,4,6-trinitroPhenol-D,/7-benzyloxy- , 2,3,4,6-tetramethylPhenyl ether Phosphine, dibutyl - , diethyl - , octyl Phosphine, phenyl - , tributyl Phosphoric acid, tributyl ester Phosphorus, white (P4) Phosphorus trichloride o-Phthalic acid - , bis(2-methylallyl) ester - , diallyl ester - , di-(3,3,5,5-tetramethyl-4-nitrosocyclohexyl) ester Piperidine Propane, l-chloro-2,3-epoxy- , l-chloro-2-methyl - , l,l,l,3-tetrabromo-3-phenyl- , 1,1,1-tribromo1,2-Propanediol 1,3-Propanediol, 2,2-bis(bromomethyl)-, diacetate 1,3-Propanedione, 1,3-diphenyl1-Propene, 3-chloro-2-methyl- , 2-methyl-, 1,3-diphenylPropionaldehyde, diallyl acetal Propionic acid
T( 0 C)
C s (xlO 4 )
60 60 79.5 100 110 110 110 110 110 100 100 100 50 60 60 60 60 60 60 60 60 60 60 60 60 60 50 60 60 25 60 100 100 60 60 100 100 25 57 75
11.36 2.6 0.285 2.3 10 170 2900 10 2600 4.2 6.3 6.9 8.1 14 290 26 6.0 -11 49 310 54 <5 43 260 <5 580 2.1IxIO 5 10 20 7.94 7.86 2.08 x 104 1.35 x 104 3.6 x 104 43.9 x 104 24.4 <0.1 400 250 800
60 60 80 60 50 60 100 90 90 60 80 100 60 60 60 100 60 60 60
6.3 6.3 1.2 x 104 1.32 xlO 4 1.0 7.5 1.4 3.0 3.65 x 104 2.41 x 104 2.08 3.90 6.80 4.05 7.0 24.0 1.7 87.3 12.3 0.05 4.3 4.5 4.65
Remarks F2 A A A A A A A A A A J
J
J J
D
A A, S E C, D
F9, J F27, J A C A A C C F24 F24 F24 A A A A C A
Refs. 442 385 474 358 433 433 433 433 433 358 358 358 247,248 122 50,121 121 122 121 121 121 121 121 122 121 121 50,121 371 50 50 368 368 296 296 295 295 156 156 99 214 494 446 446 314 314 128 449 128 128 64 64 422 422 422 325 128 128 358 567 446 128 385 323 385
Remarks page 11-157; References page 11-159
TABLE 4. cont'd Solvent/Additive Styrene (cont'd) Propionitrile, 3-phosphino- , 3,3'-phophinylidenediPropyl alcohol Propylene oxide 2-Propyn-l-ol Pyridine Pyrocatechol - , p-tert-buty\Pyrocatechol-D - , p-tert-butylPyrogallol Pyrogallol-D Sebacic acid, diallyl ester Silane, chlorotrimethyl- , dichlorodimethyl- , diethylchloro- , dimethylphenyl- , hexamethoxy-(3,3'-thiodipropyl) bis- , methyldichloro- , 3-mercaptopropyl-trimethoxy- , trichloro- , tetraethyl- , tetramethyl- , trichloromethyl- , triethyl- , trimethoxymethyl- , triphenyl-
T( 0 C)
60 60 60 80 100 50 60 60 60 60 60 60 60 60 60 50 50 60 60 79.5 60 79.5 60 100 50 50 60 70 80 79.5
Silicon chloride Siloxane, hexamethyl-di- , dodecamethyl-penta- , octamethyltriSorbit-2,5-diacetate, 1,4:3,6-, dianhydroStannane, triphenylStearamide, Af-allyl-
60 70 80 50 79.5 79.5 79.5 60 60 90
Stearic acid, methyl ester
60
Stibine, tributyl Stibene, dibromoStyrene, oe-bromo- , p-bromo-,dibromo- , a-ethyl- , a-methyl-
70 90 100 60 70 70 60 110 60 74 80 99
Succinic acid, diallyl ester Succinonitrile, tetraphenylSulfonyl chloride, benzene-,/7-chloro-benzene- , p-methyl-benzene-
110 60 50 60 60 60
C s (xlO 4 )
50000 50000 2.00 3.14 3.60 1.6 7.0 0.6 1340 3600 260 370 10400 1600 4.8 12.5 17.8 5700 2200 118 9800 5.9 x 104 1.4 x 104 8.12 3.1 19.2 1200 33.4 36.8 0.23 0.230 3700 2.44 1.3 20.0 0.387 0.285 0.069 77 3.3 x 104 5.82 8.30 1.06 526 15.6 0.676 58.0 3020 10000 2000 1950 10 0.86 95 3.2 4.9 5.6 8.5 1.67 5.4 28000 4330 7650 3180
Remarks
A A F2 F2 F2 C A A J J J
A, R A, R R A, R R A, R
A, R
R A, R
R R R C A, R A, J C, J C A A
R R R
Refs.
295 295 423 423 423 449 128 128 50,121 50,121 50 50 50,121 50 446 249 249 539 539 554 539 554 539 156 249 249 539 90 90 474 554 539 90 90 249 554 554 554 569 539 173 173 441 239 141 441 156 112 172 172 112 439 431 343 98 98 98 98 431 446 89 543 543 543
TABLE 4. cont'd Solvent/Additive Styrene (cont'd) Sulfonyl chloride,/?-methoxy-benzene-,methane- , phenylmethane- , a-phenyl-P-(methanesulfonyl)-ethaneTerephthalamide, NX-dimethyl-MAr'-dinitrosoTerephthalic acid, diallyl ester Tin, tetrabutyl Toluene
T (°) 60 60 60 60 40 60 60 100 60
80
100
-,p-bromo- , m-chloro-,p-chloro- , oc-chloro-, oc,a-dichloro-, p-ethynyl-,(X- 2 Hi, toluene -, PP- 2 H 2 , toluene - , app- 2 H 3 , toluene - , aaa-trichloro- , 2,4,6-trinitro/?-Toluidine - , AW-dimethyl- , Af-methylm-Tolunitrile, a-cyanop-Tolunitrile -,a-cyanos-Triazine, trimethylTriethylamine
Tripropylamine Trisiloxane, octamethylUrea, l,3-bis(3,3,5,5-tetramethyl-4-nitrosocyclohexyl)Water m-Xylene p-Xylene - , ot,a'-dibromo2,6-Xylenol
132 60 60 70 140 60 60 60 60 80 80 80 60 50 50 50 50 60 60 60 60 60
100 79.5 60 80 60 60 60 60 60
C s (xlO 4 ) 3110 1180 3190 27600 1400 2000 4.5 3.71 0.105 0.121 0.125 0.134 0.16 0.21 0.82 1.10 2.05 0.15 0.298 0.3 0.308 0.310 0.313 0.813 0.53 0.55 0.645 0.72 0.8 1.12 1.30 1.25 0.62 1.8 1.07 1.56 50.0 72.0 0.825 0.820 0.992 57.5 14.6 x 104 78 16 11 91.4 2.07 112 0.468 1.4 3.0 7.1 7.5 24.2 0.069 14500 15000 0.006 0.31 0.78 0.84 150 110
Remarks R R R R
C A A, 15 C C 15 C C C, F17 A C A A A, 15 A
A A K C, F17 C, F17 C, F17 A F2 F2 F2
W9 W6
F9, J F9, J A, R
Refs. 543 543 543 543 160 160 446 156 255 21,24,79 127 78 145 318 496 363 363 385 185 385 255 76,77 78,273 530 235 385 127 235 145 235 496 496 67 67 496 128 128 151 530 530 530 128 370,372 154 154 154 462 496 461 88 364 364 24 363,364 156 474 314 314 479 529 496 496 112 121
Remarks page 11-157; References page 11-159
TABLE 4. cont'd Solvent/Additive Styrene {confd) Zinc, diethyl - , p-chloroAnisole, p-isopropylBenzaldehyde -,p-chloroBenzene, p-diisopropyl-
T( 0 C) 100 60 100 100 60
Benzonitrile, p-isopropylCarbon tetrabromide Carbon tetrachloride Cumene -,p-bromo- , p-terf-butyl--, p-chloro- , p-iodoBenzene - , p-methyl Anisole, p-isopropylBenzene, p-diisopropyl-
60 60 60 60 60 60 60
Benzonitrile, p-isopropylCumene -,p-bromo- , p-terf-butyl-,p-chloro- , pentafluoroBenzene, bromo- , chloro-,ethyl- , fluoro2-Butanone, 3-methylCumene Furan, tetrahydro-
60 60 60 60 60
2-Pentanone, 4-methylToluene Styrene/Styrene, p-chloroCarbon tetrachloride
60 60
Succinimide, N-vinylAcetic acid Ethane, 1,2-dichloroValeric acid, 4-methyl-, vinyl ester Benzene Vinyl acetate Acetaldehyde
Acetamide, N-butylAcetic acid
C s (xlO 4 )
Remarks
3660 3.86 1.9 9.7 3.62 7.24 8.84 52000 45 3.44 5.71 3.52 4.97
Refs. 156
A A
F2
406 298 298 497 406 406 109 366 406 406 406 406
50
0.2
56
60 60
3.27 3.67 7.34 26.0 4.12 9.23 3.59 7.67
408 408 406 408 408 408 408 408
60 60 60 60 60 60 60
60
0 0 5.35 0.117 1.09 6.76 1.53 1.61 0.033 1.20 15 115
55 55
0.077 0.127
80
6.2
30 45 50 60
400 530 390 0.72 200 220 500 570 660 610 700 40 0.180 0.166 0.200 1.0 1.13 10 0.170
70 75 60 50 60
65
A
EF EE C, F25 C, F26
469 469 469 469 469 469 469 469 469 469 366 366 93 93 201
J 18 F2 J J C 19 F2 C
346 86 460 257 145 232 460 86 86 460 86 86 466 465 466 145 289 86 466
TABLE 4. cont'd Solvent/Additive Vinyl acetate (cont'd) Acetic acid, allyl ester - , benzyl ester - , butyl ester - , sec-butyl ester - , tert-butyl ester - , isobutyl ester - , isopropyl ester
- , methyl ester - , propyl ester - , 1,3,3,3-tetrachloropropyl ester - , bromo- , chloro- , cyano-, methyl ester - , dichloro-, ethyl ester - , phenyl- , trichloro- , ethyl ester - , trifluoro-, ethyl ester Acetic anhydride Acetoacetic acid, ethyl ester Acetone
Acetonitrile -,phenylAcetophenone - , 3'-hydroxy- , 3'-hydroxy-DAniline - , AW-dimethyl- , W-methyl-,p-nitrom-Anisaldehyde o-Anisaldehyde /7-Anisaldehyde Anisole Anthracene
- , 9-phenylBenzaldehyde
T( 0 C)
60 60 50 50 60 50 60 50 50 60 67.5 75 60 50 60 70 60 70 70 60 60 60 70 60 50 60 70 60 70 75 60 60 50 60 70 45 45 50 50 50 50 60 60 60 60 20 30 40 50 60 50 60 70 75
C s (xlO 4 )
85 94 80 13.2 4.4 8.0 1.5 6.2 9.1 3.5 3.1 8.0 9.0 10 1.56 1.6 2.5 6.2 3.4 423.2 489 4450 2550 5000 210 400 1445 4400 30 8.0 80.4 1.5 11.70 12.0 25.6 42 10 2100 91.5 100 62.0 1405 1290 149 210 260 360 48600 2500 420 370 10 6.68 x 105 6.03 x l O 5 4.55 x 105 2.057 x 105 3.64 x 105 2.78 x 105 2.73 x 105 230 460 540 421 600
Remarks
F2 J F2, J
J J
C C, J C C J J C C C
C C J J C J J F2 F2 F2 J J J F2, J J J J J J J J F2 J C,J J
Refs.
86 86 86 208 208 86 208 232 208 208 145,232 86 86 86 145,231 145,232 86 208 145,232 389 386 389 389 86 86 86 389 86 71 86 390 86 289 145 330 184 86 86 15 86 390 51 51 15 154 154 154 15 86 86 86 86 41 41 41 15 41 41 41 145,355 86 86 390 86
Remarks page 11-157; References page 11-159
TABLE 4. cont'd T( 0 C)
Solvent/Additive Vinyl acetate (cont'd) Benzaldehyde, m-chloro- , o-chloro-,p-chloro-, - , p-cyano-,/7-isopropylBenz[A]anthracene Benzene
ra-cyano-
60 60 60 60 60 60 50 60
70 75 - , bromo-
- , tert-butyl- , chloro-
Benzene, o-dichloro-,/7-dichloro- , m-dinitro- , 0-dinitro - , p-dinitro-,ethyl- , nitro- , 1,3,5-trinitroBenzo[B]chrysene Benzoic acid - , ethyl ester -,p-nitroBenzoic anhydride Benzoin Benzonitrile - , m-hydroxy- , m-hydroxy-DBenzo[GHI]perylene Benzophenone Benzo[A]pyrene Benzo[E]pyrene p-Benzoquinone, 2,3,5,6-tetramethylBenzoyl chloride Benzyl alcohol Biphenyl Borane, tributyl
50 60 70 75 60 60
70 75 75 70 45 50 45 45 50 60 50 45 50 50 60 60 50 60 60 50 45 45 50 50 50 50 45 50 70 70 50 60 10
C s (xlO 4 )
860 390 340 1070 610 540 1.17 xlO 5 1.07 1.2 1.2 2.4 2.96 20 5.27 1.4 1.40 3.6 18.9 8.0 9.2 10.0 134.2 25.2 3.61 5.6 6.8 8.0 8.35 80 2.61 12.7 42 11.8 1.05 x 106 645700 9.6 x 105 26.7 x 105 662800 55.15 100 110300 8.9 x 106 434280 2.83 x 105 50 26 245700 130 800 40.6 820 805 1.82 xlO 4 286 3.06 x 105 8400 9.5 x 105 366 300 556 263 6.4 9000
Remarks
J J J J J J J J C C J C W7 W15 C C W7 W15 J C C C C C, J C, J C, J J C, J J J J J J J J J J J J C C
Refs.
86 86 86 86 86 86 41 263 86 294 80 289 294 390 86 263 184 15 265 265 265 389 184 289 265 265 265 289 86 389 184 184 389 28 15 28 28 15 289 86 15 28 15 41 86 86 15 86 86 15 51 51 370 15 41 370 27 15 389 390 15 132 191
TABLE 4. cont'd Solvent/Additive Vinyl acetate (cont'd) Butane, 1-bromo- , 1-chloro- , 1-iodo2,3-Butanedione 2-Butanone -, 3-methyl1-Butene, 3-chloro-3-methyl2-Butene, l-chloro-3-methyll-Buten-3-yne Butyl alcohol sec-Butyl alcohol tert-Butyl alcohol
Butyl ether 3-Butyn-2-ol, 2-methylButyraldehyde
T( 0 C)
60 70 60 60 60 60 75 60 50 50 60 60 70 60 70 75 60 70 60 60 40
60 Butyric acid, ethyl ester - , methyl ester
70 50 60
Carbon tetrabromide
60 70
Carbon tetrachloride
0 20 45 60
Chloral
Chloral hydrate Chloroform
2-Chloro-3-(methyl-14C)-lbutene(4-14C) 3-Chloro-2-pentene-(2,4-14C)
70 75 60 70
70 30 60
70 50 50
C s (xlO 4 )
50 1100 10 800 670 73.80 165 118.16 28900 4300 0 20.0 20.39 29.1 31.74 6.21 95.0 0.46 0.5 1.3 12.1 76 400 440 510 590 670 650 1000 388 45 18 19 7.39 x 106 28740 1500 4700 7600 800 1300 4700 6700 7300 8000 9000 9600 10000 10500 10700 2023 10500 5000 4927
4312 100 140 125.18 130 150 160 170 554 3980 628
Remarks
C F2, J C F2 F2 J 19 C C C 19 C,J J W8 W7 W15
C C F2 C E J Ql Q2 Q3 Q4 F2 Q5 Q6 J Q7 Q8 C J C
C
19 J F2 C F2 F2
Refs.
86 389 86 86 86 289 184 289 152 152 232 145 289 390 289 390 184 289 145 86 390 86 86 500 500 500 500 232,355 86 390 71 145,232 86 109,145 389 346 309 86 10 10 10 10 86 10 10 86 210 10 10 389 86 86 389
389 345 346 289 145 86 210 86 389 509 509
Remarks page II-157; References page 11-159
TABLE 4. cont'd Solvent/Additive Vinyl acetate (cont'd) Chrysene w-Cresol m-Cresol-D p-Cresol p-Cresol-D Crotonaldehyde Cumene
Cyclohexane
T( 0 C)
50 45 45 45 45 60 60 70 75 60
-,methyl-
60
1,3-Cyclohexanedione, 5,5-dimethylCyclohexanol Cyclohexanone
70 70 60 75 60
Cyclohexene Dibenz[a,h]anthracene Dibenzo[def,mno]chrysene 1,2,3,4-Dibenzpyrene Diethylene glycol Diethylphosphonate
p-Dioxane Diphenylamine Diphenylamine-D Diphenylamine-T Ethane, 1,1-dibromo- , 1,2-dibromo- , 1,1-dichloro- , 1,2-dichloro-, -, -, -, -,
75 50 40 50 60 50 70 60 60 60 60 60 70 50 60 60 60 60 70 60 60
1,2-dichlorohexachloropentachloro1,1,2,2-tetrabromo1,1,2,2-tetrachloro-
70 70 70 60 60
- , 1,1,1-trichloro- , 1,1,2-trichloro1,1-Ethanediol, diacetate Ether, benzyl methyl - , bis(2-chloroethyl) - , dodecyl vinyl
70 60 60 60 60 70 60
-,ethyl Ethyl acetate
60 20 40 50 60
C s (xlO 4 )
3360 375 85 710 130 1800 89.9 100 139 356 6.59 7.0 100 11.75 24 5580 127 180 670 620 1600 770 8.7 x 104 156.5 x 104 129.2 xlO 4 105.4 xlO 4 73.6 x 104 85.3 350 910 830 730 20 49.1 138 240 170 230 1100 134 65 5 7 7.18 10.2 1210 1348 6000 107.03 160 67.72 71.11 35.98 40 280 245 57.2 73.5 45.3 1.52 2.11 2.9 12 1.07
Remarks
J J J J J J C C 19 F2 C C F2 C J F2 J J J J J J C Fl F2 F2 F2 F2 C
C 19 C C C
C
F2, J C C C C
C
Refs.
370 51 61 51 51 355 289 7,86 390 184 289 145 86 289 86 390 390 86 184 86 86 86 370 41 41 41 41 390 571 571 571 571 86 390 15 46 46 46 86 389 86 86 145 289 389 389 389 86 289 86 389 289 289 86 86 389 4 4 4 328 328 208 71 289
TABLE 4. cont'd Solvent/Additive
T( 0 C)
Vinyl acetate (cont'd) Ethyl acetate (cont'd)
Ethyl alcohol Ethylene, tetrabromo- , tetrachloro- , tribromo- , trichloroEthylene glycol Fluorene - , 9-phenylFormamide, N9N, -dimethylFormic acid, ethyl ester - , methyl ester 2-Furaldehyde Furfuryl alcohol Germane, diethylchloro- , dimethylchloro- , triethyl-,triphenylGlycolic acid, methyl ester Heptane 1-Heptanol, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluorol,5-Hexadien-3-yne Hexanoic acid, 2-ethyl-, ethyl ester Hydroquinone - , 2,5-di-terf-butyl- , 2,6-dimethyl- , tetramethylIsobutyl alcohol Isobutyric acid Isobutyric acid, ethyl ester -, methyl ester Isobutyronitrile Isopropyl alcohol Lactic acid, ethyl ester -, methyl ester Laurie acid, ethyl ester Malonic acid, dimethyl ester /?-Mentha-l,8-dene Mesitol Methane, bromotrichloro-
- , dichloro- , iodo- , nitro-,tribromo- , triphenylMethanol
C s (xlO 4 ) 1.25
70 60 70 70 70 70 70 70 60 70 70 60 50 60 60 70 60 60 60 60 60 50 60 60 50 50 50 50 50 60 70 60 50 60 60 70 60 60 50 60 60 50 25 60 70 60 70 60 75 70 60 10 60
2.6 2.96 3.3 3.4 7.8 25 26.3 2800 465 34720 3810 83.0 4700 3610 16240 50 22 3 15000 2520 7800 86600 4500 56000 300 17.0 33.3 0 65 7000 38000 29000 74000 21.75 32.4 5.02 160 58 71 86 100 44.6 700 640 105 17 1900 5000 > 104 6000 >4xlO5 6303 4 1230 2300 2600 34760 700 9.0 10.0 10.5 3.4 2.26
Remarks
C
C F2 C C C C C C, J J C,J C C J C, J A, R A, R A, R A, R F2 C J J J J C C
C C J J D, S C C C C F2, J J C
Refs.
80
145,232 328 86 420 390 86 390 389 389 389 389 390 86 390 390 86 71 86 86 390 539 539 539 539 86 208 442 232 71 338 338 338 338 289 390 289 71 145,232 420 86 86 390 86 86 71 86 86 338 39 39 39 389 86 389 86 86 389 45 5 5 5 190 145,231
Remarks page II-157; References page 11-159
TABLE 4. cont'd Solvent/Additive
T (0C)
Vinyl acetate (cont'd) Methanol (cont'd) Naphthacene Naphthalene
70 50 50
- , decahydroNaphtho[l,2,3,4-def]chrysene Nonanoic acid, ethyl ester 2,6-Octadiene, 2,7-dichloro- , 2,6-dimethyl-
70 60 50 50 50 60
Octanoic acid, ethyl ester Oleic acid, methyl ester
50 60
Oxalic acid, diethyl ester - , dimethyl ester
90 30 60 60
Paraldehyde Pentane, 2,2,4-trimethyl2,4-Pentanedione 1-Pentanol, n 2,2,3,3,4,4,5,5-octafluoro2-Pentanone, 4-methyl3-Pentanone
70 50 60 60 60 60
Pentyl acetate
70 75 75 50 50
Orthoformic acid, trimethyl ester
Pentyl alcohol Perylene Phenanthrene
Phenol
70 45 50 60
- , m-chloro-,p-chloro- , p-nitro- , 2,3,4,6-tetramethylPhenol-D -,m-chloro-,p-chloro-,2,3,4,6-tetramethylPhosphorus trichloride Propane, 2-bromo-2-methyl- , 2-chloro-2-methyl 1-Propanol, 2,2,3,3-tetrafluoro1-Propene, 3-chloro- , 3-chloro-2-methylPropionaldehyde
45 45 50 45 45 45 45 45 60 60 60 60 60 60 60
Propionic acid, ethyl ester - , methyl ester
70 50 60
Pyrene Pyrocatechol, 4-(l,l,3,3,-tetramethylbutyl)Pyrogallol Salicylic acid Silane, dimethylphenyl-
50 50 50 70 60
C s (xlO 4 )
4.3 6.0 5.5 8.62 x 106 1150 1457 1715 48 1.35 x 105 80 3200 430 700 70 217 1000 358 7.6 8.0 4.0 1.0 2.0 136 8.0 10 26.1 34.52 10.0 114.39 7.2 87.0 56 2.88 x 105 870 5600
3380 215 120 600 205 400 8.86 x 104 1.13 x 104 35 70 80 800 1.5 x 104 150 26 7.11 3100 400 950 1000 457 40 23 26 11500 11000 50000 296 2200
Remarks
J J C,J J C F2 C J
C F2 19 C C C J J
C,J J J J J J J J J J C, D F2 J J F2 C C J J J C A, R
Refs.
320 86 320 370 370 15 390 86 41 71 152 324 7 71 441 86 441 345 346 86 86 145,232 390 208 86 442 289 145 289 390 184 184 41 370 15
390 51 15 86 51 51 15 51 51 51 51 51 214 86 86 442 86 86 86 86 390 71 232 420 370 338 338 390 539
TABLE 4. cont'd Solvent/Additive Vinyl acetate (cont'd) Silane, methyldichloro- , trichloro- , triethyl- , triphenylStearamide, N-allylStearic acid, ehtyl ester - , methyl ester Succinic acid, diethyl ester - , dihexyl ester - , dimethyl ester m-Tolualdehyde p-Tolualdehyde Toluene
T( 0 C)
60 60 60 60 90 50 60 60 60 60 60 60
75 80 50 70 70 60 70 75 50 50 50 50 50 50 60 50 60 50 70 75 60 60 60
280 290 400000
Q(3) Q(3) Q(3)
511 511 511
50 60
20 20
R R
541 541
60 60 60 60 60
5400 8600 12000 2000 4000
A, R A, R A, R A, R A, R
539 539 539 539 539
C, Q(I-2)
572
60 70
Triphenylene Veratraldeyhyde Xylene Vinyl chloride Carbon tetrachloride Chloroform Bromotrichloromethane Vinylidene chloride Af-Methylpyrolidone 2-Vinylpyridine Silane, diethylchloro- , Methyldichloro-,trichloro-,triethyl-,triphenylVinyltrimethylsilane Bromoform
Refs.
A, R A, R A, R A, R C, J C
60
Toluene, p-nitrop-Toluidine -, N,Ar-dimethyl-, AT-methylToluonitrile Triethylamine
Remarks
5800 8800 1200 2700 620.1 140 38.2 41 40 31 570 440 3.3 12.0 14.9 100 123 17.8 20.75 20.89 21.6 34 35 49.0 69.0 21.1 21.8 29.2 66 91.6 20.6 92.86 195 450 584 118 106300 750 380 830 38.3 360 370 160 550 14.9 278 166
50
- , bromo- , o-chloro-,p-chloro- , a-chloro-
C s (xlO 4 )
1200000
J J R C R C J F2 W15 R C C C C J C C F2 F2 F2 F2 J J J C C
539 539 539 539 173 71 441 420 420 420 86 86 158 15 357 71 71 357 80 21,59,289 357 86 86 265 265 357 390 357 184 273 15 389 389 86 389 184 15 154 154 154 15 154 24,145 370 86 15 390 184
Remarks page 11-157; References page 11-159
TABLE 5. TRANSFER CONSTANTS TO SULFUR COMPOUNDS Modifier Acrylamide, A/-octadecyl-/acrylonitrile (1:1 mol ratio) 1-Dodecanethiol Acrylic acid 1-Dodecanethiol - , methyl ester 1-Butanethiol
J( 0 C)
Cx
Remarks
Refs.
60
0.539
C, F24
174
45
1.9
C, F31
549
Ethanethiol
30 60 50
2-Propanethiol
60
1.53 1.69 0.78 0.94 ±0.07 1.65 ±0.12 1.57 ±0.09 1.57 ±0.18 1.79 5.00 0.544 0.668 0.700 0.656
A A Ql Ql Q2 Q3 Q4 Q2 Q3 Ql Q2 Q3 Q4
Acrylonitrile 1-Dodecanethiol Hydrogen sulfide Methyl sulfoxide
Methyl tetrasulfide p-Toluenethiol Acrylonitrile/1,3-butadiene (10-90%) 1-Hexanethiol, - , 1,1,3,3,5,5-hexamethyl1-Pentanethiol, - , 1,1,3,3-tetramethylAcrylonitrile/1,3-butadiene (20-80%) 1-Hexanethiol - , 1,1,3,3,5,5-hexamethyl1-Pentanethiol - , 1,1,3,3-tetramethylAcrylonitrile/1,3-butadiene (30-70%) 1-Hexanethiol - , 1,1,3,3,5,5-hexamethyl1-Pentanethiol - , 1,1,3,3-tetramethylAcrylonitrile/styrene (38.5-61.5 mol%) 1-Pentanethiol - , 1,1,3,3,4-pentamethylButadiene Xanthogendisulfide, dibutyl- , diethyl- , di-2-ethylhexyl- , di-isopropyl1,3-Butadiene 1-Butanethiol, 1,1,3,3-tetramethyl1-Octanethiol - , 1,1,3,3,5,5,7,7-octamethyl1-Tetradecanethiol 1,3-Butadiene/styrene 1-Dodecanethiol Formic acid, thio-, dithiobis_, _, _, ao'-dibutyl ester
50 50 20 30 40 50 80 50 5
0.73 0.13 0.1 0.47 0.0000812 0.11 0.29 0.795 0.69 0.97
C, F8 E
J
397 69,397 330 478,507 478,507 508 330,509 330 330 477 477 477 477 378 378 248 196 458 404 197 375 85 378
1.5
C, H
380
53.3
C, H
380
5
1.2
C, H
380
5
2.1
C, H
380
5
1.1
C, H
380
5
1.8
C, H
380
50
1.02
C, H
380
60 60 60 60
6.9 8.1 7.5 8.3
J J J J
532 532 532 532
5 50 5 50
5.3 3.7 21.8 16.0 19.0 3.0 19.5
H H H H H H H
242 242 242 242 243 242 242
50 50 5
0.66
B, H, J
384
5
2.42
B, H, J
383
TABLE 5. cont'd Modifier
T( 0 C)
1,3-Butadiene/styrene {cont'd)
- , - , ao'-diisopentyl ester
-5 50 5 -5 5 50 5 -5 50 5 50 5 50 5 -5 50 5
- , - , - , 0,O'-diisopropyl ester
-5 50 5
- , - , - , O,O'-di-sec-butyl ester - , - , - 0,O'-dicyclohexyl ester _, _, _, 0,0'-diethyl ester - , - , - , 0,O'-diheptyl ester - , - , - , 0,6>'-dihexyl ester - , - , - , 0,O'-diisobutyl ester
- , - , - , 0,O'-dimethyl ester - , - , - , 0,O'-dineopentyl ester - , - , - , 0,0'-dioctyl ester - , - , - , 0,O'-dipentyl ester - , - , - , 0,0'-dipropyl ester 1-Heptanethiol - , 1,1,3,3,5,5,6-heptamethyl1-Hexanethiol - , 1,1,3,3,5,5-hexamethyl1-Octanethiol - , 1,1,3,5,5,7,7-octamethyl/7-Dioxin, 2,3-dihydro/maleic anhydride 1-Butanethil Ethylene 1-Butanethiol Ethyl sulflde Methyl sulfoxide 2-Propanethiol, 2-methylSulfur hexafluoride Methyl methacrylate Acetic acid, dithiodi-, diethyl ester - , mercapto-, methyl ester Acetophenone, 3'-mercapto- , 4'-mercapto-
-5 50 5 -5 50 5 50 5 50 5 -5 50 5 -5 50
Cx 1.75 5.34 1.65 1.565 1.78 3.71 8.43 4.23 16.04 0.41 1.12 0.74 1.78 1.87 1.573 6.43 1.21 7.0 1.85 4.38 2.83 3.4 12.5 0.40-1.31 0.80-3.01 1.40-3.70 1.80-3.50 1.80-6.0 9.78 1.185 9.78 16.43 15.86 27.04 1.01 3.40 0.23 0.64 1.45 1.70 3.20 4.42 1.815 9.20
Remarks H C, H, J B, H, J H B, H, J C, H, J B, H, J H C, H, J B, H, J C, H, J B, H, J C, H, J B, H, J H C, H, J B, H, J B, H, J H C, H, J B, H, J B, H, J B, H B, H, J, B, H, J, B, H, J, B, H, J, B, H, J,
Refs. 180 382
H C, H, J B, H, J H C, H, J B, H, J C, H, J B, H, J C, H, J B, H, J H C, H, J B, H, J H C, H, J
180 383 383 383 180 382 383 382 383 382 383 180 382 383 341 180 382 383 341 100 100 100 100 100 100 179 180 382 383 180 382 383 382 383 382 383 180 382 383 180 382
GG4 GG3 GG2 GGl GG5
5
0.64
B, H, J
384
5
1.22 4.1 2.7-4.7
B, H, J H H
384 54,55 54
5
0.34
B, H, J
384
R
169
C, W5 C, W5 C, F21, W5 C, W5 C, F21, W5
457 454 259 457 259
60 130 130 130 130 130 60 60 45 45
6300 5.8 0.027 12 15.0 0.0000 0.00065 0.63 4.2 2.6
86 274 30 30
Remarks page II-157; References page 11-159
TABLE 5. cont'd Modifier Methyl methacrylate {cont'd) Anisole, 4,4'-dithiodip-Anisoyl disulfide Benzenesulfonic acid - , compound with pyridine - , thio-, S-phenyl ester Benzenethiol - , m-bromo- , /7-bromo- , m-chloro-,p-chloroBenzoyl disulfide Benzyl disulfide Benzyl sulfide
J( 0 C) 50 60 60
0.0044 0.0052 14.6
60 60 45 60 70 45 45 45 45 60 25 50 60 25 50
0.00365 0.0196 4.7 2.7 15 3.8 5.6 3.5 4.6 10.0 0.134 0.016 0.00627 0.0183 0.0098 0.0098 0.00154 0.0040 0.0039 0.084 0.021 0.66 0.67 0.008 0.22 0.09 0.35 0.33 0.21 0.13 0.55 0.00007 0.00258 16.7 0.0046 0.0098 10.0 0.0072 0.0117 290 0.0115 694 0.0176 0.0508 0.0127 0.0193 0.7 0.55 0.42 0.33 0.17 0.15 0.43 0.62 0.40 0.00013
Benzyl sulfone Benzyl sulfoxide Benzyl tetrasulfide Benzyl trisulfide 1-Butanethiol
60 50 50 50 50 60
Carbanilide, thio-
50
_, _, 4,4/-bis(dimethylamino)- , - , 4,4'-dichloro- , - , 3,3/-dimethoxy-, -, 3,3'-dimethyl- , -, 4,4'-dimethyl- , - , 3,3'-dinitroCarbon disulfide 2,13-Dioxa-7,8-dithia-3,12-disila-tetradecane, 3,3,12,12-tetrameth oxyDisulfide, bis(p-bromobenzoyl)- , bis (p-bromophenyl)-
50 50 50 50 50 50 60 79.5 60 50 60 60 50 60 60 70 60 50 60 50 60 60 70 80 90 50 70 50 60 70 60
- , bis(p-chlorobenzoyl)- , bis(p-chlorophenyl)-, -, -, -,
bis(p-cyanobenzoyl)bis(dimethylthiocarbamoyl)bis(p-nitrobenzoyl)bis(onitrophenyl)-
- , bis(/?-nitrophenyl)1-Dodecanethiol
Ethanethiol, 2-amino-, hydrochloride Ethanol, 2-mercaptoEthyl disulfide Formamidine, A^Af'-diphenyl- , - , U'-dithiobisMethyl sufoxide
Cx
50 60
0.22 0.0000071
Remarks
Refs. 285 285 369
A
F2 D F2
F2, J F2, J A F2 C, F2 C, F2 C, F2 C, F2 C, F2 C, F2 C, F2 A
F7 F7 F2 F2 C, F2 A
490 491 30 274 566 30 30 30 30 369 368 354 368 368 252 354 368 252 252 354 354 274 69,397 251 251 251 251 251 251 251 251 288 474 369 285 285 369 285 285 369 104 369 285 285 285 285 573 573 573 573 473 473 473 274 473 310 251 438
TABLE 5. cont'd Modifier Methyl methacrylate (cont'd) 2-Naphthalenethiol 1-Penthanethiol Phenyl disulfide
Phenyl disufone Phenyl sulfide Phenyl sulfone Phenyl sulfoxide 1-Propanethiol, 3-[l,3,3,3-tetramethyl-l-(trimethylsiloxy)disiloxanyl]- , 3-(trimethoxy)2-Propanethiol - , 2-methylPropionic acid, 3-mercaptoSulfide, benzoyl dimethylthiocarbamoyl Sulfur Thiosulfuric acid, S-butyl ester - , - , sodium salt - , S-isopropyl ester - , - , sodium salt - , S-phenyl ester - , - , compound with pyridine - , - , potassium salt - , S-propyl ester - , - , sodium salt m-Toluenethiol p-Toluenethiol a-Toluenethiol p-Toluoyl disulfide p-Tolyl disulfide Styrene Acetic acid, dithiodi-, -, -, -, -, -,
-, -, -, -, -, -,
diethyl ester dimethyl ester mercaptobutyl ester ethyl ester methyl ester
- , phenyl- , - , /?,/?'-dithiodi- , thio Aniline, 2,2' dithiodi-
-, 4,4'-dithiodi- , N-dodecyl-, 4,4'-dithiodiAnisole, 2,2'-dithiodi- , 4,4'-dithiodi- , p-methyl-, a,a'-dithiobis-
T( 0 C) 45 60 50 25 50 60
Cx
Remarks
Refs.
60 25 50 60 50 50 79.5 79.5 60 60 50 70 20 60 44.1 50
1.3 3.1 0.8 0.0174 0.0038 0.0007 0.00176 0.0085 0.0110 0.0003 0.00554 0.0064 0.00132 0.0006 0.0013 0.128 0.693 0.38 0.18 0.39 0.38 5.5 0.08 1.3 0.075 0.106
60
0.00226
490
60
0.00167
490
60 60
0.374 0.00537
490 490
60 45 45 50 60 50 60
0.00190 4.7 7.4 0.027 11.0 0.0031 0.0044
490 30 30 354 369 285 285
50 99 60 99 99 50 60 60 99
< 0.005 0.2 0.015 0.1 >14.0 26.0 58.0 0.63 27.6
50 99 25 50
0.24 >14.7 3.8 3.0 3.4 3.0 0.24 0.21 3.0 0.18 0.021
75 50 50 50 50 99
H D
A A D
F2 F2 D A C F2, J
F2, J
J, R A A
J
30 274 344 368 285 310 368 285 491 491 368 252 368 252 252 474 474 274 274 473 473 280 280 118 194 354
297 96 86 96 96 146 126 323 96 89 96 297 297 297 297 89 89 89 89 96
Remarks page 11-157; References page 11-159
TABLE 5. cont'd Modifier Styrene {cont'd) /7-Anisoyl disulfide Anthranilic acid, 4,4'-dithiobisArylbenzene thiolsulfonate - , /?-chloro - , p-methoxy- , p-methylBenzenesulfonic acid - , compound with pyridine - , thio-, S-phenyl ester Benzenethiol - , o-ethoxy-,p-ethoxyBenzene thiosulfonate - , aryl-p-chloro- , aryl-p-methoxy- , aryl-p-methyl 2-Benzimidazolethiol Benzoic acid, 2,2/-dithiodi- , - , diethyl ester - , -,dimethyl ester -, 4,4'-dithiodi- , - , diethyl ester - , o-mercapto- , -, methyl ester -,thioBenzothiazole, 2,2/-dithiobis-
- , 2,2'-thiobis2-Benzothiazolethiol Benzo[B]thiophene, 4,5,6,7-tetrahydro-4(2-thienyl)Benzoyl disulfide
Benzyl alcohol, ^o'-dithiobis-,/vAdithiobisBenzyl diselenide Benzyl disulfide
T( 0 C) 60 50 60 60 60 60
96.0 3.0 0.95 2.22 1.872 1.237
60 50 60 99 99 99
0.00617 1.60 1.67 0.08 25.1 0.13
60 60 60 99 50 50 99 50
2.597 1.475 1.099 0.21 0.01 < 0.005 0.2 0.11 0.17 0.11 >14.7 17.0 6.23 2.3 2.1 2.3 2.4 2.73 < 0.005 0.03 0.26 0.011 < 0.005 0.010 0.0107 36.0 0.11 0.58 0.09 2.0 0.02 0.03 0.00878 0.01 0.011 0.548 0.069 0.00335 0.052 0.051 5.4 13.2 21.0 22.0 25 15.0 17.0 15.4
50 99 99 99 25 50 75 99 50 50 99 60 50 60 99 50 50 60 50 60
Benzyl sulfide Benzyl sulfone Benzyl sulfoxide 1-Butanethiol
Cx
99 25 50 60 50 50 25 60
70 80 99
Remarks
R, F2 R, F2 R, F2 R, F2 A A
R, F2 R, F2 R, F2
J
A
A D
D, Ql D A A A A
Refs. 369 89 544 544 544 544 490 491 491 96 96 96 544 544 544 96 89 89 96 297 89 89,297 96 96 96 297 297 297 297 96 297 297 96 419 89 545 304 369 96 89 297 128 89 297 368 128 96 368 252 368 252 252 340 340 395 69,397 131 395 395 96
TABLE 5. cont'd Modifier Styrene (cont'd) 1-Butanethiol, 1,1,3,3-tetramethyl-
1-Butanethiol-D
Butyl disulfide
sec-Butyl disulfide tert-Butyl disulfide Butyl sulfide tert-Butyl sulfide Carbanilic acid, /?,/?'-dithiodi-diethyl ester Carbon disulfide Carbonic acid, dithio- , - , S,S'-bis(carboxymethyl)ester - , trithio- , - , S,S'-bis(carboxymethyl) ester 1-Decanethiol 2,13-Dioxa-7,8-dithia-3,12-disilatetradecane, 3,3,12,12-tetramethoxyDiphenyldisulfide Disulfide, bis(/?-bromobenzoyl) - , bis(a-bromo-o-tolyl) - , bis(/?-chlorobenzoyl) - , bis(chlorobenzyl) - , bis(2-chloroethyl) - , bis(a-chloro-o-tolyl) - , bis(>-cyanobenzoyl) - , bis(diethylthiocarbamoyl) - , bis(dimethylthiocarbamoyl)
T( 0 C)
5 50 60 70 80 25 55 60 99 150 50 50 60 60 60 50 60 50 50 80 80 79.5 60 60 50 60 50 50 50 60 60 60 70 80 95 115 130
- , bis(2-ethylhexyl) - , bis(A^ethyl-A^phenylthio-carbamoyl) - , bis(l-methylheptyl) - , bis(morpholinothiocarbonyl) - , bis(l-naphthylmethyl) - , bis(/?-nitrobenzoyl - , bis(o-nitrophenyl) - , bis(l-phenylethyl) - , bis(P-(2-pyridyl)ethyl) - , bis(2,3,5,6-tetramethylphenyl) - , bis(2,4,6-triisopropylphenyl) 1-Dodecanethiol
50 60 99 60 99 60 50 50 50 50 50 60 70 70 90 100 110
Cx
5.5 6.4 4.3 5.2 4.0 7.0 0.00079 0.00154 0.0024 0.0068 0.022 < 0.005 < 0.005 0.00014 0.0022 0.025 0.24 0.00066
Remarks
H H H A A A
A
A
0.36 0.21 4.3 4.2 0.0118 0.147 745 1.0 196 < 0.005 0.01 1.3 3190 0.724 1.11 0.0136 0.568 0.620 0.780 0.860 0.939 1.035 0.984 1.150 < 0.005 1.75 0.0104 6.1 0.033 6650 <0.005 0.03 0.73 0.12 14.8 19.0 19 0.69 1.3 13.0 26.0
Refs.
242 222 242 395 395 395 448 448 304 96 359 89 89 304 304 304 89 288 297
C3, H C3, H
J
J J J
A
C3, H C3, H
297 574 574 474 546 369 297 369 297 297 297 369 286 286 104 40 481 481 40 40 481 40 481 297 286 96 286 96 369 89 89 297 297 89 69,126 59 562 574 574 156 156
Remarks page II-157; References page 11-159
TABLE 5. cont'd Modifier Styrene (cont'd) terf-Dodecanethiol Ethanethiol Ethanol, 2,2'-dithiodi- , - , di(chloroacetate) Ether, ethyl 3-mercaptopropyl Ethyl disulfide Formamidine, AW-diphenyl-, l,l'-dithiobisFormic acid, thio-, dithiobis, 0,0'-diisopropyl ester 1-Heptanethiol 1-Hexanethiol - , 1,1,3,3,5,5-hexamethylHexyl disulfide Hydrogen sulflde Isobutyl disulfide Isopropyl disulfide Lauryl disulfide Lepidine, 2,2-dithiodiMesityl disulfide Methyl disulfide Methyl sulfoxide
T( 0 C)
70 90 90 50 50 50 60 100 99 50 50 99 99 99 25 50 75 99 70 60 60 60 50 50 60 40 50
60 Morpholine, 4,4'-dithiodi1-Naphthalenemethanethiol
1-Naphthalenethiol 2-Naphthalenethiol 1-Naphthoyl disulfide 1-Naphthyl disulfide 2-Naphthyl disulfide
1-Octadecanethiol Octadecyl disulfide 1-Octanethiol - , 1,1,3,3,5,5,7,7-octamethyl2-Octanethiol 1,4,5-Oxadithiepane 1-Pentanethiol Phenetole, 2,2'-dithiodi- , 4,4'-dithiodiPhenyl disulfide
50 25 50 75 99 99 99 50 99 25 50 75 99 99 99 5 50 50 99 150 50 99 99 50 60
Phenyl disulfone Phenyl sulfide
50 60 25 50 60
Cx
1.5 1.5 1.6 17.1 < 0.005 <0.005 14.1 21.0 13.7 0.0045 6.72 5.3 7.5 15.1 15.3 3.2 2.9 2.4 0.0104 5.0 0.0020 0.00066 0.00023 0.04 0.69 0.0094 0.0000693 0.548
0.0000242 0.000048 < 0.005 12.7 18.3 15.7 24.6 0.15 0.18 0.34 1.57 0.17 0.19 0.29 0.36 14.7 0.024 19.3 23.0 19.0 4.7 3.2 0.057 20.0 0.075 0.33 0.06 0.102 0.0103 0.111 0.147 0.022 0.025 0.0325 0.056 0.00548
Remarks
C3, H C3, H C3, H
A
C, F2
A
E
A
H H H H A H
A A A A D
Refs.
574 574 574 331 297 297 126 69 69 96 251 297 96 96 96 297 297 297 96 145 304 304 128 89 89 304 458 375
429 438 297 297 297 297 96 96 96 89 96 297 297 297 96 96 96 339 242 242 242 96 359 344 96 96 297 491 368 491 285 491 491 368 252 368
Next Page
TABLE 5. cont'd Modifier Styrene (cont'd) Phenyl sulfone Phenyl sulfoxide 1-Propanethiol, 3-(trimethoxysilyl)2-Propanethiol, 2-methyl-
T( 0 C)
50 50 79.5 50 60 60 100
Propionic acid, 3,3-dithiodi- , - , dipropyl ester - , 2-mercapto- , 3-mercaptoPropyl disulfide Pyridine, 2,2'-dithiodiQuinoline, 2,2'-dithiodiSulfide, ethyl 2,4-diphenylbutyl - , ethyl phenethyl 1-Tetradecanethiol Thiosulfuric acid, S-butyl ester - , - , sodium salt - , S-isopropyl ester, sodium salt - , 5-phenyl ester - , - potassium salt - , 5-propyl ester, sodium salt p-Toluenethiol a-Toluenethiol -,/7-methoxy/7-Toluoyl disulfide o-Tolyl disulfide
p-Tolyl disulfide 2,6-Xylyl disulfide Vinyl acetate Acetic acid, dithiodi- , - , diethyl ester Acetic acid, ithio- , - , S-(2-hydroxyethyl)ester, acetate Acetyl disulfide 1-Butanethiol Butyl disulfide Butyl sulfide 1,4,5-Oxadithiepane Sulfur oc-Toluenethiol Thiol acetate
Cx
0.021 0.024 5.90 4.0 3.1 3.7 4.6 1.8 2.3
Remarks
Refs.
A A
252 252 474 344 261 69,126 59 261 69,126
H
297 178 178 297 304 89 89 331 331 242
H A A
50 50 60 50 50 50 50 50
< 0.005 7.7 9.4 6.0 0.00234 0.01 0.05 30.0 7.15 19.0
60 60
0.173 0.407
490 490
60 60 99 99 99 60 25 50
0.763 0.150 0.07 25.5 26.0 46.3 0.22 0.23 0.28 0.32 0.11 0.15 0.69
490 490 96 96 96 369 297 297 297 297 297 96 297
1.41 1.5
86 351
75 50 99 50
60
60 60 60 60 60 60 45 70 60
0.0132 0.29 48.0 1.0 0.026 0.25-2.5 470.0 0.885 0.186
J J J J J C F20
140 86 140,397 86, 351 351 351 28 390 575
C. REMARKS A. B. C.
D.
Thermal initiation Hydroperoxide initiation Peroxide initiation C1. Ammonium persulfate C2. Potassium persulf ate C3. Sodium persulf ate Photoinitiation
E. F.
y-Ray initiation Solution polymerization in: Fl. Acetonitrile F2. Benzene F3. Butyl acetate F4. Butyl chloride F5. Chlorobenzene References page 11-159
Previous Page
TABLE 5. cont'd Modifier Styrene (cont'd) Phenyl sulfone Phenyl sulfoxide 1-Propanethiol, 3-(trimethoxysilyl)2-Propanethiol, 2-methyl-
T( 0 C)
50 50 79.5 50 60 60 100
Propionic acid, 3,3-dithiodi- , - , dipropyl ester - , 2-mercapto- , 3-mercaptoPropyl disulfide Pyridine, 2,2'-dithiodiQuinoline, 2,2'-dithiodiSulfide, ethyl 2,4-diphenylbutyl - , ethyl phenethyl 1-Tetradecanethiol Thiosulfuric acid, S-butyl ester - , - , sodium salt - , S-isopropyl ester, sodium salt - , 5-phenyl ester - , - potassium salt - , 5-propyl ester, sodium salt p-Toluenethiol a-Toluenethiol -,/7-methoxy/7-Toluoyl disulfide o-Tolyl disulfide
p-Tolyl disulfide 2,6-Xylyl disulfide Vinyl acetate Acetic acid, dithiodi- , - , diethyl ester Acetic acid, ithio- , - , S-(2-hydroxyethyl)ester, acetate Acetyl disulfide 1-Butanethiol Butyl disulfide Butyl sulfide 1,4,5-Oxadithiepane Sulfur oc-Toluenethiol Thiol acetate
Cx
0.021 0.024 5.90 4.0 3.1 3.7 4.6 1.8 2.3
Remarks
Refs.
A A
252 252 474 344 261 69,126 59 261 69,126
H
297 178 178 297 304 89 89 331 331 242
H A A
50 50 60 50 50 50 50 50
< 0.005 7.7 9.4 6.0 0.00234 0.01 0.05 30.0 7.15 19.0
60 60
0.173 0.407
490 490
60 60 99 99 99 60 25 50
0.763 0.150 0.07 25.5 26.0 46.3 0.22 0.23 0.28 0.32 0.11 0.15 0.69
490 490 96 96 96 369 297 297 297 297 297 96 297
1.41 1.5
86 351
75 50 99 50
60
60 60 60 60 60 60 45 70 60
0.0132 0.29 48.0 1.0 0.026 0.25-2.5 470.0 0.885 0.186
J J J J J C F20
140 86 140,397 86, 351 351 351 28 390 575
C. REMARKS A. B. C.
D.
Thermal initiation Hydroperoxide initiation Peroxide initiation C1. Ammonium persulfate C2. Potassium persulf ate C3. Sodium persulf ate Photoinitiation
E. F.
y-Ray initiation Solution polymerization in: Fl. Acetonitrile F2. Benzene F3. Butyl acetate F4. Butyl chloride F5. Chlorobenzene References page 11-159
F6. o-Dichlorobenzene F7. Dimethylformamide F8. Dimethyl sulfoxide F9. /7-Dioxane FlO. Ethyl acetate FIl. Ethyl methyl ketone F12. Heptane F13. Water F14. Magnesium perchlorate F15. Succinonitrile F16. Sulfur dioxide F17. Toluene Fl 8. Zinc chloride F19. Octane F20. Methanol F21. Propane F22. Diethyl oxalate F23. Cyclohexane F24. Butyl alcohol F25. Acetic acid F26. 1,2-Dichloroethane F27. Ethylbenzene F28. Cylohexanone F29. Parabutyr aldehyde F30. Water-methanol mixture F31. tert-Butyl alcohol F32. Hexane F33. 1-Propanol F34. Carbon tetrachloride G. Heterogeneous polymerization H. Emulsion polymerization I. Recalculated from data of: 11. Basu, Sen, and Palit (1950) 12. Baysal and Tobolsky (1952) 13. Chadha and Misra (1958) 14. Dixon-Lewis (1949) 15. Gregg and Mayo (1953) 16. Ham (1956) 17. Kwart, Broadbent, and Bartlett (1950) 18. Matsumoto, et. al. (1959) 19. Palit and Das (1954) 110. Palit, Nandi, and Saha (1954) Il 1. Saha, Nandi, and Palit (1956) 112. Stein and Schulz (I960) 113. Wheeler, Lavin, and Crozier (1952) J. Apparent transfer constant; retardation occurred K. Average value L. Estimated from model compounds M. For end groups: M1. Tribromomethy 1 M2. Butylamino M3. Diethylamino M4. Hy droxy methyl M5. Aldehyde M6. Thioglycolate M7. -CH(OH)CH2-SH M8. Dodecyl M9. 2-Hydroxyethyl
N. O. P. Q. R. S. T. U. V. W.
X. Y. Z. AA. BB. CC. DD. EE. FF. GG.
HH.
II.
MlO. -(CH 2 )IiSH For middle groups For side chain For main chain Telomerization (number of monomer units in transferring chain) Calculated from viscosity average molecular weight Value uncertain In presence of 0.4 mol/1 lithium nitrate In presence of ( ) mol/1 sodium chloride In presence of ( ) mol/1 sodium bromide Under pressure of: Wl. 200psi (13.8bar) W2. 250psi(17.2bar) W3. 1470psi(101.4bar) W4. 5000 psi (344.8 bar) W5. 20000 psi (1379.0 bar) W6. 26600psi (1834.1 bar) W7. 28400 psi (1958.2bar) W8. 56000psi(3861.2bar) W9. 64600 psi (4454.2 bar) WlO. 168000psi (11583.6 bar) WIl. 600psi (41.4 bar) W12. 2500psi (172.4bar) W13. 18 psi (1.2bar) W14. 735 psi (50.7 bar) W15. 14200psi (979.1 bar) W16. 42600 psi (2937.3 bar) W17. 34500 psi (2378.8 bar) Wl8. 3000bar W19. 2700 bar W20. 2400 bar W21. 2000bar W22. 1800 bar W23. 150 bar W24. 600 bar Corrected for loss of low molecular weight polymer CM = 125 x exp(-7300//?r) CM = 3.0 x exp(-5673/#r) CM = 0.4 x exp(-6219//?r) CM = 0.2 x exp(-5400/#r) CM = 6.4 x exp(-4120/#r) CM = 4.77 x exp(-3540/#r) Radical is styrene Radical is p-chlorostyrene 1/C varies with polym. rate and emulsifier of: GGl. Kcaprate GG2. Klaurate GG3. K myristate GG4. Kpalmitate GG5. K rosinate C is combined constant for copolymerization, = (Csi X i J 1 X M i + CS2 XiJ 2 X M 2 )/ (Ri x Mi x Mi + 2 x Mi x M 2 +R2 x M 2 x M2) In presence of FeBr2
111. 112. JJO. JJl.
In presence of FE(CO)5 In presence of methacrylic acid methyl ester Catalyzed by Co(II)-tetramethylhematoporphyrine Catalyzed by Co(II)-hematoporphyrinetetramethyl ether JJ2. Catalyzed by Co(II)-tetra-4-tertbutylbenzoporphyrine
JJ3. In presence of ZnCl 2 ; [ZnCl 2 ]/[MMA] = (a)0 (b) 0.1 (c) 0.23 (d) 0.40 KK. Copolymerization of acrylonitrile and butyl acrylate LL. Controlled to pH 3 - 4 with acetic acid
D. REFERENCES 1. I. B. Afanas'ev, T. N. Eremina, Zh. Org. Khim., 2, 1832 (1966). 2. LB. Afanas'ev, T. N. Eremina, E. D. Safronenko, Zh. Org. Khim., 1, 844 (1965); J. Org. Chem. USSR, 1, 849 (1965). 3. LB. Afanas'ev, E. D. Safronenko, A. A. Beer, Vysokomol. Soedin., Ser. B, 9, 802 (1967). 4. G. Akazome, S. Sakai, K. Maurai, Kogyo Kagaku Zasshi, 63, 592 (1960); from CA, 56, 4924F (1962). 5. L. Alexandra, M. Oprish, Polym. Sci. USSR, 3, 99 (1962). 6. P. W. Allen, G. P. Mcsweeney, Trans. Faraday Soc, 54, 715 (1958). 7. P. W. Allen, F. M. Merrett, J. Scanlan, Trans. Faraday Soc, 51, 95 (1955). 8. U. N. Anistmov, S. S. Ivanchev, A. I. Yurzhenko, Vysokomol, Soedin., Ser. A, 9, 692 (1967). 9. I. A. Arbusova, L. I. Medvedeva, Izv. Akad. Nauk SSSR, Ser. Khim., 1957, 1349. 10. T. Asahara, T. Makishima, Kogyo Kagaku Zasshi, 69, 2173 (1966). 11. C. Aso, M. Sugabe, Kogyo Kagaku Zasshi, 68, 1970 (1965). 12. R. Autrata, J. Muller, Collect. Czech. Chem. Commun., 24, 3442 (1959). 13. D. W. E. Axford, Proc. Roy. Soc, Ser. A, 197, 137 (1949). 14. T. M. Babchinitser, K. K. Mozgova, V. V. Korshak, Dokl. Akad. Nauk SSSR, 173, 575 (1967); from CA, 67, 117314E (1967). 15. Kh. S. Bagdasar'ian, Z. A. Sinitsina, J. Polym. Sci., 52, 31 (1961). 16. C. H. Bamford, S. Brumby, Makromol. Chem., 105, 122 (1967). 17. C. H. Bamford, M. J. S. Dewar, Proc. Roy. Soc, Ser. A, 192, 309 (1948). 18. C. H. Bamford, M. J. S. Dewar, Proc. Roy. Soc, Ser. A, 197, 356 (1949). 19. C. H. Bamford, A. D. Jenkins, R. Johnston, Proc. Roy. Soc, Ser. A, 239, 214 (1957). 20. C. H. Bamford, A. D. Jenkins, R. Johnston, Proc Roy. Soc, Ser. A, 241, 364 (1957). 21. C H . Bamford, A. D. Jenkins, R. Johnston, Trans. Faraday Soc, 55, 418 (1959). 22. C. H. Bamford, A. D. Jenkins, R. Johnston, E. F. T. White, Trans. Faraday Soc, 55, 168 (1959). 23. C. H. Bamford, A. D. Jenkins, E. F. T. White, J. Polym. Sci., 34, 271 (1959). 24. C. H. Bamford, E. F. T. White, Trans. Faraday Soc, 52, 716 (1956).
25. C. H. Bamford, E. F. T. White, Trans. Faraday Soc, 54, 268 (1958). 26. S. Banerjee, M. S. Muthana, J. Polym. Sci., 37, 469 (1959). 27. P. D. Bartlett, G. S. Hammond, H. Kwart, Dis. Faraday Soc, 2, 342 (1947). 28. P. D. Bartlett, H. Kwart, J. Am. Chem. Soc, 74, 3969 (1952). 29. P. D. Bartlett, F. A. Tate, J. Am. Chem. Soc, 75, 91 (1953). 30. S. C. Barton, R. A. Bird, K. E. Russell, Can. J. Chem., 41, 2737 (1963). 31. S. Basu, J. N. Sen, S. R. Palit, Proc Roy. Soc, Ser. A, 202, 485 (1950). 32. S. Basu, J. N. Sen, S. R. Palit, Proc Roy. Soc, Ser. A, 214, 247 (1952). 33. B. Baysal, J. Polym. Sci., 33, 381 (1958). 34. B. Baysal, A. V. Tobolsky, J. Polym. Sci., 8, 529 (1952). 35. I. M. Bel'govskii, L. S. Sakhonenko, N. S. Yenikolopyan, Vysokomol. Soedin., 8, 369 (1966). 36. W. I. Bengough, W. H. Fairservice, Trans. Faraday Soc, 61, 1206 (1965). 37. W. I. Bengough, W. H. Fairservice, Trans. Faraday Soc, 63, 382 (1967). 38. W. I. Bengough, W. Henderson, Trans. Faraday Soc, 61,141 (1965). 39. W. I. Bengough, R. A. M. Thomson, Trans. Faraday Soc, 56, 407 (1960). 40. J. Beniska, E. Staudner, J. Polym. Sci. C, 16, 1301 (1967). 41. T. Berezhnykh-Foldes, F. Tudos, Eur. Polym. J., 2, 219 (1996). 42. J. C. Bevington, N. A. Ghanem, H. W. Melville, J. Chem. Soc, 1995, 2822. 43. J. C. Bevington, G. M. Guzman, H. W. Melville, Proc. Roy. Soc. Ser. A, 221, 437 (1954). 44. J. C. Bevington, H. G. Troth, Trans. Faraday Soc, 58, 2005 (1962). 45. J. C. Bevington, H. G. Troth, Trans. Faraday Soc, 59, 127 (1963). 46. J. C. Bevington, H. G. Troth, Trans. Faraday Soc, 59, 1348 (1963). 47. J. C. Bevington, A. Wahid, Polymer, 3, 585 (1962). 48. B. R. Bhattacharyya, U. S. Nandi, J. Polym. Sci. A-1,4,2675 (1966). 49. B. R. Bhattacharyya, U. S. Nandi, Makromol. Chem. 116, 8 (1968). 50. R. A. Bird, G. A. Harpell, K. E. Russell, Can. J. Chem., 40, 701 (1962). 51. R. A. Bird, K. E. Russell, Can. J. Chem., 43, 2123 (1965).
52. L. Bogetich, G. A. Mortimer, G. W. Daues, J. Polym. ScL, 61, 3 (1962). 53. E. P. Bonsall, L. Valentine, H. W. Melville, J. Polym. ScL, 7, 39 (1951). 54. C. Booth, L. R. Beason, J. Polym. ScL, 42, 93 (1960). 55. C. Booth, L. R. Beason, J. T. Bailey, J. Appl. Polym. ScL, 5, 116(1961). 56. D. Braun, T.-O. O. Ami., W. Kern, Makromol. Chem., 53, 154 (1962). 57. D. Braun, G. Arcache, R. J. Faust, W. Neumann, Makromol. Chem., 114, 51 (1968). 58. J. W. Breitenbach, Makromol Chem., 8, 147 (1952). 59. J. W. Breitenbach, Z. Elektrochem., 60, 286 (1956). 60. J. W. Breitenbach, H. Edelhauser, R. Hochrainer, Monatsh. Chem., 97, 217 (1966). 61. J. W. Breitenbach, H. Karlinger, Monatsh. Chem., 82, 245 (1951). 62. J. W. Breitenbach, O. F. Olaj, Makromol. Chem., 96, 83 (1966). 63. J. W. Breitenbach, O. F. Olaj, K. Kuchner, H. Horacek, Makromol. Chem., 87, 295 (1965). 64. J. W. Breitenbach, O. F. Olaj, A. Schindler, Monatsh. Chem., 91, 205 (1960). 65. J. W. Breintenbach, A. Schindler, Monatsh. Chem., 83, 724 (1952). 66. J. W. Breintenbach, A. Schindler, Monatsh. Chem., 86, 437 (1955). 67. J. W. Breintenbach, A. Schindler, Monatsh. Chem., 88, 53 (1957). 68. D. W. Brown, J. E. Fearn, R. E. Lowry, J. Polym. Sci. A, 3,16 (1965). 69. G. M. Burnett, Quart. Rev. (London), 4, 292 (1950). 70. G. M. Burnett, F. L. Ross, J. N. Hay, Makromol. Chem., 105, 1 (1965). 71. A. J. Buselli, M. K. Lindemann, C. E. Blades, J. Polym. ScL, 28, 485 (1958). 72. J. I. G. Cadogan, D. H. Hey, J. T. Sharp, J. Chem. Soc, B, 1966, 933. 73. M. Cantow, G. Meyerhoff, G. V. Schulz, Makromol. Chem., 49, 1 (1961). 74. E. A. S. Cavell, Makromol. Chem., 54, 70 (1962). 75. E. A. S. Cavell, I. T. Gilson, J. Polym. Sci. A-I, 4, 541 (1966). 76. R. N. Chadha, G. S. Misra, Indian J. Phys., 28, 37 (1954). 77. R. N. Chadha, G. S. Misra, Current Sci. (India), 23, 186 (1954). 78. R. N. Chadha, G. S. Misra, Makromol. Chem., 14,97 (1954). 79. R. N. Chadha, G. S. Misra, Current Sci. (India), 24, 26 (1955). 80. R. N. Chadha, G. S. Misra, Trans. Faraday Soc, 54, 1227 (1958). 81. R. N. Chadha, J. S. Shukla, G. S. Misra, Trans. Faraday Soc, 53, 240 (1957). 82. E. Y. C. Chang, C. C. Price, J. Am. Chem. Soc, 83, 4650 (1961). 83. S. R. Chatterjee, S. N. Khanna, S. R. Palit, J. Indian Chem. Soc, 41, 622 (1964).
84. A. K. Chaudhuri, Makromol. Chem., 31, 214 (1959). 85. S. Chubachi, P. K. Chatterjee, A. V. Tobolsky, J. Org. Chem., 32, 1511 (1967). 86. J. T. Clarke, R. O. Howard, W. H. Stockmayer, Makromol. Chem., 44-46, 427 (1961). 87. W. Cooper, J. Chem. Soc 1952, 2408. 88. A. T. Coscia, R. L. Kugel, J. Pellon, J. Polym. Sci., 55, 303 (1961). 89. A. J. Costanza, R. J. Coleman, R. M. Pierson, C. S. Marvel, C. King, J. Polym. Sci., 17, 319 (1955). 90. J. Curtice, H. Gilman, G. S. Hammond, J. Am. Chem. Soc, 79, 4754 (1957). 91. E S. Dainton, R. G. Jones, Trans. Faraday Soc, 63, 1512 (1967). 92. F. S. Dainton, M. Tordoff, Trans. Faraday Soc, 53, 499 (1957). 93. N. V. Daniel, A. F. Nikolaev, Vysokomol. Soedin., 8, 465 (1966). 94. F. Danusso, D. Sianesi, Chim. Ind. (Milan), 37, 695 (1955). 95. S. K. Das, S. R. Chatterjee, S. R. Palit, Proc Roy. Soc, Ser. A, 227, 252 (1955). 96. V. A. Dinaburg, A. A. Vansheidt, Zh. Obshch. Khim., 24, 840 (1954). 97. G. Dixon-Lewis, Proc. Roy. Soc, Ser. A, 198, 510 (1949). 98. K. W. Doak, M. A. Deahl, I. H. Christmas, 137th ACS Meeting, Cleveland, Ohio, Abstr. Papers, Vol. 1, No. 1, 151 (April 1960). 99. H. Drawe, A. Henglein, Makromol. Chem., 84, 203 (1965). 100. E. Dvorak, F. Hrabak, J. Polym. Sci. C, 16, 1051 (1967). 101. B. A. Englin, R. Kh. Freidlina, Izv. Akas. Nauk SSSR, Ser. Khim., 1965 (13), 425; from CA, 63, 4122E (1965). 102. B. Erussalimsky, N. Tumarkin, F. Duntoff, S. Lyubetzky, A. Goldenberg, Makromol. Chem., 104, 288 (1967). 103. T. A. Fadner, H. Morawetz, J. Polym. Sci., 45, 475 (1960). 104. T. E. Ferington, A. V. Tobolsky, J. Am. Chem. Soc, 77,4510 (1955). 105. T. G. Fox, S. Gratch, Ann. N. Y. Acad. Sci., 57, 367 (1953). 106. G. N. Freidlin, K. A. Solop, Vysokomol. Soedin., 7, 1060 (1965). 107. G. N. Freidlin, K. A. Solop, Vysokomol. Soedin., 8, 1151 (1966). 108. T. M. Frunze, V V Korshak, E. L. Baranov, B. V. Lokshin, Vysokomol. Soedin, 8, 455 (1966). 109. N. Fuhrma, R. B. Mesrobian, J. Am. Chem. Soc, 76, 3281 (1954). 110. T. R. Fukuto, J. P. Kispersky, US Dept. Com., Office Tech. Serv., Pb Rept. 147, 271 (1953). 111. S. Gadkary, S. Kapur, Makromol. Chem., 17, 29 (1955). 112. J. A. Gannon, E. M. Fettes, A. V Tobolsky, J. Am. Chem. Soc, 74, 1854 (1952). 113. M. H. George, J. Polym. Sci. A, 2, 3169 (1964). 114. M. H. George, P. F. Onyon, Trans. Faraday Soc, 59, 134 (1963). 115. M. H. George, P. F. Onyon, Trans. Faraday Soc, 59, 1390 (1963). 116. H. Gerrens, H. Ohlinger, R. Fricker, Markromol. Chem., 87, 209 (1965).
117. L. Ghosez, G. Smets, J. Polym. Sci., 37, 445 (1959). 118. G. P. Gladyshev, G. V. Leplyanin, Vysokomol. Soedin., Ser. A, 9, 2438 (1967). 119. J. E. Glass, N. L. Zutty, J. Polym. Sci. A-I, 4, 1223 (1966). 120. M. S. Gluckman, M. J. Kampf, J. L. O'Brien, T. G. Fox, R. K. Graham, J. Polym. Sci., 37, 411 (1959). 121. M. P. Godsay, G. A. Harpell, K. E. Russell, J. Polym. Sci., 57, 641 (1962). 122. M. P. Godsay, D. H. Lohmann, K. E. Russell, Chem. Ind. (London), 1959, 1603. 123. M. R. Gopalan, M. Santhappa, J. Polym. Sci., 25, 333 (1957). 124. W. W. Graessley, H. Mittelhauser, R. Maramba, Makromol. Chem., 86, 129 (1965). 125. N. Grassie, E. Vance, Trans. Faraday Soc, 52 727 (1956). 126. R. A. Gregg, D. M. Alderman, F. R. Mayo, J. Am. Chem. Soc, 70, 3740 (1948). 127. R. A. Gregg, F. R. Mayo, Disc. Faraday Soc, 2, 328 (1947). 128. R. A. Gregg, F. R. Mayo, J. Am. Chem. Soc, 70, 2373 (1948). 129. R. A. Gregg, F. R. Mayo, J. Am. Chem. Soc, 75, 3530 (1953). 130. V. F. Gromov, A. V. Matveeva, P. M. Khomikovskii, A. D. Abkin, Vysokomol. Soedin., Ser. A, 9, 1444 (1967). 131. J. Guillot, A. Guyot, Compt. Rend., Ser. C, 266,1209 (1968). 132. H. C. Haas, H. Husek, J. Polym. Sci. A, 2, 2297 (1964). 133. Y. Hachihama, H. Sumitomo, Technol. Repts. Osaka Univ., 5, 491 (1955); from CA, 51, 8474B (1957). 134. Y. Hachihama, H. Sumitomo, Technol. Repts. Osaka Univ., 5, 497 (1955); from CA, 51, 8474C (1957). 135. G. E. Ham, J. Polym. Sci., 21, 337 (1956). 136. G. E. Ham, E. L. Ringwald, J. Polym. Sci., 8, 91 (1952). 137. D. Hardy, K. Nytrai, N. Fedorova, G. Kovacs, Polym. Sci. USSR, 4, 584 (1963). 138. D. Hardy, K. Nytrai, N. Fedorova, G. Kovacs, Vysokomol. Soedin, 4, 1872 (1962). 139. D. Hardy, V Spiegel, K. Nytrai, Polym. Sci. USSR, 2, 528 (1961). 140. G. Hardy, J. Varga, K. Nytrai, I. Tsajlik, L. Zubonyai, Vysokomol. Soedin., 6, 758 (1964). 141. S. A. Harrison, W. E. Tolberg, J. Am. Oil Chem. Soc, 30, 114 (1953); calc by F. R. Mayo and C. W. Gould (1964). 142. R. A. Hayes, J. Polym. Sci., 13, 583 (1954). 143. E. J. Henley, C. Chong, J. Polym. Sci., 36, 511 (1959). 144. G. Henrici-Olive, S. Olive, Makromol. Chem., 37, 71 (1960). 145. G. Henrici-Olive, S. Olive, Fortschr. Hochpolymer. Forsch., 2, 496 (1961). 146. G. Henrici-Olive, S. Olive, Makromol. Chem., 53, 122 (1962). 147. G. Henrici-Olive, S. Olive, G. V. Schulz, Makromol. Chem., 23, 207 (1957). 148. G. Henrici-Olive, S. Olive, G. V. Schulz, Z. Phys. Chem. (Frankfurt), 20, 176 (1959). 149. R. Hiddema, Proefschrift Rijks Universitat Groningen, 1953, Ref. 16 in Breitenbach (1956). 150. K. Higashiura, Kogyo Kagaku Zasshi, 69, 349 (1966).
151. K. Higaashiura, M. Oiwa, J. Polym. Sci., A-I, 6, 1857 (1968). 152. F. Hrabak, M. Bezdek, Makromol. Chem., 115, 43 (1968). 153. F. Hrabak, M. Bezdek, Collect. Czech. Chem. Commun., 33, 278 (1968). 154. F. Hrabak, L. Jiresova, Collect. Czech. Chem. Commun., 26, 1283 (1961). 155. T. Huff, E. Perry, J. Am. Chem. Soc, 82, 4277 (1960). 156. T. Huff, E. Perry, J. Polym. Sci. A, 1, 1553 (1963). 157. F. Ide, K. Nakatsuka, H. Tamura, Kobunshi Kagaku, 23, 45 (1965); from CA, 64, 17716G (1966). 158. F. Ide, K. Okano, S. Nakano, K. Nakstsuka, Shikizai Kyokaishi, 40, 571 (1967); from CA, 69, 3162Q (1968). 159. J. L. Ihrig, S. P. Sood, J. Polym. Sci. A-3, 1573 (1965). 160. M. Imoto, K. Higashiura, Kobunshi Kagaku, 17,468 (1960); from CA, 55, 22900G (1961). 161. M. Imoto, T. Otsu, T. Oda, H. Takatsugi, M. Matsuda, J. Polym. Sci., 22, 137 (1956). 162. M. Imoto, T. Otsu, K. Tsuda, T. Ito, J. Polym. Sci. A-2,1407 (1964). 163. M. Imoto, K. Takemoto, H. Azuma, Makromol. Chem., 114, 210 (1968). 164. M. Imoto, K. Takemoto, Y. Nakai, Makromol. Chem., 48, 80 (1961). 165. S. Imoto, T. Kominami, Kobunshi Kagaku, 15, 60 (1958); from CA, 53, 8690G (1959). 166. S. Imoto, T. Kominami, Kobunshi Kagaku, 15, 279 (1958); from CA, 54, 2803A (1960). 167. S. Imoto, J. Ukida, T. Kominami, Kobunshi Kagaku, 14, 127 (1957); from CA, 52, 1670A (1958). 168. S. Imoto, J. Ukida, T. Kominami, Kobunshi Kagaku, 14, 384 (1957); from CA, 52, 5024D (1958). 169. S. Iwatsuki, K. Nishio, Y. Yamashita, Kogyo Kagaku Zasshi, 70, 384 (1967). 170. V Jaacks, F. R. Mayo, J. Am. Chem. Soc, 87, 3371 (1965). 171. D. H. Johnson, A. V. Tobolsky, J. Am. Chem. Soc, 74, 938 (1952). 172. M. H. Jones, Can. J. Chem., 34, 108 (1956). 173. E. F. Jordan, Jr., B. Artymyshyn, A. N. Wrigley, J. Polym. Sci. A-I, 6, 575 (1968). 174. E. F. Jordan, Jr., G. R. Riser, W. E. Parker, A. N. Wrigley, J. Polym. Sci. A-2, 4, 975 (1966). 175. R. M. Joshi, Makromol. Chem., 53, 33 (1962). 176. H. Kaemmerer, F. Rocaboy, Compt. Rend. Ser. AB, 256, 4440 (1963). 177. H. Kaemmerer, F. Rocaboy, Makromol. Chem., 72, 76 (1964). 178. K. Kaeriyama, Nippon Kagaku Zasshi, 88, 783 (1967); from CA, 69, 19607Z (1968). 179. M. Kalfus, J. Kopytowski, S. Lesniak, Z. Skupinska, Polimery, 9, (2) 54 (1964); from CA, 62, 9325E (1965). 180. S. Kamenar, Chem. Zvesti, 14, 525 (1960); from Chem. Zentr., 133, 493 (1961). 181. S. L. Kapur, J. Sci. Ind. Res., 108, 186 (1951). 182. S. L. Kapur, J. Polym. Sci., 11, 399 (1953). 183. S. L. Kapur, S. D. Gadkary, J. Sci. Ind. Res., 17B, 152 (1958).
184. S. L. Kapur, R. M. Joshi, J. Polym. ScL, 14, 489 (1954). 185. K. Katagiri, K. Uno, S. Okamura, J. Polym. ScL, 17, 142 (1955). 186. M. Kato, H. Kamogawa, J. Polym. ScL A-I, 4, 2771 (1966). 187. V. Ya. Katsobashvili, R. Ya. Chernaya, I. B. Afanas'ev, Vysokomol. Soedin., Ser. B, 9, 342 (1967). 188. V. Ya. Katsobashvili, E. D. Safronenko, I. B. Afanas'ev, Vysokomol. Soedin., 7, 823 (1965). 189. V. Ya. Katsobashvili, E. D. Safronenko, I. B. Afanas'ev, Vysokomol. Soedin., 8, 282 (1966). 190. H. Kawakami, N. Mori, K. Kawashima, M. Sumi, Kogyo Kagaku Zasshi, 66, 88 (1963); from CA, 59, 4042B (1963). 191. H. Kawakami, N. Mori, M. Sumi, Kobunshi Kagaku, 20,408 (1963); from CA, 61, 13422D (1964). 192. W. Kern, D. Braun, Makromol. Chem., 27, 23 (1958). 193. S. N. Khanna, S. R. Chatterjee, U. S. Nandi, S. R. Palit, Trans. Faraday Soc, 58, 1827 (1962). 194. J. L. Kice, J. Am. Chem. Soc, 76, 6274 (1954). 195. W. J. Kirkham, J. C. Robb, Trans. Faraday Soc, 57, 1757 (1961). 196. H. Kitagama, Kobunshi Kagaku, 20, 5 (1963); from Makromol. Chem., 64, 229 (1963). 197. H. Kiuchi, M. Watanabe, Kobunshi Kagaku, 21, 37 (1964) from CA, 61, 7107F (1964). 198. I. M. Kochnov, M. F. Sorokin, Polym. Sci. USSR, 6, 869 (1964). 199. M. Kubin, L. Zikmund, Collect. Czech. Chem. Commun., 32, 535 (1967). 200. C. J. Kurian, M. S. Muthana, Makromol. Chem., 29, 1 (1959). 201. C. J. Kurian, M. S. Muthana, Makromol. Chem., 29, 19 (1959). 202. H. Kwart, H. S. Broadbent, P. D. Bartlett, J. Am. Chem. Soc, 72, 1060 (1950). 203. K. S. Kwei, F. R. Eirich, J. Phys. Chem., 66, 828 (1962). 204. Z. Laita, J. Polym. Sci., 38, 247 (1959). 205. Z. Laita, Z. Machacek, J. Polym. Sci., 38, 459 (1959). 206. M. Lazar, J. Pavlinec, Chem. Zvesti, 15, 428 (1961); from CA, 55, 22896C (1961). 207. M. Lazar, J. Pavlinec, J. Polym. Sci. A, 2, 3197 (1964). 208. M. Lazar, J. Pavlinec, Z. Manasek, Collect. Czech. Chem. Commun., 26, 1380 (1961). 209. M. Lazar, R. Rado, J. Pavlinec, J. Polym. Sci., 53, 163 (1961). 210. F. M. Lewis, F. R. Mayo, J. Am. Chem. Soc, 76,457 (1954). 211. D. Lim, M. Kolinsky, J. Polym. Sci., 53, 173 (1961). 212. D. Lim, O. Wichterle, J. Polym. Sci., 29, 579 (1958). 213. M. Litt, V. Stannett, Makromol. Chem., 37, 19 (1960). 214. J. R. Little, RF. Hartman, J. Am. Chem. Soc, 88,96 (1966). 215. J. R. Little, L. W. Hartzel, F. O. Guenther, F. R. Mayo, private communication to C. Walling, "Free radicals in solution", Wiley, NY, 1957, p. 257. 216. S. Loshaek, E. Broderick, R Bernstein, J. Polym. ScL, 39, 223 (1959). 217. A. I. Lowell, J. R. Price, J. Polym. Sci., 43, 1 (1960). 218. S. G. Lyubetskii, B. A. Dolgoplosk, B. L. Erusalimskii, Polym. Sci. USSR, 3, 164 (1962).
219. Z. Machacek, F. Cermak, Chem, Prum., 16,604 (1966); from CA, 66, 18907Y (1967). 220. G. Machell, G. N. Richards, J. Chem. Soc, 1961, 3308. 221. V Mahadevan, M. Santhappa, Makromol. Chem., 16, 119 (1955). 222. K. L. Malik, Naturwissenschaften, 45, 385 (1958). 223. T. Manabe, T. Utsumi, S. Okamura, J. Polym. Sci., 58, 121 (1962). 224. M. S. Matheson, E. E. Auer, E. B. Bevilacqua, E. J. Hart, J. Am. Chem. Soc, 71, 497 (1949). 225. M. S. Matheson, E. E. Auer, E. B. Bevilacqua, E. J. Hart, J. Am. Chem. Soc, 71, 2610 (1949). 226. S. G. Matsoyan, N. N. Morlyan, F. S. Kinoyan, Vysokomol. Soedin., 7, 1159 (1965). 227. M. Matsuda, S. Abe, N. Tokura, J. Polym. Sci. A, 2, 3877 (1964). 228. M. Matsuda, K. Matsumoto, N. Tokura, Kogyo Kagaku Zasshi, 68, 1269 (1965). 229. M. Matsuda. N. Tokura, J. Polym. Sci. A, 2, 4281 (1964). 230. M. Matsuda, S. Fujii, J. Polym. ScL A-I, 5, 2617 (1967). 231. M. Matsumoto, M. Maeda, J. Polym. ScL, 17, 438 (1955). 232. M. Matsumoto, J. Ukida, G. Takayama, T. Eguchi, K. Mukumoto, K. Imai, Y. Kazusa, M. Maeda, Makromol. Chem. 32, 13 (1959). 233. B. Matuska, J. Kossler, V. Srajer, Collect, Czech. Chem. Commun., 23, 1456 (1958). 234. J. A. May, Jr., W. B. Smith, J. Phys. Chem., 72, 216 (1968). 235. F. R. Mayo, J. Am. Chem. Soc, 65, 2324 (1943). 236. F. R. Mayo, J. Am. Chem. Soc, 70, 3689 (1948). 237. F. R. Mayo, J. Am. Chem. Soc, 75, 6133 (1953). 238. F. R. Mayo. J. Am. Chem. Soc, 76, 5392 (1954). 239. F. R. Mayo, C. W. Gould, J. Am. Oil Chem. Soc, 41, 25 (1964). 240. F. R. Mayo, R. A. Gregg, M. S. Matheson, J. Am. Chem. Soc, 73, 1691 (1951). 241. V. V. Mazurek, V. G. Gasan-Zade, G. T. Nesterchuk, Polym. Sci. USSR, 6, 1587 (1964). 242. E. J. Meehan, I. M. Kolthoff, H. R. Sinha, J. Polym. Sci., 16, 471 (1955). 243. E. J. Meehan, I. M. Kolthoff, P. R. Sinha, J. Polym. Sci. A-2, 4911 (1964). 244. F. W. Mellows, M. Burton, J. Phys. Chem., 66, 2164 (1962). 245. H. W. Melville, L. Valentine, Trans. Faraday Soc, 46, 210 (1950). 246. H. S. Mickley, A. S. Michaels, A. L. Moore, J. Polym. Sci., 60, 121 (1962). 247. E. B. Milovskaya, T. G. Zhuravleva, Vysokomol. Soedin., Ser. A, 9, 1128 (1967). 248. E. B. Milovskaya, T. G. Zhuravleva, L. V Zamoyskaya, J. Polym. Sci., C, 16, 899 (1967). 249. Y. Minoura, Y. Enomoto, Kogyo Kagaku Zasshi, 70, 1021 (1967). 250. Y. Minoura, Y. Hayashi, M. Imoto, Kobunshi Kagaku, 15, 260 (1958); from CA, 54 2803F (1960). 251. Y Minoura, T. Sugimura, J. Polym. Sci. A-I, 4, 2721 (1966).
252. Y. Minoura, T. Sugimura, T. Hirahara, Kogyo Kagaku Zasshi, 70, 357 (1967). 253. Y. Minoura, N. Yasumoto, T. Ishii, Kogyo Kagaku Zasshi, 65, 1299 (1962); from CA, 58, 1538D (1963). 254. Y. Minoura, N. Yasumoto, T. Ishii, Makromol. Chem., 71, 159 (1964). 255. G. S. Misra, R. N. Chadha, Makromol. Chem., 23, 134 (1957). 256. G. S. Misra, R. C. Rastogi, V. P. Gupta, Makromol. Chem., 50, 72 (1961). 257. T. Miyake, M. Matsumoto, Kogyo Kagaku Zasshi, 62, 1101 (1959); from CA, 57, 15342A (1962). 258. Y. Mori, K. Sato, Y. Minoura, Kogyo Kagaku Zasshi, 61,462 (1958); from CA, 55, 4021F (1961). 259. G. A. Mortimer, J. Polym. Sci. A-I, 4, 881 and 1895 (1966). 260. G. A. Mortimer, L. C. Arnold, J. Am. Chem. Soc, 84, 4986 (1962). 261. M. Morton, J. A. CaIa, I. Piirma, J. Am. Chem. Soc, 78, 5394 (1956). 262. M. Morton, I. Piirma, J. Am. Chem. Soc, 80, 5596 (1958). 263. M. Morton, I. Piirma, J. Polym. Sci. A, 1, 3043 (1963). 264. A. S. Nair, M. S. Muthana, Makromol. Chem., 47, 114, 128 (1961). 265. H. Nakamoto, Y. Ogo, T. Imoto, Makromol. Chem., I l l , 93 (1968). 266. T. Nakata, T. Otsu, M. Imoto, J. Polym. Sci. A, 3, 3383 (1965). 267. T. Nakaya, K. Ohashi, M. Imoto, Makromol. Chem., 114, 201 (1968). 268. U. S. Nandi, P. Ghosh, S. R. Palit, Nature, 195, 1197 (1962). 269. A. F. Nikolaev, N. V. Meiya, G. A. Balaev, Vysokomol. Soedin., 7, 2122 (1965). 270. K. Noma, Y Tajima, M. Niwa, Sci. Eng. Rev. Doshisha Univ., 3, 91 (1962); from CA, 59, 2955C (1963). 271. R. G. W. Norrish, J. P Simons, Proc Roy. Soc, Ser. A, 251,4 (1959). 272. A. M. North, A. M. Scallan, Polymer, 5, 447 (1964). 273. K. Nozaki, Disc Faraday Soc, 2, 337 (1947). 274. J. L. O'Brien, F. Gornick, J. Am. Chem. Soc, 77, 4757 (1955). 275. J. L. O'Brien, J. R. Panchak, T. G. Fox, Abstract of 124th ACS Meeting, Chicago, 1953. 276. S. Okamura, K. Katagiri, Makromol. Chem., 28, 177 (1958). 277. S. Okamura, K. Katagiri, T. Motoyama, J. Polym. Sci., 43, 509 (1960). 278. S. Okamura, T. Motoyama, J. Polym. Sci., 58, 221 (1962). 279. S. Okamura, K. Takeya, Kobunshi Kagaku, 15, 353 (1958); from CA, 54, 8143 (1960). 280. M. Okawara, T. Nakai, E. Imoto, Kogyo Kagaku Zasshi, 69, 973 (1966). 281. O. F. Olaj, J. W. Breitenbach, I. Hofreitere, Makromol. Chem., 91, 264 (1966). 282. O. F. Olaj, J. W. Breitenbach, I. Hofreitere, Makromol. Chem., 110, 72 (1967). 283. P F. Onyon, Trans. Faraday Soc, 51, 400 (1955). 284. R F. Onyon, J. Polym. Sci., 22, 19 (1956).
285. T. Otsu, Y. Kinoshita, M. Imoto, Makromol. Chem., 73, 225 (1964). 286. T. Otsu, K. Nayatani, Makromol. Chem., 27, 149 (1955). 287. T. Otsu, A. Shimizu, M. Imoto, J. Polym. Sci. B, 2, 973 (1964). 288. T. Otsu, K. Tsuda, N. Kita, Mem. Fac Eng., Osaka City Univ., 7, 95 (1965); from CA, 66, 95434U (1967). 289. S. R. Palit, S. K. Das, Proc Roy. Soc, Ser. A, 226, 82 (1954). 290. S. R. Palit, U. S. Nandi, N. G. Saha, J. Polym. Sci., 14, 295 (1954). 291. S. K. Patra, D. Mangaraj, Makromol. Chem., Ill, 168 (1968). 292. J. Pavlinec, M. Lazar, J. Polym. Sci. C, 22, 297 (1968). 293. L. H. Peebles, J. Polym. Sci. A, 3, 341 (1965). 294. L. H. Peebles, J. T. Clarke, W. H. Stockmayer, J. Am. Chem. Soc, 82, 4780 (1960). 295. J. J. Pellon, J. Polym. Sci., 43, 537 (1960). 296. E. Perry, J. Polym. Sci., 54, S-46 (1961). 297. R. Pierson, A. Costanza, A. Weinstein, J. Polym. Sci., 17, 221 (1955). 298. G. Platau, F. R. Eirich, R. B. Mesrobian, A. E. Woodward, J. Polym. Sci., 39, 357 (1959). 299. A. Prevot-Bernas, J. Sebban-Danon, J. Chem. Phys., 53,418 (1956). 300. W. A. Pryor, J. Phys. Chem., 67, 519 (1963). 301. W. A. Pryor, D. M. Huston, T. R. Fiske, T. L. Pickering, E. Ciuffarin, J. Am. Chem. Soc, 86, 4237 (1964). 302. W. A. Pryor, G. L. Kaplan, J. Am. Chem. Soc, 86, 4234 (1964). 303. W. A. Pryor, A. Lee, C. E. Witt, J. Am. Chem. Soc, 86,4229 (1964). 304. W. A. Pryor, T. L. Pickering, J. Am. Chem. Soc, 84, 2705 (1962). 305. W. A. Pryor, E. P. Pultinas, Jr., J. Am. Chem. Soc, 85, 133 (1963). 306. R V. T. Raghuram, U. S. Nandi, J. Polym. Sci. A-I, 5, 2005 (1967). 307. S. P. Rao, M. Santhappa, Curr. Sci. (India), 34, (6) 174 (1965). 308. S. P. Rao, M. Santhappa, J. Polym. Sci. A-I, 5, 2681 (1967). 309. A. I. Restaino, W. N. Reed, J. Polym. Sci., 36, 499 (1959). 310. E. H. Riddle, "Monomeric Acrylic Ester", Reinhold, NY, 1954, Ref. 14, p. 64. 311. J. C. Robb, E. Senogles, Trans. Faraday Soc, 58,708 (1962). 312. J. C. Robb, D. Vofsi, Trans, Faraday Soc, 55, 558 (1959). 313. M. E. Rozenberg, A. F. Nikolaev, A. V. Pustovalova, Vysokomol. Soedin., 8, 1155 (1966). 314. L. V. Ruban, A. L. Buchachenko, M. B. Neiman, Yu. V. Koknanov, Vysokomol. Soedin., 8, 1642 (1966). 315. M. Ryska, M. Kolinsky, D. Lim, J. Polym. Sci. C, 16, 621 (1967). 316. N. G. Saha, U. S. Nandi, S. R. Palit, J. Chem. Soc, 427 (1956). 317. N. G. Saha, U. S. Nandi, S. R. Palit, Chem. Soc, 7 (1958). 318. N. G. Saha, U. S. Nandi, S. R. Palit, Chem. Soc, 12 (1958). 319. I. Sakurada, K. Noma, Y Ofuji, Kobunshi Kagaku, 20, 481 (1963); from CA, 63, 8487C (1965).
320. I. Sakurada, Y. Sakaguchi, K. Hashimoto, Kobunshi Kagaku, 19, 593 (1962); from CA, 61, 16159D (1964). 321. G. F. Santee, R. H. Marchessault, H. G. Clark, J. J. Kearny, V. Stannett, Makromol. Chem., 73, 177 (1964). 322. M. Santhappa, V. M. Iyer, Current Sci. (India), 24, 173 (1955). 323. M. Santhappa, V. S. Vaidhyanathan, Current Sci. (India) 23, 259 (1954). 324. J. Scanian, Trans. Faraday Soc, 50, 756 (1954). 325. E. Schonfeld, I. Waltcher, J. Polym. Sci., 35, 536 (1959). 326. G. V. Schulz, G. Henrici, S. Olive, J. Polym. Sci., 17, 45 (1955). 327. G. V. Schulz, G. Henrici, S. Olive, Z. Elektrochem., 60, 296 (1956). 328. G. V. Schulz, L. Roberts-Nowakowska, Makromol. Chem., 80, 36 (1964). 329. G. V. Schulz, D. J. Stein, Makromol. Chem., 52, 1 (1962). 330. G. P. Scott, C. C. Soong, W.-S. Huang, J. L. Reynolds, J. Org. Chem., 29, 83 (1964). 331. G. R Scott, J. C. Wang, J. Org. Chem., 28, 1314 (1963). 332. J. N. Sen, U. S. Nandi, S. R. Palit, J. Indian Chem. Soc, 40, 729 (1963). 333. K. P. Shen, F. R. Eirich, J. Polym. Sci., 53, 81 (1961). 334. A. Shimzu, T. Otsu, M. Imoto, Bull. Chem. Soc. Japan, 38, 1535 (1965). 335. T. Shimomura, Y. Kuwabara, E. Tsuchida, I. Shinohara, Kogyo Kagaku Zasshi, 71, 283 (1968). 336. T. Shimomura, E. Tsuchida, I. Shinohara, Mem. School Sci. Eng., Waseda Univ., 8, 37 (1964); from CA, 63, 14985A (1965). 337. T. Shimomura, E. Tsuchida, I. Shinohara, Mem. School Sci. Eng., Waseda Univ., 29, 1 (1965); from CA, 65, 10675A (1966). 338. M. Simonyi, F. Tudos, J. Pospisil, Eur. Polym. J., 3, 101 (1967). 339. P. R. Sinha, K. L. Mallik, J. Indian Chem. Soc, 34, 424 (1957). 340. C. Sivertz, J. Phys. Chem., 63, 34 (1959). 341. B. Skrabal, L. Rosik, Chem. Prumysl, 8, 46 (1958). 342. G. Smets, L. Convent, X. van der Borght, Makromol. Chem., 23, 162 (1957). 343. G. Smets, L. Dehaes, Bull. Soc Chim. Beiges, 59, 13 (1950). 344. w. V. Smith, J. Am. Chem. Soc, 68, 2059 (1964). 345. R. D. Spencer, M. B. Fulton, U.S. Dept. Com., Office Tech. Serv., PB Rept., 144, 990 (1961). 346. R. D. Spencer, M. B. Fulton, B. H. Beggs, Abstracts of 137th ACS Meeting, Cleveland, 1960. 347. N. T. Srinivasan, M. Santhappa, Makromol. Chem., 26, 80 (1958). 348. D. J. Stein, Makromol. Chem., 76, 170 (1964). 349. D. J. Stein, G. V. Schulz, Makromol. Chem., 38, 248 (1960). 350. D. J. Stein, G. V. Schulz Makromol. Chem., 52, 249 (1962). 351. W. H. Stockmayer, R. O. Howard, J. T. Clarke, J. Am. Chem. Soc, 75, 1756 (1953). 352. T. J. Suen, Y. Jen, J. V. Lockwood, J. Polym. Sci., 31, 481 (1958).
353. T. J. Suen, A. M. Schiller, W. N. Russell, Adv. Chem. Series No. 34, "Polymerization and Polycondensation Processes," ACS, Washington, DC, 1962, pp. 217-24. 354. T. Sugimura, Y. Ogata, Y. Minoura, J. Polym. Sci. A-I, 4, 2747 (1966). 355. G. Takayama, Kobunshi Kagaku, 15, 89 (1958); from CA, 53, 868D (1959). 356. W. M. Thomas, E. H. Gleason, J. J. Pellon, J. Polym. Sci., 17, 275 (1955). 357. C. F. Thompson, W. S. Port, L. P. Witnauer, J. Am. Chem. Soc, 81, 2552 (1959). 358. A. P Titov, I. A. Livshits, Zh. Obshch. Khim., 29, 1605 (1959). 359. A. V. Tobolsky, B. Baysal, J. Am. Chem. Soc, 75, 1757 (1953). 360. A. V. Tobolsky, J. Offenbach, J. Polym. Sci., 16, 311 (1955). 361. T. Toda, J. Polym. Sci., 58, 411 (1962). 362. N. Tokura, M. Matsuda, F. Yazaki, Makromol. Chem., 42, 108 (1960). 363. A. C. Toohey, K. E. Weale, Trans. Faraday Soc, 58, 2439 (1962). 364. A. C. Toohey, K. E. Weale, Trans. Faraday Soc, 58, 2446 (1962). 365. E. Tsuchida, Y. Ohtani, H. Nakadai, I. Shinohara, Kogyo Kagaku Zasshi, 70, 573 (1967). 366. E. Tsuchida, Y. Ohtani, H. Nakadai, I. Shinohara, Kogyo Kagaku Zasshi, 69, 1230 (1966). 367. E. Tsuchida, T. Shimomura, K. Fujimori, Y. Ohtani, I. Shinohara, Kogyo Kagaku Zasshi, 70, 566 (1967). 368. K. Tsuda, S. Kobayashi, T. Otsu, Bull, Chem. Soc. Japan, 38, 1517 (1965). 369. K. Tsuda, T. Otsu, Bull. Chem. Soc Japan, 39, 2206 (1966). 370. F. Tudos, T. Berezhnykh-Foldes, Eur. Polym. J., 2, 229 (1966). 371. F. Tudos, I. Kende, M. Azori, J. Polym. Sci., 53, 17 (1961). 372. F. Tudos, I. Kende, M. Azori, J. Polym. Sci. A, 1, 1353 (1963). 373. F. Tudos, I. Kende, M. Azori, J. Polym. Sci. A, 1, 1369 (1963). 374. J. Ulbricht, Faserforsch. Textiltech., 10, 166 (1959) 375. J. Ulbricht, Faserforsch. Textiltech., 11, 62 (1960). 376. J. Ulbricht, Z. Phys. Chem. (Frankfurt), 221, 346 (1962). 377. J. Ulbricht, B. Sandner, Faserforsch. Textiltech., 17, 208 (1966). 378. J. Ulbricht, R. Sourisseau, Faserforsch. Textiltech., 16, 213 (1965). 379. T. Uno, K. Yoshida, Kobunshi Kagaku, 15, 819 (1958); from CA, 54, 20298D (1960). 380. C. A. Uraneck, J. E. Bulreigh, J. Appl. Polym. Sci., 12, 1075 (1968). 381. W. H. Urry, F. W. Stacey, E. S. Huyser, O. O. Juveland, J. Am. Chem. Soc, 76, 450 (1954). 382. V. Vaclavek, Chem. Prumysl, 10, 103 (1960). 383. V. Vaclavek, J. Appl. Polym. Sci., 11, 1881 (1967). 384. V. Vaclavek, J. Appl. Polym. Sci., 11, 1903 (1967).
385. V. S. Vaidhyanathan, M. Santhappa, Makromol. Chem., 16, 140 (1955). 386. R. L. Vale, W. G. R Robertson, J. Polym. ScL, 33, 518 (1958). 387. B. M. E. van der Hoff, J. Polym. ScL, 44, 241 (1960). 388. B. M. E. van der Hoff, J. Polym. ScL, 48, 175 (1960). 389. A. A. Vansheidt, G. Khardi, Acta Chim. Acad. ScL Hung., 20, 261 (1959); from CA, 54, 6180B (1960). 390. A. A. Vansheidt, G. Khardi, Acta Chim. Acad. Sci. Hung., 20, 381 (1959); from CA, 54, 1152F (1960). 391. F. K. Velichko, I. P. Lavrent'ev, Yu. P Chizhov, Izv. Akad. Nauk SSSR, Ser, Khim., 1966, 172; from CA, 64, 12485C (1966). 392. G. Vidotto, A. Crosato-Amaldi, G. Talmini, Makromol. Chem., 114, 217 (1968). 393. M. Vrancken, G. Smets, Makromol. Chem., 30, 197 (1959). 394. J. Vuillemenot, B. Barbier, G. Riess, A. Banderet, J. Polym. Sci. A, 3, 1969 (1965). 395. L. A. Wall, D. W. Brown, J. Polym. ScL, 14, 513 (1954). 396. R. A. Wallace, K. L. Hadley, J. Polym. ScL A-1,4,71 (1966). 397. C. Walling, J. Am. Chem. Soc, 70, 2561 (1948). 398. C. Walling, E. R. Briggs, J. Am. Chem. Soc, 68, 1141 (1946). 399. C. Walling, Y. Chang, J. Am. Chem. Soc, 76, 4878 (1954). 400. C. Walling, L. Heaton, J. Am. Chem. Soc, 87, 38 (1965). 401. C. Walling, J. J. Pellon, J. Am. Chem. Soc, 79,4776 (1957). 402. M. Watanabe, H. Kiuchi, J. Polym. Sci., 58, 103 (1962). 403. O. L. Wheeler, E. Lavin, R. N. Crozier, J. Polym. Sci., 9,157 (1952). 404. E. F. T. White, M. J. Zissell, J. Polym. Sci. A, 1,2189 (1963). 405. T. Yamamoto, Bull. Chem. Soc Japan, 40, 642 (1967). 406. T. Yamamoto, T. Otsu, J. Polym. Sci. B, 4, 1039 (1966); see also Bull. Chem. Soc Japan, 40, 2449 (1967). 407. T. Yamamoto, T. Otsu, Koguo Kagaku Zasshi, 70, 2403 (1967). 408. T. Yamamoto, T. Otsu, M. Imoto, Kogyo Kagaku Zasshi, 69, 990 (1966). 409. S. D. Yevstratova, M. F. Margaritova, S. S. Medvedev, Polym. Sci. USSR, 5, 681 (1964). 410. M. Yoshida, K. Tanouchi, Kobunshi Kangaku, 20, 545 (1963); from Makromol. Chem., 71, 216 (1964). 411. V. V Zaitseva, V. D. Enal'ev, A. I. Yurzhenko, Vysokomol. Soedin., Ser. A, 9, 1958 (1967). 412. V. M. Zhulin, M. G. Gonikberg, V. N. Zagorbinina, Dokl. Akad. Nauk SSSR, 163, 106 (1965); from CA, 63, 11706G (1965). 413. V. M. Zhulin, M. G. Gonikberg, V. N. Zagorbinina, Izv. Akad. Nauk SSSR, Ser. Khim., 827 (1966). 414. V. M. Zhulin, M. G. Bonikberg, V N. Zagorbinina, Izv. Akad. Nauk SSSR, Ser. Khim., 997 (1966). 415. M. G. Zimina, N. P. Apukhtina, Kolloid Zh., 21, 181 (1959). 416. J. Aoyagi, K. Kitamura, I. Shinohara, Kogyo Kagaku Zasshi, 73, 2045 (1970). 417. J. Aoyagi, I. Shinohara, Kogyo Kagaku Zasshi, 74, 1191 (1971). 418. T. Asahara, M. C. Chou, Bull. Chem. Soc. Japan, 42, 1373 (1969).
419. C. Aso, T. Kunitake, M. Shinsenji, H. Miyazaki, J. Polym. Sci. A-I, 7, 1497 (1969). 420. J. C. Bevington, M. Johnson, J. P. Sheen, Eur. Polym. J., 8, 209 (1972). 421. G. C. Bhaduri, U. S. Nandi, Makroml. Chem., 128, 176 (1969). 422. G. C. Bhaduri, U. S. Nandi, Makromol. Chem., 128, 183 (1969). 423. B. R. Bhattacharyya, U. S. Nandi, Makromol. Chem., 149, 231 (1971). 424. B. R. Bhattacharyya, U. S. Nandi, Makromol. Chem., 149, 243 (1971). 425. D. Braun, F. Weiss, Makromol. Chem., 138, 83 (1970). 426. D. Braun, F. Weiss, Angew. Makromol. Chem., 15, 127 (1971). 427. C-T. Chen, W-D. Huang, J. Chin. Chem. Soc, 16,46 (1969); from CA, 71, 102247U (1969). 428. Y. Choshi, A. Tsuji, G. Akazome, K. Murai, Kogyo Kagaku Zasshi, 71, 908 (1968); from CA, 69, 67745Q (1968). 429. N. N. Dass, M. H. George, Eur. Polym. J., 6, 897 (1970). 430. H. J. Dietrich, M. A. Raymond, J. Macromol. Sci. Chem. A, 6, 191 (1972). 431. J. P. Fischer, Makromol. Chem., 155, 211 (1972). 432. J. P. Fischer, Makromol. Chem., 155, 227 (1972). 433. J. R Fischer, W. Liiders, Makromol. Chem. 155, 239 (1972). 434. R. Kh. Freidlina, A. B. Terent'ev, N. S. Ikonnikov, Dokl. Akad. Nauk SSSR, 193, 605 (1970). 435. R. Kh. Freidlina, A. V. Terent'ev, N. S. Ikonnikov, Izv. Akad. Nauk SSSR, Ser. Khim., 1970, 554. 436. S. S. Frolov, T. M. Slivchenko, Izv. Vyssh. Ucheb. Zaved., Khim. Khim. Tekhnol., 14, 1264 (1971); from CA, 76, 25660X (1972). 437. I. Geczy, H. I. Nasr, Acta Chim. (Budapest), 70, 319 (1971); from CA, 76, 100150M (1972). 438. S. N. Gupta, U. S. Nandi, J. Polym. ScL A-I, 8, 1493 (1970). 439. D. A. J. Harker, R. A. M. Thomson, I. R. Walters, Trans. Faraday Soc, 67, 3057 (1971). 440. M. Imoto, K. Ohashi, Makromol. Chem., 117, 117 (1968). 441. E. F. Jordan, Jr., B. Artymyshyn, A. N. Wrigley, J. Polym. Sci. A-I, 7, 2605 (1969). 442. I. Kar, B. M. Mandal, S. R. Palit, J. Polym. Sci. A-I, 7, 2829 (1969). 443. S. Kobayashi, Kogyo Kagaku Zasshi, 72, 2511 (1969). 444. C. Kwang-Fu, Kobunshi Kagaku, 29, 233 (1972). 445. I. M. Likhterova, E. M. Lukina, Zh. Obshch. Khim., 42, 194 (1972); from CA, 76, 127504S (1972). 446. A. Matsumoto, M. Oiwa, J. Polym. ScL A-1,10, 103 (1972). 447. J. A. May, Jr., W. B. Smith, J. Phys. Chem., 72, 2993 (1968). 448. L. A. Miller, V. Stannett, J. Polym. Sci. A-I, 7, 3159 (1969). 449. Y. Minoura, M. Mitoh, Kogyo Kagaku Zasshi, 74, 747 (1971). 450. Y. Minoura, A. Tabuse, Kogyo Kagaku Zasshi, 74, 990 (1971). 451. Y. Minoura, H. Toshima, J. Polym. ScL A-I, 7, 2837 (1969). 452. M. Modena, P. Piccardi, Eur. Polym. J., 7, 1 (1971). 453. N. Mogi, M. Shindo, Kogyo Kagaku Zasshi, 73, 786 (1970).
454. 455. 456. 457. 458. 459. 460. 461. 462. 463. 464. 465. 466. 467. 468. 469. 470. 471. 472. 473. 474. 475. 476. 477. 478. 479. 480. 481. 482. 483. 484. 485. 486.
487.
G. A. Mortimer, J. Polym. Sci. A-I, 8, 1513 (1970). G. A. Mortimer, J. Polym. Sci. A-I, 8, 1535 (1970). G. A. Mortimer, J. Polym. Sci. A-I, 8, 1543 (1970). G. A. Mortimer, J. Polym. Sci. A-I, 10, 163 (1972). I. G. Murgulescu, I. Vlagiu, Rev. Roum. Chim., 14, 411 (1969); from CA, 71, 71773F (1969). T. Nakaya, M. Tanaka, M. Imoto, Makromol. Chem., 149, 221 (1971). J. H. Ok, S. B. Pak, Hwahak Kwa Hwahak Kongop, 1971, 239 (Korean); from CA, 77, 20147U (1972). T. Ota, S. Masuda, Kogyo Kagaku Zasshi, 73, 2020 (1970). T. Ota, S. Masuda, C. Aoyama, M. Ebisudani, Kogyo Kagaku Zasshi, 74, 994 (1971). G. S. Park, D. G. Smith, Trans. Faraday Soc, 65, 1854 (1969). F. Patat, R Mehnert, Monatsh. Chem., 98, 538 (1967). S. P. Potnis, A. M. Deshpande, Makromol. Chem., 125, 48 (1969). S. R Potnis, A. M. Deshpande, Makromol. Chem., 153, 139 (1972). W. A. Pryor, J. H. Coco, Macromolecules, 3, 500 (1970). W. A. Pryor, T. R. Fiske, Macromolecules, 2, 62 (1969). W. A. Pryor, T.-L. Huang, Macromolecules, 2, 70 (1969). E. Pulat, C. B. Senvar, Commun. Fac. Sci. Univ. Ankara, Ser. B, 15, (3) 25 (1968); from CA, 72, 55934Z (1970). R V. T. Raghuram, U. S. Nandi, J. Polym. Sci. A-I, 7, 2379 (1969). R V. T. Raghuram, U. S. Nandi, J. Polym. Sci. A-I, 8, 3079 (1970). K. K. Roy, D. Pramanick, S. R. Palit, Makromol. Chem., 153, 71 (1972). J. C. Saam, D. J. Gordon, J. Polym. Sci. A-I, 8, 2509 (1970). T. Saegusa, Y. Ito, N. Yasuda, Polym. J., 1, 591 (1970). S. K. Saha, A. K. Chaudhuri, J. Polym. Sci. A-I, 10, 797 (1972). G. P. Scott, A. M. R. Elghoul, J. Polym. Sci. A-I, 8, 2255 (1970). G. R Scott, F. J. Foster, Macromolecules, 2, 428 (1969). R. B. Seymour, J. M. Sosa, V. J. Patel, J. Paint Technol., 43, (563), 45 (1971). T. Shimomura, E. Tsuchida, I. Shinohara, Kogyo Kagaku Zasshi, 71, 1074 (1968); from CA, 69, 97249Y (1968). E. Staudner, J. Beniska, Eur. Polym. J. Suppl., 1969, 537. F. Suganuma, H. Mitsui, S. Machi, M. Hagiwara, T. Kagiya, J. Polym. Sci. A-I, 6, 3127 (1968). K. Sugiyama, T. Nakaya, M. Imoto, J. Polym. Sci. A-I, 10, 205 (1972). A. B. Terent'ev, N. S. Ikonnikov, R. Kh. Freidlina, Izv. Akad. Nauk SSSR, Ser. Khim, 73 (1971). A. B. Terent'ev, N. S. Ikonnikov, R. Kh. Freidlina, Dokl. Akad. Nauk USSR, 196, 1373 (1971). A. S. Tevlina, H. S. Kolesnikov, S. N. Sividova, V. V. Ryltsev, Vysokomol. Soedin., Ser. A, 9, 2473 (1967); Polym. Sci. USSR, 9, 2797 (1967). R. A. M. Thomson, L R. Walters, Trans. Faraday Soc, 67, 3046 (1971).
488. R. A. M. Thomson, I. R. Walters, J. R. King, J. Polym. Sci., B, 10, 63 (1972). 489. E. Tsuchida, T. Tomono, Kogyo Kagaku Zasshi, 73, 2040 (1970). 490. M. Tsunooka, M. Fujii, N. Ando, M. Tanaka, N. Murata, Kogyo Kagaku Zasshi, 73, 805 (1970). 491. M. Tsunooka, T. Higuchi, M. Fujii, M. Tanaka, N. Murata, Kogyo Kagaku Zasshi, 73, 596 (1970). 492. G. Vidotto, S. Brugnaro, G. Talamini, Makromol. Chem., 140, 249 (1970). 493. G. Vidotto, S. Brugnaro, G. Talamini, Makromol. Chem., 140, 263 (1970). 494. F. Yamada, M. Kanbe, I. Shinohara, Memo. Sch. Sci. Eng. Waseda Univ. 1969, No. 33, 67: from CA, 73, 88255C (1970). 495. T. Yamamoto, M. Hasegawa, T. Otsu, Bull. Chem. Soc. Japan, 42, 1364 (1969). 496. T. Yamamoto, S. Nakamura, M. Hasegawa, T. Otsu, Kogyo Kagaku Zasshi, 72, 727 (1969). 497. T. Yamamoto, T. Otsu, J. Polym. Sci. A-I, 7, 1279 (1969). 498. N. Yamashita, T. Seita, M. Yoshihara, T. Maeshima, Kogyo Kagaku Zasshi, 74, 2157 (1971). 499. N. Yamashita, T. Seita, M. Yoshihara, T. Maeshima, J. Polym. Sci. B, 9, 641 (1971). 500. V. M. Zhulin, M. G. Gonikberg, A. L. Goff, V. N. Zagorbinina, Vysokomol. Soedin., Ser. A, 11, 777 (1969). 501. N. Ya. Kaloforov, E. Borsig, J. Polym. Sci., Polym. Chem. Ed., 11, (10) 2665 (1973). 502. O. A. Aminova, B. D. Saidov, Dokl. Akad. Nauk Uzb. SSSR, 4, 45 (1979). 503. D. Pramanick, A. K. Chaterjee, Eur. Polym. J., 16, (9) 895 (1980). 504. D. A. J. Harker, R. A. M. Thomson, I. R. Walters, Trans. Faraday Soc, 67, (Pt. 10) 3057 (1971). 505. U. A. Safaev, Kh. Rakhmatullaev, A. T. Dzhalilov, Uzb. Khim. Zh., 3, 42 (1983). 506. E. Abuin, E. A. Lissi, J. Macromol. Sci., Chem., 13 (8), 1147 (1979). 507. G. R Scott, F. J. Foster, Macromolecules, 2 (4), 428 (1969). 508. K. Yokota, H. Tomioka, A. Tazumi, J. Macromol. Sci., Chem., 6 (7), 1337 (1972). 509. M. Bezdek, J. Exner, J. Kriz, F. Hrabak, Makromol. Chem., 147, 1 (1971). 510. A. Fehervari, E. Boros Gyevi, T. Foldes-Bereznish, F. Tudos, J. Macromol. Sci. A: Chem., 18 (3), 431 (1982). 511. B. A. Englin, T. A. Onishchenko, R. Kh. Freidlina, Izv. Akad. Nauk SSSR, Ser, Khim. 12, 2542 (1971). 512. M. Raetzsch, I. Zschach, Plaste Kaut., 21 (5), 345 (1974). 513. T. Foldes-Bereznich, M. Szesztay, F. Tudos, J. Macromol. Sci. A: Chem., 16 (5), 977 (1981). 514. J. Pavlinec, E. Borsig, J. Polym. Sci., Polym. Chem. Ed., 19 (9), 2305 (1981). 515. N. S. Enikolopyan, B. R. Smirnov, G. V. Ponomarev, L M. Belgovskii, J. Polym. Sci., Polym. Chem. Ed., 19 (4), 879 (1981). 516. A. B. Terentev, N. S. Ikonnikov, R. Kh. Freidlina, Dokl. Akad. Nauk SSSR, 196, (6) 1373 (1971).
517. A. G. Shostenko, V. E. Myshkin, Vysokomol. Soedin., Ser. B, 20, 163 (1978). 518. Sl. A. Karapetyan, G. P. Shakhovskoi, N. A. Grigorev, V. M. Zhulin, B. A. Englin, Izv. Akad. Nauk SSSR, Ser. Khim., 6, 1303 (1970). 519. B. A. Englin, B. N. Ospipov, Izv. Akad. Nauk SSSR, Ser. Khim., 1, 65 (1971). 520. C. H. Bamford, J. Chem. Soc, Faraday Trans., 1, 72 (12), 2805 (1976). 521. M. R. Lachinov, T. R. Aslamazova, V. P. Zubov, V. A. Kabanov, Vysokomol. Soedin., Ser. A, 17 (5), 1146 (1975). 522. V. P. Naidenov, V. G. Syromyatnikov, Ukr. Khim. Zh. (Russ. Ed.), 45 (10), 982 (1979). 523. P. A. Zagorets, A. G. Shostenko, A. M. Dodonov, N. P. Tarsova, Zh. Org. Khim., 10 (10), 2093 (1974). 524. A. P. Titov, V. V. Kotov, Vysokomol. Soedin., Ser. B, 10 (7), 495 (1968). 525. B. R. Smirnov, V. E. Mironychev, I. V. Golikov, M. M. Mogilevich, I. V. Enikolopov, Depos. Doc, SPSTL 598 Khp-D82, 9 pp. Avail. SPSTL (1982). 526. M. Niwa, N. Higashi, Sci. Eng. Rev. Doshisha Univ., 24 (3), 129 (1983). 527. O. F. Olaj, J. W. Breitenbach, I. Hofreiter, Rec. Chem. Progr., 30 (2), 87 (1969). 528. B. R. Smirnov, A. R Marchenko, G. V. Korolev, I. M. Belgovskii, N. S. Enikolopyan, Vysokomol. Soedin., Ser. A, 23 (5), 1042 (1981). 529. R. B. Seymour, V. Patel, J. Paint Technol., 44 (569), 53 (1972). 530. N. M. Kozyreva, A. I. Kirilin, V. V. Korshak, Plast. Massy, 2, 24 (1983). 531. N. G. Podosenova, E. G. Zotilov, V. P. Budtov, Vysokomol. Soedin., Ser. A, 25 (1), 43 (1983). 532. S. K. Verma, K. Wendler, M. Fedtke, Acta Polym., 35 (1), 58 (1984). 533. A. Hrivik, J. Beniska, E. Hudecova, Chem. Zvesti, 37 (4), 503 (1983). 534. S. Raghunath, M. H. Rao, K. N. Rao, Radiat, Phys. Chem., 22(6), 1011 (1983). 535. K. Kodaira, K. Ito, Nagoya Kogyo Gijutsu Shikensho Hokoku, 31 (1/2), 22 (1982). 536. K. Kodaira, T. Ito, M. Omi, Y. Onishi, K. Ito, Nagoya Kogyo Gijutsu Shik, Hokoku, 31 (6/7), 186 (1982). 537. V. Kim, A. G. Shostenko, M. D. Gasparyan, React. Kinet. Catal. Lett., 12 (4), 479 (1979). 538. V. A. Kabanov, D. A. Topchiev, G. T. Nazhmethdinova, Izv. Akad. Nauk SSSR, Ser. Khim., 9, 2146 (1983). 539. L. A. Smirnova, Yu. D. Semchikov, L. I. Kamyshenkova, T. G. Sveshnikova, A. N. Egorochkin, G. S. Kalinina, B. A. Egorov, Vysokomol. Soedin., Ser. A, 24 (5), 999 (1982). 540. K. Yamamoto, M. Sugimoto, J. Makromol. Sci. A: Chem., 13 (8), 1067 (1979). 541. K. Matsuo, G. W. NeIb, R. G. NeIb, W. H. Stockmayer, Macromolecules, 10 (3), 654 (1977). 542. J. Lokaj, F. Hrabak, Eur. Polym. J., 14 (12), 1039 (1978). 543. M. lino, M. Igarashi, M. Matsuda, Macromolecules, 12 (4), 697 (1979).
544. M. Yoshihara, N. Miryamoto, M. Fukumura, T. Maeshima, J. Polym. Sci., Polym. Lett. Ed., 14 (2), 97 (1976). 545. W. A. Pryor, Tetrahedron Lett., 1201 (1963). 546. T. Otsu, Radical Polymerization - I, Kapakudojin, Koyoto, 1971, p. 143. 547. I. Grotewold, M. M. Hirschler, J. Polym. Sci., Polym. Chem. Ed., 15, 383 (1977). 548. U. S. Nandi, M. Singh, P. V T. Raghuram, Makromol. Chem., 183 (8), 1467 (1982). 549. B. Cellard, Ch. Pichot, A. Revillon, Makromol. Chem., 183 (8), 1935 (1982). 550. L. Vrhovac, J. Velickovic, D. Filipovic, Makromol. Chem., 185 (8), 1637 (1984). 551. B. Boutevin, Y. Pietrasanta, Makromol. Chem., 186 (4), 831 (1985). 552. M. A. Bruk, S. A. Pavlov, A. D. Abkin, Dokl. Akad. Nauk SSSR, 245, 626 (1979). 553. W. Berger, H. J. Schneider, H. Schmidt, Faserforsch. Textiltech., 27 (8), 437 (1976). 554. J. C. Saam, D. J. Gordon, J. Polym. Sci., Part. A-I, 8 (9), 2509 (1970). 555. T. Ota, Kenkyu Hokoku-Asyhi Garasu Kogyo Gijutsu Shoreikai, 42, 65 (1983). 556. B. R. Smirnov, I. M. Bel'Govskii, G. V Ponomarev, N. S. Enikolopyan, Dokl. Akad. Nauk SSSR, 254 (1), 127 (Chem.). 557. R. Kh. Freidlina, A. B. Terentjev, N. S. Ikonnikov, Dokl. Akad. Nauk, 3, 193, 605 (1970). 558. R. Kh. Freidlina, A. B. Terentjev, N. S. Ikonnikov, Isv. Akad. Nauk, Ser. Chem., 554 (1970). 559. A. B. Terentijev, N. S. Ikonnikov, R. Kh. Freidlina, Isv. Akad. Nauk, Ser. Chem., 1, 73 (1971). 560. C. F. Jasso, E. Mendizabal, M. E. Hernandez, Rev. Plast. Mod., 62, 823 (1991); from CA, 117, 131596f (1992). 561. I. Capek, Collect. Czech. Chem. Commun., 51, 2546 (1986). 562. F. Vidal, R. G. Gilbert, Macromol. Chem. Phys., 197, 1835 (1996). 563. K. G. Suddaaby, D. R. Maloney, D. M. Haddleton, Macromolecules, 30, 702 (1997). 564. L. I. Abramova, E. N. Zilberman, V. V. Leshin, Izv. Vyssh. Uchebn. Zaved., Khim. Khim. TekhnoL, 30, 117 (1987); from CA, 107, 237343e (1987). 565. B. Boutevin, Y. Pietrasanta, Makromol. Chem., 186, 831 (1985). 566. G. Bauduin, B. Boutevin, J. P. Mistral, L. Sarraf, Makromol. Chem., 186, 1445 (1985). 567. C. A. Barson, J. C. Bevington, B. J. Hunt, J. Polym. Sci., Part A, Polym. Chem., 34, 227 (1996). 568. C. A. Barson, J. C. Bevington, B. J. Hunt, J. Polym. Sci., Part A, Polym. Chem., 33, 863 (1995). 569. D. Braun, P. Hempler, Polym. Bull. (Berlin), 30, 55 (1993). 570. T. T. Vasileva, V. A. Kochetkova, B. V. Nelyubin, V. I. Dostovalova, R. K. Freidlina, Izv. Akad. Nauk SSSR, Ser. Khim., 808b (1987); from CA, 108, 111753r (1988). 571. G. Bauduin, B. Boutevin, B. Pucci, J. P. Rigaud, Makromol. Chem., 188, 2339 (1987).
572. T. T. Vasileva, V. A. Kochetkova, B. V. Nelyubin, R. K. Freidlina, Izv. Akad. Nauk. SSSR, Ser. Khim., 1397 (1986); from CA, 106, 11993e (1987). 573. F. Jahanzad, M. Kazemi, S. Sajjadi, F. A. Taromi, Polymer, 34, 3542 (1993).
574. B. K. Dietrich, W. A. Pryor, S. J. Wu, J. Appl. Polym. ScL, 36, 1129 (1988). 575. S. Y. Lee, Y. J. Shin, Pollimo, 20, 233 (1966); from CA, 124, 318076y (1996).
P h o t o p o l y m e r i z a t i o n
R e a c t i o n s
J. P. Fouassier Laboratoire de Photochimie Generale, Mulhouse, Cedex, France
A. Introduction 11-169 B. Tables 11-170 Table 1. Rate Constants of Cleavage, Electron Transfer and Monomer Quenching in Radical Photoinitiators 11-170 Annex to Table 1. Photoinitiator Compound Chemistries 11-173 Table 2. Bimolecular Rate Constants for the Reaction of Phosphonyl Radicals with Various Monomers in Cyclohexane at Room Temperature 11-176 Table 3. Bimolecular Rate Constants for the Reaction of Various Radicals with Various Olefinic Monomers at Room Temperature 11-176 Table 4. Bimolecular Rate Constants for the Reaction of Ph 2 P=O and Ph2P = S with Various Monomers 11-176 Table 5. Electron Transfer Reaction of Radicals with Diphenyliodonium Salts 11-176 Table 6. Electron Transfer Rate Constants (ke) Between Photosensitizers and Cationic Photoinitiators and Quenching Rate Constants (fcq) for Cyclohexene Oxide in Methanol (M) and Acetonitrile (AN) 11-177 Table 7. Excitation Transfer Rate Constants (kj) for Thioxanthones and Photoinitiators 11-178 Annex to Table 7. Compound Chemistries 11-178 Table 8. Triplet State Lifetimes (rT) of the Sensitizer (TXI) in Different Media, and Rate Constant (A:T) of the Interaction between TXI and TPMK 11-179 Table 9. Some Values of the Triplet State Energy Levels of Photoinitiators and Monomers 11-179 Table 10. Values of r f , rT, and k% in Solution 11-179 Table 11. Rate Constant of Interaction of Ketones and Light Stabilizers in Solution 11-179 Annex to Table 11 11-179 C. References 11-180
A.
INTRODUCTION
UV curing technologies use light beams to start photochemical and chemical reactions in organic materials (monomers, oligomers, prepolymers, polymers), mostly through a Photo-Induced Polymerization (PIP) reaction. This leads to the formation of a new polymeric material whose applications lie in various industrial sectors, such as coatings, graphic arts, imaging, microelectronics, etc. Specific advantages of these technologies over the usual thermal operations are rapid through-cure, solvent-free formulation, room temperature treatment and low energy requirements. This PIP process is concerned with the creation of a polymer P through a chain radical or cationic reaction initiated by light in the presence of a photoinitiator (PI) and a coupled Pl/photosensitizer (PS): light
light
light
add species :X
excited PS excited PI
R* or acid species
The reactivities of PI and PS govern, for a large part, the practical efficiency of the PIP reaction. The present chapter reports typical data obtained (through time-resolved laser spectroscopy experiments) on the excited state processes in PI and PS occurring after the absorption of the photon. Rate constants reported in the following tables correspond to the following processes: 1.
PI (ground singlet state)
light
1 PI* first excited singlet state
cleavage H abstraction monomer quenching electron transfer
3 Pi* triplet state
2. R' (or A# or S*...) + M — ^ 3. 3 P F + light stabilizer (LS) 3
(b) Energy and electron transfer can also occur in the first excited singlet state 1 PS*.
RM'
—-
k
4. PS* + PI —- excitation transfer 5. Tj'. Triplet state lifetime under the given conditions (equal to the reciprocal value of the sum of the first-order rate constants of the different processes) Tj: Triplet state lifetime in the presence of a given additive 6 3
- PS* + cationic photoinitiator C+ —- PS" + C* (a) Energy transfer can sometimes occur: 3 PS*+ C+ - PS+ C+*
Detailed data are available, especially in several chapters of two edited books (1) and in a recent monograph (2). Few data are known on the photopolymerization itself and largely depend on the practical formulation used as well as the experimental conditions. Typically, one photon absorbed can lead to ~10000 polymerized double bonds (3). Rate constants of propagation kp and termination fct for a polyurethane acrylate resin containing an acrylate monomer (weight ratio, 1:1) as reactive diluent are ~10 4 1/mol/s and 3 x 10 4 l/mol/s respectively (when half of the double bonds have been polymerized) (3).
B. TABLES TABLE 1. RATE CONSTANTS OF CLEAVAGE, ELECTRON TRANSFER AND MONOMER QUENCHING IN RADICAL PHOTOINITIATORS0 10~9A:e (1/mol/s)
10~6A:q (1/mol/s)
Monomers famines 7 solventsd
Ha Hb Hc lid lie Hf Hg Hh Hi Ha
1.3 2.0 1.2 1.2 0.2 0.07 1.5 0.6 0.27
Mi, AHi, Si
Ha
0.003e 0.001^ 7 2 1.9 2 0.56
66 150 2.5 2 1 13 180 8 0.05 3200 360 5.4 34
Compound
10 "8Jk0 (s"1)
Ha
Hj Ilk 111 Hm Hn Up Hq Hr Hs Ilr Hs Hr Hs Hr Ils Ilr Hs I2a I2b I2c I2d I2e I2f I2g I2h I2i
10 0.5 0.9 0.0064* 0.0025e 0.0056e 0.0043*
7.14 0.87 0.003 0.00025 0.83 0.003 0.67 1.18 0.80
0.26 < 0.001 0.08 0.20 0.08 0.17 0.15 0.05
1500 1550
56 110 5500 7400 5100 6500 49 140 9.4 50 250 20 4.5 8 22 10 29 20 21
M2, M5, M3, M4,
Refs. 4
S2 S2 S2 S2
21 21 21 21 22
S 2 , AH3 S 2 , AH4 S 2 , AH2 S 2 , AH5 S 2 , AH6 S3 M 7 , AH2, S 4
26
S2
26
S 6 , Mi
26
S6, M2
26
S6, M5
26
S6, M3
26
S6, M4
26
Mi, AHi, Si
23 25
5
TABLE 1. cont'd Compound Ba I3b 13c I3d I3e I3f I3g I3h I4a I4b I4c I4d I4e I4f I4g I4h I4i I4e I4f I4g I4h I4i I4f I4g I4h I4i I4f I4g I4h I4i I5a I6a I7a I7b I8a I9a HOa Ilia IHb IHc Hid I12a I12b I12c I12d I12e I12a I12b I12c I12d I12e I12b I12c I12d I12e I12b I12c I12d I12e I13a I14a I14b I14c I14d I15a I15b I15c
10 8A: c (s"1) 10 1 25 0.005 10 0.006 0.007 0.13 >100 >100 > 100 >100
W~9ke (1/mol/s)
10 6 A: q (I/moI/s) >200 2
0.7 6 XlO" 5 0.85 2.5
0.9 0.4
0.7 0.05 440 0.35 11
700 1200 480 800 1000 200 13 8100 4800 6500 1500 190 6 17 <10 5.7 1300 700 380 180
1.6 6.5 6.0 3.5
>5 4 >5
Mi5AHi5S1
6
Si
7
M2, S2
7
Mi, S 2
7
M3, S2
7
M4, S2
7
Mj5S1 Mi, AHi, Si
8 9 9
«10 ~4 <10~ 4 <10~ 4
> 10 7 xlO-3
1.4
Refs.
<10~ 4
8100 4800 6500 1500 190 480 800 1000 200 13 60 17 <1 5.7 1300 700 380 180
> 10 0.8 >1 0.12 0.01
Monomers famines 7 solvents^
11000 2900 15 1200
Mi7AHi9S1 Mi5AH19Si Mi, AHi, Si
9 9 10 10
M15S2
11
M25S2
11
M3, S2
11
M4, S2
11
AH 2 , S 2 M19AH15S1
12 13
S2
14
References page 11-180
TABLE 1. cont'd Compound I15d I16a I16b I17a I18a I19a I20a I21a I22a I22b I22c I22d I23a I23b I23c I23d I23e I23f I23a I23b I23c I23d I23a I23b I23c I23d I23a I23b I23c I23d I23a I23b I23c I23d I23a I23b I23c I23d I23a I23b I23c I23d I23a I23a I23b I23b I23g I23h 124 125 126 127 128 129 a
10*kc (s1)
10~9ke (1/mol/s)
10~6kq (1/mol/s)
Monomers famines 7 solvents^
Refs.
3.3 1.5 >3 0.05 0.16 0.3 29 60 -10 -5 0.02 0.014
0.7
6 5 4 4 0.01 0.017 2.5
180
AH 1 9 S 1
15
300
S1 S1 S1 S2 S2 S3
16 17 18 18 18 19
M 1 , AH3, S 2
20
AH2, S 5
24
M 2 , S 2 , AH2
20
M3, S2
20
M4, S2
20
M5, S2
20
M6, S2
20
S 2 , AH4
26
S1, M8 S19M9 S 2 , AH7 S 2 , AH8 M7, S 4
13 13 26 26 25
S 2 , Mi S2, M10 S2, M10 S2
37 37 37 39
S 7 , AH 9
41
100
93 2.3 2.0 15 2 3 3 3000 6000 6000 6000 0.2 0.02 0.03 0.04 4 0.4 1 1 40 30 5 6 1 1 0.3 0.3
8 6 6 6 26 23 8 0.85 <10~5 <10~5
4.4-f 0.3 0.015
65 37 0.016 0.006 0.007
Compound chemistries given in Annex to Table 1. 1} Monomers: Mi - methyl methacrylate; M2 - styrene; M3 - vinyl acetate; M4 - acrylonitrile; M5 - vinyl pyrrolidone; M6 - butylvinylether; M 7 - acrylamide; Mg PETA; M 9 - TMPTA; M10 - butylmethacrylate. c Amines: AHi - methyl diethanolamine; AH 2 - triethylamine; AH 3 - ethyl-4-(dimethylamino)-benzoate; AH 4 - bis-(2-hydroxy ethyl)-methylamine; AH 5 - methyl-4amino benzoate; AH 6 - 1,4-diazabicyclo [2.2.2] octane (DABCO); AH 7 - dimethylamine; AHg - 2-(dimethyl aminoethyl)-benzoate; AH 9 - diethylaniline. d Solvents: Si - toluene; S 2 - benzene; S 3 - acetonitrile; S 4 - water; S5 - 2-propanol; S 6 - acetone; S 7 - ethanol. e Rate constant of H abstraction by THF. ^Rate constant of H abstraction by isopropanol.
ANNEX TO TABLE 1. PHOTOINITIATOR COMPOUND CHEMISTRIES Compound
R
Ri
R2
R3
R4
Ha lib lie Hd He iif Hg Hh
in Hj
Ilk 111 Hm Hn Up Hq Hr
Hs
I2a I2b I2c I2d I2e I2f I2g I2h I2i Ba I3b 13c Dd I3e I3f Bg Dh I4a I4b I4c I4d I4e I4f I4g I4h I4i
References page 11-180
ANNEX TO TABLE 1. cont'd Compound
R
Ri
R2
I5a
I6a
I7a I7b Fluorenone
H CH 2 SOjNa
+
I8a I9a
I9b
HOa
C2H5
Ilia IHb IHc IHd I12a 112b I12c I12d
H H CH 3 CH 3 O OH OCOCH3 H CH 3
I12e I13a
CH 3
I14a I14b I14c I14d
H /-C 3 H 7 OC 2 H 5 J-C 4 H 9
I15a
I15b I15c
I15d
I16a
H CH 3
H CH3 H H
R3
R4
ANNEX TO TABLE 1. cont'd Compound
R
Ri
R2
R3
R4
I16b I17a I18a I19a I20a I21a
I22a I22b I22c I22d I23a I23b I23c I23d I23e I23f
H Cl CH 3 CH 3 (CH 3 ) 2 H H
I23g
-OCH 2 COOH
I23h
OCH 2 CH 2 CH 2 N(CH 3 ) 3 SO 3 Me-
124 Acridine Phenazine
125 126 127
128
129
References page 11-180
TABLE 2. BIMOLECULAR RATE CONSTANTS0 FOR THE REACTION OF PHOSPHONYL RADICALS WITH VARIOUS MONOMERS IN CYCLOHEXANE AT ROOM TEMPERATU RE *
Radical Monomer Methacrylonitrile
5.0
4.6
4.5
Styrene Methylmethacrylate Acrylonitrile Methyl acrylate n-Butyl vinyl ether Vinyl acetate
6.0 8.0 2.0 3.5 0.4 0.16
4.5 5.0 2.0 2.1 0.3 0.13
8.0 5.8 0.18 1.3 0.23 0.082
a
b
kRM in 10 7 l/mol/s. Ref. 26.
9.2
11
22 5.8 0.58 1.7 2.1 0.29
25 5.3 0.26 1.6 1.4 0.18
TABLE 3. BIMOLECULAR RATE C O N S T A N T S " FOR THE REACTION OF V A R I O U S RADICALS W I T H V A R I O U S OLEFINIC M O N O M E R S AT R O O M TEMPERATURE*
Radical
Monomer 3.5 x 10" 2
Styrene
Methylmethacrylate Acrylonitrile Methyl acrylate n-Butyl vinyl ether Vinyl acetate Af-Vinyrpyrrolidone a
4
9xlO~ 4 x 10 ~4
2
5.4xlO~ 1.6 x 10~2
7 x 10~ 4
4xlO"
5
< 10 " 6
6 x 10 ~4
4xlO~
5
1.2 x 10 ~2
6
0.9xl0~ 2 2 x 10 ~3
6 2 2 0.5 0.2
2 x 10 ~2
18C
10" 3t
IO"1*
7
kRU in 10 l/mol/s. Ref. 26. From Ref. 40. +From Ref. 16.
fo c
TABLE 4. BIMOLECULAR RATE C O N S T A N T S 0 FOR THE REACT I O N OF P h 2 R = O A N D Ph 2 P-=* W I T H V A R I O U S M O N O M E R S * 0
Radical Monomer Methacrylonitrile Styrene Methylmethacrylate Acrylonitrile Methyl acrylate rc-Butyl vinyl ether Vinyl acetate a
Ph2P = O 1.9 4.6 4.1 1.3 1.7 5.0 1.4
Ph2P = S 0.9 0.4 0.19 0.52 0.62 0.15 0.042
kRM in 10 7 l/mol/s *Ref. 27. c Experiments were carried out in CH 2 C^ solution at room temperature.
TABLE 5. ELECTRON TRANSFER REACTION O F RADICALS W I T H D I P H E N Y L I O D O N I U M SALTS
Radicals
Ph2PO Ph2COH (CHs)2COH
10"9Jt6 (1/mol/s)
Refs.
<10"3 0.03 0.06
42 43
TABLE 6. ELECTRON TRANSFER RATE CONSTANTS (ke) BETWEEN PHOTOSENSITIZERS AND CATIONIC PHOTOINITIATORS AND QUENCHING RATE CONSTANTS (kq) FOR CYCLOHEXENE OXIDE IN METHANOL (M) AND ACETONITRILE (AN) Photosensitizer Chlorothioxanthone
Chlorothioxanthone
Cationic photoinitiator
Anion
Solvent
(1/mol/s)
(1/mol/s) 0.3
AsF6" Cl" PF6BF4; AsF 6
M
AN
24 24 26 24 290
AsF 6
M
400
Refs. 28
36 Benzophenone
AsF 6 Cl" BF4"
M
15 1 47
0.33
Ketocoumarin
BF 4
M
6.4
0.04
M
14
Chlorothioxanthone
PF 6
35
PF 6
28
SbF 6
4
AsF 6
8
BF 4
570
BF 4
110
PF 6
14
AsF 6
100
BF 4
38
29
15
References page 11-180
TABLE 6. cont'd Photosensitizer
Cationic photoinitiator
Xanthone Michler's ketone Thioxanthone 10-Methylacridone Acridone Anthracene Chlorothioxanthone Pyrene Benzophenone Isopropylthioxanthone
Anion
Solvent
10-7Are (1/mol/s)
Cl"
M
140
10~7A:q (1/mol/s)
Refs. 30
0.7 200 350 740 M (NO2Cp)2I+
l
Cl"
31 28
400 130 500 250
TABLE 7. EXCITATION TRANSFER RATE CONSTANTS (kT) FOR THIOXANTHONES AND PHOTOINITIATORSa Thioxanthone
Initiator
Solvent
TXI
HMK
Toluene Methanol Toluene Methanol Toluene Methanol Toluene Methanol Toluene Methanol Toluene Methanol
OMK TPMK NMK ETX
TPMK
ITX
TPMK
10 " 6 ^ x (1/mol/s) 100 290 75 380 240 630 4700 7900 12 110 60 55
"Ref. 32.
ANNEX TO TABLE 7. COMPOUND CHEMISTRIES
TX's
R
Ri
R2
R3
R4
Abbrev.
Triplet state energy level (kcal/mol)
H H CH 3 H
Cl CH(CH 3 ) 2 H H H
H H COOET
H H H COOET
CTX ITX ETX TXI
62 61 58,5 63
Mok's H SCH 3 OCH 3 N(CH 3 ) 2
HMK TPMK OMK NMK
65 61 65 63
TABLE 8. TRIPLET STATE LIFETIMES (TT) OF THE SENSITIZER (TXI) IN DIFFERENT MEDIA*, AND RATE CONSTANT (kj) OF THE INTERACTION BETWEEN TXI AND TPMK* XT
tl
Hr6Jkx
Medium
(ns)
(cp at 28° C)
(I/moI/s)
TMPTAC (100%) Acrylate (66/33) Toluene-Ep. acrylate (50/50) Toluene-TMPTA (25/75) Toluene-TMPTA (50/50) Toluene-TMPTA (75/25) HDDA^ (100%) HDDA-Ep. acrylate (50/50) Toluene-HDDA (50/50) Toluene-HDDA-Ep. acrylate (25/50/25) Toluene-PETAe (50/50) Toluene-PETA-Ep. acrylate (43/43/14) Toluene Methanol
650 2200 1500
40 185 9.5
80 31 35
270 200 280 650 2500
5.8 1.7 0.9 5.2 58
135 <40 150 95 22
1000 850
1.2 5.8
140 68
220 360
3.1 6.9
40 69
50 140
0.53 0.52
240 630
TABLE 11. RATE CONSTANT OF INTERACTION OF KETONES AND LIGHT STABILIZERS IN SOLUTION Photoinitiator
Light stabilizer
l
Benzophenone
LSI LS2 LS3 LS4 LS5 SL6 LSI LS7
6500 8550 10300 15000 7050 5900 500 700
Acetone
Refs. 34
35 36
ANNEX TO TABLE 11. LSI:
a
Viscosity: 77. Ref. 33; for formula, see Annex to Table 7. Trimethylolpropane triacrylate. ^Hexanedioldiacrylate. Tentaerythritol triacrylate. &
LS2:
TABLE 9. SOME VALUES OF THE TRIPLET STATE ENERGY LEVELS OF PHOTOINITIATORS AND MONOMERS
Compound
Triplet state energy (AE) (kcal/mol)
Ila I4a I7a I8a I9b M2 I14a 124
69 73 53 53 59 61 75 57
Cited in Ref. 13
LS3:
Cited in Ref. 38 LS4:
TABLE 10. VALUES OF T°, T1, AND IrJt IN SOLUTION Photoinitiators
t j (ns)
Xj (ns)
4200
4000
10"6JkJ (1/mol/s)
LS5:
0.85 LS6:
3300
2000
14
470
470
<5
4000
1750
24
LS7:
determined in bulk epoxyacrylate-HDDA (60:4OwAv); a in solution b in the presence of LSI (2%).; Ref. 34.
References page 11-180
C. REFERENCES 1. (a) "Lasers in Polymer Science and Technology: Applications", J. R Fouassier, J. F. Rabek (Eds.), CRC Press, Boca Raton, 1990. (b) "Radiation Curing in Polymer Science and Technology", J. P. Fouassier, J. F. Rabek (Eds.), Chapman & Hall, London, (1993). 2. J. P. Fouassier, "Photoinitiation, Photopolymerization, Photocuring", Hanser, Munich, (1995). 3. (a) C. Decker, in: S. P Pappas, (Ed.), "Radiation Curing: Science and Technology", Plenum Press, New York, 1992. (b) C. Decker, B. Elzaouk in "Laser Curing of Photopolymers", Proc. Polymer Photochemistry Symposium, Genes, 112,(1993). (c) C. Decker, B. Elzaouk, Eur. Polym. J., 31 (12), 1155 (1995). 4. D. Ruhlmann, J. R Fouassier, Eur. Polym. J., 27 (9), 991 (1991). 5. D. Ruhlmann, J. R Fouassier, W. Schnabel, Eur. Polym. J., 28 (3), 287 (1992). 6. D. Ruhlmann, E Wieder, J. R Fouassier, Eur. Polym. J., 28 (6), 591 (1992). 7. R. Kuhlmann, W. Schnabel, Polymer, 18, 1163 (1977). 8. J. P. Fouassier, in: J. R Fouassier, J. F. Rabek (Eds.) "Lasers in Polymer Science and Technology: Applications", CRC Press, Boca Raton, 1990. 9. J. R Fouassier, D. J. Lougnot, Polymer Comm., 31, 418 (1990). 10. J. R Fouassier, D. J. Lougnot, J. Chem. Soc, Faraday Trans., 1, 83 (9), 2935 (1987). 11. G. Amirzadeh, R. Kuhlmann, W. Schnabel, J. Photochem., 10, 133 (1979). 12. J. R Fouassier, D. J. Lougnot, L. Avar, Polymer, 36 (26), 5005 (1995). 13. J. R Fouassier, in: J. R Fouassier, J. F. Rabek (Eds.) "Radiation Curing in Polymer Science and Technology", Chapman & Hall, London, vol. II, 1993. 14. T. Sumiyoshi, W. Schnabel, A. Henne, J. Photochem., 32, 191 (1986). 15. D. Ruhlmann, K. Zahouily, J. R Fouassier, Eur. Polym. J., 28 (9), 1063 (1992). 16. J. R Fouassier, D. Burr, Macromolecules, 23, 3615 (1990). 17. J. R Fouassier, D. J. Lougnot, J. C. Scaiano, Chem. Phys. Lett., 160, 335 (1989). 18. R J. Wagner, M. J. Lindstrom, Jacs, 109, 3062 (1987). 19. F. Morlet-Savary, J. R Fouassier, H. Tomioka, Polymer, 33, 4202 (1992). 20. G. Amirzadeh, W. Schnabel, Makromol. Chem., 182, 2821 (1981).
21. R. Kuhlmann, W. Schnabel, Angew. Makromol. Chem., 57, 195 (1977). 22. R. Kuhlmann, W. Schnabel, Polymer, 17, 419 (1976). 23. F. Morlet-Savary, J. R Fouassier, T. Matsumoto, K. Inomata, Polymers for Adv. Techn., 5, 56 (1994). 24. N. S. Allen, A. W. Timms, W. A. Green, F. Catalina, T. Corrales, S. Navaratnam, B. J. Parsons, J. Chem. Soc. Faraday, 90, 83 (1994). 25. D. J. Lougnot, C. Turck, J. R Fouassier, Macromolecules, 22, 108 (1989). 26. W. Schnabel, in: J. R Fouassier, J. F. Rabek (Eds.), "Lasers in Polymer Science and Technology: Applications", vol. II, CRC Press, Boca Raton, 1990. 27. T. Sumiyoshi, W. Weber, W Schnabel, Z. Naturforsch, 40a, 541 (1985). 28. J. R Fouassier, D. Burr, J. V. Crivello, J. Photochem. Photobiol., A: Chem., 49, 318 (1989). 29. G. Mannivannan, J. R Fouassier, J. V. Crivello, J. Polym. Sci. Part A: Polym. Chem., 30, 1999 (1992). 30. H. J. Timpe, K. R Kronfeld, U. Lammel, J. R Fouassier, D. J. Lougnot, J. Photochem., 52, 111 (1990). 31. M. R. V. Sahyun, R. J. DeVoe, R M. Olofson, in: J. R Fouassier, J. F. Rabek, (Eds.), "Radiation Curing in Polymer Science and Technology", vol. II, Chapman & Hall, London, 1993. 32. A. Bohrer, G. Rist, K. Dietliker, V. Desobry, J. R Fouassier, D. Ruhlmann, Macromolecules, 25, 4182 (1992). 33. J. R Fouassier, D. Ruhlmann, Eur. Polym. J., 29 (4), 505 (1993). 34. J. R Fouassier, D. Ruhlmann, A. Erddalane, Macromolecules, 26, 721 (1993). 35. J. R Guillory, C. F. Cook, Jacs, 95, 4885 (1973). 36. R Bortolus, in: J. R Fouassier, J. F. Rabek (Eds.), "Radiation Curing in Polymer Science and Technology", vol. II, Chapman & Hall, London, 1993. 37. H-J. Timpe, Topics in Current Chemistry, vol. 156, 167, (1990). 38. H-J. Timpe, K-R Kronfeld, J. Photochem. & Photobiol., A: Chem., 46, 253 (1989). 39. J. C. Netto-Ferreira, D. Weir, J. C. Scaiano, J. Photochem. & Photobiol., A: Chem., 48, 345 (1989). 40. J. C. Scaiano, L. C. Stewart, J. Am. Chem. Soc, 105 (11), 3609 (1983). 41. E. Klimtchuk, M. A. J. Rodgers, D. C. Neckers, J. Phys. Chem., 96 (24), 9817 (1992). 42. Y. Yagci, W. Schnabel, Makromol. Chem., Rapid Commun., 8, 209 (1987). 43. Y. Yagci, S. R Pappas, W. Schnabel, Z. Naturforsch, 42a, 1425 (1987).
F r e e
R a d i c a l
C o p o l y m e r i z a t i o n
R e a c t i v i t y
R a t i o s
Robert Z. Greenley* Monsanto Co., 544 Oak Valley Drive, St. Louis, MO 63131, USA A. Introduction B. Tables Table 1. Copolymer Reactivity Ratios Table 2. Listing of Quick Basic (Microsoft) Program for Calculating Reactivity Ratios C. References A.
11-181 11-182 11-182
II-288 II-290
INTRODUCTION
When a vinyl monomer is copolymerized with a second monomer, the relationship between the composition of the initially formed copolymer and the initial monomer mixture is given by
where m \ is the number of moles of monomer 1 entering the copolymer, ra2, the number of moles of monomer 2 entering the copolymer, Mi, the number of moles of monomer 1 in the monomeric mixture, M2, the number of the moles of monomer 2 in the monomer mixture, and r\ and r2 are the monomer reactivity ratios. The monomer reactivity ratios, r\ and r 2 , for any monomer pair are the ratios of the rate constants of the different propagation reactions:
with r\ = &11/&12, ri = ^22/^21- ~ M" represents a polymer chain ending in a radical derived from monomer M. The original compilations of reactivity ratios and their references were published by L. J. Young in the first two editions of this Handbook. In the third edition, the original listings and those through 1986 were re-evaluated. This fourth edition contains an additional 548 evaluated monomer pairs giving a total of 3,265 such pairs. Only free * Retired.
radical reactivity ratios are listed. When the original references were available, they were read. If the experimental data was published, the reactivity ratios were recalculated according to the methods of Kelen and Tudos (803,804). The 95% confidence limits for the reactivity ratios were also calculated (805). If the authors used this method for r-value evaluation, including adjustment of the monomer feeds for total conversion, then the reported values were utilized. There are a number of reported reactivity ratios that are not reported here. This is due to the absence of these values in the abstracts of papers which were published in journals unavailable to the author. All of the monomer pairs in Table 1 are cross-referenced. The full spelling of each monomer was included in its Monomer 1 citation. Sometimes truncated but distinguishable names have been used in the Monomer 2 lists. If only the reactivity ratios and reference are given, then, either no experimental data was given or the journal was not available and the Chemical Abstracts summary was the source of the data. If a Y or N (yes or no) appears in the conversion (Conv.) column then the reactivity ratios were recalculated. If a recalculation was performed but the 95% confidence columns (95%) are still left blank, it indicates that only two feed/polymer data pairs were available. In general, if there is a citation (Y or N) in the Conv. column but no reactivity ratios are shown in the reactivity ratio columns, the copolymerization did not follow the copolymerization equation (ionic or penultimate effects were prevalent). In a few cases, the data were too scattered to allow a reactivity ratio calculation. Recalculations yield negative reactivity ratios in several cases. We are aware that this is a physically unrealistic artifact. When the 95% confidence limits are applied to these negative numbers, a value of zero usually falls within these limits. It may be noted that a single reference sometimes contains a variety of reactivity ratios for one monomer pair. The reader may assume that these result from a change of polymerization conditions; e.g., different polymerization temperatures or polymerization media of varying polarity. For those who are interested in using the Kelen-Tudos calculations, a listing of a simplistic program written in QuickBasic (Microsoft) is also given (Table 2).
B. TABLES TABLE 1. COPOLYMER REACTIVITY RATIOS Monomer 1 Acenaphthalene Acenaphthalene Acenaphthalene Acenaphthalene Acenaphthalene Acenaphthalene Acenaphthalene Acenaphthalene Acenaphthalene Acenaphthalene Acenaphthalene Acenaphthalene Acenaphthalene Acenaphthalene Acenaphthalene Acenaphthalene Acetamide, A^-(4-methacryloyloxyphenyl)2-(4-methoxy) Acetamide, TV-vinylAcetamide, Af-vinylAcetamide, AT-vinylAcetamide, N-vinylAcetamide, N-vinylAcetamide, Af-vinylAcetanilide, 4-(2-methacryloyloxy)ethyloxy) Acetanilide, 4-(2-methacryloyloxy)hexyloxy) Acetanilide, 4-(methacryloyloxy)Acetate, 2-chloro-, vinyl Acetate, allyl Acetate, chloro-, allyl Acetate, dichloro-, allyl Acetate, isopropenyl Acetate, trichloro-, allyl Acetylene, phenylAcetylene, phenylAcetylene, phenylAcetylene, phenylAcetylene, phenylAcetylene, phenylAcetylene, phenylAcetylene, phenylAcetylene, phenylAcetylene, phenylAcetylene, phenylAcetylene, phenylAcetylene, phenylAconitate, trimethyl Aconitate, trimethyl Aconitate, trimethyl Aconitate, trimethyl Aconitate, trimethyl Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein
Monomer 2 Acrylate, (-)-menthyl Acrylonitrile Carbazole, N-vinylFumarate, diisopropyl Maleic anhydride Maleic anhydride Maleimide, N-cyclohexylMethacrylate, (-)-menthyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylonitrile Pyrrolidone, N-vinylPyrrolidone, N-vinylStilbene Styrene Methacrylate, 2-hydroxyethyl Acrylamide Methacrylate, Methacrylate, Methacrylate, Vinyl acetate Vinyl acetate Methacrylate,
rx
2.56 6.62 2.57 0.46 0.46 0.57 2.48 1.05 0.99 2.25 2.38 5.65 0.33 1.49
±95%
1.77 0.13 0.55 0.14 0.15
0.23
r2
0.02 -0.03 0.06 0.02 -0.04 0.11 0.316 0.36 0.38 0.44 0.15 -0.01 3.81 0.61
±95%
Conv.
Refs.
Y
645 575 331 1039 1039 26 1039 645 326 326 575 575 326 326 725 525 1051
0.12
N
0.05
N
0.085 0.04 0.04
Y N N
0.04
N N N
2-hydroxyethyl
0.3 0.19 0.71 0.01 5.5 21 0.67
1.4 2.65 1.18 2.1 0.6 0 1.39
984 984 984 984 984 984 1096
Methacrylate, 2-hydroxyethyl
0.87
1.19
1096
Methacrylate, 2-hydroxyethyl Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Fumarate, diisopropyl Vinyl acetate Acrylate, methyl Acrylate, methyl Acrylonitrile Isoprene Maleic anhydride Methacrylate, methyl Methacrylate, butyl Methacrylate, isobutyl Methacrylate, methyl Methacrylate, methyl Methacrylonitrile Pyridine, 2-vinylStyrene Acrylonitrile Butadiene Styrene Vinyl chloride Vinylidene chloride Acrylamide Acrylamide Acrylate, butyl Acrylate, butyl Acrylate, ethyl Acrylate, ethyl Acrylate, methyl Acrylate, methyl
1.94 1.18 0.43 0.69 0.54 0.011 0.28 0.272 0.093 0.325 0.1 0.08 0.2 0.21 0.27 1.69 0.07 0.04
0.78 0.8 1.8 0.77 0.57 0.67 0.41 0.622 0.664 0.266 3.01 0.06 1.5 1.7 1.9 -0.06 1.111 0.78
1096 892 1045 1045 1045 1038 1045 60 731 60 648 797 443 565 565 357 732 648 192 357 147 147 147 147 149 207 208 291 292 291 292 207 291
methyl methyl methyl
0.33 -0.48 0 -0.013 0.19 0.15 1.95 1.59 1.86 2.29 1.2 1.98 -0.07 1.41
0.072 0.01 0.083
26.56 0.016 0.12 0.11 0.22 0.009 0.94 0.58 0.1 0.19 0.58 0.44 0.03 0.4
0.324 4.24 0.4 1.026 0.04 64.6 0.8 0.18 0.638 1.12 0.6 1.09 7.86 0.83
0.062 0.045 0.044
Y Y Y
0.16 0.095
Y Y
23.74 0.23 0.02 0.032 0.41
Y Y Y Y Y Y N N N Y N
0.25 3.58 0.12
N N Y
0.02 0.92 0.4 0.091
TABLE 1. cont'd Monomer 1 Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein diethylacetal Acrolein diethylacetal Acrolein, methylAcrolein, methylAcrolein, methylAcrolein, methylAcrolein, methylAcrolein, methylAcrolein, methylAcrolein, methylAcrolein, methylAcrolein, methylAcrolein, methylAcrolein, methylAcrolein, 2-chloroAcryl-2/-ethyl-4,5,7-trinitro9-flurenone-2-carboxylate Acryl-2/-ethyl-4,5,7-trinitro-9-flurenone2-carboxylate Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide
Monomer 2 Acrylate, methyl Acrylic acid Acrylic acid Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Methacrylate, methyl Methacrylate, methyl Methacrylonitrile Methacrylonitrile Pyridine, 2-vinylStyrene Styrene Styrene Styrenesulfonate, /?-, sodium Styrenesulfonate, /?-, sodium Styrenesulfonate, p-, sodium Vinyl acetate Vinyl chloride Acrylonitrile Maleic anhydride Acrylate, butyl Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Methacrylate, methyl Methacrylonitrile Methacrylonitrile Methacrylonitrile Styrene Styrene Vinyl acetate Styrene Acrylate, iV-(2-hydroxyethyl)carbazolyl Methacrylate, JV-(2-hydroxyethyl)carbazolyl Acetamide, Af-vinylAcrolein Acrolein Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid, cw-3-bromoAcrylic acid, ds-3-ethylAcrylic acid, trans-3-bromoAcrylic acid, frcms-3-ethylAcrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Cinnamic acid, cisCinnamic acid, transCrotonic acid Crotonic acid Crotonic acid Crotonic acid Crotonic acid, cisCrotonic acid, trans-
r\
±95%
r2
±95%
Conv.
Refs.
0.93 1.24
0.38 0.28
N Y
0.06 0.03 0.01
N N N
0.05 0.4 0.05
Y N N
0.03 0.017 0.02 0.006 0.033 0.071 0.009 0.12 0.11
N Y N Y Y Y Y N N
0.19
Y
0.01
N
0.017
N
0.05 0.079
Y
292 57 57 207 207 208 504 291 292 208 446 208 291 292 307 57 57 57 207 271 767 767 589 455 587 589 91 589 208 587 589 223 589 589 806 715
0.096
Y
703
0.58 0.1 0.029 0.069 0.012 0.14
N N Y Y Y N
0.11 0.1 0.16 0.11 0.033 0.1 0.75
Y Y Y Y Y Y N
0.28 0.15 0.14 0.19
Y Y Y Y
0.024
Y Y
2.54 2.48 0.5 1.16 1.07 1.52 1.28 0.76 0.59 0.68 0.72 2.64 0.216 0.02 0.32 0.395 0.26 0.113 3.04 5.22 0.02 0.18 2.5 1.7 3.8 3.8 1.72 0.4 1.78 1.25 1.25 0.833 0.3 0.98 0.15 0.585
0.07 0.028
1.08 0.08 1.15 0.88 0.71 0.48 0.6 1.136 1.33 1.17 1.2 -0.12 0.257 0.22 0.205 0.327 0.047 0.01 -0.02 0.03 11.19 0.07 0.02 0.15 0.15 0.15 0.03 0.1 0.41 0.45 0.45 0.173 0.41 0.15 0.02 0.912
0.102
0.022
0.773
1.4 0.8 0.18 1.08 0.445 1.346 0.598 0.58 1.06 7.64 6.32 4.13 8.19 0.81 1.08 0.5 1.36 1.3 3.84 3.4 3.76 4.23 4.72 5.32 12
0.13 0.08 0.07 0.12 0.3 0.12 0.14 0.036 0.01 0.002 0.092 0.16 0.018 0.43 0.13
0.42 0.07 0.092
0.23 0.02 0.17 0.075 0.044 0.047 1.67 0.68 0.76 1.09 0.11 0.51 0.26 0.68 0.24 0.89 1.37
0.33
0.3 1.95 1.59 0.288 1.644 0.341 1.38 3.8 0.29 -0.2 -0.16 -0.33 -0.21 0.863 0.97 1.8 0.88 0.8 -0.24 -0.18 -0.19 0.11 0.12 -0.085
984 207 208 221 278 278 37 869 869 298 298 298 298 228 228 330 421 461 298 298 298 298 569 569 341 341
References page II - 290
TABLE 1. cont'd Monomer 1
Monomer 2
r\
Dioxolane, l,3,4-methylene-2-trichloro- 8.6 Maleic anhydride 0.56 Methacrylate, 2-hydroxyethyl 0.05 Methacrylate, 2-hydroxyethyl 0.14 Methacrylate, 3-methoxy0.04 2-hydroxypropyl Acrylamide Methacrylate, dimethylaminoethyl 0.52 sulfate Acrylamide Methacrylate, methyl 2.29 Acrylamide Methacrylate, methyl 0.53 Acrylamide Methacrylate, methyl 0.82 Acrylamide Methacrylate, methyl 0.9 Acrylamide Methacrylic acid 0.57 Acrylamide Methacrylic acid 0.58 Acrylamide Methacrylic acid 0.56 Acrylamide Methylenebutyrolactone 0.3 Acrylamide Styrene 0.58 Acrylamide Styrene 1.32 Acrylamide Styrene 0.33 Acrylamide Styrene 0.59 Acrylamide Styrene 8.97 Acrylamide Styrene 0.2 Acrylamide Succinimide, N-vinyl1.86 Acrylamide Vinyl chloride Acrylamide Vinyl methyl ketone 3.99 Acrylamide Vinyl methyl ketone 1.02 Acrylamide Vinylene carbonate 13.8 Acrylamide Vinylmethylphenylsulfonium 3.4 tetrarluoro Acrylamide Vinylsulfonic acid 3.5 Acrylamide, 2-chloro-WV-dimethylMethacrylate, methyl -0.159 Acrylamide, 2-chloro-AW-dimethylStyrene -0.036 Acrylamide, JV,7V-dibutylStyrene 0.294 Acrylamide, WV-diethylAcrylic acid 0.35 Acrylamide, iV,iV-diethylButanoate, 3-acrylamido-3-methyl-, 0.987 sodium Acrylamide, A^TV-diethylMethacrylate, methyl 0.41 Acrylamide, MN-diethylStyrene 0.39 Acrylamide, WV-diethylStyrene 0.34 Acrylamide, A^-diethylStyrene 0.18 Acrylamide, WV-dimethylMethacrylate, methyl 0.57 Acrylamide, iV,N-dimethylMethacrylate, methyl 0.59 Acrylamide, A^Af-dimethylMethacrylate, methyl 0.21 Acrylamide, A^V-dimethylStyrene 0.12 Acrylamide, A^V-dimethylStyrene 0.49 Acrylamide, A^V-dimethylStyrene 0.47 Acrylamide, MiV-dimethylSulfonate, 2-acrylamido1.108 2-methylpropane Acrylamide, N,7V-dimethylVinyl methyl ketone 0.82 Acrylamide, A^-(2-(4-hydroxyphenyl)ethyl)- Methacrylamide, A^-(2-hydroxypropyl)0.95 Acrylamide, N-(2-(propionamide)Styrene 0.86 Acrylamide, Af-methylMethacrylate, methyl 0.05 Acrylamide, N-methylol Acrylate, butyl 0.61 Acrylamide, Af-methylol Acrylate, ethyl 1.4 Acrylamide, N-methylol Acrylate, methyl 1.9 Acrylamide, iV-methylol Acrylonitrile 1.2 Acrylamide, N-methylol Acrylonitrile 2.33 Acrylamide, N-methylol Acrylonitrile 2.56 Acrylamide, TV-methylol Methacrylate, methyl 0.7 Acrylamide, N-methylol Methacrylate, methyl 0.7 Acrylamide, JV-methylol Styrene 0.48 Acrylamide, Af-methylol Vinyl chloride Acrylamide, N-methylolStyrene 0.4 Acrylamide, N-octadecylAcrylonitrile 1.4 Acrylamide, N-octadecylMethacrylate, methyl 0.42
±95%
Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide
r2
±95%
Conv.
0.037 0 1.89 0.98 3.98
616 655 689 928 689
0.05
1.9
0.2
0.44 0.09
2.34 3 2.53 3 1.63 4.4 0.15 2.85 1.17 1.21 1.49 1.13 0.65 1.05 0.17
0.17 0.09
N N
0.45
N
0.06 0.04 0.16
N N N
0.03
N
0.7 0.13
0.47 0.75 0.05 0.1
0.44 0.23
Y Y Y
0.15 0.502 0.152 0.058 0.12 0.153
0.3 2.71 1.29 1.6 0.36 0.22
0.1 0.398 0.065 0.058 0.04 0.138
N Y
0.15
1.65 1.23 1.36 1.54 2.15 2.8 2.64 1.15 1.37 1.32 0.162
0.16
N
0.08 0.1 0.15 0.35 0.1 0.12 0.949
N N N N N N Y Y
1.07
0.12 0.13 0.14 0.43
0.08 0.09 0.21 0.3 0.15 0.2 0.59
Refs.
0.36 0.09 0.3 0.72
0.1 1.01 1.84 1.14 0.87 1.4 1.3 0.7 0.98 0.22 1.62 1.62 0.03
0.43 0.09 0.21 0.09
0.03 0.17 0.11
1.55 1.034 4.119
0.05 0.02 0.07
1052
Y Y
N N
Y Y Y
314 314 314 691 1028 852 852 746 295 314 314 314 343 555 600 156 609 609 387 793 1066 917 917 806 205 857 170 739 739 739 315 315 691 170 315 315 857 609 965 295 691 441 442 441 442 577 596 593 596 596 157 891 119 290
TABLE 1. cont'd Monomer 1 Acrylamide, N-octadecylAcrylamide, N-octadecylAcrylamide, Af-octadecylAcrylamide, Af-octylAcrylamide, N-propylAcrylamide, N-propylAcrylamide, N-tert-buty\Acrylamide, N-tert-buty\Acrylamide, a-fluoroAcrylamido, 1-,-1-deoxy-D-glucitol Acrylamido, 1-,-1-deoxy-D-glucitol Acrylamido, 1-,-1-deoxy-D-glucitol Acrylamido, 2-,2-methylpropanesulfonate, sodium Acrylamido, 2-,-2-methylpropanesulfonic acid Acrylamido, 2-,-2-methylpropanesulfonic acid Acrylamido-2-methylpropane sulfonate sodium salt Acrylamidomethylamino, /?-, azobenzene Acrylamidomethylamino, p-, azobenzene Acrylate, (-)-menthyl Acrylate, (-)-menthyl Acrylate, 1,1,5-trihydroperfluoroamyl Acrylate, 2,3-dibromopropyl Acrylate, 2,4,5-trichlorophenyl Acrylate, 2,4,5-trichlorophenyl Acrylate, 2,4,6-tribromophenyl Acrylate, 2,4-dinitrophenyl Acrylate, 2,4-dinitrophenyl Acrylate, 2(0-ethyl methylphosphonoxy)-, methyl Acrylate, 2-chloroethyl Acrylate, 2-chloroethyl Acrylate, 2-chloroethyl Acrylate, 2-chloroethyl Acrylate, 2-chloroethyl Acrylate, 2-chloroethyi Acrylate, 2-chloroethyl Acrylate, 2-chloroethyl Acrylate, 2-chloroethyl Acrylate, 2-chloroethyl Acrylate, 2-chloroethyl Acrylate, 2-chloroethyl Acrylate, 2-chloroethyl Acrylate, 2-chloroethyl Acrylate, 2-chloroethylglucitol Acrylate, 2-cyano-, methyl Acrylate, 2-cyano-, methyl Acrylate, 2-cyanoethyl Acrylate, 2-ethylhexyl Acrylate, 2-ethylhexyl Acrylate, 2-ethylhexyl Acrylate, 2-ethylhexyl Acrylate, 2-ethylhexyl Acrylate, 2-ethylhexyl Acrylate, 2-hydroxyethyl Acrylate, 2-hydroxyethyl Acrylate, 2-hydroxyethyl Acrylate, 2-nitrobutyl Acrylate, 2-nitrobutyl Acrylate, 2-nitrobutyl Acrylate, 3,4-epoxyhexahydrobenzyl
Monomer 2 Styrene Vinyl acetate Vinylidene chloride Styrene Acrylate, butyl Acrylate, methyl Acrylonitrile Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Styrene Vinyl acetate Vinyl acetate
r\ 0.54 8.25 1.4 0.258 0.4 0.26 1.14 2.83 0.148 0.05 0.03 0.98 11.6
±95% 0.14 1.46 0.11 0.119
0.081 0.09 0.02 0.87
r2 2.08 0.004 0.432 2.715 0.8 1.2 0.2 0.25 2.13 3.75 2.42 0.03 0.05
±95%
Conv.
0.12 0.011 0.008 0.244
Y Y Y
0.136 0.24 0.08 0.17
Y N N N
Refs. 290 119 119 806 730 730 709 709 823 258 258 258 700
Methacrylate, 2-hydroxyethyl
0.9
0.86
618
Methacrylate, 2-hydroxypropyl
1.03
0.89
618
iV-Vinylpyrrolidone
0.66
0.13
939
0.083 0.126
858 858 645 667 809 643 840 622 643 716 716
Styrene 8.5 Vinyl acetate 12.98 Acenaphthalene Pyridine, 4-vinyl0.291 Methacrylonitrile 0.14 Styrene 0.16 Pyrrolidone, N-vinyl0.163 Styrene 0.23 Styrene 0.1 Acrylate, N-(2-hydroxyethyl)-carbazolyl 0.158 Methacrylate, A^-(2-hydroxyethyl)0.186 carbazolyl Methacrylate, methyl 0.44 Acrylate, ethyl Acrylate, methyl Acrylonitrile Itaconate, bis(tri-rc-butyltin) Itaconic anhydride Itaconic anhydride Maleic anhydride Methacrylate, methyl Pyrrolidone, Af-vinylStyrene Styrene Styrene Vinyl butyl ether Vinyl isobutyl ether Styrene Styrene, a-methylVinyl acetate Styrene Acrylate, glycidyl Methacrylate, glycidyl Styrene Styrene Vinyl acetate Vinyl chloride Acrylate, butyl Acrylate, ethyl Acrylate, methyl Acrylonitrile Methacrylate, methyl Styrene Acrylonitrile
1.03 1.07 0.87 0.683 -0.016 0.251 7.15 0.37 0.52 0.1 0.139 0.12 2.01 2.24 0.14 0.001 0.5 0.128 1.12 0.09 0.31 0.26 7.5 4.15 0.9 0.97 0.9 1.76 0.27 0.12 0.388
0.45
Y Y
0.008 0.048
Y Y
0.015 0.009
2.32 1.03 0.42 0.012 0.277 0.2 0.109 0.243
0.026 0.034
Y
0.25
0.73
0.04
0.017 0.02 0.021
0.022 0.021 0.31 0.17 0.083
0.09 0.074 0.07 0.13 0.6
0.23 0.24 0.13 0.69 0.04 0.01 0.074
0.9 0.9 1.03 0.391 2.46 2.61 0.027 2.15 0.03 0.55 0.494 0.54 0 0 0.49 0.05 0.005 0.399 1.18 2.41 0.96 0.94 0.04 0.16 0.3 0.5 0.94 0.67 1.19 0.35 0.25
882
0.38 0.32 0.004
Y Y Y
0.47 0.097
Y Y
0.2 0.032 0.06 0.46 0.3
Y N Y N
0.06 0.03 0.04 0.25 0.12 0.03 0.13
N N N N N N Y
726 726 790 940 365 365 117 790 790 140 178 790 790 790 806 452 452 178 126 674 126 463 570 510 868 868 868 234 234 234 680
References page II - 290
TABLE 1. cont'd Monomer 1 Acrylate, 3,4-epoxyhexahydrobenzyl Acrylate, 4-acetylphenyl Acrylate, P-acetoxymethyl-, methyl Acrylate, P-acetoxymethyl-, methyl Acrylate, |3-chloro-2-hydroxypropyl Acrylate, p-ethoxy-, ethyl Acrylate, (3-ethoxy-, ethyl Acrylate, N-(2-hydroxyethyl)3,6-dichlorocarbazolyl Acrylate, 7V-(2-hydroxyethyl)carbazolyl Acrylate, AH2-hydroxyethyl)carbazolyl Acrylate, iV-(2-hydroxyethyl)carbazolyl
Monomer 2 Styrene Methacrylate, glycidyl Methacrylate, methyl Styrene Acrylonitrile Acrylonitrile Styrene Methacrylate, 2,4-dinitrophenyl
Acryl^'-ethyl-^J-trinitro^-fluorene Acrylate, 2,4-dinitrophenyl Acryloyl-(3-hydroxyethyl3,5 -dinitrobenzoate Acrylate, iV-(2-hydroxyethyl)carbazolyl Methacryloyl-p-hydroxyethyl3,5-dinitrobenzoate Acrylate, A^-(2-hydroxyethyl)carbazolyl Methacryloyl-p-hydroxyethyl3,5-dinitrobenzoate Acrylate, a-(4-chlorobenzyl)-, ethyl Styrene Acrylate, a-(4-cyanobenzyl)-, ethyl Styrene Acrylate, a-(4-methoxybenzyl)-, ethyl Styrene Acrylate, a-((9-ethyl methylphosphonoxy)- Methacrylate, methyl methyl Acrylate, a-(hydroxymethyl)-, methyl Styrene Acrylate, a-[2,2-bis(carbomethoxy)ethyl]-, Methacrylate, methyl methyl Acrylate, a-[2,2-bis(carbomethoxy)ethyl]-, Styrene methyl Acrylate, a-acetoxy-, ethyl Acrylate, a-chloro-, ethyl Acrylate, a-acetoxy-, ethyl Acrylate, ethyl Acrylate, a-acetoxy-, ethyl Methacrylate, methyl Acrylate, a-acetoxy-, ethyl Styrene Acrylate, a-acetoxy-, ethyl Vinyl acetate Acrylate, a-benzyl-, methyl Styrene Acrylate, a-benzyl-, ethyl Styrene Acrylate, a-benzyl-, methyl Methacrylate methyl Acrylate, a-benzyl-, methyl Methacrylate methyl Acrylate, a-bromo-, ethyl Styrene Acrylate, a-butyl-, methyl Styrene Acrylate, a-chloro-, methyl Methacrylate, methyl Acrylate, a-chloro-, ethyl Acrylate, a-methoxy-, methyl Acrylate, a-chloro-, ethyl Acrylate, a-acetoxy-, ethyl Acrylate, a-chloro-, ethyl Acrylate, a-fluoro-, ethyl Acrylate, a-chloro-, ethyl Acrylate, methyl Acrylate, a-chloro-, ethyl Acrylonitrile, a-methoxyAcrylate, a-chloro-, ethyl Methacrylonitrile Acrylate, a-chloro-, ethyl Styrene Acrylate, a-chloro-, ethyl Vinyl acetate Acrylate, a-chloro-, methyl Acrylonitrile Acrylate, a-chloro-, methyl Methacrylate, methyl Acrylate, a-chloro-, methyl Styrene Acrylate, a-chloro-, methyl Vinylidene cyanide Acrylate, a-chloro-, sodium Styrenesulfonate, /?-, sodium Acrylate, a-cyano-, methyl Acrylonitrile Acrylate, a-cyano-, methyl Acrylate, methyl Acrylate, a-cyano-, methyl Methacrylate, methyl Acrylate, a-cyano-, methyl Methacrylate, methyl Acrylate, a-cyano-, methyl Methacrylonitrile Acrylate, a-cyano-, methyl Styrene Acrylate, a-cyclohexyl-, methyl Styrene Acrylate, a-ethyl-, methyl Styrene Acrylate, a-ethyloxymethyl-, methyl Styrene Acrylate, a-fluoro-, ethyl Acrylate, a-chloro-, ethyl Acrylate, a-fluoro-, methyl Styrene Acrylate, a-hexafluoropropyloxymethyl-, Styrene methyl
rx
±95%
r2
±95%
Conv.
Refs.
0.3 0.13
N Y
1.8 27.03 0.032
N Y Y
680 1012 1091 1091 654 194 194 736
1.97 0.292 0.24 0.19 0.7 -0.26 -0.21 0.115
0.35 0.141
0.56 0.44 0.029
0.27 0.644 0.91 0.34 0.24 2.42 46.98 1.207
0.912 0.109 0.62
0.079 0.026 0.044
0.585 0.158 0.361
0.028 0.015 0.016
Y Y Y
715 716 702
1.04
0.14
0.08
0.026
Y
702
0.334
0.022
1.364
0.018
Y
719
1.03 0.65 0.71 0.44
0.13 0.09 0.24
0.04 0.06 0.33 0.73
0.09 0.05 0.3
806 806 806 851
0.34 0.04
0.36 3.7
932 1092
0.09
0.58
1092
0.3 0.968 0.608 0.173 5.621 0.175 0.9 0.173 0.09 0.44 0.205 1.13 0.58 1.71 2.9 3.22 0.9 2 0.32 30 1.76 1.92 0.3 0.313 0.27 0.68 0.34 0.03 0.135 0.15 0.61 -0.001 0.197 0.24 0.21 0.16 0.07
0.033 0.02 0.01 0.094 0.053 0.2 0.022 0.01 0.08 0.053 0.19
0.11 0.18 0.08 0.021 0.06 0.09 0.07 0.01 0.016 0.01 0.05 0.034 0.014 0.11
1.71 0.943 1.65 0.557 0.08 0.57 0.14 2.36 3.9 0.02 0.812 0.31 0.11 0.3 0.21 0.09 0.3 0.45 0.08 0.03 0.122 0.11 0.25 0.066 1.44 0.01 0.02 0.21 0.068 0.18 0.05 1.615 0.758 0.37 2.9 0.66 0.23
0.075 0.12 0.031 0.021 0.028 0.17 0.23 0.19 0.04 0.043 0.24
Y Y Y Y Y Y N Y Y
0.07 0.081 0.09
Y N
0.07 0.31 0.02 0.04 0.02 0.014 0.01 0.01 0.048 0.014
Y Y N N N Y N N Y Y
0.17
638 244 244 244 244 49 806 610 610 806 49 6 638 638 638 638 638 638 806 638 6 31 74 82 834 141 141 141 182 143 141 49 49 1047 638 806 1047
TABLE 1. cont'd Monomer 1 Acrylate, a-hydroxymethyl-, ethyl Acrylate, a-hydroxymethyl-, ethyl Acrylate, a-hydroxymethyl-, ethyl Acrylate, a-isobutyl-, methyl Acrylate, a-isopropyl-, methyl Acrylate, a-isopropyloxymethyl-, methyl Acrylate, a-methoxy, methyl Acrylate, a-methoxy-, methyl Acrylate, a-p-chlorobenzyl-, methyl Acrylate, a-/?-methoxybenzyl-, methyl Acrylate, a-phenoxymethyl-, methyl Acrylate, a- phenoxymethyl-, methyl Acrylate, a-phenyl-, methyl Acrylate, a-phenyl-, methyl Acrylate, a-phenyl-, methyl Acrylate, a-phenyl-, methyl Acrylate, a-phenyl-, methyl Acrylate, a-phenyl-, methyl Acrylate, a-phenyl-, methyl Acrylate, a-phenyl-, methyl Acrylate, a-phenyl-, methyl Acrylate, a-phenyl-, butyl Acrylate, a-phenyl-, chloroethyl Acrylate, a-phenyl-, propyl Acrylate, a-propyl-, methyl Acrylate, a-propyloxymethyl-, methyl Acrylate, a-seobutyl-, methyl Acrylate, a-tetrafluoropropyloxymethyl-, methyl Acrylate, a-tetrafluoropropyloxymethyl-, methyl Acrylate, a-trifluoroethyloxymethyl-, methyl Acrylate, a-trifluoromethyl-, methyl Acrylate, a-trifluoromethyl-, methyl Acrylate, a-trifluoromethyl-, methyl Acrylate, a-trifluoromethyl-, methyl Acrylate, a-trimethylsiloxy-, methyl Acrylate, benzyl Acrylate, benzyl Acrylate, benzyl Acrylate, benzyl Acrylate, benzyl Acrylate, benzyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl
Monomer 2
rx
±95%
Conv.
Refs.
0.229 0.17 0.03 0.022 0.052
Y N Y Y Y
0.078 0.222 0.109 0.038 0.05
Y Y Y Y
0.015 0.022 0.015 0.015 0.029
Y Y Y Y Y
0.068
Y
1011 1027 982 49 49 1047 638 806 905 905 1048 1048 141 141 141 49 143 141 399 488 49 488 488 488 49 1047 49 1047
0.668 1.34 0.546 0.202 0.036 0.26 0.11 0.513 0.255 0.13 0.755 0.256 1 6.7 0 0 0.25 1 0.4 0.45 1.275 0.107 0.201 0.126 0.208 0.29 0.004 0.61
Styrene
0.17
0.37
1047
Styrene
0.2
0.26
1047
-0.17 0 0.1 0 1.42 0.72 0.63 9.9 0.19 0.2 0.248 0.24 0.638 1.12 0.02 0.8 0.87 0.3 1.08 0.91 0.19 1.06 0.894 0.82 0.9 1.2 10.2 5.83 0.041 0.074 13.94 0.118
0.058 0.034 0.008 0.061 0.102
0.008 0.055 0.09 0.063 0.07 0.024
0.18 0.1 0.1 0.03 0.16 0.2 0.12 0.041 0.01 0.032 0.41
0.06 0.18 0.13 0.15 0.019 0.13 42.2 0.043 0.03 0.38 0.019
0.389 1.26 0.468 0.974 1.872 0.41 0.58 1.131 1.87 1.71 1.13 0.176 0.06 0.08 0.21 0.3 0.19 0.06 0.03 0.06 1.176 0.04 0.025 0.03 0.821 0.47 2.29 1.43
±95%
Azlactone, 2-vinyl-4,4-dimethylMethacrylate, methyl Styrene Styrene Styrene Styrene Acrylate, a-chloro-, ethyl Styrene Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Styrene Acrylate, methyl Acrylonitrile Methacrylate, methyl Methacrylate, methyl Methacrylonitrile Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Methacrylate, methyl
Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Styrene, p-chloroStyrene Acrylonitrile Acrylonitrile Allyl chloride Methacrylate, methyl Styrene Styrene 2-Oxazoline, 2-isopropenylAcrolein Acrolein Acrolein, methylAcrylamide, N-propylAcrylamide, Af-methylolAcrylate, 2-hydroxyethyl Acrylic acid Acrylic acid Acrylic acid, a-bromoAcrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Allyl acetate Allyl chloride Benzofuran, 2-vinylButadiene Ethylene Furan, 2-vinyl-5-methyl
0.12 0.062 0.127 0.042 0.034
r2
1.8 3.2 2.3 0.24 0.46 0.28 1.49 0.06 2.23 0.494 0.534 1.4 1.86 2.29 2.5 0.4 0.61 0.9 0.59 1.31 0.09 1.679 0.781 1.08 1 1 0.039 0.1 7.8 1.04 0.01 0.392
0.23 0.5 0.2 0.02
Y N N N
0.19
N
0.14 0.05 0.028 0.08 0.19 0.58
Y Y Y Y N
0.23 0.27 0.3
N N N
0.058 0.083 0.08
Y Y N
0.066
N
1.36 0.11 0.003 0.051
N Y N Y
681 825 825 825 1101 23 385 438 277 178 277 894 291 292 589 730 441 868 187 252 733 118 162 233 513 513 1053 438 1020 257 42 1105
References page II - 290
TABLE 1. cont'd Monomer 1 Acrylate, Acrylate, Acrylate, Acrylate,
butyl butyl butyl butyl
Acrylate, butyl Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate,
butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl cis-B-cyano-, methyl c/s-B-cyano-, methyl cresyl cyclododecyl cyclododecyl cyclododecyl cyclohexyl cyclohexyl cyclohexyl cyclohexyl cyclohexyl cyclohexyl di-, copper
Acrylate, di-, copper Acrylate, di-, copper
Monomer 2 Itaconate, bis(tri-w-butyltin) Itaconate, dimethyl Maleimide, iV-(2,4-dimethylphenyl)Methacrylate, 2-(Af,AT-dimethylcarbamoyloxy)ethyl Methacrylate, 2-chloro2,3,3,3-fluoropropyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxypropyl Methacrylate, 2-hydroxypropyl Methacrylate, butyl Methacrylate, glycidyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylic acid Oxazoline, 2,2-isopropenylPyridine, 2-vinylPyridine, 2-vinylPyridine, 4-vinylStyrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene, o-chloroStyrene, p-l-(2-hydroxybutyl)Styrene, p-octylamine sulfonate Succinimide, iV-vinylThiophene, 3-vinyl Vinyl acetate Vinyl bromide Vinyl bromide Vinyl chloride Vinyl fluoride Vinyl fluoride Vinyl methyl ketone Vinyl,/?-, benzylethylcarbinol Vinylanthracene, 9Vinylidene chloride Vinylidene chloride Vinylidene chloride Acrylonitrile Styrene Acrylonitrile Styrene Styrene Styrene N-Vinylpyrrolidone Styrene Styrene Styrene Styrene Styrene Methacrylate, di-, dicyclopentadienyltitanium Styrene Styrene
/*i
±95%
0.91 0.4 o.62 0.47
r2
±95%
Conv.
0.422 0.94 0.2 1.89
Refs. 940 398 788 600
0.079
0.304
0.221
0.636
N
927
0.09 0.171 0.24 0.3 0.083 0.13 0.11 0.43 0.31 0.24 0.1 0.11 0.23 0.25 0.34 0.38 -0.106 0.29 0.18 0.19 0.21 0.15 0.164 0.164 0.2 0.17 0.3 1.54 0.386 3.48 4.07 3.7 4.4 19 19 0.8 0.17 3.717 0.873 0.46 0.58
0.11 0.041 0.16
4.75 5.35 3.3 2.2 2.16 0.92 2.86 1.88 1.25 1.4 2.51 2.59 4.3 0.79 0.79 0.75 1.23 0.44 0.84 0.66 0.82 0.8 0.698 0.698 2.25 0.4 2.3 0.15 0.499 0.018 0.18 0.19 0.07 0.01 0.01 1.81 0.4 0.126 0.934 0.84 0.87
4.2 0.32 6.82
Y Y Y
0.57 0.2 0.32 0.4 0.31
Y N Y N N
0.14 0.34 0.08 0.11 0.1 0.21 0.03 0.2
N N
0.072 0.16
Y N
0.24
N
0.054 0.006
Y Y
358 333 662 187 674 30 639 87 187 862 236 78 78 1032 1032 1032 19 20 38 38 463 549 612 632 558 548 817 789 1000 301 268 268 518 604 606 53 591 123 118 464 464 1034 1034 363 806 806 806 1061 1061 806 806 806 806 876
0.052 0.15 0.018 0.07 0.1 0.01 0.04 0.05 0.06 0.05 0.099 0.05 0.03
3.39 0.44
0.06 0.046 0.022
0.773 0.34 0.31 0.301 1.297 0.272 0.254 0.16 0.17 0.18 1.09
0.067 0.15 0.08 0.072 0.088 0.048 0.141 0.13 0.09 0.07
0.72 0.47 0.54 0.461 0.122 0.913 0.885 0.53 0.7 0.58 0.89
0.15 0.14 0.08 0.07 0.014 0.107 0.102 0.11 0.12 0.1
0.12 0.56
0.08 0.09
5.94 1.74
0.05 0.03
N N N
N N Y
N N
829 829
TABLE 1.
cont'd
Monomer 1 Acrylate, di-, nickel Acrylate, di-, nickel Acrylate, di-, zinc Acrylate, di-, zinc Acrylate, dibutylchlorotin Acrylate, diethylaluminum Acrylate, diethylaluminum Acrylate, dodecyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ferrocenylmethyl
Monomer 2 Methacrylate, di-, dicyclopentadienyltitanium Styrene Acrylonitrile Styrene Acrylate, methyl Styrene Styrene Acrylonitrile 2-Oxazoline, 2-isopropenylAcrolein Acrolein Acrylamide, Af-methylolAcrylate, 2-chloroethyl Acrylate, 2-hydroxyethyl Acrylate, oc-acetoxy-, ethyl Acrylate, hydroxyethyl Acrylic acid Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Allyl chloride Benzofuran, 2-vinylCarbazole, N-vinylEthylene, 1,1-diphenylImidazolid-2-one, 1,3-divinylImidazolid-2-one, l-ethyl-3-vinylIsopropenylisocyanate Maleimide, 2,3-dimethylAf-(2-methacryloyloxy)ethyl Methacrylate, 2-(sulfonic acid)ethyl Methacrylate, 2-bromoethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxypropyl Methacrylate, 2-hydroxypropyl Methacrylate, butyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylic acid Norbornadiene Oxazoline, 2-, 2-isopropenylPropanesulfonate, 3-[diethyl2- (2-methacroy loxyethoxy)] ethyl Pyridine, 2-vinylPyridine, 2-vinylPyridine, 4-vinylPyrimid-2-one, 1,3-divinylhexahydroStyrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene 3-tri-rc-butylstannylTropone, 2-methacryloyloxyVinyl 2-chloroethyl ether Vinyl 2-chloroethyl ether Vinyl isobutyl sulfide Vinyl isobutyl sulfide Vinylanthracene, 9Vinylidene chloride Acrylate, methyl
r\
±95%
0.95 0.53 0.24 0.9 0.09 0.046 0.88 0.19 0.6 1.09 1.4 0.9 0.5 0.943 0.5 1.02 1.2 0.81 4 0.95 7.73 0.015 1.1 0.8 0.41 0.47 0.79 0.28 0.3 0.37 0.189 0.273 0.207 0.22 0.47 0.28 0.22
r2
±95%
Conv.
0.65 0.06 0.07 0.035 0.16 0.02 0.25 0.03 0.075 0.05 0.07 0.27
0.01 0.13 0.06 1.15
0.008 0.054 0.045 0.17 0.05
2.39 0.19 3.97
0.44
0.21 0.21 0.29 0.59 0.139 0.16 0.19 0.2 0.48 0.152 0.152 10.4 0.387 5 4.65 0.36 0.32 3.498 0.72 0.14
0.06
1.03
0.13 0.085
0.027 0.02 0.02 0.041 0.39
876
1.83 0.41 1.1 0.81 -0.002
0.02
N
0.02
N
0.016
2.37 1.39 1.2 1.98 1.4 1.03 0.97 0.968 0.88 0.91 0.92 1.16 0.66 0.44 0.08 5.76 0.27 0.5 -0.08 0.01 0.15 1.55
0.07 0.06
Y Y N
3.2 2.7 11.21 13.32 9.08 2.43 1.83 2 2.04
Refs.
0.44
N
0.24 0.033 0.09
N Y
0.08 0.78
N
0.334
N
0.03 0.01
N N
3.06
Y
0.43 1.05 3.95 0.39
Y Y Y Y
0.28
-0.01 1.39 0.19
0.03
N N N
0.02
Y
0.28 2.25 2.58 -0.05 0.699 1.01 0.79 0.8 0.8 0.787 0.787 0.01 3.13 0.15 0 0.05 0.05 0.295 0.58 4.46
0.1
N
0.03 0.072
N Y
0.528
Y
0.04 0.05 0.056 0.15
N N Y Y
829 646 829 659 652 652 233 894 291 292 442 726 868 244 890 711 1023 198 389 542 438 1020 757 65 800 800 434 619 564 657 358 333 662 690 30 469 87 1065 267 862 962 250 832 832 800 178 463 530 530 542 673 677 985 1104 439 726 285 336 123 65 293
References page II - 290
TABLE 1. cont'd Monomer 1 Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate,
ferrocenylmethyl ferrocenylmethyl ferrocenylmethyl ferrocenylmethyl ferrocenylmethyl ferrocenylmethyl furfuryl glycidyl glycidyl glycidyl glycidyl glycidyl heptafluorobutyl heptafluorobutyl heptafluorobutyl heptyl heptyl hydroxyethyl hydroxyethyl hydroxyethyl isobutyl isobutyl isobutyl isopropyl m-chlorophenyl m-nitrophenyl methyl methyl
Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl
Monomer 2 Maleic anhydride Methacrylate, methyl Methacrylate, methyl Styrene Styrene Styrene Methacrylate, 2-hydroxyethyl Acrylate, 2-ethylhexyl Acrylonitrile Styrene Styrene Vinyl acetate Butadiene Methacrylate, methyl Styrene Maleimide, AH2,4-dimethylphenyl)Methacrylate, methyl Acrylate, ethyl Acrylate, methyl Acrylate, methyl Methacrylate, methyl Methacrylate, glycidyl Methacrylate, methyl Styrene Acrylonitrile Methacrylate methyl 2-Oxazoline, 2-isopropenyl2-Oxazolinium BF4, 3-methyl2-isopropenyl2-Oxazolinium, 2-isopropenylAcetylene, phenylAcetylene, phenylAcrolein Acrolein Acrolein Acrylamide, Af-methylolAcrylamide, Af-propylAcrylate, 2-chloroethyl Acrylate, 2-hydroxyethyl Acrylate, a-chloro-, ethyl Acrylate, a-cyano-, methyl Acrylate, ot-phenyl-, methyl Acrylate, dibutylchlorotin Acrylate, ferrocenylmethyl Acrylate, hydroxyethyl Acrylate, hydroxyethyl Acrylate, tributyltin Acrylic acid, oe-bromoAcrylonitrile Acrylonitrile Acrylonitrile Acryloyl chloride Allyl acetate Allyl acrylate Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allylbenzene Benzophenone, p-vinylBenzophenone,/7-vinylButadiene Butadiene, 2-chloroCarbamate, WV-diethyl-, vinyl
rx
±95%
-0.3 0.024 0.08 -0.016 0.02 0.02 0.88 1.18 1 0.17 0.24 7.6 0.073 0.177 0.049 0.14 0.46 0.88 1 0.94 0.135 0.282 0.29 0.195 0.85 1.04 0.16 0.096
2.96 0.064
0.191 0.622 0.664 7.86 0.83 1.08 1.3 1.2 0.9 0.94 0.09 0.02 0.06 0.81 4.46 1 0.23 0.82 0.24 0.51 0.844 0.85 0.34 5 0.52
0.031 0.062 0.045 3.58 0.12 0.38
0.06 0.19 0.06
0.031 0.013 0.02 0.09 0.1 0.1 0.02 0.026 0.04 0.027 0.036 0.135 0.04 0.057
0.04 0.04
0.1 0.03 0.02 0.037 0.2
r2 0.09 2.8 2.9 1.87 2.3 2.5 1.35 1.12 1.01 0.6 0.73 0.003 0.359 0.084 0.31 0.2 2.51 0.5 1 0.23 4.1 1.24 1.04 0.755 1.3 0.928 1.9 0.251 2.08 0.272 0.093 - 0.07 1.41 2.54 1.9 0.26 1.07 0.9 3.22 0.34 1 0.09 0.14 1 0.94 0.03 0.1 0.56 1.54 1.31 2.3 0 0.33
±95%
Conv.
Refs.
0.14 0.19
Y Y
0.17
Y
0.08 0.07
N
0.34
N
0.039
Y Y Y
325 293 293 293 293 576 1063 126 114 114 126 553 206 206 206 788 980 890 890 890 639 674 30 178 363 1074 894 908
0.01 0.13 0.05 0.1 0.03 0.5 0.12 0.08 0.024 0.073 0.248 0.08 0.483
Y Y N Y Y Y Y
0.327 0.072 0.01 0.03 0.4 0.93
Y Y Y N Y N
0.13
N
0.07
N
0.1 0.1 0.03 0.044 0.08
Y N
Y 8.45 5.45 6.46 9.1 11.35 0.09 1.1 0.07 0.06 4.78
0.66 0.02 0.02 0.87 0.22
0.05 0.07 0.4 -0.02 -0.036 3.6 3.54 1.09 10.4 - 0.027
0.016 1.06 0.077 4.53 0.049
Y Y Y Y Y Y
908 60 731 207 291 292 441 730 726 868 638 141 141 659 293 890 890 659 733 1024 151 233 508 470 578 204 437 437 437 437 351 866 911 257 61 92
TABLE 1. cont'd Monomer 1 Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl
Monomer 2
rx
Carbazole, JV-vinyl0.53 Carbazole, N-vinyl0.43 Carbazole, N-vinyl0.51 Cinnamate, dibutylchlorotin 1.65 Diallyl phthalate 6.208 Diallyl phthalate 6.18 Diallylcyanamide 6.7 Diallylcyanamide 6.7 Ethylene Ethylene 19.4 Ethylene 1,1-diphenyl0.09 Ethylene, 1,1-diphenyl0.12 Ethylene tetrachloro830 Ethylene, trichloro33 Fumarate, diisopropyl 1.9 Hexatriene, tetrachloro0.262 Hexene-1 -0.13 Imidazole, l-vinyl-2-methyl1.28 Indene 0.63 Indene 0.62 Isoprene 0.12 Isoprene, 3-acetoxy0.27 Isopropenyl, 3-1-cyclohexenyl, acetate 0.37 Isopropenylisocyanate 0.6 Isopropenylisocyanate 0.799 Maleic anhydride 2.788 Maleic anhydride 2.5 Maleimide, A^-(4-bromophenyl)0.429 Maleimide, A^-(4-chlorophenyl)0.684 Maleimide, JV-(4-tolyl)0.64 Maleimide, N-phenyl0.554 Methacrylate, 2,3-epithiopropyl 0.34 Methacrylate, 2-(AyV-dimethyl 0.22 carbamoyloxy)ethyl Methacrylate, 2-chloroethyl 0.29 Methacrylate, 2-hydroxyethyl - 0.005 Methacrylate, 2-hydroxypropyl 0.013 Methacrylate, ferrocenylmethyl 1.4 Methacrylate, methyl 0.4 Methacrylate, f-butyl dimethylsilyl 0.288 Methacrylic anhydride 0.16 Oxazoline, 2-,2-isopropenyl0.16 Oxazoline, 2-,2-isopropenyl0.328 Oxazoline, 2-,2-isopropenyl0.46 4,4-dimethyl Oxazoline, 2-,4-acryloxy-methyl0.29 2,4-dimethyl Oxazoline, 2-,4-methacryl-oxy0.4 2,4-dimethyl Oxazolinium, 2-, tetrafluoro-borate, 0.552 3-methyl Phthalimide, 7V-(4-vinylphenyl)1.14 Phthalimide, N-(methacryloyloxy)0.193 Propenyl, 2-chloro-, acetate 0.7 Pyridine, 2-methyl-5-vinyl0.18 Pyridine, 2-vinyl0.37 Pyridine, 2-vinyl0.17 Pyridine, 2-vinyl0.2 Pyridine, 2-vinyl-5-ethyl0.18 Pyridine, 4-vinyl0.2 Pyridine, 4-vinyl0.15 Pyrrolidone, 1 -benzyl-3-methylene0.125 5-methyl Styrene 0.24 Styrene 0.8
±95%
r2
0.13
0.049 0.11 0.028 -0.2 0.028 0.038 0.05 0.05
0.073 0.069 0.16
±95%
Conv.
Refs.
0.029
Y
0.045
Y
0.005 0.008
Y Y
13 551 98 659 297 297 603 604 41 768 334 334 402 470 1038 5 60 465 606 606 424 770 770 434 99 260 470 628 628 644 644 787 600
N 0.01 0.01
0.087 0.6
0.049 0.051 0.099 0.052 0.16 0.048
0.036 0.007 0.35 0.12 0.057 0.032
0.043
0.02 -0.24 0.21 0 0 0.091 3.19 -0.67 0.05 0.1 0.12 0.75 5.71 0.57 0.11 0.079 0.012 0 0.39 0.155 0.14 0.103 2.81 1.32 2.19 8.67 7.335 0.042 2.15 1.07 4.75 1.9 2.07 1.3
1.36 0.03
Y Y
0.047 0.013
Y Y
0.17 0.052 0.16 0.052
Y Y Y Y
8.28 0.083 0.085 0.04 0.21
Y Y Y N Y
0.191
Y
726 358 333 293 324 1069 275 862 877 596 596
0.56
596
0.344
0.025 0.21
0.82 0.192
0.05 0.4 0.03 0.03 0.004 0.03
N N
0.11
1.56 1.23 0 1 2.13 1.72 2.12 1.32 1.78 2.14 1.58
0.028
0.15 0.05
0.105
Y
877
0.168
Y
0.3 0.54 0.26 0.1 0.03 0.32
N Y N N N N
0.24
Y
636 979 445 232 2 231 749 231 231 424 633
0.057
Y
139 14
References page II - 290
TABLE 1. cont'd Monomer 1 Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, mono-, ethylene glycol Acrylate, o-chlorophenyl Acrylate, o-chlorophenyl Acrylate, octadecyl Acrylate, octadecyl Acrylate, octadecyl Acrylate, octadecyl Acrylate, octadecyl Acrylate, octadecyl Acrylate, octadecyl Acrylate, octadecyl Acrylate, octadecyl Acrylate, octyl Acrylate, octyl
Monomer 2 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, a-methoxyStyrene, m-methylStyrene, p-l-(2-hydroxybutyl)Styrene, /?-Af,N-dimethylaminoStyrene, /?-dimethylaminoStyrene, p-methoxyStyrene, /?-methylSuccinimide, N-vinylVinyl 2-chloroethyl ether Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl butyl ether Vinyl butyl ether Vinyl butylsulfonate Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl cymantrene Vinyl ethyl ether Vinyl fluoride Vinyl fluoride Vinyl hendecanoate Vinyl isobutyl ether Vinyl isobutyl sulfide Vinyl isobutyl sulfide Vinyl methyl sulfide Vinyl phenyl sulfide Vinyl stearate Vinyl thiolacetate Vinyl, 2-bromo-, ethyl ether Vinyl, /?-, benzylethylcarbinol Vinylanthracene, 9Vinylhydroquinone dibenzoate Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylisocyanate Acrylonitrile Acrylonitrile Methacrylate, methyl Acrylonitrile Acrylonitrile Acrylonitrile Methacrylate, methyl Styrene Styrene Styrene Styrene Vinylidene chloride Acrylonitrile Styrene
r\ 0.168 0.18 0.18 0.14 0.07 0.3 0.16 0.148 0.142 0.288 0.17 0.14 0.18 0.06 0.192 0.07 0.17 0.357 3.27 7.28 6.38 2.58 6.7 6.3 3.65 3.6 4.14 4.4 7.66 5 4 0.46 3.3 43 43 3.615 3.63 0.3 0.29 0.209 0.57 5.8 0.8 16.83 0.18 2.998 0.46 0.95 0.8 1 1.38 1.2 1.171 0.4 1.04 1.35 0.32 0.464 0.37 0.18 0.31 0.18 1 0.84 0.01
±95% 0.067
0.026 0.054 0.069 0.02 0.01 0.01 0.063 0.37 0.3 0.07 0.58 0.22 0.5 0.14
0.012 0.04 0.01 0.01 0.034 0.1 2.34 0.067 0.21
0.023 0.38 0.4 0.35 0.07 0.12
0.14 0.74 0.53
r2 0.722 0.75 0.75 0.68 0.9 0.65 0.4 0.871 3.93 4.47 0.003 1.65 0.48 0.38 0.372 2 1.54 0.9 0 0.04 0.03 0.405 0.03 0.03 0.01 0 0 0.093 0.002 0 0.06 0.211 0 0.01 0.01 0.033 0 0.05 0.06 0.084 -0.02 0.03 0.23 -0.79 0.48 0.08 0.75 0.9 0.7 1 0.14 0.8 1.123 1.25 1.91 4.39 1.76 2.477 0.777 0.44 0.79 0.44 0.9 1.98 0.39
±95%
Conv.
Refs.
0.056
Y
0.022 1.38 0.15 0.01
Y Y Y N
0.16 0.055
Y Y
0.17
Y
151 393 397 463 495 496 496 865 136 2 142 558 548 866 911 558 558 80 726 1067 158 25 489 568 345 574 185 151 46 470 518 354 470 604 606 145 347 285 336 195 193 537 566 194 591 123 440 107 107 377 435 682 363 621 118 233 290 290 290 290 290 290 118 118 806
0.01 0.043
Y Y
0.01
N
0.4 0.002 0.01
Y Y Y
0.067
Y
0.008 0.002 0.02 0.02 0.086 0.22
Y N N N Y Y
0.32
Y
0.092
Y
0.11
Y
0.037
Y
0.1 0.64 0.2 0.024 0.018
Y N Y Y Y
0.037 0.3 0.11
Y Y
TABLE 1. cont'd Monomer 1 Acrylate, octyl Acrylate, octyl Acrylate, p-(cinnamoylamino)phenyl Acrylate,/7-bromophenyl Acrylate,/7-bromophenyl Acrylate,/7-chlorophenyl Acrylate,/7-chlorophenyl Acrylate,/?-chlorophenyl Acrylate, p-methylphenyl Acrylate, pentabromophenyl Acrylate, pentachlorophenyl Acrylate, pentachlorophenyl Acrylate, phenyl Acrylate, phenyl Acrylate, phenyl Acrylate, phenyl Acrylate, sodium Acrylate, tert-buty\ Acrylate, tetrahydrofurfuryl Acrylate, thio- butyl Acrylate, thio-, ethyl Acrylate, thio-, tert-butyl Acrylate, tributyltin Acrylate, trifluoro-, methyl Acrylate, trifluoro-, methyl Acrylate, trifluoro-, methyl Acrylate, trifluoro-, methyl Acrylate, trifluoro-, methyl Acrylate, trifluoro-, methyl Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid
Monomer 2 Vinyl chloride Vinylidene chloride Styrene Acrylonitrile Methacrylate, methyl Acrylonitrile Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Styrene Acrylic acid Styrene Acrylonitrile Fumarate, diisopropyl Methacrylate, methyl Methacrylate, methyl Vinyl acetate Methacrylate, glycidyl Styrene Styrene Styrene Styrene Acrylate, methyl Styrene Styrene Vinyl acetate Vinyl acetate Vinyl chloride Vinyl chloride Acrolein Acrolein Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide, A^-dimethylAcrylate, pentachlorophenyl Acrylate, butyl Acrylate, butyl Acrylate, ethyl Acrylic acid, 2-benzamidoAcrylic acid, N-acetyl-a-aminoCarbamate, AW-diethyl-, vinyl Carbamate, //-vinyl-, ethyl Imidazole, 1-vinylMethacrylate, isopropyl Methacrylate, methyl Methacrylate, butyl N-Vinylimidazole Phosphonic acid, oc-phenylvinylPropenyl, 2-chloro-, acetate Propylene Pyrrolidone, N-vinylStyrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Vinyl acetate Vinyl chloride
rx 4.8 0.679 0.35 1.026 0.191 0.951 0.235 0.3 0.223 0.1 1.12 0.9 0.327 3.4 0.45 0.416
±95%
0.057 0.062 0.014 0.063 0.023 0.036
0.045 0.041
0.463 0.489 0.421 0.291 0.368 0.03 0 0 0 0 0 0 0.08 1.15 0.288 1.644 0.341 1.38 3.8 0.29 0.36 0.82 0.59 1.31 0.91 0.48 1.41 5.58 4.69 0.0025 1.03 1.73 0.24 1.932 0.7 1
0.079 0.196 0.17 0.075 0.055
0.88 0.05 0.08 0.25 0.35 0.136 0.15 0.45 0.25 8.66 6.69
0.69
0.28 0.029 0.069 0.012 0.14 0.04 0.27 0.3
0.32
0.096 0.21 0.077 0.13
0.029
6.63 0.88
r2 0.12 0.851 1.08 0.8 0.926 0.32 1.01 1.09 1.45 0.16 0.82 2.11 0.43 0.07 1.56 1.54 2.096 0.475 0.439 0.18 0.157 0.82 1.4 1.4 0.24 0.24 1.5 1.5 2.48 0.5 1.08 0.445 1.346 0.598 0.58 1.06 0.35 1.12 1.08 0.91 1.02 2.08 0.49 -0.097 0.26 0.32 0.68 0.418 3.53 0.187 0.04 0 0.1 0.25 1.1 0.15 0.22 0.253 0.25 0.25 0.15 0.021 0.107
±95%
Conv.
0.018
Y
0.13 0.056 0.056 0.132
Y Y Y Y
0.275
Y
0.13
Y
0.14
Y Y Y
0.443 0.186 0.14 0.038 0.034
1.24
Y
0.17 0.075 0.044 0.047
Y Y Y Y
0.12
N
0.18 0.13
N N
0.068
Y Y
0.02 0.42 0.025 0.83
N N Y Y
0.21
Y N
0.069
Y
0.059 0.011
Y Y
Refs. 518 118 685 363 1074 63 1074 621 1074 643 900 900 363 1038 621 672 37 814 806 806 806 806 659 595 598 595 598 595 598 57 57 221 278 278 37 869 869 205 900 187 252 711 1019 661 92 81 955 847 964 187 879 132 445 183 250 312 312 397 414 47 490 542 561 37 135
References page II-290
TABLE 1. cont'd Monomer 1 Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid, 2-benzamidoAcrylic acid, 2-benzamidoAcrylic acid, 2-ethyl Acrylic acid, 2-ethyl Acrylic acid, 2-ethyl Acrylic acid, N-acetyl-a-amino Acrylic acid, N-acetyl-a-aminoAcrylic acid, oc-bromo Acrylic acid, a-bromo Acrylic acid, a-bromo Acrylic acid, a-bromo Acrylic acid, a-bromo Acrylic acid, ds-3-bromoAcrylic acid, c/s-3-ethyl Acrylic acid, trans-3-bxomoAcrylic acid, frarcs-3-ethylAcrylic anhydride Acrylic anhydride Acrylic anhydride Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile
Monomer 2 Vinyl chloride Vinyl chloride Vinyl chloride Vinylhydroquinone Vinylhydroquinone dibenzoate Vinylidene chloride Vinylidene cyanide Acrylic acid Styrene Methacrylic acid Methacrylic acid Methacrylic acid Acrylic acid Styrene Methacrylate, methyl Acrylate, butyl Acrylate, methyl Methacrylate, butyl Pyrrolidone, Af-vinyl Acrylamide Acrylamide Acrylamide Acrylamide Allyl chloride Methacrylonitrile Styrene 1,3-pentadiene, cis1,3-pentadiene, cis1,3-pentadiene, trans1,3-pentadiene, trans2-Oxazoline, 2-isopropenylAcenaphthalene Acetylene, phenylAconitate, trimethyl Acrolein Acrolein Acrolein Acrolein Acrolein diethylacetal Acrolein, methylAcrolein, methylAcrolein, methylAcrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide, Af-methylolAcrylamide, N-methylolAcrylamide, Af-methylolAcrylamide, JV-octadecylAcrylamide, N-tert-butylAcrylate, 2-chloroethyl Acrylate, 2-nitrobutyl Acrylate, 3,4-epoxyhexahydrobenzyl Acrylate, p-chloro-2-hydroxypropyl Acrylate, P-ethoxy-, ethyl Acrylate, a-chloro-, methyl Acrylate, a-cyano-, methyl Acrylate, a-phenyl-, methyl Acrylate, benzyl Acrylate, benzyl Acrylate, butyl Acrylate, butyl Acrylate, butyl
rx 9.28 7.04 6.8 0.29 0.44 1.246 0.212 2.08 0.78 0.194 0.069 0.23 0.49 0.44 0.11 0.09 0.1 0.13 0.07 -0.2 -0.16 -0.33 -0.21 11.66 1 0.1 0.026 0.06 0.069 0.068 0.13 0.02 0.266 4.24 0.88 0.71 0.48 0.6 11.19 0.15 0.15 0.03 0.863 0.97 1.8 0.88 0.8 0.7 0.98 0.22 1.034 0.2 1.03 0.67 0.25 0.24 2.42 0.122 0.01 0.08 0.28 1.49 1.679 0.781 1.08
±95% 0.51 0.33 0.11 0.042 0.016 0.027 0.04
0.11 0.1 0.16 0.11 0.56 0.13 0.004 0.173 0.242 0.104 0.096 0.04 0.044 0.92 0.06 0.03 0.01
0.19 0.033 0.1 0.75
0.02 0.25 0.13 1.8 0.081 0.02 0.19 0.058 0.083 0.08
r2 0.03 0.024 0.11 0.026 0.95 0.437 0.291 0.48 0.13 1.12 2.29 1.14 1.41 0.91 0.37 0.19 0.24 0.85 0.25 7.64 6.32 4.13 8.19 0.02 0.42 0.16 0.017 0.071 0.018 0.064 0.52 2.56 0.325 -0.48 1.16 1.07 1.52 1.28 0.02 1.7 3.8 1.72 0.81 1.08 0.5 1.36 1.3 1.2 2.33 2.56 1.4 1.14 0.87 1.76 0.388 0.7 -0.26 1.76 0.68 6.7 0.72 0.63 1.06 0.894 0.82
±95%
Conv.
Refs.
0.09 0.069
N Y
0.092
Y
0.065 0.042
Y Y
0.132 0.417
Y Y Y
1.67 0.68 0.76 1.09 0.02 0.04 0.01 0.012 0.029 0.01 0.02 0.06
Y Y Y Y N N N Y Y Y Y
0.083 0.11 0.13 0.08 0.07
Y Y N N N
0.42 0.11 0.51 0.26
Y Y Y N
0.17
Y
0.69 0.074
N Y
0.56 0.18 0.09
N Y N
0.16
N
0.15 0.019 0.13
Y Y N
229 288 379 337 444 288 82 1019 1019 1004 1004 961 661 661 733 733 733 733 694 298 298 298 298 219 219 219 912 912 912 912 894 575 60 147 207 207 208 504 767 455 587 91 228 228 330 421 461 442 577 596 119 709 790 234 680 654 194 6 141 141 23 385 118 162 233
TABLE 1. cont'd Monomer 1 Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile
Monomer 2 Acrylate, butyl Acrylate, butyl Acrylate, cis-(3-cyano-, methyl Acrylate, cresyl Acrylate, di-, zinc Acrylate, dodecyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, glycidyl Acrylate, m-chlorophenyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, mono-, ethylene glycol Acrylate, tf-chlorophenyl Acrylate, octadecyl Acrylate, octadecyl Acrylate, octadecyl Acrylate, octyl Acrylate, /?-bromophenyl Acrylate, /7-chlorophenyl Acrylate, phenyl Acryloyl chloride Acryloylpyrrolidone Allyl acetate Allyl alcohol Allyl alcohol Allyl alcohol Allyl alcohol Allyl chloride Allyl chloride Allylbenzene Allylbenzene Allylcyclohexane Allylstearamide, NBenzothiazole, vinylmercaptoButadiene Butadiene Butadiene Butadiene Butadiene Butadiene, 1,4-dicarboxylate, diethyl Butadiene, l-(diethylamino)Butadiene, l-(diethylamino)Butadiene, 1-acetoxyButadiene, 1-ethoxy Butadiene, 1-ethoxy Butadiene, 2-chloroButadiene, 2-chloroButadiene, 2-chloroButadiene, 2-fluoroButadiene, 2-trimethylsilyloxyButadiene-1-carboxylate, ethyl Butadiene-1-carboxylic acid Butadiene-1-carboxylic acid Butene-1 Butene-1, 4-(/?-chlorophenyl)Butene-1, 4-(p-methoxy-phenyl)Butene-1, 4-cyclohexylButene-1, 4-phenylButene-2, cis Butene-2, trans Carbazole, N-vinyl-
rt
±95%
1 1 0.72 0.41 2.37 0.92 1.16 0.66 0.44 1.01 1.3 0.56 1.54 1.31 0.8 1.123 1.91 4.39 1.76 1.98 0.8 0.32 0.43 1.2 1.56 6.57 2.6 3.9 1.79 2.145 3.45 3.82 5.35 3.81 3.79 0.191 0.046 0.1 0.05 0.06 0.03 0.29 0.481 0.208 -0.012 0.02 0.01 0.04 0.05 0.056 0.077 0.036 0.3 0.2 0.03 13.46 4.68 2.56 5.03 4.51 22.32 62.99 0.39
r2
±95%
Conv.
0.9 1.2 0.15 0.07 0.08 0.78
0.073 0.03 0.044 0.08 0.037 0.1 0.64 0.2 0.3 0.13 0.056 0.13 2.11 1.06 0.11 0.049 0.65 1.7 0.3 11.42 0.28 0.014 0.006 0.059 0.02 0.12 0.049 0.049 0.043 0.008 0.008 0.023 0.021
3.61 0.63 1.11 0.76 0.86 10.67 0.04
0.773 0.24 0.88 1.2 0.81 4 0.95 1 0.85 0.51 0.844 0.85 1.2 1.171 1.04 1.35 0.32 0.84 1.026 0.951 0.327 1 0.43 -0.09 0.05 0.1 0.12 -0.152 0.08 -0.05 -0.026 -0.18 0.03 0.178 0.358 0.452 0.35 0.1 0.2 2.79 0.426 0.425 0.82 0.065 0.065 5.35 4.8 5.38 0.6 0.065 3.2 4 11 0.24 0.066 -0.085 0.014 0.024 0.11 0.84 0.09
0.067 0.16 0.07 0.27
N Y N N
0.036 0.02 0.037 0.2
Y N
0.023 0.38 0.4 0.35 0.74 0.062 0.063 0.045
Y Y N Y Y Y Y Y
0.12
Y N
0.16 0.37 0.008 0.03 0.15 0.022 1.01 0.27 0.081 0.046 0.023
N Y Y Y Y Y Y Y Y Y Y
0.01 0.9 0.208 0.48 0.68 0.009 0.02
N N Y Y Y Y Y
0.45 0.18
Y Y
0.81 0.044 0.088 0.055 0.069
Y Y Y Y Y Y Y N
0.6 0.04
Y
Refs. 513 513 1034 363 646 233 1023 198 389 542 114 363 1024 151 233 682 363 118 233 290 118 363 363 363 580 666 108 108 108 176 300 108 47 24 351 24 119 763 21 255 418 501 66 327 864 889 91 864 889 402 504 61 174 993 791 791 799 211 24 24 24 24 211 211 269
References page II - 290
TABLE 1. cont'd Monomer 1 Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile
Monomer 2 Cinnamate, a-cyano-, ethyl Cinnamonitrile Cinnamonitrile, a-cyanoCitraconimide, N-methylCrotonaldehyde Crotonaldehyde Crotonate, a-chloro-, ethyl Crotonate, a-cyano-, ethyl Crotonate, a-methoxy-, methyl Crotonate, a-methyl-, methyl Crotonate, a-acetyl-, methyl Crotonate, a-carboethoxy-, ethyl Crotonate, ethyl Crotonic acid Cyclopentene, 4-, -1,3-dione Cyclopropene, 3,3-dimethoxyDiallyl phthalate Diallyl phthalate Ethylene Ethylene, 1,1-diphenylEthylene, tetrachloroEthylene, tetrachloroEthylene, trichloroEthylene, trichloroFumarate, diisopropyl Fumarate, diethyl Fumarate, diethyl Hexatriene, tetrachloroHexene-1 Indene Indene Isobutylene Isobutylene Isobutylene Isoprene Isopropenyl methyl ketone Isopropenyl methyl ketone Isopropenylisocyanate Itaconic acid Itaconic anhydride Maleate, diethyl Maleate, diethyl Maleic anhydride Maleimide, 7V-(2-bromophenyl)Maleimide, A^-(2-chlorophenyl)Maleimide, iV-(4-chlorophenyl)Maleimide, N-2-bromophenylMaleimide, N-2-chlorophenylMaleimide, N-4-chlorophenylMaleimide, N-octadecylMaleimide, N-octadecylMethacrylamide, N-(/?-chlorophenyl)Methacrylamide, iV-(/?-methoxyphenyl)Methacrylamide, A^-methylphenyl)Methacrylamide, Af-(p-nitrophenyl)Methacrylamide, N-phenylMethacrylate, 2,2,6,6-tetramethyl4-piperidinyl Methacrylate, 2-(AUV-dimethylcarbamoyloxy)ethyl Methacrylate, 2-bromoethyl Methacrylate, 2-chloroethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl
r\ 12.6 8.46 0.53 8 25 9.53 11.4 1 2.97 8.68 18.7 25.2 21 3.02 1.424 4.23 2.78 7 0.05 456 470 67 62.1 16 8 10 0.234 2.07 0.281 0.29 1.295 0.98 1.02 0.03 0.3 0.36 0.24 0.59 0.034 12 20 6 2.029 0.956 0.972 2.02 0.955 0.972 2.482 2.46 0.399 0.337 0.336 0.37 0.381 0.02
±95% 2.3 0.37
0.71 0.038 0.15 0.52 0.01
0.05 0.05 0.12 0.008 0.25
0.34 0.014
0.214 0.095 0.112 0.205 0.095 0.112 0.119 0.115 0.019 0.019 0.026 0.14 0.085
r2 -0.18 0.36 0.6 0 0.01 0 0.06 0 0 0 0 0 0 0.04 0.245 0.04 0.037 0 -0.02 0 0 0 0 0.2 0 0.1 4.01 -1.08 0.09 0.07 0 0.02 0 0.45 1.2 0.7 0.1 0.86 4.83 0 0 0 0.338 1.078 0.743 0.348 1.08 0.743 0.389 0.39 0.627 0.559 0.549 2.34 0.71 14
±95%
Conv.
Refs.
0.15 0.1
Y Y Y
0.058 0.037 0.012 0.031
Y Y Y Y
0.01
N
1.25 0.25 0.24 0.002 0.38
Y Y Y Y Y Y
0.74 0.33
Y Y
0.045 0.048 0.048 0.044 0.048 0.048 0.023 0.023 0.051 0.048 0.06 1.07 0.19
Y Y Y Y Y Y Y Y Y Y Y Y Y
310 310 310 460 429 504 785 785 785 785 785 785 785 402 95 838 153 153 415 143 571 59 470 572 1038 470 640 4 60 360 360 21 211 484 417 490 542 434 164 365 470 640 470 863 863 863 915 915 915 863 915 352 352 352 352 352 664
0.38
1.89
600
0.31 0.14 0.2 0.15 0.094
2.38 1.3 1 1.17 1.02
657 382 689 611 611
0.2 0.099
0.2 0.19
Y Y
TABLE 1. cont'd Monomer 1 Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile
Monomer 2
rx
Methacrylate, 2-naphthyl 0.06 Methacrylate, 2-naphthyl -0.01 Methacrylate, 3,5-dimethyladamantyl 0.19 Methacrylate, benzyl 0.2 Methacrylate, butyl 0.291 Methacrylate, ferrocenylmethyl 0.15 Methacrylate, glycidyl 0.95 Methacrylate, glycidyl 0.14 Methacrylate, isobutyl 0.217 Methacrylate, methyl 0.138 Methacrylate, methyl -0.016 Methacrylate, mono-, ethylene glycol 0.19 Methacrylate, phenyl 0.36 Methacrylate, potassium 0.226 Methacrylate, potassium 18-crown0.07 6-ether Methacrylic acid 0.04 Methacrylic acid 0.092 Methacrylonitrile 0.43 Methacryloyl chloride 0.35 Methacryloyl acetone 0.01 Methylenebutyrolactone 0.09 WV-Divinylaniline 0.246 AA-Vinylimidazole 3.393 Naphthalene, 1-vinyl0.107 Norbornadiene 0.48 Norbornadiene 0.66 Oct-1-ene, 6,6-dimethyl-4,8-dioxaspiro 0.985 Oxazoline, 2-,2-isopropenyl0.13 Oxazoline, 2-,2-isopropenyl-, 0.24 4-dimethyl Oxazoline, 2-,4-methacryloxy0.11 2,4-dimethyl Pentadiene, trans-1,30.06 Pentadiene, as-1,30.026 Pentadiene, cis-1,30.056 Pentadiene, cis-1,30.033 Pentadiene, trans-1,30.07 Pentadiene, trans-1,30.085 Pentadiene, trans-1,30.079 Pentadiene, cis-1,30.06 Pentadienoate, trans-4-ethoxy-2,4-, ethyl 0.01 Pentene-1, 5-cyclohexyl4.22 Pentene-1, 5-phenyl3.84 Phosphate, diethyl isopropenyl 15.2 Phosphine oxide, diphenylvinyl3.8 Phosphonic acid, a-phenylvinyl0.34 Phosphonic acid, a-phenylvinyl2.36 Phthalide, 3-(4-vinylphenoxy)0.084 Phthalimide, N-vinyl0.43 Phthalimide, AHmethacryloyloxy)0.204 Pinene 0.07 Propene, 2-chloro1.164 Propene, 3,3,3-trichloro12.2 Propene, 1-chloro-, cis23.37 Propene, 1-chloro-, trans19.61 Pyridazinone, 3-(2-vinyl)-6-methyl0.32 Pyridazinone, 3-(2-vinyl)-6-methyl-4,50.74 Pyridine, 2-methyl-5-vinyl0.16 Pyridine, 2-vinyl0.05 Pyridine, 2-vinyl0.1 Pyridine, 2-vinyl-5-ethyl0.02 Pyridine, 2-vinyl-5-ethyl0.06 Pyridine, 4-vinyl0.11 Pyridine, 4-vinyl0.09
±95% 0.1 0.16 0.01 0.1 0.039 0.04 0.06 0.037 0.037 0.048
0.04 0.006 0.13 0.06 0.04 0.004 0.014 0.008 0.028 0.27 0.01 0.675
r2
±95%
Conv.
0.76 0.64 1.3 0.96 0.98 0.82 0.85 1.32 1.05 1.322 1.11 1.5 0.46 0.203 0.175
0.18 0.24 0.23 0.1 0.2 0.42 0.05
Y N N N Y Y N
0.22 0.05 0.12
Y Y Y
0.086 0.018
Y Y
0.2 2.38 1.67 2.8 3.74 1.1 -0.006 0.832 0.451 0.05 0.44 1.484 0.52 1.83
0.26 0.29 0.12
Y Y N
0.22
Y
0.07 0.044 0.088 0.23 0.05 1.078
Y Y N N Y
0.89 0.064 0.018 0.017 0.017 0.018 0.071 0.45 0.48
0.12 0.053 0.01 0.016 0.01 0.053 2.99 1.72 0.02 0.02 0.01 0.03 0.07 0.04
0.095 0.172 0.198 0.188 0.104 0.132 0.114 0.241 5.4 -0.043 -0.026 0.03 0.16 -0.45 0 0.43 0.24 1.45 13.5 -0.023 0.1 -0.12 0.01 0.19 0.02 0.31 21.9 0.44 0.43 0.43 0.41 0.34
Refs. 611 611 335 23 165 325 114 433 165 216 681 682 363 808 808 16 216 198 580 339 745 45 879 967 267 69 838 862 596 596
0.021 0.012
Y Y
0.011 0.01
N Y
0.009 0.029
N Y
0.044 0.046
N Y
0.41
Y
0.19 0.02 0.072 0.1 0.062
Y Y
0.19 0.17 0.04 0.02 0.02
Y Y N N N
0.08
N
0.18
N
0.13
N
Y
867 867 952 997 867 952 997 867 723 24 24 650 843 132 590 721 1046 979 936 181 402 181 181 340 340 232 456 50 115 50 115 50
References page 11-290
TABLE 1. cont'd Monomer 1 Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile
Monomer 2
r\
Pyrrolidone, N-vinylSilane, y-methacryloxypropyltrimethoxy- 0.094 Styrene 0 Styrene 0.02 Styrene 0.05 Styrene 0.03 Styrene 0.06 Styrene 0.05 Styrene 0.07 Styrene 0.04 Styrene 0.17 Styrene 0.17 Styrene 0.15 Styrene 0.17 Styrene 0.07 Styrene 0.06 Styrene 0.03 Styrene 0.06 Styrene 0.01 Styrene, 2,4,6-trimethyl0.874 Styrene, 2,5-dichloro0.22 Styrene, 2,5-dichloro0.25 Styrene, 2,5-dichloro0.26 Styrene, 3-tri-rc-butylstannyl4.88 Styrene, 4-methyl0.079 Styrene, a-(trimethylsilyloxy)0.05 Styrene, a-methoxy0.06 Styrene, a-methyl0.07 Styrene, a-methyl0.04 Styrene, a-methyl0.04 Styrene, a-methyl0.04 Styrene, a-methyl0.063 Styrene, a-methyl0.34 Styrene, a-methyl0.03 Styrene, a-methyl- 0.02 Styrene, m-methyl0.07 Styrene, /?-l-(2-hydroxy-butyl)0.04 Styrene, /?-l-(2-hydroxy-propyl)0.1 Styrene, /?-2-(2-hydroxy-propyl)0.05 Styrene, p-acetoxy0.07 Styrene, /?-chloro-0.09 Styrene, p-chloromethyl0.067 Styrene/7-methyl0.05 Succinimide, N-vinyl0.116 Tetrazole, 2-methyl-5-(4/-vinyl)phenyl0.42 Tetrazole, 5-phenyl-2-(4/-vinyl)phenyl0.32 Tetrazole, 1-vinyl0.54 Toluenesulfonamide, A^V-methyl-vinyl- 0.42 Triallyl citrate 1.76 Tricyclo[4.2.2.0{2,5}]dec-7-ene2.75 3,4,9,10-tetracarboxylic acid Vinyl 12-ketostearate 3.3 Vinyl 2-chloroethyl ether 1.09 Vinyl 2-ethylhexanoate 9.24 Vinyl 3,3-bis(ethoxycarbonyl)propyl 1.02 ether Vinyl acetate 4.05 Vinyl acetate Vinyl acetate 5.51 Vinyl acetate 5.29 Vinyl acetate 9.2 Vinyl benzoate 5.03 Vinyl bromide 2.79 Vinyl bromide 2.25 Vinyl butyl ether
±95% 0.034 0.06
0.051 0.01
0.005 0.01 0.04 0.005 0.041 0.15 0.27
0.01 0.06 0.024 0.032 0.12 0.082 0.5 1.96
r2 3.79 0.33 0.29 0.4 0.36 0.39 0.37 0.37 0.4 0.3 0.33 0.33 0.36 0.46 0.41 0.43 0.55 0.35 0.065 0.08 0.07 0.09 0.001 0.227 0 - 0.002 0.08 0.17 0.24 0.14 0.09 0.103 0.14 0.08 0.43 0.31 0.53 0.41 0.4 0.92 0.56 0.33 0.516 1.1 1.4 0.314 0.04 -0.08 0.25 -0.18 0 -0.047 0.06
±95%
Conv.
Refs.
0.594
Y Y
0.04
N
0.048 0.03
Y N
0.021
Y
0.01 0.03
N N
0.03 0.024 0.036
N Y Y
0.07
N
0.03 0.06
N N
213 977 140 198 269 396 403 417 543 60 727 727 727 727 727 727 727 727 812 58 84 84 84 985 929 970 142 171 265 265 65 75 75 835 94 378 548 380 547 47 825 1035 378 80 583 583 925 80 367 963
0.081 0.066 1.04 0.1
Y Y Y
0.36
Y
0.05
Y Y N Y Y Y Y N
0.82
0.04
0.067
0.91 1.13 6.39 1.08 0.2
0.06 -0.06 - 0.03 0.019 0.06 0.06
0.22 0.08 0.09 0.051 0.04
N
146 597 47 1015 158 235 6 75 75 47 268 268 345
TABLE 1. cont'd Monomer 1 Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile
Monomer 2 Vinyl butyl ether Vinyl butyl sulfide Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloroacetate Vinyl chloroacetate Vinyl chloroethyl ether Vinyl chloromethyl ketone Vinyl cymantrene Vinyl dichloroacetate Vinyl dichloroacetate Vinyl dodecyl ether Vinyl ether Vinyl ethyl ether Vinyl ethyl oxalate Vinyl ethyl sulfide Vinyl ethyl sulfide Vinyl ethyl sulfoxide Vinyl fluoride Vinyl fluoride Vinyl formate Vinyl hendecanoate Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl sulfide Vinyl isobutyl sulfide Vinyl isobutyl sulfide Vinyl isothiocyanate Vinyl laurate Vinyl methyl ketone Vinyl methyl ketone Vinyl octadecyl ether Vinyl octyl ether Vinyl phenyl ether Vinyl phenyl sulfide Vinyl phenyl sulfide Vinyl stearate Vinyl terf-butyl sulfide Vinyl trichloroacetate Vinyl, a-chloro-, triethoxysilane Vinyl,/?-, benzylethylcarbinol Vinyl, /?-, benzylmethylcarbinol Vinyl-tris(trimethoxysiloxy)-silane Vinyl-tris(trimethoxysiloxy)-silane Vinylbenzoate, p-, sodium Vinylbenzoic acid, pVinylene carbonate Vinylethynyl-4-piperidinol, 1,2,5-trimethyl Vinylferrocene Vinylferrocene Vinylhydroquinone Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride
r\ 0.98 0.086 3.26 2.55 2.62 3.62 3.65 4 4.18 0.34 1.04 0.064 0.446 7.45 0.25 0.82 0.94 0.69 1.34 0.09 0.06 1.63 44 24 2.54 1.88 - 0.24 - 0.05 0.98 1.26 0.08 0.062 0.08 0.36 4 0.59 0.63 0.85 0.81 2.5 0.11 0.11 4.639 0.09 7.34 0.04 0.11 3.9 3.85 0.174 0.06 14.9 0.08 0.186 0.16 0.56 0.92 1.04 0.44 0.58 0.65 0.57 0.5
±95% 0.13 0.01 0.34 0.12 0.25 0.21 0.22 0.33 0.05 0.019 0.048 0.32
0.12 0.45 0.01 0.01 0.16 1.79 0.44 0.26 0.07 0.15 0.19 0.005 0.004 0.004 0.13
0.01 0.01 0.015 0.024 0.9 0.17 0.04 0.009
0.025 0.36 0.11 0.2
r2 -0.03 0.041 -0.01 0.07 0.02 0.044 0.052 0.04 -0.007 0.09 -0.02 0.88 - 0.065 0.044 0.18 0 0.02 0.06 0.06 0.06 0.05 -0.08 0.005 1 -0.004 0.09 0.7 0.99 -0.04 -0.04 0.03 0.022 0.03 1.4 0.04 1.75 1.39 0 0 0.23 0.03 0.03 0.078 0 0.047 0.31 0.54 0.07 0.08 0.23 1.63 0.08 0.38 0.165 0.15 0.04 0.32 0.28 0.4 0.42 0.49 0.69 0.76
±95%
Conv.
0.01 0.028 0.037 0.03 0.08 0.002 0.01
N Y Y N N Y Y
0.016
Y
0.02 0.12 0.093 0.015
N Y Y N
0.12 0.03 0.03 0.03 0.14
N N N N Y
0.12 0.91 0.09 0.06 0.01 0.02 0.01 0.038 0.01
Y Y N N N N N Y N
0.11
Y
0.02 0.01 0.007 0.013 0.039
N N Y Y Y Y
0.2
N
0.34 0.42
Y Y
0.092
Y
0.03 0.14 0.034
N Y Y
Refs. 347 303 140 202 22 238 46 529 362 542 116 356 354 362 542 373 386 194 285 285 336 286 528 590 47 145 322 322 347 347 285 303 336 542 381 140 504 373 373 556 285 336 145 303 362 591 48 209 573 175 175 579 783 294 294 338 138 238 404 404 404 404 404
References page II - 290
TABLE 1. cont'd Monomer 1 Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile, 2-chloroAcrylonitrile, 2-fluoroAcrylonitrile, oc-chloroAcrylonitrile, oc-fluoroAcrylonitrile, a-hydroxymethylAcrylonitrile, a-methoxy Acrylonitrile, a-methoxy Acrylonitrile, a-perfluoropropylAcryloxymethylpentamethyldisiloxane Acryloyl chloride Acryloyl chloride Acryloyl chloride Acryloyl chloride Acryloyl chloride Acryloyl chloride Acryloyl chloride Acryloyl chloride Acryloyl chloride Acryloyl-P-hydroxyethyl-3,5dinitrobenzoate Acryloyl-P-hydroxyethyl-3,5dinitrobenzoate Acryloyloxy, 2-, benzoic acid Acryloyloxy, 2-, benzoic acid Acryloylpyrrolidone Adipate, divinyl Allyl acetate Allyl acetate Allyl acetate Allyl acetate Allyl acetate Allyl acetate Allyl acetate Allyl acetate Allyl acetate Allyl acetate Allyl acetate Allyl acetate Allyl acetate Allyl acetate Allyl acetate Allyl acetate Allyl acrylate Allyl acrylate Allyl acrylate Allyl alcohol Allyl alcohol Allyl alcohol Allyl alcohol
Monomer 2
ri
Vinylidene chloride 0.48 Vinylidene chloride 0.65 Vinylidene chloride 0.65 Vinylidene chloride 0.66 Vinylidene chloride 0.63 Vinylidene chloride 0.63 Vinylidene chloride 0.58 Vinylisocyanate 0.19 Vinylmethyldiacetoxysilane 2.246 Vinylmethylphenylsulfonium 2.2 tetrafluoroborate Vinyltriethoxysilane 6.59 Vinyltriethoxysilane 26.83 Vinyltrimethoxysilane 9.09 Vinyltrimethylsilane 4.08 Styrene 0.087 Styrene Styrene 0.03 Styrene 0.03 Styrene 0.528 Acrylate, a-chloro-, ethyl 0.3 Styrene 0.312 Methacrylate, methyl 0 Methacrylate, 2-hydroxyethyl 0.52 Acrylate, methyl 2.3 Acrylonitrile 1 Methacrylate, 2-hydroxypropyl 0.29 Methacrylate, methyl 1.51 Methacrylate, methyl 0.05 Pyrrolidone, N-vinyl 0.15 Styrene 0.02 Vinyl chloride 3.03 Vinylidene chloride 1.12 Acrylate, A^-(2-hydroxyethyl)-carbazolyl 0.361 Methacrylate, N-ethyl3-hydroxymethylcarbazolyl Methacrylate, N-methyl-N-phenyl2-amino Styrene Acrylonitrile Styrene Acrylate, butyl Acrylate, methyl Acrylonitrile Isobutylene, 3-chloroMaleic anhydride Methacrylate, ethyl Methacrylate, methyl Methacrylate, methyl Styrene Styrene Vinyl acetate Vinyl acetate Vinyl acetate Vinyl chloride Vinyl chloride Vinylidene chloride Acrylate, methyl Allyl chloride Vinyl acetate Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile
±95%
0.054 0.6 29.59 0.76 0.04 0.02
r2 0.95 0.95 1.3 1.74 1.43 1.8 0.39 0.16 -0.11 0.1 0.41 2.69 0.45 0.1 0.014
±95%
Conv.
0.23
Y
0.38 2.5
Y Y Y Y Y Y
Refs. 404 404 404 404 404 404 468 435 754 793
0.05 0.029
N Y
0.044
Y
209 237 237 209 884 884 806 850 981 638 806 926 822 508 580 649 508 776 599 220 288 288 702
0.27 0.004
0.016
0.13 0.44 0.205 0.9 0.534 1.9 0.86 0.34 1.2 1.79 0.48 0.42 0.04 0.1 0.02 0.5 0.62
0.103
0.015
1.425
0.09
Y
701
1.82
0.2
0.22
0.03
N
651
0.64 0.43 0.011 0.039 0 -0.09 0.15 -0.001 -0.57 -2.42 0 0.01 0 0.45 0.7 0.7 1.2 0 0 0.33 10.4 17.35
0.02
0.06 1.56 20.36 10.2 5 6.57 4.5 0.028 81.27 99.24 23 62.8 90 0.6 1 1
0.02
N
0.26 42.2
Y N
2.11
Y
0.019 1.93 24.6
Y N N
82.7
N
651 666 815 1053 470 108 412 27 210 210 470 1053 470 140 502 998 470 475 470 578 578 578 108 108 176 300
0.086 0.054 0.05
0.02 0.22
0.011 0.066 0.12 0.007 0.82 37.66 0.05
0.04 0.029
Y
0.069 0.3
1.16 6.6 0.52 0.08 0.11 N
0.05 0.1 0.12
0.16 0.37
2.6 3.9 1.79
1.06 0.11
N Y
TABLE 1. cont'd Monomer 1 Allyl alcohol AUyI alcohol Allyl butyrate Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloroacetate Allyl chloroacetate Allyl glycidyl hexahydrophthalate Allyl glycidyl phthalate Allyl isobutyrate Allyl propionate Allyl trichloroacetate Allyl trimethylacetate Allyl valerate Allylbenzene Allylbenzene Allylbenzene Allylbenzene Allylbenzene Allylbenzene Allylcyclohexane Allylstearamide, NAllylstearamide, NAllylstearamide,//Allyltriethoxysilane Allylurea Azlactone, 2-vinyl-4,4-dimethylAzlactone, 2-vinyl-4,4-dimethylAzobenzene, 4-(acrylamidomethylamino)Azobenzene, 4-(acrylamidomethylamino)Benzenesulfamide,/?-methacrylamideBenzimidazole, vinylmercaptoBenzoate, p-(acryloylethoxy)-, /?-butoxy phenyl Benzoate, /?-(acryloylethoxy)-, phenyl Benzoate, /?-(acryloyloxy)-, p-butoxy phenyl Benzoate, /?-(acryloyloxy)-, p-butoxy phenyl Benzoate, /?-(acryloyloxy)-, p-methoxy phenyl
Monomer 2 Methacrylate, ethyl Methacrylate, methyl Vinyl acetate Acrylate, benzyl Acrylate, butyl Acrylate, ethyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylic anhydride Acrylonitrile Acrylonitrile Allyl acrylate Methacrylate, benzyl Methacrylate, methyl Styrene Styrene Styrene Vinyl acetate Vinyl acetate Vinyl acetate Vinyl benzoate Vinyl butyrate Vinyl formate Vinyl propionate Vinylidene chloride Methacrylic anhydride Styrene Styrene Styrene Vinyl acetate Vinyl acetate Styrene Vinyl acetate Vinyl acetate Acrylate, methyl Acrylonitrile Acrylonitrile Maleic anhydride Methacrylonitrile Triallyl citrate Acrylonitrile Acrylonitrile Vinyl acetate Vinylidene chloride Vinyl chloride Methacrylic anhydride Acrylate, a-hydroxymethyl-, ethyl Styrene Styrene Vinyl acetate Vinyl butyl ether Styrene Benzoate, /?-(acryloyloxy)-, p-butoxy phenyl Benzoate, p-(acryloyloxy)-, p-butoxy phenyl Benzoate, /?-(acryloyloxy)-, p-butoxy phenyl Benzoate, /?-(acryloyloxy)-, phenyl Benzoate, p-(acryloyloxy)-, phenyl p-butoxyphenyl
ri
±95%
r2
±95%
Conv.
Refs.
-0.02 -1.62 0.64 0.06 0.1 0.08
1.92 2.9
107.4 78.79 0.97 9.9 5.83 7.73
5.3 6.5
N N
210 210 998 438 438 438 204 437 437 437 437 219 108 47 578 438 204 10 204 438 204 3 438 438 438 438 438 3 106 782 782 782 998 998 913 998 998 351 24 351 351 351 367 24 119 119 119 237 106 1011 1011 880 880 1005 764 881
Y 0.05 0.07 0.4 -0.02 0.02 -0.152 0.08 0.08 0.02 0.05 0.03 -2.4 0.61 0.75 0.88 1.15 0.78 0.68 0.24 -0.01 0.06 0.06 0.14 0.51 0.42 0.81 0.34 0.58 -0.036 -0.05 -0.026 -0.061 0.339 -0.18 0.03 0.68 -0.24 -0.94 -0.06 0.389 0.237 8.5 12.98 3.4 0.56 0.36
0.02 0.008 0.03
0.16 3.21 0.15
0.24 0.13
0.02 0.016 0.15 0.022 0.03 0.039 1.01 0.27 0.26 0.19 0.48 0.17 0.229 0.129 0.1 0.41
8.45 5.45 6.46 9.1 11.66 2.145 3.45 10.4 58.7 35.55 36.8 1.355 0.66 0.34 0.46 0.31 0.57 0.62 3.49 29.76 34.3 34.3 34.8 1.04 1.29 2.32 1.15 1.07 11.35 3.82 5.35 16.24 2.01 3.81 3.79 0.923 5.22 1.68 29.01 0.668 0.175 0.083 0.126 0 6.51 0.91
0.56 0.049 0.65
15.82 0.089 0.15
1.4 13
N Y Y Y Y Y Y
Y Y
0.15 0.66 1.7 0.3 1.36 0.5 11.42 0.28 0.092 0.15 0.38 18.48 0.12 0.054
Y Y Y Y Y Y Y Y Y Y Y Y Y Y
0.51
Y
0.61
0.32
881
0.91
0.36
881
0.32
0.61
881
0.49
1.5
881
References page 11-290
TABLE 1. cont'd Monomer 1 Benzoate, /?-(acryloyloxy)-, phenyl p-butoxy phenyl Benzoate, /?-(acryloyloxy)-, phenyl p-butoxy phenyl Benzoate, /?-(acryloyloxy)-, /7-butoxy phenyl Benzoate, /?-(acryloyloxy)-, p-butoxy phenyl Benzoate, p-(acryloyloxy)-, phenyl Benzoate, p-(acryloyloxy)-, phenyl Benzoate, p-(acryloyloxy-ethoxy)-, p-butoxy phenyl Benzoate, p-(acryloyloxy-ethoxy)-, p-methoxy phenyl Benzoate, p-(acryloyloxy-ethoxy)-,phenyl Benzoate, p-(methacryloyloxy)-, p-octyloxy phenyl Benzoate, p-(methacryloyloxyethoxy)-, p-octyloxy phenyl Benzocyclobutane, a-methyleneBenzocyclobutane, a-methyleneBenzocyclobutene, 4-vinylBenzofuran, 2-vinylBenzofuran, 2-vinylBenzofuran, 2-vinylBenzophenone, 2-hydroxy4-(methacryloxy)Benzophenone, p-vinylBenzophenone, p-vinylBenzophenone, p-vinylBenzophenone, p-vinylBenzophenone, p-vinylBenzophenone, p-vinylBenzothiazole, vinylmercaptoBenzothiazole, vinylmercaptoBenzothiazole, vinylmercaptoBenzothiazole, vinylmercaptoBenzothiazole, vinylmercaptoBenzothiazole, vinylmercaptoBenzothiazole, vinylmercaptoBenzothiazole, vinylmercaptoBenzothiazolone, Aq(methacroyloxy)methyl] Benzoxazole, vinylmercaptoBicyclo[2,2,l]hept-2-ene-5,6-dicarboximide, Af-benzyl Bicyclo[2,2,l]hept-2-ene-5,6-dicarboximide, N-benzyl Bicyclo[2,2,l]hept-2-ene-5,6-dicarboximide, N-benzyl Bicyclo[2,2,l]hept-2-ene-5,6-dicarboximide, Af-benzyl Bicyclo[2,2,l]hept-2-ene-5,6-dicarboximide, Af-benzyl Bicyclo[2,2,l]hept-2-ene-5,6-dicarboximide, TV-benzyl Bicyclo[2,2,l]hept-2-ene-5,6-dicarboximide, Af-benzyl Borazine, p-vinyl Butadiene Butadiene Butadiene
Monomer 2 Benzoate,/?-(acryloyloxy)-, /7-methoxyphenyl Benzoate,/?-(methacryloyloxy)-, (p-octyloxy)phenyl Benzoate, /?-(acryloyloxy-ethoxy)-, /?-butoxy phenyl Benzoate, p-(acryloyloxy-ethoxy)-, phenyl Benzoate, /?-(acryloyloxy-ethoxy)-, p-methoxy phenyl Benzoate, p-(methacryloyloxyethoxy)-, p-methoxy phenyl Benzoate, p-(acryloyloxy)-, p-butoxy phenyl Benzoate, p-(acryloyloxy)-, phenyl
T1
±95%
r2
±95%
Conv.
Refs.
1.5
0.49
881
0.23
1.26
881
0.91
0.36
856
0.32
0.61
856
1.5
0.49
856
0.23
1.26
856
0.36
0.91
856
0.49
1.5
856
Benzoate, p-(acryloyloxy)-, p-butoxy phenyl Benzoate, p-(acryloyloxy)-, phenyl butoxy phenyl Benzoate, p-(acryloyloxy)-, phenyl
0.61
0.32
856
1.26
0.23
881
1.26
0.23
856
Maleic anhydride Methacrylate, methyl Methacrylate, methyl Acrylate, butyl Acrylate, ethyl Methacrylate, methyl Methacrylate, methyl
0.002 0.46 1.47 7.8 5.76 3.89 1.65
1.36 0.334 0.617 0.114
0.025 0.32 0.6 0.041 0.015 0.006 0.315
0.043 0.01 0.02 0.036
N N N Y
1083 1083 1085 1020 1020 1020 934
Acrylate, methyl Acrylate, methyl Styrene, /?-A^A^imethyl-aminomethylStyrene, p-WV-dimethylaminoStyrene, p-dimethylaminoStyrene, p-dimethylaminomethylAcrylonitrile Fumaronitrile Maleic anhydride Methacrylate, methyl Styrene Styrene Vinyl acetate Vinyl phenyl sulflde Styrene
3.6 3.54 2.54 0.84 0.842 2.54 0.178
1.06 0.077 0.136 0.18 0.072 0.259 0.081
0.09 1.1 0.26 0.07 0.176 0.135 0.191
0.02 0.02 0.017 0.05 0.046 0.017 0.014
0.43 0.349 0.5 2.53 0.95 3.1
0.14 0.087 0.095 0.47 0.61 0.01
1.25 2.171 3.02 0.013 0.24 0.35
0.083 0.07 0.14 0.037 0.12 0.02
Y Y Y Y Y Y Y Y Y Y Y Y Y Y
866 911 86 866 911 911 763 763 763 763 764 764 763 763 960
Styrene Methacrylate, methyl
0.24 0
0.12
Y
764 994
Methacrylate, methyl
0
Styrene
0
18.2
994
Styrene
0
89.2
994
Vinyl acetate
0.35
1.26
994
Vinyl acetate
0.15
1.46
994
Vinyl acetate
0.014
1.99
994
Styrene Aconitate, trimethyl Acrylate, butyl Acrylate, heptafluorobutyl
0.001 0.4 1.04 0.359
2.87 30.5
0.19
108
0.016 0.4 0.11 0.039
4.53 0 0.074 0.073
994
0.62 0.22 0.03 0.031
Y Y Y
1018 147 257 206
TABLE 1. cont'd Monomer 1 Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene monoxide Butadiene, 1,4-dicarboxy late-,diethyl Butadiene, 1,4-dicarboxy late-, diethyl Butadiene, l,4-dicarboxylate-,diethyl Butadiene, l-(2-hydroxyethylthio)Butadiene, l-(diethylamino)Butadiene, l-(diethylamino)Butadiene, 1-acetoxy-
Monomer 2 Acrylate, methyl Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Butadiene, 2,3-dimethylButadiene, 2,3-dimethylButadiene, 2-chloroButadiene, 2-phthalidomethyl Cyclobutane, 1,2-dimethyleneCyclobutane, 1,2-dimethyleneEthylene, trichloroFerrocene, ethyl-oc-cylopentadienylide Fumarate, diethyl Isoprene Isoprene Maleamic acid, N-3-dimethylamino6-methyl phenyl Maleate, diethyl Methacrylate, 2-(AW-dimethylcarbamoyloxy)ethyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylonitrile Methyleneglutaronitrile, 2Pentadiene, cis-1,3Pentadiene, trans-1,3Pyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylStyrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, p-chloromethyl Styrene, ot-methylStyrene, /7-chloroVinyl chloride Vinyl chloride Vinylhendecanoate Vinyl pelargonate Vinyl stearate Vinylferrocene Vinylidene chloride Maleic anhydride Acrylonitrile Pyridine, 2-vinylStyrene Styrene, /?-chloroAcrylonitrile Acrylonitrile Acrylonitrile
rx 1.09 0.358 0.452 0.35 0.1 0.2 1.26 0.3 0.06 1.014 0.1 0.1 9.64 0.02 2.13 0.94 0.14 0.37
±95% 4.53 0.046 0.23 0.01 0.92 0.049 0.05 0.21
0.37 0.04
8.08 1.06 0.75 0.504 0.7 0.39 0.63 1.22 0.61 1.32 1.29 1.44 1.55 1.37
r2 0.07 0.046 0.1 0.05 0.06 0.03 0.78 0.86 3.41 1.35 5.76 5.76 -0.03 1.51 0.25 1.06 0.608 - 0.08
±95%
Conv.
Refs.
0.87 0.006 0.059
Y Y Y
0.02
N
0.24
Y
0.45
Y
0.36 0.07
N
0.062 0.03
Y N
257 21 255 418 501 66 173 83 418 735 854 885 89 699 466 173 83 679
0.11 0.35 0.024 0.15
0.02 0.56 0.14
0.25 0.027 0.32 0.053 0.26 0.09 0.47 0.72 0.41 0.84 0.37 0.38
466 600 0.004
Y
0.016
Y N
0.02 0.4 0.25
N Y N Y
1.35 1.59 1.8 1.4 1.4 0.5 1.38 1.83 1.38 0.449 0.662 0.87 1.5 1.22 8.8 5.27 22.56 26.3 42.5 4.34 1.97 0.05 2.79 0.69 0.55 3.27 0.426 0.425 0.82
0.11 0.41 0.043 0.017 0.13 2.16 3.35 24.54 4.73 0.18 0.25 0.18 0.9 0.23 0.1 0.208 0.48 0.68
0.58 0.44 0.6 0.44 0.38 0.68 0.82 0.83 0.64 0.45 0.187 0.42 0.139 1.6 0.04 -0.11 -0.22 0.02 0.02 0.16 -0.044 0.64 0.29 0.41 0.09 0.24 0.481 0.208 -0.012
0.13 0.21
N Y
0.17 0.049
Y Y
0.087 5.7
Y Y
0.31 1.26
Y Y
0.27 0.15 0.038 0.06 0.12 0.07 0.014
Y Y Y N N Y
0.049 0.049 0.043
Y Y Y
140 257 467 257 196 743 743 462 520 56 140 159 173 21 418 428 473 486 486 491 56 83 83 255 8 1075 70 255 517 717 145 145 145 802 257 1064 327 327 327 810 864 889 91
References page II - 290
TABLE 1. cont'd Monomer 1 Butadiene, 1-chloroButadiene, 1-ethoxyButadiene, 1-ethoxyButadiene, 1-phthalimidoButadiene, 1-succinimidoButadiene, 2,3-bis(diethylphosphono)Butadiene, 2,3-bis(diethylphosphono)Butadiene, 2,3-bis(diethylphosphono)Butadiene, 2,3-bis(diethylphosphono)Butadiene, 2,3-bis(diethylphosphono)Butadiene, 2,3-bis(diethylphosphono)Butadiene, 2,3-dichloroButadiene, 2,3-dichloroButadiene, 2,3-dichloroButadiene, 2,3-dichloroButadiene, 2,3-dichloroButadiene, 2,3-dichloroButadiene, 2,3-dichloroButadiene, 2,3-dimethylButadiene, 2,3-dimethylButadiene, 2,3-dimethylButadiene, 2,3-dimethylButadiene, 2,3-chloroButadiene, 2,3-chloroButadiene, 2,3-chloroButadiene, 2,3-chloroButadiene, 2,3-chloroButadiene, 2,3-chloroButadiene, 2,3-chloroButadiene, 2,3-chloroButadiene, 2,3-chloroButadiene, 2,3-chloroButadiene, 2,3-chloroButadiene, 2,3-chloroButadiene, 2,3-chloroButadiene, 2,3-chloroButadiene, 2,3-chloroButadiene, 2,3-chloroButadiene, 2,3-dichloroButadiene, 2-chloroButadiene, 2-chloroButadiene, 2-chloroButadiene, 2-chloroButadiene, 2-chloroButadiene, 2-chloroButadiene, 2-chloroButadiene, 2-chloroButadiene, 2-chloroButadiene, 2-chloroButadiene, 2-chloroButadiene, 2-chloroButadiene, 2-chloroButadiene, 2-chloroButadiene, 2-chloroButadiene, 2-chloroButadiene, 2-fluoroButadiene, 2-fluoroButadiene, 2-fluoroButadiene, 2-fluoroButadiene, 2-fluoroButadiene, 2-fluoroButadiene, 2-fluoroButadiene, 2-fluoroButadiene, 2-phthalidomethylButadiene, 2-trimethylsilyloxyButadiene, 2-trimethylsilyloxy-
Monomer 2 Styrene Acrylonitrile Acrylonitrile Styrene Styrene Maleimide Maleimide, Af-(2-hydroxyethyl)Maleimide, iV-(4-chlorophenyl)Maleimide, N-(4-methoxy-phenyl)Maleimide, N-chloromethylMaleimide, N-phenylButadiene, 2-chloroEthylene, 1,1-diphenylMethacrylate, methyl Phosphonic acid, a-phenylvinylPhosphonic acid, a-phenylvinylStyrene Styrene Butadiene Butadiene Isoprene Styrene Acrylate, methyl Acrylonitrile Acrylonitrile Acrylonitrile Butadiene Butadiene, l-(2-hydroxyethyl-thio)Butadiene, 2,3-dichloroButadiene, 2-fluoroButadiene, hexafluoroButadiene, hexafluoroEthylene, 1,1-diphenylFumarate, diethyl Hexatriene, tetrachloroIsoprene Isopropenyl methyl ketone Methacrylate, methyl Maleic anhydride Methacrylate, isobutyl Methacrylate, methyl Methacrylic acid Phosphonate, vinyl-,dimethyl Phosphonic acid, a-phenylvinylPhosphonic acid, a-phenylvinylQuinoline, 2-vinylStyrene Styrene Vinyl acetate Vinyl butyrate Vinyl formate Vinyl formate Vinyl propionate Vinylidene cyanide Acrylonitrile Butadiene, 2-chloroButadiene, hexafluoroIsoprene Methacrylate, methyl Styrene Styrene Styrene, a-methylButadiene Acrylonitrile Styrene
T1 1.44 0.065 0.065 1.56 1.68 0.14 0.12 0.03 0.04 0.05 0.05 1.98 3.58 11.04 7.75 7.75 8.65 10.6 0.78 0.86 0.84 1.048 5.19 10.4 5.35 4.8 5.38 3.41 1 0.31 3.7 5.47 5.52 3.4 6.51 3.6 2.82 4.035 11.04 0.026 1.8 6.33 2.52 7.5 7.5 7.5 2.1 7.84 5.98 33.52 15 11.91 0.6 0.22 2.93 2.63 1.23 2.1 1.24 2.22 1.35 0.065 1.2
±95% 3.1 0.009 0.02 0.63 0.16
r2
±95%
Conv.
Refs. 695 864 889 163 163 759 759 759 759 759 759 122 61 61 588 597 587 61 173 83 173 173 457 61 402 504 61 418 810 122 493 127 453 61 61 459 418 259 61 1068 1057 61 259 594 546 597 456 61 8 247 247 127 247 247 82 174 493 453 174 174 174 174 174 735 993 993
0.27 0.02 0.01 0.299 0.286 0.43 0.49 0.41 0.47 0.3 0.42 0.31 -0.08 0.08 0.07 0.07 0.25 0.05 1.26 0.3 1.18 0.534 0.06 0.06 0.04 0.05 0.056 0.06 0.2 1.98 0.22 0.1 0.1 0.03 0.02 0.2 0.06 0.14
0.27 0.008 0.008 0.049 0.018
Y Y Y Y Y
0.12
Y Y Y
0.107 0.088
0.5 8.98
0.329 0.9 0.08 - 0.035 0.1 0.1 0.1 0.38 0.05 0.025 - 0.02
3.89
-0.04 -0.05
0.25
0.24 0.066
0.45 0.12
0.087 0.08 0.03 0.06 0.2
0.18 0.96 1.77 0.12 0.61 0.7 0.45
0.077 3.7 0.24 0.25 0.76 0.214 0.22 0.72 1.014 0.036 0.64
Y 0.92
Y
0.035
Y Y
0.023
Y
0.25
Y
Y Y 0.01
0.058
0.047 0.09 0.01
Y Y N N Y Y
Y Y N N
0.021
N N Y Y
0.12 0.77 0.03 0.15 0.24 0.049
Y Y Y Y Y Y
TABLE 1. cont'd Monomer 1 Butadiene, hexafluoroButadiene, hexafluoroButadiene, hexafluoroButadiene, hexafluoroButadiene, l-(2-hydroxyethylthio)Butadiene-lcarboxylate, ethyl Butadiene-lcarboxylate, S-(-)oc-phenethylammonium Butadiene-1-carboxylate, ethyl Butadiene-1-carboxylate, ethyl Butadiene-1-carboxylic acid Butadiene-1-carboxylic acid Butadiene-1-carboxylic acid Butadiene-1-carboxylic acid Butanoate, 3-acrylamido-3-methyl-, sodium Butene, cis-2Butene-1 Butene-1 Butene-1 Butene-1 Butene-1 Butene-1, 2-ethylButene-1, 2-methylButene-1, 3,3-dimethylButene-1, 3,3-dimethylButene-1, 4-(p-chlorophenyl)Butene-1, 4-(/?-methoxyphenyl)Butene-1, 4-cyclohexylButene-1,4-phenylButene-2 Butene-2 Butene-2, 2-methylButene-2, cwButene-2, cwButene-2, cisButene-2, transButene-2, transButenoate, 3-phenyl-3-, methyl Butyrolactone, oc-methyleneCaprolactam, N-vinylCaprolactam, TV-vinylCaprolactam, N-vinylCaprolactam, N-vinylCaprolactam, N-vinylCaprolactam, N-vinylCaprolactam, N-vinylCaprolactam, N-vinylCaprolactam, N-vinylCaprolactam, N-vinylCaprolactam, N-vinylCaprolactam, N-vinylCaprolactam, JV-vinylCaprolactam, TV-vinylCaprolactam, N-vinylCaprolactam, TV-vinylCaprolactam, TV-vinylCarbamate, TV,TV-diethyl-, vinyl Carbamate, TV,TV-diethyl-, vinyl Carbamate, TV,TV-diethyl-, vinyl Carbamate, TV,TV-diethyl-, vinyl Carbamate, TV,TV-diethyl-, vinyl Carbamate, TV-phenyl-, vinyl Carbamate, TV-phenyl-, vinyl Carbamate, N-vinyl-, ethyl
Monomer 2 Butadiene, Butadiene, Butadiene, Isoprene Butadiene, Styrene Styrene
2-chloro2-chloro2-fluoro2-chloro-
Acrylonitrile Pyridine, 2-vinylAcrylonitrile Acrylonitrile Styrene Styrene Acrylamide, TV,TV-dimethylMaleimide, TV-cyclohexylAcrylonitrile Ethylene Ethylene Vinyl acetate Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Ethylene Vinyl chloride Vinyl chloride Acrylonitrile Vinyl acetate Vinyl chloride Acrylonitrile Vinyl acetate Styrene Styrene Crotonaldehyde Crotonaldehyde N-Vinyl pyrrolidone Pyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 4-vinylPyridine, 4-vinylPyrrolidone, N-vinylStyrene Vinyl acetate Vinyl acetate Vinyl acetate Vinyl butyl ether Vinyl isopropyl ether Vinyl phenyl ether Acrylate, methyl Acrylic acid Maleic anhydride Styrene Vinyl acetate Methacrylate, butyl Methacrylate, di-, triethylene-glycol Acrylic acid
rx 0.1 0.1 0.24 0.78 0.2 0.56 6.81 3.2 0.8 4 11 0.52 5.55 0.22 3 0.24 3.25 0.16 0.11 0.12 -1.05 -1.18 -0.44 -0.07 -0.066 -0.085 0.014 0.024 -1.79 0.3 0.11 0.03 0 0.84 -0.03 -0.532 0.85 0.31 0.31 1.7 0.04 0.04 0.12 0.12 0.1 0.1 1.7 1.02 0.31 2.5 2.5 3.1 0.22 1.3 - 0.027 -0.097 0.024 -0.08 0.13 0.329 0.034 0.26
±95%
r2
1.68
5.47 5.52 2.93 1.19 1 0.12 0.45
0.138
0.3 0.4 0.2 0.03 0.15 0.08 0.987
0.81
0.42 0.12 0.89 1.2 0.28 2.5 0.044 0.088 0.055 0.069 5.22 5.31 0.25 0.6 0.44 0.512 0.06 0.005 0.2
0.01
5.3 1.95 2.43 0.049 0.068 0.066 0.18 0.19
0 13.46 3.6 1.55 3.34 1.56 1.01 5.64 6.18 4.68 2.56 5.03 4.51 7.5 3.3 8.52 22.32 8.27 8.8 62.99 7.2 1.97 0.14 0 0 2.8 11.58 11.58 4.35 4.35 4.43 4.43 2.8 0.2 0.63 0.35 0.35 0.03 0.01 0.26 4.78 5.58 0.025 29.56 1.7 0.418 0.504 4.69
±95%
Conv.
Refs.
Y
127 453 453 453 810 791 748
0.153
Y
791 791 791 799 791 799 857
3.61
Y
0.24 0.58 0.26 0.31 0.2 13.57 0.63 1.11 0.76 0.86
Y Y N N N Y Y Y Y Y
2.18 10.54 1.05
N N Y Y
10.67 1.69 0.364 0.01
Y Y Y N
0.13
0.2
0.01
0.73 0.96 0.37 0.22 0.32 0.034 3.59 0.04
Y Y Y Y Y Y Y Y
Y
995 211 388 407 211 30 329 329 329 6 24 24 24 24 477 329 329 211 211 230 211 211 1008 663 875 907 883 589 592 589 592 589 592 859 916 557 859 883 215 215 214 92 92 92 197 197 833 833 81
References page II - 290
TABLE 1. cont'd Monomer 1 Carbamate, N-vinyl-, ethyl Carbamate, N-vinyl-, ethyl Carbamate, N-vinyl-, ethyl Carbamate, TV-vinyl-, ter/-butyl Carbamate, N-vinyl-, terf-butyl Carbamate, N-vinyl-, terf-butyl Carbazole, 2-butenylCarbazole, 9-propenylCarbazole, 9-vinylCarbazole, 9-vinylCarbazole, N-butenylCarbazole, N-methyl-3-vinyl Carbazole, N-propenylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbon monoxide Carbon monoxide Carbon monoxide Carbon monoxide Carbon monoxide Carbon monoxide Cinnamat, methyl Cinnamate, 2-chloroethyl Cinnamate, a-cyano-, 2-ethylhexyl Cinnamate, a-cyano-, benzyl Cinnamate, a-cyano-, butyl Cinnamate, a-cyano-, cyclohexyl Cinnamate, a-cyano-, ethyl Cinnamate, a-cyano-, ethyl Cinnamate, a-cyano-, hexyl Cinnamate, a-cyano-, methyl Cinnamate, a-cyano-, methyl Cinnamate, benzyl
Monomer 2 Pyrrolidone, N-vinylVinyl acetate Vinyl acetate Vinyl acetate Methacrylate, methyl N-Vinylpyrrolidone Carbazole, 9-vinylCarbazole, 9-vinylCarbazole, 2-butenylCarbazole, 9-propenylCarbazole, N-vinylStyrene Carbazole, N-vinylAcenaphthalene Acrylate, ethyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylonitrile Carbazole, N-butenylCarbazole, N-propenylFumarate, diisopropyl Maleate, diethyl Maleate, dimethyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Propene, 2,3-dichloroStyrene Styrene Styrene Styrene, /?-chloroSuccinimide, N-vinylVinyl acetate Vinyl acetate Vinyl acetate Vinyl butyrate Vinyl chloride Vinyl formate Vinyl propionate Vinyl thiolacetate Vinylidene chloride Vinylidene chloride Ethylene Ethylene Ethylene Ethylene Vinyl acetate Vinyl chloride Styrene Styrene Styrene Styrene Styrene Styrene Acrylonitrile Styrene Styrene Pyrrolidone, N-vinylStyrene Styrene
/*i
±95%
r2
±95%
Conv.
Refs.
0.371 2.09 0.4 0.46 0.17 2.4 0.02 0.02 2.6 2.8 0.02 1.404 0.02 -0.03 0.27 0.049 0.11 0.028 0.09 2.6 2.8 0 0.21 0.51 0.14 0.033 0.06 0.75 0.08 0.33 0.031 1 -0.02 0.026 0.032 0.02 0.04 2.67 3.02 3.9 1.33 4.77 4.142 1.69 0.44 3.6 3.65 0.32 0.004 -0.15 0 0.33 0.121 0.04 0.01 0.06 -0.16 - 0.09 - 0.24 -0.18
0.05
0.12
Y
0.063 0.07 0.2 0.06 0.5 0.5 0.003 0.003
Y N
0.011 0.13 0.11 0.01 0.17 0.08 0.22 0.15
1.77 0.39 0.418 1.12 1.87 0.4 2.6 2.8 0.02 0.02 2.6 0.735 2.8 6.62 1.1 0.53 0.43 0.51 0.39 0.02 0.02 0 0 0 1.55 2.12 1.8 0.57 1.84 0.44 2.123 0 6 5.93 5.72 7 0.11 0.126 0.15 0.13 0.07 0.17 0.192 0.081 0.45 -0.023 -0.008 0.068 0.025 0.04 0.5 0.24 13.52 1.799 1.394 0.58 0.4 0.47 0.37 12.6
0.26 0.001 0.35 0.13
0.39 0.044 0.4 1.33
81 629 81 827 991 991 904 904 904 904 871 806 871 331 757 13 551 98 269 871 871 1038 361 361 11 13 738 738 758 758 98 376 11 13 98 551 284 246 246 551 246 427 246 246 97 13 98 51 51 52 52 474 184 488 488 282 282 282 282 310 134 282 816 282 488
-0.17 -0.001 -0.21 0.14
0.26 0.03 0.1 0.5 0.003 0.003 0.5 0.5 0.146 0.12 0.029 0.045 0.04
0.05 0.11 0.03 0.015 0.05 0.18 0.022 0.06 0.034 0.057 0.09 0.13 0.34 0.011 0.21 0.28 0.12 0.3 0.65 0.012 0.07
0.067 1.77
N
0.13
Y
0.073 0.04
Y N
0.01 0.01 0.16 0.14
N N N Y
0.26 0.22 0.048
N N Y
1.34 1.05 0.4
N Y Y
0.83 0.023
Y Y
0.12
Y
0.001 0.073 0.15 0.068 0.018 0.012 0.006 0.01
Y Y N Y Y Y Y N
0.25 0.073 0.068 0.004 0.03 0.03 0.04 2.3
Y Y Y N N N N Y Y N Y N Y
0.04 0.008 0.06 0.12
TABLE 1.
coni'd
Monomer 1 Cinnamate, butyl Cinnamate, dibutylchlorotin Cinnamate, ethyl Cinnamate, ethyl Cinnamate, methyl Cinnamate, p-chloro-, methyl Cinnamate, /?-methyl-, methyl Cinnamate, phenyl Cinnamate, tert-butyl Cinnamic acid, cisCinnamic acid, transCinnamide, AW-diethylCinnamide, p-chloro-, AW-diethylCinnamide, p-methyl-, AW-diethylCinnamonitrile Cinnamonitrile Cinnamonitrile, a-cyanoCinnamonitrile, a-cyanoCitraconate, di-sec-buiy\ Citraconate, dibenzyl Citraconate, dibutyl Citraconate, dicyclohexyl Citraconate, diethyl Citraconate, diisobuty Citraconate, diisopropyl Citraconate, dimethyl Citraconate, dipropyl Citraconic acid Citraconic anhydride Citraconimide, p-iso-, N-(4-acetylphenyl)Citraconimide, p-iso-, AK4-acetylphenyl)Citraconimide, p-iso-, A^-(4-ethoxycarbonylphenyl)Citraconimide, p-iso-, 7V-(4-methoxyphenyl)Citraconimide, p-iso-, N-{p-to\y\)Citraconimide, p-iso-, N-phenylCitraconimde, TV-(I-menthylcarboxylatomethyl)Citraconimide, A^-(4-acetoxyphenyl)Citraconimide, A^-(4-acetoxyphenyl)Citraconimide, A^-(4-chlorophenyl)Citraconimide, Af-(4-chlorophenyl)Citraconimide, A^-(4-ethoxycarbonylphenyl)Citraconimide, A^-(4-ethoxycarbonylphenyl)Citraconimide, N-(4-methoxyphenyl)Citraconimide, A^-(4-methoxyphenyl)Citraconimide, N-aHyl Citraconimide, N-benzylCitraconimide, Af-benzyl Citraconimide, TV-butylCitraconimide, TV-butylCitraconimide, TV-ethylCitraconimide, TV-ethylCitraconimide, TV-hexylCitraconimide, TV-hexylCitraconimide, TV-isobutylCitraconimide, TV-isobutylCitraconimide, TV-isopropylCitraconimide, JV-isopropylCitraconimide, TV-methylCitraconimide, TV-methylCitraconimide, TV-methyl-
Monomer 2 Styrene Acrylate, methyl Styrene Styrene Styrene Styrene Styrene Styrene Styrene Acrylamide Acrylamide Styrene Styrene Styrene Acrylonitrile Styrene Acrylonitrile Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
r\
±95%
0.04 -0.2 -0.076 0.082 0.02 0.04 0 0.029 0.1 -0.48 -0.24 0.01 0.01 0.01 0.36 -0.008
0.15
0.13 0.047 0.054 0.03 0.029 0.03 0.076 0.049 0.027 0 0.021 0 0 0
0.054 0.045
0.055 0.12 0.28 0.15
0.1 0.021
0.058
r2 1.757 1.65 1.52 1.566 1.27 2.24 2.84 1.66 1.692 3.84 3.4 4.17 2.99 4.95 8.46 2.549 2 1.55 2.74 1.88 2.48 1.8 1.62 1.58 2.19 1.36 0.16 0.42 0.28 0.3
±95%
Conv.
Refs.
0.082
Y
0.31 0.035
Y Y
0.12 0.087 0.68 0.24
Y Y Y Y
0.37 0.092
Y Y Y Y
0.15
Y
488 659 200 488 653 653 653 488 488 298 298 737 737 737 310 134 310 134 841 841 841 841 841 841 841 841 841 1021 47 608 608 608
Styrene
0
0.27
608
Styrene Styrene Methacrylate, methyl
0 0 0.109
0.115
0.4 0.39 3.47
0.335
Y
608 608 950
Methacrylate, methyl Styrene Methacrylate, methyl Styrene Methacrylate, methyl
0.18 0.015 -0.01 0.075 -0.027
0.13 0.086 0.18 0.093 0.084
1.88 0.151 2.93 0.181 2.72
0.16 0.054 0.4 0.057 0.18
Y Y Y Y Y
728 728 728 728 728
0.004
0.033
0.148
0.018
Y
728
0.19 0.11
3.16 0.63 0.142 2.77 0.19 2.17 0.169 3.25 0.231 2.38 0.316 1.78 0.326 2.7 0.244 0.53 3.24 0.15
0.73 0.19
Y Y
0.28 0.087 0.56 0.028 0.79 0.044 0.45 0.086 0.85 0.094 0.51 0.055
Y Y Y Y Y Y Y Y Y Y Y Y
728 728 959 714 714 714 714 714 714 714 714 714 714 714 714 460 460 460
Styrene Methacrylate, Styrene Styrene Methacrylate, Styrene Methacrylate, Styrene Methacrylate, Styrene Methacrylate, Styrene Methacrylate, Styrene Methacrylate, Styrene Acrylonitrile Methacrylate, Styrene
methyl methyl methyl methyl methyl methyl methyl methyl
-0.1 0.04 0.004 0.02 -0.066 -0.12 0.03 -0.04 -0.002 -0.08 -0.03 -0.18 0.07 0.09 -0.014 0.6 0.15 0.24
0.14 0.082 0.36 0.045 0.33 0.05 0.28 0.11 0.42 0.14 0.27 0.063
References page II - 290
TABLE 1. cont'd Monomer 1 Citraconimide, Af-methylCitraconimide, AT-phenylCitraconimide, N-phenylCitraconimide, Af-propylCitraconimide, N-propylCitraconimide, N-tert-buty\Citraconimide, N-tert-butylCitraconimide, N-tolylCitraconimide, JV-tolylCitraconimide, a-iso-, 7V-(4-acetylphenyl)Citraconimide, a-iso-, A^-(4-chlorophenyl)Citraconimide, a-iso-, N-(4-ethoxycarbonylphenyl)Citraconimide, a-iso-, N-(4-methoxyphenyl)Citraconimide, a-iso-, TV-(p-tolyl)Citraconimide, a-iso-, TV-phenylCopper diacrylate Crotonaldehyde Crotonaldehyde Crotonaldehyde Crotonaldehyde Crotonaldehyde Crotonaldehyde Crotonaldehyde Crotonaldehyde Crotonaldehyde Crotonaldehyde Crotonate, hydrocortisone 21Crotonate, a-acetyl-, methyl Crotonate, a-acetyl-, methyl Crotonate, a-bromo-, ethyl Crotonate, a-carboethoxy-, ethyl Crotonate, a-carboethoxy-, ethyl Crotonate, a-chloro-, ethyl Crotonate, a-chloro-, ethyl Crotonate, a-cyano-, ethyl Crotonate, a-cyano-, ethyl Crotonate, a-methoxy-, methyl Crotonate, a-methoxy-, methyl Crotonate, a-methyl-, methyl Crotonate, a-methyl-, methyl Crotonate, ethyl Crotonate, ethyl Crotonate, methyl Crotonic acid Crotonic acid Crotonic acid Crotonic acid Crotonic acid' Crotonic acid Crotonic acid Crotonic acid Crotonic acid Crotonic acid Crotonic acid Crotonic acid, cisCrotonic acid, transCrotononitrile Crotononitrile Crotononitrile, a-phenylCyclobutane, 1,2-dimethyleneCyclobutane, 1,2-dimethyleneCyclobutane, 1,2-dimethylene-
Monomer 2 Styrene Methacrylate, Styrene Methacrylate, Styrene Methacrylate, Styrene Methacrylate, Styrene Styrene Styrene Styrene
methyl methyl methyl methyl
rx 0.24 0.001 -0.001 -0.03 -0.014 0.038 0.045 0.003 -0.02 0 0 0
±95%
0.033 0.023 0.43 0.087 0.072 0.05 0.088 0.18
r2 0.14 3.081 0.175 3.23 0.196 2.88 0.465 2.75 0.31 0.81 1.03 0.96
±95%
0.074 0.016 0.98 0.062 0.19 0.039 0.19 0.13
Conv.
Y Y Y Y Y Y Y Y
Refs. 506 728 728 714 714 714 714 728 728 608 608 608
Styrene
0
0.39
608
Styrene Styrene Titanium, dicylopentadienyl-, dimethacrylate Acrylonitrile Acrylonitrile Caprolactam, N-vinylCaprolactam, N-vinylPyrrolidone, N-vinylStyrene Styrene Styrene Vinyl chloride Vinylidene chloride N-Vinyl pyrrolidone Acrylonitrile Styrene Styrene Acrylonitrile Styrene Acrylonitrile Styrene Acrylonitrile Styrene Acrylonitrile Styrene Acrylonitrile Styrene Acrylonitrile Styrene Styrene Acrylamide Acrylamide Acrylamide Acrylamide Acrylonitrile Pyrrolidone, TV-vinylStyrene Vinyl acetate Vinyl acetate Vinyl acetate Vinylidene chloride Acrylamide Acrylamide Styrene Styrene Styrene Butadiene Butadiene Styrene
0 0 1.09
1.69 1.76 0.89
608 608 895
0 0.01 0 0 -0.15 0.03 0.07 0.12 -0.56 0 0.05 0 0 0 0 0 0 0 0.06 0.02 0 0.04 0 0.02 0 0 -0.27 -0.18 -0.19 0.11 0.12 0 0 0 0.04 0.01 0.001 -0.2
8 25 0.31 0.31 0.42 14.7 14.7 14.7 1.55
429 504 875 907 248 428 428 428 271 405 1022 785 785 785 785 785 785 785 785 785 785 785 785 785 785 785 112 298 298 569 569 402 245 402 47 526 94 47 341 341 112 785 785 854 885 854
-0.085 -0.012 0 0 5.76 5.76 3.6
0.01
0.25 0.05
0.22 0.14 0.19
0.03 0.14 0.1 1.03 0.024 0.06
0.36
0.75 8.68 2.7 4.42 18.7 8.24 9.53 5.13 11.4 0.26 1 18.4 2.97 30.7 25.2 27 9.68 3.76 4.23 4.72 5.32 21 0.84 20 0.317 0.3 0.31 18.1 7.2 23.29 23.8 0.43 0.1 0.1 0.26
0.005 0.02
N
0.26
N
0.02
1.86 0.89 1.37
Y Y Y
0.07
N
0.081
Y
0.07 43.7 0.33 1.7
0.05
N Y Y Y Y
TABLE 1. cont'd Monomer 1 Cyclobutane, 1,2-dimethyleneCyclopentene, 4-,-1,3-dione Cyclopentene, 4-,-1,3-dione Cyclopentene, 4-,-1,3-dione Cyclopentene, 4-,-1,3-dione Cyclopentene, 4-,-1,3-dione Cyclopropane, l,l-bis(ethoxycarbonyl)2-vinylCyclopropane, l,l-bis(ethoxycarbonyl)2-vinylCyclopropene, 3,3-dimethoxyDiallyl P-cyanoethylisocyanurate Diallyl melamine Diallyl melamine Diallyl melamine Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl, l,3-,5-(2-hydroxy3-phenoxypropyl)isocyanate Diallyl, l,3-,5-(2-hydroxy3-phenoxypropyl)isocyanate Diallylcyanamide Diallylcyanamide Diallylcyanamide Diallylcyanamide Diallylcyanamide Diallylcyanamide Diallylcyanamide Diallyldimethylammonium chloride Dicyclopentadiene Dihydroxydiphenylsulfone diallyl ether Dimethyleneheptanedioate, 2,6-,dimethyl Dioxolane,l,3-,4,4-dimethyl-5-methylene2-trichloroDioxolane,l,3-,4-methylene2-trichloromethylDioxolane,l,3-,4-methylene2-trichloromethylDiphenylsulfone,3,3'-bisitaconimido-m,m'Dithiane, 2-methylene-l,3Dithiane, 2-methylene-1,3Divinylbenzene, mDivinylbenzene, p-
Monomer 2
rx
±95%
r2
±95%
Conv.
Refs. 885 95 95 263 264 264 1076
Styrene Acrylonitrile Methacrylate, methyl Styrene Styrene, p-chloroVinylidene chloride Methacrylate, methyl
3.6 0.04 0.094
0.16 0.058 0.017
0.28 3.02 8.11
0.05 0.71 0.38
0.014 0.113 0.223
0.006 0.027 0.194
0.294 1.88 4.21
0.081 0.35 0.905
Y Y Y Y Y Y
Methacrylate, methyl
0.111
0.194
2.5
Y
1076
Acrylonitrile Vinyl acetate Methacrylate, methyl Styrene Vinyl acetate Acrylate, methyl Acrylate methyl Acrylonitrile Acrylonitrile Fumarate, dibutyl Fumarate, diethyl Fumarate, dioctyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Vinyl acetate Vinyl acetate Vinyl acetate Vinyl chloride Vinylidene chloride Vinyl acetate
0.245 4.6
0.037
1.424 0.06
0.038
Y
-0.32 0.318 0.028 0.038 0.04 0.037 0.02 0.01 0.02 -0.001 0.029 0.076 0.041 0.026 0.038 0.08 0.09 0.1 0.1 0.13 2.19 1.66 2 0.7 0.2 5.5
0.2 0.073 0.005 0.008 0.012 0.031
36.96 0.68 6.208 6.18 4.23 2.78 1.01 1.25 0.96 26.56 22.73 21.52 36.41 25.59 23.67 18.8 27.5 16.9 23.8 15.1 0.336 0.414 0.72 0.833 5 0.15
4.02 0.026 0.069 0.16 0.15 0.52
Y Y Y Y Y Y Y
1.98 1.48 0.39 1.23 2.19 1.2
Y Y Y Y Y Y
0.049 0.029
Y Y
0.012
Y
838 778 201 201 201 297 297 153 153 665 665 665 153 153 153 152 152 152 152 152 152 152 152 297 297 509 296 376 671
0.011 0.026 0.006 0.038 0.071 0.04
0.34 0.16 0.046
18.3
Vinyl acetate
3.65
0.16
676
Acrylate, methyl Acrylate, methyl Methacrylate, methyl Methacrylate, methyl Vinyl acetate Vinyl chloride Vinyl chloride Vinyl acetate Maleic anhydride Styrene Methacrylate, methyl Pyrrolidone, N-vinyl-
0.05 0.05 0.04 0.04 1.62 0.68 0.68 1.95 0.037 0.92 0.53 0.01
6.7 6.7 25 25 0.01 0.44 0.44 0.35 0.071 0.975 2.36 3.87
603 604 603 604 581 602 603 1029 914 1016 795 647
Acrylamide
0.037
8.6
616
Pyrrolidone, N-vinyl-
0.04
2.98
647
Methacrylic acid
0.015
Methacrylate, methyl Styrene Styrene Maleic anhydride
4.12 3.35 0.58 0.01
0.112 0.16 0.02
0.058
0.564
0.04 0.01
0.08 0.03 0.58 0.09
0.045 0.015 0.25
0.032
0.15 0.01
Y N
Y
N
1042 1031 1031 262 943
References page II - 290
TABLE 1. cont'd Monomer 1 Divinylbenzene, pEthene, 2-phenyl-l,l-dicyanoEthylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene, 1,1 -dichloro-2,2-difluoro Ethylene, 1,1-diphenylEthylene, 1,1-diphenylEthylene, 1,1-diphenylEthylene, 1,1-diphenylEthylene, 1,1-diphenylEthylene, 1,1-diphenylEthylene, 1,1-diphenylEthylene, 1,1-diphenylEthylene, 1,1-diphenylEthylene, 1,1-diphenylEthylene, 1,1-diphenyl-
Monomer 2 Styrene N-Vinylpyrrolidone Acrylate, butyl Acrylate, methyl Acrylate, methyl Acrylonitrile Butene-1 Butene-1 Butene-2 Carbon monoxide Carbon monoxide Carbon monoxide Carbon monoxide Ethylene, tetrafluoroEthylene, tetrafluoroEthylene, tetrafluoroEthylene, tetrafluoroFumarate, diethyl Maleate, diethyl Maleic anhydride Methacrylate, di-, zinc Methacrylate, methyl Phosphonate, vinyl-, diphenyl Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl- diisobutyl Propylene Propylene Styrene Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl butyrate Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl diethylphosphinate Vinyl diphenylphosphinate Vinyl ethyl ether Vinyl fluoride Vinyl fluoride Vinyl propionate Vinylidene chloride Vinyl acetate Acrylate, ethyl Acrylate, methyl Acrylate, methyl Acrylonitrile Butadiene, 2,3-dichloroButadiene, 2-chloroMethacrylate, methyl Methacrylate, methyl Methacrylonitrile Styrene Styrene
r\
±95%
r2
±95%
Conv.
Refs.
1.18
0.17
0.26
0.25
0.01
0.003
13.94
0.38
N Y N N
262 947 42 41 768 415 388 407 477 51 51 52 52 1093 1094 563 563 41 41 620 935 41 801 801 801 388 477 615 309 41 413 42 559 68 68 766 605 180 270 42 472 536 63 63 64 68 311 311 584 42 590 605 299 6 65 334 334 143 61 61 65 901 143 189 281
0.02 0 3.25 3.6 7.5 0.068 0.025 0.04 0.5 0.52 0.575 0.61 0.38 0.11 0.25 0.04 0.19 0.088 0.077 3.43 3.2 0.05 0.16 0.28 0.88 0.74 0.67 0.13 0.79 0.7 0.19 0.24 0.34 0.2 0.21 0.21 0.14 0.23 0.16 0.15 0.05 2.7 2.52 1.7 0.67 0.018 -0.13 0.5 -0.24 0.21 -0.02 -0.08 0.03 0.09 0 -0.45 0.01 -0.02
19.4 7 0.16 0.012 0.006 0.01 0.18 0.09 1.14
0.32 0.004 -0.15 0 0.067 0.065 0.02 0.1 1.91 10 0 40
0.65 0.012 0.07
Y Y N
0.12 0.027 3.4
N
N Y Y Y
0.01 0.003
1.66 7.73
2.22 2.19
0.03
0.62 14.88 0.72
1.2
N N
0.77
N
0.64 0.21
N N
0.42 0.58 0.44
N N N
0.1 0.22 0.22 0.18 80.64 34.66
N N N N Y Y
0.15
N
1.96 0.58
Y Y
0.01 0.01 0.01
N N N Y Y
0.1 0.02 0.01
N N N
0.52 0.03 0.01 0.17 0.13 0.13 0.01 0.12 0.01 0.01 0.16 0.01 0.32 0.005 0.36 0.15 0.05 0.01
0.11 0.02 0.01
1.14 1.03 1.52 3.74 1.23 1.4 1.5 1.99 1.74 4.38 2 3.21 1.85 0.96 1.63 1.55 -11.99 -62.84 0 0.01 0.3 1.5 15.71 0.33 0.8 0.09 0.12 0.05 3.58 3.4 2.1 8.7 0.48 0.33 0.34
Next Page
TABLE 1. cont'd Monomer 1 Ethylene, 1,1-diphenylEthylene, chlorotrifluoroEthylene, chlorotrifluoroEthylene, chlorotrifluoroEthylene, chlorotrifluoroEthylene, chlorotrifluoroEthylene, chlorotrifluoroEthylene, chlorotrifluoroEthylene, chlorotrifluoroEthylene, chlorotrifluoroEthylene, chlorotrifluoroEthylene, chlorotrifluoroEthylene, chlorotrifluoroEthylene, chlorotrifluoroEthylene, dichloro-, cis Ethylene, dichloro-, cis Ethylene, dichloro-, cis Ethylene, dichloro-, cis Ethylene, dichloro-, cis Ethylene, dichloro-, cis Ethylene, dichloro-, cis Ethylene, dichloro-, cis Ethylene, dichloro-, cis Ethylene, dichloro-, cis Ethylene, dichloro-, cis Ethylene, p-vinyl- 1,1-diphenylEthylene, tetrachloroEthylene, tetrachloroEthylene, tetrachloroEthylene, tetrachloroEthylene, tetrachloroEthylene, tetrachloroEthylene, tetrachloroEthylene, tetrachloroEthylene, tetrachloroEthylene, tetrachloroEthylene, tetrachloroEthylene, tetrachloroEthylene, tetrafluoroEthylene, tetrafluoroEthylene, tetrafluoroEthylene, tetrafluoroEthylene, trichloroEthylene, trichloroEthylene, trichloroEthylene, trichloroEthylene, trichloroEthylene, trichloroEthylene, trichloroEthylene, trichloroEthylene, trichloroEthylene, trichloroEthylene, trichloroEthylene, trichloroEthylene, trichloroFerrocene, ethyl-a-cyclopentadienylidene Ferrocene, ethyl-a-cyclopentadienylidene Formaldehyde-S-vinyl-O-ethylthioacetal Fumarate, allyl methyl Fumarate, bis(2-butyl) Fumarate, bis(3-[tris(trimethylsiloxy)silyl)propyl] Fumarate, bis(3-[tris(trimethylsiloxy)silyl)propyl] Fumarate, bis(3-chloro-2-butyl)
Monomer 2 Styrene Ethylene, tetrafluoroIsobutylene Methacrylate, methyl Propionate, vinyl Propylene Pyrrolidone, N-vinylStyrene Styrene Vinyl acetate Vinyl acetate Vinyl chloride Vinyl fluoride Vinylidene chloride Styrene Styrene Styrene Styrene Styrene Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinylidene cyanide Vinylidene cyanide Styrene Acrylate, methyl Acrylonitrile Acrylonitrile Methacrylate, methyl Styrene Styrene Styrene Styrene Styrene Vinyl acetate Vinyl acetate Ethylene Ethylene Ethylene Ethylene Ethylene, chlorotrifluoroAcrylate, methyl Acrylonitrile Acrylonitrile Butadiene Methacrylate, methyl Styrene Styrene Styrene Styrene Styrene Vinyl acetate Vinyl acetate Vinyl isobutyl ether Butadiene Isoprene Styrene Styrene Styrene Fumarate, di-te/t-butyl Fumarate, diisopropyl Styrene
r\ 1.15 1 0.01 -0.074 0.08 0.02 0.3 -0.1 0.01 0.04 - 0.02 0.01 1.2 0.02 -3.1 -2.2 -0.28 -0.02 0.067 0.055 0.01 0.058 0.1
±95%
0.02 0.062 0.01 0.08 0.21 0.02
0.12 0.062 0.053 0.024 0.03 0.14
1.31 0 0 0
r2 0.87 1 0.06 51.36 0.63 0.08 0.38 4.38 5.2 0.68 0.47 2.53 0.8 17.14 3.1 63.1 21.4 161.3 24.75 1.02 6.4 0.898 4.13
±95%
Conv.
0.03 3.31 0.04 0.07
N Y N
0.99
Y
0.11 Y
4.9 30.3 2.64 0.27 0.06 1.94
Y Y Y Y Y Y Y Y Y Y Y
0.46 830 456 470 Y Y
200 Y 0 0 -0.07 0.067 0.065 0.02 0.1 1 0 0 0 -0.03 0 0 0 0 0 -0.006 -0.06 -0.006 0.014 1.51 1.91 0.32 0.03 0 0.21
0.15 0.12 0.027
0.07
0.37 0.34 0.019 0.003 0.24 0.02 0.01
0.07 - 0.06
187 185 4.45 0.52 0.575 0.61 0.38 1 33 67 62.1 9.64 100 17.1 16.5 12.1 12.7 16 0.607 0.7 0.05 0.02 0.01 7.75 0.25 0.51 0.67
1.87
Y Y
0.18 0.09
0.21
N
11 0.076 0.1 0.009
Y Y Y Y
0.68 0.01 0.04
Y N N
0.87 0.03
0.26
Refs. 901 392 318 236 1097 318 830 236 567 1097 236 454 406 454 137 137 40 9 9 137 137 9 9 82 82 742 402 571 59 204 204 204 40 40 59 3 59 1093 1094 563 563 392 470 470 572 89 470 40 40 40 40 59 158 9 332 699 699 273 713 249 1040 1040
0.04
N
249
References page II - 290
Previous Page
TABLE 1. cont'd Monomer 1 Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate,
di-(2-chloroethyl) di-(2-cyanoethyl) di-(2-(methoxyethyl) di-(2-phenylethyl) di-^c-butyl di-terf-amyl di-tert-butyl
Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate,
di-terf-butyl di-tert-buty\ di-terf-butyl dibenzyl dibutyl dibutyl dibutyl dibutyl dicyclohexyl dicyclopentyl diethyl diethyl diethyl diethyl diethyl diethyl diethyl diethyl diethyl diethyl diethyl diethyl diethyl diethyl diethyl diethyl diethyl diethyl diethyl diethyl diethyl diethyl diisobutyl diisopropyl diisopropyl diisopropyl diisopropyl diisopropyl diisopropyl diisopropyl
Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate,
diisopropyl diisopropyl diisopropyl diisopropyl diisopropyl diisopropyl diisopropyl dimethyl dimethyl dimethyl dioctyl dioctyl dipropyl dipropyl isopropyl butyl isopropyl butyl
Monomer 2 Styrene Styrene Styrene Styrene Styrene Styrene Fumarate, bis(3-[tris(trimethylsiloxy) silyl)propyl Fumarate, dimethyl Maleate, dimethyl Styrene Styrene Diallyl phthalate Imidazole, 1-vinylStyrene Styrene, terf-butoxy Styrene Styrene Acrylonitrile Acrylonitrile Butadiene Butadiene, 2-chloroDiallyl phthalate Ethylene Methacrylate, methyl Methacrylate, methyl A^-Vinylimidazole Styrene Styrene Styrene Styrene Styrene Styrene Styrene Vinyl acetate Vinyl acetate Vinyl chloride Vinyl ethyl ether Vinyl isobutyl ether Vinylidene chloride Styrene Acenaphthalene Acetate, isopropenyl Acrylate, methyl Acrylate, phenyl Acrylonitrile Carbazole, iV-vinylFumarate, bis(3-[tris(trimethylsiloxy) silyl)propyl Isobutylene Methacrylate, methyl Methacrylonitrile Styrene Vinyl acetate Vinyl chloride Vinylidene chloride Fumarate, di-tert-buty\ JV-Vinylimidazole Styrene Diallyl phthalate Pyrrolidone, N-vinylImidazole, 1-vinylStyrene Styrene Styrene
r\
±95%
0 0.09 0.03 O 0.04 0.08 0.67 1.57 18.2 0.04 O 1.01 0.182 0.04 0.01 0.06 0.06 0 0.1 0.25 0.02 1.25 1.91 0.04 0.05 0.191 0.02 0.081 0.11 0.07 0 0.1 0.02 0.443 0.33 0.48 1.63 0.52 0.012 0.05 0.06 0.67 0.091 0.07 0.2 0 0.87 0.42 0.17 0 0.055 0.9 0.49 0.095 0.156 0.252 0.03 0.96 0.04 0.163 0.02 0.01 0.01
r2
±95%
Conv.
0.18 0.07 0.35 0.27 0.55 0.69 0.21 0.365 6.7
0.054
3.4 0.004 0.022 0.005 0.022 0.01 0.007 0.1 0.16 0.038
0.227 0.015 0.04 0.69
0.156 0.011 0.57 0.32 0.02 0.03 0.35 0.18 0.49 0.3 8 10 2.13 6.51 0.01 0.11 40.3 2.1 0.113 0.29 6.3 0.394 0.3 0.31 0.36 0.29 0.011 0.09 0.13 -0.124 0 12.19 0.37 2.57 0.011 1.9 3.4 16 0 0.07 0 23 85 0.4 0.012 0.29 48 1.57 0.133 0.39 0.02 0.02 0.009 0.32 0.42 0.3
Refs. 1038 1038 1038 1038 1038 1038 1040
0.227 0.037
Y Y
0.01
Y
Y 1.14 0.6
N N
0.019
Y
0.26 0.06
Y Y
0.02
N
0.004
Y
0.1 0.059
Y Y
1.58
Y
0.365 0.021
Y Y
0.01 0.012
N Y
1049 1049 1038 1038 665 614 1038 1077 1038 1038 470 640 466 61 665 41 28 394 879 1038 139 139 139 249 562 640 137 718 137 194 640 59 1038 1039 1038 1038 1038 1038 1038 1040 1038 1038 1038 1038 1038 1038 1038 1049 879 1038 665 121 614 1038 1056 1056
TABLE 1. cont'd Monomer 1 Fumarate, isopropyl isobutyl Fumarate, isopropyl methyl Fumarate, isopropyl sec-butyl Fumarate, methyl butyl Fumarate, methyl ethyl Fumarate, methyl isobutyl Fumarate, methyl isopropyl Fumarate, methyl propyl Fumarate, methyl 5ec-butyl Fumarate, methyl terf-amyl Fumarate, methyl tert-bvXy\ Fumarate, mono-2-butyl Fumarate, tert-buiyl 2-ethylhexyl Fumarate, terr-butyl 4-methyl-2-pentyl Fumarate, tert-b\xiy\ ethyl Fumarate, terf-Butyl isoamyl Fumarate, tert-buiy\ methyl Fumarate, tert-bxxtyX sec-butyl Fumaricacid Fumaronitrile Fumaronitrile Fumaronitrile Fumaronitrile Fumaronitrile Fumaronitrile Fumaronitrile Fumaryl chloride Fumaryl chloride Furan, 2,3-dihydroFuran, 2-vinyl-5-methyl Furan, 2-vinyl-5-methyl Furan, 2-vinyl-5-methyl Hex-3-yne-5-ene, 2-methyl-terf-butyl peroxide Hexatriene, tetrachloroHexatriene, tetrachloroHexatriene, tetrachloroHexatriene, tetrachloroHexatriene, tetrachloroHexatriene, tetrachloroHexatriene, tetrachloroHexene, 1-, 3,4-dioic anhydride Hexene, 2-, 3,4-dioic anhydride Hexene, 3-, 3,4-dioic anhydride Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene-1 Hexene-1 Hexene-1 Hexene-1, 2,5-dicarboxylate, dimethyl Imidazole, 1-vinyl Imidazole, 1-vinylImidazole, 1-vinylImidazole, 1-vinyl-
Monomer 2 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene N-vinylimidazole Benzothiazole, vinylmercaptoMethacrylate, methyl Styrene Styrene Styrene Styrene Styrene, a-methylStyrene Vinyl acetate Styrene Acrylate, butyl Methacrylate, isobutyl Methacrylate, methyl Maleic anhydride Acrylate, methyl Acrylonitrile Butadiene, 2-chloroIsoprene Methacrylate, methyl Styrene Vinyl acetate Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Acrylate, methyl Acrylonitrile Vinyl chloride Styrene Triazole, 1-N-vinyl-1,2,4Acrylic acid Fumarate, dibutyl Fumarate, dipropyl
rx 0.01 0.16 0.02 0.02 0.02 0.03 0.16 0.05 0.02 0.06 0.03 - 0.04 0.01 0.01 0.04 0.06 0.03 0.07 0.313
±95%
0.03
0.012
r2 0.46 0.3 0.54 0.36 0.32 0.32 0.3 0.28 0.45 0.53 0.45 0.33 0.54 0.57 0.25 0.45 0.45 0.55 0.121
±95%
Conv.
0.03
N
0.01
Y Y Y Y Y
-0.064 -0.016 0.006 0
0.096 0.021 0.031
6.74 0.202 0.294 0.3
0.79 0.058 0.044
-0.01
0.078
0.094
0.02
0.051 0.169 0.292
20 0.118 0.105 0.183 0.01
0.019 0.044 0.146
Y Y Y
0.087 0.05
Y Y
0.057 0.042
Y Y Y Y Y Y
0 0.392 0.716 0.867 0.36 3.19 4.01 0.2 1.58 1.76 0.85 -0.052 -0.08 -0.54 1.22 1.38 1.52 1.73 1.91 1.91 2.07 2.46 2.69 2.93 3.19 4.11 -0.67 -1.08 -1.72 0.196 0.32 0.03 0.009
1.36 1.25
0.28 0.22 1 1.17 5.83
0.262 0.234 3.6 0.58 0.504 0.123
9.23 0.043
8.57 3.63 17.17 0.031 0.049 0.066 0.07 0.171 0.179 0.173 0.121 0.24 0.014 0.044 0.028 -0.13 2.07 1.54 0.678
0.01 0.012
0.002 0.182 0.163
0.03
8.4 5.6 436
0.6 0.98 0.031
0.054 0.069
Y Y Y Y
Y Y N Y N Y Y
Refs. 1056 1056 1056 1056 1056 1056 1056 1056 1056 1056 1056 249 1056 1056 1056 1056 1056 1056 879 763 191 137 199 478 77 77 91 91 806 1105 1105 1105 637 5 4 459 459 5 4 4 933 933 933 931 931 931 931 931 931 931 931 931 931 931 931 60 60 329 828 972 955 614 614
References page II - 290
TABLE 1. cont'd Monomer 1 Imidazole, 1-vinylImidazole, 1-vinylImidazole, 1-vinylImidazole, 1-vinylImidazole, 1-vinylImidazole, 1-vinylImidazole, 1-vinylImidazole, 1-vinylImidazole, l-vinyl-2-methylImidazole, l-vinyl-2-methylImidazole, l-vinyl-2-methylImidazole, l-vinyl-2-methylImidazole, l-vinyl-2-methylImidazole, l-vinyl-2-methylImidazole, N-vinylImidazole, N-vinylImidazole, TV-vinylImidazolid-2-one, 1,3-divinylImidazolid-2-one, l-ethyl-3-vinylIndene Indene Indene Indene Indene Indene Indene Indene Indene Indene Indene Isobutene Isobutylene Isobutylene Isobutylene Isobutylene Isobutylene Isobutylene Isobutylene Isobutylene Isobutylene Isobutylene Isobutylene Isobutylene, 3-chloroIsobutylene, 3-chloroIsobutylene, 3-chloroIsobutylene, 3-chloroIsooctene Isoprene Isoprene Isoprene Isoprene Isoprene Isoprene Isoprene Isoprene Isoprene Isoprene Isoprene Isoprene Isoprene Isoprene Isoprene Isoprene Isoprene
Monomer 2 Maleate, dibutyl Maleate, dipropyl Maleate, monomethyl Maleic acid Methacrylate, methyl Pyrrolidone, N-vinylStyrene Vinyl acetate Acrylate, methyl Methacrylate, methyl Methacrylate, methyl Styrene Styrene Vinyl chloride Silane, methacryloxypropyldimethoxy methylSilane, methacryloxypropyltrimethoxyStyrene, /?-trimethyoxysilylAcrylate, ethyl Acrylate, ethyl Acrylate, methyl Acrylate, methyl Acrylonitrile Acrylonitrile Styrene, /?-chloroVinyl acetate Vinyl 1-menthyl ether Vinyl methyl ketone Vinyl methyl ketone Vinylidene chloride Vinylidene chloride Maleimide, Af-cyclohexylAcrylonitrile Acrylonitrile Acrylonitrile Ethylene, chlorotrifluoroFumarate, diisopropyl Maleic anhydride Vinyl acetate Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Allyl acetate Vinyl acetate Vinyl chloride Vinylidene chloride Maleimide, JV-cyclohexylAcetylene, phenylAcrylate, methyl Acrylonitrile Butadiene Butadiene Butadiene, 2,3-dimethylButadiene, 2-chloroButadiene, 2-fluoroButadiene, hexafluoroFerrocene, ethyl-oc-cyclo-pentadienylide Hexatriene, tetrachloroMethacrylate, methyl Methacrylate, methyl Methacrylate, methyl Pyridine, 2-vinylPyridine, 2-vinylPyridine, 4-vinyl-
T1 0.486 0.314 0.4 0.3 0.014 0.96 0.071 1.9 0.05 0.047 0.003 0.09 0.07 2.15 0.079 0.158 0.002 -0.08 0.01 0.1 0.12 0.09 0.07 -0.069 8.64 12.64 0.2 0.25 0.293 0.34 0.41 0 0.02 0 0.06 0 0.012 0.17 0.06 0.268 -0.54 0.08 4.5 0 0 0 0.72 3.01 0.75 0.45 1.06 0.608 1.18 0.06 0.25 1.19 0.01 0.58 0.65 0.64 0.64 0.59 0.58 0.32
±95% 0.057 0.028 0.03 0.19 0.029 6.99 0.088 0.064 0.26 0.04 0.03 0.01 0.25 0.24 0.066 2.8 12.59 0.095 0.85 0.002 0.38 0.03 0.19 0.8 0.043 5.8
0.062 0.12
0.23
r2
±95%
Conv.
Refs. 614 614 724 635 364 364 364 364 465 364 479 364 479 154 1095
0.093 0.053 0.6 0.6 4.36 0.16 9.94 -0.11 1.28 4 3.48 8.87 8.97 0.188 1.39
0.08 0.035
Y Y
1.86 0.074 0.24 1.17
Y Y Y Y
0.54
Y
0.62
Y
0.077
Y
2.27 6.9 0.41 0.47 0.63 0.62 0.281 0.29 2.86 0.39 0.67 2.63 2.9 0.49 -0.02 0 1.295 0.98 1.02 0.01 0.42 0.065 1.66 2.04 2.12 1.2 1.54 0.15 0.13 0.31 1.1 0 0.1 0.12 0.03 0.94 0.14 0.84 2.82 2.63 0.78 1.91 1.58 0.26 0.25 0.25 0.47 0.46 2.49
1.12
Y
0.13 0.06
N N
0.05 0.12 0.83 0.2 2.82
Y Y Y Y Y
0.15 1.15
Y Y
0.008 0.25
Y Y
0.02
N
0.18 1.82 0.2 2.05
Y Y Y N
0.37
Y
0.96
Y
0.21
Y
1088 1095 800 800 606 606 360 360 6 360 750 606 606 6 6 995 21 211 484 318 1038 988 211 140 155 329 560 412 475 475 470 995 648 424 417 173 83 173 418 174 453 699 459 302 698 704 456 458 424
TABLE 1.
cont'd
Monomer 1 Isoprene Isoprene Isoprene Isoprene Isoprene Isoprene Isoprene, 3-acetoxyIsoprene, 3-acetoxyIsoprene, 3-acetoxyIsopropenyl acetate Isopropenyl acetate Isopropenyl acetate Isopropenyl acetate Isopropenyl methyl ketone Isopropenyl methyl ketone Isopropenyl methyl ketone Isopropenyl methyl ketone Isopropenyl methyl ketone Isopropenyl methyl ketone Isopropenyl, 3-(l-cyclohexenyl), acetate Isopropenyl, 3-(l-cyclohexenyl), acetate Isopropenyl, 3-(l-cyclohexenyl), acetate Isopropenyl-, p-, phenol glycidyl ether Isopropenylacetophenone, pIsopropenylisocyanate Isopropenylisocyanate Isopropenylisocyanate Isopropenylisocyanate Isopropenylisocyanate Isopropenylisocyanate Isopropenylisocyanate Isopropenylisocyanate Isopropenylisocyanate Isopropenyltoluene Isopropenyltoluene Isopropylidene, 2,3:4,5-di-0-, -1 - vinylbenzyl- (3-D-fructose Itaconamate, N-(4-carboethoxyphenyl)-, butyl Itaconamate, Af-(4-carboethoxyphenyl)-, ethyl Itaconamate, N-(4-carboethoxyphenyl)-, ethyl Itaconamate, N-(4-carboethoxyphenyl)-, methyl Itaconamate, Af-(4-carboethoxyphenyl)-, propyl Itaconamate, A^-(4-carboethoxyphenyl)-, propyl Itaconamate, A^-(4-chlorophenyl)-, ethyl Itaconamate, N-(4-chlorophenyl)-, ethyl Itaconamate, A^-(4-chlorophenyl)-, methyl Itaconamate, Af-(4-chlorophenyl)-, propyl Itaconamate, A^-(4-chlorophenyl)-, propyl Itaconamate, Af-(4-methoxyphenyl)-, butyl Itaconamate, N-(4-methoxyphenyl)-, ethyl Itaconamate, A^-(4-methoxyphenyl)-, ethyl Itaconamate, N-(4-methoxyphenyl)-, methyl Itaconamate, Af-(4-methoxyphenyl)-, propyl Itaconamate, AH4-methoxyphenyl)-, propyl Itaconamate, Af-(4-methylphenyl)-, propyl Itaconamate, Af-(4-methylphenyl)-, propyl
Monomer 2 Quinoline, 2-vinylStyrene Styrene Styrene Styrene Styrene Acrylate, methyl Methacrylate, methyl Styrene Maleic anhydride Methacrylate, methyl Vinyl acetate Vinyl chloride Acrylonitrile Acrylonitirle Butadiene, 2-chloroStyrene Styrene Vinylidene chloride Acrylate, methyl Methacrylate, methyl Styrene Maleic anhydride Styrene Acrylate, ethyl Acrylate, methyl Acrylate, methyl Acrylonitrile Methacrylate, methyl Styrene Styrene Vinyl chloride Vinylidene chloride Methacrylate, methyl Methacrylate, methyl Styrene
r\ 1.88 1.922 1.957 1.98 2.02 1.3 5.71 2.81 4.47 0.034 -0.09 1.082 0.23 1.2 0.7 0.14 0.29 0.66 4.06 0.57 0.4 0.56 0.003 0.84 0.15 0.11 0.079 0.1 0.14 0.07 0.122 3 0.31 0.04 0.04 3.26
±95%
0.016 0.011
0.022 0.12 0.074 0.16 0.01 0.66
0.59 0.047
0.047
1.12
r2 0.53 0.513 0.476 0.44 0.42 0.48 0.27 0.16 0.34 0.002 17.36 1.171 2.26 0.3 0.36 4.035 0.44 0.32 0.134 0.37 0.81 1.59 0.002 0.3 0.79 0.6 0.799 0.24 3.1 8.12 6.84 0.39 0.85 0.68 0.68 0.14
±95%
Conv.
0.02 0.018
Y Y
0.011 1.95 0.038 0.13
Y Y Y Y
0.087
Y
0.099
Y
0.18
Y
0.049
Y
0.18
Y
0.055
Y
Refs. 456 366 366 544 544 83 770 770 770 260 100 100 100 490 542 259 542 542 47 770 770 770 937 266 434 434 99 434 434 434 99 777 434 688 722 772
Styrene
0.61
0.2
678
Methacrylate, methyl
0.48
1.21
678
Styrene
0.2
0.23
678
Styrene
0.58
0.15
678
Methacrylate, methyl
0.53
1
678
Styrene
0.4
0.26
678
Methacrylate, methyl Styrene Styrene Methacrylate, methyl Styrene Styrene Methacrylate, methyl Styrene Styrene
0.36 0.16 0.18 0.31 0.31 0.69 0.43 0.34 0.41
1.24 0.35 0.38 1.26 0.39 0.12 1.31 0.33 0.26
678 678 678 678 678 678 678 678 678
Methacrylate, methyl
0.4
1.03
678
Styrene
0.4
0.38
678
Methacrylate, methyl Styrene
0.28 0.19
1.11 0.54
678 678
References page II - 290
TABLE 1. cont'd Monomer 1 Itaconamate, N-(4-methylphenyl)-, butyl Itaconamate, Af-(4-methylphenyl)-, ethyl Itaconamate, A^-(4-methylphenyl)-, ethyl Itaconamate, Ar-(4-methylphenyl)-, methyl Itaconamate, N-phenyl-, butyl Itaconamate, N-phenyl-, ethyl Itaconamate, N-phenyl-, ethyl Itaconamate, N-phenyl-, methyl Itaconamate, N-phenyl-, methyl Itaconamate, Af-phenyl-, propyl Itaconamate, Af-phenyl-, propyl Itaconate, bis(2-ethylhexyl) Itaconate, bis(tri-w-butyltin) Itaconate, bis(tri-rc-butyltin) Itaconate, bis(tri-n-butyltin) Itaconate, bis(tri-rc-butyltin) Itaconate, di-2[-2(2-methoxyethoxy)ethoxy]ethyl Itaconate, di-^-butyl Itaconate, diamyl Itaconate, dibutyl Itaconate, dibutyl Itaconate, dibutyl Itaconate, dibutyl Itaconate, diethyl Itaconate, diethyl Itaconate, diethyl Itaconate, dimenthyl Itaconate, dimenthyl Itaconate, dimenthyl Itaconate, dimenthyl Itaconate, dimethyl Itaconate, dimethyl Itaconate, dimethyl Itaconate, dimethyl Itaconate, dimethyl Itaconate, dimethyl Itaconate, dimethyl Itaconate, dimethyl Itaconate, dimethyl Itaconate, dimethyl Itaconate, dioctyl Itaconate, dipropy Itaconate, ethyl hexafluoroisopropyl Itaconate, glycidyl methyl Itaconate, mono-methyl Itaconate, mono-methyl Itaconate, mono-methyl Itaconate, mono-methyl Itaconate, mono-methyl Itaconate, mono-methyl Itaconate, mono-methyl Itaconate, mono-methyl Itaconate, monomethyl Itaconic acid Itaconic acid Itaconic acid Itaconic acid Itaconic acid Itaconic acid mono(/?-sulfamidoanilide) Itaconic anhydride Itaconic anhydride Itaconic anhydride Itaconic anhydride Itaconic anhydride
Monomer 2 Styrene Methacrylate, methyl Styrene Styrene Styrene Methacrylate, methyl Styrene Styrene Styrene Methacrylate, methyl Styrene Maleimide, N-cyclohexylAcrylate, 2-chloroethyl Acrylate, butyl Methacrylate,allyl N-Vinylpyrrolidone Styrene Maleimide, N-cyclohexyl Styrene Itaconate, dimethyl Methacrylate, methyl Methacrylate, methyl Styrene Pyridine, 2-methyl-5-vinylStyrene Vinyl chloride Maleimide, 7V-cyclohexylMethacrylate, methyl Styrene Vinyl acetate Acrylate, butyl Itaconate, dibutyl Methacrylate, methyl Methacrylonitrile Pyridine, 2-methyl-5-vinylStyrene Styrene Styrene Styrene, /?-chloroVinyl chloride Styrene Styrene Styrene Styrene Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Styrene Styrene Styrene Styrene Methacrylate, methyl Acrylonitrile Methacrylate, methyl Methacrylate, methyl Styrene Styrene Methacrylate, propargyl Acrylate, 2-chloroethyl Acrylate, 2-chloroethyl Acrylonitrile Methacrylate, methyl Styrene
rx 0.31 0.63 0.26 0.16 0.49 0.47 0.21 0.52 0.18 0.15 0.18 0.38 0.391 0.422 0.038 0.065 0.2 0.34 0.5 1.1 0.717 0.4 0.34 0.17 0.34 5.65 0.318 -0.156 0.483
±95%
0.04 0.015 0.04 0.09 0.11 0.05 0.12 0.213 0.02 0.364
r2 0.19 1.43 0.38 0.3 0.12 1.32 0.45 0.31 0.39 1.13 0.5 0.34 0.683 0.91 1.08 0.21 0.53 0.21 0.36 1.1 1.33 0.8 0.42 0.51 0.23 0.06 0.601 3.34 0.502
0.94 1.1 0.3 0.28 0.22
0.4 1.1 1.2 1.26 0.88
0.14 0.06 0.15 5 0.14 0.28 0.039 0.041 0.31 0.36 0.135 0.04 0.111 0.33 0.33 0.218 0.139 0.86 0 0 0 0.12 0.58 2.46 2.61 4.83 1.17 0.405
0.48 0.5 0.69 0.05 0.33 0.16 0.435 0.376 0.52 0.59 0.223 0.189 0.029 0.34 0.52 0.404 1.1 0.59 1.23 1.14 0.34 0.26 1.65 -0.016 0.251 0.034 0.155 0.004
±95%
0.013 0.022 0.04 0.05
Conv.
Y
N
0.09 0.06
N
0.11
N
0.193 0.557 0.188
Y Y Y Y
N
0.12 0.06 0.035 0.079 0.42 0.21 0.028 0.11 0.052 0.15 0.11 0.086 0.103 0.74
0.67 0.05 0.38 0.32 0.33 0.33 0.09
0.16 0.07 0.025 0.036 0.16 0.14 0.02 0.055 0.039 0.077 0.085 0.06 0.071 0.34
0.08 0.02 0.022 0.021 0.014 0.024 0.01
N N N Y Y Y Y Y Y Y Y Y Y
Y Y Y Y Y Y
Refs. 678 678 678 678 678 678 678 1059 678 678 678 1060 940 940 940 941 1098 1014 39 398 1073 398 39 545 39 480 975 975 975 975 398 398 398 398 545 39 398 586 398 479 39 39 1103 806 613 613 613 613 656 656 656 656 1010 164 260 408 420 76 957 365 365 365 1010 365
TABLE 1. cont'd Monomer 1 Itaconic anhydride Itaconic anhydride Itaconic anhydride Itaconic anhydride Itaconimide, AH2-chloroethyl)Itaconimide, AK2-chloroethyl)Itaconimide, AH4-acetoxyphenyl)Itaconimide, Af-(4-chlorophenyl)Itaconimide, N-(4-ethoxycarbonylphenyl)Itaconimide, N-(p-chlorophenyl)Itaconimide, N-(p-lo\y\)Itaconimide, Af-benzylItaconimide, Af-benzylItaconimide, Af-butylItaconimide, iV-ethylItaconimide, JV-ethylItaconimide, N-isobutylItaconimide, AMsopropylItaconimide, N-methylItaconimide, N-methylItaconimide, N-naphthylItaconimide, W-phenylItaconimide, Af-phenylItaconimide, N-phenylItaconimide, N-propylItaconimide, N-XxAyV Malemic acid, A^-3-dimethylamino6-methylphenylMalemic acid, A^-3-dimethylamino6-methylphenylMaleate, chloro-, diethyl Maleate, dibutyl Maleate, allyl methyl Maleate, butyl stannylallyl Maleate, di-tert-butyl Maleate, dibutyl tin Maleate, dibutyl tin Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, dimethyl Maleate, dimethyl Maleate, dimethyl Maleate, dimethyl Maleate, dimethyl Maleate, dimethyl Maleate, dimethyl Maleate, dioctyl
Monomer 2 Styrene Styrene Vinyl acetate Vinyl acetate Methacrylate, Styrene Styrene Styrene Styrene Styrene Styrene Methacrylate, Styrene Styrene Methacrylate, Styrene Styrene Styrene Methacrylate, Styrene Styrene Styrene Styrene Styrene Styrene Styrene Butadiene
rx 0.456 0.785 1.57 2.87 0.54 0.162 0.21 0.2 0.112 0.14 0.24 1.06 0.2 -0.019 0.42 0.172 -0.03 0.045 1.12 0.12 0.35 0.109 0.08 0.998 0.04 0.219 - 0.08
Styrene Styrene Imidazole, 1-vinylStyrene Styrene Vinyl acetate Methacrylate, methyl Styrene Acrylonitrile Acrylonitrile Butadiene Carbazole, N-vinylEthylene Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl iV-Vinylimidazole Styrene Styrene Styrene Styrene Styrene Vinyl acetate Vinyl chloride Vinyl chloride Vinyl chloride Vinyl isobutyl ether Vinylidene chloride Carbzole, Af-vinylFumarate, di-tert-butyl N-Vinylimidazole Styrene Styrene Succinimide, Af-vinylVinyl acetate Vinyl chloride
methyl
methyl methyl
methyl
±95%
±95%
Conv.
Refs.
0.015 0.005 0.045 0.024 0.11 0.045 0.12 0.084 0.032
Y Y Y Y Y Y Y Y Y
0.18 0.048 0.03 0.066 0.029 0.11 0.043 0.22 0.069
Y Y Y Y Y Y Y Y Y
0.043
Y
0.123 0.18 0.079 0.03
0.086 0.003 -0.019 - 0.04 0 0.069 0.35 0.159 0.232 0.15 0.16 0.46 0.056 0.22 0.486 0.232 0.44 0.308 0.38 0.153 0.08 0.116 0.05 0.05 0.28 0.134 0.37
0.248 0.12 0.031 0.04
N Y Y N
62 62 365 365 642 642 729 729 729 740 740 642 642 642 642 642 642 642 642 642 740 729 740 978 642 729 679
-0.19
0.03
0.55
0.03
N
679
-0.043 0.093 0.02 0.06 0.199 -0.095 0.194 0 0 0.11 0 10 -0.1 0 -0.02 0.106
0.021 0.08 0.01 0.03 0.02 0.199 0.121
2.07 0.486 8.29 0.1 0.005 72.7 2.08 12 20 8.08 0.21 0.25 341 20 285.8 0.057
0.14 0.057 0.14 0.02 0.024 5.93 0.118
Y Y N N Y Y Y
0.05
N
14 614 713 811 1049 987 987 470 640 466 361 41 28 470 873 879 14 139 640 874 888 137 137 449 6 640 3 361 1049 879 137 317 284 1049 3
-0.013 0.07 0.01 0.001 0.04 -0.003 0 0.046 0.17 12.5 0 0.011 0.046 0.15 0.105 -0.012 0.257 0.608
0.09 0.05 0.3 0.32 0.39 0.092 0.21 0.18 0.054
r2
0.75 0.11 0.04 0.13 0.06 0.11 0.064 0.73 0.12 0.082
0.01 0.05 0.015 0.147 0.022 0.01 0.012 0.044 0.07 0.01 0.037 0.438 0.12 0.058 0.021 0.086 0.099
6.59 8 6.07 6.592 0.171 0.768 0.8 0.9 0 0.51 18.2 0.046 10.65 0.083 1.25 -0.006 0.05
46
N
35.9 0.028 0.46
Y Y Y Y
0.07
N
0.025 0.078
Y Y
0.11
Y
0.11 6.7 0.046 2.81 0.015 0.16 0.084 0.14
N Y Y Y Y Y Y Y
References page II - 290
TABLE 1. cont'd Monomer 1 Maleate, dipropyl Maleate, monoallyl Maleate, monoallyl Maleate, monomethyl Maleate, tributylstannyl allyl Maleic Anhydride Maleic acid Maleic acid Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic
anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride
Monomer 2 Imidazole, 1-vinylMaleic anhydride Styrene Imidazole, 1-vinylMaleic anhydride Isopropenyl-, /?-, phenol glycidyl ether Imidazole, 1-vinylN-Vinylimidazole Acenaphthalene Acenaphthalene Acetylene, phenylAcrolein diethylacetal Acrylamide Acrylate, 2-chloroethyl Acrylate, ferrocenylmethyl Acrylate, methyl Acrylate, methyl Acrylonitrile Allyl acetate Allylbenzene Benzocyclobutane, oc-methyleneBenzothiazole, vinylmercaptoButadiene monoxide Butadiene, 2-chloroCarbamate, AUV-diethyl-, vinyl Dicyclopentadiene Divinylbenzene, p Ethylene Hex-3-yne-5-ene, 2-methyl-terf-butylperoxide Isobutylene Isopropenyl acetate Maleate, monoallyl Maleate, tributylstannyl allyl Maleimide, N-phenylMaleimide, N-phenylMethacrylate, ferrocenylmethyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, di-, di-rc-butylstannyl Methacrylate, benzyl Methacrylate, benzyl Phthalimide, N-vinylPropene, 1-chloro-, cisPropene, 1-chloro-, transStyrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene, a-methyl-
rx
±95%
0.053 0.027 0.07 0.6 0.095 0.002 0.6 0.094 0.02 -0.04 0.06 0.07 0 0.027
0.035 0.014 0.02
0.012 0 0 0.028
0.013
0.104 0.027 0.05
0.004
0.019
0.025
r2 0.314 0.051 0.14 0.4 0.032 0.003 0.3 0.018 0.46 0.46 0.08 0.18 0.56 7.15 2.788 2.5 6 -0.001
±95%
Conv.
Refs.
0.028 0.054 0.01
Y N N
0.017
N
0.007
Y
0.13
N
0.31 2.96 0.051
Y Y Y Y
614 906 811 724 906 937 635 879 1039 326 797 767 655 117 325 260 470 470 27 351 1083 763 1064 1068 92 914 943 620 637
0.007
Y Y
0.002 Y
0.64 0.329 0.025 0.071 0.09 0 0.01 0.065 0.002 0.051 0.032 -0.095 0.02 0.24 -0.163 -0.019 0.08 0.02 0.01 0.01 0.01 0.02 0.024 0.372 0.008 0.347 0.28 0.001 0 0.003 0.02 0 0 0.02 0.01 0.001 0.005 0.01 0.02 0.05
0.06 0.107 0.034 0.045 0.01
0.011 0.054 0.017 0.106 0.65 0.28 0.027 0.026 1.77 0.004
0.008 0.093 0.012 0.082 0.012 0.008 0.13 0.03 0.01
0.05 0.026 0.024 0.037 0.01 0.04 0.36 0.012 0.034 0.027 0.095 1.08 1.92 0.33 4.18 6.36 0.46 5.2 3.1 3.85 3.4 3.85 0.012 - 0.075 0.344 -0.022 0.05 0.097 0.04 0.02 0 0.02 0.02 0.04 0.04 0.04 0.05 0.02 0.04 0.04
0.18 0.03 0.066 0.112 0.01
N Y Y
0.022 0.014 0.104 0.13 11.83 0.65 0.31 0.64 0.69 0.47
Y N N Y Y Y Y Y N N
0.016
Y Y Y Y Y Y N Y N N
0.088 0.061 0.08 0.015 0.002 0.12 0.003 0.01
N 0.08
0.04
988 260 906 906 990 341 325 169 260 320 33 524 524 524 524 954 720 720 284 181 181 105 12 17 241 384 397 483 506 522 522 522 522 522 923 492
TABLE 1. cont'd Monomer 1 Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride, a-chloroMaleimide Maleimide Maleimide Maleimide Maleimide Maleimide Maleimide, N-hydroxymethyl Maleimide, 2,3-dimethylAf-(2-methacryloxyethyl)Maleimide, 2,3-dimethylAf-(2-methacryloxyethyl)Maleimide, 2,3-dimethylAf-(2-methacryloxyethyl)Maleimide, A^-(2,4-dimethylphenyl)Maleimide, N-(2,4-dimethylphenyl)Maleimide, N-(2,6-diethylphenyl)Maleimide, A^-(2,6-diethylphenyl)Maleimide, A^-(2,6-diisopropylphenyl)Maleimide, Af(2,6-dimethylphenyl)Maleimide, J/V-(2,6-dimethylphenyl)Maleimide, A^-(2-bromophenyl)Maleimide, AH2-chlorophenyl)Maleimide, N-(2-chlorophenyl)Maleimide, iV-(2-chlorophenyl)Maleimide, iV-(2-chlorophenyl)Maleimide, N-(2-chlorophenyl)Maleimide, A^-(2-chlorophenyl)Maleimide, N-(2-hydroxyethyl)Maleimide, 7V-(2-hydroxyethyl)Maleimide, iV-(2-hydroxyethyl)Maleimide, A^-(2-hydroxyethyl)Maleimide, A^-(2-hydroxyethyl)Maleimide, A^-(2-hydroxyethyl)Maleimide, TV-(2-methylphenyl)Maleimide, iV-(3,5-dimethylphenyl)Maleimide, AK3-dimethylaminophenyl)Maleimide, N-(3-methylphenyl)Maleimide, A^-(3-trifluoromethylphenyl)Maleimide, A^-(4-bromophenyl)Maleimide, A^-(4-bromophenyl)Maleimide, A^-(4-carboxyethylphenyl)Maleimide, JV-(4-carboxyethylphenyl)a-chloroMaleimide, A^-(4-carboxyethylphenyl)a-chloroMaleimide, A^-(4-chlorophenyl)Maleimide, A^-(4-chlorophenyl)Maleimide, 7V-(4-chlorophenyl)Maleimide, A^-(4-chlorophenyl)Maleimide, N-(4-chlorophenyI)-a-chloroMaleimide, A^-(4-chlorophenyl)-a-chloroMaleimide, iV-(4-hydroxyphenyl)Maleimide, A^-(4-hydroxyphenyl)Maleimide, AT-(4-hydroxyphenyl)Maleimide, Af-(4-hydroxyphenyl)-
Monomer 2
rx
Succinimide, N-vinyl0.021 Vinyl 2-chlorocyclohexyl ketone 0.83 Vinyl 4-chlorocyclohexyl ketone 0.08 Vinyl acetate -0.058 Vinyl chloride -0.22 Vinyl chloride 0.4 Vinyl chloride 0.67 Vinylidene cyanide Styrene 0 Butadiene, 2,3-bis(diethyl-phosphono)0.43 Methacrylate, methyl 0.166 Methacrylate, methyl 0.17 Piperidinol, 4-, TV-methyl0.49 4-(vinylethynyl)Styrene 0.088 Vinylidene chloride 0.464 Methacrylate, methyl 0.263 Acrylate, ethyl 1.55
±95% 0.027
0.074 0.38
r2 0.148 1.7 0.12 0.019 0.098 0.04 0.1
±95%
Conv.
0.073
Y
0.008 0.042
Y Y
Y
Refs. 284 836 836 260 260 521 521 82 845 759 251 992 948
0.061
0.01
0.07 0.14 2.576 2.5 2.05
0.036 0.083 0.026 3.06
0.057 0.666 1.745 0.28
0.012 0.056 0.03 1.15
Y Y Y Y
251 251 323 619
0.047
Y
0.03
Methacrylate, methyl
1.1
3.58
0.51
1.66
Y
619
Methacrylic acid
1.33
0.1
0.746
0.059
Y
619
Acrylate, butyl Acrylate, heptyl Methacrylate, methyl Styrene Methacrylate, methyl Methacrylate, methyl Styrene Acrylonitrile Acrylonitrile Methacrylate, methyl Styrene Styrene Styrene Styrene Butadiene, 2,3-bis(diethyl-phosphono)Methacrylate, methyl Pyrrolidone, TV-vinylStyrene Vinyl acetate Vinyl acetate Methacrylate, methyl Methacrylate, methyl Styrene Methacrylate, methyl Methacrylate, methyl Acrylate, methyl Styrene Vinyl chloride Methacrylate, methyl
0.2 0.2 0.05 0.02 0.02 0.07 0.08 0.338 1.078 0.1 0.013 0.028 0.01 0.006 0.49 0.201 0.038 0.011 0.61 0.88 0.09 0.28 0.19 0.22 0.1 0.39 0.018 3.29 -0.004
0.17 0.007 0.18 0.168
0.62 0.14 4.78 0.19 10.9 3.62 0.14 2.029 0.956 2.1 0.011 0.038 0.013 0.038 0.12 1.396 0.002 0.046 -0.014 0.01 2.22 1.63 0.03 1.18 1.57 0.429 0.02 0.04 0.472
0.045 0.048 0.002 0.003 0.005 0.003 0.083 0.01 0.027 0.12 0.17
0.214 0.095
Y Y
0.004 0.006 0.012 0.28
Y Y Y Y
0.089 0.002 0.017 0.037 0.041
Y Y Y Y Y
0.099 0.006 0.03 0.114
Y N Y
788 788 992 992 992 992 992 863 863 992 853 853 910 910 759 323 323 323 323 323 992 992 747 992 992 628 1030 306 973
Styrene
0.022
0.041
0.059
0.021
Y
973
Acrylate, methyl Acrylonitrile Butadiene, 2,3-bis(diethyl-phosphono)Vinyl chloride Methacrylate, methyl Styrene Methacrylate, methyl Styrene Vinyl acetate Butadiene, 2,3-bis(diethyl-phosphono)-
0.155 0.743 0.41 3.65 0.02 0.019 0.345 0.13 1.75 0.47
0.052 0.048
0.684 0.972 0.03 0.026 0.562 0.149 1.392 -0.059 -0.011 0.04
0.052 0.112
Y Y
0.044 0.025 0.048 0.001 0.041 0.027
Y Y Y Y Y Y
628 863 759 306 973 973 323 323 323 75
0.39 0.03 0.038 0.001 0.1 0.17
References page II - 290
TABLE 1. cont'd Monomer 1 Maleimide, A^-(4-methoxyphenyl)-a-chloroMaleimide, AH4-methoxyphenyl)-a-chloroMaleimide, TV-(4-methylphenyl)Maleimide, TV-(4-methylphenyl)Maleimide, AK4-methylphenyl)-a-chloroMaleimide, iV-(4-methylphneyl)-a-chloroMaleimide, TV-(4-tolyl)Maleimide, TV-(P-chloroethyl)-a-chloroMaleimide, AHP-chloroethyl)-oc-chloroMaleimide, TV-(p-chloroethyl)-a-chloroMaleimide, TV-(L-menthoxycarbonylmethyl)Maleimide, TV-(L-menthoxycarbonylmethyl)Maleimide, TV-2-bromophenylMaleimide, TV-2-chlorophenylMaleimide, TV-4-chlorophenylMaleimide, TV-[TV'-a-methylbenzyl) aminocarbonylpentyl]Maleimide, TV-[TV'-a-methylbenzyl) aminocarbonylpenty 1] Maleimide, TV-[TV'-a-methylbenzyl) aminocarbonylpenty I]Maleimide, TV-a-methylbenzylMaleimide, TV-a-methylbenzylMaleimide, TV-allylMaleimide, TV-benzylMaleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide,
TV-benzylTV-benzylTV-benzyl-a-chloroTV-butylTV-butylTV-butylTV-butylTV-chloromethylTV-cyclohexyliV-cyclohexylTV-cyclohexylTV-cyclohexylTV-cyclohexylTV-cyclohexylTV-cyclohexylTV-cyclohexylTV-cyclohexylTV-cyclohexylTV-cyclohexylTV-cyclohexylTV-cyclohexylTV-ethyl-a-chloroTV-ethyl-a-chloroTV-hexylTV-hexyliV-hydroxymethylTV-hydroxymethylTV-methyl-a-chloroTV-methyl-a-chloroTV-octadecylTV-octadecylTV-phenylTV-phenylTV-phenylTV-phenylTV-phenyl-
Maleimide, TV-phenyl-
Monomer 2
T1
±95%
Methacrylate, methyl Styrene Methacrylate, methyl Vinyl chloride Methacrylate, methyl Styrene Acrylate, methyl Methacrylate, methyl Methacrylate, methyl Styrene Maleimide, TV-benzyl Maleimide, TV-phenyl-
0.064 0.049 0.34 4.49 0.029 0.019 0.14 0.05 0.11 0 0.848 0.79
0.189 0.061
Acrylonitrile Acrylonitrile Acrylonitrile Methacrylate, methyl Styrene
r2
±95%
Conv.
Refs.
0.145 0.031
Y Y
0.34 0.158 0.078 0.16 0.04 0.05 0.06 0.221 0.261
0.556 0.112 0.83 0.022 0.564 0.107 0.64 0.94 0.59 0.29 0.474 0.798
0.048 0.117 0.048 0.16 0.06 0.06 0.05 0.087 0.141
Y Y Y Y
Y Y
973 973 992 306 973 973 644 974 974 974 1089 1089
0.348 1.08 0.743 0.582
0.044 0.048 0.048 0.359
2.02 0.955 0.972 1.37
0.205 0.095 0.112 0.291
Y Y Y Y
915 915 915 1099
0.258
0.25
0.198
0.143
Y
1099
Y
1099 1055 1055 1003 1089
Styrene Maleimide, TV-cyclohexyl1.07 Maleimide, TV-phenyl0.683 Styrene 0.035 Maleimide, TV-(L-menthoxycarbonyl0.474 methyl)Methacrylate, methyl 0.03 Styrene 0.013 Styrene 0 Methacrylate, methyl -0.1 Styrene Styrene 60 Vinyl chloride -12.7 Butadiene, 2,3-bis(diethyl-phosphono)0.3 Methacrylate, methyl 0.24 Acenaphthalene 0.11 Butene, cis-20 Isobutene 0 Itaconate, bis(2-ethylhexyl) 0.34 Itaconate, di-n-butyl 0.21 Itaconate, dimenthyl 0.601 Maleimide, TV-a-methylbenzyl0.392 Methacrylate, methyl 0.19 Methacrylate, methyl 0.106 Styrene 0.1 Styrene 0.162 Isooctene 0 Methacrylate, methyl 0.13 Styrene 0 Methacrylate, methyl 0.1 Styrene 0.09 Styrene 0.06 Vinyl acetate 1.45 Methacrylate, methyl 0.11 Styrene 0 Acrylonitrile 0.389 Acrylonitrile 0.39 Acrylate, methyl 0.103 Butadiene, 2,3-bis(diethyl-phosphono)0.42 Maleic anhydride 1.92 Maleic anhydride 1.08 Maleimide, TV-(L-menthoxycarbonyl0.798 methyl)Maleimide, TV-a-methylbenzyl0.788
0.177 0.177
0.214 0.5
Y Y
0.087
0.392 0.788 0.056 0.848
0.221
Y
0.23 0.031 0.06 0.16
1.28 0.058 0.42 1.41
0.23 0.021 0.06 0.19
Y Y
1.13
Y
0.04 0.213 0.177
Y Y
0.066
Y
0.017
Y
106.2
0.04 0.193 0.214 0.048 0.054 0.03 0.04 0.15 0.16 0.11 0.21 0.03 0.03 0.023 0.023 0.052 11.83 0.13 0.141 0.5
0.02 0.24 0.05 1.35 0.57 3 0.41 0.38 0.34 0.318 1.07 1.31 2.26 0.102 -0.01 0.72 0.53 0.9 1.9 -0.041 -0.035 0.017 0.63 0.63 2.482 2.46 0.554 0.05 0.02 -0.095 0.79
0.04 0.05 0.2 0.069 0.053 0.037 0.34 0.04 0.119 0.115 0.048
Y Y Y
0.65 0.106 0.261
Y Y Y
348 348 974 115 115 50 305 759 992 1039 995 995 1060 1014 975 1055 1100 348 1100 348 995 974 974 348 348 323 323 974 974 863 915 644 759 341 990 1089
0.683
0.177
Y
1055
Y Y
Y Y Y Y
TABLE 1. cont'd Monomer 1 Maleirnide, W-phenylMaleimide, N-phenylMaleimide, N-phenylMaleimide, N-phenylMaleimide, 7V-phenylMaleimide, N-phenylMaleimide, iV-phenylMaleimide, JV-phenylMaleimide, N-phenyl-a-chloroMaleimide, N-phenyl-a-chloroMaleimide, N-propylMaleimido-A^V-dimethylaniline, 4-(2-chlorophenyl)azo Mesaconate, dibenzyl Mesaconate, di-seobutyldithiol Mesaconate, diamyl Mesaconate, dibenzyldithiol Mesaconate, dibutyl Mesaconate, dibutyldithiol Mesaconate, dicyclohexyl Mesaconate, diethyl Mesaconate, diethyldithiol Mesaconate, dihexyl Mesaconate, diisoamyl Mesaconate, diisobutyl Mesaconate, diisobutyldithiol Mesaconate, diisopropyl Mesaconate, diisopropyldithiol Mesaconate, dimethyl Mesaconate, dimethyldithiol Mesaconate, dioctyl Mesaconate, diphenyl Mesaconate, diphenyldithiol Mesaconate, dipropyl Mesaconate, dipropyldithiol Mesaconic acid Methacryl-2'-ethyl-4,5J-trinitro9-fluorenone-2-carboxylate Methacrylamide Methacrylamide Methacrylamide Methacrylamide Methacrylamide Methacrylamide Methacrylamide Methacrylamide Methacrylamide Methacrylamide Methacrylamide, 1-deoxy-D-glucitol Methacrylamide, AK2-hydroxypropyl)Methacrylamide, A^-(4/-nitro-4-stilbenyl)Methacrylamide, iV-(4-stilbenyl)Methacrylamide, N-(p-chloroprienyl)Methacrylamide, N-(/?-methoxyphenyl)Methacrylamide, Af-(/?-methyrphenyl)Methacrylamide, 7V-(/?-nitrophenyl)Methacrylamide, A^-[4-(4-methoxyphenylacetyloxy)phenyl]Methacrylamide, iV-methoxymethylMethacrylamide, Af-/?-bromophenylMethacrylamide, N-p-tolylMethacrylamide, N-phenyl Methacrylamide, N-phenylMethacrylamide, N-phenyl-
Monomer 2 Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Styrene Styrene Styrene Vinyl acetate Vinyl chloride Methacrylate, methyl Styrene Vinyl chloride Styrene
rx 0.3 0.164 0.3 0.044 0.01 1.284 4.01 0.077 - 0.002 2.38 0.04
0.065 0.017 0.046 0.18 0.098 0.073 0.16
r2 0.98 1.014 0.91 0.016 0.07 -0.003 0.023 0.657 0.087 0.06 0.05
Conv.
0.06
Y
0.004
N Y
0.006 0.026 0.083 0.04 0.05
Y Y Y Y N
Refs. 323 328 992 1026 328 992 328 306 973 973 305 747
0.593 0.7 0.627 0.559 0.549 2.34 0.29
0.047 0.23 0.051 0.048 0.06 1.07
1.474 1.842 0.399 0.337 0.336 0.37 1.47
0.05 0.062 0.019 0.019 0.026 0.14
Y Y Y Y Y Y
342 342 352 352 352 352 1051
Methacrylate, Methacrylate, Methacrylate, Methacrylate, Acrylonitrile Methacrylate,
0.265 0.38 0.78 0.28 0.71 0.56
0.009 0.2 0.2 0.2 0.19 0.12
1.678 3.48 1.43 1.95 0.381 1.42
0.048 0.2 0.2 0.2 0.085 0.096
Y
227 968 968 968 352 352
methyl
1.27 0.425 0.49 0.33 1.28 0.2 0.48 1.24 3 1.72 0.56 1.01
0.014 0.24 0.085 0.25 0.014 0.2 0.38 0.18 0.26 0.09
0.73 0.45 1.27 0.28 1.28 0.41 1.25 1.24 0.4 1.51 1.34 1.29 0.41 1.31 0.44 0.98 0.35 1.23 0.45 0.16 1.22 0.39 1.6 0.63
±95%
Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Methacrylate, AT-(2-hydroxyethyl)carbazolyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylic acid Methacrylic acid Methacrylic acid Styrene Styrene Vinyl methyl ketone Vinyl methyl ketone Vinyl acetate Acrylamide, AH2-(4-hydroxyphenyl)ethyl)Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Methacrylate, 2-hydroxyethyl methyl methyl methyl methyl
0.08 0.02 0.02 0.06 0.05 0.05 0.1 0.06 0.03 0.1 0.07 0.1 0.03 0.04 0.05 0.04 0.07 0.01 0.07 0.15 0.05 0.06 0 0.382
±95%
1.57 1.39 1.65 2.73 1.55 2.006 1.4 1.42 0.25 0.28 0.16 0.95
0.041
Y
0.11 0.074
N Y
0.28
Y
0.09 0.13 0.17 0.12 0.24
Y N N Y Y
0.09
Y Y
658 624 658 624 658 624 658 658 624 658 658 658 624 658 624 658 624 658 658 624 658 624 1021 703 316 54 55 190 527 55 316 316 609 609 258 965
References page II - 290
TABLE 1. cont'd Monomer 1 Methacrylamide, N-phenylMethacrylamide, 1-deoxy-D-glucitol Methacrylamide, 1-deoxy-D-glucitol Methacrylamide, Af-/?-nitrophenylMethacrylate, 2-ethylhexyl Methacrylate, ferrocenylmethyl Methacrylate, ferrocenylmethyl Methacrylate, octyl Methacrylate, potassium 18-crown6-ether Methacrylate, tert-butyl Methacrylate, (-)-menthyl Methacrylate, (2,2-dimethyl1,3-dioxolane-4-yl)methyl Methacrylate, 1,1-diphenylethyl Methacrylate, 1-naphthyl Methacrylate, 1-naphthyl Methacrylate, 1-naphthyl Methacrylate, 1-naphthyl Methacrylate, 2,2,6,6-tetramethyl4-piperidinyl Methacrylate, 2,2,6,6-tetramethyl4-piperidinyl Methacrylate, 2,2,6,6-tetramethyl4-piperidinyl Methacrylate, 2,2,6,6-tetramethyl4-piperidinyl Methacrylate, 2,2-dimethylaminoethyl Methacrylate, 2,3-epithiopropyl Methacrylate, 2,3-epithiopropyl Methacrylate, 2,3-epithiopropyl Methacrylate, 2,3-epithiopropyl Methacrylate, 2,4,6-trinitrophenyl Methacrylate, 2,4-dinitrophenyl ethyl Methacrylate, 2,4-dinitrophenyl Methacrylate, 2,6-(diphenyl)phenyl Methacrylate, 2-(2-carboxybenzoyloxy)ethyl Methacrylate, 2-(2-carboxybenzoyloxy)ethyl Methacrylate, 2-(N,Ar-dimethylcarbamoyloxy)ethyl Methacrylate, 2-(AW-dimethylcarbamoyloxy)ethyl Methacrylate, 2-(N,N-dimethylcarbamoyloxy)ethyl Methacrylate, 2-(AW-dimethyl carbamoyloxy)ethyl Methacrylate, 2-(N,AT-dimethylcarbamoyloxy)ethyl Methacrylate, 2-acetoxyethyl Methacrylate, 2-acetoxyethyl Methacrylate, 2-acetoxyethyl Methacrylate, 2-acetylsalicylicoyloxy3-hydroxypropyl Methacrylate, 2-bromoethyl Methacrylate, 2-bromoethyl Methacrylate, 2-bromoethyl Methacrylate, 2-bromoethyl Methacrylate, 2-bromoethyl Methacrylate, 2-bromoethyl Methacrylate, 2-chloro-2,3,3,3-fluoropropyl
Monomer 2
rx
±95%
Styrene Methacrylate, methyl Styrene Methacrylate, methyl Methacrylate, 2-hydroxypropyl Maleic anhydride Pyrrolidone, Af-vinylMethacrylonitrile Acrylonitrile
0.88 0.04 0.005 0.29 0.083 0.33 2.57 0.61 0.175
0.17
Methacrylate, 2-chloroethyl Acenaphthalene Methacrylate, methyl
0.98 0.316 1.1
0.22 0.085
Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Acrylonitrile
methyl methyl methyl methyl methyl
Styrene Vinyl acetate
0.77 1.8 1.68 2.62 1.52 14
0.2 0.006 0.65 2.77 0.05 0.018
0.73 0.38 0.47
r2
±95%
Conv.
1.24 4.2 2.09 5.05 4.56 0.24 0.073 0.75 0.07
0.06
N
0.2 0.18 0.28 0.096 0.04 0.006
Y Y Y N Y
1.18 2.48 0.9
0.11 0.55
Y Y
0.14 0.078 0.084
Y Y Y
0.72 0.77 0.809 0.851 0.61 0.02
Refs. 352 258 258 968 708 325 325 44 808 179 645 807 761 752 752 752 761 664
0.3
0.63
664
13.7
0.2
664
0.41
664
Vinyl methyl ketone
0.53
Methacrylate, methyl Acrylate, methyl Methacrylate glycidyl Methacrylate, methyl Styrene Methacrylate, 2-naphthyl Acrylate, AK2-hydroxyethyl)-oxy) 3,6-dichloro Methyacrylate, A^-(2-hydroxyethyl)3,6-dichloro Methacrylate, methyl Methacrylate, butyl
1.01 2.81 0.78 0.97 0.28
0.54
0.42 0.34 0.81 0.83 0.41
0.02
N
1.207
0.032
0.115
0.029
Y Y
1.112
0.026
0.126
0.026
Y
0.071 0.85
0.004
1.42 0.75
0.06
Methacrylate, butyl
0.85
0.75
1041
Acrylate, butyl
1.89
0.47
600
Acrylate, methyl
1.32
0.22
600
Acrylonitrile
1.89
0.38
600
Butadiene
0.35
1.06
600
Methacrylate, methyl
0.42
0.59
600
Methacrylate, 2-hydroxyethyl Methacrylate, methyl Styrene Af-Vinylpyrrolidone
0.99 1.12 0.58 0.85
Acrylate, ethyl Acrylonitrile Methacrylate, methyl Pyrrolidone, N-vinylStyrene Vinyl butyl ether Acrylate, butyl
2.7 2.38 1.18 2.44 0.41 13.7 0.221
0.02 0.06 0.04
0.636
1.02 0.94 0.44 0.34 0.37 0.31 0.79 0.02 0.32 0 0.079
0.01 0.02 0.02
0.304
691 787 787 787 787 744 736
1079 1009
N N N
N
346 346 346 1080 657 657 657 657 657 657 927
TABLE 1. cont'd Monomer 1 Methacrylate, propyl Methacrylate, propyl Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
Monomer 2
r2
±95%
Conv.
Refs.
Methacrylate, methyl
0.583
1.17
0.984
0.395
N
927
2-chloro-2,3,3,3-fluoro-
Styrene
0.243
0.15
0.121
0.068
N
927
2-chloroethyl 2-chloroethyl 2-chloroethyl 2-chloroethyl 2-chloroethyl 2-chloroethyl 2-chloroethyl 2-chloroethyl 2-chloroethyl 2-chloroethyl 2-chloroethyl 2-chloroethyl 2-chloroethyl 2-ethylhexyl 2-hydroxyethyl
Acrylate, methyl Acrylonitrile Methacrylate, benzyl Methacrylate, butyl Methacrylate, isobutyl Methacrylate, methyl Methacrylate, methyl Methacrylate, phenyl Methacrylate, tert-buiy\ Styrene Styrene Styrene Methacrylate, tributyltin Methacrylate, 2-hydroxypropyl Acetamide, 7V-(4-methacryloyloxyphenyl)-2-(4-methoxy) Acetanilide, 4-(2-(methacryloyloxy) ethyloxy) Acetanilide, 4-(2-(methacryloyloxy) hexyloxy) Acetanilide, 4-(methacryloyloxy)Acrylamide Acrylamide Acrylamido, 2-,2-methylpropanesulfonic Acrylate, butyl Acrylate, ethyl Acrylate, furfuryl Acrylate, methyl Acrylonitrile Acryloxymethylpentamethyl disiloxane Methacrylate, 2-hydroxypropyl Methacrylamide, AK4'-nitro-4-stilbenyl)Methacrylamide, J/V-(4-stilbenyl)Methacrylamide, Af-[4-(4-methoxyphenylacetyloxy )phenyl] Methacrylate, 2-acetoxyethyl Methacrylate, dodecyl Methacrylate, dodecyl Methacrylate, dodecyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacryloxymethylpentamethyl disiloxane Pyridine, 2-vinylPyridine, 3-vinylPyridine, 4-vinylPyrrolidone, N-vinylStyrene Styrene Styrene Styrene Styrene Styrene Styrene Acrylamido, 2-, 2-methylpropanesulfonic Acrylate, butyl Acrylate, butyl Acrylate, ethyl Acrylate, ethyl
2.19 1.3 0.989 0.82 0.85 0.97 0.48 1.02 1.18 0.341 0.34 0.23 0.53 0.083 0.61
Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl 2-hydroxyethyl 2-hydroxyethyl 2-hydroxyethyl 2-hydroxyethyl 2-hydroxyethyl 2-hydroxyethyl 2-hydroxyethyl 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxypropyl Methacrylate, Methacrylate, Methacrylate, Methacrylate,
±95%
2-chloro-2,3,3,3-fluoro-
Methacrylate, 2-hydroxyethyl
Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
T1
2-hydroxypropyl 2-hydroxypropyl 2-hydroxypropyl 2-hydroxypropyl
0.098 0.041 0.14 0.18 0.21 0.11 0.075 0.08 0.16 0.006
0.29 0.14 1.068 1.086 1.014 1.156 0.55 0.785 0.98 0.35 0.345 0.42 0.2 4.56 1.49
0.042 0.02 0.064 0.082
Y Y Y Y
0.083 0.22 0.046 0.048
Y Y Y Y
0.444 0.18
N Y
726 382 179 179 179 179 382 179 179 179 179 382 945 692 1051
1.39
0.67
1096
1.19
0.87
1096
0.78 1.89 0.98 0.86 4.75 11.21 1.35 8.67 1 0.86 0.55 1.474 1.842 1.47
1.94 0.05 0.14 0.9 0.09 0.189 0.88 - 0.005 0.2 0.52 1.82 0.593 0.7 0.29
1096 689 928 618 358 358 1063 358 689 822 686 342 342 1051
1.02 11.2 1.6 0.8 0.63 0.81 1.5 0.97 0.56 0.69 0.62 4.841 0.54 0.856 0.65 1.65 0.53 0.59 1.65 0.89 5.35 3.3 13.32 9.08
4.2 0.43 0.08 8.28
0.05 0.062 0.01
0.076 1.02
0.04 0.01 0.04 0.133 0.03 0.018
0.32 6.82 1.05 3.95
0.11 0.008 0.19 0.036
Y
0.047 0.23
Y Y
0.02
N
0.01 0.09
Y Y
0.64 0.73 0.9 -0.019 0.44 0.332 0.57 0.5 0.59 0.53 0.5 1.03
0.16 0.04 0.09 0.046 0.02 0.006
N N N Y N Y
342 342 342 840 346 350 463 878 878 903 903 618
0.171 0.24 0.273 0.207
0.041 0.16 0.054 0.045
Y Y Y Y
333 662 333 662
0.99 0.7 0.5 0.8 0.824 0.192 0.75 0.33
Y Y
346 837 837 837 350 358 710 822
References page II - 290
TABLE 1. cont'd Monomer 1 Methacrylate, 2-hydroxypropyl Methacrylate, 2-hydroxypropyl Methacrylate, 2-hydroxypropyl Methacrylate, 2-hydroxypropyl Methacrylate, 2-hydroxypropyl Methacrylate, 2-hydroxypropyl Methacrylate, 2-hydroxypropyl Methacrylate, 2-hydroxypropyl Methacrylate, 2-hydroxypropyl Methacrylate, 2-hydroxypropyl Methacrylate, 2-hydroxypropyl Methacrylate, 2-hydroxypropyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacryiate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl-, methyl Methacrylate, 2-naphthyl-, methyl Methacrylate, 2-naphthyl-, methyl Methacrylate, 2-naphthyl-, methyl Methacrylate, 2-sulfonic acid)ethyl Methacrylate, 2-sulfonic acid)ethyl Methacrylate, 2-sulfonic acid)ethyl Methacrylate, 2-sulfonic acid)ethyl Methacrylate, 2-methoxyethyl Methacrylate, 3,5-dimethyladamantyl Methacrylate, 3,5-dimethyladamantyl Methacrylate, 3,5-dimethyladamantyl Methacrylate, 3,5-dimethyladamantyl Methacrylate, 3-methoxy-2-hydroxypropyl Methacrylate, 5-oxo-pyrrolidinylmethyl Methacrylate, 5-oxo-pyrrolidinylmethyl Methacrylate, p-(2-benzothiazolylthio) ethyl Methacrylate, A^-(2-hydroxyethyl)3,6-dichlorocarbazolyl Methacrylate, N-(2-hydroxyethyl)carbazolyl Methacrylate, JV-(2-hydroxyethyl)carbazolyl Methacrylate, A^-(2-hydroxyethyl)carbazolyl Methacrylate, iV-ot-benzothiazolonylmethyl Methacrylate, iV-ethyl3-hydroxymethylcarbazolyl Methacrylate, N-ethyl-3hydroxymethylcarbazolyl Methacrylate, Af-methyl-N-phenyl2-aminoethyl Methacrylate, A^-methyl-A^-phenyl2-aminoethyl Methacrylate, N-methyl-N-phenyl2-aminoethyl
Monomer 2
T1
±95%
Acrylate, methyl Acryloyl chloride Methacrylate, 2-ethylhexyl Methacrylate, 2-ethylhexyl Methacrylate, 2-hydroxyethyl Methacrylate, butyl Methacrylate, butyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, methyl Methacrylate, tributyltin Methacrylic acid Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Itaconate, mono-methyl Itaconate, mono-methyl Itaconate, mono-methyl Itaconate, mono-methyl Methacrylate, 2,4,6-trinitrophenyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Styrene Styrene Styrene Styrene Styrene Acrylate, ethyl Methacrylate, ethyl Styrene Vinylidene chloride Styrene Acrylonitrile Methacrylate, methyl Styrene Vinyl chloride Acrylamide Methacrylate, methyl Styrene Vinyl chloride
7.335 1.79 4.56 4.56 1.82 2.35 2.35 1.878 1.844 1.055 1.81 0.31 1.17 1.02 0.76 0.64 0.52 0.59 0.223 0.189
0.083
0.85 2.57 2.53 1.91 4.41 3.83 0.534 0.113 0.321 0.576 0.216 3.2 2 0.6 3.6 0.48 1.3 0.45 0.63 1.85 3.98 0.694 0.411 0.26
0.34 0.48 0.27 0.6 0.76 0.57 0.099 0.126 0.098 0.477 0.422
Methacrylate, 2,4-dinitrophenyl
0.126
Acryl-2/-ethyl-4,5,7-trinitroflourenone
r2
±95%
Conv.
Refs.
0.013 0.29 0.083 0.083 0.55 0.158 0.158 0.245 0.267 0.402 0.728 0.99 0.15 0.094 0.06 -0.01 0.31 0.36 0.135 0.04
0.007
Y
0.006 0.006
Y Y
0.007 0.007 0.007 0.005 0.017 0.517
Y Y Y Y Y N
0.2 0.099 0.1 0.16 0.42 0.21 0.028 0.11
0.75 0.602 0.581 0.532 0.614 0.623 0.56 0.786 0.486 0.61 0.384 0.3 1 0.37 0.22 0.46 0.19 0.68 0.89 0.21 0.04 0.421 0.342 0.64
0.16 0.059 0.023 0.055 0.051 0.048 0.025 0.16 0.117 0.195 0.225
Y Y Y N Y Y Y Y Y Y Y Y Y Y Y Y Y Y Y Y
0.01 0.04 0.14 0.04
N N N N
0.033 0.013
Y Y
0.026
1.112
0.026
Y
736
0.773
0.096
0.102
0.022
Y
703
Acrylate, 2,4-dinitrophenyl
0.243
0.034
0.186
0.009
Y
716
Methacryl-2/-ethyl-4,5,7-trinitro9-fluorenone Methacrylate, methyl Acryloyl-p-hydroxyethyl3,5-dinitrobenzoate Methacryloyl-P-hydroxyethyl3,5-dinitrobenzoate Acryloyloxy, 2-, benzoic acid
0.63
0.041
0.382
0.014
Y
703
0.6 1.425
0.02 0.09
0.5 0.103
0.01 0.015
Y
887 701
0.729
0.051
0.554
0.019
Y
701
0.22
0.03
1.82
0.2
N
651
Methacrylic acid
0.2
0.01
2.16
0.18
N
651
Methacryloyloxy, 2-,benzoate, methyl
0.55
0.04
1.11
0.18
N
651
0.18 0.18 0.13 0.13 0.056 0.039 0.04 0.275 0.2 0.19 0.18 0.24 0.16 0.14 0.02 0.055
0.23 0.16 0.21 8.87 0.087 0.033
333 649 692 708 686 692 708 692 708 333 945 886 611 611 611 611 613 613 613 613 744 540 760 760 760 760 760 540 924 924 924 924 564 564 564 564 918 335 335 335 335 689 633 633 741
TABLE 1. cont'd Monomer 1
Monomer 2
Methacrylate, N-methyl-Ar-phenyl2-aminoethyl Methacrylate, A^-methyl-A^-phenyl2-aminoethyl Methacrylate, a,a-dimethylbenzyl Methacrylate, oc-naphthoyloxy-, ethyl Methacrylate, acetonyl Methacrylate, allyl Methacrylate, amyl Methacrylate, benzyl Methacrylate, benzyl Methacrylate, benzyl Methacrylate, benzyl Methacrylate, benzyl Methacrylate, benzyl Methacrylate, benzyl Methacrylate, benzyl Methacrylate, benzyl Methacrylate, benzyl Methacrylate, benzyl Methacrylate, benzyl Methacrylate, benzyl Methacrylate, benzyl Methacrylate, benzyl Methacrylate, benzyl Methacrylate, benzylmethylaminoethyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, Methacrylate, Methacrylate, Methacrylate,
butyl butyl butyl butyl
Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, chloromethyl Methacrylate, chloromethyl
rx
±95%
r2
±95%
Conv.
Methacryloyloxy, 2-,benzoic acid
0.2
0.01
2.6
0.08
N
651
Styrene
0.58
0.02
0.44
0.04
N
651
Methacrylate, methyl Styrene Styrene Itaconate, bis(tri-w-butyltin) Styrene Acrylonitrile Allyl chloride Maleic anhydride Maleic anhydride Methacrylate, 2-chloroethyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, phenyl Styrene Styrene Styrene Styrene Styrene Styrene Vinylidene chloride Methacrylate, methyl Acetylene, phenylAcrylate, butyl Acrylate, ethyl Acrylic acid Acrylic acid, a-bromoAcrylonitrile Carbamate, Af-phenyl-, allyl Methacrylate, 2-(2-carboxybenzoyloxy)ethyl Methacrylate, 2-(2-carboxybenzoyloxy)ethyl Methacrylate, 2-chloroethyl Methacrylate, 2-hydroxypropyl Methacrylate, 2-hydroxypropyl Methacrylate, ethyleneglycolAf-phenylcarbamate Methacrylate, glycidyl Methacrylate, methyl Methacrylate, methyl Methacrylic acid Methacrylic acid Methacrylonitrile Styrene Styrene Styrene Styrene Styrene Styrene Styrene, o-chloroStyrene, p-chloroStyrene p-chloroStyrene chloromethylStyrene/?-octylamine sulfonate Thioindigoid Vinyl acetate Vinyl chloride Vinylidene chloride Methacrylate, methyl Styrene
0.92 0.242 0.505 1.08 0.46 0.96 58.7 - 0.075 1.068 1.112 1.05 1.38 0.67 0.658 0.467 0.51 0.42 0.3 0.5 3.3 0.296 1.7 2.2 2.43 3.53 0.85 0.98 0.418 0.75
0.018 0.115 0.2 0.1 0.088 0.042 0.093 0.06 0.084 0.048
0.38 0.123 0.39 0.42 0.2
0.75
0.372 0.989 0.808 0.93 0.78 1.42 0.463 0.435 0.45 0.48 0.8 0.45 0.34 0.523 0.21 0.3 0.22 0.24 0.13 0.291 0.329 0.85
0.043 0.041
Y
0.11 0.1
Y N
0.093 0.098 0.03
Y Y Y Y
0.09 0.041 0.026
N Y Y
0.32 0.134
Y
0.17 0.21
Y N
0.039
Y
0.85
1.086 0.158 0.158 0.395
0.02 0.007 0.007
0.85 2.11 1.2 1.26 1.15 0.75 0.31 2.52 0.47 0.64 0.64 0.59 0.32
0.03 0.08
0.564 0.38 0.7 11.5 30.18 13.5 2.07 1.02 0.298
0.81 0.216 0.285 0.038 0.52 0.2 0.02
0.12 0.12 0.07 0.2 1.1
0.1 0.131
14.47 0.18 0.16 0.03
0.82 2.35 2.35 0.299 0.94 0.52 1.27 0.8 0.73 0.56 0.56 -0.05 0.52 0.63 0.54 0.74 1.24 1.025 1.46 1.5 0.5 -0.003 0.05 0.35 0.477 0.208
Refs.
761 1102 958 940 179 23 438 720 720 179 111 32 540 32 111 179 487 540 602 806 432 1081 565 187 690 187 733 165 833 1009 1041
0.041 0.13 0.13
Y Y Y
179 692 708 833
0.06 0.07
N N
0.16 0.2 0.15 0.12 1.09
N N N Y N
0.1 0.124
N
0.15
Y
0.03 0.029 0.006
Y Y Y
224 30 844 187 224 44 179 43 463 530 530 835 558 872 966 1035 817 1007 165 519 3 712 712
References page II - 290
TABLE 1. cont'd Monomer 1 Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, titanate Methacrylate, titanate Methacrylate, Methacrylate, Methacrylate,
Monomer 2
T1
cyanomethyl cyanomethyl cyclohexyl cyclohexyl decyl di-, di-n-butylstannyl di-, di-rc-butylstannyl di-, zinc di-, dicyclopentadienyl-
Methacrylate, methyl Styrene Methacrylate, tributyltin Styrene Oxazolidone, TV-vinylMaleic anhydride Vinyl acetate Ethylene Acrylate, di-, copper
0.73 0.28 0.891 0.57 12.19 0.012 0.013 40 0.89
di-, dicyclopentadienyl-
Acrylate, di-, nickel
0.65
di-, ethylene glycol di-, triethyleneglycol di-, triethyleneglycol
Styrene Carbamate, N-phenyl-, allyl Methacrylate, ethylene-glycol Af-phenylcarbamate Methacrylate, methyl Methacrylic acid Methacrylate, methyl Acrylamide Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, dodecyl Methacrylate, methyl Styrene Allyl acetate Allyl alcohol Methacrylate, 2-(sulfonic acid)ethyl Methacrylate, 2-hydroxypropyl Methacrylate, 2-hydroxypropyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, tributyltin Methacrylic acid Methacrylonitrile Styrene Styrene Styrene Styrene Styrene, o-chloroStyrene, p-chloromethylVinyl acetate Vinylidene chloride Methacrylate, butyl
0.67 0.504 0.59
Methacrylate, diethylaminoethyl Methacrylate, diethylaminoethyl Methacrylate, dimethylaminoethyl Methacrylate, dimethylaminoethyl sulfate Methacrylate, diphenylmethyl Methacrylate, diphenylmethyl Methacrylate, diphenylmethyl Methacrylate, diphenylmethyl Methacrylate, diphenylmethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyleneglycolAf-phenylcarbamate Methacrylate, ethyleneglycolAf-phenylcarbamate Methacrylate, ferrocenylmethyl Methacrylate, ferrocenylmethyl Methacrylate, ferrocenylmethyl Methacrylate, ferrocenylmethyl Methacrylate, ferrocenylmethyl Methacrylate, furfuryl Methacrylate, glycidyl Methacrylate, glycidyl Methacrylate, glycidyl Methacrylate, glycidyl Methacrylate, glycidyl Methacrylate, glycidyl Methacrylate, glycidyl Methacrylate, glycidyl Methacrylate, glycidyl Methacrylate, glycidyl Methacrylate, glycidyl
Methacrylate, di-, triethyleneglycol Acrylate, methyl Acrylonitrile Styrene Styrene Vinyl acetate N-Vinylpyrrolidone Acrylate, 2-ethylhexyl Acrylate, 4-acetylphenyl Acrylate, butyl Acrylate, isobutyl Acrylate, tert-butyl Acrylonitrile Acrylonitrile Methacrylate, 2,3-epithiopropyl Methacrylate, butyl Methacrylate, methyl Methacrylate, methyl
1.44 2.34 1.2 1.9 0.5 0.8 0.7 1.07 0.3 81.27 107.4 1 0.245 0.267 1.08 1 0.601 0.71 0.83 0.36 0.26 0.29 0.33 0.45 0.36 131.8 2.18 0.299
±95% 0.11 0.041 0.136 0.28 1.35 0.016 0.036
0.399 0.144 0.395 0.586 -0.052 0.024 0.013 0.19 1.09
±95% 0.019 0.011 0.428 0.088 0.049 0.008 0.018
Conv. Y Y N Y Y Y Y
0.95 0.08
0.085 1.59 0.154 0.2
0.1 1.93 5.3 0.007 0.005 0.09 0.123 0.05 0.12
29.8 0.1
0.24 0.042 0.82 -0.01 0.01 1.52 5.16 2.41 0.644 2.16 1.24 2.096 0.85 1.32 0.81 0.94 0.52 0.934
r2
0.39 0.034 0.24 0.843 0.63 0.699 0.52 1.6 0.8 11.2 0.81 0.528 -0.57 -0.02 2 1.878 1.844 1.08 1.16 0.299 0.57 0.46 0.55 0.67 0.65 0.55 1.34 1.29 -0.77 0.353 0.395
1.13 0.46 0.13 0.57 0.12 0.443 0.05 0.06 0.06 0.085
1.4 0.15 3.6 0.2 0.0036 0.09 0.292 0.083 0.282 0.463 0.95 0.14 0.78 0.85 0.71 0.726
625 625 945 179 36 954 949 935 876 876
0.15
N
262 833 833
0.128 1.47 0.051 0.05
Y Y Y
0.05 0.82 1.92
Y N N
0.056 0.039
Y Y N
0.19 0.607
N N
0.04 0.062
N Y
5.29 0.02
N Y
1081 16 1081 1052 837 837 837 761 179 210 210 564 692 708 32 844 87 945 820 44 179 530 530 570 558 1035 210 3 833
0.59 0.085 0.42 0.14
Refs.
833 0.35 0.04 3.63
Y Y Y
0.02 0.13 0.141 0.052 0.026 0.079 0.06
Y Y Y Y Y Y N
0.03 0.08 0.042
N Y Y
293 325 293 576 293 1050 674 1012 674 674 814 114 433 787 224 113 226
TABLE 1. cont'd Monomer 1 Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
Monomer 2 glycidyl glycidyl glycidyl glycidyl glycidyl glycidyl glycidyl glycidyl glycidyl glycidyl glycidyl glycidyl glycidyl glycidyl hexyl hydroxyethyl
Methacrylate, hydroxyethyl Methacrylate, iso-butyl Methacrylte, isobornyl Methacrylate, isobutyl Methacrylate, isobutyl Methacrylate, isobutyl Methacrylate, isobutyl Methacrylate, isobutyl Methacrylate, isobutyl Methacrylate, isobutyl Methacrylate, isobutyl Methacrylate, isobutyl Methacrylate, isobutyl Methacrylate, isobutyl Methacrylate, isobutyl Methacrylate, isobutyl Methacrylate, isobutyl Methacrylate, isobutyl Methacrylate, isobutyl Methacrylate, isobutyl Methacrylate, m-chlorophenyl Methacrylate, m-nitrophenyl Methacrylate, methoxymethyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl
rx
Methacrylate, methyl 1.05 Methacrylate, methyl 0.501 Methacrylic acid 1.2 Af-Vinylpyrrolidone 4.29 Styrene 0.16 Styrene 0.539 Styrene 0.46 Styrene 0.54 Styrene 0.55 Styrene 0.74 Styrene 0.73 Styrene 0.514 Vinyl phenyl ketone 0.719 Vinyl, mono-, ethylene glycol ether 4.41 Styrene 0.44 Methacrylate, tetra(2-hydroxypropyl) 0.606 ethylenediamine Methacrylate, tributyltin 2.33 Butadiene, 2-chloro0.9 Styrene 0.24 Acetylene, phenyl1.9 Acrylic acid 0.68 Acrylonitrile 1.05 Furan, 2-vinyl-5-methyl 0.105 Methacrylate, 2-chloroethyl 1.014 Methacrylate, methyl 1.88 Methacrylate, methyl 1.2 Methacrylate, methyl 0.488 Methacrylic acid 0.47 Methacrylonitrile 0.68 Methacrylonitrile 0.94 Styrene 0.271 Styrene 0.58 Styrene 0.42 Styrene 0.4 Styrene 0.74 Vinyl acetate 29.7 Styrene 0.209 Styrene 0.185 Styrene 0.586 2-Oxazoline, 2-isopropenyl0.69 3-Pyridazone, 2-vinyl 0.63 3-Pyridazone, 2-vinyl-6-methyl0.16 3-Pyridazone, 2-vinyl-6-methyl1.65 4,5-benz-33-Pyridazone, 2-vinyl-6-phenyl0.58 4H-1,3-Oxazinium F 3 CSO 3 , 3-methyl0.37 2-vinyl-5,6-dihydroAcenaphthalene 0.36 Acenaphthalene 0.38 Acenaphthalene 0.44 Acetamide, N-vinyl2.65 Acetamide, N-vinyl1.18 Acetamide, N-vinyl2.1 Acetylene, phenyl-0.06 Acetylene, phenyl1.5 Acetylene, phenyl1.111 Acrolein 1.136 Acrolein 1.33 Acrolein, methyl0.1 Acrylamide 2.34 Acrylamide 3 Acrylamide 2.53 Acrylamide 3 Acrylamide, 2-chloro-AyV-dimethyl2.71
±95%
0.027 0.1 0.498 0.03 0.04 0.08 0.1 0.284 0.098 0.13 0.416 0.185 0.088 0.3 0.22 0.044 0.064 0.07 0.029 0.05 0.12 0.036
24.16 0.013 0.054 0.069 0.02
r2 0.8 0.688 0.98 0.003 0.54 0.278 0.47 0.44 0.45 0.31 0.11 0.435 0.697 0 0.58 1.44 0.282 1.8 0.61 0.27 1.03 0.217 0.716 0.85 0.62 0.89 0.92 2.01 0.74 0.43 0.509 0.56 0.5 0.55 0.47 -0.06 0.375 0.44 0.395 0.99 1.56 0.3 0.27
±95%
Conv.
0.076 0.16 0.018 0.07 0.086 0.02
Y N
0.04 0.045 0.033
N N Y
0.07 1
Y Y
0.424 0.06 0.45
N N
0.037 0.169 0.14 0.08
Y Y Y N
0.15
Y
0.07 0.08 0.014
N N Y
0.22 0.05 0.16 0.014 0.07
Y Y Y Y
N Y N
0.49 0.31 0.04 0.04
0.16 0.095 0.05 0.4 0.17 0.09 0.45 0.398
1.05 0.99 2.25 0.19 0.71 0.01 1.69 0.2 0.07 0.76 0.59 0.4 2.29 0.53 0.82 0.9 -0.159
Refs. 463 639 224 1017 114 217 225 225 463 849 893 999 946 780 179 996 945 1057 806 565 847 165 1105 179 30 541 639 847 44 44 179 463 463 487 541 165 177 177 821 894 897 897 897 897 909
0.14 0.15
N N
26.56
Y
0.016 0.12 0.3
Y Y N
0.44 0.09
N N
1.07 0.502
N Y
326 326 575 984 984 984 357 443 732 291 292 589 314 314 314 691 917
References page II - 290
TABLE 1. cont'd Monomer 1
Monomer 2
Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl
Methacrylate, Methacrylate, Methacrylate, Methacrylate,
methyl methyl methyl methyl
Methacrylate, methyl Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl
Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl
Acrylamide, N,N-dimethylAcrylamide, AA,A^-dimethylAcrylamide, WV-dimethylAcrylamide, WV-dimethylAcrylamide, N-methylAcrylamide, N-methylolAcrylamide, N-methylol Acrylamide, N-octadecylAcrylamide, N-tert-butylAcrylamide, a-fluoroAcrylamido, 1-,-1-deoxy-D-glucitol Acrylate, a-benzyl-, methyl Acrylate, a-chloro-methyl Acrylate, ferrocenylmethyl Acrylate, 2-(0-ethyl methylphosphonoxy)-, methyl Acrylate, 2-chloroethyl Acrylate, 2-nitrobutyl Acrylate, p-acetoxymethyl-, methyl Acrylate, a-(0-ethyl methylphosphenoxy) Acrylate, a-[2,2-bis(carbomethoxy)ethyl]-, methyl Acrylate, oc-acetoxy-, ethyl Acrylate, a-benzyl-, methyl Acrylate, a-chloro-, methyl Acrylate, oc-cyano-, methyl Acrylate, a-cyano-, methyl Acrylate, a-hydroxymethyl-, ethyl Acrylate, a-phenoxymethyl-, methyl Acrylate, a-phenyl-, methyl Acrylate, a-phenyl-, methyl Acrylate, oc-tetrafluoropropyloxymethyl-, methyl Acrylate, a-trifluoromethyl-, methyl Acrylate, a-trifluoromethyl-, methyl Acrylate, a-trifluoromethyl-, methyl Acrylate, benzyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ferrocenylmethyl Acrylate, heptafluorobutyl Acrylate, heptyl Acrylate, isobutyl Acrylate, isobutyl Acrylate, m-nitrophenyl Acrylate, methyl Acrylate, o-chlorophenyl Acrylate, octadecyl Acrylate, p-bromophenyl Acrylate, p-chlorophenyl Acrylate,/?-chlorophenyl Acrylate, methylphenyl Acrylate, phenyl Acrylate, phenyl Acrylate, a-p-chlorobenzyl-, methyl Acrylate, a-p-methoxybenzyl-, methyl Acrylic acid Acrylic acid, a-bromoAcrylonitrile Acrylonitrile, a-trifluoromethyl-
rx 1.65 2.15 2.8 2.64 1.14 1.62 1.62 4.119 0.25 2.13 3.75 3.9 0.11 2.9 0.73 2.15 1.19 0.91 0.73
±95% 0.16 0.08 0.1 0.15 0.09 0.07 0.136 0.24 0.19 0.09 0.04 0.12
3.7
r2 0.41 0.57 0.59 0.21 0.05 0.7 0.7 0.42 2.83 0.148 0.05 0.09 1.92 0.08 0.44 0.37 0.27 0.24 0.44
±95%
Conv.
0.15 0.08 0.09 0.21 0.72
N N N N N
0.11
Y
0.081 0.09 0.01 0.08
Y N N N
0.25 0.04
N
0.04
1.65 2.36 0.31 0.21 0.068 1.26 1.13 0.21 0.3 1.43
0.12 0.23 0.24 0.02 0.014 0.17 0.038
1.8 3.2 2.3 2.23 0.92 2.86 1.88 1.83 2 2.04 2.8 1.387 2.51 1.04 4.1 0.928 2.15 1.25 2.477 0.926 1.01 1.09 1.45 1.56 1.54 1.87 1.71 0.418 0.37 1.322 1.11
0.23 0.5 0.2 0.14 0.2 0.32 0.4 0.28 0.19 0.072 0.13 0.08 0.5 0.248 0.04 0.024 0.056 0.132 0.275 0.14 0.222 0.109 0.02 0.05 0.12
Refs. 170 315 315 691 691 593 596 290 709 823 258 610 31 293 882 790 234 1091 851 1092
0.608 0.173 1.13 0.03 0.135 1.34 0.755 0 0 0.61
0.02 0.022 0.19 0.01 0.016 0.062 0.061
Y Y Y N Y N Y
244 610 6 141 182 1027 1048 141 49 1047
-0.17 0 0.1 0.19 0.13 0.11 0.43 0.47 0.28 0.22 0.024 0.177 0.46 0.29 0.135 1.04 0.4 0.4 0.464 0.191 0.235 0.3 0.223 0.45 0.416 0.255 0.13 1.73 0.11 0.138 -0.016
0.18 0.1 0.1 0.2 0.15 0.018 0.07
Y N N Y N Y N
0.05 0.064 0.084 0.02 0.04 0.02 0.135 0.12
N Y Y N Y Y N
0.07 0.014 0.023
Y Y Y
0.036
Y
0.041 0.034 0.008 0.096
Y Y Y N
0.037 0.048
Y Y
681 825 825 277 30 639 87 30 469 87 293 206 980 30 639 1074 324 621 290 1074 1074 621 1074 621 672 905 905 964 733 216 681
TABLE 1. cont'd Monomer 1 Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
Monomer 2 methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl
Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl
Methacrylate, methyl Methacrylate, methyl Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl
Methacrylate, methyl Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
methyl methyl methyl methyl methyl methyl methyl
Methacrylate, methyl Methacrylate, methyl
Acrylonitrile, a-perfluoropropylAcryloyl chloride Acryloyl chloride Allyl acetate Allyl acetate Allyl alcohol Allyl chloride Benzocyclobutane, a-methyleneBenzocyclobutene, 4-vinylBenzofuran, 2-vinylBenzophenone, 2-hydroxy4-(methacryloxy)Benzothiazole, vinylmercaptoBicyclo[2,2,l]hept-2-ene5,6-dicarboximide, TV-benzyl Bicyclo[2,2,l]hept-2-ene5,6-dicarboximide, TV-benzyl Butadiene Butadiene Butadiene Butadiene, 2,3-dichloroButadiene, 2-chloroButadiene, 2-fluoroCarbamate, TV-vinyl-f-butylCarbazole, TV-vinylCarbazole, TV-vinylCarbazole, TV-vinylCarbazole, TV-vinylCarbazole, TV-vinylCarbazole, TV-vinylCarbazole, TV-vinylCitraconimide, TV-(4-acetoxyphenyl)Citraconimide, TV-(4-chlorophenyl)Citraconimide, TV-(4-ethoxycarbonylphenyl)Citraconimide, TV-(4-methoxyphenyl)Citraconimide, TV-( 1 -menthylcarboxylatomethyl)Citraconimide, TV-benzylCitraconimide, TV-butylCitraconimide, TV-ethylCitraconimide, TV-hexylCitraconimide, TV-isobutylCitraconimide, TV-isopropylCitraconimide, TV-methyl Citraconimide, TV-phenyl Citraconimide, Af-propyl Citraconimide, N-tert-butylCitraconimide, TV-tolylCyclopentene, 4-,-1,3-dione Cyclopropane, l,l-bis(ethoxycarbonyl)-2-vinylCyclopropane, 1,1-bis(ethoxycarbonyl)-2-vinylDiallyl melamine Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallylcyanamide Diallylcyanamide Dimethyleneheptanedioate, 2,6-dimethyl Ditiane, 2-methylene-l,3Ethylene
rx
±95%
r2
1.9 0.48 0.42 99.24 23 78.79
0.3
0 1.51 0.05 -2.42 0 -1.62
0.32 0.6 0.006 0.315 1.25 30.5
24.6 6.5
0.02 0.036 0.083
108 0.25 0.027 0.32 0.08 0.08 0.76 1.87 1.55 2.12 1.8 0.57 1.84 0.44 2.123 1.88 2.93 2.72
0.46 1.47 3.89 1.65 0.43 0
±95%
Conv.
0.05
37.66
N
2.9
N Y
0.617 0.114
N Y
0.14
Y
0
Refs. 926 508 776 210 470 210 204 1083 1085 1020 934 763 994 994
0.26 0.22 0.048 0.16 0.4 0.18
0.75 0.504 0.7 11.04 6.33 1.23 0.17 0.14 0.033 0.06 0.75 0.08 0.33 0.031 0.18 -0.01 -0.027
3.16 3.47
0.73 0.335
-0.1 0.109
0.19 0.115
Y Y
728 950
2.77 2.17 3.25 2.38 1.78 2.7 3.24 3.081 3.23 2.88 2.75 8.11 4.21
0.28 0.56 0.79 0.45 0.85 0.51
0.02 -0.12 -0.04 -0.18 -0.18 0.09 0.15 0.001 -0.03 0.038 0.003 0.094 0.223
0.14 0.36 0.33 0.28 0.42 0.27
Y Y Y Y Y Y
0.033 0.43 0.072 0.088 0.017 0.194
Y Y Y Y Y Y
714 714 714 714 714 714 460 728 714 714 728 95 1076
0.111
0.194
Y
1076
-0.001 0.029 0.076 0.04 0.04 0.53
0.011 0.026 0.006
Y Y Y Y
0.02
N
201 153 153 153 603 604 795
N
1031 41
0.004
0.77 0.2 0.16 0.14
0.074 0.98 0.19 0.19 0.38 0.905
18.3
2.5
26.56 22.73 21.52 25 25 2.36
1.98 1.48 0.39
0.08
0.25
1.77 0.1 0.03 0.015
N Y
0.05 0.18 0.022 0.13 0.18 0.084
N N Y Y Y Y
140 257 467 61 61 174 991 11 13 738 738 758 758 98 728 728 728
0.024
Y Y Y Y
4.12
References page II - 290
TABLE 1. cont'd Monomer 1 Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
Monomer 2 methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl
Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl
rt
Ethylene, 1,1-diphenyl2.1 Ethylene, 1,1-diphenyl8.7 Ethylene, chlorotrifluoro51.36 Ethylene, tetrachloroEthylene, trichloro100 Fumarate, diethyl 40.3 Fumarate, diethyl 2.1 Fumarate, diisopropyl 23 Fumaronitrile 6.74 Furan, 2-vinyl-5-methyl 0.183 Hexatriene, tetrachloro0.504 Imidazole, 1-vinyl4.36 Imidazole, l-vinyl-2-methyl4 Imidazole, l-vinyl-2-methyl3.48 Isoprene 0.26 Isoprene 0.25 Isoprene 0.25 Isoprene, 3-acetoxy0.16 Isopropenyl acetate 17.36 Isopropenyl, 3-(l-cyclohexenyl), acetate 0.81 Isopropenylisocyanate 3.1 Isopropenyltoluene 0.68 Isopropenyltoluene 0.68 Itaconamate, Af-(4-chlorophenyl)-, ethyl 1.24 Itaconamate, Ar-(4-chlorophenyl)-, 1.26 propyl Itaconamate, N-(4-methoxyphenyl)-, 1.31 ethyl Itaconamate, A^-(4-carboethoxyphenyl)1.21 ethyl Itaconamate, Ar-(4-methylphenyl)-, ethyl 1.43 Itaconamate, iV-(4-methoxyphenyl)-, 1.03 propyl Itaconamate, A^-(4-methylphenyl)-, 1.11 propyl Itaconamate, Af-phenyl-, ethyl 1.32 Itaconamate, N-phenyl-, propyl 1.13 Itaconamate, Af-(4-carboethoxyphenyl)1 propyl Itaconate, dibutyl 1.33 Itaconate, dibutyl 0.8 Itaconate, dimethyl 3.34 Itaconate, dimethyl 1.2 Itaconate, monomethyl 1.1 Itaconic acid 1.23 Itaconic acid 1.14 Itaconic anhydride 0.155 Itaconimide, N-(2-chloroethyl)0 Itaconimide, N-benzyl0.46 Itaconimide, JV-ethyl0.486 Itaconimide, N-methyl0.38 Maleate, dibutyl tin 72.7 Maleate, diethyl 341 Maleate, diethyl 20 Maleate, diethyl 285.8 Maleic anhydride 4.18 Maleic anhydride 6.36 Maleic anhydride 0.46 Maleic anhydride 5.2 Maleic anhydride 3.1 Maleic anhydride 3.85 Maleic anhydride 3.4 Maleic anhydride 3.85 Maleimide 2.576 Maleimide 2.5
±95%
3.31 0.6 0.79 0.146 0.057 1.86 0.54 0.21
1.95
0.09 0.557 0.071 0.024 0.11 0.18 0.066 0.22 5.93 46 35.9 0.31 0.64 0.69 0.47
0.061
r2 0.09 O -0.074 0 0.04 0.05 0.17 -0.064 0.867 1.76 0.014 0.047 0.003 0.65 0.64 0.64 2.81 -0.09 0.4 0.14 0.04 0.04 0.36 0.31
±95%
Conv.
0.062
Y Y
0.004
N
0.096 0.292 0.28 0.03 0.088
Y Y Y Y Y
0.23
Y
0.12
Y
Refs. 65 901 236 204 470 28 394 1038 191 1105 5 364 364 479 302 698 704 770 100 770 434 688 722 678 678
0.43
678
0.48
678
0.63 0.4
678 678
0.28
678
0.47 0.15 0.53
678 678 678
0.717 0.4 -0.156 0.3 0.139 0 0 1.17 0.54 1.06 0.42 1.12 -0.095 -0.1 0 -0.02 -0.163 -0.019 0.08 0.02 0.01 0.01 0.01 0.02 0.166 0.17
0.11 0.02
Y
0.103
Y
0.33 0.39 0.75 0.13 0.73 0.199 0.05
Y Y Y Y Y Y N
0.015 0.027 0.026 1.77 0.004
Y Y Y N N
0.047
Y
1073 398 975 398 1010 260 408 1010 642 642 642 642 987 28 470 873 169 260 320 33 524 524 524 524 251 992
TABLE 1. cont'd Monomer 1
Monomer 2
Methacrylate, methyl Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl
Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
methyl methyl methyl methyl methyl methyl methyl methyl methyl
Maleimide, 2,3-dimethylA^-(2-methacryloyloxyethyl) Maleimide, A^-(4-hydroxyphenyl)Maleimide, 7V-(2-hydroxyethyl)Maleimide, Af-(2,6-diethylphenyl)Maleimide, 7V-(2,6-diisopropylphenyl)Maleimide, AT-(2,6-dimethylphenyl)Maleimide, A^-(2-chlorophenyl)Maleimide, 7V-(2-methylphenyl)Maleimide, Af-(3,5-dimethylphenyl)Maleimide, 7V-(3-methylphenyl)Maleimide, AK3-trifluoromethylphenyl)Maleimide, 7V-(4-carboxyethylphenyl)a-chloroMaleimide, 7V-(4-chlorophenyl)-a-chloroMaleimide, Af-4-methoxyphenyl)a-chloroMaleimide, AK4-methylphenyl)Maleimide, A^-(4-methylphenyl)a-chloroMaleimide, AK|3-chloroethyl)-a-chloroMaleimide, AH (3-chloroethyl)-a-chloroMaleimide, N-[JV'-(a-methylbenzyl) aminocarbonylpenty 1] Maleimide, TV-benzyl Maleimide, TV-butyl Maleimide, 7V-cyclohexyl Maleimide, N-cyclohexyl Maleimide, Af-cyclohexyl Maleimide, AT-ethyl-a-chloroMaleimide, TV-hexylMaleimide, 7V-hydroxymethylMaleimide, 7V-methyl-a-chloroMaleimide, 7V-phenylMaleimide, 7V-phenylMaleimide, Af-phenyl-a-chloroMaleimide, N-phenylMethacrylate, 2-acetoxyethyl Methacrylate, cyanomethyl Methacrylate, diphenylmethyl Methacrylamide Methacrylamide Methacrylamide Methacrylamide Methacrylamide, Af-methoxymethylMethacrylamide, iV-p-bromophenyl~ Methacrylamide, N-p-tolylMethacrylamide, N-phenyl Methacrylamide, N-phenylMethacrylamide, 1-deoxy-D-glucitol Methacrylamide, N-/?-nitrophenylMethacrylate, tert-butyl Methacrylate, a,a-dimethylbenzyl Methacrylate, (2,2-dimethyl1,3-dioxolane) Methacrylate, 1,1-diphenylethyl Methacrylate, 1-naphthyl Methacrylate, 1-naphthyl Methacrylate, 1-naphthyl Methacrylate, 1-naphthyl Methacrylate, 2,2-dimethylaminoethyl Methacrylate, 2,3-epithiopropyl Methacrylate, 2,6-(diphenyl)phenyl Methacrylate, 2-(Ar,N-dimethylcarbamoyloxy)ethyl
/*i
±95%
r2
±95%
Conv.
0.51
1.66
1.1
3.58
Y
619
1.392 1.396 4.78 10.9 3.62 2.1 2.22 1.63 1.18 1.57 0.472
0.001 0.089
0.001 0.083
Y Y
0.114
0.345 0.201 0.05 0.02 0.07 0.1 0.09 0.28 0.22 0.1 -0.004
0.168
Y
323 323 992 992 992 992 992 992 992 992 973
0.562 0.556
0.025 0.145
0.02 0.064
0.03 0.189
Y Y
973 973
0.83 0.564
0.117
0.34 0.029
0.158
Y
992 973
0.94 0.59 1-37
0.06 0.06 0.291
0.05 0.11 0.582
0.04 0.05 0.359
Y
974 974 1009
1.28 1.41 1.35 1.31 2.26 0.53 1.9 1.745 0.63 0.98 0.91 0.657 1.014 0.94 0.399 0.81 1.57 1.7 1.39 1.65 1.678 3.48 1.43 1.95 1.42 4.2 5.05 0.96 0.81 0.9
0.23 0.19
0.23 0.16
Y Y
0.048 0.03 0.15 0.026 0.03
Y
0.72 0.77 0.809 0.851 0.61 0.42 0.83 1.42 0.59
0.066 0.04 0.2 0.03 0.34 0.083 0.06 0.02 0.019 0.11 0.04 0.074 0.048 0.2 0.2 0.2 0.096 0.2
0.14 0.078 0.084 0.02 0.06
0.03 -0.1 0.24 0.19 0.106 0.13 0.1 0.263 0.11 0.3 0.3 0.077 0.164 1.12 0.73 1.07 1.27 0.44 0.425 0.49 0.265 0.38 0.78 0.28 0.56 0.04 0.29 1.35 0.92 1.1 0.77 1.8 1.68 2.62 1.52 1.01 0.97 0.071 0.42
Y Y
0.098 0.065 0.06 0.11
Y Y N Y
0.24 0.06 0.085
N N Y
0.009 0.2 0.2 0.2 0.12
Y
Y
0.2
0.73 0.38 0.47
Y Y Y
0.54
N
0.004
Refs.
348 115 992 1100 348 974 348 323 974 323 992 973 328 346 625 761 316 316 54 55 227 968 968 968 352 258 968 761 761 807 761 752 752 752 761 691 787 1079 600
References page II - 290
TABLE 1. cont'd Monomer 1
Monomer 2
Methacrylate, methyl Methacrylate, methyl Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl
Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl
Methacrylate, 2-bromoethyl Methacrylate, 2-chloro2,3,3,3-fluoropropyl Methacrylate, 2-chloroethyl Methacrylate, 2-chloroethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxypropyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-phenylethyl Methacrylate, 3,5-dimethyladamantyl Methacrylate, 5-oxo-pyrrolidinylmethyl Methacrylate, N-a-benzothiazolonylmethyl Methacrylate, benzyl Methacrylate, benzyl Methacrylate, benzyl Methacrylate, benzylmethylaminoethyl Methacrylate, butyl Methacrylate, butyl Methacrylate, chloromethyl Methacrylate, diethylaminoethyl Methacrylate, dimethylaminoethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, glycidyl Methacrylate, glycidyl Methacrylate, glycidyl Methacrylate, glycidyl Methacrylate, isobutyl Methacrylate, isobutyl Methacrylate, isopropyl Methacrylate, methyl diphenylsilyl Methacrylate, methylthiomethyl Methacrylate, /?-acetylphenyl Methacrylate, /?-chlorophenyl Methacrylate, /?-methoxyphenyl Methacrylate, /7-tolyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, propyl Methacrylate, sulfolanyl Methacrylate, f-butyl dimethylsilyl Methacrylate, f-butyl diphenylsilyl Methacrylate, tributyltin Methacrylate, tributyltin Methacrylate, trimethyltin Methacrylate, trimethyltin Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid
/*i 0.79 0.984 1.156 0.55 0.824 0.192 0.75 0.402 0.602 0.581 0.532 0.614 0.623 0.75 0.68 0.421 0.5 0.808 0.93 0.78 0.523 0.52 1.27 0.477 0.843 0.699 0.81 1.08 1.16 0.71 0.726 0.8 0.688 0.62 0.92 0.89 0.438 0.639 0.47 0.54 0.72 0.59 0.53 0.58 0.56 0.66 0.55 1.21 1.07 0.897 0.636 0.58 0.62 0.63 0.6 0.63 0.1 0.78 0.31 0.27 0.1 0.78 0.32
±95%
0.395 0.082 0.01 0.09 0.017 0.059 0.023 0.055 0.051 0.048 0.16 0.04 0.033 0.01 0.03 0.134 0.07 0.029 0.128 0.051 0.22 0.19 0.08 0.042 0.076 0.08 0.15 0.075 0.057
2.48 0.05 0.014
0.03 0.01 0.03 0.02 0.03 0.01 0.03 0.02
r2
±95%
Conv.
Refs.
1.17
N
657 927
0.97 0.48 0.63 0.81 1.5 1.055 2.57 2.53 1.91 4.41 3.83 0.85 0.45 0.694 0.6
0.18
Y
0.076 1.02
Y Y
0.04 0.48 0.27 0.6 0.76 0.57 0.34 0.16 0.087 0.02
Y Y Y Y Y Y Y N Y
1.112 1.05 1.38 0.296 2.11 1.2 1.02 1.44 1.2 0.86 1.08 1 0.52 0.934 1.05 0.501 1.88 0.488 1.2 0.38 1.1 0.67 1.08 1.19 1.28 1.67 1.69 1.72 1.55 0.99 1.24 7.16 0.725 0.396 0.62 0.87 1.07 0.68 0.25 1.06 0.33 0.63 0.46 1.06 0.33 0.63
0.093
Y
0.123 0.08
Y N
0.16 0.085 0.154 0.12
Y Y Y N
0.09 0.06 0.085
N Y Y
0.027 0.07 0.029
Y N Y
0.178 0.356
Y Y
23.7 0.455 0.257
N Y Y
1.18 0.583
0.05 0.02 0.02 0.02 0.03 0.02 0.02 0.02
179 382 350 358 710 333 760 760 760 760 760 540 335 633 887 111 32 540 1081 30 844 712 1081 1081 32 844 87 113 226 463 639 30 639 541 1069 920 769 769 769 769 32 32 32 761 769 844 359 1069 1069 1082 1082 1082 1082 1071 1072 1072 1072 1072 1087 1087 1087
TABLE 1.
cont'd
Monomer 1 Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
Monomer 2 methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl
Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl
Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic anhydride Methacrylophenone, aMethacrylophenone, aMethacryloyl chloride Methacryloyl chloride Methacryloyl fluoride Methacryloyl fluoride Methacryloyl isocyanate Methacryloyloxy-, o-, benzoic acid Methylenebutyrolactone Methyleneglutaronitrile, 2Methyleneglutaronitrile, 2Myrcene AW-divinylaniline W-Vinylimidazole N-Vinylpyrrolidone N-Vinylpyrrolidone iV-Vinylpyrrolidone Af-Vinylpyrrolidone Naphthalene, 1-vinylNorbornadiene Oxazolidone, N-vinylOxazolidone, Af-vinylOxazoline, 2-,2-isopropenyl 4,4-dimethyl Oxazoline, 2-,2-isopropenyl Oxazoline, 2-,4-acryloxymethyl 2,4-dimethyl Oxazoline, 2-,4-methacryloxy2,4-dimethyl Pentadiene, trans-1,3Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl
/*i
±95%
r2
±95%
Conv.
Refs.
0.87 1.81 0.56 0.29 1.28 0.77 0.36 1.18 0.55 0.209 1.25 0.48 0.22 1.79 1.74 0.45 0.45 0.405 0.53 0.75 0.908 0.6 1.36 1.27 0.256 1.06 4.306 4.78 5.93 2.07 4.04 0.321 14.68 6.75 9.46 0.53
0.05 0.16 0.23 0.04 0.1 0.05 0.08
2.16 1.63 0.99 1.18 0.48 1.84 1.38 0.63 1.55 1.26 0.78 0.68 1.58 0.11 0.119 0.2 0.2 0.43 0.9 0.35 1.37 1.67 0.12 0.12 0.448 0.005 0.663 0.006 0.014 0.027 0.066 0.574 - 0.5 0.04 0.027 0.82
0.28 6.25 0.55 0.19 0.1 0.24 0.27
N N Y N N N N
0.2
Y
0.06 0.02 0.009
N N Y
0.12 0.16
Y N
0.64
Y
0.74
N
0.06 0.018 0.104 2.29 0.899 0.062 3.96 0.073 0.52 0.13 0.008
Y Y Y
203 210 216 276 276 312 313 313 424 54 630 819 275 798 798 591 593 617 660 944 938 746 196 196 1062 45 879 1084 1084 1084 1084 967 267 102 36 596
0.05 0.02 0.07 0.22 0.037 0.06 0.252 0.28 0.013 0.18 0.185 0.236 0.198 0.247 0.956 0.096 16.78 0.37 0.39
N Y Y
0.69 0.41
0.99 0.11
862 596
1.17
0.19
596
0.404 0.555 0.424 0.591 0.443 0.34 0.57 0.606 0.269 0.715 0.528 0.597 0.38 0.513 0.43 0.474 0.581 0.616 0.663 0.528 2.37 2.23 1.87
0.038 0.032 0.022 0.046 0.032 0.031 0.023 0.045 0.027 0.048 0.02 0.03 0.034 0.022 0.034 0.023 0.025 0.024 0.023 0.02 0.046 0.047 0.086
0.379 3.39 2.02 3.06 1.67 1.24 1.72 1.69 0.72 1.55 1.09 2.56 0.748 1.14 0.952 1.67 1.04 1.05 0.725 1.09 0.486 0.521 0.946
0.013 0.263 0.141 0.349 0.183 0.168 0.123 0.236 0.12 0.224 0.09 0.218 0.155 0.109 0.164 0.143 0.111 0.108 0.08 0.09 0.088 0.138 0.436
Y N N N N N N N N N N N N N N N N N N N N N N
1058 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 971 971 971
References page II - 290
TABLE 1. cont'd Monomer 1 Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
Monomer 2 methyl methyl methyl methyl methyl methyl
Methacrylate, methyl Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl
Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl
Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphonate, a-bromovinyl-,diethyl Phosphonate, a-carboethoxyvinyl-, diethyl Phosphonate, a-carbomethoxyvinyl-, diethyl Phosphonate, isopropenyl-, dimethyl Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl-, diethyl Phosphonic acid, a-phenylvinylPhthalimide,-N-)methacryloyloxy)Pinene, aPropene, 2,3-dichloroPropene, 2-chloro-3-hydroxyPropenyl, 2-chloro-, acetate Propenyl, 2-methyl, acetate Pyridazinone, 3-(2-vinyl)-6-methyl-4,5Pyridazinone 3-(2-vinyl)-6-methylPyridine, 2-methyl-5-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinyl-5-ethylPyridine, 4-vinylPyridine, 4-vinylPyrrolidone, l-benzyl-3-methylene5-methyl Pyrrolidone, N-vinylPyrrolidone, N-vinylPyrrolidone, A^-vinylPyrrolidone, N-vinylPyrrolidone, Af-vinylPyrrolidone, a-methylene-AT-methylSilane, y-methacryloxypropyltrimethoxyStyrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
rx 1.97 2.1 2.56 2.04 1.25 1
±95%
0.01
684
30 29.9 11.1 1.362 0.69 10 6.02 4.4 1 10 1.19 0.86 0.42 0.42 0.4 0.35 0.31 0.27 0.39 0.57 0.54 0.387
0.2 0.26
684 410 684 131 979 48 11 445 445 470 340 340 232 231 532 6 623 749 231 231 691 33
0.04 0.02 0.09 0.02 0.19 0.04 0.02 0.02 0.01 0.07
0.3 0.34 0.61 0.61 0.058 0.082
0.13 0.085 0.029 0.011 0.01
N N N N
Refs.
4.7
1.66
0.248 0.097 0.226 0.052
Conv.
0.05
0.04 0.084 0.048
1.16 0.42 0.258 0.0701
±95%
971 971 971 971 684 684
5.62 4.63 4.36 4.04 0.577 0.788 0.5 0.46 0.46 0.42 0.45 0.46 0.47 0.48 0.5 0.22 0.32 0.418 0.54 0.478 0.45 0.45 0.49 0.47 0.48 0.46 0.42 0.5 0.46 0.44 0.49 0.49
0.029 0.045 0.094 0.012 0.04
r2
-0.063 1.45 0.08 0.18 0 0 0 0.08 0.56 0.54 0.73 0.86 0.76 0.64 1.1 0.68 0.77 0.99 2.28
0.077 0.151
Y Y
0.1
N
0.03 0.04 0.19 0.06
N N N N
0.12
Y
0.08 0.06 0.07 0.18 0.47
N N N N Y
- 0.05 -0.032 -0.052 0.01 0.24 2.06 0.5 0.52 0.52 0.48 0.52 0.49 0.45 0.58 0.44 0.396 0.42 0.49 0.564 0.585 0.44 0.47 0.54 0.52 0.38 0.52 0.54 0.44 0.52 0.5 0.56 0.53
0.08 0.068 0.028 0.15 0.14 0.309
Y N Y Y N Y Y
0.048
Y
0.14 0.047 0.007 0.08
Y Y Y N
213 320 321 36 691 641 977 138 139 179 20 21 21 21 21 21 241 241 254 254 287 324 324 403 416 451 463 492 492 505 531 531 534
TABLE 1. cont'd Monomer 1 Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
Monomer 2 methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl
Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl
Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene, 2,4,6-trimethylStyrene, 2,4,6-trimethylStyrene, 2,5-dichloroStyrene, 2,6-dichloroStyrene, 3-methyl Styrene, 3-methyl Styrene, 3-methyl Styrene, 3-tri-rc-butylstannylStyrene, 4-methylStyrene, a-methoxyStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, m-bromoStyrene, m-chloroStyrene, m-methylStyrene, m-nitroStyrene, /?-chloroStyrene, o-chloroStyrene, /?-l-(2-hydroxypropyl)Styrene, p-JVyV-dimethylaminoStyrene, p-bromoStyrene, /?-chloroStyrene, p-chloroStyrene, /7-chloroStyrene, /?-chloromethylStyrene,/?-cyanoStyrene, /?-methoxyStyrene, p-methylStyrene,/7-octylamine sulfonate Styrene, p-tert-buty\Styrene, pentachloroSuccinamete, potassium N-vinylSuccinimide, TV-vinylSuccinimide, N-vinylTetrazole, 1-VinylTetrazole, 2-methyl-5-vinylTetrazole, 2-phenyl-5(4/-vinyl) phenylThiophene, 3-vinyl Thioxanthone, 2-(acryloyloxy)Toluenesulfonamide, Af,N-methylvinylTriallyl cyanurate Triallyl isocyanurate Triazole, 1,2,3-, 1-p-bromophenyl4-vinyl Triazole, 1,2,3-, 4(5)-vinylUrea, TV-vinyl-AT'-ethyl-
r\ 0.409 0.504 0.611 0.59 0.6 0.63 0.58 0.64 0.41 0.454 0.464 0.422 0.41 0.314 1.511 1.45 0.44 1.98 0.48 0.38 0.41 0.69 0.345 2.5 0.48 0.55 0.55 0.5 0.42 0.47 0.48 0.512 0.35 0.5 0.46 0.26 0.204 0.4 0.334 0.42 0.43 0.408 0.22 0.29 0.4 0.6 0.44 3.65 1.1 9.94 0.01 7.13 1.026 0.7 0.563 1.36 1.87
±95% 0.02 0.026 0.028
0.072 0.16 0.13 0.16 0.04 0.03 0.04 0.008 0.39 0.02
0.036 0.11
r2 0.485 0.48 0.371 0.62 0.52 0.5 0.55 0.55 0.41 0.472 0.497 0.432 0.57 0.275 0.083 -0.01 2.66 -0.15 0.53 0.36 0.51 0.03 0.46 - 0.02 0.27 0.51 0.6 0.14 0.22 0.48 1.17
±95%
Conv.
Refs.
0.052 0.059 0.055
Y Y Y
0.045 0.11 0.38 0.27 0.04 0.06 0.05
Y Y Y N
0.022 0.04 0.07
Y N N
0.02 0.32
Y Y Y
0.016
Y
0.12
Y
0.15
Y
0.05 0.12 0.026 0.096 0.026 0.075
N Y Y Y Y Y
0.26
Y
751 751 751 753 753 753 753 753 753 824 824 824 835 860 58 58 3 324 1087 1087 1087 985 929 142 265 265 265 532 835 899 256 150 256 222 532 558 380 256 256 150 256 476 756 256 35 256 817 634 7 771 104 693 925 670 583 1000 986 80
0.19
0.486 0.8 1.37 1.34 1 0.101 1.1 0.77 0.89 0.47 0.91 1.41 0.32 0.44 2.6 0.5 0.3 -0.02 0.048 -0.059 0.262 0.486 0.4 0.25 0.5 -1.83
16.12 16.88 0.832
0.56 6.64 0.022
-0.005 -0.49 0.266
0.05 0.94 0.058
Y Y Y
201 201 670
0.839 1.85
0.055 0.23
0.27 -0.008
0.13 0.029
Y Y
670 101
0.022 0.016
0.038
0.85 0.17 0.27 0.031 0.093 0.029
References page II - 290
TABLE 1. cont'd Monomer 1 Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl
Monomer 2 Vinyl 2-chloroethyl ether Vinyl 4-chlorocyclohexyl ketone Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl benzoate Vinyl bromide Vinyl bromide Vinyl bromide Vinyl bromide Vinyl butyl ether Vinyl butyrate Vinyl chloride Vinyl chloromethyl ketone Vinyl ether Vinyl ethyl ether Vinyl ethyl ketone Vinyl ethyl oxalate Vinyl ethyl sulfide Vinyl ethyl sulfide Vinyl ethyl sulfoxide Vinyl isobutyl sulfide Vinyl isobutyl sulfide Vinyl isobutyl sulfide Vinyl isopropyl ketone Vinyl isopropyl ketone Vinyl isopropyl sulfide Vinyl isothiocyanate Vinyl m-cresyl ether Vinyl methyl sulfide Vinyl o-cresyl ether Vinyl /7-cresyl ether Vinyl phenyl ether Vinyl phenyl ether Vinyl phenyl ketone Vinyl phenyl sulfide Vinyl phenyl sulfide Vinyl propionate Vinyl sulfone Vinyl tert-butyl ketone Vinyl, 4-, dithiobenzoate, methyl Vinyl, /?-,benzylmethylcarbinol Vinyl-tris(trimethoxysiloxy)silane Vinylacetophenone, p Vinylanthracene, 9Vinylbenzoic acid, p Vinylbenzyl chloride Vinylene carbonate Vinylferrocene Vinylhydroquinone Vinylhydroquinone dibenzoate Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene cyanide Vinylisocyanate
T1 18.8 0.77 2.71 137.5 26 28.6 22.21 20.3 14.11 17.1 25.1 19.84 25 8.99 0.121 4.9 37 0.42 4.74 1.03 2.7 11.17 0.89 0.985 0.88 0.81 0.54 0.822 0.85 3.3 1 1.8 2.6 11.34 2.8 0.71 0.79 0.85 24 4.5 1.21 0.151 0.24 34 0.33 4.068 0.398 0.46 126 1.22 0.49 0.34 2.6 2.38 2.16 2.5 2.5 2.1 1.8 2.83 1.23 2.77 3.3
±95%
0.25 5.9
0.67 0.88 2.58 2.97 0.021 0.99 0.17 2.95 0.11 0.48 0.01 0.077 0.02 0.22 0.064
5.76 0.6 0.06 0.49 0.11 0.092 0.26 0.36 0.04 0.097 298 0.21 0.02 0.06
0.95 0.06 0.012
r2 0 0.51 -0.2 -0.81 0.03 0.04 0.07 0.07 0.12 0.33 0.052 0.05 0.03 0.07 0.593 -0.15 0.01 0.65 -0.05 0.036 0.3 0.37 0.05 0.021 0.03 1.44 0.6 0.046 0.6 0.2 0.03 0.1 0 0.01 0 0.59 0.06 0.08 0.03 0.1 0.65 0.3 0.98 0.02 1.65 0.117 1.16 1.02 -0.04 0.52 0.02 0.41 0.3 0.36 0.18 0.5 0.34 0.09 0.094 0.19 0.02 0.27 0.01
±95%
Conv.
0.01 1.17
N
0.06
N
0.026 0.074
Y Y N
0.047 0.092 0.16
Y Y Y
0.42 0.44 0.017
Y Y Y
0.06 0.03 0.034 0.02
Y N Y N
0.47 0.025
Y Y
0.32
Y
1.9 0.09
Y N
0.16 0.15 0.29 0.28
Y Y Y Y
3.81 0.043 0.3
Y Y Y
0.85
Y
0.13
Y
0.03 0.18
Y N N
0.032
Y
0.01 0.013
N Y
Refs. 597 668 158 210 272 383 471 272 268 268 34 34 127 272 3 356 45 106 794 124 303 507 286 285 303 336 601 794 303 422 605 106 605 605 172 605 794 239 239 272 45 794 697 48 482 266 123 266 792 103 294 337 440 138 324 324 426 432 538 65 762 762 786 82 422
TABLE 1. cont'd Monomer 1 Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl diphenylsilyl Methacrylate, methylthiomethyl Methacrylate, methylthiomethyl Methacrylate, mono-,ethylene glycol Methacrylate, octyl Methacrylate, octyl Methacrylate, octyl Methacrylate, /?-(cinnamoylamino)phenyl Methacrylate, /?-acetylphenyl Methacrylate,/?-carbomethoxyphenyl Methacrylate, p-chlorophenyl Methacrylate, p-chlorophenyl Methacrylate, /?-methoxyphenyl Methacrylate, p-methoxyphenyl Methacrylate, p-methylphenyl Methacrylate, p-methylphenyl Methacrylate, p-tolyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, potassium Methacrylate, propargyl Methacrylate, propyl Methacrylate, propyl Methacrylate, sodium (2-sulphoxyethyl)Methacrylate, sulfolanyl Methacrylate, sulfolanyl Methacrylate, sufolanyl Methacrylate, f-butyl dimethylsilyl Methacrylate, f-butyl dimethylsilyl Methacrylate, f-butyl diphenylsilyl Methacrylate, terf-butyl Methacrylate, terf-butyl Methacrylate, tetra(2-hydroxypropyl)ethylenediamine Methacrylate, tetra(2-hydroxypropyl)ethylenediamine Methacrylate, tributyltin Methacrylate, tributyltin Methacrylate, tributyltin Methacrylate, tributyltin Methacrylate, tributyltin Methacrylate, tributyltin Methacrylate, triethyltin Methacrylate, trimethyltin Methacrylate, triphenyltin Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid
Monomer 2
rx
Vinylphenyldimethylsilane 29.79 Vinyltrimethylsilane 35.66 Xanthate, 5-methacryloyl O-ethyl 0.76 Methacrylate, methyl 0.38 Methacrylate, methyl 1.1 Styrene 0.512 Acrylonitrile 1.5 Styrene 0.56 Styrene 0.68 Vinyl chloride 14 Styrene 0.31 Methacrylate, methyl 0.67 Styrene 0.178 Methacrylate, methyl 1.08 Styrene 0.243 Methacrylate, methyl 1.19 Styrene 0.244 Styrene 0.225 Styrene 0.185 Methacrylate, methyl 1.28 Acrylonitrile 0.46 Methacrylate, 2-chloroethyl 0.785 Methacrylate, benzyl 1.42 Methacrylate, methyl 1.67 Methacrylate, methyl 1.69 Methacrylate, methyl 1.72 Methacrylate, methyl 1.55 Methacrylate, methyl 0.99 Methacrylic, acid 1.89 Methacrylic, acid 0.589 N-Vinylpyrrolidone 4.17 Styrene 0.48 Styrene 0.55 Styrene 0.51 Acrylonitrile 0.203 Itaconic acid mono(/?-sulfamidoanilide) 1.65 Methacrylate, methyl 1.24 Styrene 0.38 Methacrylic, acid 1.2 Methacrylate methyl 7.16 Methacrylic, acid 0.81 Styrene -0.2 Acrylate, methyl 1.07 Methacrylate, methyl 0.725 Methacrylate, methyl 0.396 Methacrylate, methyl 1.35 Styrene 0.61 Methacrylate, hydroxyethyl 1.44
±95% 1.89 0.85 0.04 0.178 0.356 0.05
r2
0.51 1
-0.009 0.028 0.6 0.438 0.639 0.338 0.19 0.65 0.56 0.04 0.62 0.47 0.482 0.54 0.34 0.72 0.499 0.49 0.223 0.59 0.36 1.02 0.67 0.53 0.58 0.56 0.66 0.55 0.211 0.398 -0.026 0.246 0.247 0.26 0.226 0.58 1.21 0.565 0.78 1.07 0.81 0.2 0.288 0.897 0.636 0.96 0.545 0.606
0.16
0.027 0.022 0.026 0.04 0.039
0.083 0.09
0.17 0.081 0.756 0.23 0.33 0.086 0.02 0.11 0.19 23.7 0.24 2.46 0.21 0.455 0.257
±95%
Conv.
Refs.
Y Y
0.034 0.016 0.08 0.075 0.057 0.01
Y Y Y
0.1
Y
0.084
Y
0.11
Y
0.089 0.25 0.09
Y Y Y
0.21 0.06
Y N
0.018 0.019 0.032 0.049 0.064
Y Y Y Y Y
0.04 0.05
Y
0.081 0.08 2.48 0.03 0.1 0.057 0.05 0.014
Y N N N N Y Y Y
0.054 0.416
Y Y
482 482 1086 1069 920 920 682 179 463 511 685 769 177 769 177 769 177 177 177 769 363 179 32 32 32 32 761 769 88 88 1013 177 179 463 808 957 844 179 745 359 359 359 1069 1069 1069 761 179 996
Methacrylic acid
0.328
0.181
1.56
0.237
Y
996
Methacrylate, 2-ethoxyethyl Methacrylate, 2-hydroxypropyl Methacrylate, cyclohexyl Methacrylate, ethyl Methacrylate, hydroxyethyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Acrylamide Acrylamide Acrylamide Acrylate, butyl
0.2 0.728 0.395 0.299 0.282 0.62 0.87 1.07 0.68 1.63 4.4 0.15 1.25
0.444 0.517 0.428 0.607 0.424
0.53 1.81 0.891 0.601 2.33 0.58 0.62 0.63 0.6 0.57 0.58 0.56 0.31
0.16 0.275 0.136 0.123 0.185
N N N N N
0.1
N
945 945 945 945 945 1082 1082 1082 1082 1028 852 852 187
0.31
References page II - 290
TABLE 1. cont'd Monomer 1 Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic
Monomer 2 acid acid acid acid acid acid acid acid
Methacrylic acid Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic
acid acid acid acid acid
Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic
acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid
Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic
acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid
rx
Acrylate, ethyl Acrylic acid, 2-ethyl 1.12 Acrylic acid, 2-ethyl 2.29 Acrylic acid, 2-ethyl 1.14 Acrylonitrile 0.2 Acrylonitrile 2.38 Butadiene, 2-chloro-0.035 Diphenyl sulfone, 0.564 3,3 '-bisitaconimido-m,ra 'Maleimide, 2,3-dimethyl0.746 AH2-methacryl) Methacrylamide 2.73 Methacrylamide 1.55 Methacrylamide 2.006 Methacrylate, 2-hydroxypropyl 0.99 Methacrylate, N-methyl-N-phenyl2.16 2-amino Methacrylate, butyl 0.8 Methacrylate, butyl 0.73 Methacrylate, diethylaminoethyl 0.63 Methacrylate, ethyl 0.57 Methacrylate, glycidyl 0.98 Methacrylate, isopropyl 2.01 Methacrylate, methyl 0.25 Methacrylate, methyl 1.06 Methacrylate, methyl 0.33 Methacrylate, methyl 0.63 Methacrylate, methyl 0.46 Methacrylate, methyl 1.06 Methacrylate, methyl 0.33 Methacrylate, methyl 0.63 Methacrylate, methyl 2.16 Methacrylate, methyl 1.63 Methacrylate, methyl 0.99 Methacrylate, methyl 1.18 Methacrylate, methyl 0.48 Methacrylate, methyl 1.84 Methacrylate, methyl 1.38 Methacrylate, methyl 0.63 Methacrylate, methyl 1.55 Methacrylate, methyl 1.26 Methacrylate, methyl 0.78 Methacrylate, methyl 0.68 Methacrylate, phenyl 0.211 Methacrylate, phenyl 0.398 Methacrylate, sodium (2-sulphoxyethyl)- 0.78 Methacrylate, sulfolanyl 0.81 Methacrylate, tetra(21.56 hydroxypropyl)ethylenediamine Methacrylonitrile 1.74 Methacrylonitrile 0.54 7V-Vinylimidazole 1.384 Phosphonate, vinyl-, diethyl 1.9 Phosphonic acid, a-phenylvinyl1.49 Piperylene, cis0.4 Piperylene, trans0.38 Propene, 2,3-dichloro4 Propene, 2-chloro-3-hydroxy4.5 Pyridine, 2-methy 1-5-vinyl0.43 Pyridine, 2-vinyl0.58 Pyridine, 2-vinyl0.44 Styrene 0.55 Styrene 0.64 Styrene 0.66 Styrene 0.49
±95%
r2
±95%
Conv.
Refs. 1065 1004 1004 961 16 216 259 1042
0.027 0.04
0.26 0.29 0.058 0.032
0.194 0.069 0.23 0.04 0.092 2.52 0.015
0.13 0.06 0.2 0.058
N Y Y Y Y Y Y Y
0.059
1.33
0.1
Y
619
0.28
0.33 1.28 0.2 0.31 0.2
0.25
Y
0.014
Y
0.01
N
190 527 55 886 651
0.12 0.12 1.59
N N Y
0.1
N
0.03 0.01 0.03 0.02 0.03 0.01 0.03 0.02 0.05 0.16 0.23 0.04 0.1 0.05 0.08
N N Y N N N N
0.05
Y
0.17 0.081 0.19 0.24 0.181
Y Y N N Y
0.07 0.32 0.022
N N Y
0.3
Y
0.71
Y
0.02
N
0.04
N
0.132 0.417
0.09 0.18 0.16 0.2 1.47 0.16 0.05 0.02 0.02 0.02 0.03 0.02 0.02 0.02 0.28 6.25 0.55 0.19 0.1 0.24 0.27 0.2 0.018 0.019 0.08 0.03 0.237 0.1 3.71 0.034 0.16
0.21 0.66 0.08
1.26 1.15 2.34 0.71 1.2 0.47 0.63 0.1 0.78 0.31 0.27 0.1 0.78 0.32 0.87 1.81 0.56 0.29 1.28 0.77 0.36 1.18 0.55 0.209 1.25 0.48 1.89 0.589 1.2 0.81 0.328 0.64 0.52 0.145 0.15 0.17 0.38 0.33 0 0 0.85 1.69 1.38 0.21 0.22 0.2 0.15
187 224 16 820 224 847 1071 1072 1072 1072 1072 1087 1087 1087 203 210 216 276 276 312 313 313 424 54 630 819 88 88 745 359 996 44 85 879 431 130 773 773 445 445 552 15 498 166 166 203 312
TABLE 1. cont'd Monomer 1 Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic
Monomer 2 acid acid acid acid acid acid acid acid acid acid acid acid acid acid
Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic
acid acid acid acid acid acid
Methacrylic acid Methacrylic anhydride Methacrylic anhydride Methacrylic anhydride Methacrylic anhydride Methacrylic anhydride Methacrylic anhydride Methacrylic anhydride Methacrylic anhydride Methacrylic anhydride Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile
Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene, 3-methyl Styrene, 3-methyl Styrene, 3-methyl Styrene, o-chloroSulfonic acid, o-methacryloylaminobenzeneSulfonic acid, o-methacryloylaminobenzeneSulfonic acid,/7-methacryloylaminobenzeneSulfonic acid, p-methacryloylaminobenzeneVinyl acetate Vinyl chloride Vinyl chloride Vinyl chloride Vinyl, mono-, diethyleneglycol ether Vinylethynyl-4-piperidinol, 1,2,5-trimethyl Vinylidene chloride Acrylate, methyl Allyl chloroacetate Allylurea Methacrylate, methyl Methacrylonitrile Styrene Styrene Vinyl benzyl sulfide Vinyl chloroethyl ether Acenaphthalene Acetylene, phenylAcrolein Acrolein Acrolein, methylAcrolein, methylAcrolein, methylAcrylate, 1,1,5-trihydroperfluoroamyl Acrylate, a-chloro-, ethyl Acrylate, oc-cyano-, methyl Acrylate, oc-phenyl-, methyl Acrylic anhydride Acrylonitrile Allylbenzene Butadiene Ethylene 1,1-diphenylFumarate, diisopropyl Itaconate, dimethyl Methacrylate, butyl Methacrylate, ethyl Methacrylate, isobutyl Methacrylate, isopropyl Methacrylate, octyl Methacrylic acid Methacrylic acid Methacrylic anhydride Phosphonic acid, a-phenylvinyl-
rx 0.56 0.28 0.602 0.85 0.631 0.6 0.44 0.39 0.12 0.35 0.18 0.51 0.622 0.203
±95%
±95%
Conv.
Refs.
0.04
N
0.092
Y
0.146 0.249 0.089 0.199 0.118 0.08 0.02 0.01 0.058 0.067
0.2 0.38 0.124 0.17 0.041 0.067 0.627 0.55 0.221 0.06 0.33 0.42 0.101 0.217
0.03 0.046 0.031 0.06 0.048 0.03 0.02 0.01 0.034 0.122
Y Y Y Y Y
Y Y
313 313 47 812 842 842 842 842 842 1087 1087 1087 6 1006
0.188
0.076
0.523
0.195
Y
1006
0.156
0.081
1.08
0.338
Y
1006
0.155
0.052
1.65
0.27
Y
1006
0.008 0.02
Y Y
0.047
Y
0.13 0.17 0.02 0.06 0.01
Y Y N N N
0.033
Y Y
0.12
N
0.07
N
0.01
N
0.13 0.04 0.03 0.15 0.11
N N Y Y N
0.07 0.05 0.05 0.12 0.05 0.1 3.71 0.18
N N N N N N N N
0.2 23.52 23.26 9.05 0 0.4 3.368 4.75 29.76 29.01 1.58 1.45 0.27 0.33 0.97 0.15 0.78 1.17 1.2 0.41 0.45 0.45 1.03 0.45 0.18 0.19 0.42 1.67 16.24 0.053 0.48 85 1.26 0.56 0.46 0.74 0.43 0.75 0.64 0.52 0.26 2.24
0.19
r2
0.088
0.98 0.96
0.098 13 18.48 0.06 0.18 0.02 0.27
0.05 0.01
0.01 0.04 0.12 1.36 0.016 0.1 0.15 0.04 0.07 0.08 0.04 0.07 0.32 0.06
0.01 0.064 -0.022 0.07 2.2 0.05 0.154 0.16 -0.01 -0.06 0.22 0.26 0.13 0.1 - 0.048 2.38 0.04 0.68 0.72 1.78 1.25 1.25 0.14 2 0.15 0.25 1 0.43 -0.061 0.39 -0.45 0 0.28 0.75 0.83 0.68 0.94 0.61 1.74 0.54 1.45 0
377 135 229 46 831 734 6 275 106 106 275 219 219 275 106 106 575 648 208 446 208 587 589 809 638 143 143 219 198 351 257 143 1038 398 44 44 44 44 44 44 85 219 590
References page II - 290
Next Page TABLE 1.
cont'd
Monomer 1 Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylophenone, aMethacrylophenone, aMethacryloxymethylpentamethyldisiloxane Methacryloxypropyltrimethoxysilane Methacryloyl chloride Methacryloyl chloride Methacryloyl chloride Methacryloyl chloride Methacryloyl chloride Methacryloyl fluoride Methacryloyl fluoride Methacryloyl fluoride Methacryloyl fluoride, perfluoroMethacryloyl isocyanate Methacryloyl-P-hydroxyethyl3,5-dinitrobenzoate Methacryloyl-P-hydroxyethyl3,5-dinitrobenzoate Methacryloyl-P-hydroxyethyl3,5-dinitrobenzoate Methacryloylacetone Methacryloylacetone Methacryloylacetone Methacryloyloxy, 2-benzoate methyl Methacryloyloxy, 2-benzoate methyl Methacryloyloxy, 2-benzoic acid methyl Methacryloyloxy, 2-benzoic acid Methacryloyloxy, 4-,2,2,6,6-tetramethylpiperidine Methacryloyloxy-, o-, benzoic acid Methacryloyloxy-, o-, benzoic acid Methylenebutyrolactone Methylenebutyrolactone Methylenebutyrolactone Methylenebutyrolactone Methyleneglutaronitrile, 2Methyleneglutaronitrile, 2Methyleneglutaronitrile, 2Methyleneglutaronitrile, 2Methyleneglutaronitrile, 2Methyleneglutaronitrile, 2Methyleneglutaronitrile, 2Myrcene Myrcene Myrcene N-N-Divinylaniline N-TV-Divinylaniline JV-JV-Divinylaniline N-N-Divinylaniline TV-N-Divinylaniline
Monomer 2
rx
Styrene Styrene Styrene Styrene Styrene Styrene Styrene, oc-methoxyStyrene, a-methylStyrene, ochloroVinyl acetate Vinyl cinnamate Vinylidene chloride Vinylidene chloride Methacrylate, methyl Methacrylate, methyl Methacrylate, 2-hydroxyethyl Styrene Acrylonitrile Methacrylate, methyl Methacrylate, methyl Pyrrolidone, N-vinylVinyl chloride Methacrylate, methyl Methacrylate, methyl Styrene Vinylidene fluoride Methacrylate, methyl Acrylate, Af-(2-hydroxyethyl)carbazolyl
0.41 0.42 0.28 0.21 0.25 0.21 0.83 0.21 0.86 12 4.6 2.43 2.38 0.11 0.119 0.33 0.58 2.8 0.2 0.2 0.58 2 0.43 0.9 0.164 0.02 0.35 0.08
Acrylate, N-(2-hydroxyethyl)carbazolyl Methacrylate, N-ethyl-3-hydroxymethylcarbazolyl Acrylonitrile Pyrrolidone, TV-vinylStyrene Methacrylate, N-methyl-JV-phenyl2-amino ethyl Styrene Methacrylate, Af-methyl-7V-phenyl2-amino ethyl Styrene Styrene Methacrylate, methyl Vinylchloride Acrylamide Acrylonitrile Methacrylate, methyl Styrene Butadiene Methacrylate, methyl Methacrylate, methyl Styrene Styrene Styrene Vinyl methyl ketone Methacrylate, methyl Styrene Styrene/7-fluoroAcrylonitrile Methacrylate, methyl Styrene Styrene, p-methylVinyl acetate
±95%
r2
±95%
Conv.
Refs.
0.026
0.37 0.38 0.43 0.34 0.25 0.34 - 0.02 0.15 0.78 0.01 0.15 0.3 0.36 1.79 1.74 0.97 0.36 0.35 0.45 0.45 0.05 0.3 0.405 0.53 0.069 7.6 0.75 1.04
1.364
0.018
0.334
0.022
Y
719
0.554
0.019
0.729
0.051
Y
701
3.74 5.66 1.66 1.11
0.22 0.4 0.16 0.18
0.01 0.008 0.067 0.55
0.004 0.004 0.007 0.04
Y Y Y N
339 339 339 651
0.48 2.6
0.02 0.08
0.27 0.2
0.04 0.01
N N
651 651
1.17 0.32
0.03
0.15 0.6
0.04
N
651 687
1.37 11.26 2.85 1.1 1.67 0.7
0.64 3.5
0.908 0.004 0.3 0.09 0.6 0.09
0.252 0.052
Y Y
0.12 0.12 -0.02 0.02 0.25 1.24 0.448 1.38 0.87 -0.006 0.005 0.033 0.06 3.99
0.74
1.36 1.27 0.42 0.5 0.85 5.05 0.256 0.891 0.362 0.246 1.06 5.38 6.15 0.058
0.28
N N
0.52
N
0.013 0.015 0.022 0.014 0.18 0.36 0.16 0.009
Y Y Y Y Y Y Y Y
938 938 746 745 746 746 196 196 196 196 196 512 512 1062 1062 1062 45 45 45 45 45
0.04
0.1 0.05 0.02 0.009
0.12 0.16 0.045
1.3
0.06 0.081 0.143 0.07 0.018 0.067 0.03 0.12
0.005
N
0.1 0.05 0.07 0.22
N N N Y
0.037 0.06 0.014
Y N Y
0.14
Y
311 311 542 707 75 835 143 542 44 75 200 781 781 798 798 822 951 580 591 593 599 432 617 660 660 669 944 702
Previous Page
TABLE 1. cont'd Monomer 1 JV-Vinylimidazole N-Vinylimidazole Af-Vinylimidazole N-Vinylimidazole N-Vinylimidazole N-Vinylimidazole N-Vinylimidazole N-Vinylimidazole Af-Vinylimidazole Af-Vinylimidazole W-Vinylimidazole N-Vinylpyrolidone AT-Vinylpyrolidone Af-Vinylpyrrolidone Af-Vinylpyrrolidone N-Vinylpyrrolidone N-Vinylpyrrolidone Af-Vinylpyrrolidone AT-Vinylpyrrolidone N-Vinylpyrrolidone N-Vinylpyrrolidone N-Vinylpyrrolidone Af-Vinylpyrrolidone N-Vinylpyrrolidone JV-Vinylpyrrolidone N-Vinylpyrrolidone N-Vinylpyrrolidone N-Vinylpyrrolidone N-Vinylpyrrolidone N-Vinylpyrrolidone Af-Vinylpyrrolidone Af-Vinylpyrrolidone Af-Vinylpyrrolidone Naphthalene, 1-vinylNaphthalene, 1-vinylNaphthalene, 1-vinylNaphthalene, l-vinyl-4-chloroNaphthalene, 2-vinylNaphthalene, 2-vinyl-6-chloroNaphthalene, 6-vinyl-2-tert-butyl Nickel diacrylate Norbornadiene Norbornadiene Norbornadiene Norbornadiene Norbornadiene Norbornadiene Norbornadiene Norbornadiene OcM-ene, 4,8-dioxaspiro(2.5)Oct-1-ene, 6,6-dimethyl4,8-dioxaspiro(2.5)Oct-1-ene, 6,6-dimethyl4,8-dioxaspiro(2.5)Oct-1-ene, 6,6-dimethyl4,8-dioxaspiro(2.5)Oct-1-ene, 6,6-dimethyl4,8-dioxaspiro(2.5)Octene-1 Oxazinium F3CSO3, 3-methyl-2-vinyl5,6-dihydro-4H-l,3-
Monomer 2
rx
±95%
r2
±95%
Acrylic acid 0.187 Acrylonitrile 0.832 Fumarate, diethyl 0.113 Fumarate, dimethyl 0.133 Fumaric acid 0.121 Maleate, diethyl 0.057 Maleate, dimethyl 0.046 Maleic acid 0.018 Methacrylate, methyl 0.663 Methacrylic acid 0.145 Styrene 0.68 Caprolactam, N-vinyl2.8 Crotonate, hydrocortisone 210.75 2-Oxazoline, 2-isopropenyl0.01 Acrylamido-2-methylpropane sulfonate 0.13 sodium salt Acrylate, cyclohexyl 0.122 Carbamate, N-vinyl-f-butyl0.4 Ethene, 2-phenyl-l,l-dicyanoItaconate, bis(tri-rc-butyltin) 0.21 Methacrylate, 2-acetylsalicylicoyloxy0.34 3-hydroxypropyl Methacrylate, furfuryl 0.0036 Methacrylate, glycidyl 0.003 Methacrylate, methyl 0.006 Methacrylate, methyl 0.014 Methacrylate, methyl 0.027 Methacrylate, methyl 0.066 Methacrylate, phenyl -0.026 Pyridine, 2-methyl-5-vinyl0.039 Pyridine, 2-vinyl0.014 Pyridine, 4-vinyl0.01 Quinine 2.2 Styrene sulfonate, sodium salt 0.084 Vinyl trimethylammonioethyl ether 11.6 iodide Acrylonitrile 0.451 Methacrylate, methyl 0.574 Styrene 2.02 Styrene 0.75 Styrene 1.345 Styrene 2.44 Styrene 1.014 Titanium, dicylopentadienyl-, 0.95 dimethacrylate Acrylate, ethyl -0.01 Acrylonitrile 0.05 Acrylonitrile 0.44 Methacrylate, methyl -0.5 Styrene, p-chloro0 Vinyl acetate 1.354 Vinyl chloride 0.41 Vinylidene chloride 0.09 Styrene 0.246 Acrylonitrile 1.484
0.025 0.044 0.019 0.021 0.01 0.028 0.046 0.007 0.104 0.022 0.02 0.2 0.02 0.02
1.932 3.393 0.191 0.252 0.313 0.106 0.046 0.094 4.306 1.384 8.377 1.7 0.05 3.5 0.66
0.077 0.008 0.022 0.015 0.012 0.147 0.438 0.027 0.185 0.034 0.149 0.2 0.05 1.2
0.014 0.06
1.297 2.4
0.088 0.5
0.013
0.065 0.85
0.04
Pyridine, 2-vinyl-
0.02 0.018 2.29 0.899 0.062 3.96 0.032 0.006 0.002 0.002 0.03
5.16 4.29 4.78 5.93 2.07 4.04 4.17 13 12.4 9.8 0.37 7.19 0
1.13 0.498 0.236 0.198 0.247 0.956 0.756 2 2.3 1.5
Conv.
Refs.
Y Y Y Y Y Y Y Y Y Y Y
879 879 879 879 879 879 879 879 879 879 879 883 1022 894 939
Y Y Y
Y
0.02
1061 991 947 941 1080 1050 1017 1084 1084 1084 1084 1013 1070 1070 1070 922 939 1037
0.088 0.073 0.401 0.45 0.093 1.38 0.244
0.107 0.321 0.699 0.76 0.395 0.39 0.616 0.65
0.028 0.096 0.233 0.68 0.049 0.6 0.069
0.03 0.23 0.05 0.52 0.12 0.07 0.01 0.17 0.024 1.078
2.39 0.48 0.66 14.68 69.93 0.818 0.67 1.36 1.831 0.985
0.44 0.27 0.01 16.78 24.19 0.019 0.02 0.63 0.027 0.675
N N N N Y Y N N Y Y
267 267 69 267 188 188 267 267 838 838
0.073
0.04
2.216
0.062
Y
838
Pyrrolidone, Af-vinyl-
0.552
0.075
-0.009
0.018
Y
838
Styrene
0.271
0.109
1.93
0.098
Y
838
0.85
3.26 0.37
0.45
N
329 909
Vinyl chloride Methacrylate, methyl
-0.57 0.31
967 967 967 806 806 806 806 895
ReferencespageII-290
TABLE 1. cont'd Monomer 1 Oxazolidone, N-vinylOxazolidone, N-vinylOxazolidone, N-vinylOxazolidone, N-vinylOxazolidone, TV-vinylOxazolidone, N-vinylOxazolidone, JV-vinylOxazolidone, N-vinylOxazoline, 2-, 2-isopropenylOxazoline, 2-, 2-isopropenylOxazoline, 2-, 2-isopropenylOxazoline, 2-, 2-isopropenylOxazoline, 2-, 2-isopropenylOxazoline, 2-, 2-isopropenylOxazoline, 2-, 2-isopropenylOxazoline, 2-, 2-isopropenylOxazoline, 2-, 2-isopropenylOxazoline, 2-, 2-isopropenyl4,4-dimethylOxazoline, 2-, 2-isopropenyl4,4-dimethylOxazoline, 2-, 2-isopropenyl4,4-dimethylOxazoline, 2-, 2-isopropenyl4,4-dimethylOxazoline, 2-, 4-acryloxymethyl2,4-dimethylOxazoline, 2-, 4-acryloxymethyl2,4-dimethylOxazoline, 2-, 4-acryloxymethyl2,4-dimethylOxazoline, 2-, 4-acryloxymethyl2,4-dimethylOxazoline, 2-, 4-methacryloxy2,4-dimethylOxazoline, 2-, 4-methacryloxy2,4-dimethylOxazoline, 2-, 4-methacryloxy2,4-dimethylOxazoline, 2-, 4-methacryloxy2,4-dimethylOxazoline, 2-isopropenyl-2Oxazoline, 2-isopropenyl-2Oxazoline, 2-isopropenyl-2Oxazoline, 2-isopropenyl-2Oxazoline, 2-isopropenyl-2Oxazoline, 2-isopropenyl-2Oxazoline, 2-isopropenyl-2Oxazoline, 2-isopropenyl-2Oxazolinium BF4, 3-methyl2-isopropenyl-2Oxazolinium BF4, 3-methyl2-isopropenyl-2Oxazolinium, 2-, tetrafluoroborate 3-methyl-2-isopropenylOxazolinium, 2-, tetrafluoroborate 3-methyl-2-isopropenylOxazolinium, 2-isopropenyl-2Oxirane, 4-vinylphenylPentadiene, cis-1,3Pentadiene, cis-1,3Pentadiene, cis-1,3Pentadiene, cis-1,3Pentadiene, cis-1,3Pentadiene, cis-1,3-
Monomer 2 Methacrylate, decyl Methacrylate, methyl Methacrylate, methyl Styrene Vinyl acetate Vinyl acetate Vinyl chloride Vinylidene chloride Acrylate, butyl Acrylate, ethyl Acrylate, methyl Acrylate, methyl Acrylonitrile Methacrylate, methyl Pyrrolidone, N-vinylStyrene Vinyl acetate Acrylate, methyl
T1 -0.052 0.04 0.027 -0.029 1.55 2.04 0.822 0.091 1.4 1.39 1.9 2.07 0.52 0.99 3.5 0.64 7.1 1.3
±95% 0.049 0.13 0.008 0.014 0.28 0.13 0.048 0.077
0.191
r2 12.19 6.75 9.46 29.42 0.602 0.55 0.313 1.42 0.24 0.19 0.16 0.328 0.13 0.69 0.01 0.67 0.25 0.46
±95%
Conv.
Refs.
1.35 0.37 0.39 2.19 0.038 0.18 0.095 0.11
Y Y Y Y Y Y Y Y
0.032
Y
36 102 36 36 102 36 36 102 862 862 862 877 862 862 862 862 862 596
Acrylonitrile
1.83
0.24
596
Methacrylate, methyl
0.82
0.53
596
Styrene
0.68
0.55
596
Acrylate, methyl
0.11
0.29
596
Methacrylate, methyl
0.11
0.41
596
Styrene
0.14
0.56
596
Vinyl acetate
1.41
0.03
596
Acrylate, methyl
0.56
0.4
596
Acrylonitrile
0.89
0.11
596
Methacrylate, methyl
0.19
1.17
596
Vinyl acetate
6.2
0.05
596
Acrylate, butyl Acrylate, ethyl Acrylate, methyl Acrylonitrile Methacrylate, methyl 7V-Vinylpyrrolidone Styrene Vinyl acetate Acrylate, methyl
1.4 1.39 1.9 0.52 0.99 3.5 0.64 7.1 0.251
0.08 0.06 0.08 0.06 0.07 1.2 0.03 2 0.483
0.24 0.19 0.16 0.13 0.69 0.01 0.67 0.25 0.096
0.01 0.02 0.04 0.04 0.02 0.02 0.02 0.04 0.057
Y
894 894 894 894 894 894 894 894 908
Vinyl acetate
0.413
0.005
0.114
0.021
Y
908
Acrylate, methyl
0.344
0.105
0.552
0.043
Y
877
Vinyl acetate
0.366
0.151
0.43
0.057
Y
877
Acrylate methyl Styrene Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile
2.08 1.06 0.172 0.241 0.017 0.071 0.198 0.188
0.327
0.191 0.78 0.026 0.06 0.026 0.06 0.056 0.033
0.031
Y
0.018 0.071 0.173 0.242
Y Y Y Y
0.017
N
908 1001 867 867 912 912 952 997
0.012 0.029 0.012 0.029 0.011
TABLE 1. cont'd Monomer 1 Pentadiene, cis-1,3Pentadiene, cis-1,3Pentadiene, trans-1,3Pentadiene, trans-1,3Pentadiene, trans-1,3Pentadiene, trans-1,3Pentadiene, trans-1,3Pentadiene, trans-1,3Pentadiene, trans-1,3Pentadiene, trans-1,3Pentadiene, trans-1,3Pentadienoate, frarcs-4-ethoxy-2,4-,ethyl Pentadienoate, frarcs-4-ethoxy-2,4-,ethyl Pentadienoate, trans-4-ethoxy-2,4Penten-2,4-one Pentene-1 Pentene-1 Pentene-1, 2-methylPentene-1, 5-cyclohexylPentene-1, 5-phenylPentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-OXO-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-OXO-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Phenol, 3-(methacryloylamino)Phenol, 4-(methacryloylamino)Phosphate diethyl isopropenyl Phosphate diethyl isopropenyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl
Monomer 2 Butadiene Pentadiene, trans-1,3Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Butadiene Methacrylate, methyl Pentadiene, cis-1,3Styrene Acrylonitrile Styrene Styrene Vinyl chloride Vinyl chloride Vinyl chloride Acrylonitrile Acrylonitrile Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Styrene Styrene Acrylonitrile Vinyl acetate Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Styrene Styrene Styrene Styrene Styrene Styrene
T1 0.26 0.86 0.104 0.095 0.018 0.064 0.132 0.114 0.09 0.379 0.37 12.2 5.4 11.8 -0.033 0.001 0.81 -1.16 -0.043 -0.026 3.29 1.57 1.29 1.4 0.923 0.747 0.635 1.12 0.568 3.39 2.02 3.06 1.67 1.24 1.72 1.69 0.72 1.55 1.09 2.56 0.748 1.14 0.952 1.67 1.04 1.05 0.725 1.09 0.99 0.86 0.03 0.44 0.486 0.521 0.946 1.16 0.42 0.258 0.0701 0.171 0.15 0.146 0.168 0.094 0.23
±95%
0.01 0.021 0.01 0.02 0.009 0.013
0.055 5.2 2.31 0.044 0.046 0.712 0.193 0.309 0.322 0.075 0.073 0.068 0.112 0.035 0.263 0.141 0.349 0.183 0.168 0.123 0.236 0.12 0.224 0.09 0.218 0.155 0.109 0.164 0.143 0.111 0.108 0.08 0.09 0.04 0.03 0.088 0.138 0.436 0.248 0.097 0.226 0.052 0.01 0.05 0.073 0.355 0.02 0.187
r2 0.63 0.37 0.07 0.06 0.069 0.068 0.085 0.079 1.22 0.404 0.86 0.04 0.01 0.08 13.84 4 2.08 1.59 4.22 3.84 0.233 0.161 0.215 0.189 0.179 0.164 0.162 0.178 0.217 0.555 0.424 0.591 0.443 0.34 0.57 0.606 0.269 0.715 0.528 0.597 0.38 0.513 0.43 0.474 0.581 0.616 0.663 0.528 0.5 0.71 15.2 1.56 2.37 2.23 1.87 1.97 2.1 2.56 2.04 0.629 0.612 0.595 0.597 0.633 0.61
±95%
Conv.
0.017 0.064 0.104 0.096
Y Y Y Y
0.018
N
0.038
Y
0.57
Y
1.78 0.68 0.45 0.48 0.069 0.028 0.051 0.05 0.014 0.015 0.015 0.02 0.009 0.032 0.022 0.046 0.032 0.031 0.023 0.045 0.027 0.048 0.02 0.03 0.034 0.022 0.034 0.023 0.025 0.024 0.023 0.02 0.06 0.04
N N N Y N N N N N N N N N N N N N N N N N N N N N N N N N N N N
0.046 0.047 0.086 0.029 0.045 0.094 0.012 0.003 0.004 0.005 0.044 0.002 0.018
N N N N N N N N N N N N N
Refs. 743 743 867 867 912 912 952 997 743 1058 743 723 723 723 112 3 329 329 24 24 930 930 930 930 930 930 930 930 930 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 896 896 650 650 971 971 971 971 971 971 971 971 971 971 971 971 971
References page II - 290
TABLE 1. cont'd Monomer 1 Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, vinyl bis(chloroethyl) Phosphate, vinyl diethyl Phosphate, vinyl diethyl Phosphate, vinyl diphenyl Phosphate, vinyl diphenyl Phosphazene, isopropenylpentafluoroPhosphazene, isopropenylpentafluoroPhosphine oxide, diphenylvinylPhosphine oxide, diphenylvinylPhosphonate, 2-(4-vinylphenyl)ethyl, diethyl Phosphonate, 4-vinylphenyl, diethyl Phosphonate, a-bromovinyl-, diethyl Phosphonate, a-carboethoxyvinyl-, diethyl Phosphonate, a-carboethoxy vinyl-, diethyl Phosphonate, a-carboethoxy vinyl-, diethyl Phosphonate, isopropenyl-, dimethyl Phosphonate, isopropenyl-, dimethyl Phosphonate, isopropenyl-, dimethyl Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl-, dibutyl Phosphonate, vinyl-, diethyl Phosphonate, vinyl-, diethyl Phosphonate, vinyl-, diethyl Phosphonate, vinyl-, diethyl Phosphonate, vinyl-, diethyl Phosphonate, vinyl-, diethyl Phosphonate, vinyl-, diethyl Phosphonate, vinyl-, diethyl Phosphonate, vinyl-, diethyl Phosphonate, vinyl-, diisobutyl Phosphonate, vinyl-, diisobutyl Phosphonate, vinyl-, diisopropyl Phosphonate, vinyl-, dimethyl Phosphonate, vinyl-, dimethyl Phosphonate, vinyl-, dimethyl Phosphonate, vinyl-, dimethyl Phosphonate, vinyl-, dimethyl Phosphonate, vinyl-, dimethyl Phosphonate, vinyl-, dimethyl Phosphonate, vinyl-, diphenyl Phosphonate, vinyl-, diphenyl Phosphonate, vinyl-, dipropyl Phosphonic acid, a-phenylvinyl Phosphonic acid, a-phenylvinylPhosphonic acid, a-phenylvinylPhosphonic acid, a-phenylvinylPhosphonic acid, a-phenylvinylPhosphonic acid, a-phenylvinylPhosphonic acid, a-phenylvinylPhosphonic acid, a-phenylvinylPhosphonic acid, a-phenylvinylPhosphonic acid, a-phenylvinylPhosphonic acid, a-phenylvinyl-
Monomer 2
r\
Styrene Styrene Vinyl chloride Vinyl chloroacetate Vinyl chloride Vinyl chloroacetate Styrene Styrene, p-chloromethylAcrylonitrile Vinyl acetate Styrene
0.108 0.03 0.15 0.374 0.327 0.53 -0.121 —0.048 0.16 1.7 1.36
Styrene Methacrylate, methyl Methacrylate, methyl Phosphonate, vinyl-, diethyl Methacrylate, methyl Methacrylate, methyl Styrene Vinyl acetate Ethylene Methacrylate, methyl Styrene Styrene Styrene Styrene Styrene Vinyl acetate Vinyl acetate Vinyl acetate Styrene Methacrylate, methyl Methacrylic acid Phosphonate, a-carbomethoxyvinyl-, diethyl Styrene Styrene Styrene Styrene Vinyl acetate Vinyl acetate Ethylene Styrene Styrene Butadiene, 2-chloroStyrene Styrene Styrene Styrene Vinyl acetate Vinyl acetate Ethylene Styrene Styrene Vinylidene cyanide Acrylic acid Acrylonitrile Acrylonitrile Butadiene, 2,3-dichloroButadiene, 2,3-dichloroButadiene, 2-chloroButadiene, 2-chloroMethacrylate, methyl Methacrylic acid Methacrylonitrile
1.4 0.04 0.05 0.55 0.01 0.2 0.23 0.99 7.73 0.26 0.02 0.16 0.2 0.18 0.18 0.85 0.85 0.47 -0.12 0.04 0.15 0.62
±95% 0.034 0.23 0.047 0.046 0.023 0.12 0.088 0.067
2.19 0.39
2.33
r2 0.599 2.47 3.4 2.01 3.009 1.42 1.6 1.64 3.8 0.38 0.55 0.7 1.25 1 0.62 4.7 30 8.6 0.14 0.077 29.9 2.46 2.3 2.2 6.32 6.32 0.09 0.09 0.33 4.97 11.1 1.9 0.55
±95% 0.002 0.78 0.21 0.2 0.077 0.15 0.27 0.58
Conv.
Refs.
N Y Y Y Y Y Y Y
971 133 779 779 779 779 765 765 843 843 796
0.003
Y
0.43
Y
3.44
Y
-0.15 -0.52 0.02 0 0.74 0.6
2.18 0.22
4.36 1.59 2.45 3.88 0.04 0.09
4.27 0.24
Y Y
-0.32 -0.52 0.1
1.46 2.52
3.87 2.57 7.5
1.59 2.13
Y Y Y Y
0.4 0.15 0.02 0.74 0.74 1.66 -0.38 -0.41 0.1 0.04 -0.45 0 0.07 0.07 0.1 0.1 -0.063 0.17 0
2.22 0.29 0.72 0.83 0.41
0.077 0.3
4.61 2.45 2.45 0.04 0.04 0.088 1.74 3.81 4.58 0.7 0.34 2.36 7.75 7.75 7.5 7.5 1.362 1.49 2.24
0.01 0.16 0.68
Y Y Y
0.13 0.12
Y Y
0.084 0.16
Y Y
796 684 684 684 684 684 684 684 801 410 133 410 485 592 594 592 594 595 129 684 431 684 129 18 592 684 592 684 801 129 129 594 129 129 592 594 592 594 801 129 129 921 132 132 590 588 597 546 597 131 130 590
TABLE 1. cont'd Monomer 1 Phthalide, 3-(4-vinylphenyl)Phthalimide, N-(4-vinylphenyl)Phthalimide, Af-(methacryloyloxy)Phthalimide, AKmethacryloyloxy)Phthalimide, AA-(methacryloyloxy)Phthalimide, N-vinylPhthalimide, TV-vinylPhthalimide, N-vinylPinene Pinene, aPiperidinol, 4-, A/-methyl-4-(vinylethynyl)Piperylene, cisPiperylene, transPropanesulfonate, 3-[diethyl[2-(2-methacroyloxyethoxy)ethyl Propene, 3,3,3-trichloroPropene, 3,3,3-trichloroPropene, 3,3,3-trichloroPropene, 1-chloro-cwPropene, 1-chloro-cwPropene, 1-chloro-cwPropene, 1-chloro-cwPropene, \-ch\oxo-transPropene, \-ch\oxo-transPropene, \-c\\\oxo-transPropene, \-c\\\oxo-transPropene, 2,3-dichloroPropene, 2,3-dichloroPropene, 2,3-dichloroPropene, 2,3-dichloroPropene, 2,3-dichloroPropene, 2-chloroPropene, 2-chloroPropene, 2-chloroPropene, 2-chloroPropene, 2-chloroPropene, 2-chloro-3-hydroxyPropene, 2-chloro-3-hydroxyPropene, 2~chloro-3-hydroxyPropene, 3-chloro-2-chloromethylPropenyl methyl ketone Propenyl, 2-, acetate Propenyl, 2-chloro-, acetate Propenyl, 2-chloro-, acetate Propenyl, 2-chloro-, acetate Propenyl, 2-chloro-, acetate Propenyl, 2-chloro-, acetate Propenyl, 2-methyl-, acetate Propenyl, 2-chloro-, acetate Propenyl, 2-methyl-, acetate Propenyltriethoxysilane Propiolactam, A^-phenyl-a-methylenePropionate, vinyl Propylene Propylene Propylene Propylene Propylene Propylene Propylene Propylene Propylene Pyrazole, 3-methyl-l-vinylPyrazole, 5-methyl-l-vinylPyrazole, N-vinyl-3,5-dimethyl-
Monomer 2 Acrylonitrile Acrylate, methyl Acrylate, methyl Acrylonitrile Methacrylate, methyl Acrylonitrile Maleic anhydride Styrene Acrylonitrile Methacrylate, methyl Maleimide Methacrylic acid Methacrylic acid Acrylate, ethyl Acrylonitrile Styrene Vinyl acetate Acrylonitrile Maleic anhydride Vinyl acetate Vinyl chloride Acrylonitrile Maleic anhydride Vinyl acetate Vinyl chloride Carbazole, TV-vinylMethacrylate, methyl Methacrylic acid Styrene Styrene Acrylonitrile Vinyl acetate Vinyl chloride Vinyl chloride Vinylidene cyanide Methacrylate, methyl Methacrylic acid Styrene Styrene Styrene Vinyl chloride Acrylate, methyl Acrylic acid Methacrylate, methyl Styrene Vinyl chloride Methacrylate, methyl Styrene Vinylidene chloride Vinyl chloride Styrene Ethylene, chlorotrifluoroAcrylic acid Ethylene Ethylene Ethylene, chlorotrifluoroVinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Pyrazole, 5-methyl-l-vinylPyrazole, 3-methyl-l-vinylStyrene
rx 0.43 1.56 1.23 1.45 1.45 0.24 0.344 0.07 13.5 0.08 2.05 0.38 0.33 0.19 0.1 0 0.19 -0.12 -0.022 -0.012 0.1 0.01 0.05 0.011 0.33 0 0.18 0 0.05 0.036 -0.023 1.65 4.75 0.58 0.001 0 0 0 0.01 0.08 0.25 0 0 0 0 0 0 0 0 0.406 0.63
±95% 0.19 0.168 0.072 0.151 0.02 0.061 0.11 0.1 0.03
0.02
0.19 0.08 0.061 0.63 0.17 0.015 0.074 0.4 0.1 0.01 0.062 0.36 5.12 0.003
0.1 0.3
0.106 0.04
r2 0.084 1.14 0.193 0.204 0.69 0.43 0.008 6.27 0.07 10 0.49 0.4 0.38 3.97 12.2 6.9 0.19 23.37 0.347 7.08 11.52 19.61 0.28 3.13 4.45 1 6.02 4 3.51 3 1.164 0.186 0.095 0.75 0.204 4.4 4.5 12.5 3.37 18.12 2.2 0.7 1 1 4.1 0.7 10 71 2.4 0.626 0.08
±95%
Conv.
Refs.
0.053
Y
0.028 0.016 0.048 0.01 0.012 0.66 0.01
Y Y Y
721 636 979 979 979 1046 284 163 936 848 948 773 773 962
Y Y
0.01
1.03
Y
2.99 0.082 0.35 2.14 1.72 0.012 0.15 0.81
Y Y Y Y Y Y Y Y
1.66
N
0.18
N
0.053 0.091 0.085
Y Y Y
0.079
Y
0.73 6.09
0.025 0.01
Y Y Y
0.62 0.08 0.196 3.1 -0.02 0.09 0.42 1.35 0.049
0.07 0.023 0.21 0.04
0.011
3.43 3.2 0.02 2.35 -0.05 5.16 2.45 2.9 1.35 0.42 8.663
0.08 0.14 0.1 0.06
0.196
N Y N N
402 402 402 181 181 181 181 181 181 181 181 376 11 445 11 983 181 181 181 517 82 445 445 445 806 806 189 445 445 445 445 445 470 470 470 237 1002 1097 183 388 477 318 155 329 355 560 588 898 898 806
References page II - 290
TABLE 1. cont'd Monomer 1 Pyridazinone, 3-(2-vinyl)-6-methylPyridazinone, 3-(2-vinyl)-6-methylPyridazinone, 3-(2-vinyl)-6-methylPyridazinone, 3-(2-vinyl)-6-methyl4,5-dihydroPyridazinone, 3-(2-vinyl)-6-methyl4,5-dihydroPyridazinone, 3-(2-vinyl)-6-methyl4,5-dihydroPyridazone, 2-vinyl-3Pyridazone, 2-vinyl-3Pyridazone, 2-vinyl-6-methyl-3Pyridazone, 2-vinyl-6-methyl-3Pyridazone, 2-vinyl-6-methyl-4,5-benz-3Pyridazone, 2-vinyl-6-methyl-4,5-benz-3Pyridazone, 2-vinyl-6-phenyl-3Pyridazone, 2-vinyl-6-phenyl-3Pyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-methy 1-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinyl-
Monomer 2
T1
±95%
r2
±95%
Conv.
Refs.
Acrylonitrile Methacrylate, methyl Styrene Acrylonitrile
0.19 0.56 0.85 0.02
0.04 0.04 0.05 0.02
0.32 0.86 0.9 0.74
0.02 0.02 0.03 0.02
N N N N
340 340 340 340
Methacrylate, methyl
0.08
0.03
1.19
0.04
N
340
Styrene
0.13
0.03
5.92
0.1
N
340
Methacrylate, methyl Styrene Methacrylate, methyl Styrene Methacrylate, methyl Styrene Methacrylate, methyl Styrene Acrylate, methyl Acrylonitrile Butadiene Butadiene Butadiene Caprolactam, N-vinylCaprolactam, Af-vinylItaconate, diethyl Itaconate, dimethyl Methacrylate, methyl Methacrylic acid N-Vinylpyrrolidone Styrene Styrene Styrene Styrene Sulfonic acid, o-methacryloylaminobenzeneSulfonic acid, p-methacryloylaminobenzeneVinyl acetate Acetylene, phenylAcrolein Acrylate, butyl Acrylate, butyl Acrylate, ethyl Acrylate, ethyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylonitrile Acrylonitrile Butadiene, 1,4-dicarboxylate-, diethyl Butadiene, 1-carboxylate, ethyl Butadiene, 2-chloroCaprolactam, N-vinylCaprolactam, N-vinylIsoprene Isoprene Methacrylate, 2-hydroxyethyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylic acid Methacrylic acid N-Vinylpyrrolidone
1.56 0.43 0.3 1.2 0.27 0.24 0.49 1.45 1 0.31 0.47 0.72 0.41 11.58 11.58 0.51 0.88 0.54 0.85 13 0.75 0.68 1.2 0.78 -0.002 -0.054
0.03 0.031
0.63 0.53 0.16 0.9 1.65 0.7 0.58 0.51 0.18 0.16 0.61 1.32 1.29 0.04 0.04 0.17 0.22 0.42 0.43 0.039 0.74 0.6 0.72 0.73 1.83
0.048
2.72
0.3 0.02 0.02
0.19 2 0.08
9 -0.12 2.51 2.59 0.28 2.25 2.13 1.72 2.12 21.9 0.44 0.41 0.4 0.06 4.35 4.35 0.47 0.46 0.64 0.73 0.86 0.76 0.64 1.1 1.69 1.38 12.4
0.05 0.01
N N
0.02
N
0.09
N
0.006 0.03
N
0.03 0.218
N Y
897 897 897 897 897 897 897 897 232 232 462 520 56 589 592 545 545 232 552 1070 232 500 514 56 1006
0.525
Y
1006
0.14
Y N
0.01 0.06
N N
0.4 0.03 0.03
Y N N
0.03 0.23
N
0.04 0.02
N N
0.19
Y
0.04 0.21
N Y
0.11 0.03 0.14 0.1 0.54 0.26 0.1 0.08 0.07
0.16 0.06 0.12 0.08 0.71 2.3
2.64 0.1 0.11 0.21 0.21 0.37 0.17 0.2 0.05 0.1 0.69 0.8 5.19 0.12 0.12 0.59 0.58 0.56 0.42 0.4 0.35 0.31 0.27 0.58 0.44 0.014
0.002
812 192 208 236 78 250 832 2 231 749 456 50 327 791 457 589 592 456 458 342 231 532 6 623 749 15 498 1070
TABLE 1. cont'd Monomer 1 Pyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinyl-5-ethylPyridine, 2-vinyl-5-ethylPyridine, 2-vinyl-5-ethylPyridine, 2-vinyl-5-ethylPyridine, 2-vinyl-5-ethylPyridine, 3-ethynyl-6-methylPyridine, 3-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, TV-oxide-, 2-vinyl-5-ethylPyrimidine-2-one, 1,3-divinylhexahydroPyrimidine, 2-TV-TV-dimethylamino-4-vinylPyrimidine, 4-vinylPyrrolidone, l-benzyl-3-methylene5-methylPyrrolidone, l-benzyl-3-methylene5-methylPyrrolidone, l-benzyl-3-methylene5-methylPyrrolidone, TV-vinylPyrrolidone, N-vinylPyrrolidone, TV-vinylPyrrolidone, N-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, AT-vinylPyrrolidone, N-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, N-vinylPyrrolidone, N-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinyl-
Monomer 2
rx
±95%
r2
±95%
Conv.
Refs.
0.04 0.15
Y N
0.18 0.17
N Y
0.004
N
0.07 0.02 0.05
N N N
0.01 0.017 0.04
N Y N
0.03
N
0.04
N
0.09 0.07 0.18 1.5 0.16 0.22
0.073 0.46 0.5 0.55 0.57 0.55 0.14 -0.11 O 0.18 0.02 0.06 0.39 0.74 2.3 0.69 0.291 0.23 0.29 0.2 0.15 0.11 0.09 0.1 0.1 0.32 0.62 0.57 0.54 0.01 0.52 -0.73
0.04 0.02 0.01 0.002 0.07 1.09
N N N
0.4 0.88 0.03 0.071 1.06 0.24
0.03 - 0.23 0.06 0.59 0.338 0.219 0.125
0.36 0.11 0.13 0.017 0.095 0.025
Y N Y Y Y
838 231 41 456 499 532 2 6 6 231 115 50 231 231 784 342 667 78 832 231 424 115 50 589 592 424 342 231 691 1070 231 79 154 395 337 806 800 243 243 633
Oct-1-ene, 6,6-dimethyl-4,8-dioxaspiro 2.216 Styrene 0.75 Styrene 1.27 Styrene 1.81 Styrene 1.33 Styrene 1.14 Styrene, 2,5-dichloro0.62 Vinyl acetate 13.65 Vinyl acetate 30 Acrylate, methyl 1.32 Acrylonitrile 0.43 Acrylonitrile 0.43 Methacrylate, methyl 0.68 Styrene 1.09 Styrene 0.15 Methacrylate, 2-hydroxyethyl 0.73 Acrylate, (-)-menthyl 2.32 Acrylate, butyl 4.3 Acrylate, ethyl 2.58 Acrylate, methyl 1.78 Acrylate, methyl 2.14 Acrylonitrile 0.41 Acrylonitrile 0.34 Caprolactam, TV-vinyl4.43 Caprolactam, TV-vinyl4.43 Isoprene 2.49 Methacrylate, 2-hydroxyethyl 0.9 Methacrylate, methyl 0.77 Methacrylate, methyl 0.99 TV-Vinylpyrrolidone 9.8 Styrene 0.69 Styrene 1.04 Vinyl chloride Vinyl ether 32 Vinylhydroquinone 0.53 Styrene 2.27 Acrylate, ethyl -0.05 Styrene 1.404 Styrene 2.38 Acrylate, methyl 1.58
0.062 0.32
Methacrylate, methyl
2.28
0.47
0.387
0.07
Y
633
Styrene
0.71
0.17
0.555
0.053
Y
633
0.008
0.163 0.52 0.88 0.07
0.02
N Y
0.69
N
326 840 790 250 694 213 599 859 81 816 248 245 647 647 830 121 364 323 657 840
Acenaphthalene Acrylate, 2,4,5-trichlorophenyl 0.012 Acrylate, 2-chloroethyl 0.03 Acrylic acid 0.1 Acrylic acid, oc-bromo0.25 Acrylonitrile Acryloyl chloride 0.04 Caprolactam, N-vinyl2.8 Carbamate, N-vinyl-, ethyl 1.77 Cinnamate, a-cyano-, methyl 0.044 Crotonaldehyde 0.42 Crotonic acid 0.84 Dioxolane, l,3,4-methylene-2-trichlor 2.98 Dioxolane, 1,3-, 4,4-dimethyl-5-methyl 3.87 Ethylene, chlorotrirluoro0.38 Fumarate, dioctyl 0.02 Imidazole, 1-vinyl0.16 Maleimide, TV-(2-hydroxyethyl)0.002 Methacrylate, 2-bromoethyl 0.02 Methacrylate, 2-hydroxyethyl -0.019
0.12 3.64 0.03 0.18 0.06 0.12 0.04 0.45 0.34 0.32 0.13
0.21
N Y Y
Y 0.12 0.008 0.02 0.07
0.01 0.074 0.002 0.046
0.15 1.7 0.371 -0.001 -0.15 0 0.04 0.01 0.3 0.04 0.96 0.038 2.44 4.841
0.05 0.001 0.01 0.03
Y Y N N
0.04 0.19 0.01
N Y Y
0.133
Y
References page II-290
TABLE 1. cont'd Monomer 1 Pyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, a-methylene-TV-methylQuinine Quinoline, 2-vinylQuinoline, 2-vinylQuinoline, 2-vinylQuinoline, 2-vinyl5-Ethyl TV-vinyl-TV-methylthiolcarbamate S-Ethyl TV-vinyl-TV-methylthiolcarbamate S-Vinyl TV, TV-diethylthiolcarbamate 5-Vinyl ,V, TV-diethylthiolcarbamate Silane, 7-methacryloxypropyltrimethoxySilane, 7-methacryloxypropyltrimethoxySilane, 7-methacryloxypropyltrimethoxySilane, methacryloxypropyldimethoxymethylSilane, methacryloxypropyltrimethoxyStilbene Stilbene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
Monomer 2 Methacrylate, ferrocenylmethyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacryloyl chloride Methacryloylacetone Oct-1-ene, 6,6-dimethyl-4,8-dioxaspiro Oxazoline, 2-, 2-isopropenylStyrene Succinimide, TV-vinylTriazine, 2-allyloxy-4,6-dichloroVinyl acetate Vinyl acetate Vinyl acetate Vinyl benzoate Vinyl butyl ether Vinyl chloride Vinyl chloride Vinyl chloride Vinyl cinnamate Vinyl cyclohexyl ether Vinyl cymantrene Vinyl ethylene glycol glycidyl ether Vinyl ethyleneglycol glycidyl ether Vinyl isopropyl ether Vinyl phenyl ether Vinylene carbonate Vinylferrocene Methacrylate, methyl TV-Vinylpyrrolidone Butadiene, 2-chloroIsoprene Styrene Styrene Styrene Vinyl acetate Styrene Vinyl acetate Acrylonitrile Methacrylate, methyl Styrene Imidazole, TV-VinylImidazole, TV-VinylAcenaphthalene Styrene 2-Oxazoline, 2-isopropenyl3-Pyridazone, 2-vinyl3-Pyridazone, 2-vinyl-6-methyl3-Pyridazone, 2-vinyl-6-methyl4,5-benz-33-Pyridazone, 2-vinyl-6-phenyl4-Pentenoate, 3-oxo-, ethyl 4-Pentenoate, 3-oxo-, ethyl 4-Pentenoate, 3-oxo-, ethyl 4-Pentenoate, 3-oxo-, ethyl 4-Pentenoate, 3-oxo-, ethyl 4-Pentenoate, 3-oxo-, ethyl 4-Pentenoate, 3-oxo-, ethyl 4-Pentenoate, 3-oxo-, ethyl 4-Pentenoate, 3-oxo-, ethyl Acenaphthalene Acetylene, phenyl-
rx
±95%
r2
±95%
Conv.
Refs. 325 213 320 321 36 691 599 339 838 862 36 96 826 103 121 36 253 215 40 582 582 200 214 308 369 818 215 214 103 308 641 922 456 456 456 458 197 197 197 197 977 977 977 1095
0.073
0.096
2.57
2.77
- 0.05 -0.032 -0.052 0.01 0.05 0.008 -0.009 0.01 0.057 0.97 0.98 1.06 1.75 3.4 2.507 1.49 0.38 0.34 0.73 0.01 1.91 0.037 1.4 1.4 0.87 4.48 1.08 0.364 0.24 0.37 0.38 0.53 2.09 2.69 -0.11 1.22 0.1 1.89 3.79 2.06 0.868 1.39
0.08 0.068 0.028 0.15
5.62 4.63 4.36 4.04 0.58 5.66 0.552 3.5 17.2 3.67 0.5 0.26 0.19 0.195 0.408 -0.027 0.53 0.55 0.74 1.2 -0.11 0.093 0.06 0.06 0.03 0.253 0.056 0.71 0.577 2.2 2.1 1.88 0.49 0.49 10 0.67 4.45 0.133 0.094 0.788 0.425 0.079
0.3 0.34 0.61 0.61
Y Y N Y Y N
0.4 0.075
Y Y
1.55 0.89
Y N
0.25 1.77 0.057 0.03 0.063
Y N Y Y Y
0.59 0.053
Y Y
2.09 0.007 0.059 0.16 0.058
Y Y Y Y Y
1.72 0.1 0.48 0.025 0.034 0.082 0.048
Y Y Y Y Y Y Y
0.04 0.23 0.17 0.03
Y N N
0.712 0.193 0.309 0.322 0.075 0.073 0.068 0.112 0.035
N N N N N N N N N
0.12
Y
2.27 -0.01 0 0.67 0.53 0.9 0.7 0.51 0.233 0.161 0.215 0.189 0.179 0.164 0.162 0.178 0.217 3.81 0.324
0.004 0.018 0.028 0.42 0.25 2.79 0.21 0.039 0.95
9.39 0.03 9.3 0.1 0.11 0.068 0.14
0.26 1.17 0.34 0.77 0.594 0.309 0.096 1.12 0.04 0.09 0.02
0.069 0.028 0.051 0.05 0.014 0.015 0.015 0.02 0.009 0.02
0.158 5.65 3.92 0.64 0.43 1.2 0.24 1.45 3.29 1.57 1.29 1.4 0.923 0.747 0.635 1.12 0.568 0.33 0.33
1088 725 725 894 897 897 897 897 930 930 930 930 930 930 930 930 930 525 357
TABLE 1. cont'd Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
Monomer 2 Aconitate, trimethyl Acrolein Acrolein Acrolein Acrolein, 2-chloroAcrolein, methylAcrolein, methylAcrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide, 2-chloro-AyV-dimethylAcrylamide, AT,iV-dibutylAcrylamide, N,N-diethy\Acrylamide, JV,N-diethylAcrylamide, AW-diethyl Acrylamide, AW-dimethylAcrylamide, iV,iV-dimethylAcrylamide, MW-dimethylAcrylamide, N-(2-propionamido)Acrylamide, N-methylolAcrylamide, N-methylolAcrylamide, N-octadecylAcrylamide, Af-octylAcrylamido, 1- , -1-deoxy-D-glucitol Acrylamidomethylamino, p-, azobenzene Acrylate, 2,3-dibromopropyl Acrylate, 2,4,5-trichlorophenyl Acrylate, 2,4,6-tribromophenyl Acrylate, 2-chloroethyl Acrylate, 2-chloroethyl Acrylate, 2-chloroethyl Acrylate, 2-chloroethylglucitol Acrylate, 2-cyanoethyl Acrylate, 2-ethylhexyl Acrylate, 2-ethylhexyl Acrylate, 2-nitrobutyl Acrylate, 3,4-epoxyhexahydrobenzyl Acrylate, P-acetoxymethyl-, methyl Acrylate, p-ethoxy-, ethyl Acrylate, a-(4-chlorobenzyl)-, ethyl Acrylate, a-(4-cyanobenzyl)-, ethyl Acrylate, a-(4-methoxybenzyl)-, ethyl Acrylate, a-(hydroxymethyl)-, methyl Acrylate, a-[2,2-bis(carbomethoxy)ethyl]-, methyl Acrylate, a-acetoxy-, ethyl Acrylate, a-benzyl-, ethyl Acrylate, a-benzyl-, methyl Acrylate, oc-bromo-, ethyl Acrylate, oc-butyl-, methyl Acrylate, a-chloro-, ethyl Acrylate, a-chloro-, methyl Acrylate, a-cyano-, methyl Acrylate, a-cyclohexyl-, methyl Acrylate, a-ethyl-, methyl Acrylate, a-ethyloxymethyl-, methyl Acrylate, a-fluoro-, methyl Acrylate, a-hexafluoropropyloxymethyl-, methyl Acrylate, a-hydroxymethyl-, ethyl Acrylate, a-isobutyl-, methyl
rx 1.026 0.257 0.22 0.205 0.02 0.173 0.41 1.17 1.21 1.49 1.13 0.65 1.05 1.29 1.6 1.23 1.36 1.54 1.15 1.37 1.32 1.84 0.03 1.55 2.08 2.715 2.42 0.083 0.42 0.277 0.2 0.55 0.494 0.54 0.49 0.399 0.96 0.94 0.35 0.27 0.34 46.98 0.04 0.06 0.33 0.36 0.58
±95% 0.091 0.017 0.02 0.006 0.05 0.017 0.06 0.04 0.16 0.03 0.065 0.058
0.35 0.1 0.12 0.21 0.05 0.12 0.244 0.08 0.048 0.47 0.097 0.2 0.032 0.3 0.03 0.3 27.03 0.09 0.05 0.3
0.557 0.14 0.57 0.02 0.812 0.08 0.25 0.05 1.615 0.758 0.37 0.66 0.23
0.031 0.17 0.028 0.04 0.043 0.07
0.468 0.974
0.03 0.022
0.01 0.048 0.014 0.17
r2
±95%
Conv.
Refs. 147 291 292 307 806 223 589 295 314 314 314 343 555 917 806 739 739 739 170 315 315 295 596 891 290 806 258 858 643 622 643 140 178 790 806 178 126 463 234 680 1091 194 806 806 806 932 1092
-0.013 0.216 0.02 0.32 0.15 0.833 0.3 0.58 1.32 0.33 0.59 8.97 0.2 -0.036 0.294 0.39 0.34 0.18 0.12 0.49 0.47 0.86 0.48 0.4 0.54 0.258 0.03 8.5 0.16 0.23 0.1 0.1 0.139 0.12 0.14 0.128 0.31 0.26 0.12 1.97 0.19 -0.21 1.03 0.65 0.71 0.34 0.09
0.009 0.036 0.01 0.002 0.07 0.092
Y Y N Y
0.12 0.13 0.14
N N N
0.43
N
0.152 0.058
Y
0.3 0.15 0.2 0.3
N N N N
Y
0.03 0.14 0.119 0.02
N
0.021
Y
0.17 0.083
Y Y
0.09 0.074 0.6
Y N
0.01 0.35
N N
0.44 0.13 0.09 0.24
Y
0.173 0.9 0.175 0.44 0.205 0.32 0.3 0.61 -0.001 0.197 0.24 0.16 0.07
0.01 0.2 0.053 0.08 0.053 0.11
Y
0.546 0.202
0.127 0.042
0.05 0.034 0.014
Y
Y Y N Y Y
0.11 Y Y
244 806 49 806 49 806 74 141 49 49 1047 806 1047 982 49
References page II-290
TABLE 1. cont'd Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
Monomer 2
#*i
Acrylate, a-isopropyl-, methyl 1.872 Acrylate, a-isopropyloxymethyl-, 0.41 methyl Acrylate, a-methoxy-, methyl 1.131 Acrylate, a-phenoxymethyl-, methyl 0.176 Acrylate, a-phenyl-, chloroethyl 0.025 Acrylate, a-phenyl-, methyl 0.06 Acrylate, a-phenyl-, methyl 0.03 Acrylate, a-phenyl-, methyl 0.06 Acrylate, a-phenyl-, methyl 1.176 Acrylate, a-phenyl-, propyl 0.03 Acrylate, a-phenyl-, butyl 0.04 Acrylate, a-propyl-, methyl 0.821 Acrylate, a-propyloxymethyl-, methyl 0.47 Acrylate, a-sec-butyl-, methyl 2.29 Acrylate, a-tetrafluoropropyloxymethyl-, 0.37 methyl Acrylate, a-trifluoroethyloxymethyl-, 0.26 methyl Acrylate, a-trimethylsiloxy-, methyl 0.46 Acrylate, benzyl 0.494 Acrylate, benzyl 0.534 Acrylate, butyl 0.79 Acrylate, butyl 0.79 Acrylate, butyl 0.75 Acrylate, butyl 1.23 Acrylate, butyl 0.44 Acrylate, butyl 0.84 Acrylate, butyl 0.66 Acrylate, butyl 0.82 Acrylate, butyl 0.8 Acrylate, butyl 0.698 Acrylate, butyl 0.698 Acrylate, c/s-(3-cyano-, methyl Acrylate, cyclododecyl 0.47 Acrylate, cyclododecyl 0.54 Acrylate, cyclododecyl 0.461 Acrylate, cyclohexyl 0.913 Acrylate, cyclohexyl 0.885 Actylate, cyclohexyl 0.53 Acrylate, cyclohexyl 0.7 Acrylate, cyclohexyl 0.58 Acrylate, di-, copper 1.74 Acrylate, di-, copper 5.94 Acrylate, di-, nickel 1.83 Acrylate, di-, zinc 1.1 Acrylate, diethylaluminum -0.002 Acrylate, diethylaluminum Acrylate, ethyl 0.699 Acrylate, ethyl 1.01 Acrylate, ethyl 0.79 Acrylate, ethyl 0.8 Acrylate, ethyl 0.8 Acrylate, ethyl 0.787 Acrylate, ethyl 0.787 Acrylate, ferrocenylmethyl 1.87 Acrylate, ferrocenylmethyl 2.3 Acrylate, ferrocenylmethyl 2.5 Acrylate, glycidyl 0.6 Acrylate, glycidyl 0.73 Acrylate, heptafluorobutyl 0.31 Acrylate, isopropyl 0.755 Acrylate, methyl 0.82 Acrylate, methyl 0.192 Acrylate, methyl 0.722
±95%
r2
±95%
Conv.
Refs. 49 1047
0.052
0.036 0.26
0.034
Y
0.078 0.05 0.015
0.513 0.256 0.201 1 0.4 0.45 1.275 0.126 0.107 0.208 0.29 0.004 0.17
0.058 0.102 0.09
Y Y
0.008 0.063 0.055 0.07
Y Y Y Y
0.024
Y
0.015 0.015 0.022 0.029 0.068
0.2 0.05 0.028 0.08 0.11 0.1 0.21 0.03 0.2
1.42 0.2 0.248 0.25 0.34 0.38 -0.106 0.29 0.18 0.19 0.21 0.15 0.164 0.164
1047 0.12 0.041 0.05 0.06 0.05 0.099 0.05 0.03
Y Y
N N N
N 0.14 0.08 0.07 0.107 0.102 0.11 0.12 0.1 0.03 0.05 0.02 0.02 0.016
0.34 0.31 0.301 0.272 0.254 0.16 0.17 0.18 0.56 0.12 0.53 0.9 0.046
0.15 0.08 0.072 0.048 0.141 0.13 0.09 0.07 0.09 0.08 0.06 0.07 0.035
0.072
0.139 0.16 0.19 0.2 0.48 0.152 0.152 -0.016 0.02 0.02 0.17 0.24 0.049 0.195 0.24 0.8 0.168
0.085
N N N N Y Y Y
0.06
Y
0.58 0.013 0.027
N Y Y
0.21 0.067
Y Y
0.17
0.34 0.01 0.024 0.057 0.056
806 1048 488 141 399 488 49 488 488 49 1047 49 1047
1101 178 277 1032 1032 1032 19 20 38 38 463 549 612 632 1034 806 806 806 1061 806 806 806 806 829 829 829 829 652 652 178 463 530 530 542 673 677 293 293 576 114 126 206 178 139 14 151
TABLE 1. cont'd Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
Monomer 2 Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, octadecyl Acrylate, octadecyl Acrylate, octadecyl Acrylate, octadecyl Acrylate, octyl Acrylate, p-(cinnamoylamino)phenyl Acrylate, pentabromophenyl Acrylate, pentachlorophenyl Acrylate, tetrahydrofurfuryl Acrylate, thio-, butyl Acrylate, thio-, ethyl Acrylate, thio-, tert-butyl Acrylate, trifluoro-, methyl Acrylate, trifluoro-, methyl Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid, 2-benzamidoAcrylic acid, Af-acetyl-oc-aminoAcrylic anhydride Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile- 2-chloroAcrylonitrile, 2-fluoroAcrylonitrile, a-chloroAcrylonitrile, a-fluoroAcrylonitrile, oc-hydroxymethylAcrylonitrile, a-methoxyAcryloyl chloride Acryloyloxy, 2-, benzoic acid Adipate, divinyl Allyl acetate Allyl acetate Allyl chloride Allyl chloride Allyl chloride Allyl glycidyl hexahydrophthalate Allyl glycidyl phthalate
rx 0.75 0.75 0.68 0.9 0.65 0.4 0.871 0.777 0.44 0.79 0.44 0.39 1.08 0.16 2.11 0.475 0.439 0.18 0.157 1.4 1.4 0.25 1.1 0.15 0.22 0.253 0.25 0.25 0.15 0.13 0.91 0.16 0.33 0.29 0.4 0.36 0.39 0.37 0.37 0.4 0.3 0.33 0.33 0.36 0.46 0.41 0.43 0.55 0.35 0.014 0.13 0.44 0.205 0.534 0.1 0.06 20.36 62.8 90 35.55 36.8 34.3 34.8
±95%
0.022 0.018
0.11
0.186 0.14 0.038 0.034
0.069
0.01 0.04
0.004 0.04 0.029 0.069 0.05 0.02 0.26 82.7 15.82
r2 0.18 0.18 0.14 0.07 0.3 0.16 0.148 0.37 0.18 0.31 0.18 0.01 0.35 0.1 0.9 0.489 0.421 0.291 0.368 0 0 0.05 0.08 0.25 0.35 0.136 0.15 0.45 0.25 0.78 0.44 0.1 0 0.02 0.05 0.03 0.06 0.05 0.07 0.04 0.17 0.17 0.15 0.17 0.07 0.06 0.03 0.06 0.01 0.087 0.03 0.03 0.528 0.312 0.02 0.64 0.011 0.01 0 0.05 0.03 0.06 0.14
±95%
0.026 0.12
Conv.
Y Y
0.53
0.196 0.17 0.075 0.055
0.029
Y
0.004
N
0.06
N
0.04
Y Y
0.02 0.086 0.054 0.02 0.02 0.011 0.05 0.16
Y N N Y N Y Y
Refs. 393 397 463 495 496 496 865 290 290 290 290 806 685 643 900 806 806 806 806 595 598 312 312 397 414 47 490 542 561 1019 661 219 140 198 269 396 403 417 543 60 727 727 727 727 727 727 727 727 812 884 884 806 850 981 806 220 651 815 1053 470 10 204 438 782 782
References page II - 290
TABLE 1. cont'd Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
Monomer 2 Allyl trichloroacetate Azlactone, 2-vinyl-4,4-dimethylAzobenzene, 4-(acrylamidomethylamino)Benzimidazole, vinylmercaptoBenzothiazole, vinylmercaptoBenzothiazole, vinylmercaptoBenzothiazolone, N- [(methacroyloxy )methyl] Benzoxazole, vinylmercaptoBicyclo[2,2,l]hept-2-ene5,6-dicarboximide, iV-benzyl Bicyclo[2,2,l]hept-2-ene5,6-dicarboximide, N-benzyl Borazine, (3-vinyl Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene, 1,4-dicarboxylate-, diethyl Butadiene, 1-chloroButadiene, 1-phthalimidoButadiene, 1-succimmidoButadiene, 2,3-dichloroButadiene, 2,3-dichloroButadiene, 2,3-dimethylButadiene, 2-chloroButadiene, 2-chloroButadiene, 2-fluoroButadiene, 2-fluoroButadiene, 2-trimethylsilyloxyButadiene-1-carboxylate, 5(-)-a-phenethyl Butadiene-1-carboxylate, ethyl Butadiene- 1-carboxylic acid Butadiene-1-carboxylic acid Butenoate, 3-phenyl-3-, methyl Bntyrolactone, a-methyleneCaprolactam, N-vinylCarbamate, N, N-diethyl-, vinyl Carbazole, N-methyl-3-vinylCarbazole, JV-vinylCarbazole, Af-vinylCarbazole, N-vinylCinnamate, 2-chloroethyl Cinnamate, a-cyano-, 2-ethylhexyl Cinnamate, oc-cyano-, benzyl Cinnamate, a-cyano-, butyl Cinnamate, a-cyano-, cyclohexyl Cinnamate, a-cyano-, ethyl Cinnamate, a-cyano-, hexyl Cinnamate, a-cyano-, methyl Cinnamate, benzyl Cinnamate, butyl Cinnamate, ethyl Cinnamate, ethyl
r\
±95%
r2
±95%
Conv.
Refs.
Y
913 1011 880
2.32 0.175 0.083
0.15 0.054 8.5
0.81 0.237
0.02 0.129
6.51 2.171 3.02 0.35
0.51 0.07 0.14 0.02
0.56 0.349 0.5 3.1
0.41 0.087 0.095 0.01
Y Y Y
764 764 764 960
0.19
0.24 0
0.12
Y
764 994
2.87 18.2 89.2 4.53 0.84 0.37 0.38
0 0.62 0.4 0.25
0.001 1.44 1.55 1.37
994 0.016 0.56 0.14
Y N Y
0.58 0.44 0.6 0.44 0.38 0.68 0.82 0.83 0.64 0.09 0.27 0.299 0.286 0.25 0.05 0.534 0.05 0.025 0.214 0.22 0.64 0.45
0.13
1.35 1.59 1.8 1.4 1.4 0.5 1.38 1.83 1.38 0.55 1.44 1.56 1.68 8.65 10.6 1.048 7.84 5.98 2.1 1.24 1.2 6.81
0.12 0.15 0.08 1.97 0.14 0.2 29.56 0.735 6 5.93 5.72 1.394 0.58 0.4 0.47 0.37
0.364 0.01 0.01 3.59 0.067 1.34 1.05 0.4 0.068 0.004 0.03 0.03 0.04
0.56 0.52 5.55 -0.532 0.85 1.02 -0.08 1.404 -0.02 0.026 0.032 0.01 -0.06 -0.16 - 0.09 - 0.24
0.512 0.06 0.01 0.18 0.146 0.06 0.034 0.057 0.11 0.01 0.17 0.08 0.22
0.39 0.4 1.33 1.757 1.52 1.566
0.04 0.06 0.12 0.082 0.31 0.035
-0.17 -0.21 0.14 0.04 -0.076 0.082
0.26 0.35 0.13 0.15 0.054 0.045
0.13 0.21 0.014 0.27 0.049 0.018 0.035 0.047 0.03 0.15
0.11 0.41
N Y
0.1 3.1 0.63 0.16
Y Y Y Y
0.5 0.12 0.61
Y Y Y Y Y Y
1.68
Y
0.066
Y N Y N Y Y Y N N N N Y N N Y Y Y Y
1018 140 159 173 21 418 428 473 486 486 491 56 83 83 327 695 163 163 587 61 173 61 8 174 174 993 748 791 791 799 1008 663 916 197 806 11 13 98 488 282 282 282 282 134 282 282 488 488 200 488
TABLE 1. cont'd Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
Monomer 2 Cinnamate, methyl Cinnamate, methyl Cinnamate, p-chloro-, methyl Cinnamate, /?-methyl-, methyl Cinnamate, phenyl Cinnamate, tert-buty\ Cinnamide, AW-diethylCinnamide, p-chloro-, N, N-diethylCinnamide, /?-methyl-, 7V,N-diethylCinnamonitrile Cinnamonitrile, a-cyanoCitraconate, di-^c-butyl Citraconate, dibenzyl Citraconate, dibutyl Citraconate, dicyclohexyl Citraconate, diethyl Citraconate, diisobutyl Citraconate, diisopropyl Citraconate, dimethyl Citraconate, dipropyl Citraconic acid Citraconic anhydride Citraconimide, P-iso-, A^-(4-acetylphenyl)Citraconimide, p-iso-, N-(4-chlorophenyl)Citraconimide, p-iso-, Ar-(4-ethoxycarbonylphenyl)Citraconimide, p-iso-, Af(4-methoxyphenyl)Citraconimide, P-iso-, N-(p-to\y\)Citraconimide, P-iso-, N-phenylCitraconimide, N-(4-acetoxyphenyl)Citraconimide, JV-(4-chlorophenyl)Citraconimide, Af-(4-ethoxycarbonylphenyl)Citraconimide, AH4-methoxyphenyl)Citraconimide, N-allyl Citraconimide, N-benzylCitraconimide, N-butylCitraconimide, Af-ethylCitraconimide, N-hexylCitraconimide, N-isobutylCitraconimide, N-isopropylCitraconimide, N-methylCitraconimide, N-methylCitraconimide, N-phenylCitraconimide, N-propylCitraconimide, N-tert-buty\Citraconimide, 7V-tolylCitraconimide, a-iso-, A^-(4-acetylphenyl)Citraconimide, a-iso-, Af-(4-chlorophenyl)Citraconimide, a-iso-, Af-(4-ethoxycarbonylphenyl)Citraconimide, a-iso-, N-(4-methoxyphenyl)Citraconimide, a-iso-, N-(p-toly\)Citraconimide, a-iso-, Af-phenylCrotonaldehyde Crotonaldehyde Crotonaldehyde Crotonate, a-acetyl-, methyl Crotonate, a-bromo-, ethyl
rx 1.799 1.27 2.24 2.84 1.66 1.692 4.17 2.99 4.95 2.549 2 1.55 2.74 1.88 2.48 1.8 1.62 1.58 2.19 1.36 0.16 0.42
±95% 0.073
0.12 0.087
0.092
0.15
r2 0.04 0.02 0.04 0 0.029 0.1 0.01 0.01 0.01 -0.008 0.13 0.047 0.054 0.03 0.029 0.03 0.076 0.049 0.027 0 0.021 0
±95%
Conv.
Refs.
0.13
Y
0.055 0.12
Y Y
0.021
Y Y
0.058
Y
488 653 653 653 488 488 737 737 737 134 134 841 841 841 841 841 841 841 841 841 1021 47 608
0.28
0
608
0.3
0
608
0.27
0
608
0.4 0.39 0.151 0.181 0.148
0 0 0.015 0.075 0.004
608 608 728 728 728
0.63 0.142 0.19 0.169 0.231 0.316 0.326 0.244 0.15 0.14 0.175 0.196 0.465 0.31 0.81
0.054 0.057 0.018 0.19 0.087 0.028 0.044 0.086 0.094 0.055
0.016 0.062 0.039 0.13
0.04 0.004 -0.066 0.03 -0.002 -0.03 0.07 -0.014 0.24 0.24 -0.001 -0.014 0.045 -0.02 0
0.086 0.093 0.033
Y Y Y
0.11
Y
0.082 0.045 0.05 0.11 0.14 0.063
Y Y Y Y Y Y
0.023 0.087 0.05 0.18
Y Y Y Y
728 959 714 714 714 714 714 714 460 506 728 714 714 728 608
1.03
0
608
0.96
0
608
0.39
0
608
0 0 0.03 0.07 0.12 0 0
608 608 428 428 428 785 785
1.69 1.76 14.7 14.7 14.7 2.7 4.42
References page II - 290
TABLE 1. cont'd Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
Monomer 2
ri
Crotonate, oc-carboethoxy-, ethyl 8.24 Crotonate, oc-chloro-, ethyl 5.13 Crotonate, a-cyano-, ethyl 0.26 Crotonate, oc-methoxy-, methyl 18.4 Crotonate, a-methyl-, methyl 30.7 Crotonate, ethyl 27 Crotonate, methyl 9.68 Crotonic acid 20 Crotononitrile 23.29 Crotononitrile 23.8 Crotononitrile, a-phenyl0.43 Cyclobutane, 1,2-dimethylene0.26 Cyclobutane, 1,2-dimethylene0.28 Cyclopentene, 4-, -1,3-dione Diallyl melamine 36.96 Diallyl phthalate 36.41 Diallyl phthalate 25.59 Diallyl phthalate 23.67 Diallyl phthalate 18.8 Diallyl phthalate 27.5 Diallyl phthalate 16.9 Diallyl phthalate 23.8 Diallyl phthalate 15.1 Dihydroxydiphenylsulfone diallyl ether 0.975 Dithiane, 2-methylene-l,30.03 Divinylbenzene, m0.58 Divinylbenzene, p 0.26 Ethylene 14.88 Ethylene, 1,1 -diphenyl0.34 Ethylene, 1,1-diphenyl0.87 Ethylene, 1-diphenyl0.33 Ethylene, chlorotrifluoro4.38 Ethylene, dichloro-, cis3.1 Ethylene, dichloro-, cis63.1 Ethylene, dichloro-, cis21.4 Ethylene, dichloro-, cis161.3 Ethylene, dichloro-, cis24.75 Ethylene, p-vinyl-1,1 -diphenyl0.46 Ethylene, tetrachloroEthylene, tetrachloro200 Ethylene, tetrachloroEthylene, tetrachloro187 Ethylene, tetrachloro185 Ethylene, tetrafluoro5.2 Ethylene, trichloro17.1 Ethylene, trichloro16.5 Ethylene, trichloro12.1 Ethylene, trichloro12.7 Ethylene, trichloro16 Formaldehyde,-S-vinyl-O7.75 ethylthioacetal Fumarate, allyl methyl 0.25 Fumarate, bis(2-butyl) 0.51 Fumarate, bis(3-chloro-2-butyl) 0.26 Fumarate, di-(2-chloroethyl) 0.18 Fumarate, di-(2-cyanoethyl) 0.07 Fumarate, di-(2-methoxyethyl) 0.35 Fumarate, di-(2-phenylethyl) 0.27 Fumarate, di-^obutyl 0.55 Fumarate, di-tert-amyl 0.69 Fumarate, di-terf-butyl 0.57 Fumarate, dibenzyl 0.32 Fumarate, dibutyl 0.35 Fumarate, dicyclohexyl 0.49 Fumarate, dicyclopentyl 0.3
±95%
1.86 1.7
0.05 4.02 1.23 2.19 1.2
0.015 0.15 0.25 0.01 0.02 0.99 4.9 30.3 2.64
r2 0 0 0.02 0.04 0.02 0 -0.27 0 -0.012 0 0 3.6 3.6 -0.32 0.041 0.026 0.038 0.08 0.09 0.1 0.1 0.13 0.92 3.35 0.58 1.18 0.05 -0.02 1.15 0.01 -0.1 -3.1 -2.2 -0.28 -0.02 0.067 1.31
±95%
Conv.
0.22
Y
0.06
Y
0.16 0.2 0.038 0.071 0.04
Y Y Y Y Y
0.16 0.04 0.17
N N
0.01
N
0.02 0.21
N Y Y Y Y Y Y
0.12 0.062 0.053
Y Y
11 0.68 0.01 0.04 0.04
0 0 0.01 0 0 0 0 -0.006 0.32 0.03 0 - 0.06 0 0.09 0.03 0 0.04 0.08 0.04 0 0.04 0.06 0.06
0.37 0.24
Y Y
0.02 0.01 0.03
N N N
Refs. 785 785 785 785 785 785 112 402 112 785 785 854 885 263 201 152 152 152 152 152 152 152 152 1016 1031 262 262 615 281 901 189 236 137 137 40 9 9 742 204 204 40 40 59 567 40 40 40 40 59 273 713 249 249 1038 1038 1038 1038 1038 1038 1038 1038 1038 1038 1038
TABLE 1. cont'd Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
Monomer 2 Fumarate, diethyl Fumarate, diethyl Fumarate, diethyl Fumarate, diethyl Fumarate, diethyl Fumarate, diethyl Fumarate, diethyl Fumarate, diisobutyl Fumarate, diisopropyl Fumarate, dimethyl Fumarate, dipropyl Fumarate, isopropyl butyl Fumarate, isopropyl ethyl Fumarate, isopropyl isobutyl Fumarate, isopropyl methyl Fumarate, isopropyl sec-butyl Fumarate, methyl butyl Fumarate, methyl ethyl Fumarate, methyl isobutyl Fumarate, methyl isopropyl Fumarate, methyl propyl Fumarate, methyl sec-butyl Fumarate, methyl tert-amyl Fumarate, methyl tert-butyl Fumarate, mono-2-butyl Fumarate, tert-butyl 2-ethylhexyl Fumarate, tert-butyl 4-methyl-2-pentyl Fumarate, tert-butyl ethyl Fumarate, tert-butyl isoamyl Fumarate, tert-butyl methyl Fumarate, tert-butyl sec-butyl Fumaronitrile Fumaronitrile Fumaronitrile Fumaronitrile Fumaronitrile Fumaryl chloride Furan, 2,3-dihydroHexatriene, tetrachloroHexene, 1-, 3,4-dioic anhydride Hexene, 2-, 3,4-dioic anhydride Hexene, 3-, 3,4-dioic anhydride Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene-1,5-dicarboxylate, dimethyl Imidazole, 1-vinylImidazole, l-vinyl-2-methylImidazole, l-vinyl-2-methylIsoprene Isoprene Isoprene Isoprene Isoprene Isoprene, 3-acetoxyIsopropenyl methyl ketone
rt 0.29 6.3 0.394 0.3 0.31 0.36 0.29 0.37 0.4 0.39 0.32 0.42 0.3 0.46 0.3 0.54 0.36 0.32 0.32 0.3 0.28 0.45 0.53 0.45 0.33 0.54 0.57 0.25 0.45 0.45 0.55 0.202 0.294 0.3
±95%
0.26 0.06 0.02
0.03
0.058 0.044
r2 0.02 0.081 0.11 0.07 O 0.1 0.02 0.05 0.055 0.03 0.02 0.01 0.01 0.01 0.16 0.02 0.02 0.02 0.03 0.16 0.05 0.02 0.06 0.03 - 0.04 0.01 0.01 0.04 0.06 0.03 0.07 -0.016 0.006 0
±95%
Conv.
0.005 0.022
Y Y
0.01
N
0.03
N
0.021
Y Y Y
0.031
Y Y 20 0.123 8.57 3.63 17.17 0.031 0.049 0.066 0.07 0.171 0.179 0.173 0.121 0.24 0.014 0.044 0.028 0.678 9.94 8.87 8.97 0.513 0.476 0.44 0.42 0.48 0.34 0.44
0.0428 8.4 5.6 436
0.031 0.24 0.62 0.02 0.018
0 0.85 -0.052 -0.08 -0.54 1.22 1.38 1.52 1.73 1.91 1.91 2.07 2.46 2.69 2.93 3.19 4.11 0.196 0.071 0.09 0.07 1.922 1.957 1.98 2.02 1.3 4.47 0.29
0.22 1 1,17 5.83
Y Y Y Y
0.043 0.029 0.064
Y Y Y
0.016 0.011
Y Y
Refs. 1038 139 139 139 249 562 640 1038 1038 1038 1038 1056 1056 1056 1056 1056 1056 1056 1056 1056 1056 1056 1056 1056 249 1056 1056 1056 1056 1056 1056 137 191 199 478 77 91 806 4 933 933 933 931 931 931 931 931 931 931 931 931 931 931 931 828 364 364 479 366 366 544 544 83 770 542
References page II - 290
TABLE 1. cont'd Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
Monomer 2 Isopropenyl methyl ketone Isopropenyl, 3-(l-cyclohexenyl), acetate Isopropenylacetophenone, pIsopropenylisocyanate Isopropenylisocyanate Isopropylidene, 2,3:4,5-di-O-, -1-vinylbenzylItaconamate, A^-(4-carboethoxyphenyl)-, butyl Itaconamate, 7V-(4-carboethoxyphenyl)-, ethyl Itaconamate, N-(4-carboethoxyphenyl)-, methyl Itaconamate, Af-(4-carboethoxyphenyl)-, propyl Itaconamate, N-(4-chlorophenyl)-, ethyl Itaconamate, A^-(4-chlorophenyl)-, methyl Itaconamate, Af-(-chlorophenyl)-, propyl Itaconamate, N-(4-methoxyphenyl-, butyl Itaconamate, N-(4-methoxyphenyl)-, ethyl Itaconamate, A^-(4-methoxyphenyl)-, methyl Itaconamate, Af-(4-methoxyphenyl)-, propyl Itaconamate, N-(4-methylphenyl)-, butyl Itaconamate, A^-(4-methlyphenyl)-, ethyl Itaconamate, N-(4-methylphenyl)-, methyl Itaconamate, A^-(4-methylphenyl)-, propyl Itaconamate, N-phenyl, methyl Itaconamate, N-phenyl-, butyl Itaconamate, N-phenyl, ethyl Itaconamate, N-phenyl-, methyl Itaconamate, A^-phenyl-, propyl Itaconate, di-2[-2(2-methoxyethoxy)ethoxy]ethyl Itaconate, diamyl Itaconate, dibutyl Itaconate, diethyl Itaconate, dimenthyl Itaconate, dimethyl Itaconate, dimethyl Itaconate, dimethyl Itaconate, dioctyl Itaconate, dipropyl Itaconate, ethyl hexafluoroisopropyl Itaconate, glycidyl methyl Itaconate, mono-methyl Itaconate, mono-methyl Itaconate, mono-methyl Itaconate, mono-methyl Itaconic acid Itaconic acid Itaconic anhydride Itaconic anhydride Itaconic anhydride Itaconimide, A^-(2-chloroethyl)Itaconimide, N-(4-acetoxyphenyl)Itaconimide, N-(4-chlorophenyl)-
rY 0.32 1.59 0.3 8.12 6.84 0.14
±95%
0.18 0.18 0.055
r2 0.66 0.56 0.84 0.07 0.122 3.26
±95%
Conv.
Refs.
0.59
Y
0.047 1.12
Y Y
542 770 266 434 99 772
0.2
0.61
678
0.23
0.2
678
0.15
0.58
678
0.26
0.4
678
0.35 0.38
0.16 0.18
678 678
0.39 0.12
0.31 0.69
678 678
0.33
0.34
678
0.26
0.41
678
0.38
0.4
678
0.19
0.31
678
0.38
0.26
678
0.3
0.16
678
0.54
0.19
678
0.39 0.12 0.45 0.31 0.5 0.53
0.022
0.18 0.49 0.21 0.52 0.18 0.2
0.015
678 678 678 1059 678 1098
0.36 0.42 0.23 0.502
0.05 0.06 0.11 0.188
0.5 0.34 0.34 0.483
0.09 0.05 0.12 0.364
N N N Y N
0.12 0.06 0.035 0.079 0.052 0.15 0.11 0.086
N N N
0.67 0.09 0.09 0.05 0.092 0.21 0.18
Y Y Y Y Y Y Y
0.48 0.5 0.33 0.16 0.435 0.376 0.029 0.34 0.52 0.404 0.34 0.26 0.004 0.086 0.003 0.069 0.35 0.159
0.16 0.07 0.025 0.036 0.039 0.077 0.085 0.06 0.08 0.01 0.015 0.005 0.045 0.12 0.084
0.14 0.06 0.14 0.28 0.039 0.041 0.111 0.33 0.33 0.218 0 0.12 0.405 0.456 0.785 0.162 0.21 0.2
Y Y Y Y
39 39 39 975 39 398 586 39 39 1103 806 656 656 656 656 420 76 365 62 62 642 729 729
TABLE 1. cont'd Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
Monomer 2
rx
Itaconimide, 0.232 iV-(4-ethoxycarbonylphenyl) Itaconimide, Af-(/?-chlorophenyl)0.15 Itaconimide, N-(p-tolyl)0.16 Itaconimide, N-benzyl0.056 Itaconimide, Af-butyl0.22 Itaconimide, AT-ethyl 0.232 Itaconimide, AMsobutyl0.44 Itaconimide, Af-Isopropyl0.308 Itaconimide, Af-methyl0.153 Itaconimide, Af-naphthyl0.08 Itaconimide, Af-phenyl0.116 Itaconimide, N-phenyl0.05 Itaconimide, AT-phenyl0.05 Itaconimide, JV-propyl0.28 Itaconimide, N-tolyl0.134 Maleamic acid, 0.55 A^3-dimethylamino-6-methyl Maleate, allyl methyl 8.29 Maleate, butyl stannyl, allyl 0.1 Maleate, chloro-, diethyl 2.07 Maleate, dibutyl tin 2.08 Maleate, diethyl 6.59 Maleate, diethyl Maleate, diethyl 8 Maleate, diethyl 6.07 Maleate, diethyl 6.592 Maleate, dimethyl 10.65 Maleate, dimethyl 0.083 Maleate, monoallyl 0.14 Maleic anhydride 0.097 Maleic anhydride 0.04 Maleic anhydride 0.02 Maleic anhydride 0 Maleic anhydride 0.02 Maleic anhydride 0.02 Maleic anhydride 0.04 Maleic anhydride 0.04 Maleic anhydride 0.04 Maleic anhydride 0.05 Maleic anhydride 0.02 Maleic anhydride 0.04 Maleic anhydride 0.04 Maleic anhydride Maleic anhydride, a-chloro0.07 Maleimide 0.057 Maleimide, A^-(2,6-diethylphenyl)0.19 Maleimide, A^-(2,6-dimethylphenyl)0.14 Maleimide, N-(2-chlorophenyl)0.011 Maleimide, 7V-(2-chlorophenyl)0.038 Maleimide, A^-(2-chlorophenyl)0.013 Maleimide, AH2-chlorophenyl)0.038 Maleimide, N-(2-hydroxyethyl)0.046 Maleimide, A^-(3-dimethylaminophenyl)- 0.03 Maleimide, AK4-bromophenyl)0.02 Maleimide, A^-(4-carboxyethylphenyl)0.059 a-chloroMaleimide, A^-(4-chlorophenyl)0.149 oc-chloroMaleimide, N-(4-hydroxyphenyl)-0.059 Maleimide, A^-(4-methoxyphenyl)0.112 a-chloroMaleimide, 7V-(4-methylphenyl)0.107 oc-chloroMaleimide, 7V-(p-chloroethyl)-a-chloro- 0.29
±95% 0.032
r2 0.112
0.248 0.12 0.031 0.03
0.14 0.24 0.2 -0.019 0.172 -0.03 0.045 0.12 0.35 0.109 0.08 0.998 0.04 0.219 -0.19
0.14 0.02 0.14 0.118 0.46
0.02 0.06 -0.043 0.194 -0.013
0.048 0.03 0.029 0.11 0.043 0.069 0.043
±95% 0.054
Conv. Y
0.11 0.04 0.06 0.11 0.064 0.12
Y Y Y Y Y Y
0.082
Y
0.123 0.18 0.079 0.03
N Y Y N
0.01 0.03 0.021 0.121 0.022
N N Y Y Y Y
0.01
N
0.12 0.058 0.02 0.008 0.13 0.03 0.01
Y Y N N Y N N
Refs. 729 740 740 642 642 642 642 642 642 740 729 740 978 642 729 679
0.036
Y
0.002 0.003 0.005 0.003 0.027
Y Y Y Y Y
0.007 0.041
Y Y
713 811 14 987 139 14 640 874 888 137 317 811 105 12 17 241 384 397 483 506 522 522 522 522 522 923 845 251 992 992 853 853 910 910 323 747 1030 973
0.019
0.038
Y
973
0.041 0.031
0.13 0.049
0.1 0.061
Y Y
323 973
0.048
0.019
0.078
Y
973
0.05
0
0.06
0.07 2.81 0.015 0.01 0.002 0.12 0.003 0.01
0.07 0.01 0.001 0.15 0.105 0.07 0.001 0 0.003 0.02 0 0 0.02 0.01 0.001 0.005 0.01 0.02 0.05
N
0.006 0.021
0 0.088 0.02 0.08 0.013 0.028 0.01 0.006 0.011 0.19 0.018 0.022
0.048
0.012 0.004 0.006 0.012 0.028 0.017
974
References page II - 290
TABLE 1. Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
cont'd Monomer 2 Maleimide, TV-[TV'-(a-methylbenzyl)aminocarbonylpentyl] Maleimide, AKN'-(a-methylbenzyl)aminocarbonylundecy 1] Maleimide, TV-allyl Maleimide, iV-benzylMaleimide, TV-benzyl-a-chloroMaleimide, TV-butylMaleimide, TV-butylMaleimide, TV-cyclohexylMaleimide, TV-cyclohexylMaleimide, TV-ethyl-a-chloroMaleimide, TV-hexylMaleimide, iV-hydroxymethylMaleimide, TV-methyl-a-chloroMaleimide, TV-phenylMaleimide, TV-phenylMaleimide, TV-phenylMaleimide, TV-phenyl-a-chloroMaleimide-TV,TV-dimethylaniline, 4-(2-chlorophenyl)Mesaconate, di-sec-butyldithiol Mesaconate, diamyl Mesaconate, dibenzyl Mesaconate, dibenzyldithiol Mesaconate, dibutyl Mesaconate, dibutyldithiol Mesaconate, dicyclohexyl Mesaconate, diethyl Mesaconate, diethyldithiol Mesaconate, dihexyl Mesaconate, diisoamyl Mesaconate, diisobutyl Mesaconate, diisobutyldithiol Mesaconate, diisopropyl Mesaconate, diisopropyldithiol Mesaconate, dimethyl Mesaconate, dimethyldithiol Mesaconate, dioctyl Mesaconate, diphenyl Mesaconate, diphenyldithiol Mesaconate, dipropyl Mesaconate, dipropyldithiol Mesaconic acid Methacrylamide Methacrylamide Methacrylamide, 1-deoxy-D-glucitol Methacrylamide, TV-phenylMethacrylate, 2,2,6,6,-tetramethyl4-piperidinyl Methacrylate, 2,3-epithiopropyl Methacrylate, 2-(sulfonic acid)ethyl Methacrylate, 2-acetoxyethyl Methacrylate, 2-bromoethyl Methacrylate, 2-chloro2,3,3,3-fluoropropyl Methacrylate, 2-chloroethyl Methacrylate, 2-chloroethyl Methacrylate, 2-chloroethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl
rx 0.198
0.056 0.058 0.42
±95% 0.143
r2 0.258
0.021 0.06
0.035 0.013 0
0.017 0.05 0.069 0.053 0.04
0.06 0.1 0.162 0 0.09 0.06 0
±95% 0.25
0.031 0.06
Conv.
Refs.
Y
1099
Y
1099
Y Y
0.02 0.102 -0.01 0.9 -0.041 -0.035 0.63 0.016 0.07 0.087 0.05 0.45 1.27 0.73 0.28 1.28 0.41 1.25 1.24 0.4 1.51 1.34 1.29 0.41 1.31 0.44 0.98 0.35 1.23 0.45 0.16 1.22 0.39 1.6 1.4 1.42 2.09 1.24 0.63 0.41 0.37 0.44 0.32 0.121 0.35 0.345 0.42 0.44 0.332 0.57 0.5 0.59 0.53
0.004 0.04
0.13 0.17 0.06
0.02 0.068 0.046 0.048 0.02 0.006
0.044 0.01 - 0.002 0.04 0.02 0.02 0.08 0.06 0.05 0.05 0.1 0.06 0.03 0.1 0.07 0.1 0.03 0.04 0.05 0.04 0.07 0.01 0.07 0.15 0.05 0.06 0 0.48 1.24 0.005 0.88 0.3 0.28 0.6 0.58 0.41 0.243 0.341 0.34 0.23 0.54 0.856 0.65 1.65 0.53 0.59
0.054 0.04 0.16 0.11 0.03
Y Y Y
0.017
N Y
0.073
Y
0.2 0.38
N N
0.17
N
0.04
N
0.15
N
0.075 0.08
Y Y
0.03 0.018
N Y
1003 348 974 115 50 1100 348 974 348 323 974 1026 328 992 973 747 624 658 658 624 658 624 658 658 624 658 658 658 624 658 624 658 624 658 658 624 658 624 1021 316 316 258 352 664 787 564 346 657 927 179 179 382 346 350 463 878 878 903
TABLE 1. cont'd Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
Monomer 2
rx
Methacrylate, 2-hydroxyethyl 0.5 Methacrylate, 2-methoxyethyl 0.46 Methacrylate, 2-naphthyl-, methyl 0.786 Methacrylate, 2-naphthyl-, methyl 0.486 Methacrylate, 2-naphthyl-, methyl 0.61 Methacrylate, 2-naphthyl-, methyl 0.384 Methacrylate, 2-phenethyl 0.56 Methacrylate, 3,5-dimethyladamantyl 0.89 Methacrylate, 5-oxo-pyrrolidinylmethyl 0.342 Methacrylate, A^-methyl-7V-phenyl0.44 2-aminoethyl Methacrylate, a-naphthoyloxy-, ethyl 0.216 Methacrylate, acetonyl 0.285 Methacrylate, amyl 0.52 Methacrylate, benzyl 0.463 Methacrylate, benzyl 0.435 Methacrylate, benzyl 0.45 Methacrylate, benzyl 0.48 Methacrylate, benzyl 0.8 Methacrylate, bornyl 0.45 Methacrylate, butyl 0.56 Methacrylate, butyl -0.05 Methacrylate, butyl 0.52 Methacrylate, butyl 0.63 Methacrylate, butyl 0.54 Methacrylate, butyl 0.74 Methacrylate, chloromethyl 0.208 Methacrylate, cyanomethyl 0.144 Methacrylate, cyclohexyl 0.586 Methacrylate, di-ethylene glycol 0.39 Methacrylate, dodecyl 0.528 Methacrylate, ethyl 0.55 Methacrylate, ethyl 0.67 Methacrylate, ethyl 0.65 Methacrylate, ethyl 0.55 Methacrylate, ferrocenylmethyl 3.63 Methacrylate, ferrocenylmethyl 3.6 Methacrylate, glycidyl 0.54 Methacrylate, glycidyl 0.278 Methacrylate, glycidyl 0.47 Methacrylate, glycidyl 0.44 Methacrylate, glycidyl 0.45 Methacrylate, glycidyl 0.31 Methacrylate, glycidyl 0.11 Methacrylate, glycidyl 0.435 Methacrylate, hexyl 0.58 Methacrylate, isobornyl 0.61 Methacrylate, isobutyl 0.509 Methacrylate, isobutyl 0.56 Methacrylate, isobutyl 0.55 Methacrylate, isopropyl 0.5 Methacrylate, isopropyl 0.47 Methacrylate, m-chlorophenyl 0.375 Methacrylate, ra-nitrophenyl 0.44 Methacrylate, methoxymethyl 0.395 Methacrylate, methyl 0.5 Methacrylate, methyl 0.52 Methacrylate, methyl 0.52 Methacrylate, methyl 0.48 Methacrylate, methyl 0.52 Methacrylate, methyl 0.49 Methacrylate, methyl 0.45 Methacrylate, methyl 0.58 Methacrylate, methyl 0.44 Methacrylate, methyl 0.396
±95%
0.16 0.117 0.195 0.225 0.025 0.14 0.013 0.04 0.043 0.041 0.11 0.041 0.026
0.32 0.12 1.09
0.006 0.011 0.088 0.15 0.05 0.062
0.14 0.07 0.086 0.02 0.04 0.045 0.033 0.07 0.45 0.014
0.05 0.16 0.014
0.048
r2 1.65 0.48 0.113 0.321 0.576 0.216 0.534 0.63 0.411 0.58 0.242 0.505 0.46 0.658 0.467 0.51 0.42 0.3 0.5 0.31 2.52 0.47 0.64 0.64 0.59 0.298 0.28 0.57 0.67 0.3 0.36 0.26 0.29 0.33 -0.019 0.01 0.16 0.539 0.46 0.54 0.55 0.74 0.73 0.514 0.44 0.24 0.271 0.58 0.4 0.42 0.74 0.209 0.185 0.586 0.5 0.46 0.46 0.42 0.45 0.46 0.47 0.48 0.5 0.22
±95%
Conv.
0.126 0.098 0.477 0.422 0.099 0.21 0.033 0.02
Y Y Y Y Y N Y N
0.018 0.115 0.2 0.084 0.048
Y Y Y Y
0.38 0.2 1.1
Y N
0.03 0.041 0.28 0.08 0.1 0.12
Y Y Y N Y Y
0.022
Y
0.03 0.04 0.08
N Y N
0.1 0.284 0.098 0.13 0.3 0.036
N N Y Y
0.013 0.054 0.069
Y Y Y
0.13
Y
Y
Refs. 903 918 924 924 924 924 540 335 633 651 1102 958 179 111 179 487 540 602 806 179 43 463 530 530 835 712 625 179 262 179 179 530 530 570 293 576 114 217 225 225 463 849 893 999 179 806 179 463 487 463 541 177 177 821 138 139 179 20 21 21 21 21 21 241
References page II - 290
TABLE 1. cont'd Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
Monomer 2 Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methylthiomethyl Methacrylate, octyl Methacrylate, octyl Methacrylate, /?-(cinnamoylamino)phenyl Methacrylate,/7-carbomethoxyphenyl Methacrylate, /?-chlorophenyl Methacrylate,/7-methoxyphenyl Methacrylate, p-methylphenyl Methacrylate, p-nitrophenyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, propyl Methacrylate, sulfolanyl Methacrylate, tert-buty\ Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic anhydride Methacrylic anhydride Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile
T1 0.42 0.49 0.564 0.585 0.44 0.47 0.54 0.52 0.38 0.52 0.54 0.44 0.52 0.5 0.56 0.53 0.485 0.48 0.371 0.62 0.52 0.5 0.55 0.55 0.41 0.472 0.497 0.432 0.57 0.275 0.338 0.65 0.56 0.62 0.482 0.34 0.499 0.49 0.223 0.246 0.247 0.26 0.565 0.2 0.545 0.21 0.22 0.2 0.15 0.2 0.38 0.124 0.17 0.041 0.067 0.627 0.55 0.221 0.13 0.1 0.37 0.38 0.43 0.34
±95%
0.14 0.047 0.007 0.08
0.052 0.059 0.055
0.1
0.084 0.11 0.089 0.25 0.09 0.049 0.064 0.081 0.1 0.054 0.02 0.04 0.04 0.092 0.03 0.046 0.031 0.06 0.048 0.01
r2 0.32 0.418 0.54 0.478 0.45 0.45 0.49 0.47 0.48 0.46 0.42 0.5 0.46 0.44 0.49 0.49 0.409 0.504 0.611 0.59 0.6 0.63 0.58 0.64 0.41 0.454 0.464 0.422 0.41 0.314 0.512 0.56 0.68 0.31 0.178 0.243 0.244 0.225 0.185 0.48 0.55 0.51 0.38 -0.2 0.61 0.55 0.64 0.66 0.49 0.56 0.28 0.602 0.85 0.631 0.6 0.44 0.39 0.12 0.27 0.33 0.41 0.42 0.28 0.21
±95%
Conv.
0.085 0.029 0.011 0.01
Y Y Y N
0.02 0.026 0.028
Y Y Y
0.05 0.16
Y Y
0.027 0.022 0.026 0.04 0.039 0.23 0.33
Y Y Y Y Y Y Y
0.11 2.46 0.51 0.66
Y N Y N
0.08 0.19
N N
0.088
Y
0.146 0.249 0.089 0.199 0.118 0.02
Y Y Y Y Y N
Refs. 241 254 254 287 324 324 403 416 451 463 492 492 505 531 531 534 751 751 751 753 753 753 753 753 753 824 824 824 835 860 920 179 463 685 177 177 177 177 177 177 179 463 179 359 179 166 166 203 312 313 313 47 812 842 842 842 842 842 219 275 311 311 542 707
TABLE 1. cont'd Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
Monomer 2 Methacrylonitrile Methacrylonitrile Methacryloxypropyltrimethoxysilane Methacryloyl fluoride Methacryloylacetone Methacryloyloxy, 2-, benzoate, methyl Methacryloyloxy, 2-, benzoic acid Methacryloyloxy, 4-, 2,2,6,6-tetramethyl Methylenebutyrolactone Methyleneglutaronitrile, 2Methyleneglutaronitrile, 2Methyleneglutaronitrile, 2Myrcene AW-Divinylaniline N-Vinylimidazole Naphthalene, 1-vinylNaphthalene, l-vinyl-4-chloroNaphthalene, 2-vinylNaphthalene, 2-vinyl-6-chloroNaphthalene, 6-vinyl-2-tert-butyl Oct-1-ene, 4,8-dioxaspiro(2,5)Oct-1-ene, 6,6-dimethyl-4,8-dioxaspiro Oxazolidone, N-vinylOxazoline, 2-, 2-isopropenyl4,4-dimethyl Oxazoline, 2-, 4-acryloxymethyl2,4-dimethyl Oxazoline, 2-isopropenylOxirane, 4-vinylphenylPentadienoate, trans-4-ethoxy-2,4-, ethyl Pentadienonitrile, trans-4-ethoxy-2,4Penten, 2-,-4-one Phenol, 3-(methacryloylamino)Phenol, 4-(methacryloylamino)Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, vinyl bis(chloroethyl) Phosphazene, isopropenylpentafluoroPhosphonate, 2-(4-vinylphenyl)ethyl, diethyl Phosphonate, 4-vinylphenyl, diethyl Phosphonate, oc-carbomethoxyvinyl-, diethyl Phosphonate, isopropenyl-, dimethyl Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl-, dibutyl Phosphonate, vinyl-, diethyl Phosphonate, vinyl-, diethyl Phosphonate, vinyl-, diethyl Phosphonate, vinyl-, diisobutyl Phosphonate, vinyl-, diispropyl Phosphonate, vinyl-, dimethyl Phosphonate, vinyl-, dimethyl Phosphonate, vinyl-, dimethyl Phosphonate, vinyl-, dimethyl
rx 0.25 0.34 0.36 0.069 0.067 0.27 0.15 0.6 0.09 0.42 0.5 0.85 0.891 5.38 8.377 0.699 0.76 0.395 0.39 0.616 1.831 1.93 29.42 0.55
±95%
0.014 0.007 0.04 0.04
0.52
0.015 0.36 0.149 0.233 0.68 0.049 0.6 0.069 0.027 0.098 2.19
r2 0.25 0.21 0.58 0.164 1.66 0.48 1.17 0.32 0.7 -0.02 0.02 0.25 1.38 0.033 0.68 2.02 0.75 1.345 2.44 1.014 0.246 0.271 -0.029 0.68
±95%
Conv.
0.045 0.16 0.02 0.03
Y Y N N
1.3
N
0.081 0.067 0.02 0.401 0.45 0.093 1.38 0.244 0.024 0.109 0.014
Y Y Y
Y Y Y
Refs. 75 835 951 660 339 651 651 687 746 196 196 512 1062 45 879 967 806 806 806 806 838 838 36 596
0.56
0.14
596
0.67 0.78 0.04 0.08 13.84 0.5 0.71 0.629 0.612 0.595 0.597 0.633 0.61 0.599 2.47 1.6 0.55
0.64 1.06 12.2 11.8 -0.033 0.99 0.86 0.171 0.15 0.146 0.168 0.094 0.23 0.108 0.03 -0.121 1.36
862 1001 723 723 112 896 896 971 971 971 971 971 971 971 133 765 796
0.57 0.06 0.04 0.003 0.004 0.005 0.044 0.002 0.018 0.002 0.78 0.27
0.7 3.88 8.6 2.46 2.3 2.2 6.32 6.32 4.97 4.36 1.59 2.45 3.87 2.57 4.61 2.45 2.45
0.055 0.04 0.03 0.01 0.05 0.073 0.355 0.02 0.187 0.034 0.23 0.088
Y
N N N N N N N Y Y
1.4 0
0.43
3.44 4.27 0.24 1.59 2.13
0.23 0.02 0.16 0.2 0.18 0.18 -0.12 -0.15 -0.52 0.02 -0.32 -0.52 0.4 0.15 0.02
796 684
0.39
Y
2.33 2.18 0.22
Y Y Y
1.46 2.52
Y Y Y
684 133 410 485 592 594 129 129 18 592 129 129 129 129 592 594
References page II - 290
TABLE 1. cont'd Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
Monomer 2 Phosphonate, vinyl-, diphenyl Phosphonate, vinyl-, dipropyl Phthalimide, N-vinylPropene, 2,3-dichloroPropene, 2,3-dichloroPropene, 2-chloro-3-hydroxyPropene 3,3,3-trichloroPropene, 3-chloro-2-chloromethylPropneyl methyl ketone Propenyl, 2-chloro-, acetate Propenyl, 2-methyl, acetate Propiolactam, Af-phenyl-a-methylenePyrazole, N-vinyl-3,5-dimethylPyridazinone, 3-(2-vinyl)-6-methylPyridazinone, 3-(2-vinyl)-6-methyl4,5-dihydro Pyridine, 2-methyl-5-vinylPyridine, 2-methy 1-5-vinylPyridine, 2-methy 1-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinyl-5-ethylPyridine, 3-ethynyl-6-methylPyridine, 4-vinylPyridine, 4-vinylPyridine, AT-oxide-, 2-vinyl-5-ethylPyrimidine, 2-WV-dimethylamino4-vinyl Pyrimidine, 4-vinylPyrrolidone, l-benzyl-3-methylene5-methyl Pyrrolidone, Af-vinylQuinoline, 2-vinylQuinoline, 2-vinyl5-Ethyl Ar-vinyl-N-methylthiolcarbamate 5-Vinyl AW-diethylthiolcarbamate Silane, y-methacryloxypropyltrimethoxyStilbene Styrene, 2,4-dibromoStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,4,5-tribromoStyrene, 3-m-n-butylstannylStyrene, 4-(f-butyldimethylsilyloxy)Styrene, 4-(trimethylsilyl)Styrene, 4-phenoxyStyrene, a-(trimethylsilyloxy)Styrene, a-methoxyStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, m-aminoStyrene, m-aminoStyrene, m-bromoStyrene, m-bromo-
r\
±95%
r2
±95%
Conv.
Refs.
1.74 3.81 6.27 3.51 3 12.5 6.9 3.37 18.12 4.1 71 0.626 8.663 0.9 5.92
0.16 0.68 0.66 0.18
-0.38 -0.41 0.07 0.05 0.036 0 0 0.01 0.08 0 0 0.406 0.049 0.85 0.13
0.29 0.72 0.11 0.01
Y Y Y N
0.106 0.011 0.05 0.03
N N
129 129 163 11 983 445 402 806 806 445 470 1002 806 340 340
0.74 0.6 0.72 0.73 0.46 0.5 0.55 0.57 0.55 0.74 2.3 0.52 -0.73 0.06 0.338
0.03
0.08
N
0.23 0.32
N N
0.12
N
0.07 1.09 0.11 0.017
0.75 0.68 1.2 0.78 0.75 1.27 1.81 1.33 1.14 1.09 0.15 0.69 1.04 2.27 1.404
0.16 0.22 0.88 0.071
N Y Y
232 500 514 56 231 41 456 499 532 231 784 231 79 806 243
0.095 0.053
2.38 0.71
1.06 0.17
Y Y
243 633
1.55
0.057 2.09 2.69 -0.11
0.028
Y
0.26
Y
36 456 458 197
0.219 0.555 17.2 0.49 0.49 10
0.73 6.09 0.025 0.196 0.03 0.1
0.03 0.15
0.05
1.72
0.1 0.3 Y
4.45 0.425
0.48 0.048
0.1 0.868
0.34 0.096
Y Y
197 977
3.92 0.14 0.268 0.18 0.23 0.26 0.23 18.5 0.877 0.48 1.38 1.48 2.51 1.21 0.96 1.09 1.13 1.08 1.12 1.04 0.786 0.5 0.55
0.17 1.61 0.08
0 0.91 0.81 0.25 2.2 0.14 2.78 0.03 0.863 0.28 0.94 0 0.07 0.14 0.05 0.3 0.4 0.521 0.63 1.16 1.18 1.6 1.05
0.09 2.88 0.14
N
0.04
N
0.193
Y
0.05 0.06 0.13
N N N
0.084
Y
0.007
Y
725 806 14 411 419 84 1054 985 976 1036 602 970 142 171 281 281 281 289 289 775 989 168 256
0.17 0.351
0.34 0.41 0.03 0.11 0.01
Y
TABLE 1. cont'd Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
Monomer 2 Styrene, ra-chloroStyrene, m-chloroStyrene, m-cyanoStyrene, m-diethylaminoethylStyrene, m-dimethylaminoStyrene, m-hydroxyStyrene, m-methoxyStyrene, m-nitroStyrene, m-sulfonic acid fluoride Styrene, p-2-methoxyphenyl ketone Styrene, p-4-methoxyphenyl ketone Styrene, p-phenyl ketone Styrene, p-phenyl ketone Styrene, p-l-(2-hydroxypropyl)Styrene, p-2-(2-hydroxypropyl)Styrene, p-2-(2-hydroxypropyl)Styrene, p-acetoxyStyrene, p-acetoxyStyrene,/7-aminoStyrene, p-aminoStyrene, p-bromoStyrene, p-bromoStyrene, p-bromoStyrene, p-bromoStyrene, p-bormoStyrene, p-chloroStyrene, p-chloroStyrene, p-chloroStyrene, p-chloroStyrene, p-chloroStyrene, p-chloroStyrene, p-chloroStyrene, p-chloromethylStyrene, p-chloromethylStyrene, p-chloromethylStyrene, p-cyanoStyrene, p-cyanoStyrene, p-decylStyrene, p-diethylaminoethylStyrene, p-ethoxy Styrene, p-fluoromethylStyrene, p-formylStyrene, p-formylStyrene, p-iodoStyrene, p-iodoStyrene, p-mercaptoStyrene, p-methoxyStyrene, p-methoxyStyrene, p-methoxyStyrene, p-methoxyStyrene, p-methylStyrene, p-nitroStyrene, p-octylamine sulfonate Styrene, p-sulfonic acid fluoride Styrene, p-trimethoxysilylStyrene, p-trimethylsilylStyrene, pentachloroSuccinimide, N-vinylSuccinimide, N-vinylSuccinimide, N-vinylSuccinimide, N-vinylTerpyridinyl, 4/-vinyl-2,2/:6/,2//Tetrazole, 1-vinylTetrazole, 2-methyl-5-(4/-vinyl)phenylTetrazole, 2-methy 1-5-vinyl-
r\ 0.57 0.64 0.851 1.2 1.027 0.78 1.742 0.279 0.788 0.23 0.423 0.11 0.13 0.97 0.5 0.79 0.835 0.887 0.41 0.876 0.7 0.67 0.71 0.71 0.69 0.62 0.744 0.816 0.74 0.39 0.76 0.74 0.622 0.62 0.6 0.24 0.28 0.88 1.12 0.98 0.474 0.2 0.16 0.485 0.629 0.607 0.85 1.14 1.16 1.05 0.891 0.193 0.7 0.171 0.774 1.26 1.33 10.74 10.09 2.31 0.052 0.53 3.85 0.65 1.124
±95%
0.534 0.28 0.248 0.07 0.456 0.055 0.183 0.07 0.071 0.15 0.02
0.029 0.034 0.007 0.03 0.09 0.14 0.1 0.08 0.029 0.043 0.047 0.15 0.3 0.07 0.22 0.19 0.19 0.151 0.093 0.039 0.188 0.19 0.6 0.086 0.092 0.045 0.126 0.47 0.19 0.49 0.46 0.98 0.032 0.384 0.045 0.081
r2 2.3 1.09 0.363 1.21 0.617 1.33 0.661 0.5 1.268 1.52 1.85 2.58 0.55 0.91 0.56 1.25 1.305 1.218 0.22 1.07 1.05 1.1 0.99 1.05 1 1.08 1.029 1.062 1.03 0.76 1.76 1.02 1.12 1.12 1.66 1.22 1.16 0.26 0.59 0.71 1.399 3 1.43 1.044 0.965 0.907 0.69 1.01 0.82 0.79 0.993 1.13 2.7 1.372 1.581 1.15 0.07 0.045 0.045 0.01 7 1.26 0.184 1.3 0.62
±95%
0.08 0.26 0.264 0.06 0.232 0.14 0.236 0.58 0.93 0.83 9.44
Conv.
N Y
0.05 0.069 0.004 0.07 0.05 0.11
Y N N Y
0.07 0.056 0.014
N Y Y
0.12
Y
0.17 0.2 0.46 0.11
Y N
1.32 0.19 0.14 0.236 0.159 0.124 0.223 0.1 1.27
N N
0.028 0.13
Y Y
0.188 0.342 0.72 0.1 0.036 0.072 0.23 1.6 0.33 0.031
N Y Y Y Y N Y
0.21
Y
Y
Refs. 168 256 806 806 806 35 806 222 806 806 806 806 806 380 390 547 806 806 775 989 125 128 256 447 554 128 139 139 140 150 523 554 756 806 806 128 256 806 806 806 806 1025 956 806 839 806 128 160 256 535 261 256 817 806 806 806 7 104 163 693 80 953 925 583 670
References page II - 290
TABLE 1. cont'd Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
Monomer 2
rx
Tetrazole, 2-phenyl-5-(4/-vinyl)phenyl0.95 Tetrazole, 5-phenyl-2-(4/vinyl)phenyl0.48 Tetrazole, 5-vinyl0.78 Tetrazole, 5-vinyl0.78 Toluenesulfonamide, 7V,N-methyl-vinyl5.6 Triallyl citrate 20.02 Triallyl cyanurate 32.45 Triallyl isocyanurate 28.6 Triazine, 1,3,5-, 2-amino-4-(N-methyl0.306 /7-aminoanilino)Triazine, 1,3,5-, 2-amino-4-(7V-methyl0.169 p-nitroanilino)Triazine, 1,3,5-, 2-amino-4-(/?-nitroanil)- 0.257 Triazine, 4,6-diamino-2-vinyl1.104 Triazole, 1,2,3-, l-/?-bromophenyl-4-vi 1.32 Triazole, 1,2,3-, 4(5)-vinyl1.48 Urea, l,3-divinyl-l,3-diphenyl3.62 Urea, N-acryloyl-W-benzoyl0.404 Urea, TV-vinyl-iV'-ethyl10.78 Valerolactone, a-methylen0.097 Valerolactone, a-methylene0.096 Vinyl 2-, 1,1-dichlorocyclopropane 17.98 Vinyl 2-, 2-methyl-4,4,6-6-tetraphenyl 0.11 cyclotrisiloxane Vinyl 2-chloroethyl ether 160 Vinyl 4, dithiobenzoate methyl 0.111 Vinyl 4-chlorocyclohexyl ketone 0.53 Vinyl acetate 42.48 Vinyl acetate 18.8 Vinyl acetate 56 Vinyl acetate 48 Vinyl acetate 60 Vinyl acetate 57.8 Vinyl acetoxymethyl ketone 0.103 Vinyl benzoate 34.8 Vinyl benzoate 31.56 Vinyl benzyl sulfide 2.32 Vinyl bromide 16.88 Vinyl bromide 18 Vinyl bromide 15 Vinyl butyl ether 21.25 Vinyl butyl sulfide 2.69 Vinyl butylsulfonate 1.74 Vinyl chloride 27.54 Vinyl chloride 17.24 Vinyl chloride 23.92 Vinyl chloride 25 Vinyl chloride 12.4 Vinyl chloride 14.7 Vinyl chloroacetate 14.57 Vinyl chloroacetate 45 Vinyl chloromethyl ketone 0.127 Vinyl cymantrene 2.324 Vinyl dichloroacetate 20 Vinyl dodecyl ether 27 Vinyl dodecyl ether 56 Vinyl ether 152 Vinyl ethyl ether 90 Vinyl ethyl ether 111 Vinyl ethyl ketone 13.83 Vinyl ethyl ketone 0.2 Vinyl ethyl ketone 0.29 Vinyl ethyl ketone 0.665 Vinyl ethyl oxalate 5.62 Vinyl ethyl sulfide 4.76
±95%
r2
±95%
Conv.
Refs.
0.3 1.13 0.81 1.27 1.39 0.054
1 2.2 0.31 0.31 -0.58 0.076 0.22 -0.05 0.44
0.02 0.44 0.041 0.12 0.11 0.12
Y Y Y Y Y
583 583 870 902 80 367 201 201 364
0.013
1.676
0.065
Y
364
0.062 0.157 0.15 0.12 0.98
0.91 0.538 0.73 0.52 -1.76 0.053 -0.33 1.42 1.44 0 0.8
0.18 0.141 0.4 0.26 1.36
Y Y Y Y
0.33
Y
364 806 670 670 800 1090 101 919 855 806 626
2.07
0.59
0.009 26.85 2.87
0.011 29.3 4.33 0.25 0.94 8.26 16.53 0.25 0.27 7.35 1.12 3.6 5 29.2 62.41 0.047 0.06
185 15.5 1.44 0.08 0.16 0.021 1.06 0.2
0.07 2.08 0.58 -0.04 0.02 0.01 0.05 0.16 0.08 0.368 -0.02 0.06 0.04 0.012 0.06 0.09 -0.08 -0.06 0 -0.06 0.058 0.16 0.005 0.04 0.01 -0.04 0.03 0.507 0.096 0.28 0 0 1.2 0 -0.122 -0.033 0.43 0.332 0.122 -0.12 0.113
0.034
0.81
Y
0.072 0.12
Y Y
0.018 1.62 0.15 0.17 0.049
Y N Y Y
0.2 0.78 0.18 0.16 0.08 0.003 0.08 0.031
N Y Y Y Y Y N Y
0.87 0.24
Y Y
0.039 0.014
Y Y
5.3
Y
0.066 0.023 0.06 0.043 0.017 0.19 0.032
Y Y N Y Y Y Y
597 697 668 158 241 481 481 481 812 806 26 696 303 34 34 368 241 303 185 109 238 242 46 516 59 212 542 353 354 542 374 374 45 140 194 112 344 353 550 124 303
TABLE 1. cont'd Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
Monomer 2 Vinyl ethyl sulfide Vinyl ethyl sulfioxde Vinyl ethyl sulfoxide Vinyl hendecanoate Vinyl iodide Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl sulfide Vinyl isopropyl ketone Vinyl isopropyl ketone Vinyl isopropyl ketone Vinyl isopropyl sulfide Vinyl isothiocyanate Vinyl isothiocyanate Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl sulfide Vinyl methyl sulfide Vinyl methyl sulfide Vinyl methyl sulfone Vinyl methyl sulfoxide Vinyl octyl ether Vinyl pelargonate Vinyl phenyl ether Vinyl phenyl ketone Vinyl phenyl ketone Vinyl phenyl sulfide Vinyl phenyl sulfide Vinyl phenyl sulfone Vinyl stearate Vinyl sulfone Vinyl tert-butyl ketone Vinyl tert-butyl ketone Vinyl tert-butyl sulfide Vinyl thiolacetate Vinyl, 1-cyano, acetate Vinyl, 2-bromo-, ethyl ether Vinyl, p-benzylmethylcarbinol Vinyl-frts(trimethoxysiloxy)silane Vinyl-fns(trimethoxysiloxy)silane Vinylacetophenone, pVinylanthracene, 9Vinylanthracene, 9Vinylbenzoic acid, /?Vinylene carbonate Vinylene carbonate Vinylferrocene Vinylferrocene Vinylhydroquinone dibenzoate Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene cyanide Vinylidene cyanide Vinylisocyanate Vinylisocyanate Vinylmethyldiacetoxysilane Vinylmethyldiethoxysilane Vinylmethyldiethoxysilane Vinylphenyldimethylsilane
rx 6 9.64 6 24.89 7.401 11.58 11.96 50 2.38 0.46 0.36 0.4 4.61 0.65 0.8 0.288 0.237 0.35 4.5 4.46 5 1.146 3.57 65 49.5 1.7 0.24 0.21 3.63 3.96 1.562 15.96 0.731 0.3 0.36 4.36 4 0.181 0.98 26 24 0.246 2.12 2.12 0.282 411 21.03 4.37 2.76 0.22 1.81 1.79 1.8 1.839 1.81 1.7 0.015 0.003 8.13 6.9 4.08 5.68 11.29 32.53
±95%
0.54 1.22 0.315 1.91 2.32 0.41 0.05 0.1 0.18 0.092 0.023 0.11 0.24 0.087
0.04 0.042 0.12 0.27 0.091 13.32 0.058 0.31 0.11 0.76 0.409 0.32 0.072 0.011 23.45 1.44 0.22 0.35 0.14 0.024 0.12 0.007 0.001 0.14 0.1 0.43 0.49
r2 0.25 0.101 0.1 -0.17 0.126 0.65 0.29 0.01 -0.11 0.26 0.272 0.3 0.16 0.37 0.5 0.349 0.348 0.27 0.15 0.066 0.046 -0.22 0.01 0 0.01 0.01 0.3 0.465 0.019 0.26 -0.31 -0.39 -0.027 3.2 0.248 0.158 0.25 0.147 0.94 0 0.01 1.12 0.25 0.3 1.029 3.16 -0.73 0.2 0.14 0.43 0.134 0.098 1.5 0.87 0.15 0.11 0.72 0.001 0.08 0.1 0 0.08 -0.08 0.024
±95%
Conv.
0.044
Y
0.18 0.035 0.39 0.33
Y N N
0.2 0.07 0.046
Y N Y
0.068
Y
0.068 0.009
Y Y
0.056 0.084 0.17
Y Y Y
0.02 0.03 0.054 0.18 0.16 0.71 0.047 0.46 0.05 0.073
N Y Y N Y Y Y N Y Y
0.033 0.15
Y Y
0.42
Y
0.06 0.98 0.1 0.14
Y Y Y Y Y
0.48 0.01
Y Y
0.007
Y
0.005 0.16 0.001
N Y Y
0.15 0.14 0.2 0.016
Y Y Y Y
Refs. 507 286 286 145 806 349 349 490 303 344 353 599 303 422 542 140 353 550 193 195 303 195 737 374 145 423 344 353 193 239 193 145 45 344 353 303 566 806 194 48 209 482 266 123 48 266 103 120 274 294 440 138 238 393 59 812 93 134 82 435 533 754 754 754 482
References page II-290
TABLE 1. cont'd Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene sulfonate, sodium salt Styrene, 2,4,6-trimethylStyrene, 2,4,6-trimethylStyrene, 2,4,6-trimethylStyrene, 2,4,6-trimethylStyrene, 2,4-dibromoStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dimethylStyrene, 2,6-dichloroStyrene, 2,4,5-tribromoStyrene, 3-tri-rc-butylstannylStyrene, 3-tri-/2-butylstannylStyrene, 3-tri-n-butylstannylStyrene, 3-tri-rc-butylstannylStyrene, 3-tri-rc-butylstannylStyrene, 4-(te?t-butyldiinethylsilyloxy)Styrene, 4-(trimethylsilyl)Styrene, 4-methylStyrene, 4-methylStyrene, 4-phenoxyStyrene, a-(trimethylsiryloxy)Styrene, a-(trimethylsilyloxy)Styrene, a-methoxyStyrene, a-methoxyStyrene, a-methoxyStyrene, a-methoxyStyrene, a-methoxyStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methyl-
Monomer 2 Vinylphenylpropanol, 2-pVinyltriethoxysilane Vinyltrimethylsilane Vinyltrimethylsilane Vinyltrimethylsilane Xanathate, 5-methacryloyl O-ethyl N-Vinylpyrrolidone Acrylonitrile Methacrylate, methyl Methacrylate, methyl Styrene, /7-chloroStyrene Acrylate, methyl Acrylate, methyl Acrylonitrile Acrylonitrile Acrylonitrile Butadiene Butadiene Methacrylate, methyl Pyridine, 2-vinylStyrene Styrene Styrene Styrene Styrene, 2,5-dimethylStyrene, a-methylVinyl methyl ketone Vinylidene cyanide Styrene, 2,5-dichloroMethacrylate, methyl Styrene Acrylate, ethyl Acrylonitrile Methacrylate, methyl Styrene Vinyl acetate Styrene Styrene Acrylonitrile Methacrylate, methyl Styrene Acrylonitrile Styrene Acrylate, methyl Acrylonitrile Methacrylate, methyl Methacrylonitrile Styrene Acrylate, 2-cyano-, methyl Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Butadiene Butadiene, 2-fluoroFumaronitrile Maleic anhydride Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl
rx
±95%
r2
±95%
Conv.
Refs.
Y Y Y Y Y
72 209 209 482 73 1086 939 58 58 58 58 806 136 2 84 84 84 255 8 3 2 14 411 419 84 91 377 375 82 91 324 1054 985 985 985 985 985 976 1036 929 929 602 970 970 142 142 142 143 142 452 171 265 265 265 75 75 835 94 70 174 77 492 265 265 265
0.48 20.86 14.66
0.3 1.99 5.15
0.41 -0.09 -0.19
0.4 0.14 0.36
5.98 0.44 7.19 0.065 0.083 -0.01 0.34 0.91 3.93 4.47 0.08 0.07 0.09 0.45 0.187 2.66 0.14 0.81 0.25 2.2 0.14 1.543 3 2 0.026 0.263 -0.15 2.78 0.01 0.001 0.03 0.03 0.38 0.863 0.28 0.227 0.46 0.94 0 0 0.003 -0.002 -0.02 -0.02 0.07 0.05 0.08 0.14 0.17 0.24 0.09 0.103 0.14 0.08 0.139 0.72 0.094 0.04 0.27 0.51 0.6
0.18 0.06
0.049 0.36 0.084 0.874 1.511 1.45 17.83 0.14 0.142 0.288 0.22 0.25 0.26 0.449 0.662 0.44 0.62 0.268 0.18 0.23 0.26 0.263 0.14 0.5 0.005 1.543 1.98 0.23 10.4 4.88 0.69 18.5 5.33 0.877 0.48 0.079 0.345 1.38 0.05 1.48 0.17 0.06 2.5 0.83 2.51 0.001 0.07 0.04 0.04 0.04 0.063 0.34 0.03 - 0.02 1.5 2.22 -0.01 0.08 0.48 0.55 0.55
0.025 0.08
0.048 0.045 0.11 1.05 2.88 1.38 0.15 0.03 0.17 0.049 0.38 0.18 0.14 0.04 0.068 0.006 0.022 0.27
0.193 0.021 0.022
0.01 0.01 0.04 0.005 0.05 0.03 0.03 0.024 0.036 0.07 0.087 0.24 0.02 0.07
0.051 0.072 0.16 5.24 1.61 0.054 0.069 0.01
Y Y Y Y
0.043 0.017 0.13 0.12 0.08
Y Y Y N Y
0.17 0.022
N Y
0.009 0.068 0.16
Y Y N
0.351
Y
0.005 0.008
Y Y
0.02 0.01 0.39 0.04 0.34
N N N N N
0.04 0.005
N N
0.041 0.15
Y Y
0.27 0.13 0.7 0.078
N Y Y Y
0.02
N
Y Y N
Next Page
TABLE 1. cont'd Monomer 1 Styrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, ra-aminoStyrene, ra-aminoStyrene, m-aminoStyrene, ra-bromoStyrene, ra-bromoStyrene, ra-bromoStyrene, ra-bromoStyrene, ra-bromoStyrene, ra-chloroStyrene, ra-chloroStyrene, ra-chloroStyrene, ra-cyanoStyrene, ra-diethylaminoethylStyrene, ra-dimethylaminoStyrene, ra-hydroxyStyrene, ra-methoxyStyrene, ra-methyl Styrene, ra-methyl Styrene, ra-methyl Styrene, ra-methyl Styrene, ra-methyl Styrene, ra-methyl Styrene, ra-methyl Styrene, ra-methylStyrene, m-methylStyrene, ra-nitroStyrene, ra-nitroStyrene, ra-nitroStyrene, ra-sulfonic acid fluoride Styrene, o-chloroStyrene, o-chloroStyrene, ochloroStyrene, o-chloroStyrene, o-chloroStyrene, ochloroStyrene, o-chloroStyrene, o-chloroStyrene, p-2-methoxyphenyl ketone Styrene, p-phenyl ketone Styrene, p-phenyl ketone Styrene, p-1 -(2-hydroxybutyl)Styrene,/7-1-(2-hydroxybutyl)Styrene, p-1-(2-hydroxybutyl)Styrene, p-1-(2-hydroxypropyl)Styrene, p-1-(2-hydroxypropyl)Styrene, p-1-(2-hydroxypropyl)Styrene, p-1-(2-hydroxypropyl)Styrene, p-2-(2-hydroxypropyl)Styrene, p-2-(2-hydroxypropyl)Styrene, p-2-(2-hydroxypropyl)Styrene, p-2-(2-hydroxypropyl)-
Monomer 2 Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylonitrile Styrene Styrene Styrene Styrene Styrene Styrene Styrene, 2,5-dichloroStyrene, p-chloroVinyl chloromethyl ketone Vinylhydroquinone dibenzoate Styrene Styrene Styrene, p-aminoMethacrylate, methyl Styrene Styrene Styrene, p-methoxyMethacrylate, methyl Styrene Styrene Styrene, p-methoxyStyrene Styrene Styrene Styrene Styrene Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylic acid Methacrylic acid Methacrylic acid Acrylate, methyl Acrylonitrile Methacrylate, methyl Methacrylate, methyl Styrene Styrene, p-chloroStyrene Acrylate, butyl Indene Methacrylate, butyl Methacrylate, ethyl Methacrylate, methyl Methacrylate, methyl Methacrylic acid Methacrylonitrile Styrene Styrene Styrene Acrylate, butyl Acrylate, methyl Acrylonitrile Acrylonitrile Methacrylate, methyl Styrene Styrene, p-chloroAcrylonitrile Styrene Styrene Styrene, p-chloro-
rx 0.14 0.22 0.48 0.15 0.14 0.05 0.3 0.4 0.521 0.63 0.14 0.21 0.009 0.11 1.16 1.18 0.63 1.17 1.6 1.05 1.4
±95%
0.06 0.13 0.084 0.2 0.01 0.007
r2 0.5 0.42 0.47 0.21 1.21 0.96 1.09 1.13 1.08 1.12 3 1.56 0.386 0.3 1.04 0.786 0.49 0.48 0.5 0.55 0.25
±95%
Conv.
0.41 0.03
N N
0.11
Y
0.42 0.034
Y Y
0.01
Y
Y 2.3 1.09 1.9 0.363 1.21 0.617 1.33 0.661 0.53 0.36 0.51 0.06 0.33 0.42 1.65 0.43 0.486 0.8 0.5 1.73 1.268 2.25 2.86 1.24 1.34 1.37 1.34 0.101 0.78 1.52 2.58 0.55 0.4 0.48 0.31 0.53 1 0.91 0.63 0.41 0.56 1.25 0.53
0.08 0.26 0.264 0.06 0.232 0.04 0.06 0.05 0.03 0.02 0.01 0.02 0.32 0.14 0.47 0.236 0.83
0.034 0.58 0.83 9.44
0.57 0.64 0.2 0.851 1.2 1.027 0.78 1.742 0.48 0.38 0.41 0.35 0.18 0.51 0.14 0.07 0.512 0.35 0.279 0.3 0.788 0.2 - 0.069 0.32 0.45 0.5 0.46 0.622 0.86 0.23 0.11 0.13 0.17 0.18 0.04 0.1 0.26 0.97 0.91 0.05 0.5 0.79 1.24
0.534 0.28 0.248 0.07 0.456 0.04 0.03 0.04 0.08 0.02 0.01
N
0.036 0.11 0.055 0.14 0.183
Y Y Y Y
0.066
Y
0.058
Y
0.07 0.15 0.02
Refs. 532 835 899 542 171 281 281 281 289 289 377 218 356 440 775 989 774 256 168 256 168 150 168 256 168 806 806 806 35 806 1087 1087 1087 1087 1087 1087 558 378 256 222 222 222 806 558 6 558 558 532 558 6 44 806 806 806 548 548 548 380 380 380 380 547 390 547 547
References page II - 290
Previous Page
TABLE 1. cont'd Monomer 1 Styrene, p-4-methoxyphenyl ketone Styrene, p-WV-dimethylaminoStyrene, p-WV-dimethylaminoStyrene, p-WV-dimethylaminoStyrene, p-AW-dimethylaminomethylStyrene, p-acetoxyStyrene,/7-acetoxyStyrene, p-acetoxyStyrene, p-aminoStyrene, p-aminoStyrene, p-aminoStyrene, p-bromoStyrene, p-bromoStyrene, p-bromoStyrene, p-bromoStyrene, p-bromoStyrene, p-bromoStyrene, p-bromoStyrene, /?-chloroStyrene, p-chloroStyrene, p-chloroStyrene,/7-chloroStyrene, p-chloroStyrene, p-chloroStyrene,/7-chloroStyrene,/7-chloroStyrene,/7-chloroStyrene,/?-chloroStyrene, /7-chloroStyrene, /7-chloroStyrene,/7-chloroStyrene, p-chloroStyrene,/7-chloroStyrene,/7-chloroStyrene,/?-chloroStyrene,/7-chloroStyrene,/7-chloroStyrene,/7-chloroStyrene,/7-chloroStyrene,/7-chloroStyrene, p-chloroStyrene, p-chloroStyrene, p-chloroStyrene, p-chloroStyrene, p-chloroStyrene, p-chloroStyrene, p-chloroStyrene, p-chloroStyrene, p-chloroStyrene, p-chloromethylStyrene, p-chloromethylStyrene, p-chloromethylStyrene, p-chloromethylStyrene, p-chloromethylStyrene, p-chloromethylStyrene, p-chloromethylStyrene, p-chloromethylStyrene, p-chloromethylStyrene, p-cyanoStyrene, p-cyanoStyrene, p-cyanoStyrene, p-cyanoStyrene, p-cyanoStyrene, p-decylStyrene, p-diethylaminoethyl-
Monomer 2 Styrene Acrylate, methyl Benzophenone, p-vinylMethacrylate, methyl Benzophenone, p-vinyl Acrylonitrile Styrene Styrene Styrene Styrene Styrene, m-aminoMethacrylate, methyl Styrene Styrene Styrene Styrene Styrene Styrene, p-methoxyAcrylate, a-trifluoromethyl-, methyl Acrylonitrile, a-trifluoromethylButadiene Butadiene, l-(2-hydroxyethylthio)Carbazole, Af-vinylCyclopentene, 4-,-1,3-dione Itaconate, dimethyl Methacrylate, butyl Methacrylate, butyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Norbornadiene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene, 2,4,6-trimethylStyrene, a-methylStyrene, m-nitroStyrene, p-l-(2-hydroxypropyl)Styrene, p-2-(2-hydroxypropyl)Styrene, p-cyanoStyrene, p-methoxyStyrene, p-methoxyStyrene, p-methylVinyl methyl sulfoxide Vinyl, p-, benzylmethylcarbinol Acrylonitrile Butadiene Methacrylate, butyl Methacrylate, ethyl Methacrylate, methyl Phosphazene, isopropenylpentafluoroStyrene Styrene Styrene Methacrylate, methyl Styrene Styrene Styrene, p-chloro Styrene, p-methoxyStyrene Styrene
r\ 1.85 0.38 0.07 0.101 0.26 0.4 1.305 1.218 0.22 1.07 0.49 1.1 1.05 1.1 0.99 1.05 1 1.15 0.24 0.92 1.6 0.24 7 0.294 0.69 1.036 1.025 0.77 0.89 0.47 69.93 1.08 1.029 1.062 1.03 0.76 1.76 1.02 17.83 1.56 0.3 0.91 1.24 0.26 0.47 0.86 1.15 6.46 1 0.56 0.42 1.46 1.29 0.91 1.64 1.12 1.12 1.66 1.41 1.22 1.16 1.28 0.89 0.26 0.59
±95% 0.93 0.16 0.05 0.016 0.017 0.03 0.05 0.069 0.004 0.07 0.05 0.11 0.08 0.02 0.06 5.7 0.081 0.1 0.124 0.12 24.19 0.07 0.056 0.014 0.12 5.24 0.42 0.14 0.08 0.16
0.15 0.58 0.17 0.2 0.46 0.11 0.13 0.03 1.32 0.19
r2 0.423 0.06 0.84 0.204 2.54 0.07 0.835 0.887 0.41 0.876 0.63 0.4 0.7 0.67 0.71 0.71 0.69 0.44 0 - 0.09 1.22 3.27 0.02 0.014 0.15 0.517 0.564 0.334 0.42 0.43 0 0.62 0.744 0.816 0.74 0.39 0.76 0.74 0.34 0.21 1.73 0.63 0.53 1.28 0.41 0.56 0.61 0.01 1 0.067 0.87 0.38 0.36 0.408 -0.048 0.622 0.62 0.6 0.22 0.24 0.28 0.26 0.14 0.88 1.12
±95%
Conv.
0.071 0.01 0.18 0.022 0.136 0.01 0.029 0.034
Y Y Y Y N
0.007
Y
0.03 0.09 0.14
N N Y
0.02 0.03 0.06 2.16
N N N Y
0.006
Y
0.1 0.131 0.016
N
0.12 0.1 0.08 0.029
Y N Y Y
0.043
Y
1.05 0.2 0.47
Y Y Y
0.13 0.08
N N
Y
Y
0.038 0.067 0.047 0.15 0.3
Y Y Y
0.07
N
0.08 0.05 0.22 0.19
N N
Refs. 806 866 866 256 86 47 806 806 775 989 774 256 125 128 256 447 554 128 825 825 255 810 551 264 398 872 966 150 256 476 188 128 139 139 140 150 523 554 58 218 222 380 547 128 128 256 256 737 48 1035 1075 1035 1035 756 765 756 806 806 256 128 256 128 128 806 806
TABLE 1. cont'd Monomer 1 Styrene,/7-dimethylaminoStyrene, /7-dimethylaminoStyrene,/7-dimethylaminomethylStyrene,/7-ethoxyStyrene, p-fluoroStyrene, /7-fluoromethylStyrene,/7-formylStyrene,/7-formylStyrene, /7-iodoStyrene,/7-iodoStyrene,/7-mercaptoStyrene, /7-methoxyStyrene, /7-methoxy Styrene,/7-methoxy Styrene,/7-methoxy Styrene,/?-methoxy Styrene, p-methoxy Styrene, /7-methoxy Styrene,/7-methoxy Styrene,/7-methoxy Styrene,/7-methoxy Styrene, /7-methoxy Styrene,/7-methoxy Styrene,/7-methyl Styrene,/7-methyl Styrene, /7-methyl Styrene,/7-methyl Styrene,/7-methyl Styrene,/?-methyl Styrene, p-methyl Styrene, p-nitro Styrene,/7-octylamine sulfonate Styrene,/7-octylamine sulfonate Styrene,/?-octylamine sulfonate Styrene,/7-octylamine sulfonate Styrene, p-sulfonic acid fluoride Styrene, p-tert-buty\Styrene, p-tert-buty\Styrene, p-trimethoxysilylStyrene,/7-trimethylsilylStyrene, pentachloroStyrene, pentachloroStyrene, pentachloroStyrene, tert-butoxyStyrenesulfonate,/7-, sodium Styrenesulfonate, p-, sodium Styrenesulfonate,/?-, sodium Styrenesulfonate,/?-, sodium Succinamate, potassium TV-vinylSuccinimide, TV-vinylSuccinimide, TV-vinylSuccinimide, TV-vinylSuccinimide, TV-vinylSuccinimide, TV-vinylSuccinimide, TV-vinylSuccinimide, TV-vinylSuccinimide, TV-vinylSuccinimide, N-vinylSuccinimide, TV-vinylSuccinimide, TV-vinylSuccinimide, TV-vinylSuccinimide, TV-vinylSuccinimide, N-vinylSuccinimide, N-vinylSuccinimide, TV-vinyl-
Monomer 2 Acrylate, methyl Benzophenone, p-vinylBenzophenone,/?-vinylStyrene Myrcene Styrene Styrene Styrene Styrene Styrene Styrene Acrylate, methyl Methacrylate, methyl Styrene Styrene Styrene Styrene Styrene; m-bromoStyrene, m-chloroStyrene, /7-bromoStyrene,/?-chloroStyrene, /7-chloroStyrene,/?-cyanoAcrylate, methyl Acrylonitrile Methacrylate, methyl TV,TV-Divinylaniline Styrene Styrene,/?-chloroVinyl methyl sulfoxide Styrene Acrylate, butyl Methacrylate, butyl Methacrylate, methyl Styrene Styrene Methacrylate, methyl Styrene Imidazole, TV-vinylStyrene Methacrylate, methyl Styrene Vinyl chloride Fumarate, dibutyl Acrolein Acrolein Acrolein Acrylate, oc-chloro-, sodium Methacrylate, methyl Acrylamide Acrylate, butyl Acrylate, methyl Acrylonitrile Carbazole, N-vinylMaleate, dimethyl Maleic anhydride Methacrylate, methyl Methacrylate, methyl Pyrrolidone, TV-vinylStyrene Styrene Styrene Styrene Vinyl acetate Vinyl acetate
rx 0.372 0.176 0.135 0.71 0.362 1.399 3 1.43 1.044 0.965 0.907 2 0.32 0.69 1.01 0.82 0.79 0.25 0.2 0.44 0.41 0.56 0.14 1.54 0.33 0.44 6.15 0.993 0.61 2.73 1.13 2.3 1.5 2.6 2.7 1.372 0.5 1.581 6.9 1.15 0.3 0.07 5.3 0.18 0.047 0.327 0.01 1.44 -0.02 0.17 0.15 0.9 0.516 0.11 1.25 0.148 0.048 -0.059 3.67 0.045 0.045 0.01 7 5.68 4.49
±95% 0.055 0.046 0.017 0.14 0.022 0.236
0.159 0.124 0.223
0.1 1.27
0.02 0.08 0.05
0.16 0.028
0.13
0.188 0.342 0.72 0.05 0.1
0.071 0.033 0.009 0.31 0.12
0.17 0.081 0.83 0.16 0.073 0.026 0.096 0.89 0.036 0.072 0.23 1.6 0.12 9.49
r2 0.192 0.842 2.54 0.98 0.87 0.474 0.2 0.16 0.485 0.629 0.607 0.07 0.29 0.85 1.14 1.16 1.05 1.4 1.9 1.15 0.47 0.86 0.89 0.17 0.05 0.4 0.06 0.891 1.15 0.01 0.193 0.3 0.7 0.6 0.7 0.171 0.44 0.774 0.002 1.26 3.65 1.33 0.43 0.01 0.26 0.395 0.113 0.27 1.1 1.86 1.54 0.357 0.116 0.04 -0.012 0.021 9.94 0.01 0.97 10.74 10.09 2.31 0.052 0.072 0.18
±95% 0.01 0.072 0.259 0.19 0.143 0.151
Conv.
Refs.
Y Y Y
911 911 911 806 1062 806 1025 956 806 839 806 558 35 128 160 256 535 168 168 128 128 256 128 558 378 256 45 261 256 737 256 817 817 817 817 806 634 806 1095 806 7 7 516 1077 57 57 57 834 771 600 789 80 80 284 284 284 104 693 96 104 163 693 80 104 167
Y
0.093 0.039 0.188
Y
0.19 0.6
N N
0.08 0.16
N N
0.03
N
0.03 0.086
Y Y
0.092
Y
0.045 0.126 0.47 0.85 0.19
N N
0.16 0.092 0.018 0.06 0.17
Y Y Y Y Y
0.063 0.024 0.09 0.021 0.027 0.27 0.031 0.42 0.49 0.46 0.98 0.32 0.009 0.54
Y Y Y Y Y Y Y N Y Y Y Y Y Y
References page II - 290
TABLE 1. cont'd Monomer 1 Succinimide, N-vinylSuccinimide, N-vinylSuccinimide, N-vinylSulfonate, 2-acrylamido2-methylpropane-, sodium Sulfonic acid, o-methacryloylaminobenzeneSulfonic acid, o-methacryloylaminobenzeneSulfonic acid, o-methacryloylaminobenzeneSulfonic acid,/?-methacryloylaminobenzeneSulfonic acid,/7-methacryloylamino benzeneSulfonic acid, /?-methacryloylamino benzeneTerpyridinyM'-vinyl^'tf'^''Tetrazole, 1-vinylTetrazole, 1-vinylTetrazole, 1-vinylTetrazole, 2-methyl-5-(4/-vinyl)phenylTetrazole, 2-methyl-5-(4/-vinyl)phenylTetrazole, 2-methyl-5-(4/-vinyl)phenylTetrazole, 2-methyl-5-vinylTetrazole, 2-methyl-5-vinylTetrazole, 2-methyl-5-vinylTetrazole, 2-phenyl-5-(4/-vinyl)phenylTetrazole, 2-phenyl-5-(4/-vinyl)phenylTetrazole, 2-phenyl-5-(4'-vinyl)phenylTetrazole, 2-phenyl-5-(4/-vinyl)phenylTetrazole, 2-phenyl-5-(4 '-vinyl)phenylTetrazole, 2-phenyl-5-(4/-vinyl)phenylTetrazole, 5-vinylTetrazole, 5-vinylThioindigoid Thiophene, 3-vinyl Thiophene, 3-vinyl Thioxanthone, 2-(acryloyloxy)Titanium, dicylopentadienyl-, dimethacrylate Titanium, dicylopentadienyl-, dimethacrylate Toluenesulfonamide, A^V-methyl-vinylToluenesulfonamide, AW-methyl-vinylToluenesulfonamide, WV-methyl-vinylToluenesulfonamide, AW-methyl-vinylTriallyl citrate Triallyl citrate Triallyl citrate Triallyl citrate Triallyl citrate Triallyl cyanurate Triallyl cyanurate Triallyl cyanurate Triallyl isocyanurate Triallyl isocyanurate Triallyl isocyanurate Triazine, 4,6-diamino-2-vinylTriazine, l,3,5-2-amino-4-(A^-methylp-aminoanilino)-6-isopropenylTriazine, l,3,5-2-amino-4-(N-methyl/?-aminoanilino)-6-isopropenylTriazine, 1,3,5-2-amino4-(p-nitroanilino)-6-isopropenyl-
Monomer 2
r\
±95%
r2
±95%
Conv.
Refs.
Vinyl acetate Vinyl thiolacetate Vinylidene chloride Acrylamide, AW-dimethyl-
1.99 0.17 0.311 0.162
0.43 0.15 0.058 0.949
0.229 2.47 1.441 1.108
0.06 0.37 0.061 0.59
Y N Y Y
80 97 104 857
Methacrylic acid
0.217
0.122
0.203
0.067
Y
1006
Methacrylic acid
0.523
0.195
0.188
0.076
Y
1006
Pyridine, 2-methyl-5-vinyl-
1.83
0.218
-0.002
0.031
Y
1006
Methacrylic acid
1.08
0.338
0.156
0.081
Y
1006
Methacrylic acid
1.65
0.27
0.155
0.052
Y
1006
Pyridine, 2-methyl-5-vinyl-
2.72
0.525
- 0.054
0.048
Y
1006
1.26 0.314 0.262 0.184 1.1 1.3 1.9 0.486 0.62 28.51 0.4 1 1.8 1.4 2.2 1.9 0.31 0.31 0.5 0.499 0.25 0.5 0.89
0.33 0.066 0.026 0.031
0.53 0.54 7.13 3.85 0.42 0.65 0.13 1.026 1.124 0.04 0.7 0.95 0.25 0.32 0.48 0.11 0.78 0.78 11.5 0.386 0.563 1.36 1.09
0.384 0.032 0.093 0.045
N Y Y Y
0.029 0.081 0.16
Y Y Y
953 925 925 925 583 583 583 670 670 670 583 583 583 583 583 583 870 902 1007 1000 1000 986 895
Styrene Acrylonitrile Methacrylate, methyl Styrene Acrylonitrile Styrene Vinylidene chloride Methacrylate, methyl Styrene Vinyl acetate Methacrylate, methyl Styrene Vinylidene chloride Acrylonitrile Styrene Vinylidene chloride Styrene Styrene Methacrylate, butyl Acrylate, butyl Methacrylate, methyl Methacrylate, methyl Copper diacrylate Nickel diacrylate Acrylonitrile Methacrylate methyl Styrene Vinyl butyl ether Acrylonitrile Allylbenzene Styrene Vinyl acetate Vinyl chloride Methacrylate, methyl Styrene Vinyl acetate Methacrylate, methyl Styrene Vinyl acetate Styrene Styrene
0.075 0.21 31.34
0.02
0.65
0.3
0.95
895
0.04 -1.83 -0.58 -0.31 -0.08 2.01 0.076 2.97 1.03 -0.005 0.22 1.29 - 0.49 -0.05 1.95 0.538 0.44
1.04 0.26 0.44 0.29 0.1 0.5 0.041 0.38 0.17 0.05 0.12 0.42 0.94 0.11 0.42 0.141 0.12
0.42 1.87 5.6 3.37 1.76 0.339 20.02 0.222 0.605 16.12 32.45 0.197 16.88 28.6 0.278 1.104 0.306
0.12 0.19 1.13 1.65 0.082 0.039 0.81 0.025 0.033 0.56 1.27 0.053 6.64 1.39 0.043 0.157 0.054
Y Y Y Y Y Y Y Y Y Y Y Y Y Y Y Y
80 80 80 80 367 367 367 367 367 201 201 201 201 201 201 806 364
Styrene
1.676
0.065
0.169
0.013
Y
364
Styrene
0.91
0.18
0.257
0.062
Y
364
TABLE 1. cont'd Monomer 1 Triazine, 2-allyloxy-4,6-dichloroTriazine, 4,6-diamino-2-vinylTriazole, 1,2,3-, l-/?-bromophenyl-4-vinylTriazole, 1,2,3-, l-p-bromophenyl-4-vinylTriazole, 1,2,3-, l-p-bromophenyl-4-vinylTriazole, 1,2,3-, 4(5)-vinylTriazole, 1,2,3-, 4(5)-vinylTriazole, 1 -N- vinyl-1,2,4Tricyclo[4,2,2,0{2,5}]dec-7-ene3,4,9,10-tetracarboxylicacid Tropone, 2-methacryloyloxyUrea, l,3-divinyl-l,3-diphenylUrea, JV-acryloyl-N'-benzoylUrea, N-vinyl-iV'-ethylUrea, N-vinyl-N'-ethylUrea, N-vinyl-W-ethylUrea, N-vinyl-N'-ethylUrea, JV-vinyl-iV'-ethylValerolactone, a-methyleneValerolactone, a-methyleneVinyl 1-cyano- acetate Vinyl 12-ketostearate Vinyl 12-ketostearate Vinyl 12-ketostearate Vinyl 12-ketostearate Vinyl 2-, 1,1-dichlorocyclopropane Vinyl 2-bromo-ethyl ether Vinyl 2-bromo-ethyl ether Vinyl 2-chlorocyclohexyl ketone Vinyl 2-chloroethyl ether Vinyl 2-chloroethyl ether Vinyl 2-chloroethyl ether Vinyl 2-chloroethyl ether Vinyl 2-chloroethyl ether Vinyl 2-chloroethyl ether Vinyl 2-chloroethyl ether Vinyl 2-chloroethyl ether Vinyl 2-ethylhexanoate Vinyl 3,3-bis(ethoxycarbonyl)propyl ether Vinyl 4-dithiobenzoate methyl Vinyl 4-dithiobenzoate methyl Vinyl 4-chlorocyclohexyl ketone Vinyl 4-chlorocyclohexyl ketone Vinyl 4-chlorocyclohexyl ketone Vinyl 4-chlorocyclohexyl ketone Vinyl 4-chlorocyclohexyl ketone Vinyl N,N-methylacetamide Vinyl oc-chloro-, triethoxysilane Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate
Monomer 2
r\
Pyrrolidone, N-vinylVinyl methyl ketone Methacrylate, methyl Styrene Vinyl acetate Methacrylate, methyl Styrene Imidazole, 1-Af-vinyl Acrylonitrile
0.5 1.35 0.266 0.73 42.47 0.27 0.52
Acrylate, ethyl Styrene Styrene Methacrylate, methyl Styrene Vinyl acetate Vinyl acetate Vinyl acetate Styrene Styrene Styrene Acrylonitrile Vinyl acetate Vinyl chloride Vinylidene chloride Styrene Acrylate, methyl Styrene Maleic anhydride Acrylate, ethyl Acrylate, ethyl Acrylate, methyl Acrylonitrile Methacrylate, methyl Styrene Vinyl acetate Vinyl chloride Acrylonitrile Acrylonitrile
3.13 -1.76 0.053 -0.008 -0.33 0.621 3.61 1.45 1.42 1.44 0.147 -0.18 -0.28 -0.01 0.26 0 -0.79
Methacrylate, methyl Styrene Maleic anhydride Methacrylate, methyl Styrene Vinyl acetate Vinyl cyclohexyl ketone Vinyl acetate Acrylonitrile 2-Oxazoline, 2-isopropenyl2-Oxazolinium BF4, 3-methyl2-isopropenylAcetamide, N-vinylAcetamide, N-vinylAcetate, 2-chloro-, vinyl Acetate, allyl Acetate, chloro-, allyl Acetate, dichloro-, allyl Acetate, trichloro-, allyl Acrolein Acrolein, methyl Acrylamide, N-octadecylAcrylamido, 1-, -1-deoxy-D-glucitol Acrylamido, 2-, -2-methylpropanesulfonate
±95%
0.68 0.058 0.4 9.84 0.13 0.26
0.25
1.7 0.15 0 0 0 0 0.07 0.16 -0.07 -0.047 0.06
r2 0.98 0.17 0.832 1.32 -0.011 0.839 1.48
±95%
Conv.
0.11 0.022 0.15 0.008 0.055 0.12
Y Y Y Y Y Y N
0.027 0.98
Y Y
0.23 2.07 0.029
Y Y Y
2.75 0.528 1.36 0.029 0.33 0.081
0.033 0.36 2.61 0.034 0.32
0.11 0.05
0.387 3.62 0.404 1.85 10.78 0.463 0.16 0.38 0.097 0.096 0.181 3.3 0.18 0.03 4.4 17.98 16.83 0.83 5 4.65 3.27 1.09 18.8 160 2.36 2.46 9.24 1.02
0.409 0.5 4.8 0.59 2.34
Y Y Y Y Y Y
0.52 1.96
Y Y Y Y
0.3 2.08 0.12 0.51 0.58 0.15 0.5 0.93
0.29 0.81
0.151 0.111 0.08 0.77 0.53 0.1 1.6 0.49
0.092 0.009
0.25 0.114
0.04 0.021
7.1 0.413
2 0.005
Y
0.6 0 0.8 1.8 0.77 0.57 0.41 -0.02 0.15 0.004 0.03 0.05
0.12 0.011 0.17
5.5 21 1.18 0.43 0.69 0.54 0.28 3.04 0.98 8.25 0.98 11.6
Y
0.43
N
1.46 0.87
Y N
Refs. 826 243 670 670 670 670 670 972 963 1104 800 1090 101 101 101 683 683 919 855 806 146 146 146 146 806 194 194 836 439 726 726 597 597 597 597 304 47 1015 697 697 836 668 668 668 668 631 237 894 908 984 984 892 1045 1045 1045 1045 207 589 119 258 700
References page II - 290
TABLE 1. cont'd Monomer 1 Vinyl acetate Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl
acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate
Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl
acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate
Monomer 2 Acrylamidomethylamino, p-, azobenzene Acrylate, 2-cyano-, methyl Acrylate, 2-ethylhexyl Acrylate, a-acetoxy-, ethyl Acrylate, a-chloro-, ethyl Acrylate, butyl Acrylate, glycidyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, sodium Acrylate, trifluoro-, methyl Actylate, trifluoro-, methyl Acrylic acid Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Allyl acetate Allyl acetate Allyl acetate Allyl acrylate Allyl butyrate Allyl chloride Allyl chloride Allyl chloride Allyl isobutyrate Allyl propionate Allyl trimethylacetate Allyl valerate Allystearamide, NAzobenzene, 4-(acrylamidomethylamino)Benzothiazole, vinylmercaptoBicyclo[2,2,l]hept-2-ene5,6-dicarboximide, N-benzyl Bicyclo[2,2,l]hept-2-ene5,6-dicarboximide, N-benzyl Bicyclo[2,2,l]hept-2-ene5,6-dicarboximide, Af-benzyl Butadiene, 2-chloroButene-1 Butene-2, cisButene-2, transCaprolactam, Af-vinylCaprolactam, N-vinylCaprolactam, Af-vinylCarbamate, N,N-diethyl-, vinyl Carbamate, N-vinyl-, ethyl Carbamate, N-vinyl-, ethyl Carbamate, N-vinyl-, tert-buty\ Carbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbon monoxide Crotonic acid Crotonic acid Crotonic acid Diallyl P-cyanoethylisocyanurate Diallyl melamine Diallyl phthalate
rx
±95%
r2
±95%
Conv.
Refs.
0.126
12.98
858
0.005 0.04 0.08 0.03 0.018 0.003 0.04 0.03 0.405 0.03 0.03
0.05 7.5 5.621 30 3.48 7.6 7.28 6.38 2.58 6.7 6.3
452 570 244 638 301 553 1067 158 25 489 568 37 595 598 37 158 235 6 75 75 140 502 998 578 998 204 3 438 998 998 998 998 119 880
0.021 0.072 0.01 0.043
0.094
Y
3.39
Y
0.37 0.3
Y Y
Y 0.24 0.24 0.021 0.04 0.06 -0.06 -0.03 0.6 1 1 0.11 0.97 1.355 0.66 0.34 1.04 1.29 1.15 1.07 0.923 0.126 0.013 1.26
0.059 0.067 0.22 0.08 0.09
0.089 0.15
0.092
0.037
0 0 8.66 4.05
Y Y N Y Y Y
5.51 5.29 9.2 0.45 0.7 0.7 17.35 0.64 -2.4 0.61 0.75 0.51 0.42 0.34 0.58 0.68 12.98
0.91 1.13 6.39
0.26
Y
2.53 0.35
0.47
Y
1.46
3.21
Y Y
0.15
0.15
1.99 - 0.02 1.55 %21 12 0.63 0.35 0.35 1.7 0.39 0.418 0.07 0.126 0.15 0.13 0.24 0.317 0.3 0.31 0.06 0.68 0.336
6.63 0.82
994
0.014 0.09 0.24 1.05 1.69
0.04 0.063 1.12 0.023
0.081 0.07 0.026 0.049
33.52 0.11 0.03 -0.03 0.31 2.5 2.5 0.13 2.09 0.4 0.46 2.67 3.02 3.9 0.33 0.04 0.01 0.001 4.6 0.318 2.19
763 994
994 8.98 0.42 0.25 0.44
N Y Y Y
0.19
Y
0.26 0.03 0.13
Y N Y
0.14
Y
0.1
N
0.073 0.34
Y Y
247 211 211 211 557 859 883 197 629 81 827 246 246 551 474 47 526 94 778 201 297
TABLE 1. cont'd Monomer 1 Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate
Monomer 2 Diallyl phthalate Diallyl phthalate Diallyl, 1,3-, 5-(2-hydroxy3-phenoxypropyl) Diallyl, 1,3-, 5-(2-hydroxy3-phenoxypropyl) Diallylcyanamide Diallyldimethylammonium chloride Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene, chlorotrifluoroEthylene, chlorotrifluoroEthylene, dichloro-, cisEthylene, dichloro-, cisEthylene, dichloro-, cisEthylene, dichloro-, cisEthylene, tetrachloroEthylene, tetrachloroEthylene, trichloroEthylene, trichloroFumarate, diethyl Fumarate, diethyl Fumarate, diisopropyl Fumaryl chloride Hexatriene, tetrachloroImidazole, 1-vinylIndene Isobutylene Isobutylene, 3-chloroIsopropenyl acetate Itaconate, dimenthyl Itaconic anhydride Itaconic anhydride Maleate, di-terf-butyl Maleate, diethyl Maleate, dimethyl Maleic anhydride Maleimide, A^-(2-hydroxyethyl)Maleimide, N-(2-hydroxyethyl)Maleimide, A^-(2-hydroxyphenyl)Maleimide, N-hydroxymethylMaleimide, W-phenylMethacrylamide, 1-deoxy-D-glucitol Methacrylate, 2,2,6,6-tetramethyl4-piperidinyl Methacrylate, butyl Methacrylate, di-, di-n-butylstannyl Methacrylate, ethyl Methacrylate, ferrocenylmethyl Methacrylate, isobutyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate acid Methacrylonitrile tyAr-Divinylaniline
rx 0.414 0.72 0.15
±95% 0.029
r2
±95%
Conv.
Refs.
1.66 2 5.5
0.16
Y
297 509 671
0.16
3.65
676
0.01 0.35 0.72
1.62 1.95 0.16
581 1029 309 41 413 42 559 68 68 766 6 1097 236 137 137 9 9 3 59 158 9 137 718 1038 91 4 364 360 211 475 100 975 365 365 1049 137 1049 260 323 323 323 323 328 258 664
1.14 1.03 1.52 3.74 1.23 1.4 0.33 0.68 0.47 1.02 6.4 0.898 4.13 4.45 0.607 0.7 0.011 0.09 0.012
1.2 0.77 0.64 0.21 0.58 0.11 0.27 0.06 1.94 1.87 0.076 0.1 0.004
0.28 0.88 0.74 0.67 0.13 0.79 -0.13 0.04 - .0.02 0.055 0.01 0.058 0.1 -0.07 -0.06 -0.006 0.443 0.33 0.9
N N
0.52
N
0.03 0.01
N N
0.36 0.02
Y
0.34 0.019 0.007
Y Y Y Y Y Y Y Y Y Y
6.99 2.8 0.19
Y Y Y Y Y
0.024 0.03 0.14 0.015
-0.11 0.39 1.66 0.13 1.171
1.17 0.2 0.18
-0.019 - 0.04 0.005 0.171 -0.006 0.019 -0.014 0.01 -0.011 0.017 -0.003 0.16 0.2
0.045 0.024 0.024 0.025 0.084 0.008 0.037 0.041 0.027 0.037 0.006
1.57 2.87 0.199 0.04 0.257 -0.058 0.61 0.88 1.75 1.45 1.284 0.56 13.7
0.36 0.32 0.02 0.012 0.086 0.074 0.12 0.17 0.17 0.21 0.046
Y Y Y Y Y Y Y Y Y Y Y Y Y
-0.003 0.013 -0.77 0.2 -0.06 -0.2 -0.81 0.03 0.04 0.07 0.01 0.01 0.058
0.15 0.018 5.29
30.18 0.013 131.8 1.52 29.7 2.71 137.5 26 28.6 22.21 0.2 12 3.99
14.47 0.036 29.8
Y Y N
24.16 0.25 5.9
Y Y N
0.12
Y
0.038
0.22 0.01 1.17
0.009
1.9 8.64 0.17 0 1.082
0.03
0.074
165 949 210 293 165 158 210 272 383 471 377 75 45
References page II - 290
TABLE 1. cont'd Monomer 1 Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate
Monomer 2
rx
Norbornadiene 0.818 Oxazolidone, N-vinyl0.602 Oxazolidone, Af-vinyl0.55 Oxazoline, 2-, 2-isopropenyl0.25 Oxazoline, 2-, 4-acryloxymethyl0.03 dimethyl-2,4-dimethyl Oxazoline, 2-, 4-methacryloxy0.05 2,4-dimethyl Oxazolinium, 2- tetrafluoroborate, 0.43 3-methyl Phosphate, diethyl isopropenyl 1.56 Phosphine oxide, diphenylvinyl0.38 Phosphonate, oc-carbomethoxyvinyl-, 0.09 diethyl Phosphonate, isopropenyl-, dimethyl 0.14 Phosphonate, vinyl-, bis(2-chloroethyl) 0.09 Phosphonate, vinyl-, bis(2-chloroethyl) 0.09 Phosphonate, vinyl-, bis(2-chloroethyl) 0.33 Phosphonate, vinyl-, diethyl 0.04 Phosphonate, vinyl-, dimethyl 0.04 Phosphonate, vinyl-, dimethyl 0.04 Propene, 1-chloro-, cis7.08 Propene, 1-chloro-, trans3.13 Propene, 2-chloro0.186 Propene, 3,3,3-trichloro0.19 Pyridine, 2-methyl-5-vinyl0.11 Pyridine, 2-vinyl-0.11 Pyridine, 2-vinyl0 Pyrrolidone, N-vinyl0.26 Pyrrolidone, Af-vinyl0.19 Pyrrolidone, N-vinyl0.195 5-Ethyl AT-vinyl-iV-methylthiolcarbamate 0.67 5-Vinyl AW-diethylthiolcarbamate 0.133 Styrene -0.04 Styrene 0.02 Styrene 0.01 Styrene 0.05 Styrene 0.16 Styrene 0.08 Styrene, 3-fn-rc-butylstannyl5.33 Succinimide, N-vinyl0.072 Succinimide, N-vinyl0.18 Succinimide, N-vinyl0.229 Tetrazole, 2-methyl-5-vinyl0.04 Triallyl citrate 0.222 Triallyl cyanurate 0.197 Triallyl isocyanurate 0.278 Triazole, 1,2,3-, l-/?-bromophenyl-0.011 4-vinylUrea, W-vinyl-AA'-ethyl0.463 Urea, N-vinyl-7V'-ethyl0.16 Urea, N-vinyl-Ar'-ethyl0.38 Vinyl 12-ketostearate 0.18 Vinyl 2-chloroethyl ether 2.36 Vinyl 4-chlorocyclohexyl ketone 0.1 Vinyl benzenesulfonate 0.628 Vinyl benzoate 0.455 Vinyl benzoate 0.35 Vinyl benzoate 0.78 Vinyl benzoate 0.7 Vinyl benzoate 0.66 Vinyl benzoate 0.24 Vinyl bromide 0.41 Vinyl bromide 0.6 Vinyl bromide 0.38
±95% 0.019 0.038 0.18
r2 1.354 1.55 2.04 7.1 1.41
±95%
Conv.
0.07 0.28 0.13
Y Y Y
6.2 0.057
0.35 0.15 0.091 0.17 0.25 1.77 0.057 0.1 0.025 0.072 0.12
0.009 0.54 0.06 0.16 0.025 0.053 0.043 0.008 0.029
0.036 0.069 0.52 0.2 0.13 0.09
0.366
Refs. 188 102 36 862 596 596
0.151
Y
877
0.44 1.7 0.6
650 843 684
0.99 0.85 0.85 0.47 0.74 0.74 0.74 -0.012 0.011 1.65 0.19 9 13.65 30 1.06 1.75 3.4 1.22 1.89 42.48 18.8 56 48 60 57.8 0.38 5.68 4.49 1.99 28.51 2.97 1.29 1.95 42.47
684 592 594 595 592 592 594 181 181 181 402 812 6 6 103 121 36 197 197 158 241 481 481 481 812 985 104 167 80 670 367 201 201 670
0.621 3.61 1.45 -0.28 0.16 0.15 -1.34 1.07 0.99 1.64 1.13 1.74 1.98 5.26 1.92 3
0.061 0.074 0.36
Y Y Y
3.64
Y
0.25 2.79 0.21 1.17 0.77 26.85 2.87
Y N Y Y Y Y Y
0.12 9.49 0.43 31.34 0.38 0.42 0.42 9.84
Y Y Y Y Y Y Y Y
0.081
Y Y
1.7 0.27
Y Y
1.93
Y
0.98 1.23 0.35
N Y N
101 683 683 146 597 668 942 253 253 26 272 430 696 158 268 268
TABLEI. cont'd Monomer 1 Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetoxymethyl ketone Vinyl benzenesulfonate Vinyl benzoate
Monomer 2 Vinyl butyl ether Vinyl butyl ether Vinyl butyl ether Vinyl butylsulfonate Vinyl butyrate Vinyl butyrate Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloroacetate Vinyl chloroacetate Vinyl chloroacetate Vinyl chloroformate Vinyl chloroformate Vinyl chloromethyl ketone Vinyl cinnamate Vinyl cyclohexyl ketone Vinyl cymantrene Vinyl dodecyl ether Vinyl ethyl ether Vinyl ethyl ketone Vinyl ethyl oxalate Vinyl fluoride Vinyl formate Vinyl formate Vinyl isopropyl ketone Vinyl isopropyl ketone Vinyl laurate Vinyl methanesulfonate Vinyl methyl ketone Vinyl methyl sulfone Vinyl octadecyl ether Vinyl octyl ether Vinyl phenyl carbonate Vinyl phenyl carbonate Vinyl phenyl ketone Vinyl phenyl sulfone Vinyl propionate Vinyl propionate Vinyl stearate Vinyl stearate Vinyl tert-butyl sulfide Vinyl tert-butyl sulfide Vinyl thiolacetate Vinyl, N-, N-methylacetamide Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene cyanide Vinylidene fluoride Styrene Vinyl acetate Acrylonitrile
rx
±95%
3.72 0.71 2.5 0.025 1 1.35 0.43 0.981 0.24 0.263 0.25 0.65 0.26 0.83 0.803 0.8 0.67 0.66 0.044 0.04 0.08 0.072 3.67 3.42 -0.13 1.35 3.5 0.94 1.41 0.3 -0.154 1.4 0.639
0.09
0 4.5 3.47 0.85 0.85 -0.06 0.171 0.98 0.9 0.953 0.9 13 13 0.05 0.49 3.2 3 7.16 7.3 3.83 3.92 0.03 0.05 0.05 -0.002 0.12 0.003 6 0.368 -1.34 0.019
0.02
0.006 0.14 0.036 0.15 0.028 0.15 0.14 0.12 0.089 0.16 0.12 0.054 0.003 0.18 0.84 0.14 0.073 0.014
0.23 0.23 0.057 0.064 0.015
0.62 0.64 0.18 0.32 0.1 0.026 0.002 0.018 1.7 0.051
r2
±95%
Conv.
0.01 0.2 0.16 0.13 0.97 1.25 1.63 1.032 1.84 2.13 1.64 1.35 2.3 1.39 0.88 1.18 0.579 0.586 49.52 1.2 13.76 7.21 0 0.26 10.18 9.89 0.25 0.98 0.68 7.87 6.47 0.7 0.206
0.02
N
0.33
Y
0.32 0.097 0.68 0.2 0.12
Y Y Y Y Y
0.64 0.3 0.19
N N Y Y Y Y
0.355 0 0 0.384 0.384 5.81 -0.35 0.98 1 0.96 0.73 0.07 0.07 5.5 0.93 0.3 0.27 0.05 0.13 0.044 0.08 4.66 6.7 5 3.49 4.7 0.1 0.08 0.103 0.628 5.03
0.076 0.052 15.79 1.01
Y
6.62 8.44
Y Y Y
0.06
N
2.18
Y
0.427 0.21
Y Y Y
0.083 0.083 0.96 0.37
Y Y Y Y
0.17
Y
0.3
Y
0.16
Y
0.039 0.11 0.26
Y Y Y
0.17
Y
0.11
Y
0.011 0.036 1.08
Y Y
Refs. 345 448 553 185 272 515 109 148 158 283 3 450 86 71 779 861 675 706 356 200 846 354 372 158 794 124 755 272 401 601 794 503 942 91 195 372 372 675 705 794 193 272 425 1 537 598 601 566 631 103 103 120 120 144 90 3 432 436 59 812 82 627 806 942 47
References page II - 290
TABLE 1. cont'd Monomer 1 Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl benzyl sulfide Vinyl benzyl sulfide Vinyl bromide Vinyl bromide Vinyl bromide Vinyl bromide Vinyl bromide Vinyl bromide Vinyl bromide Vinyl bromide Vinyl bromide Vinyl bromide Vinyl bromide Vinyl bromide Vinyl bromide Vinyl bromide Vinyl butyl ether Vinyl butyl ether Vinyl butyl ether Vinyl butyl ether Vinyl butyl ether Vinyl butyl ether Vinyl butyl ether Vinyl butyl ether Vinyl butyl ether Vinyl butyl ether Vinyl butyl ether Vinyl butyl ether Vinyl butyl ether Vinyl butyl ether Vinyl butyl ether Vinyl butyl ether Vinyl butyl ether Vinyl butyl ether Vinyl butyl sulfide Vinyl butyl sulfide Vinyl butylsulfonate Vinyl butylsulfonate Vinyl butylsulfonate Vinyl butylsulfonate Vinyl butylsulfonate Vinyl butyrate Vinyl butyrate Vinyl butyrate Vinyl butyrate Vinyl butyrate
Monomer 2 Allyl chloride Methacrylate, methyl Pyrrolidone, N-vinylStyrene Styrene Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl chloride Vinyl chloride Vinyl chloride Vinyl p-bromobenzoate Vinyl p-chlorobenzoate Vinyl p-cyanobenzoate Vinylidene chloride Vinylidene cyanide Methacrylic anhydride Styrene Acrylate, butyl Acrylate, butyl Acrylonitrile Acrylonitrile Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Styrene Styrene Styrene Vinyl acetate Vinyl acetate Vinyl acetate Acrylate, 2-chloroethyl Acrylate, methyl Acrylate, methyl Acrylonitrile Acrylonitrile Benzenesulfamide, /?-methacrylamideCaprolactam, TV-vinylMethacrylate, 2-bromoethyl Methacrylate, methyl Pyrrolidone, N-vinyl Styrene Toluenesulfonamide, AW-methyl-vinylVinyl acetate Vinyl acetate Vinyl acetate Vinyl chloride Vinyl chloroacetate Vinylidene chloride Acrylonitrile Styrene Acrylate, methyl Styrene Vinyl acetate Vinyl chloride Vinyl chloride Allyl chloride Butadiene, 2-chloroCarbazole, N-vinylEthylene Methacrylate, methyl
T1 0.46 0.07 0.408 -0.02 0.06 1.07 0.99 1.64 1.13 1.74 1.98 0.343 0.5 0.28 0.716 0.832 0.659 0.065 0 - 0.048 0.04 0.18 0.19 0.06 0.06 0.12 0.33 0.052 0.05 0.012 0.06 0.09 5.26 1.92 3 0 0.01 0 -0.03 0 0.03 0 -0.027 -0.08 3.37 0.01 0.2 0.16 0.023 0.12 0.004 0.041 -0.06 0 0 0.13 0.267 0.083 0.31 0.07 1.5 0.03
±95%
0.03 1.62 0.15 0.27 1.93 0.98 0.036 0.031 0.028 0.033 0.093 0.017 0.033 0.17 0.16 0.04 0.06 0.026 0.074 0.049 0.2 1.23 0.35 0.01 0.01 0.73 0.063 0.78 1.65 0.02 0.001 4.39 0.001 0.028 0.18 0.14 0.16 0.33 0.046 0.096 0.12
r2 0.88 20.3 2.507 34.8 31.56 0.455 0.35 0.78 0.7 0.66 0.24 1.66 1.7 0.72 1.17 0.81 0.878 5.58 0.061 0.97 2.32 4.07 3.7 2.25 2.79 14.11 17.1 25.1 19.84 16.88 18 15 0.41 0.6 0.38 2.01 3.65 3.6
±95%
Conv.
0.039 29.3 4.33 0.069
Y Y N Y
0.52
Y
0.2 0.16
N Y
0.13 0.072 0.094 1.76 0.047 0.27 0.25 0.44
Y Y Y Y Y Y Y N
0.2 0.67
N N
0.88 2.58 0.94
Y Y Y
8.26 0.13 0.09
N Y N
0.07
N N N
0.98 3.4 3.1 13.7
0.13 0.1 5.3
1.49 21.25 -0.31 3.72 0.71 2.5 2.084 1.49 1.75 0.086 2.69 4.14 1.74 0.025 0.325 8.47 1.15
0.95 16.53 0.29 0.09
N Y Y Y N
0.016 34.5 0.11 0.01 0.25 0.58 0.27 0.006 0.013 0.86
Y Y Y Y Y Y Y Y Y Y
0.34
N Y
1.33 0.7 25
Y
Refs. 438 272 253 26 696 253 253 26 272 430 696 283 450 519 110 110 110 47 82 106 303 268 268 268 286 268 268 34 34 34 34 368 158 268 268 790 345 574 345 347 1005 215 657 127 215 241 80 345 448 553 279 212 279 303 303 185 185 185 185 185 438 247 246 605 272
TABLE 1.
cont'd
Monomer 1 Vinyl butyrate Vinyl butyrate Vinyl butyrate Vinyl butyrate Vinyl butyrate Vinyl caproate Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride
Monomer 2 Vinyl acetate Vinyl acetate Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Aconitate, trimethyl Acrolein Acrylamide Acrylamide, Af-methylolAcrylate, 2-ethylhexyl Acrylate, butyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, octyl Acrylate, trifluoro-, methyl Acrylate, trifluoro-, methyl Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acryloyl chloride Allyl acetate Allyl acetate Allyltriethoxysilane Butadiene Butadiene Butene-1 Butene-1, 2-ethylButene-1, 2-methylButene-1,3, 3-dimethylButene-1,3, 3-dimethylButene-2 Butene-2, 2-methylButene-2, cisCarbazole, N-vinylCarbon monoxide Crotonaldehyde Diallyl phthalate Diallylcyanamide Diallylcyanamide Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene, chlorotrifluoroFumarate, diethyl Fumarate, diisopropyl Hexene-1 Imidazole, l-vinyl-2-methylIsobutylene
rx 0.97 1.25 0.302 0.55 0.65 0.348 0.04 0.03
0.16 0.07 0.093 0.002 0 0.06 0.12 1.5 1.5 0.107 0.03 0.024 0.11 -0.01 0.07 0.02 0.044 0.052 0.04 0.02 1.2 1.16 1.68 0.04 -0.11 3.34 1.56 1.01 5.64 6.18 3.3 8.52 8.8 0.17 13.52 1.55 0.833 0.44 0.44 3.82 1.99 1.74 4.38 2 3.21 1.85 0.96 1.63 1.55 2.53 0.13 0.29 1.54 0.188 2.04
±95%
0.013
0.05 0.11
0.002 0.01
0.011 0.09 0.069 0.037 0.03 0.08 0.002 0.01 0.029
0.38 0.31 0.58 0.26 0.31 0.2 13.57 2.18 10.54
0.25 0.26 0.012
0.59 0.42 0.58 0.44
0.1 0.22 0.22 0.18 0.1 0.98 0.077 1.82
r2 1 1.35 2.092 1.75 1.35 2.26 0.19 5.22
4.15 4.4 4.4 7.66 5 4 4.8 0 0 6.69 9.28 7.04 6.8 3.26 2.55 2.62 3.62 3.65 4 3.03 0 -0.94 8.8 5.27 0.12 -1.05 -1.18 -0.44 -0.07 -1.79 0.3 0 4.77 0.121 -0.56 0.7 0.68 0.68 0.02 0.19 0.24 0.34 0.2 0.21 0.21 0.14 0.23 0.16 0.01 0.48 0.49 -1.72 2.15 0.06
±95%
Conv.
0.074
Y
0.22 0.13
Y Y N Y Y
0.22 0.5
Y Y
0.88 0.51 0.33
Y N Y
0.34 0.12 0.25 0.21 0.22
Y N N Y Y
0.22
Y
0.48
Y
3.35 0.12 0.89 1.2 0.28 2.5 5.22 5.31
Y Y N N N Y N N
0.011 0.25 0.046
Y N Y
0.06 0.17 0.13 0.13
N N N N
0.01 0.12 0.01 0.01
N N N N
0.1
Y
9.23 0.26 0.8
N Y Y
Refs. 272 515 283 400 494 283 147 271 156 157 510 518 151 46 470 518 518 595 598 135 229 288 379 140 202 22 238 46 529 288 470 475 237 517 717 230 329 329 329 6 329 329 230 427 184 271 296 602 603 161 180 270 42 472 536 63 63 64 68 454 137 1038 329 154 140
References page II - 290
TABLE 1. cont'd Monomer 1 Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl
chloride chloride chloride chloride chloride chloride chloride chloride chloride chloride chloride chloride chloride chloride chloride chloride chloride chloride chloride chloride chloride chloride chloride
Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride
Monomer 2
rx
Isobutylene 2.12 Isobutylene 1.2 Isobutylene 1.54 Isobutylene, 3-chloro0.31 Isopropenyl acetate 2.26 Isopropenylisocyanate 0.39 Itaconate, diethyl 0.06 Itaconate, dimethyl 0.05 Maleate, diethyl 0.768 Maleate, diethyl 0.8 Maleate, diethyl 0.9 Maleate, dioctyl 0.05 Maleic anhydride 0.098 Maleic anhydride 0.04 Maleic anhydride 0.1 Maleimide, N-(4-carboxyethylphenyl)0.04 Maleimide, N-(4-chlorophenyl)0.026 Maleimide, AH4-methylphenyl)0.022 Maleimide, N-butyl0.24 Maleimide, N-phenyl0.023 Maleimide, Af-propyl0.06 Methacrylate, 3,5-dimethyladamantyl 0.21 Methacrylate, p-(2-benzothiazolylthio)- 0.64 ethyl Methacrylate, butyl 0.05 Methacrylate, methyl 0.07 Methacrylate, octyl 0.04 Methacrylic acid 0.064 Methacrylic acid -0.022 Methacrylic acid 0.07 Methacryloyl chloride 0.3 Methacryloyloxy-, 0-, benzoic acid 0.004 Norbornadiene 0.67 Octene-1 3.26 Oxazolidone, Af-vinyl0.313 Pentene-1 4 Pentene-1 2.08 Pentene-1, 2-methyl1.59 Phosphate, vinyl diethyl 3.4 Phosphate, vinyl diphenyl 3.009 Propene, 1-chloro-, ds11.52 Propene, 1-chloro-, trans4.45 Propene, 2-chloro0.095 Propene, 2-chloro0.75 Propenyl, 2-, acetate 2.2 Propenyl, 2-chloro-, acetate 0.7 Propenyltriethoxysilane Propylene 2.35 Propylene -0.05 Propylene 5.16 Propylene 2.45 Propylene 2.9 Pyridine, 4-vinylPyrrolidone, N-vinyl0.53 Pyrrolidone, N-vinyl0.55 Pyrrolidone, Af-vinyl0.74 Styrene -0.06 Styrene 0.058 Styrene 0.16 Styrene 0.005 Styrene 0.04 Styrene 0.01 Styrene, pentachloro0.43 Triallyl citrate 0.605 Vinyl 12-ketostearate 0.03
±95% 0.2 2.05 0.13
0.078 0.11 0.14 0.042 0.03 0.044 0.048 1.13 0.026 0.05 0.04
0.047 0.008 0.02 0.052 0.02 0.45 0.095 1.78 0.68 0.21 0.077 2.14 0.81 0.085
0.14 0.1 0.06
r2 0.268 -0.54 0.08 0 0.23 3 5.65 5 -0.003 0 0.046 0.608 -0.22 0.4 0.67 3.29 3.65 4.49 -12.7 4.01 2.38 1.85 0.26 13.5 8.99 14 23.52 23.26 9.05 2 11.26 0.41 -0.57 0.822 0.001 0.81 -1.16 0.15 0.327 0.1 0.33 4.75 0.58 0.25 0 0.196 3.1 -0.02 0.09
±95%
Conv.
Refs.
0.043 5.8
Y N
0.16
Y
0.044
Y
0.07 0.099 0.38
Y Y Y
155 329 560 475 100 777 480 479 137 449 6 3 260 521 521 306 306 306 305 306 305 335 741
0.18 0.39 0.34 106.2 0.18 0.16 8.87
N Y Y Y Y N N
2.97
Y
0.98 0.96
Y Y
3.5 0.01 0.85 0.048 5.2 2.31 0.047 0.023 0.63 0.4 5.12
Y N N Y Y N N Y Y Y Y Y
0.023 0.21 0.04
Y Y N N Y
0.08 0.003 0.08 0.031 0.87 0.033
0.38 0.34 0.73 27.54 17.24 23.92 25 12.4 14.7 5.3 1.03 - 0.01
7.35 1.12 3.6 5 29.2 0.17
Y Y N Y Y Y Y
519 3 511 135 229 46 432 938 267 329 36 3 329 329 779 779 181 181 181 517 189 445 237 155 329 355 560 588 154 40 582 582 109 238 242 46 516 59 516 367 146
TABLE 1. cont'd Monomer 1 Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloroacetate Vinyl chloroacetate
Monomer 2 Vinyl 2-chloroethyl ether Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl butyl ether Vinyl butylsulfonate Vinyl butylsulfonate Vinyl butyrate Vinyl butyrate Vinyl butyrate Vinyl caproate Vinyl chloroacetate Vinyl dichloroacetate Vinyl dodecyl ether Vinyl fluoride Vinyl fluoride Vinyl hendecanoate Vinyl isobutyl ether Vinyl laurate Vinyl m-cresyl ether Vinyl methyl ketone Vinyl o-cresyl ether Vinyl octadecyl ether Vinyl octyl ether Vinyl p-chlorophenyl ether Vinyl /?-cresyl ether Vinyl p-terf-butylphenyl ether Vinyl p-vinyloxybenzoate Vinyl pelargonate Vinyl phenyl ether Vinyl phenyl ether Vinyl phenyl ether Vinyl propionate Vinyl propionate Vinyl stearate Vinyl tert-buty\ sulfide Vinyl terf-butyl sulfide Vinyl valerate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylethyldiethoxysilane Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene cyanide Vinylidene cyanide Vinylisocyanate Vinylphenylisocyanate, p Vinyltriethoxysilane Vinyltrimethoxysilane Acrylonitrile Acrylonitrile
rx 2.46 1.63 1.032 1.84 2.13 1.64 1.35 2.3 1.66 1.7 0.72 2.084 0.325 8.47 2.092 1.75 1.35 2.26 1.64 1.3 1.93 11 11.6 1.081 2.19 7.4 1.23 0.1 1.33 2.1 1.9 1 1.17 1.08 0.58 1.16 1.28 1.06 1.21 1.6 1.35 0.71 3 3 2.006 4.82 15.38 17.81 0.94 0.071 0.14 0.25 0.3 0.2 0.2 0.16 0.205 0.01 0.016 0.46 0.01 0.82 0.93 -0.007 0.09
±95% 0.52 0.32 0.097 0.68 0.2 0.12 0.64 0.16 0.016 0.013 0.86 0.074 0.22 0.34 0.55
0.016 1.43 0.04 0.02 0.04 0.02 0.06 0.06 0.14 0.03 0.097 0.071 0.49 1.44 7.84 1.53 0.025 0.32
0.003 0.002 0.16 0.016
r2 -0.07 0.43 0.981 0.24 0.263 0.25 0.65 0.26 0.343 0.5 0.28 0.023 0.267 0.083 0.302 0.55 0.65 0.348 0.421 0.91 0.15 0.05 0.11 0.38 0.04 0.2 0.13 8.3 0.14 -0.1 0.1 0.63 0.13 0.14 0.78 0.28 0.01 0.16 0.17 0.6 0.65 0.24 0.15 0.15 0.277 0.03 0.069 0 -0.44 2.06 3.39 8.92 3.2 4.5 1.8 4.5 3.068 0.72 0.6 3.7 11.9 -0.04 0.09 4.18 0.34
±95%
Conv.
0.11 0.14 0.036 0.15 0.028 0.15
Y Y Y Y Y Y
0.14 0.036
N Y
0.001 0.046 0.096 0.013
Y Y Y Y
0.05 0.055 0.49
Y Y Y
0.022 0.37
Y Y
0.02
Y
0.01
Y
0.05 0.01 0.02 0.07
Y Y Y N
0.59
Y
0.03
N
0.64
Y
0.014 0.12 0.068 0.22 2.97 0.32 1.16
Y Y Y Y Y Y N Y
0.076
Y
0.068
Y
0.44
Y Y Y
0.33
Refs. 304 109 148 158 283 3 450 86 283 450 519 279 185 185 283 400 494 283 283 283 370 590 755 145 47 450 279 375 279 370 370 279 279 279 497 145 172 279 280 400 450 145 598 601 283 103 319 319 237 238 29 3 470 517 539 585 67 409 82 777 777 237 237 362 542
References page II-290
TABLE 1. cont'd Monomer 1 Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl
chloroacetate chloroacetate chloroacetate chloroacetate chloroacetate chloroacetate chloroacetate chloroacetate chloroacetate chloroacetate chloroacetate chloroacetate chloroethyl ether chloroethyl ether chloroformate chloroformate chloromethyl ketone chloromethyl ketone chloromethyl ketone chloromethyl ketone chloromethyl ketone chloromethyl ketone cinnamate cinnamate cinnamate cyclohexyl ether cyclohexyl ketone cyclohexyl ketone cymantrene cymantrene cymantrene cymantrene cymantrene dichloroacetate dichloroacetate dichloroacetate dichloroacetate diethylphosphinate diethylphosphinate dodecyl ether dodecyl ether dodecyl ether dodecyl ether dodecyl ether dodecyl ether ether ether ether ether ethyl ether ethyl ether ethyl ether ethyl ether ethyl ether ethyl ether ethyl ether ethyl ether ethyl ether ethyl ether ethyl ketone ethyl ketone ethyl ketone ethyl ketone ethyl ketone ethyl ketone
Monomer 2 Phosphate, vinyl diethyl Phosphate, vinyl diphenyl Styrene Styrene Vinyl acetate Vinyl acetate Vinyl acetate Vinyl butyl ether Vinyl chloride Vinyl ethyl ether Vinyl phenyl ether Vinylidene cyanide Acrylonitrile Methacrylic anhydride Vinyl acetate Vinyl acetate Acrylonitrile Methacrylate, methyl Styrene Styrene, a-methylVinyl acetate Vinylidene chloride Methacrylonitrile Pyrrolidone, N-vinylVinyl acetate Pyrrolidone, A^-vinylVinyl 4-chlorocyclohexyl ketone Vinyl acetate Acrylate, methyl Acrylonitrile Pyrrolidone, N-vinylStyrene Vinyl acetate Acrylonitrile Acrylonitrile Styrene Vinyl chloride Ethylene Ethylene Acrylonitrile Styrene Styrene Vinyl acetate Vinyl chloride Vinylidene chloride Acrylonitrile Methacrylate, methyl Pyridine, 4-vinylStyrene Acrylate, methyl Acrylonitrile Ethylene Fumarate, diethyl Methacrylate methyl Styrene Styrene Vinyl acetate Vinyl chloroacetate Vinylidene chloride Methacrylate, methyl Styrene Styrene Styrene Styrene Vinyl acetate
rt 2.01 1.42 -0.04 0.03 1.39 0.88 1.18 1.49 0.421 1.92 0.84 0 -0.02 0.579 0.586 0.88 0.593 0.507 0.386 49.52 6.8 0.15 1.2 1.2 -0.11 1.6 13.76 0.211 - 0.065 0.093 0.096 7.21 0.044 0.18 0.28 0.91 -11.99 -62.84 0 0 0 0 0.15 0 0.02 -0.15 0.03 1.2 0 0.06 0 -0.124 0.01 0 -0.122 0.26 0.43 0 0.65 -0.033 0.43 0.332 0.122 10.18
±95% 0.2 0.15 0.24 0.3 0.19 34.5 0.055 17.19 1.67 0.006 0.02 0.076 0.052 0.12 0.092 0.039 0.034 15.79 0.3
0.59
0.067 0.093 0.053 0.014 1.01 0.015
0.49 80.64 34.66
0.16 5.3 0.12 0.059
0.066 3.9 0.42 0.023 0.06 0.043 0.017 6.62
r2
±95%
Conv.
0.374 0.53 14.57 45 0.83 0.803 0.8 0.12 1.64 0.43 0.55 0.137 1.04
0.046 0.12 62.41
Y Y Y
0.12 0.089
N Y
4.39 0.34 3.9 0.61 0.037 0.05
0.67 0.66 0.064 0.121 0.127 0.009 0.044 0.018 4.6 0.01 0.04 1.91 0.5 0.08 0.46 0.446 0.037 2.324 0.072 7.45 0.25 20 1.3 0.15 0.05 0.82 27 56 3.67 1.93 1.3 0.94 4.9 32 152 3.3 0.69 2.7 1.63 37 90 111 3.42 1.92 3.2 0.42 13.83 0.2 0.29 0.665 -0.13
0.16 0.12 0.019 0.021 0.047 0.01 0.054 0.009
Y Y Y Y Y N Y Y Y Y Y Y Y Y Y
9.39
Y
0.14 0.048 0.03 0.06 0.003 0.32
Y Y Y Y Y Y
0.55 0.16 0.01
Y Y Y
0.99
Y
185
Y
0.12
N
0.16
Y
15.5 17.19 0.17 1.44 0.08 0.16 0.021 0.18
Y Y Y Y Y N Y Y Y
Refs. 779 779 212 542 71 779 861 212 283 212 212 82 116 106 675 706 356 356 353 356 356 356 200 200 200 214 668 846 354 354 308 354 354 362 542 542 283 311 311 373 374 374 372 370 371 386 45 395 45 470 194 584 194 106 140 194 158 212 470 794 112 344 353 550 794
TABLE 1. cont'd Monomer 1 Vinyl ethyl oxalate Vinyl ethyl oxalate Vinyl ethyl oxalate Vinyl ethyl oxalate Vinyl ethyl sulfide Vinyl ethyl sulfide Vinyl ethyl sulfide Vinyl ethyl sulfide Vinyl ethyl sulfide Vinyl ethyl sulfide Vinyl ethyl sulfoxide Vinyl ethyl sulfoxide Vinyl ethyl sulfoxide Vinyl ethyl sulfoxide Vinyl ethylene glycol glycidyl ether Vinyl ethylene glycol glycidyl ether Vinyl fluoride Vinyl fluoride Vinyl fluoride Vinyl fluoride Vinyl fluoride Vinyl fluoride Vinyl fluoride Vinyl fluoride Vinyl fluoride Vinyl fluoride Vinyl fluoride Vinyl fluoride Vinyl fluoride Vinyl formate Vinyl formate Vinyl formate Vinyl formate Vinyl formate Vinyl formate Vinyl formate Vinyl hendecanoate Vinyl hendecanoate Vinyl hendecanoate Vinyl hendecanoate Vinyl hendecanoate Vinyl hendecanoate Vinyl iodide Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl sulfide Vinyl isobutyl sulfide Vinyl isobutyl sulfide Vinyl isobutyl sulfide Vinyl isobutyl sulfide Vinyl isobutyl sulfide Vinyl isobutyl sulfide Vinyl isobutyl sulfide
Monomer 2
r\
Acrylonitrile Methacrylate, methyl Styrene Vinyl acetate Acrylonitrile Acrylonitrile Methacrylate, methyl Methacrylate, methyl Styrene Styrene Acrylonitrile Methacrylate, methyl Styrene Styrene Pyrrolidone, AT-vinylPyrrolidone, N-vinylAcrylate, butyl Acrylate, butyl Acrylate, methyl Acrylate, methyl Acrylonitrile Acrylonitrile Ethylene Ethylene Ethylene, chlorotrifluoroVinyl acetate Vinyl chloride Vinyl chloride Vinylidene chloride Acrylonitrile Allyl chloride Butadiene, 2-chloroButadiene, 2-chloroCarbazole, iV-vinylVinyl acetate Vinyl acetate Acrylate, methyl Acrylonitrile Butadiene Styrene Vinyl chloride Vinylidene chloride Styrene Acrylate, 2-chloroethyl Acrylate, methyl Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Ethylene, trichloroFumarate, diethyl Maleate, diethyl Styrene Styrene Styrene Vinyl chloride Vinylene carbonate Acrylate, ethyl Acrylate, ethyl Acrylate, methyl Acrylate, methyl Acrylonitrile Acrylonitrile Acrylonitrile Methacrylate, methyl
0 -0.05 -0.12 9.89 0.06 0.05 0.036 0.3 0.113 0.25 -0.08 -0.037 0.101 0.1 0.06 0.06 0.01 0.01 0.01 0.01 0.005 1 0.01 0.3 0.8 0.25 0.05 0.11 0.16 -0.004 0.57 -0.04 -0.05 0.192 0.98 0.68 0.033 0.09 -0.22 -0.17 0.38 0.04 0.126 0 0 0.7 0.99 -0.04 -0.04 0.05 0 0 0.65 0.29 0.01 0.04 0.18 0.05 0.05 0.05 0.06 0.03 0.022 0.03 0.05
±95% 0.28 0.44 0.19 8.44 0.03 0.03 0.017 0.032 0.14 0.06 0.044
0.15
0.12 0.01 0.001 0.06 0.008 0.91 1.26 0.18 0.022 0.16 0.035 0.002 0.09 0.06 0.01 0.02 0.009 0.39 0.33 0.37 0.04 0.05 0.02 0.02 0.01 0.038 0.01 0.03
r2
±95%
Conv.
1.34 4.74 5.62 1.35 0.09 0.06 1.03 2.7 4.76 6 1.63 11.17 9.64 6 1.4 1.4 19 19 43 43 44 24 2.52 1.7 1.2 3.5 11 11.6 6 2.54 0.78 15 11.91 4.142 0.94 1.41 3.615 1.88 22.56 24.89 1.081 2.72 7.401 2.24 3.63 - 0.24 - 0.05 0.98 1.26 0.014 0.52 0.17 11.58 11.96 50 2.19 0.16 0.36 0.32 0.3 0.29 0.08 0.062 0.08 0.89
0.45 2.95 1.06 0.84 0.01 0.01 0.11
Y Y Y Y N N Y
0.2
Y
0.16 0.48 0.54
Y Y Y
0.32
N
1.79
Y
3.89 0.011 0.14
N Y N
0.012 0.44 24.54 1.22 0.016 0.37 0.315
Y Y Y Y Y Y
0.04 0.26 0.07 0.15 0.19 0.003
N N N N N Y
1.91 2.32
N N
1.43
Y
0.02 0.02 0.01 0.01 0.005 0.004 0.004 0.01
N N N N N Y N N
Refs. 124 124 124 124 285 336 303 507 303 507 286 286 286 286 369 818 604 606 604 606 528 590 42 590 406 755 590 755 607 47 438 127 247 246 272 401 145 145 145 145 145 145 806 790 347 322 322 347 347 332 640 640 349 349 490 47 322 285 336 285 336 285 303 336 285
References page II-290
TABLE 1. cont'd Monomer 1 Vinyl isobutyl sulfide Vinyl isobutyl sulfide Vinyl isobutyl sulfide Vinyl isopropyl ether Vinyl isopropyl ether Vinyl isopropyl ketone Vinyl isopropyl ketone Vinyl isopropyl ketone Vinyl isopropyl ketone Vinyl isopropyl ketone Vinyl isopropyl ketone Vinyl isopropyl ketone Vinyl isopropyl sulfide Vinyl isopropyl sulfide Vinyl isothiocyanate Vinyl isothiocyanate Vinyl isothiocyanate Vinyl isothiocyanate Vinyl 1-methyl ether Vinyl laurate Vinyl laurate Vinyl laurate Vinyl m-cresyl ether Vinyl m-cresyl ether Vinyl m-cresyl ether Vinyl methanesulfonate Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl sulfide Vinyl methyl sulfide Vinyl methyl sulfide Vinyl methyl sulfide Vinyl methyl sulfide Vinyl methyl sulfide Vinyl methyl sulfone Vinyl methyl sulfone Vinyl methyl sulfoxide Vinyl methyl sulfoxide Vinyl methyl sulfoxide Vinyl mono-diethyleneglycol ether Vinyl mono-ethyleneglycol ether Vinyl o-cresyl ether Vinyl o-cresyl ether Vinyl o-cresyl ether
Monomer 2 Methacrylate, methyl Methacrylate, methyl Styrene Caprolactam, N-vinylPyrrolidone, TV-vinylMethacrylate, methyl Methacrylate, methyl Styrene Styrene Styrene Vinyl acetate Vinyl acetate Methacrylate, methyl Styrene Acrylonitrile Methacrylate, methyl Styrene Styrene Indene Acrylonitrile Vinyl acetate Vinyl chloride Methacrylate, methyl Vinyl chloride Vinylidene chloride Vinyl acetate Acrylamide Acrylamide Acrylamide, AyV-dimethyl Acrylate, butyl Acrylonitrile Acrylonitrile Indene Indene Methacrylamide Methacrylamide Methacrylate, 2,2,6,6-tetramethyl4-piperidinyl Methyleneglutaronitrile, 2Styrene Styrene Styrene Styrene, 2,5-dichloroTriazine, 4,6-diamino-2-vinylVinyl acetate Vinyl chloride Vinyl phenyl ether Vinyl phenyl ketone Vinylidene chloride Acrylate, methyl Methacrylate, methyl Styrene Styrene Styrene Vinylene carbonate Styrene Vinyl acetate Styrene Styrene, /?-chloroStyrene, /7-methylMethacrylic acid Methacrylate, glycidyl Methacrylate, methyl Vinyl chloride Vinylidene chloride
rx 0.021 0.03 -0.11 0.01 0.03 1.44 0.6 0.26 0.272 0.3 7.87 6.47 0.046 0.16 1.4 0.6 0.37 0.5 0.67 0.04 0.7 0.2 0.2 0.13 0.04 0.206 0.47 0.75 0.1 1.81 1.75 1.39 2.63 2.9 0.25 0.28 0.41 5.05 0.349 0.348 0.27 0.5 0.17 8.3 4.4 0.74 1.8 0.084 0.03 0.15 0.066 0.046 7.72 -0.22 0.55 0.01 0.01 0.01 2.2 0 0.1 0.14 0.04
±95% 0.034 0.02 0.2 0.96 2.09 0.47 0.07 0.046 2.18 0.025 0.068
2.82
0.02 0.004 0.427 0.44 0.23 0.43 0.24 0.11
0.12 0.24
0.068 0.009 0.11
0.086 0.056 0.084 1.68 0.17 0.21
0.01 0.01
r2 0.985 0.88 2.38 0.22 0.87 0.81 0.54 0.46 0.36 0.4 0.3 -0.154 0.822 4.61 0.36 0.85 0.65 0.8 12.64 4 1.4 7.4 3.3 1.23 1.95 0.639 3.99 1.02 0.82 0.8 0.59 0.63 0.2 0.25 3 1.72 0.53 1.24 0.288 0.237 0.35 2 1.35 0.1 0.01 0.671 0.55 0.209 1 4.5 4.46 5 -0.08 1.146 0 3.57 6.46 2.73 0 4.41 1.8 1.33 2.1
±95%
Conv.
0.077 0.02 0.41 1.95 9.3
Y N Y Y Y
0.22 0.05 0.1
Y N Y
0.073 0.064 0.18
Y Y Y
12.59
Y
0.04 0.07 0.014 0.7 0.13 0.36 0.06 0.13
Y Y Y Y Y Y N Y
0.18 0.26
Y Y
0.092 0.023
Y Y
0.68
Y Y
0.034
Y
0.11 0.24 0.17 0.087 0.02
Y Y Y Y Y
0.02 0.1
Y Y
Refs. 303 336 303 215 215 601 794 344 353 599 601 794 303 303 542 422 422 542 750 381 503 450 605 279 279 942 609 609 609 53 140 504 606 606 609 609 664 512 140 353 550 375 243 91 375 423 946 375 195 106 193 195 303 120 195 195 737 737 737 831 780 605 279 279
TABLE 1. cont'd Monomer 1 Vinyl octadecyl ether Vinyl octadecyl ether Vinyl octadecyl ether Vinyl octadecyl ether Vinyl octyl ether Vinyl octyl ether Vinyl octyl ether Vinyl octyl ether Vinyl p-benzylethylcarbinol Vinyl p-benzylethylcarbinol Vinyl p-benzylethylcarbinol Vinyl p-benzylmethylcarbinol Vinyl p-benzylmethylcarbinol Vinyl p-benzylmethylcarbinol Vinyl p-benzylmethylcarbinol Vinyl p-bromobenzoate Vinyl p-bromobenzoate Vinyl p-bromobenzoate Vinyl p-bromobenzoate Vinyl p-chlorobenzoate Vinyl p-chlorobenzoate Vinyl p-chlorobenzoate Vinyl p-chlorobenzoate Vinyl p-chlorophenyl ether Vinyl p-chlorophenyl ether Vinyl p-cresyl ether Vinyl p-cresyl ether Vinyl p-cresyl ether Vinyl p-cyanobenzoate Vinyl p-cyanobenzoate Vinyl p-cyanobenzoate Vinyl p-cyanobenzoate Vinyl/?-cyanobenzoate Vinyl p-methoxybenzoate Vinyl p-methoxybenzoate Vinyl p-methoxybenzoate Vinyl p-methylbenzoate Vinyl p-methylbenzoate Vinyl p-methylbenzoate Vinyl p-tert-butylphenyl ether Vinyl p-terf-butylphenyl ether Vinyl p-vinyloxybenzoate Vinyl pelargonate Vinyl pelargonate Vinyl pelargonate Vinyl pelargonate Vinyl phenyl carbonate Vinyl phenyl carbonate Vinyl phenyl ether Vinyl phenyl ether Vinyl phenyl ether Vinyl phenyl ether Vinyl phenyl ether Vinyl phenyl ether Vinyl phenyl ether Vinyl phenyl ether Vinyl phenyl ether Vinyl phenyl ether Vinyl phenyl ether Vinyl phenyl ether Vinyl phenyl ether Vinyl phenyl ketone Vinyl phenyl ketone Vinyl phenyl ketone Vinyl phenyl ketone
Monomer 2
rx
Acrylonitrile Vinyl acetate Vinyl chloride Vinylidene chloride Acrylonitrile Styrene Vinyl acetate Vinyl chloride Acrylate, butyl Acrylate, methyl Acrylonitrile Acrylonitrile Methacrylate, methyl Styrene Styrene, p-chloroVinyl benzoate Vinyl p-cyanobenzoate Vinyl p-methoxybenzoate Vinyl p-methylbenzoate Vinyl benzoate Vinyl p-cyanobenzoate Vinyl p-methoxybenzoate Vinyl p-methylbenzoate Vinyl chloride Vinylidene chloride Methacrylate, methyl Vinyl chloride Vinylidene chloride Vinyl benzoate Vinyl p-bromobenzoate Vinyl/7-chlorobenzoate Vinyl p-methoxybenzoate Vinyl/7-methylbenzoate Vinyl/7-bromobenzoate Vinyl p-chlorobenzoate Vinyl p-cyanobenzoate Vinyl p-bromobenzoate Vinyl p-chlorobenzoate Vinyl p-cyanobenzoate Vinyl chloride Vinylidene chloride Vinyl chloride Butadiene Styrene Vinyl chloride Vinylidene chloride Vinyl acetate Vinyl acetate Acrylonitrile Caprolactam, N-vinylMethacrylate, methyl Methacrylate, methyl Pyrrolidone, N-vinylStyrene Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloroacetate Vinyl methyl ketone Vinylidene chloride Vinylidene chloride Methacrylate, glycidyl Methacrylate, methyl Styrene Styrene
0 0 -0.1 0 0 0 0 0.1 0.4 0.48 0.31 0.54 0.98 0.94 1 1.17 0.83 1.08 1.05 0.81 0.813 1 0.853 0.63 0.14 0 0.13 0.03 0.878 0.901 1.031 0.63 0.81 0.72 0.699 0.685 0.594 0.682 0.624 0.14 0.05 0.78 0.02 0.01 0.28 0 0.384 0.384 0.23 0.26 0.01 0 0.253 0.01 0.01 0.16 0.17 0.55 0.01 0.433 0.04 0.697 0.59 0.3 0.465
±95%
0.2 0.28 0.15 0.13 0.021 0.29 0.17 0.072 0.014 0.14 0.054 0.05 0.01 0.01 0.004 0.094 0.034 0.028 0.22 0.1 0.1 0.057 0.075 0.045 0.021 0.04 0.02 0.004 0.07
0.083 0.083 0.37 0.32 0.007 0.59 0.03 0.61 0.051 0.03 1.9 0.02 0.03
r2 0.85 4.5 2.1 1.5 0.81 65 3.47 1.9 0.17 0.18 0.04 0.11 0.24 0.98 1 0.716 0.901 0.72 0.594 0.832 1.031 0.699 0.682 1 2.44 2.6 1.17 1.97 0.659 0.83 0.813 0.685 0.624 1.08 1 0.63 1.05 0.853 0.81 1.08 2.04 0.58 26.3 49.5 1.16 4.08 0.85 0.85 2.5 1.3 11.34 2.8 4.48 1.7 1.28 1.06 1.21 0.84 4.4 2.45 2.11 0.719 0.71 0.24 0.21
±95%
0.17 0.26 0.32
Conv.
0.031 0.034 0.1 0.045 0.028 0.028 0.057 0.021 0.04 0.04
N Y Y Y Y Y Y Y Y Y Y Y Y Y
0.02 0.06 0.033 0.021 0.014 0.075 0.04 0.29 0.14 0.22 0.17 0.054 0.1 0.06 0.06 0.06
Y Y Y Y Y Y Y Y Y Y Y Y Y Y Y N
0.23 0.23
Y Y
2.43 5.76
Y Y
0.1
Y
0.14
Y
0.03 1.67
N Y
0.34 0.11
Y N
0.6 0.04 0.042
Y N Y
Refs. 373 372 370 371 373 374 372 370 591 591 591 48 48 48 48 110 110 110 110 110 110 110 110 279 279 605 279 279 110 110 110 110 110 110 110 110 110 110 110 279 279 497 145 145 145 145 675 705 556 214 172 605 214 423 172 279 280 212 423 240 280 946 794 344 353
References page II - 290
Next Page
TABLE 1. cont'd Monomer 1 Vinyl phenyl ketone Vinyl phenyl ketone Vinyl phenyl sulfide Vinyl phenyl sulfide Vinyl phenyl sulfide Vinyl phenyl sulfide Vinyl phenyl sulfide Vinyl phenyl sulfide Vinyl phenyl sulfide Vinyl phenyl sulfide Vinyl phenyl sulfone Vinyl phenyl sulfone Vinyl propionate Vinyl propionate Vinyl propionate Vinyl propionate Vinyl propionate Vinyl propionate Vinyl propionate Vinyl propionate Vinyl propionate Vinyl stearate Vinyl stearate Vinyl stearate Vinyl stearate Vinyl stearate Vinyl stearate Vinyl stearate Vinyl stearate Vinyl sulfone Vinyl sulfone Vinyl tert-butyl ketone Vinyl tert-butyl ketone Vinyl tert-butyl sulfide Vinyl tert-buty\ sulfide Vinyl tert-butyl sulfide Vinyl tert-butyl sulfide Vinyl tert-butyl sulfide Vinyl tert-butyl sulfide Vinyl tert-butyl sulfide Vinyl thiolacetate Vinyl thiolacetate Vinyl thiolacetate Vinyl thiolacetate Vinyl thiolacetate Vinyl thiolacetate Vinyl trichloroacetate Vinyl trimethylammonioethyl ether iodide Vinyl valerate Vinyl, 2-, 2-methyl-4,4,6,6-tetraphenylcyclotrisiloxane Vinyl-tris(trimethoxysiloxy)silane Vinyl-tris(trimethoxysiloxy)silane Vinyl-tris(trimethoxysiloxy)silane Vinyl-tris(trimethoxysiloxy)silane Vinyl-tris(trimethoxysiloxy)silane Vinylacetophenone Vinylacetophenone Vinylanthracene, 9Vinylanthracene, 9Vinylanthracene, 9Vinylanthracene, 9Vinylanthracene, 9Vinylanthracene, 9Vinylbenzoate, /?-, sodium
Monomer 2 Vinyl acetate Vinyl methyl ketone Acrylate, methyl Acrylonitrile Acrylonitrile Benzothiazole, vinylmercaptoMethacrylate, methyl Methacrylate, methyl Styrene Styrene Styrene Vinyl acetate Allyl chloride Butadiene, 2-chloroCarbazole, JV-vinylEthylene Methacrylate, methyl Vinyl acetate Vinyl acetate Vinyl chloride Vinyl chloride Acrylate, methyl Acrylonitrile Butadiene Styrene Vinyl acetate Vinyl acetate Vinyl chloride Vinylidene chloride Methacrylate, methyl Styrene Methacrylate, methyl Styrene Styrene Acrylonitrile Styrene Vinyl acetate Vinyl acetate Vinyl chloride Vinyl chloride Acrylate, methyl Carbazole, Af-vinylStyrene Succinimide, N-vinylVinyl acetate Vinylene carbonate Acrylonitrile Af-Vinylpyrrolidone Vinyl chloride Styrene Acrylonitrile Acrylonitrile Methacrylate, methyl Styrene Styrene Methacrylate, methyl Styrene Acrylate, butyl Acrylate, ethyl Acrylate, methyl Methacrylate, methyl Styrene Styrene Acrylonitrile
T1
±95%
r2
5.81 0.671 -0.02 0.03 0.03 0.24 0.06 0.08 0.019 0.26 -0.31 -0.35 0.62
0.96
-0.06 0.74 0.57 0.11 0.1.1 0.95 0.79 0.85 3.63 3.96 1.562 0.171 0.68
0.081 1.5 0.03 0.98 1 0.6 0.65 0.03 0.078 0.02 -0.39 0.96 0.73 0.24 0.08 0.1 -0.027 0.65 3.2 0.248 0 0.158 0.07 0.07 0.15 0.15 0.23 0.45 0.25 2.47 5.5 13.57 0.047 0 0.277 0.8 0.07 0.08 0.02 0 0.01 1.65 1.12 0.126 0.295 0.08 0.117 0.25 0.3 0.23
0.22 0.02 0.01 0.12 0.09 0.054 0.18 0.16 0.37 0.073
0.007 0.27 0.71 0.17 0.64 0.17 0.16 0.047 0.15 0.46 0.05 0.013 0.073
0.15 0.37 1.04 0.039 0.02 0.014
3.81 0.42 0.054 0.056 0.092 0.043 0.34
1.69 0.67 24 0.98 0.9 1.6 1.35 5.8 4.639 42.5 15.96 0.953 0.9 0.71 3.92 4.5 0.731 1.21 0.3 0.36 0.09 4.36 13 13 3 3 0.8 0.44 4 0.17 0.05 0.041 7.34 11.6 2.006 0.11 3.9 3.85 34 26 24 0.33 0.246 3.717 3.498 2.998 4.068 2.12 2.12 0.174
±95%
Conv.
Refs.
0.057
Y
0.1 0.01 0.01 0.61 0.06
Y N N Y N
0.12 0.27 0.091 0.064
Y N Y Y
0.21
N Y
0.015 4.73 13.32 0.015
Y Y Y Y
0.097 0.14 0.49 0.058 0.11 0.31 0.11 0.024 0.76
Y Y Y Y Y N Y Y Y
0.28
N
0.15
N
0.01 0.9 0.03 0.071
Y Y
794 946 193 285 336 763 239 239 193 239 193 193 438 247 246 605 272 272 425 400 450 537 145 145 145 1 537 145 145 45 45 794 344 353 303 303 598 601 598 601 566 97 566 97 566 186 362 1037 283 626
Y
0.36 0.072 0.046 0.041 0.067 0.04
Y Y Y Y Y Y
0.04
Y
209 573 482 209 482 266 266 123 123 123 123 123 48 175
Previous Page
TABLE 1. cont'd Monomer 1 Vinylbenzoic acid, pVinylbenzoic acid, pVinylbenzoic acid, pVinylbenzyl chloride Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylethyldiethoxysilane Vinylethynyl-4-piperidinol, l,2,5-trimethyl-4Vinylethynyl-4-piperidinol, l,2,5-trimethyl-4Vinylferrocene Vinylferrocene Vinylferrocene Vinylferrocene Vinylferrocene Vinylferrocene Vinylferrocene Vinylhydroquinone Vinylhydroquinone Vinylhydroquinone Vinylhydroquinone Vinylhydroquinone dibenzoate Vinylhydroquinone dibenzoate Vinylhydroquinone dibenzoate Vinylhydroquinone dibenzoate Vinylhydroquinone dibenzoate Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride
Monomer 2 Acrylonitrile Methacrylate, methyl Styrene Methacrylate, methyl Acrylamide Acrylonitrile Methacrylate, methyl Pyrrolidone,//-vinylStyrene Styrene Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl chloride Vinyl chloride Vinyl chloride Vinyl isobutyl ether Vinyl 1-menthyl ether Vinyl methyl sulfide Vinyl thiolacetate Vinyl chloride Acrylonitrile Methacrylic acid Acrylonitrile Acrylonitrile Butadiene Methacrylate, methyl Pyrrolidone, N-vinylStyrene Styrene Acrylic acid Acrylonitrile Methacrylate, methyl Pyridine, 4-vinylAcrylate, methyl Acrylic acid Methacrylate, methyl Styrene Styrene, a-methylAconitate, trimethyl Acrylamide, N-octadecylAcrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, ethyl Acrylate, methyl Acrylate, methyl Acrylate, methyl' Acrylate, octadecyl Acrylate, octyl Acrylic acid Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile
rx 1.63 1.16 1.029 1.02 0.05 0.08 - 0.04 0.056 3.16 -0.73 0.3 0.27 0.05 0.13 0.044 0.08 0.03 0.069 0 0.16 0.14 -0.08 0.041 -0.44 0.38
±95% 0.42 0.3 0.06
0.85 0.059 0.98 0.3 0.16 0.039 0.11 0.12 0.068 0.22 1.91 0.17 0.01 2.97
0.05 0.165 0.15 0.16 0.52 0.71 0.2 0.14 0.026 0.04 0.02 - 0.23 0.75 0.95 0.41 0.43 0.3 64.6 0.432 0.934 0.84 0.87 0.58 0.9 0.7 1 0.9 0.851 0.437 0.32 0.28 0.4 0.42 0.49 0.69 0.76 0.95 0.95
r2 0.06 0.398 0.282 0.46 13.8 14.9 126 1.08 411 21.03 3.2 3 7.16 7.3 3.83 3.92 4.82 15.38 17.81 0.18 0.25 7.72 13.57 0.94 0.08
±95% 0.009 0.097 0.011
298 0.11
Conv. Y Y Y
23.45 0.62
Y Y Y Y Y
0.64
Y
0.18 0.32 0.49 1.44 7.84
Y Y Y Y Y
3.32 1.68 1.04 1.53
Y Y Y Y
0.4 0.092 0.15 0.16 0.1 0.14 0.092 0.03 0.13 0.36
23.74 0.008 0.006
0.15 0.11
0.037 0.018 0.065 0.14 0.034
0.186 0.16 4.34 1.22 0.364 4.37 2.76 0.29 0.56 0.49 0.53 0.46 0.44 0.34 0.22 0.11 0.15 1.4 0.873 0.46 0.58 0.72 0.95 0.8 1 1 0.679 1.246 0.92 1.04 0.44 0.58 0.65 0.57 0.5 0.48 0.65
Refs. 175 266 266 792 387 579 103 103 103 120 103 103 120 120 144 90 103 319 319 322 750 120 186 237 783 734
0.025
Y
0.18
Y
0.068 1.44 0.22 0.11 0.36 0.21 0.4
Y Y Y Y N Y Y
0.94 0.11 0.022
N Y Y
0.39 0.21
Y Y
0.14 0.057 0.042 0.11 0.2
Y Y Y Y Y
294 294 802 294 308 274 294 337 338 337 337 440 444 440 440 440 149 119 118 464 464 65 107 107 377 118 118 288 138 238 404 404 404 404 404 404 404
References page II - 290
TABLE 1. cont'd Monomer 1 Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride
Monomer 2 Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acryloyl chloride AHyI acetate Allyl chloride Allylstearamide, NButadiene Carbazole, N-vinylCarbazole, TV-vinylCrotonaldehyde Crotonic acid Cyclopentene, 4-, 1,3-dione Diallyl phthalate Ethylene Ethylene chlorotrifluoroFumarate, diethyl Fumarate, diisopropyl Indene Indene Isobutylene, 3-chloroIsopropenyl methyl ketone Isopropenylisocyanate Maleate, diethyl Maleimide Methacrylate, 2-(sulfonic acid)ethyl Methacrylate, benzyl Methacrylate, butyl Methacrylate, ethyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylic acid Methacrylonitrile Methacrylonitrile Norbornadiene Oxazolidone, AT-vinylPropenyl 2-methyl, acetate Styrene Styrene Styrene Styrene Styrene Styrene Succinimide, Af-vinylTetrazole, 2-methyl-5-(4/-vinyl)phenylTetrazole, 2-phenyl-5-(4'-vinyl)phenylTetrazole, 5-phenyl-2-(4'-vinyl)phenylVinyl 12-ketostearate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl benzoate Vinyl butyl ether
rx 1.3 1.74 1.43 1.8 0.39 0.5 6.6 3.49 5.22 -0.044 -0.023 -0.008 18.1 1.88 5 15.71 17.14 12.19 48 0.49 -0.02 1.1 0.134 0.85 12.5 0.666 0.22 0.34 0.35 0.353 0.3 0.36 0.18 0.5 0.34 0.09 0.094 0.19 0.02 0.27 0.154 0.3 0.036 1.36 1.42 2.4 0.134 0.098 1.5 0.087 0.15 0.11 1.441 0.13 0.25 0.11 4.4 4.66 6.7 5 3.49 4.7 5.58 1.75
±95%
1.4 0.15 0.038 0.068 0.018 43.7 0.35 1.96 1.58 0.15 1.15 0.099 0.056 0.03 0.02 0.03 0.18
0.032 0.01 0.047 0.1 0.05 0.63 0.11 0.048 0.01 0.007 0.005 0.061
4.8 0.26 0.17 1.76 0.11
r2 0.65 0.66 0.63 0.63 0.58 1.12 0 0.24 -0.24 1.97 3.6 3.65 0 -0.2 0.113 0.2 0.018 0.02 0.012 0.095 0.293 0.34 0 4.06 0.31 0.464 3.6 3.3 2.07 2.18 2.6 2.38 2.16 2.5 2.5 2.1 1.8 2.83 1.23 2.77 3.368 2.43 2.38 0.09 0.091 0 1.81 1.79 1.8 1.839 1.81 1.7 0.311 1.9 1.8 1.9 0.26 0.03 0.05 0.05 -0.002 0.12 0.065 0.004
±95%
Conv.
0.24 0.19 0.25 0.12 0.3
Y Y Y Y Y
1.03 0.027
Y Y
0.005
Y
0.038
Y
0.095 0.85
Y Y
0.66
Y
0.083
Y
0.18 0.1 0.02 0.06
Y Y Y N N
0.95
Y
0.06 0.098 0.1 0.05 0.17 0.077
N Y N N N Y
0.35 0.14
Y Y
0.024
Y
0.12 0.058
N Y
2.61 0.1
Y Y
0.026
Y
0.093 0.001
Y Y
Refs. 404 404 404 404 468 288 470 3 119 257 13 98 405 47 264 376 299 454 59 1038 6 6 470 47 434 3 251 564 432 3 3 138 324 324 426 432 538 65 762 762 786 6 781 781 267 102 470 138 238 393 59 812 93 104 583 583 583 146 3 432 436 59 812 47 279
TABLE 1. cont'd Monomer 1 Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene cyanide Vinylidene cyanide Vinylidene cyanide Vinylidene cyanide Vinylidene cyanide Vinylidene cyanide Vinylidene cyanide Vinylidene cyanide Vinylidene cyanide Vinylidene cyanide Vinylidene cyanide Vinylidene cyanide Vinylidene cyanide Vinylidene cyanide Vinylidene cyanide Vinylidene cyanide Vinylidene cyanide Vinylidene cyanide Vinylidene fluoride Vinylidene fluoride Vinylisocyanate Vinylisocyanate Vinylisocyanate Vinylisocyanate Vinylisocyanate Vinylisocyanate Vinylisocyanate Vinylmethyldiacetoxysilane Vinylmethyldiacetoxysilane Vinylmethyldiethoxysilane Vinylmethyldiethoxysilane Vinylmethylphenylsulfonium tetrafluoroborate Vinylmethylphenylsulfonium tetrafluoroborate Vinylphenyldimethylsilane Vinylphenyldimethylsilane Vinylphenylisocyanate, pVinylphenylpropanol, 2-p-
Monomer 2 Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloromethyl ketone Vinyl dodecyl ether Vinyl ethyl ether Vinyl fluoride Vinyl hendecanoate Vinyl m-cresyl ether Vinyl methyl ketone Vinyl o-cresyl ether Vinyl octadecyl ether Vinyl p-chlorophenyl ether Vinyl /?-cresyl ether Vinyl p-tert-buty\ phenyl ether Vinyl pelargonate Vinyl phenyl ether Vinyl phenyl ether Vinyl stearate Vinylidene cyanide Vinylisocyanate Acrylate, a-chloro-, methyl Acrylic acid Butadiene, 2-chloroEthylene, dichloro-, cisEthylene, dichloro-, cisMaleic anhydride Methacrylate, methyl Phosphonic acid, 1-phenylvinyl Propene, 2-chloroStyrene Styrene Styrene, 2,5-dichloroVinyl acetate Vinyl benzoate Vinyl chloride Vinyl chloride Vinyl chloroacetate Vinyl chloride Methacryloyl fluoride, perfluoroVinyl acetate Acrylate, methyl Acrylonitrile Methacrylate, methyl Styrene Styrene Vinyl chloride Vinylidene chloride Acrylonitrile Styrene Styrene Styrene Acrylamide Acrylonitrile Methacrylate, methyl Styrene Vinyl chloride Styrene
rx 2.06 3.39 8.92 3.2 4.5 1.8 4.5 3.068 0.018 1.3 3.2 6 2.72 1.95 0.55 2.1 1.5 2.44 1.97 2.04 4.08 2.45 2.11 3.92 0.009 1.46 0.066 0.291
0.028 4.58 0.204 0.72 0.001 0.005 0.1 0.061 0.72 0.6 0.137 0.049 7.6 0.08 0.14 0.16 0.01 0.08 0.1 3.7 0.33 -0.11 0 0.08 -0.08 0.1
±95% 0.32 1.16
0.076 0.009
0.37 0.07 0.1 0.04 0.06 0.06 0.34 0.11 0.14 0.001 0.07 0.042
0.013 0.079 0.16 0.001 0.009 0.11 0.047 0.068 0.037 0.02
0.23 0.15 0.14 0.2
0.1 -0.009 0.024 11.9 0.41
r2 0.071 0.14 0.25 0.3 0.2 0.2 0.16 0.205 6.8 0 0 0.16 0.04 0.04 1.8 0.04 0 0.14 0.03 0.05 0 0.433 0.04 0.08 0.049 0.33 0.313 0.212
0.057 0.1 0.001 0.015 0.003 0.026 0.003 0 0.01 0.016 0 0.009 0.02 6 1.38 0.19 3.3 8.13 6.9 0.46 1.46 2.246 4.08 5.68 11.29 3.4
±95%
Conv.
Refs.
0.025 0.32
Y N Y
0.003 0.3
Y Y
0.16 0.004
Y Y
0.01
Y
0.01 0.004 0.004
Y Y Y
0.051 0.03 0.17 0.02
Y N Y Y
0.021 0.016
0.012
Y Y Y Y Y Y Y
0.03 0.007 0.001 0.006 0.002 0.017
Y Y Y Y Y Y
0.002 0.006 0.001
Y Y Y
0.054 0.14 0.1 0.43
Y Y Y Y
238 29 3 470 517 539 585 67 356 371 470 607 145 279 375 279 371 279 279 279 145 240 280 145 82 435 82 82 82 82 82 82 82 921 82 134 82 82 82 82 409 82 82 82 669 627 435 435 422 435 533 777 435 754 754 754 754 793
2.2 0.034 0.016 0.4
29.79 32.53 0.1 0.48
793 1.89 0.49
Y Y
0.3
Y
482 482 777 72
References page II - 290
TABLE 1. cont'd Monomer 1 Vinylsulfonic acid Vinyltriethoxysilane Vinyltriethoxysilane Vinyltriethoxysilane Vinyltriethoxysilane Vinyltrimethoxysilane Vinyltrimethoxysilane Vinyltrimethylsilane Vinyltrimethylsilane Vinyltrimethylsilane Vinyltrimethylsilane Vinyltrimethylsilane Xanthate, S-methacryloyl O-ethyl Xanthate, S-methacryloyl O-ethyl
Monomer 2 Acrylamide Acrylonitrile Acrylonitrile Styrene Vinyl chloride Acrylonitrile Vinyl chloride Acrylonitrile Methacrylate, methyl Styrene Styrene Styrene Methacrylate, methyl Styrene
T1
±95%
r2
±95%
0.3 0.41 2.69 -0.09 -0.04 0.45 0.09 0.1 0.028 -0.19
0.1 0.38 2.5 0.14 0.44
0.15 0.6 29.59 1.99 0.16
0.27 0.016 0.36
3.5 6.59 26.83 20.86 0.82 9.09 0.93 4.08 35.66 14.66
0.025 0.08 0.08
5.98 0.76 0.44
0.18 0.04 0.06
0.049 0.6 0.36
TABLE 2. LISTING OF QUICK BASIC (MICROSOFT) PROGRAM FOR CALCULATING REACTIVITY RATIOS* 100 OPTION BASE 1 110 DIM eta (20) 120 DIM ksi (20) 130 DIM gee (20) 140 DIM ef (20) 150 DIM t (20) 151 F O R b = I TO 20 152 READ t(b) 153 NEXT b 170 DATA 12.71,4.3,3.18,2.78,2.57,2.45,2.37,2.31,2.26,2.23,2.2,2.18,2.16,2.14,2.13,2.12,2.11,2.1,2.09,2.09 180 DEF FNLog 10(X) = LOG(X)/LOG( 10#) 190 PRINT "Calculation of reactivity ratios by the method of Kelen and Tudos" 210 PRINT "Enter 0 for monomer 1 in the feed to start the calculation" 220 REM initialize all of the summing addresses 230 n = 0 231 m = 0 232 var = 0 233 sumasi = 0 234 sumi = 0 235 suma = 0 236 sumsqi = 0 237 sumnegi = 0 238 sum2i = 0 250 INPUT "Do you wish to stop (Y/N)?";f$ 260 IF f$ = "y" THEN GO TO 1510 270 REM enter the names and molecular weights of the monomers 280 INPUT "Monomer 1 is:"; mone$ 290 INPUT "Monomer 2 is:"; mtwo$ 340 REM enter the feed, polymer and conversion values 350 PRINT "Are the feed and polymer values in mol fractions (mol), mol ratios (ratio) or weight fractions (wt) ?" 370 INPUT type$ 380 IF type$ = "ratio" THEN GOTO 1210 390 IF type$ = "wt" THEN GOTO 1360 400 PRINT "Mol fraction of"; mone$; "in the feed = " 410 INPUTmIO 420 IF mlO = 0 THEN GOTO 800 430 n = n + 1 440 m20=l-ml0 450 PRINT "Mol fraction of"; mone$; "in the polymer= " 460 INPUTpI 470 p 2 = l - p l 480 PRINT "Conversion, weight fraction = ? (If none given enter 0)" 490 INPUT w 500 IF w = 0 THEN GOTO 680 * Method of Kelen and Tudos (803,804).
0.76 0.85 5.15
Conv.
Refs.
Y Y Y Y Y Y Y Y Y Y Y
1066 209 237 209 237 2.37 237 209 482 209 482 73 1086 1086
510 520 530 540 550 560 570 580 590 600 610 620 630 640 650 660 670 680 690 700 710 720 730 740 750 760 770 780 790 800 810 820 830 840 850 860 870 880 890 900 910 920 930 940 950 960 970 980 990 1000 1010 1020 1030 1040 1050 1060 1070 1080 1090 1100 1110 1120 1130 1140 1150 1160 1170 1180 1190
REM calculate G and F X = ml0/m20 y = pl/p2 mu = mw2/mw 1 zeta2 - w * (mu + X)/(mu -f y) zetal=(y/X)*zeta2 z = (FNLoglO(l-zetal))/(FNLoglO(l-zeta2)) g = (y-l)/z f=y/(zA2) I F n = I THEN fmin = f IF n = 1 THEN fmax = f IF fmin>f THEN fmin = f IF fmax
f THEN fmin = f IF fmax
References page 11-290
1200 1210 1220 1230 1240 1250 1260 1270 1280 1290 1300 1310 1320 1330 1340 1350 1351 1352 1353 1354 1360 1370 1380 1390 1400 1410 1420 1430 1440 1450 1460 1470 1480 1490 1500 1510 1520
C.
REM calculation of Ml and M2 from mol ratios PRINT "MoI ratio of"; mone$; "in the feed = " ; INPUT qf IF qf = 0 THEN GOTO 800 n= n+l ml0 = q£/(qf+l) m20=l-ml0 PRINT "Mole ratio of"; mone$ "in the polymer= " INPUT qp pl=qp/(qp+l) p2=l-pl PRINT '' Weight fraction conversion = '' INPUTw IF w - 0 THEN GOTO 680 GOTO 510 REM calculation of Ml and M2 from weight fractions PRINT "The molecular weight of"; mone$; "is" INPUT mwl PRINT "The molecular weight of"; mtwo$; "is" INPUT mw2 PRINT "Weight fraction of"; mone$ "in the feed = " INPUT rfl If rfl = 0 THEN GOTO 800 n= n+l rf2 = 1-rfl mlO = (if l/mwl)/((rf 1/mwl) + (rf2/mw2)) m20=l-ml0 PRINT "Weight fraction of"; mone$; "in the polymer= " INPUT rpl rp2 = l-rpl pi = (rpl/mwl)/((rpl/mwl) + (rp2/mw2)) PRINT "Weight fraction conversion= " INPUTw IF w = 0 THEN GOTO 680 GOTO 510 PRINT "FINI" END
REFERENCES
1. A. Adicoff, A. Buselli, J. Polym. ScL, 21, 340 (1956). 2. S. L. Aggarwal, F. A. Long, J. Polym. Sci., 11, 127 (1953). 3. P. Argon, T. Alfrey, J. Bohrer, H. Hass, H. Wechsler, J. Polym. Sci., 3, 157 (1948). 4. A. N. Akopyan, G. Ye. Krbekyan, Vysokomol. Soedin., 5, 201 (1963). 5. A. N. Akopyan, G. Ye. Krbekyan, E. G. Sinanyan, Vysokomol. Soedin., 5, 681 (1963). 6. T. Alfrey, J. Bohrer, H. Haas, C. Lewis, J. Polym. Sci., 5, 719 (1950). 7. T. Alfrey, W. H. Ebelke, J. Am. Chem. Soc, 71, 3235 (1949). 8. T. Alfrey, A. I. Goldberg, W. P. Hohenstein, J. Am. Chem. Soc, 68, 2464 (1946). 9. T. Alfrey, S. Greenberg, J. Polym. Sci., 3, 297 (1948). 10. T. Alfrey, J. G. Harrison, J. Am. Chem. Soc, 68, 299 (1946). 11. T. Alfrey, S. L. Kapur, J. Polym. Sci., 4, 215 (1949). 12. T. Alfrey, E. Lavin, J. Am. Chem. Soc, 67, 2044 (1945). 13. T. Alfrey, B. Magel, quoted by Hart, Makromol. Chem., 47, 143 (1961). 14. T. Alfrey, E. Mertz, H. Mark, J. Polym. Sci., 1, 37 (1946).
15. T. Alfrey, H. Morawetz, J. Am. Chem. Soc, 74,436 (1952). 16. T. Alfrey, C. G. Overberger, S. H. Pinner, J. Am. Chem. Soc, 75, 4221 (1953). 17. T. L. Ang, H. J. Hardwood, Am. Chem. Soc, Div. Polymer Chem. Preprints, 5, 306 (1964). 18. C. L. Arcus, R. J. S. Mathews, J. Chem. Soc, 4607, (1956). 19. E. J. Arlman, H. W. Melville, Proc Roy. Soc (London) A, 203, 301 (1950). 20. E. J. Arlman, H. W. Melville, L. Valentine, Rec Trav. Chim., 68, 945 (1949). 21. H. Asai, T. Imoto, J. Polym. Sci. B, 2, 553 (1964). 22. N. Ashikari, A. Nishimura, J. Polym. Sci., 31, 250 (1958). 23. M. A. Askarov, A. S. Bank, Vysokomol. Soedin., 8, 1012 (1966). 24. C. Aso, T. Kunitake, K. Watanabe, Kogyo Kagaku Zasshi, 70, 1001 (1967). 25. I. S. Avetisyan, V. I. Eliseeva, O. G. Larinovo, Vysokomol Soedin. A, 9, 570 (1967). 26. S. Banarjee, M. S. Muthana, J. Polym. Sci., 35, 292 (1959). 27. P. D. Bartlett, K. Nozaki, J. Am. Chem. Soc, 68, 1495 (1946).
28. W. I. Bengough, D. Goldrich, R. A. Young, Eur. Polym. J., 3, 117 (1967). 29. W. I. Bengough, R. G. W. Norrish, Proc. Roy. Soc. (London) A, 218, 155 (1953). 30. J. C. Bevington, D. O. Harris, J. Polym. Sci. B, 5, 799 (1967). 31. J. C. Bevington, M. Johnson, Makromol. Chem., 87, 66 (1965). 32. J. C. Bevington, B. W. Malpass, Eur. Polym. J., 1, 85 (1965). 33. D. C. Blackley, H. W. Melville, Makromol. Chem., 18, 16 (1956). 34. G. Blauer, L. Goldstein, J. Polym. Sci., 25, 19 (1957). 35. E. P. Bonsall, L. Valentine, H. W. Melville, Trans Faraday Soc, 48, 763 (1952). 36. J. F. Bork, L. E. Coleman, J. Polym. Sci., 43, 413 (1960). 37. J. Bourdais, Bull. Soc. Chim. France, 485 (1955). 38. J. H. Bradbury, H. W. Melville, Proc. Roy. Soc. (London) A, 222, 456 (1954). 39. D. Braun, T.-O. Ahn, Kolloid Z., 188, 1 (1963). 40. J. W. Breitenbach, A. Schindler, C. Pflug, Monatsh. Chem., 81, 21 (1950). 41. F. E. Brown, G. E. Ham, J. Polym. Sci. A, 2, 3623 (1964). 42. R. D. Burkhart, N. L. Zutty, J. Polym. Sci. A, 1, 1137 (1963). 43. G. M. Burnett, P. Evans, H. W. Melville, Trans. Faraday Soc, 49, 1096 (1953). 44. G. G. Cameron, D. H. Grant, N. Grassie, J. E. Lamb, I. C. McNeill, J. Polym. Sci., 36, 173 (1959). 45. E. Y. C. Chang, C. C. Price, J. Am. Chem. Soc, 83, 4650 (1961). 46. E. C. Chapin, G. E. Ham, R. G. Fordyce, J. Am. Chem. Soc, 70, 538 (1948). 47. E. C. Chapin, G. E. Ham, C. L. Mills, J. Polymer Sci., 4,597 (1949); errata, J. Polymer Sci., 55, S-6 (1961). 48. K. Anda, S. Iwai, Kogyo Kagaku Zasshi, 70, 557 (1967). 49. K. Chikanishi, T. Tsuruta, Makromol. Chem., 81, 211 (1965). 50. L. E. Coleman, J. A. Conrady, J. Polym. Sci., 38, 241 (1959). 51. P. Colombo, L. E. Kukacka, J. Fontana, R. N. Chapman, M. Steinberg, J. Polym. Sci. A-I, 4, 29 (1966). 52. P. Colombo, M. Steinberg, J. Fontana, J. Polym. Sci. B, 1, 447 (1963). 53. W. Cooper, E. Catterall, Can. J. Chem., 34, 387 (1956). 54. K. Crauwels, G. Smets, Bull. Soc. Chim. BeIg., 59, 443 (1950). 55. K. Crauwels, G. Smets, Bull. Soc Chim. BeIg., 59, 182 (1950). 56. I. Crescentini, G. B. Getchele, A. Zanella, J. Appl. Polym. Sci., 9, 1323 (1965). 57. G. F. D'Alelio, T. Huemmer, J. Polym. Sci. A-I, 5, 77 (1967). 58. A. DePauw, G. Smets, Bull. Soc. Chim. BeIg., 59, 629 (1950). 59. K. W. Doak, J. Am. Chem. Soc, 70, 1525 (1948). 60. K. W. Doak, J. Am. Chem. Soc, 72, 4681 (1950).
61. K. W. Doak, D. L. Dineen, J. Am. Chem. Soc, 73, 1084 (1951). 62. J. Drougas, R. L. Guile, J. Polym. Sci., 55, 297 (1961). 63. F. I. Duntov, B. L. Erusalimskii, Vyskomol. Soedin., 7,1075 (1965). 64. F. I. Duntov, A. L. Gol'denberg, M. A. Litvinova, B. L. Erusalimskii, Vysokomol. Soedin. A, 9, 1920 (1967). 65. B. G. Elgood, B. J. Sauntson, Chem. Ind. (London), 1558 (1965). 66. W. H. Embree, J. M. Mitchell, H. L. Williams, Can. J. Chem., 29, 253 (1951). 67. S. Enomoto, J. Polym. Sci., 55, 95 (1961). 68. B. Erussalimsky, N. Tumarkin, F. Duntoff. S. Lyubetzky, A. Goldenberg, Makromol. Chem., 104, 288 (1967). 69. E. S. Ferdinandi, W. P. Garby, D. G. L. James, Can. J. Chem., 42, 2568 (1964). 70. R. E. Florin, J. Am. Chem. Soc, 71, 1867 (1949). 71. J. W. L. Fordham, G. H. McCain, L. E. Alexander, J. Polym. Sci., 39, 335 (1959). 72. D. Braun, H.-G. Keppler, Makromol. Chem., 82, 132 (1965). 73. V. G. Filippova, N. S. Nametkin, S. G. Durgaryan, , Izv. Akad. Nauk SSR, Ser. Khim., 1727 (1966). 74. R. G. Fordyce, E. C. Chapin, J. Am. Chem. Soc, 69, 581 (1947). 75. R. G. Fordyce, E. C. Chapin, G. E. Ham, J. Am. Chem. Soc, 70, 2489 (1948). 76. R. G. Fordyce, G. E. Ham, J. Am. Chem. Soc, 69, 695 (1947). 77. R. G. Fordyce, G. E. Ham, J. Am. Chem. Soc, 73, 1186 (1951). 78. B. L. Funt, E. A. Ogryzlo, J. Polym. Sci., 25, 279 (1957). 79. R. M. Fuoss, G. I. Cathers, J. Polym. Sci., 4, 97 (1949). 80. J. Furukawa, T. Tsuruta, N. Yamamoto, H. Fukutani, J. Polym. Sci., 37, 215 (1959). 81. L. Ghosez, G. Smets, J. Polym. Sci., 35, 215 (1959). 82. H. Gilbert, F. F. Miller, S. J. Averill, E. J. Carlson, V. L. FoIt, H. J. Heller, F. D. Stewart, R. F. Schmidt, H. L. Trumbull, J. Am. Chem. Soc, 78, 1669 (1956). 83. R. D. Gilbert, H. L. Williams, J. Am. Chem. Soc, 74, 4114 (1952). 84. G. Goldflnger, M. Steidlitz, J. Polym. Sci., 3, 786 (1948). 85. N. Grassie, I. C. McNeill, J. Polym. Sci., 27, 207 (1958). 86. N. Grassie, I. C. McNeill, I. F. McLaren, J. Polym. Sci. B, 3, 897 (1965). 87. N. Grassie, B. J. D. Torrance, J. D. Fortune, J. D. Gemmell, Polymer, 6, 653 (1965). 88. E. Yun, L. V. Lobanova, A. D. Litmanovich, N. A. Plate, M. V. Shishkina, T. A. Polikarpova, Vysokomol. Soedin., 12, 2488 (1970). 89. E. Grzyma, Z. Jedlinski, Vysokomol. Soedin., 8, 1653 (1966). 90. H. C. Haas, N. W. Schuler, J. Polym. Sci., 31, 237 (1958). 91. H. C. Hass, M. S. Simon, J. Polym. Sci., 9, 309 (1952). 92. G. Hagele, H. Frolich, D. Bischoff, K. Hamann, Makromol. Chem., 75, 98 (1964). 93. R. A. Haldron, J. N. Hay, J. Polym. Sci. A-I, 6, 951 (1968).
94. G. E. Ham, J. Polym. ScL, 14, 87 (1954). 95. F. L. Hamb, A. Winston, J. Polym. Sci. A, 2, 4475 (1964). 96. G. Hardy, J. Varga, G. Nagy, Makromol. Chem., 85, 58 (1965). 97. G. Hardy, J. Varga, K. Nytrai, I. Tsajlik, L. Zubonyai, Vysokomol. Soedin., 6, 758 (1964). 98. R. Hart, Makromol. Chem., 47, 143 (1961). 99. R. Hart, A. E. vanDormael, Bull. Soc. Chim. BeIg., 65, 571 (1956). 100. R. Hart, G. Smets, J. Polym. Sci., 5, 55 (1950). 101. R. Hart, D. Timmerman, Bull. Soc. Chim. BeIg., 67, 123 (1958). 102. R. Hart, D. Timmerman, Makromol. Chem., 31,223 (1959). 103. K. Hayashi, G. Smets, J. Polym. Sci., 27, 275 (1958). 104. H. Hopff, P. Schlumbom, Makromol. Chem., 43, 173 (1961). 105. M. B. Huglin, Polymer, 3, 335 (1962). 106. J. C. H. Hwa, L. Miller, J. Polym. Sci., 55, 197 (1961). 107. M. Ibonai, T. Kato, Kogyo Kagaku Zasshi, 70, 2078 (1967). 108. M. Imoto, T. Otsu, B. Yamada, Kogyo Kagaku Zasshi, 68, 1132(1965). 109. T. Imoto, Y. Ogo, H. Nakamoto, Bull. Chem. Soc. Japan, 41, 543 (1968). 110. K. Ito, Y. Yamashita, J. Polym. Sci. B, 3, 637 (1965). 111. K. Ito, Y. Yamashita, Kogyo Kagaku Zasshi, 68, 1469 (1965). 112. Y. Minoura, T. Tadokoro, Y. Suzuki, J. Polym. Sci. A-I, 5, 2641 (1967). 113. Y. Iwakura, T. Kurosaki, N. Ariga, T. Ito, Makromol. Chem., 97, 128 (1966). 114. Y. Iwakura, T. Kurosaki, N. Nakabayashi, Makromol. Chem., 46, 570 (1961). 115. Y. Iwakura, T. Tamikado, M. Yamaguchi, K. Takei, J. Polym. Sci., 39, 203 (1959). 116. S. Iwatsuki, M. Murakami, Y. Yamashita, Kogyo Kagaku Zasshi, 68, 1967 (1965). 117. S. Iwatsuki, Y. Yamashita, Kogyo Kagaku Zasshi, 68, 1963 (1965). 118. E. F. Jordan, K. M. Doughty, W. S. Port, J. Appl. Polym. Sci., 4, 203, (1960). 119. E. F. Jordan, A. N. Wrigley, J. Appl. Polym. Sci., 8, 527 (1964). 120. J. M. Judge, C. C. Price, J. Polym. Sci., 41, 435 (1959). 121. D. J. Kahn, H. H. Horowitz, J. Polym. Sci., 54, 363 (1961). 122. N. G. Karapetyan, I. S. Boshnyakov, A. S. Magaryan, Vysokomol. Soedin., 7, 1993 (1965). 123. D. Katz, J. Relis, J. Polym. Sci. A-I, 6, 2079 (1968). 124. N. Kawabata, T. Tsuruta, J. Furukawa, Makromol. Chem., 48, 106 (1961). 125. R. Kerber, Makromol. Chem., 96, 30 (1966). 126. J. T. Khamis, Polymer, 6, 98 (1965). 127. A. M. Khomutov, Izv. Akad. Nauk SSSR Otd. Khim. Nauk, 352 (1961). 128. M. Kinoshita, M. Imoto, Kogyo Kagaku Zasshi, 68, 2454 (1965).
129. G. S. Kolesnikov, E. F. Rodionova, I. G. Safaralieva, Izv. Akad. Nauk SSSR, Ser. Khim., 2028, (1963). 130. G. S. Kolesnikov, A. S. Tevlina, A. B. Alovitdinov, Vysokomol. Soedin., 7, 1913 (1965). 131. G. S. Kolesnikov, A. S. Tevlina, A. B. Alovitdinov, Plasticheskie Massy, 12 (1966). 132. G. S. Kolesnikov, A. S. Tevlina, S. R Novikova, S. N. Sividova, Vysokomol. Soedin., 7, 2160 (1965). 133. S. Konya, M. Yokoyama, Kogyo Kagaku Zasshi, 68, 1080 (1965). 134. M. Kreisel, U. Garbatski, D. H. Kohn, J. Polym. Sci. A, 2, 105 (1964). 135. A. G. Kronman, I. V. Pasmanik, B. I. Fedoseev, V. A. Kargin, Vysokomol. Soedin. A, 9, 2503 (1967). 136. F. Leonard, W. P. Hohenstein, E. Merz, J. Am. Chem. Soc, 70, 1283 (1948). 137. F. M. Lewis, F. R. Mayo, J. Am. Chem. Soc, 70, 1533 (1948). 138. F. M. Lewis, F. R. Mayo, W. F. Hulse, J. Am. Chem. Soc, 67, 1701 (1945). 139. F. M. Lewis, C. Walling, W. Cummings, E. R. Briggs, F. R. Mayo, J. Am. Chem. Soc, 70, 1519 (1948). 140. F. M. Lewis, C. Walling, W. Cummings, E. R. Briggs, W. J. Wenisch, J. Am. Chem. Soc, 70, 1527 (1948). 141. H. Lussi, Makromol. Chem., 103, 62 (1967). 142. H. Lussi, Makromol. Chem., 103, 68 (1967). 143. H. Lussi, Makromol. Chem., 110, 100 (1967). 144. H. L. Marder, C. Schuerch, J. Polym. Sci., 44, 129 (1960). 145. C. S. Marvel, W. G. Dipierri, J. Polym. Sci., 27, 39 (1958). 146. C. S. Marvel, T. K. Dykstra, F. C. Magne, J. Polym. Sci., 62, 369 (1962). 147. C. S. Marvel, J. W. Johnson, J. P. Economy, G. P. Scott, W. K. Taft, B. G. Labbe, J. Polym. Sci., 20, 437 (1956). 148. C. S. Marvel, G. D. Jones, T. W. Mastin, G. L. Schertz, J. Am. Chem. Soc, 64, 2356 (1942). 149. C. S. Marvel, E. B. Mano, J. Polym. Sci., 31, 165 (1958). 150. C. S. Marvel, G. L. Schertz, J. Am. Chem. Soc, 65, 2045 (1943). 151. C. S. Marvel, R. Schwen, J. Am. Chem. Soc, 79, 6003 (1957). 152. A. Matsumoto, M. Oiwa, Kogyo Kagaku Zasshi, 70, 360 (1967). 153. A. Matsumoto, S. Shoda, T. Harada, M. Oiwa, Kogyo Kagaku Zasshi, 70, 1007 (1967). 154. K. Matsuoka, M. Otsuka, K. Takemoto, M. Imoto, Kogyo Kagaku Zasshi, 69, 137 (1966). 155. K. Matsuoka, K. Takemoto, M. Imoto, Kogyo Kagaku Zasshi, 68, 1941 (1965). 156. K. Matsuoka, K. Takemoto, M. Imoto, Kogyo Kagaku Zasshi, 69, 134 (1966). 157. K. Matsuoka, K. Takemoto, M. Imoto, Kogyo Kagaku Zasshi, 69, 142 (1966). 158. F. R. Mayo, C. Walling, F. M. Lewis, W. F. Hulse, J. Am. Chem. Soc, 70, 1523 (1948). 159. E. J. Meehan, J. Polym. Sci., 1, 318 (1946). 160. H. W. Melville, L. Valentine, Trans. Faraday Soc, 51, 1474 (1955).
161. A. Misono, Y. Uchida, Bull. Chem. Soc. Japan, 39, 2458 (1966). 162. J. Muller, Collection Czech. Chem. Commun., 20, 241 (1955). 163. K. Murata, A. Terada, Bull. Chem. Soc. Japan, 39, 2494 (1966). 164. S. Nagai, Bull. Chem. Soc. Japan, 36, 1459 (1963). 165. A. S. Nair, M. S. Muthana, Makromol. Chem., 47, 138 (1961). 166. A. F. Nikolaev, V. M. Gaperin, Vysokomol. Soedin. A, 9, 2469 (1967). 167. A. F. Nikolaev, S. N. Ushakov, L. S. Mishkileeva, Vysokomol. Soedin., 6, 287 (1964). 168. M. Nishigaki, M. Kinoshita, M. Imoto, Kogyo Kagaku Zasshi, 70, 1938 (1967). 169. A. M. North, D. Postlethwaite, Polymer, 5, 237 (1964). 170. A. M. North, A. M. Scallan, Polymer, 5, 447 (1964). 171. K. F. O'Driscoll, F. P. Gasparro, J. Macromol. Sci. A: Chem., 1, 643 (1967). 172. E. Ohmori, Y. Ohi, T. Otsu, M. Imoto, Kogyo Kagaku Zasshi, 68, 1600 (1965). 173. R. J. Orr, H. L. Williams, Can. J. Chem., 30, 108 (1952). 174. R. J. Orr, H. L. Williams, Can. J. Chem., 33, 1328 (1955). 175. E. Osawa, K. Wang, O. Kurihara, Makromol. Chem., 83, 100 (1965). 176. G. Oster, Y. Mizutani, J. Polym. Sci., 22, 173 (1956). 177. T. Otsu, T. Ito, Y. Fujii, M. Imoto, Bull. Soc. Chem. Japan, 41, 204 (1968). 178. T. Otsu, T. Ito, T. Fukumizu, M. Imoto, Bull. Soc. Chem. Japan, 39, 2257 (1966). 179. T. Otsu, T. Ito, M. Imoto, Kogyo Kagaku Zasshi, 69, 986 (1966). 180. T.Otsu, Y. Kinoshita, A. Nakamachi, Makromol. Chem., 115, 27 (1968). 181. T. Otsu, A. Shimizu, M. Imoto, J. Polym. Sci. A, 3, 615 (1965). 182. T. Otsu, B. Yamada, Makromol. Chem., 110, 297 (1967). 183. M. Otsuka, K. Takemoto, M. Imoto, Kobunshi Kagaku, 23, 765 (1966). 184. M. Otsuka, Y. Yashuhara, K. Takemoto, M. Imoto, Makromol. Chem., 103, 291 (1967). 185. C. G. Overberger, D. E. Baldwin, H. P. Gregor, J. Am. Chem. Soc, 72, 4864 (1950). 186. C. G. Overberger, H. Biletch, R. G. Nickerson, J. Polym. Sci., 27, 381 (1958). 187. T. R. Paxton, J. Polym. Sci. B, 1, 73 (1963). 188. J. Pellon, R. L. Kugel, R. Marcus, R. Rabinowitz, J. Polym. Sci., A-2, 4105 (1964). 189. J. R Fischer, Makromol. Chem., 156, 227 (1972). 190. S. H. Pinner, J. Polym. Sci., 10, 379 (1953). 191. C. C. Price, R. D. Gilbert, J. Polym. Sci., 8, 580 (1952). 192. C. C. Price, C. E. Greene, J. Polym. Sci., 6, 111 (1951). 193. C. C. Price, H. Morita, J. Am. Chem. Soc, 75, 4747 (1953). 194. C. C. Price, T. C. Schwan, J. Polym. Sci., 16, 577 (1955). 195. C. C. Price, J. Zomlefer, J. Am. Chem. Soc, 72, 14 (1950).
196. E. G. Pritchett, P M. Kamath, J. Polym. Sci. B, 4, 849 (1966). 197. H. Ringsdorf, N. Weinshenker, C. G. Overberger, Makromol. Chem., 64, 126 (1963). 198. W M. Ritchey, L. E. Ball, J. Polym. Sci. B, 4, 557 (1966). 199. L. Rodriguez, Makromol. Chem., 12, 110 (1954). 200. J. Roovers, G. Smets, Makromol. Chem., 60, 89 (1963). 201. R. W. Roth, R. F. Church, J. Polym. Sci., 55, 41 (1961). 202. E. W. Rugeley, T. A. Field, G. H. Fremon, Ind. Eng. Chem., 40, 1724 (1948). 203. A. V. Ryabov, Yu. D. Semchikov, N. N. Slavnitskaya, Dokl. Akad. Nauk SSSR, 145, 822 (1962). 204. M. K. Saha, P. Ghosh, S. R. Palit, J. Polym. Sci. A, 2, 1365 (1964). 205. G. Saini, G. Polla-Mattiot, M. Meirone, J. Polym. Sci., 50, S-13 (1961). 206. C. L. Sandberg, F. A. Bovey, J. Polym. Sci., 15, 553 (1955). 207. R. C. Schulz, H. Cherdron, W. Kern, Makromol. Chem., 28, 197 (1958). 208. R. C. Schulz, E. Kaiser, W. Kern, Makromol. Chem., 58, 160 (1962). 209. C. E. Scott, C. C. Price, J. Am. Chem. Soc, 81,2670 (1959). 210. P. K. Sengupta, A. R. Mukherjee, P. Ghosh, J. Macromol. Chem., 1, 481 (1966). 211. A. Shimizu, T. Otsu, M. Imoto, Bull. Chem. Soc. Japan, 38, 1535 (1965). 212. M. F. Shostakovskii, A. M. Khomutov, A. R Alimov, Izv. Akad. Nauk SSSR, Ser. Khim., 1839, (1963). 213. M. F. Shostakovskii, A. M. Khomutov, F. P. Sidel'kovskaya, Izv. Akad. Nauk SSSR, Ser. Khim., 2222, (1961). 214. F. P. Sidel'kovskaya, M. A. Askarov, F. Ibragimov, Vysokomol. Soedin., 6, 1810 (1964). 215. F. P. Sidel'kovskaya, M. F. Shostakovskii, F. Ibragimov, M. A. Askarov, Vysokomol. Soedin., 6, 1585 (1964). 216. C. Simionescu, N. Asandei, A. Liga, Makromol. Chem., 110, 278 (1967). 217. J. A. Simms, J. Appl. Polym. Sci., 5, 58 (1961). 218. G. Smets, L. Dehaes, Bull. Soc Chim. BeIg., 59,13 (1950). 219. G. Smets, N. Deval, P. Hous, J. Polym. Sci. A, 2, 4835 (1964). 220. G. Smets, E. Dysseleer, Makromol. Chem., 91, 160 (1966). 221. G. Smets, A. M. Hesbain, J. Polym. Sci., 40, 217 (1959). 222. G. Smets, A. Reckers, Rec Trav. Chim., 68, 983 (1949). 223. W. E. Smith, G. E. Ham, H. D. Anspon, S. E. Gebura, D. W. Alwani, J. Polym. Sci. A-I, 6, 2001 (1968). 224. M. F Sorokin, M. M. Babkina, Vysokomol. Soedin., 7, 734 (1965). 225. M. F. Sorokin, L M. Kochnov, Vysokomol. Soedin., 6, 798 (1964). 226. M. F Sorokin, K. A. Lyalyushko, R. A. Dudakova, V. S. Vasil'ev, A. N. Shuvalova, Plasticheskie Massy, 3 (1963). 227. E. Muccer, K. Dinges, W. Graulich, Makromol. Chem., 57, 27 (1962). 228. A. Takahashi, H. Tanaka, I. Kagawa, Kogyo Kagaku Zasshi, 70, 988 (1967). 229. K. Takemoto, Y. Kikuchi, M. Imoto, Kogyo Kagaku Zasshi, 69, 1367 (1966).
230. K. Takemoto, K. Matsuoka, M. Otsuka, M. Imoto, Kogyo Kagaku Zasshi, 69, 2026 (1966). 231. T. Tamikado, J. Polym. ScL, 43, 489 (1960). 232. T. Tamikado, Makromol. Chem., 38, 85 (1960). 233. T. Tamikado, Y. Iwakura, J. Polym. ScL, 36, 529 (1959). 234. A. Tanaka, K. Sasaki, Y. Hozumi, O. Hashimoto, J. Appl. Polym. ScL, 8, 1787 (1964). 235. M. Taniyama, G. Oster, Bull. Chem. Soc. Japan, 30, 856 (1957). 236. W. M. Thomas, M. T. O'Shaughnessy, J. Polym. ScL, 11, 455 (1953). 237. B. R. Thompson, J. Polym. ScL, 19, 373 (1956). 238. B. R. Thompson, R. H. Raines, J. Polym. ScL, 41, 265 (1959). 239. K. Tsuda, S. Kobayashi, T. Otsu, J. Polym. ScL A-I, 6, 41 (1968). 240. N. A. Tyukavkina, A. V. Kalabina, G. I. Deryabina, G. T. Zhikarev, A. D. Biryukova, Vysokomol. Soedin., 6, 1573 (1964). 241. K. Uehara, T. Nishi, T. Tsuyuri, F. Tamura, N. Murata, Kogyo Kagaku Zasshi, 70, 750 (1967). 242. J. Ulbricht, J. Giesemann, M. Gebauer, Angew. Makromol. Chem., 3, 69 (1968). 243. C. G. Overberger, F. W. Michelotti, J. Am. Chem. Soc, 80, 988 (1958). 244. C. C. Unruh, T. M. Laasko, J. Polym. ScL, 33, 87 (1958). 245. S. N. Ushakov, V. A. Kropachev, L. B. Trukhmanova, R. I. Gruz, T. M. Markelova, Vysokomol. Soedin. A, 9, 1807 (1967). 246. S. N. Ushakov, A. F. Nikolaev, Izv. Akad. Nauk SSSR, Ser. Khim., 83 (1956). 247. S. N. Ushakov, L. B. Trukhmanova, Izv. Akad. Nauk SSSR, Ser. Khim., 980 (1957). 248. S. N. Ushakov, L. B. Trukhmanova, T. M. Markelova, V. A. Kropachev, Vysokomol. Soedin. A, 9, 999 (1967). 249. L. F. Vandenburgh, C. E. Brockway, J. Polym. ScL A, 3,575 (1965). 250. G. vanPaesschen, G. Smets, Bull. Soc. Chim. BeIg., 64,173 (1955). 251. G. vanPaesschen, D. Timmerman, Makromol. Chem., 78, 112(1964). 252. B. Vollmert, Angew. Makromol. Chem., 3, 1 (1968). 253. M. Vrancken, G. Smets, Makromol. Chem., 30,197 (1969). 254. F. T. Wall, R. E. Florin, C. J. Delbecq. J. Am. Chem. Soc, 72, 4769 (1950). 255. F. T. Wall, R. W. Powers, G. D. Sands, G. S. Stent, J. Am. Chem. Soc, 70, 1031 (1948). 256. C. Walling, F. R. Briggs, K. B. Wolfstirn, F. R. Mayo, J. Am. Chem. Soc, 70, 1537 (1948). 257. C. Walling, J. A. Davison, J. Am. Chem. Soc, 73, 5736 (1951). 258. R. L. Whistler, J. L. Goatley, J. Polym. ScL, 50, 127 (1961). 259. G. S. Wich, N. Brodoway, J. Polym. Sci. A, 1, 2163 (1963). 260. M. C. DeWilde, G. Smets, J. Polym. ScL, 5, 253 (1950). 261. R. H. Wiley, B. Davis, J. Polym. Sci., 46, 423 (1960). 262. R. H. Wiley, E. E. Sale, J. Polym. Sci., 42, 497 (1960). 263. A. Winston, F. L. Hamb, J. Polym. ScL A, 3, 583 (1965).
264. A. Winston, G. T. C. Li., J. Polym. Sci. A-I, 5, 1223 (1967). 265. P. Wittmer, Makromol. Chem., 103, 188 (1967). 266. B. A. Zaitsev, G. A. Shtraikhman, Vysokomol. Soedin. A, 10, 438 (1968). 267. N. L. Zutty, J. Polym. ScL A, 1, 2231 (1963). 268. J. Aoyagi, I. Shinohara, Nippon Kagaku Kaishi, 788, 1972. 269. S. Tazuke, S. Okamura, J. Polym. Sci. A-I, 6, 2907 (1968). 270. T. Otsu, T.-C. Lai, Y. Kinoshita, A. Nakamachi, M. Imoto, Kogyo Kagaku Zasshi, 71, 904 (1968). 271. K. Takemoto, S. Takahashi, M. Imoto, Kogyo Kagaku Zasshi, 71, 742 (1968). 272. J. C. Bevington, M. Johnson, Eur. Polym. J., 4, 669 (1968). 273. R. Kroker, H. Ringsdorf, Makromol. Chem., 121, 240 (1969). 274. C. Aso, T. Kunitake, T. Nakashima, Kogyo Kagaku Zasshi, 72, 1411 (1969). 275. F. C. Baines, J. C. Bevington, Polymer, 11, 647 (1970). 276. V. D. Bezuglyi, I. B. Voskresenskaya, T. A. Alekseeva, M. M. Gemer, Vysokomol. Soedin. A, 14, 540 (1972). 277. D. Braun, G. Mott, Angew. Makromol. Chem., 18, 183 (1971). 278. W. R. Cabaness, T. Y-C. Lin, C. Parkanyi, J. Polym. Sci. A-I, 9, 2155 (1971). 279. G. I. Deryabina, Yu. L. Frolov, A. V. Kalabina, Vysokomol. Soedin., A13, 1162(1971). 280. G. I. Deryabina, G. I. Gershengorn, Vysokomol. Soedin. A, 11, 941 (1969). 281. J. P. Fischer, Makromol. Chem., 155, 211 (1972). 282. A. Gilath, S. H. Ronel, M. Shmueli, D. H. Kohn, J. Appl. Polym. Sci., 14, 1491 (1970). 283. K. Hayashi, T. Otsu, Makromol. Chem., 127, 54 (1969). 284. H. Hopff, G. Becker, Makromol. Chem., 133, 1 (1970). 285. H. Inoue, T. Otsu, Makromol. Chem., 153, 21 (1972). 286. H. Inoue, I. Umeda, T. Otsu, Makromol. Chem., 147, 271 (1971). 287. T Ito, T. Otsu, J. Macromol. Sci. Chem., 3, 197 (1969). 288. Z. Janovic, C. S. Marvel, M. J. Diamond, D. J. Kertesz, G. Fuller, J. Polymer Sci. A-I, 9, 2639 (1971). 289. H. K. Johnson, A. Rudin, J. Paint Technol., 42, 435 (1970). 290. E. F. Jordan, R. Bennett, A. C. Shuman, A. N. Wrigley, J. Polym. Sci. A-I, 8, 3113 (1970). 291. Y. Kinoshita, J. Kobayashi, F. Ide, K. Nakatsuka, Kobunshi Kagaku, 27, 469 (1970). 292. Y. Kinoshita, J. Kobayashi, F. Ide, K. Nakatsuka, Kobunshi Kagaku, 28, 430 (1971). 293. J. C. Lai, T. D. Rounsefell, C. U. Pittman, Macromolecules, 4, 155 (1971). 294. J. C. Lai, T. Rounsefell, C. U. Pittman, J. Polym. Sci. A-1,9, 651 (1971). 295. A. Leoni, S. Franco, Macromolecules, 4, 355 (1971). 296. A. Matsumoto, T. Ise, M. Oiwa, Nippon Kagaku Kaishi, 209 (1972). 297. A. Matsumoto, H. Muraoka, M. Taniguchi, M. Oiwa, Kogyo Kagaku Zasshi, 74, 1913 (1971). 298. K. Matsuo, S. Machida, J. Polym. Sci. A-1,10, 187 (1972).
299. H. Mitsui, K. Tsuneta, T. Kagiya, Kogyo Kagaku Zasshi, 74, 1918 (1971). 300. Z. Moniyama, A. Yamamoto, M. Kagiyama, R. Chujo, J. Macromol. Sci. A: Chem., 4, 1649 (1970). 301. A. F. Nikolaev, L. P. Vishnevetskaya, O. A. Gromova, M. M. Grigor'eva, M. S. Kleshcheva, Vysokomol. Soedin. A, 11, 2418 (1969). 302. E. Oikawa, K. Yamamoto, Polym. J., 1, 669 (1970). 303. T. Otsu, H. Inoue, J. Macromol. Sci. A-I, 4, 35 (1970). 304. T. Otsu, O. Nakatsuka, Kobunshi Kagaku, 29, 168 (1972). 305. M. Otsuka, K. Matsuoka, K. Takemoto, M. Imoto, Kogyo Kagaku Zasshi, 72, 2505 (1969). 306. M. Otsuka, K. Matsuoka, K. Takemoto, M. Imoto, Kogyo Kagaku Zasshi, 73, 1062 (1970). 307. T. Ouchi, M. Oiwa, Kogyo Kagaku Zasshi, 72,1587 (1969). 308. C. U. Pittman, P. L. Grube, J. Polym. Sci. A-I, 9, 3175 (1971). 309. M. Ratzch, W. Schneider, D. Musche, J. Polym. Sci. A-I, 9, 785 (1971). 310. S. H. Ronel, D. H. Kohn, J. Polym. Sci. A-1,7,2209 (1969). 311. R. A. Terteryan, Vysokomol. Soedin., 11, 1798 (1969). 312. A. V. Ryabov, Yu. D. Semchikov, N. N. Sivanitskaya, Vysokomol. Soedin. A, 12, 553 (1970). 313. A. V. Ryabov, L. A. Smirnova, V. A. Soldatov, Dokl. Akad. Nauk SSSR, 194, 1338 (1970). 314. G. Saini, A. Leoni, S. Franco, Makromol. Chem., 144, 235 (1971). 315. G. Saini, A. Leoni, S. Franco, Makromol. Chem., 146, 165 (1971). 316. G. Saini, A. Leoni, S. Franco, Makromol. Chem., 147, 213 (1971). 317. F. F. Shcherbina, O. I. Bakumenko, Vysokomol. Soedin. A, 11, 772 (1969). 318. Y. Tabata, K. Ishigure, H. Higaki, K. Oshima, J. Macromol. Sci. A: Chem., 4, 801 (1970). 319. S. Takahashi, K. Takemoto, M. Imoto, Kobunshi Kagaku, 27, 156 (1970). 320. H. Tamura, M. Tanaka, N. Murata, Kobunshi Kagaku, 27, 652 (1970). 321. H. Tamura, M. Tanaka, N. Murata, Kobunshi Kagaku, 27, 736 (1970). 322. S. Tazuke, S. Okamura, J. Polym. Sci. A-I, 7, 715 (1969). 323. M. Yamada, I. Takase, T. Tsukano, Y. Ueda, N. Koutou, Kobunshi Kagaku, 26, 593 (1969). 324. V. R Zubov, L. I. Valuev, V. A. Kabanov, V A. Kargin, J. Polym. Sci. A-I, 9, 833 (1971). 325. O. E. Ayers, S. P. McManus, C. U. Pittman, J. Polym. Sci., Polym. Chem. Ed., 11, 1201 (1973). 326. J. Ballesteros, G. J. Howard, L. Teasdale, J. Macromol. Sci. A: Chem., 11, 29 (1977). 327. Y. Bando, T. Dodou, Y. Minoura, J. Polym. Sci., Polym. Chem. Ed., 15, 1917 (1977). 328. J. M. Barrales-Rienda, J. I. Gonzalez de Ia Campa, R. J. Gonzalez, J. Macromol. Sci. A: Chem., 11, 267 (1977). 329. A. R. Cain, Am. Chem. Soc, Div. Polym. Chem. Preprints, 11, 312 (1970). 330. A. Chapiro, L. Perec-Spitzer, Eur. Polym. J., 11, 59 (1975).
331. A. Chapiro, P. Lessulnier, Eur. Polym. J., 12, 761 (1976). 332. T. A. DuPlessis, A. C. Thomas, J. Polym. Sci., Polym. Chem. Ed., 11, 2681 (1973). 333. N. B. Gaddam, S. F. Xavioir, T. C. Goel, J. Polym. Sci., Polym. Chem. Ed., 15, 1473 (1977). 334. C. V. Hinton, H. G. Spencer, Macromolecules, 9, 864 (1976). 335. M. E. Hoaglund, I. N. Duling, Am. Chem. Soc, Petrol. Chem. Preprints, 15, B85 (1970). 336. H. Inoue, T. Otsu, Makromol. Chem., 153, 21 (1972). 337. S. Iwabuchi, K. Kojima, T. Nakahira, M. Ueda, M. Kobayashi, M. Iwakura, J. Polym. Sci., Polym. Chem. Ed., 12,2801 (1974). 338. S. Iwabuchi, M. Ueda, M. Kobayashi, K. Kojima, Polym. J., 6, 185 (1974). 339. V. V. Kopeikin, E. F. Panarin, I. S. Milevskaya, N. S. Redi, Vysokomol. Soedin. A, 19, 861 (1977). 340. Y. Matsubara, M. Yoshihara, T. Maeshima, Nippon Kagaku Kaishi, 2186 (1974). 341. D. R. Abayasekara, R. M. Ottenbrite, Polym. Prepr. (Am. Chem. Soc, Div. Polym. Chem.), 25, 164 (1984). 342. F. Mikes, P. Strop, O. Seycek, J. Roda, J. Kalal, Eur. Polym. J., 10, 1029 (1974). 343. L. M. Minsk, C. Kotlarchik, G. N. Meyer, J. Polym. Sci., Polym. Chem. Ed., 11, 3037 (1973). 344. J. C. Salmone, R Taylor, B. Snider, S. C. Israel, Am. Chem. Soc, Polym. Chem. Preprints, 15, 462 (1974). 345. M. Niwa, Kobunshi Kagaku, 29, 52 (1972). 346. M. Niwa, S. Iida, Y. Nakazato, Kobunshi Robunshu, 32,189 (1975). 347. K. Noma, M. Niwa, K. Morita, Kobunshi Kagaku, 29, 907 (1972). 348. T. Oishi, T. Kimura, Kobunshi Robunshu, 33, 685 (1976). 349. S. Okamura, K. Hayashi, Polym. J., 4, 495 (1973). 350. T. Okano, J. Aoyagi, I. Shinohara, Nippon Kagaku Kaishi, 161 (1976). 351. T. Masuda, C. Aoyama, Kobunshi Kagaku, 30, 223 (1973). 352. T. Otsu, M. Inoue, Kobunshi Robunshu, 31, 250 (1974). 353. T. Otsu, H. Tanaka, J. Polym. Sci. Polym. Chem. Ed., 13, 2605 (1975). 354. C. U. Pittman, G. Marlin, T. D. Rounsefell, Macromolecules, 6, 1 (1973). 355. G. Sielaff, D. O. Hummel, Makromol. Chem., 175, 1579 (1974). 356. H. Tanaka, T. Otsu, J. Macromol. Sci. A: Chem., 11, 231 (1977). 357. A. Kh. Usbekova, V. V. Razumovskii, Vysokomol. Soedin. A, 14, 1681 (1972). 358. I. K. Varma, S. Patnaik, Eur. Polym. J., 12, 259 (1976). 359. A. I. Vorob'eva, E. I. Ablyakimov, G. V Leplyanin, Vysokomol. Soedin. A, 16, 349 (1974). 360. T. Yala-Lutokanu, G. Jenner, A. Deluzarche, Bull. Soc Chim. France, 609 (1974). 361. M. Yoshimura, Y. Shirota, H. Mikawa, Macromolecules, 8, 713 (1975). 362. A. Miller, J. Szafko, E. Turska, J. Polym. Sci., Polym. Chem. Ed., 15, 51 (1977).
363. A. Miller, J. Szafko, J. Polym. ScL, Polym. Chem. Ed., 15, 1595 (1977). 364. K. L. Petrak, J. Polym. ScL, Polym. Letters Ed., 16, 393 (1978). 365. M. Sharabash, R. L. Guile, J. Macromol. Sci. A: Chem., 10, 1039 (1976). 366. R. H. Wiley, B. Davis, J. Polym. Sci. A, 1, 2819 (1963). 367. T. Ohata, A. Matsumoto, M. Oiwa, Bull. Chem. Soc. Japan, 47, 928 (1974). 368. J. Aoyagi, I. Shinohara, Kogyo Kagaku Zasshi, 74, 1191 (1971). 369. L. V. Morozova, T. T. Minakova, B. A. Troflmov, Deposited Doc, VINITI 1228 (1983). 370. G. Akasome, S. Sakai, Y. Choshi, K. Murai, Kobunshi Kagaku, 17, 478 (1960). 371. G. Akasome, S. Sakai, Y. Choshi, K. Murai, Kobunshi Kagaku, 17, 558 (1960). 372. G. Akasome, S. Sakai, K. Murai, Kobunshi Kagaku, 17,449 (1960). 373. G. Akasome, S. Sakai, K. Murai, Kobunshi Kagaku, 17,452 (1960). 374. G. Akasome, S. Sakai, K. Murai, Kobunshi Kagaku, 17,482 (1960). 375. T. Alfrey, L. Arond, C. G. Overberger, quoted by Alfrey, "Coporymerization", p. 35. 376. T. Alfrey, jr., J. Bohrer, H. Mark, "Copolymerization", High Polymer Series, Vol. VIII, Interscience, New York, 1952, p. 40. 377. T. Alfrey, B. Magel, quoted by Alfrey, "Copolymerization", Wiley, New York. 378. American Cyanamid Co., "Chemistry of Acrylonitrile", 2nd Ed., 1960, p. 34. 379. American Cyanamid Co., private communication to L. J. Young. 380. K. Anda, S. Iwai, Kogyo Kagaku Zasshi, 70, 557 (1967). 381. T. Asahara, K. Mitsuhashi, Yukagaku, 6, 331 (1957). 382. M. A. Askarov, S. R. Pinkhasov, A. S. Bank, Vysokomol. Soedin. B, 9, 601 (1967). 383. J. N. Atherton, A. M. North, Trans. Faraday Soc, 58, 2049 (1962). 384. C. H. Bamford, W. G. Barb, Discussions Faraday Soc, 14, 208 (1953). 385. A. S. Bank, S. D. Savranskaya, M. A. Askarov, Khim. iFiz.Khim. Prirodn. iSintetich. Polimerov, Akad. NaukUz. SSR, Inst. Khim. Polimerov No. 2, 110 (1964). 386. I. M. Barton, G. B. Butler, E. C. Chapin, J. Polym. Sci. A, 3, 501 (1965). 387. T. F. Baskova, O. M. Klimova, Vysokomol. Soedin. B, 10, 63 (1968). 388. L. Bogetich, G. A. Mortimer, G. W. Daues, J. Polym. ScL, 61, 3, (1962). 389. J. Brandrup, Faserforsch. Textiltech., 12, 135 (1961). 390. D. Braun, H.-G. Keppler, Makromol. Chem., 82, 132 (1965). 391. J. W. Breitenbach, H. Edelhauser, Ric ScL, 25, 242 (1955).
392. M. A. Bruk, A. D. Abkin, P M. Khomikovskii, G. A. Gold'er, H.-L. Chu, Dokl. Akad. Nauk SSSR, 157, 1399 (1964). 393. W. J. Burlant, D. H. Green, J. Polym. Sci., 31, 227 (1958). 394. G. M. Burnett, J. M. Pearson, J. D. B. Smith, J. Polym. Sci. A-I, 4, 2024 (1966). 395. G. B. Butler, G. Vanhaeren, M.-F. Ramadier, J. Polym. Sci. A-I, 5, 1265 (1967). 396. A. Chapiro, A.-M. Jendrychowska-Bonamour, J. Polym. ScL C, 1, 1211 (1963). 397. C. B. Chapman, L. Valentine, J. Polym. Sci., 34, 319 (1959). 398. Chas. Pfizer, Co., Product News, quoted by L. J. Young (1961). 399. K. Chikanishi, T. Tsuruta, Makromol. Chem., 73, 231 (1964). 400. M. A. Chilingaryan, A. E. Akopyan, M. G. Barkudaryan, Arm. Khim. Zh., 20, 428 (1967). 401. L. E. DeMiIIo, G. A. Shtraikhman, E. N. Rostovskii, Zh. Prikl. Khim., 39, 1360 (1966). 402. K. W. Doak, quoted by Mayo, Walling, 1950. 403. K. W. Doak, M. A. Deahl, I. H. Christmas, 137th ACS Meeting, Cleveland, Ohio, Abstr. Papers, Vol. 1, No. 1, 151 (April, 1960). 404. T. Doi, M. Matsuki, A. Sugiyama, Kogyo Kagaku Zasshi, 70, 1792 (1967). 405. G. Dolgin, P. Gordon, quoted by Alfrey, "Copolymerization", Wiley, New York, p. 40. 406. DuPont Co., British Patent, 593, 605 (1947). 407. E H. C. Edgecombe, Nature, 198, 1085 (1963). 408. J. Exner, M. Bohdanecky, Chem. Listy, 48, 483 (1954). 409. V. L. FoIt, Canadian Patent, 509, 259 (1955). 410. S. Fujii, Radiation Res., 33, 249 (1968). 411. J. Furukawa, T. Tsuruta, N. Yameda, Kogyo Kagaku Zasshi, 61, 734 (1958). 412. L. H. Gale, J. Org. Chem., 31, 2475 (1966). 413. A. L. Gol'denberg, S. G. Lubetskii, Dokl. Nauk SSSR, 179, 900 (1968). 414. M. Goodstein, quoted in Alfrey, "Copolymerization", Wiley, New York, p. 35. 415. VF. Gromov, P. M. Khomikovskii, A. D. Abkin, Vysokomol. Soedin., 3, 1015 (1961). 416. A. Guyot, J. Guillot, J. Chem. Phys., 61, 1434 (1964). 417. K. R. Henery-Logan, R. V. V Nichlos, quoted by Simha and Wall. 418. K. R. Henery-Logan, R. V V. Nichlos, quoted by Mayo and Walling. 419. R. Hess, quoted in Alfrey, "Copolymerization", Wiley, New York, p. 36, p. 37. 420. T. Higuchi, H. Imoto, Kogyo Kagaku Zasshi, 61, 1053 (1958). 421. A. Hunyar, H. Reichert, Faserforsch. Textiltech., 5, 204 (1954). 422. E. Husemann, Univ. Freiberg i. Br. Germany, private communication to L. J. Young. 423. F. Ida, K. Uemura, S. Abe, Kagaku to Kogyo (Osaka), 38, 215 (1964).
424. F. Ida, K. Uemura, S. Abe, Kagaku to Kogyo (Osaka), 39, 565 (1965). 425. F. Ide, K. Okano, S. Nakano, K. Nakstuka, Shikizai Kyokaishi, 40, 571 (1967). 426. M. Imoto, T. Otsu, Y. Harada, Makromol. Chem., 65, 180 (1963). 427. M. Imoto, S. Shimizu, Kobunshi Kagaku, 18, 747 (1961). 428. T. Imoto, Y. Ogo, S. Goto, T. Mitani, Kogyo Kagaku Zasshi, 69, 1371 (1966). 429. T. Imoto, Y. Ogo, T. Mitani, Kogyo Kagaku Zasshi, 70, 1217 (1967). 430. T. Irie, M. Kinoshita, M. Imoto, Kogyo Kagaku Zasshi, 69, 980 (1966). 431. O. A. Iskhakov, E. V. Kuznetzov, G. M. Eliseeva, Vysokomol. Soedin. B, 10, 32 (1968). 432. K. Ito, S. Iwase, Y. Yamashita, Makromol. Chem., 110, 233 (1967). 433. Y. Iwakura, K. Matsuzaki, Kobunshi Kagaku, 17, 187 (1960). 434. Y. Iwakura, M. Sato, T. Tamikado, S. Mimashi, Kobunshi Kagaku, 13, 125 (1956). 435. Y. Iwakura, M. Sato, T. Tamikado, T. Mizoguchi, Kobunshi Kagaku, 13, 390 (1956). 436. U. Johnsen, K. Kolbe, Kolloid-Z. Z. Polymer, 216, 97 (1967). 437. R. M. Joshi, S. L. Kapur, J. Sci. Ind. Res., 16B, 379 (1957). 438. R. M. Joshi, S. L. Kapur, J. Sci. Ind. Res., 16B, 441 (1957). 439. N. Kamiya, H. Matsuura, Nippon Gomu Kyokaishi, 40, 64 (1967). 440. H. Kamogawa, H. G. Cassidy, J. Polym. Sci. A, 1, 1971 (1963). 441. H. Kamogowa, R. Murase, T. Sekiya, Kogyo Kagaku Zasshi, 62, 1749 (1959). 442. H. Kamogawa, T. Sekiya, Kogyo Kagaku Zasshi, 62, 1117 (1959). 443. R. G. Karzhaubaeva, G. P. Gladyshev, S. R. Rafikov, Vysomokol. Soedin. B, 9, 453 (1967). 444. v. F. Kazanskaya, O. M. Klimova, B. M. Khlebnikov, Vysomokol. Soedin., 6, 1799 (1964). 445. W. O. Kenyon, J. H. vanCampen, U.S. Patent, 2,419,221 (1947). 446. W. Kern, Univ. Mainz, private communication to L. J. Young. 447. W. Kern, D. Braun, Makromol. Chem., 27, 23 (1958). 448. A. M. Khomutov, Vysokomol. Soedin., 5, 1121 (1963). 449. T. Kimura, K. Yoshida, Kagaku to Kogyo (Osaka), 27, 288 (1953). 450. T. Kimura, K. Yoshida, Kagaku to Kogyo (Osaka), 32, 223, 341 (1958). 451. J. B. Kinsinger, J. S. Bartlett, N. H. Rauscher, J. Appl. Polym. Sci., 6, 529 (1962). 452. J. B. Kinsinger, J. R. Panchak, R. L. Kelso, J. S. Bartlett, R. K. Graham, J. Appl. Polym. Sci., 9, 429 (1965). 453. A. L. Klebanskii, O. A. Timofeev, Zh. Prikl. Khim., 32, 2294 (1959). 454. N. Kliman, M. Lazar, Chem. Prum., 9, 668 (1959).
455. A. R. Kol'k, A. A. Konkin, Z. A. Rogovin, Khim. Volokna, 12 (1963). 456. M. M. Koton, J. Polym. Sci., 30, 331 (1958). 457. M. M. Koton, Inst. Akad. Nauk Latv. SSR Riga, 119 (1957). 458. M. M. Koton, O. K. Sumina, Dokl. Akad. Nauk SSSR, 113, 1063 (1957). 459. G. E. Krybekyan, E. G. Sinanyan, A. N. Akopyan, Izv. Akad. Nauk Arm. SSR, Khim. Nauki, 15, 527 (1962). 460. G. N. Larina, Z. V. Borisova, T. V. Sheremeteva, Vysokomol. Soedin., 3, 1664 (1961). 461. F.-M. Li, Y-L. Ch'en, L.-C. Wang, H.-C. Wei, L.-H. Yeh, Ko Fen Tzu T'ung Hsun, 8, 1 (1966). 462. P. T. Li, K.-K. Wu, K'O Hsueh Ch'u Pan She, 151 (1963). 463. L. S. Luskin, R. J. Myers, "Encyclopedia of Polymer Science and Technology", Vol. 1, Interscience Publishers, 1964, p. 246. 464. Z. Machacek, Chem. Listy, 48, 477 (1954). 465. S. Machida, Y. Shimizu, T. Makita, Kamipa Gikyoshi, 21, 352 (1967). 466. M. F. Margaritova, G. D. Berezhnov, Tr. Mosk. Khim.Tekhnol. Inst., 4, 46 (1953). 467. M. F. Margaritova, V. A. Raiskaya, Tr. Mosk. Khim.Tekhnol. Inst., 4, 37 (1953). 468. L. Marker, O. J. Sweeting, J. G. Wepsic, J. Polym. Sci., 57, 855 (1962). 469. G. Markert, Makromol. Chem., 103, 109 (1967). 470. F. R. Mayo, F. M. Lewis, C. Walling, J. Am. Chem. Soc, 70, 1529 (1948). 471. Min. (Szu-Kwei), Chen Ho Chu, Hua Hsueh Hsueh Pao, 23, 262 (1957). 472. A. Misono, Y. Uchida, K. Yamada, Bull. Chem. Soc. Japan, 40, 2366 (1967). 473. J. M. Mitchell, H. L. Williams, Can. J. Res., 27, 35 (1949). 474. A. Mitsutani, M. Yono, Kogyo Kagaku Zasshi, 67, 935 (1964). 475. E. W. Moffett, R. E. Smith, U.S. Patent 2,356,871 (1944). 476. R. B. Mohite, S. Gundiah, S. L. Kapur, Makromol. Chem., 108, 52 (1967). 477. G. A. Mortimer, J. Polymer Sci. B, 3, 343 (1965). 478. D. T. Mowry, U.S. Patent 2,417,607 (1947). 479. S. Murahashi, S. Nozakura, A. Umehara, K. Obata, Kobunshi Kagaku, 21, 625 (1964). 480. S. Nagai, K. Yoshida, Kobunshi Kagaku, 17, 77 (1960). 481. T. Nakata, T. Otsu, M. Imoto, J. Polym. Sci. A, 3, 3383 (1965). 482. N. S. Nametkin, S. G. Durgar'yan, V. G. Filippova, Dokl. Akad. Nauk SSSR, 177, 853 (1967). 483. K. Noma, M. Niwa, K. Iwasaki, Kobunshi Kagaku, 20, 646 (1963). 484. S. Okamura, T. Yamashita, J. Soc. Textile Cellulose Ind. Japan, 9, 446 (1953). 485. V. A. Orlov, O. G. Tarakanov, Plasticheskie Massy, 6 (1964). 486. R. J. Orr, Polymer, 2, 79 (1961). 487. T. Otsu, T. Ito, M. Imoto, J. Polym. Sci. B, 3, 113 (1965). 488. T. Otsu, B. Yamada, T. Nozaki, Kogyo Kagaku Zasshi, 70, 1941 (1967).
489. G. S. Park, private communication to L. J. Young, (1966). 490. N. Platzer, Monsanto Co., private communication to L. J. Young. 491. Polymer Corp. Ltd., Sarnia, Can., private communication to L. J. Young. 492. C. C Price, J. G. Walsh, J. Polym. ScL, 6, 239 (1951). 493. N. V. Rakityanskii, R. L. Rabinovich, Rept. Allunion Sci. Inst. Synthetic Rubber, 1951. 494. R. C. Reinhardt, Ind. Eng. Chem., 35, 422 (1943). 495. N. N. Rozovskaya, A. P. Sheinker, A. D. Abkin, Vysokomol. Soedin., 7, 1383 (1965). 496. N. N. Rozovskaya, A. R Sheinker, A. D. Abkin, Vysokomol. Soedin., 7, 1500 (1965). 497. M. Kinoshita, S. Kataoka, M. Imoto, Kogyo Kagaku Zasshi, 72, 969 (1969). 498. A. V. Ryabov, Yu. D. Semchikov, N. N. Slavnitskaya, Tr. Khim. Khim. TekhnoL, 334 (1963). 499. A. V. Ryabov, Yu. D. Semchikov, V. N. Vakhrusheva, Tr. Khim. Khim. TekhnoL, 188 (1963). 500. I. Sakurada, Kobunshi Kagaku, 18, 496 (1961). 501. I. Sakurada, T. Okada, S. Hatakeyama, F. Kimura, J. Polym. Sci. C, 1, 1233 (1963). 502. I. Sakurada, G. Takahashi, Kobunshi Kagaku, 11, 286 (1954). 503. I. Sakurada, G. Takahashi, H. Mata, Kobunshi Kagaku, 12, 362 (1955). 504. B. Sandner, J. Ulbricht, Faserforsch. Textiltech., 17, 286 (1966). 505. A. P. Sheinker, A. D. Abkin, Tr. Tashkentsk Konf. po Mimomu Ispol Z. at. Energii Akad. Nauk Uz. SSR, 1, 395 (1961). 506. T. V. Sheremeteva, G. N. Larina, Dokl. Akad. Nauk SSSR, 162, 1323 (1965). 507. M. F. Shostakovskii, E. N. Prilezhaeva, J. M. Karavaeva, Vysokomol. Soedin., 1, 781 (1959). 508. G. Smets, A. Poot, G. L. Duncan, J. Polym. ScL, 54, 65 (1961). 509. G. Takashi, Kobunshi Kagaku, 14, 151 (1957). 510. G. Talamini, G. Vidotto, C. Garbuglio, Chim. Ind. (Milan), 47, 955 (1965). 511. A. Tanaka, Y. Hozumi, K. Hatada, Kobunshi Kagaku, 22, 216 (1965). 512. M. Tanaka, A. Asai, S. Takeya, Kogyo Kagaku Zasshi, 62, 1786 (1959). 513. H. Tatemichi, S. Suzuki, Kogyo Kagaku Zasshi, 63, 1843 (1960). 514. S. Tazuke, N. Sato, S. Okamura, J. Polym. Sci. A-I, 4, 2461 (1966). 515. R. W. Tess, W. T. Tsatsos, A. Chem. Soc, Div. Org. Coatings Plast. Chem., Preprints, 26, 276 (1966). 516. G. V. Tkachenko, V. S. Etlis, L. V. Stupen, L. P. Kofman, Zh. Fiz. Khim, 33, 25 (1959). 517. G. V. Tkachenko, P. H. Khomikovskii, A. D. Abkin, S. S. Medvedev, Zh. Fiz. Khim., 31, 242 (1957). 518. G. V. Tkachenko, L. V. Stupen, L. R Kofman, L. Z. Frolova, Zh. Fiz. Khim., 31, 2676 (1957).
519. G. V. Tkachenko, L. V. Stupen, L. P. Kofman, L. A. Karacheva, Zh. Fiz. Khim., 32, 2492 (1958). 520. V. L. Tsailingol'd, M. I. Farberov, G. A. Burgova, Vysokomol. Soedin., 1, 415 (1959). 521. E. Tsuchida, T. Kawagoe, Enka Biniiru to Porima, 8, 21 (1968). 522. E. Tsuchida, Y. Ohtani, H. Nakadai, I. Shinohara, Kogyo Kagaku Zasshi, 70, 573 (1967). 523. E. Tsuchida, Z. Okuno, T. Yao, I. Shinohara, Kogyo Kagaku Zasshi, 69, 1230 (1966). 524. E. Tsuchida, T. Shimomura, K. Fujimora, Y Ohtani, I. Shinohara, Kogyo Kagaku Zasshi, 70, 1230 (1966). 525. K. Ueberreiter, W. Krull, Z. Physik. Chem. (Frankfort), 12, 303 (1957). 526. S. N. Ushakov, E. M. Lavrent'eva, Zh. Prikl. Khim., 31, 1686 (1958). 527. Kh. U. Usmanov, R. S. Tillaev, U. N. Musaev, M. M. Nauchn. Tr., Tashkenysk. Gos. Univ. No. 257, 30 (1964). 528. Kh. U. Usmanov, A. A. Yul'chibaev, Kh. Yuldasheva, Uzb. Khim. Zh., 11, 27 (1967). 529. Kh. U. Usmanov, A. A. Yul'chibaev, Kh. Yuldasheva, Uzb. Khim. Zh., 11, 41 (1967). 530. J. W. Vanderhoff in E. H. Riddle, "Monomeric Acrylic Esters", Reinhold, New York, 1954, p. 94, Ref. 154. 531. F. T. Wall, quoted by F. R. Mayo and C. Walling. 532. C. Walling, E. R. Briggs, K. B. Wolfstirn, J. Am. Chem. Soc, 70, 1543 (1948). 533. G. Welzel, G. Greber, Makromol. Chem., 31, 230 (1959). 534. R. H. Wiley, B. Davis, J. Polym. Sci., 62, S-132 (1962). 535. R. H. Wiley, L. K. Heidemann, B. Davis, J. Polym. Sci. B, 1, 521 (1963). 536. C. E. Wilkes, J. C. Westfahl, R. H. Backderf, Am. Chem. Soc, Div. Polym. Chem., Preprints, 8, 386 (1967). 537. L. P. Witnauer, E. Watkins, W. S. Port, J. Polym. Sci., 20, 213 (1956). 538. D. M. Woodford, Chem. Ind. (London), 1966, 316. 539. N. Yamazaki, S. Kambara, J. Polym. Sci. C, 22, 75 (1968). 540. K. Yokota, Y. Ishii, Kogyo Kagaku Zasshi, 69, 1057 (1966). 541. K. Yokota, M. Kani, Y Ishii, J. Polym. Sci. A-I, 6, 1325 (1968). 542. L. J. Young, unpublished data, quoted in J. Polym. Sci., 54, 411 (1961). 543. N. L. Zutty, R. D. Burkhart, Advances in Chem. Series No, 34, "Polymerization and Condensation Processes", ACS, Washington D. C, 1962, p. 52. 544. M. P. Zverev, M. F. Margaritova, Ukr. Khim. Zh., 24, 626 (1958). 545. D. D. Al-Khashimi, T. R. Abdurashidov, M. A. Askarov, Uzb. Khim. Zh., 14, 87 (1970). 546. A. B. Alovitdinov, A. B. Kuchkarov, A. I. Kurbanov, Vysokomol. Soedin. B, 13, 657 (1971). 547. K. Anda, S. Iwai, J. Polym. Sci. A-I, 7, 2414 (1969). 548. K. Anda, S. Iwai, Kobunshi Kagaku, 29, 212 (1972). 549. J. Aoyagi, K. Kitamura, I. Shinohara, Kogyo Kagaku Zasshi, 73, 2045 (1970). 550. J. Ushirone, T. Otsu, Kogyo Kagaku Zasshi, 71,772 (1968). 551. A. M. North, K. E. Whitelock, Polymer, 9, 590 (1968).
552. B. K. Basov, V. L. Tsailingol'd, E. G. Lazaryants, Prom. Sin. Kauch., 17 (1967). 553. J. M. Carcamo, F. Arranz, Rev. Plast. Mod., 22, (182), 1169 (1971). 554. A. V. Chernobai, Zh. Kh. Zelichenko, Vysokomol. Soedin. A, 11, 1470 (1969). 555. K. H. Chung, Daehan Hwahak Hwoejee, 14, 333 (1970). 556. G. I. Deryabina, A. K. Khaliullin, S. Yu. Federova, L. A. Kron, Izv. Nauch.-Issled. Inst. Nefte-Uglekhim. Sin. Irkutsk. Univ., 12, 57 (1970). 557. M. Z. El-Sabban, S. I. Dmitrieva, A. I. Meos, Vysokomol. Soedin. B, 12, 243 (1970). 558. J. W. H. Faber, W. F. Fowler, J. Polym. Sci. A-I, 8, 1777 (1970). 559. A. L. German, D. Heikens, J. Polym. Sci. A-I, 9, 2225 (1971). 560. K. Hamanoue, Rev. Phys. Chem. Japan, 38, 120 (1968). 561. G. W. Hastings, J. Chem. Soc. D, 1039, (1969). 562. K. Horie, I. Mita, H. Kambe, J. Polym. Sci. A-I, 7, 2561 (1969). 563. A. S. Kabankin, S. A. Balabanova, A. M. Markevich, Vysokomol. Soedin. A, 12, 267 (1970). 564. D. A. Kangas, R. R. Pelletier, J. Polym. Sci. A-I, 8, 3543 (1970). 565. R. G. Karzhaubaeva, G. M. L'dokova, G. P. Gladyshev, S. R. Rafikov, Tr. Inst. Khim. Nauk Akad. Nauk Kaz. SSR, 28, 115(1970). 566. M. Kinoshita, T. Me, M. Imoto, Kogyo Kagaku Zasshi, 72, 1210 (1969). 567. K. Kitanaka, Y. Tabata, Kobunshi Kagaku, 28, 206 (1971). 568. N. G. Kulkami, N. Krishnamurti, P. C. Chatterjee, M. A. Sivasamban, Makromol. Chem., 139, 165 (1970). 569. S. Machida, K. Matsuo, Yukei Gosei Kagaku Kyokoi Shi, 27, 759 (1969). 570. K. Moser, R. Signer, H. U. Stuber, Chimia, 23, 393 (1969). 571. S. U. Mullik, M. A. Quddus, Pak. J. Sci., Ind. Res., 12, 186 (1970). 572. S. U. Mullik, M. A. Quddus, Pak. J. Sci., Ind. Res., 12, 181 (1970). 573. N. S. Nametkin, I. N. Kozhukhova, S. G. Durgar'yan, V. G. Filippova, Vysokomol. Soedin. A, 11, 2523 (1969). 574. K. Noma, M. Niwa, Kobunshi Kagaku, 29, 52 (1972). 575. K. Noma, M. Niwa, H. Norisada, Doshisha Daigaku Rikogaku Kenkyu Hokoku, 10, 349 (1970). 576. C. U. Pittman, N. C. Lai, D. P. Vanderpool, Macromolecules, 3, 105 (1970). 577. G. P. Popova, T. R. Kirpichenko, K. L. Glazomitskii, B. E. Glo'tsin, E. S. Roskin, E. N. Rostovskii, Izv. Vyssh. Ucheb. Zaved., Khim. Khim. Tekhnol., 13, 259 (1970). 578. M. Ratzsch, L. Stephan, Plaste Kautschuk, 18, 572 (1971). 579. E. A. Rassolova, M. A. Zharkova, G. I. Kudryavtsev, V. S. Klimenkov, Khim. Volokna, 50 (1969). 580. S. A. Rostovtseva, Vysokomol. Soedin. B, 12, 588 (1970). 581. A. G. Sayadyan, D. A. Simonyan, Arm. Khim. Zh., 22, 528 (1969). 582. Yu. L. Spirin, T. S. Yatsmirskaya, Vysokomol. Soedin. B, 11, 515 (1969).
583. J. K. Stille, L. D. Gotter, Macromolecules, 2, 468 (1969). 584. R. A. Tterteryan, N. V. Fomicheva, V. N. Monastyrskii, Vysokomol. Soedin. B, 13, 485 (1971). 585. Y. Yamashita, K. Ito, H. Ishii, S. Hoshino, M. Kai, Macromolecules, 1, 529 (1968). 586. K. Yokota, J. Macromol. Sci. A: Chem., 4, 65 (1970). 587. A. B. Alovitdinov, A. I. Kurbanov, A. B. Kuchkarov, Izv. Vyssh. Uchebn. Zaved., Khim. Khim. Tekhnol., 17, 1443, (1974). 588. A. B. Alovitdinov, A. I. Kurbanov, A. B. Kuchkarov, Izv. Vyssh. Uchebn. Zaved., Khim. Khim. Tekhnol., 18, 160 (1975). 589. L. Ambroz, J. Caskova, M. Jelinek, J. Majer, Chem. Prum., 26, 27 (1976). 590. A. B. Alovitdinov, Kh. U. Kochkarova, D. K. Khamdamova, A. B. Kuchkarov, Tr. Tashk. Politekh. Inst., 135, 12 (1974). 591. K. Anda, S. Iwai, Kobunshi Kagaku, 29, 212 (1972). 592. N. Cobianu, C. Boghina, B. Marculescu, C. Cincu, I. Amalinei, Rev. Roum. Chim., 19, 1251 (1974). 593. A. T. Dzhalilov, O. M. Yariev, N. N. Yadgarov, Uzb. Khim. Zh., 29, (1976). 594. G. B. Fridman, Ya. A. Levin, B. E. Ivanov, Sb. Nekot. Probl. Org. Khim., Mater. Nauch. Sess., Inst. Org. Fiz. Khim., Akad. Nauk SSSR, 89, (1972). 595. J.-I. Jin. H.-S. Byun, Y-M. Park, Taehan Hwahak Hoechi, 21, 219 (1977). 596. T. G. Kulagina, M. A. Askarov, A. S. Bank, Sin. Vysokomol. Soedin., 9, (1972). 597. A. I. Kurbanov, A. B. Kucharov, A. B. Alovitdinov, Tr. Tashk. Politekh. Inst., 90, 133 (1972). 598. Z. Laita, O. Paleta, A. Posta, E Liska, Collect. Czech. Chem. Commun., 40, 2059 (1975). 599. Sh. Nadzhimutdinov, A. S. Turnev, A. Bazarbaev, Kh. U. Usmanov, Vysokomol. Soedin. B, 15, 574 (1973). 600. A. F. Nikolaev, V. Bondarenko, L. E. Klubikova, S. A. Golenishcheva, Izv. Vyssh. Uchebn. Zaved., Khim. Khim. Tekhnol., 19, 1141 (1976). 601. T. Otsu, I. Umeda, H. Inoue, Mem. Fac. Eng., Osaka City Univ., 16, 107 (1975). 602. V. S. Romanova, M. A. Bulatov, V. V. Sinitsyn, Deposited Doc, 1975, VINITI 2407. 603. A. G. Savadyan, O. A. Dzhanikyan, V. A. Mirzoyan, Arm. Khim. Zh., 29, 708 (1976). 604. A. G. Sayadyan, O. A. Dzhanikyan, M. G. Ketikyan, Arm. Khim. Zh., 30, 433 (1977). 605. E. M. Shaikhutdinov, B. A. Zhubanov, N. Kadyrsizov, A. B. Sagyndykova, Izv. Akad. Nauk Kaz. SSR, Ser. Khim., 25, 55 (1974). 606. Kh. U. Usmanov, A. A. Yul'chibaev, A. A. Mat'yakubov, Kh. Kuzieva, S. Kazakov, Dokl. Akad. Nauk Uzb. SSR, 29, 37 (1972). 607. Kh. U. Usmanov, Kh. Kuzieva, A. A. Yul'chibaev, M. Zh. Akimdzhanova, Izv. Vyssh. Ucheb. Zaved., Khim. Khim. Tekhnol., 16, 948 (1973). 608. T. Oishi, S. Maruyama, M. Momoi, M. Fujimoto, T. Kimura, Makromol. Chem., 185, 479 (1984). 609. N. Yamashita, K. Ikezawa, S. Ayukawa, T. Toshihisa, J. Macromol. Sci. A: Chem., 21, 621 (1984).
610. E. L. Madruga, J. San Roman, M. A. Lavia, J. Polym. ScL, Poly. Chem. Ed., 22, 801 (1984). 611. Kh. Budevska, V. Sinigerski, Makromol. Chem., 185, 531 (1984). 612. G. Kaszas, T. Foldes-Berezsnich, F. Tudos, Eur. Polym. J., 20, 395 (1984). 613. H. Boudevska, O. Todorova, Makromol. Chem., 185, 353 (1984). 614. J. Tanaka, A. Yamada, J. Macromol. Sci. A: Chem., 21, 253 (1984). 615. R. A. Terteryan, S. D. Livshits, Sb. Nauch. Tr.-Vses. Nauchno-Issled. Inst. Pererab. Nefti, 41, 118 (1982). 616. V. A. Kruglova, V. V. Annenkov, I. V. Zaitseva, A. V. Kalabina, A. N. Mirskova, Vysokomol. Soedin. B, 25, 852 (1983). 617. M. Ueda, T. Kumakura, Y. Imai, C. U. Pittman, E. Wallace, J. Polym. Sci., Polym. Chem. Ed., 22, 85 (1984). 618. Y. K. Sung, S. Y. Lee, J. O. Pollimo, 7, 392 (1983). 619. J. Berger, H. Zweifel, Angew. Makromol. Chem., 115, 163 (1983). 620. R. A. Terteryan, V. S. Khrapov, Vysokomol. Soedin. A, 25, 1850 (1983). 621. J. San Roman, E. L. Madruga, M. A. Del Puerto, J. Polym. Sci., Polym. Chem. Ed., 21, 3303 (1983). 622. B. S. R. Reddy, R. Arshady, M. H. George, Macromolecules, 16, 1813 (1983). 623. G. Yuan, Huaxue Xuebao, 41, 746 (1983). 624. T. Oishi, M. Momoi, M. Fujimoto, T. Kimura, J. Macromol. Sci. A: Chem., 20, 763 (1983). 625. M. Ueda, T. Suzuki, Y Imai, C. U. Pittman, E. Wallace, J. Polym. Sci., Polym. Chem. Ed., 21, 2997 (1983). 626. A. A. Zhdanov, B. G. Zavin, O. G. Blokhina, Vysokomol. Soedin. B, 25, 582 (1983). 627. T. L. Latypov, A. A. Yul'chibaev, Kh. Yu. Kuzieva, Uzb. Khim. Zh., 62 (1983). 628. J. D. Patel, M. R. Patel, J. Polym. Sci., Polym. Chem. Ed., 21, 3027 (1983). 629. W. S. Kim, O. R. Kwan, I. K. Kang, U. R. Cho, Pollimo, 7, 242 (1983). 630. Y. Kihira, K. Moriwaki, H. Nishio, H. Yamamura, Kinki Daigaku Kogakubu Kenkyu Hokoku, 16, 1 (1982). 631. J. R Fishcer, S. Roesinger, Makromol. Chem., 184, 1247 (1983). 632. G. Kaszas, T. Foldes-Berezsnich, F. Tudos, Magy. Kern. FoIy., 89, 154 (1983). 633. C. Samyn, G. Smets, Makromol. Chem., 184, 949 (1983). 634. J. J. Uebel, F. J. Dinan, J. Polym. Sci., Polym. Chem. Ed., 21, 1773 (1983). 635. V. Konsulov, Yu. Piruleva, Vysokomol. Soedin. B, 25, 307 (1983). 636. R. N. Majumdar, S. L. Yang, H. J. Harwood, J. Polym. Sci., Polym. Chem. Ed., 21, 1717 (1983). 637. V. S. Kurganskii, V. A. Puchin, S. A. Voronov, V. S. Tokarev, Vysokomol. Soedin. A, 25, 997 (1983). 638. B. Yamada, T. Hayashi, T. Otsu, J. Macromol. Sci. A: Chem., 19, 1023 (1983).
639. J. C. Brosse, J. M. Gauthier, J. C. Lenain, Makromol. Chem., 184, 505 (1983). 640. N. Toyoda, M. Yoshida and T. Otsu, Polym. J. (Tokyo), 15, 255 (1983). 641. M. Ueda, M. Takahashi, T. Suzuki, Y. Imai, C. U. Pittman, J. Polym. Sci., Polym. Chem. Ed., 21, 1139 (1983). 642. T. Oishi, M. Momoi, M. Fujimoto, T. Kimura, J. Polym. Sci., Polym. Chem. Ed., 21, 1139 (1983). 643. K. Saric, Z. Janovic, O. Vogl, J. Macromol. Sci. A: Chem., 19, 837 (1983). 644. J. D. Patel, M. R. Patel, J. Macromol. Sci. A: Chem., 19, 801 (1983). 645. G. Galli, R. solaro, E. Chiellini, A. Ledwith, Macromolecules, 16, 497 (1983). 646. Z. Wojtczak, T. Czerniawski, B. Rozwadowska, Acta Polym., 34, 125 (1983). 647. V. A. Kruglova, N. I. Skobeeva, A. A. Antonovich, L. M. Dobrynina, A. V. Kalabina, A. N. Mirskova, Deposited Doc, SPSTL 744, Khp-D81 (1981). 648. C. I. Simionescu, B. C. Simionescu, C. Mihailescu, Acta Polym., 34, 62 (1983). 649. A. C. Constantinescu, S. Dumitriu, C. I. Simionescu, Acta Polym., 34, 60 (1983). 650. J. I. Jin, H. K. Shim, S. M. Lee, Taehan Hwahakhoe Chi, 26, 421 (1982). 651. F. Hrabak, M. Bezdek, V. Hynkova, J. Svobodova, Makromol. Chem., 183, 2675 (1982). 652. L. Lukasik, W. Kuran, J. Kiryjow, J. Polym. Sci., Polym. Lett. Ed., 21, 17 (1983). 653. J. Asakura, M. Yoshihara, H. Fujihara, Y. Matsubara, T. Maeshima, J. Macromol. Sci. A: Chem., 19, 311 (1983). 654. E. Dumitriu, S. Oprea, G. Datcu, Mater. Plast. (Bucharest), 19, 141 (1982). 655. M. Tomescu, S. E Cretu, BuI. Inst. Politeh. "Gheorghe Gheorghiu-Dej" Bucuresti, Ser. Chim.-Metal., 44, 67 (1982). 656. Kh. Budevska, S. Plachkova, O. Todorova, Makromol. Chem., 183, 2583 (1982). 657. M. Niwa, N. Higashi, K. Noma, Sci. Eng. Rev. Doshisha Univ., 23, 87 (1982). 658. T. Oishi, M. Fujimoto, T. Kimura, J. Polym. Sci., Polym. Chem. Ed., 20, 2999 (1982). 659. G. Ayrey, M. J. Humphrey, R. C. Poller, Eur. Polym. J., 18, 693 (1982). 660. M. Ueda, T. Kumakura, Y. Imai, C. U. Pittman, J. Polym. Sci., Polym. Chem. Ed., 20, 2829 (1982). 661. H. I. Park, C. K. Lee, J. H. Choi, J. I. Jin, Taehan Hwahakhoe Chi, 26, 235 (1982). 662. G. N. Babu, A. Deshpande, D. D. Deshpande, Angew. Makromol. Chem., 105, 83 (1982). 663. M. Ueda, M. Takahashi, Y. Imai, C. U. Pittman, J. Polym. Sci., Polym. Chem. Ed., 20, 2819 (1982). 664. H. Feng, X. Zhou, W. Liang, Q. Lu, R. Zhao, Gaofenzi Tongxun, 126, (1982). 665. A. Matsumoto, H. Kamigaki, M. Oiwa, J. Polym. Sci., Polym. Chem. Ed., 20, 2611 (1982). 666. H. G. Woo, S. K. Choi, Taehan Hwahakhoe, 26, 179 (1982).
667. R. N. Majumdar, C. Carlini, C. Bertucci, Makromol. Chem., 183, 2047 (1982). 668. A. G. Ismailov, S. G. Karaeva, N. Sh. Rasulov, Azerb. Khim. Zh., 66, (1982). 669. S. G. Khodzhaev, F. Z. Yusupbekova, A. A. Yul'chibaev, Sb. Nauchn. Tr.-Tashk. Gos. Univ. im V. I. Lenina, 667, 34 (1981). 670. G. Wouters, G. Smets, Makromol. Chem., 183, 1861 (1982). 671. A. V. Agasaryan, M. L. Eritsyan, A. O. Marukyan, Arm. Khim. Zh., 35, 329 (1982). 672. J. San Roman, E. L. Madruga, Eur. Polym. J., 18, 481 (1982). 673. A. Fehervari, T. Foldes-Berezsnich, F. Tudos, J. Macromol. Sci. A: Chem., 18, 337 (1982). 674. R K. Dhal, M. S. Ramakrishna, G. N. Babu, J. Polym. Sci., Polym. Chem. Ed., 20, 1581 (1982). 675. G. Meunier, P. Hemery, S. Boileau, Polymer, 23, 855 (1982). 676. M. L. Eritsyan, A. V. Agasaryan, Arm. Khim. Zh., 35, 265 (1982). 677. A. Fehervari, T. Foldes-Berezsnich, F. Tudos, Magy. Kem. FoIy., 88, 226 (1982). 678. T. Oishi, M. Fujimoto, T. Kimura, Polym. J. (Tokyo), 14, 323 (1982). 679. O. Sosanwo, J. Lokaj, F. Hrabak, Eur. Polym. J., 18, 341 (1982). 680. S. Yu Zaitsev, A. E. Batog, A. V. Bondarenko, V. V. Zaitseva, Vysokomol. Soedin. A, 24, 778 (1982). 681. H. Ito, D. C. Miller, C. G. Willson, Macromolecules, 15, 915 (1982). 682. O. I. Sorokina, M. L. Syrkina, G. A. Kiselev, Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol., 25, 227 (1982). 683. W. S. Kim, D. H. Oh, O. R. Kwon, I. K. Kang, K. H. Seo, Pollimo, 6, 113 (1982). 684. Ya. A. Levin, G. B. Fridman, V. Sh. Gurskaya, L. Kh. Gazizova, S. V. Shulyndin, B. E. Ivanov, Vysokomol. Soedin. A, 24, 601 (1982). 685. L. P. Paskal, V. G. Syromyatnikov, Ukr. Khim. Zh. (Russ. Ed.), 48, 204 (1982). 686. M. Macret, G. HiId, Polymer, 23, 81 (1982). 687. C. Hu, H. Feng, D. Jiang, Gaofenzi Tongxun, 275, (1981). 688. A. K. Askerov, A. D. Aliev, G. R. Slamanovva, A. A. Ibragimov, Mater. Sumgaitskoi Gor. Nauchno-Tekh. Konf. Probl. "Org. Khlororg. Sint", 1980, p. 45. 689. K. Qiu, Y. Sun, X. Feng, Gaofenzi Tongxun, 1981, 373. 690. S. Pitchumani, R. C. Rami, S. Rajadurai, J. Polym. Sci., Polym. Chem. Ed., 20, 277 (1982). 691. M. Orbay, R. Laible, L. Dulog, Makromol. Chem., 183, 47 (1982). 692. G. N. Babu, A. Deshpande, J. Macromol. Sci., Chem., A17, 717 (1982). 693. S. G. Bondarenko, A. F. Nikolaev, S. A. Baranova, N. I. Plyashechnik, G. A. Smirnova, S. V. Obukhova, I. V. Baidenok, E. M. Stepanov, I. N. Gluschenok, E. D. Andreeva, Vysokomol. Soedin. A, 23, 2639 (1981).
694. M. K. Abdullaeva, K. M. Muminov, M. A. Askarov, A. T. Dzhalilov, Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol., 24, 1022 (1981). 695. S. Kohjiya, H. Takeuchi, K. Kawamoto, S. Yamashita, Bull. Chem. Soc. Jpn., 54, 3245 (1981). 696. B. Plavljanic, Z. Janovic, J. Polym. Sci., Polym. Chem. Ed., 19, 1795 (1981). 697. R. Haraoubia, C. Bonnans-Plaisance, G. Levesque, Makromol. Chem., 182, 2409 (1981). 698. D. Jiang, C. Hu, G. Yuan, Sci. Sin. (Engl. Ed.), 24, 1248 (1981). 699. V. I. Gulimov, T. P. Vishnyakova, I. D. Vlasova, T. Z. Tabasaranskaya, Vysokomol. Soedin. B, 23, 633 (1981). 700. K. Arai, Y. Ogiwara, Makromol. Chem., Rapid Commun., 2, 363 (1981). 701. V. Percec, A. Natansohn, C. I. Simionescu, Polym. Bull. (Berlin), 4, 255 (1981). 702. V. Percec, A. Natansohn, C. I. Simionescu, Polym. Bull. (Berlin), 4, 247 (1981). 703. C. I. Simionescu, V. Percec, A. Natansohn, Polym. Bull., 4, 623 (1981). 704. D.-Z. Jiang, C. Hu, G.-Q. Yuan, Proc. China-U.S. Bilateral Symp. Polym. Chem. Phys., 1979, 138. Sci. Press: Peking, Peop. Rep. China. 705. G. Meunier, P. Hemery, J. P. Senet, S. Boileau, Polym. Bull. (Berlin), 4, 705 (1981). 706. G. Meunier, P. Hemery, J. P. Senet, S. Boileau, Polym. Bull. (Berlin), 4, 699 (1981). 707. B. C. Simionescu, A. Natansohn, M. Leanca, C. Ananiescu, C. L Simionescu, Polym. Bull. (Berlin), 4, 569 (1981). 708. G. N. Babu, A. Deshpande, J. Macromol. Sci. A: Chem., 16, 1299 (1981). 709. T.-C. Chiang, K.-H. Yu, Polym. Bull. (Berlin), 4, 425 (1981). 710. J. K. Fink, Makromol. Chem., 182, 2105 (1981). 711. M. Niwa, M. Kobayashi, T. Matsumoto, Kobunshi Robunshu, 38, 413 (1981). 712. M. Ueda, K. M, Y Imai, C. U. Pittman, Macromolecules, 14, 1046 (1981). 713. K. Urushido, A. Matsumoto, M. Oiwa, J. Polym. Sci., Polym. Chem. Ed., 19, 245 (1981). 714. T. Oishi, Polym. J. (Tokyo), 13, 65 (1981). 715. C. I. Simionescu, V Percec, A. Natansohn, Polym. Bull. (Berlin), 3, 551 (1980). 716. C. I. Simionescu, V. Percec, A. Natansohn, Polym. Bull. (Berlin), 3, 529 (1980). 717. K. Hayashi, M. Tachibana, Y. Tanaka, S. Okamura, J. Polym. Sci., Polym. Chem. Ed., 19, 1571 (1981). 718. J. L. De Ia Pena, J. Guzman, An. Quim. C, 76, 245 (1980). 719. C. I. Simionescu, V. Percec, A. Natansohn, Polym. Bull. (Berlin), 3, 535 (1980). 720. Kh. Budevska, S. Plachkova, Makromol. Chem., 182, 1119 (1981). 721. T. Shimidzu, M. Yoshikawa, B. Ohtani, Macromolecules, 14, 506 (1981). 722. A. K. Askerov, A. D. Aliev, G. R. Salmanova, A. A. Ibragimov, Azerb. Khim. Zh., 65, (1980).
723. M. Kamachi, R. Miwa, S. Nozakura, Polym. J. (Tokyo), 12, 899 (1980). 724. V. Konsulov, Yu. Piruleva, V. Mircheva, I. Mladenov, Dokl. bolg. Akad. Nauk, 33, 807 (1980). 725. A. I. Shepeleva, V. D. Bezuglyi, Vysokomol. Soedin. A, 23, 121 (1981). 726. K. Noma, N. Higashi, M. Kobayashi, M. Niwa, Sci. Eng. Rev. Doshisha Univ., 21, 141 (1980). 727. J. Asakura, M. Yoshihara, Y. Matsubara, T. Maeshima, J. Macromol. Sci. A: Chem., 15, 1473 (1981). 728. T. Oishi, Polym. J. (Tokyo), 12, 799 (1980). 729. T. Oishi, Polym. J. (Tokyo), 12, 719 (1980). 730. S. Oprea, E. Dumitriu, BuI. Inst. Politeh. Iasi, Sec. 2: Chim. Ing. Chim., 26, 71 (1980). 731. C. I. Simionescu, A. Natansohn, V. Percec, J. Macromol. Sci. A: Chem., 15, 659 (1981). 732. C. I. Simionescu, A. Natansohn, V. Percec, J. Macromol. Sci. A: Chem., 15, 643 (1981). 733. M. K. Shaikhova, K. M. Muminov, A. T. Dzhalilov, M. A. Askarov, Uzb. Khim. Zh., 48, (1980). 734. O. Sh. Kurmanaliev, E. M. Shaikhutdinov, Sh. S. Tul'baev, T. M. Mukhametkaliev, Vysokomol. Soedin. B, 22, 526 (1980). 735. F. Borg-Visse, F. Dawans, E. Marechal, J. Polym. Sci., Polym. Chem. Ed., 18, 2481 (1980). 736. V. Percec, A. Natansohn, V. Barboiu, B. C. Simionescu, D. Galea, Polym. Bull. (Berlin), 2, 505 (1980). 737. H. Fujihara, T. Shindo, M. Yoshihara, T. Maeshima, J. Macromol. Sci. A: Chem., 14, 1029 (1980). 738. E. Chiellini, G. Galli, R. Solaro, A. Ledwith, Conv. Ital. Sci. Macromol., {Atti}, 4th 85. Univ. Genova, 1st Chim. Ind.: Genoa, Italy. 739. H. Fujihara, M. Yoshihara, T. Maeshima, J. Macromol. Sci. A: Chem., 14, 867 (1980). 740. T. Oishi, I. Seo, T. Kimura, Technol. Rep. Yamaguchi Univ., 2, 199 (1979). 741. M. A. Askarov, E. N. Shakirova, S. Masharipov, A. S. Bank, Kh. D. Islomov, Vysokomol. Soedin. B, 22, 68 (1980). 742. Sh. S. Vezirov, S. M. Aliev, N. F. Shakhmamedova, E. S. Zeinalova, Vysokomol. Soedin. B, 22, 22 (1980). 743. V. V. Rabotnov, L. I. Batik, B. K. Basov, V. A. Lysanov, V. A. Kotov, Prom-st. Sint. Kauch., 1979, 5. 744. C, I. Simionescu, V. Percec, A. Natansohn, Polym. Bull. (Berlin), 2, 57 (1980). 745. H. Boudevska, C. Brutchkov, V. Veltchev, Eur. Polym. J., 15, 907 (1979). 746. M. K. Akkapeddi, Polymer, 20, 1215 (1979). 747. F. Hrabak, J. Lokaj, Eur. Polym. J., 15, 701 (1979). 748. Y. Bando, Y. Minoura, Eur. Polym. J., 15, 333 (1979). 749. A. Natansohn, S. Maxim, D. Feldman, Polymer, 20, 629 (1979). 750. M. Kurokawa, Y Minoura, J. Polym. Sci., Polym. Chem. Ed., 17, 3297 (1979). 751. E. L. Madruga, J. San Roman, M. A. Del Puerto, J. Macromol. Sci., Chem., 13 1105 (1979). 752. E. L. Madruga, J. San Roman, J. Guzman, J. Macromol. Sci., Chem., 13 1089 (1979).
753. H. Fujihara, K. Yamazaki, Y Matsubara, M. Yoshihara, T. Maeshima, J. Macromol. Sci., Chem., 13, 1081 (1979). 754. R Bajaj, D. C. Gupta, Eur. Polym. J., 15, 271 (1979). 755. D. Raucher, M. Levy, J. Polym. Sci., Polym. Chem. Ed., 17, 2663 (1979). 756. S. Kondo, T. Ohtsuka, K. Tsuda, J. Macromol. Sci., Chem., 13, 767 (1979). 757. J. L. Acosta, R. Sastre, J. A. Penaranda, Rev. Plast. Mod., 37, 709 (1979). 758. A. Ledwith, G. Galli, E. Chiellini, R. Solaro, Polym. Bull. (Berlin), 1, 491 (1979). 759. S. V. Shulyndin, V. A. Byl'ev, E. F. Gubanov, Kh. G. Sanatullin, E. P. Dikolenko, T. G. Valeeva, B. E. Ivanov, Vysokomol. Soedin. A, 21, 985 (1979). 760. M. Sorm, S. Nespurek, Eur. Polym. J., 14, 977 (1978). 761. H. Yuki, Y. Okamoto, Y. Shimada, K. Ohta, K. Hatada, J. Polym. Sci., Polym. Chem. Ed., 17, 1215 (1979). 762. N. N. Bazhenova, B. A. Egorov, Yu. D. Semchikov, Dokl. Akad. Nauk SSSR, 245, 621 (1979). 763. H. Ohnishi, T. Otsu, J. Macromol. Sci. A: Chem., 12, 1491 (1978). 764. T. Otsu, H. Ohnishi, J. Macromol. Sci. A: Chem., 12, 1477 (1978). 765. J. G. DuPont, C. W. Allen, Macromolecules, 12,169 (1979). 766. R. Van der Meer, A. L. German, J. Polym. Sci., Polym. Chem. Ed., 17, 571 (1979). 767. R. Sastre, J. L. Mateo, J. Acosta, Angew. Makromol. Chem., 73, 25 (1978). 768. M. Raetzsch, H. Lange, Plaste Kautsch., 26, 6 (1979). 769. M. Kamachi, D. J. Liaw, S. Nozakura, Polym. J., 10, 641 (1978). 770. C. Bonnans-Plaisance, P. F. Casals, G. Levesque, Makromol. Chem., 180, 79 (1979). 771. S. G. Bondarenko, A. F. Nikolaev, N. I. Dubkova, V. P. Kochanenkov, Vysokomol. Soedin. A, 20, 2433 (1978). 772. W. K. Busfield, F. P. Franke, R. D. Guthrie, Aust. J. Chem., 31, 2559 (1978). 773. A. I. Vorob'eva, G. V. Leplyanin, S. R. Rafikov, Vysokomol. Soedin. B, 20, 763 (1978). 774. A. P. Donya, A. M. Shur, Deposited Doc, VINITI 2672 (1972). 775. A. P. Donya, A. M. Shur, G. N. Agafanova, Z. Z. Malinina, S. I. Sokhina, Deposited Doc, VINITI 2675 (1976). 776. T. Tajima, T. Otsu, Mem. Fac Eng., Osaka City Univ., 18, 107 (1977). 777. S. Hoering, D. Kleine, J. Ulbricht, J. Prakt. Chem., 320,473 (1978). 778. M. L. Eritsyan, V. V Zolotukhin, G. I. Zolotukhina, Deposited Doc, VINITI 3792 (1976). 779. K. Hayashi, Makromol. Chem., 179, 1753 (1978). 780. E. F. Osadchaya, R. G. Karzhaubaeva, B. A. Zhubanov, E. M. Shaikhutdinov, Prikl. Teor. Khim., 6, 135 (1975). 781. J. R. Suggate, Makromol. Chem., 179, 1219 (1978). 782. Y. Yamamoto, A. Fukami, Nippon Kagaku Kaishi, 1978, 288. 783. O. Sh. Kurmanaliev, E. M. Shaikhutdinov, Sh. S. Tul'baev, Izv. Akad. Nauk Kaz. SSR, Ser. Khim., 28, 53 (1978).
784. Yu. M. Rodionov, M. G. Chauser, M. I. Cherkashin, Tezisy Dokl.-Vses. Konf. Khim. Atsetilena, 5th, 404. "Metsniereba": Tiflis, USSR (1975). 785. B. Yamada, M. Itahashi, T. Otsu, J. Macromol. Sci. A: Chem., 11, 1773 (1977). 786. T. C. Chiang, C. Graillat, J. Guillot, Q. T. Pham, J. Polym. Sci., Polym. Chem. Ed., 15, 2961 (1977). 787. H. Egawa, T. Nonaka, Kobunshi Robunshu, 35, 21 (1978). 788. E. N. Konstantinova, V. K. Smirnova, V. S. Ivanov, Vestn. Leningr. Univ., Fiz. Khim., 155, (1977). 789. A. F. Nikolaev, V. M. Bondarenko, L. M. Lopukhinskii, Deposited Doc, VINITI 3271 (1975). 790. K. Noma, S. Emi, N. Niwa, Doshisha Daigaku Rikogaku Kenkyu Hokoku, 18, 28 (1977). 791. Y. Bando, T. Dodou, Y. Minoura, J. Polym. Sci., Polym. Chem. Ed., 15, 1917 (1977). 792. M. A. Askarov, A. T. Dzhalilov, G. A. Babakhanov, Deposited Doc, VINITI 1693 (1975). 793. S. Kondo, M. Tsumadori, K. Tsuda, J. Polym. Sci., Polym. Lett. Ed., 15, 333 (1977). 794. R. Sastre, J. L. Acosta, R. Garrido, J. Fontan, Angew. Makromol. Chem., 62, 85 (1977). 795. E. Casorati, A. Martina, M. Guaita, Makromol. Chem., 178, 765 (1977). 796. M. Hartmann, U. C. Hipler, K. Huebig, Z. Chem., 16, 487 (1976). 797. S. N. Novikov, D. V. Pebalk, L. K. Vasyanina, A. N. Pravednikov, Vysokomol. Soedin. A, 18, 2333 (1976). 798. R. Roussel, M. Galin, J. C. Galin, J. Macromol. Sci. A: Chem., 10, 1479 (1976). 799. Y. Bando, Y. Minoura, J. Polym. Sci., Polym. Chem. Ed., 14, 693 (1976). 800. G. C. Corfield, H. H. Monks, L. P. Ellinger, Polymer, 16, 770 (1975). 801. S. M. Samoilov, S. D. Yankova, L. S. Sememova, V. N. Monastyrskii, Vysokomol. Soedin. A, 18, 340 (1976). 802. M. H. George, G. F. Hayes, Makromol. Chem., 177, 399 (1976). 803. T. Kelen, F. Tudos, J. Macromol. Sci. A: Chem., 9,1 (1975). 804. F. Tudos, T. Kelen, T. Foldes-Berezsnich, B. Turcsanyi, J. Macromol. Sci. A: Chem., 10, 1513 (1976). 805. T. Kelen, E Tudos, B. Turcsanyi, Polym. Bull., 2,71 (1980). 806. D. Braun, W. Czerwinski, G. Disselhoff, F. Tudos, T. Kelen, B. Turcsanyi, Angew. Makromol. Chem., 125, 161 (1984). 807. S. Hudecek, J. Otoupalova, M. Ryska, J. Svetlik, P. Cefelin, Collect. Czech. Chem. Commun., 48, 2015 (1983). 808. L. Lukasik, W. Kuran, B. Laguna, J. Gosk, J. Polym. Sci., Polym. Chem. Ed., 21, 3333 (1983). 809. G. Bajoras, R. Gedraitis, A. V. Kashkin, S. Slaucka, Vysokomol. Soedin. A, 25, 2626 (1983). 810. G. D. Jones, H. E. Doorenbos, J. Macromol. Sci. A: Chem., 21, 155 (1984). 811. Z. Rzaev, K. I. Gurbanov, S. G. Mamedova, M. M. Guseinov, G. S. Sharifov, Vysokomol. Soedin. A, 26, 736 (1984). 812. Yu. D. Semchikov, L. A. Smirnova, T. E. Knyazeva, S. A. Bulgakova, G. A. Voskoboinik, V. I. Sherstyanykh, Vysokomol. Soedin. A, 26, 704 (1984).
813. M. F. Sorokin, E. L. Gershanova, T. P. Skopina, Deposited Doc, VINITI 1642 (1983). 814. R K. Dahl, G. N. Babu, J. Polym. Sci., Polym. Chem. Ed., 22, 1817 (1984). 815. B. G. Zadontsev, V. G. Neroznik, O. I. Vasilova, T. V Novikova, S. I. Kuznetsova, Yu. S. Zaitsev, Vysokomol. Soedin. A, 26, 1591 (1984). 816. G. B. Kharas, M. H. Litt, Polym. Bull. (Berlin), 12, 65 (1984). 817. Y. Oda, T. Shintani, N. Emura, Toyo Soda Kenkyu Hokoku, 28, 71 (1984). 818. T. T. Minakova, L. V Morozova, B. A. Troflmov, Zh. Prokl. Khim. (Leningrad), 57, 1667 (1984). 819. E. A. Gonyukh, E. V. Kuznetsov, L. Kh. Khazryatova, V P. Prokop'ev, M. A. Akhmerov, Isv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol., 27, 1070 (1984). 820. Y. Kihira, H. Yamamura, Kinki Daigaku Kogakubu Kenkyu Hokoku, 17, 1 (1983). 821. M. Ueda, S. Ishibashi, T. Suzuki, T. Masuko, C. U. Pittman, J. Polym. Sci., Polym. Chem. Ed., 22, 2305 (1984). 822. M. A. Al-Issa, T. P. Davis, M. B. Huglin, I. B. Yahya, D. C. F. Yip, Eur. Polym. J., 20, 947 (1984). 823. M. Ueda, S. Shouji, T. Ogata, M. Kamachi, C. U. Pittman, Macromolecules, 17, 2800 (1984). 824. K. E O'Driscoll, L. T Kale, L. H. Rubio, R M. Reilly, J. Polym. Sci., Polym. Chem. Ed., 22, 2777 (1984). 825. S. Iwatsuki, A. Kondo, H. Harashina, Macromolecules, 17, 2473 (1984). 826. O. P. Kosharnaya, Yu. V Korshak, M. I. Shtil'man, T. M. Yarmizina, Deposited Doc, VINITI 5295 (1983). 827. W. M. Brouwer, P. Piet, A. L. German, J. Polym. Sci., Polym. Chem. Ed., 22, 2353 (1984). 828. M. Miura, F. Akutsu, M. Yamamoto, K. Naruchi, K. Nagakubo, Makromol. Chem., Rapid Commun., 5, 745 (1984). 829. Z. Wojtczak, A. Gronowski, Makromol. Chem., 186, 139 (1985). 830. C. Jin, K. Kazushige, Y Tabata, J. Macromol. Sci. A: Chem., 22, 379 (1985). 831. O. Sh. Kurmanaliev, E. M. Shaikhutdinov, K. A. Akhmetkarimov, Deposited Doc, VINITI 1114 (1984). 832. M. Niwa, T. Matsumoto, M. Kagami, K. Kajiyama, Sci. Eng. Rev. Doshisha Univ., 25, 192 (1984). 833. M. F. Sorokin, L. A. Onosova, L. G. Shode, O. F. Guseva, Izv. Vyssh. Uchebn. Zaved., Khim. Khim. Tekhnol., 28, 91 (1985). 834. G. B. Kharas, S. Ponrathnam, S. Jiarui, Y. Ozcayir, A. Blumstein, Polym. Bull. (Berlin), 13, 357 (1985). 835. C. Simionescu, B. C. Simionescu, S. loan, J. Macromol. ScL A: Chem., 22, 765 (1985). 836. N. Sh. Rasulov, L. V. Medyakova, N. Yu. Lezgiev, Z. M. Rzaev, Vysokomol. Soedin. B, 27, 247 (1985). 837. K. Ito, K. Uchida, T. Kitano, E. Yamada, T. Matsumoto, Polym. J. (Tokyo), 17, 761 (1985). 838. G. A. Cook, G. B. Butler, J. Macromol. Sci. A: Chem., 22, 1049 (1985). 839. D. Braun, D. Chaudhari, W. Czerwinski, Makromol. Chem., 186, 1435 (1985).
840. B. S. R. Reddy, R. Arshady, M. H. George, Eur. Polym. J., 21,511 (1985). 841. T. Oishi, M. Fujimoto, J. Macromol. Sci. A: Chem., 22, 1201 (1985). 842. H. Boudevska, O. Todorova, Makromol. Chem., 186, 1711 (1985). 843. J. I. Jin, H. K. Shim, Pollimo, 9, 301 (1985). 844. Y. Musha, Y. Hori, Y. Sato, M. Katayama, Nihon Daigaku Kogakubu Kiyo, Bunrui A, 26, 175 (1985). 845. K. Nagai, K. Akiyama, N. Kuramoto, Makromol. Chem., 186, 1855 (1985). 846. N. Sh. Rasulov, Sh. Z. Mekhtieva, N. Yu. Lezgiev, S. Z. Rizaeva, Z. M. Rzaev, Azerb. Khim. Zh., 60 (1985). 847. Y. Kihira, H. Yamamura, Kinki Daigaku Kogakubu Kenkyu Hokoku, 18, 1 (1984). 848. A. H. K. Yousafzai, A. R. Khan, T. Akhtar, Pak. J. Sci. Ind. Res., 28, 135 (1985). 849. P. K. Dhal, J. Macromol. Sci. A: Chem., 23, 181 (1986). 850. M. Ueda, M. Yazawa, Nippon Kagaku Kaishi, 1862 (1985). 851. V. Likhterov, V. S. Etlis, Vysokomol. Soedin. B, 27, 664 (1985). 852. C. Pichot, C. Graillat, V. Glukhikh, Makromol. Chem., Suppl., 10/11, 199 (1985). 853. A. A. Mohamed, F. H. Jebrael, M. Z. Maher, Macromolecules, 19, 32 (1986). 854. A. V. Yurkovetskii, V. L. Kofman, G. N. Bondarenko, A. M. Taber, K. L. Makovetskii, Vysokomol. Soedin. B, 27, 786 (1985). 855. M. Ueda, T. Suzuki, M. Takahashi, Z. B. Li, K. Koyama, C. U. Pittman, Macromolecules, 19, 558 (1986). 856. J. Horvath, F. Cser, G. Hardy, Magy. Kern. FoIy., 91, 529 (1985). 857. C. L. McCormick, D. L. Elliott, Macromolecules, 19, 542 (1986). 858. K. R. Cho, K. H. Kim, Han'guk Somyu Konghakhoechi, 22, 320 (1985). 859. E. E. Skorikova, T. M. Karaputadze, A. M. Ovespyan, A. I. Aksenov, Yu. E. Kirsh, Vysokomol. Soedin. B, 27, 869 (1985). 860. S. A. Chen, L. C. Tsai, Makromol. Chem., 187, 653 (1986). 861. S. Das, F. Rodriguez, Polym. Mater. Sci. Eng., 54, 32 (1986). 862. D. M. Dibona, R. F. Fibiger, E. F. Gurnee, J. E. Shuetz, J. Appl. Polym. Sci., 31, 1509 (1986). 863. M. W. Sabaa, M. G. Mikhael, A. Yassin, M. Z. Elsabee, Angew. Makromol. Chem., 139, 95 (1986). 864. G. B. Butler, J. C. Chen, Polym. Prepr. (Am. Chem. Soc, Div. Polym. Chem.), 27, 94 (1986). 865. C. Simionescu, V. Barboiu, B. C. Simionescu, V. Talmaciu, C. Sava, J. Polym. Sci., Polym. Chem. Ed., 24, 851 (1986). 866. T. J. Oh, G. Smets, J. Polym. Sci., Polym. Lett., 24, 229 (1986). 867. A. Petti, J. Neel, J. Polym. Sci., Polym. Chem. Ed., 24, 883 (1986). 868. J. M. Catala, A. Nonn, J. M. Pujol, J. Brossas, Polym. Bull. (Berlin), 15, 311 (1986).
869. F. Canadau, Z. Zekhnini, F. Heatley, Macromolecules, 19, 1895 (1986). 870. V. A. Kruglova, V. V. Annenkov, S. R. Buzilova, Vysokomol. Soedin. B, 28, 257 (1986). 871. L. I. Leonenko, S. I. Kudinova, N. N. Chernyshova, E. E. Sirotkina, Izv. Vyssh. Uchebn. Zaved., Khim. Khim. Tekhnol., 29, 92 (1986). 872. D. Braun, E. Manger, Colloid Polym. Sci., 264, 494 (1986). 873. D. Braun, G. Cei, Makromol. Chem., 187, 1699 (1986). 874. D. Braun, G. Cei, Makromol. Chem., 187, 1713 (1986). 875. U. M. Mirzaev, M. D. Inoyatov, I. F. Shadrin, Uzb. Khim. Zh., 39 (1986). 876. G. I. Dzhardimalieva, V. A. Zhorin. I. N. Ivleva, A. D. Pompgailo, N. S. Enikolopyan, Dokl. Akad. Nauk SSSR, 287, 654 (1986). 877. M. Miyamoto, Y. Sano, Y. Kimura, T. Saegusa, Makromol. Chem., 187, 1807 (1986). 878. J. Lebduska, J. Snuparek, L. Pryskyric, Chem. Prum., 36, 472 (1986). 879. J. Tanaka, A. Yamada, J. Macromol. Sci. A: Chem., 19,453 (1983). 880. K. R. Cho, K. H. Kim, H. Kyung, Han'guk Somyu Konghakhoechi, 22, 320 (1985). 881. J. Horvath, F. Cser, G. Hardy, Magy. Kern. FoIy., 91, 529 (1095). 882. V. R. Likhterov, V. S. Etlis, Vysokomol. Soedin., Ser. B, 27, 664 (1985). 883. E. E. Skorikova, T. M. Karaputadze, A. M. Ovsepyan, A. I. Aksenov, Yu. E. Kirsh, Vysokomol. Soedin., Ser. B, 27, 869 (1985). 884. M. Ueda, M. Yazawa, Nippon Kagaku Kaishi, 10, 1862 (1985). 885. A. V. Yurkovetskii, V. I. Kofman, G. N. Bondarenko, A. M. Taber, K. L. Makovetskii, Vysokomol. Soedin., Ser. B, 27, 786 (1985). 886. V. S. Aliev, Z. G. Asadov, A. Yu. Yusubov, A. D. Agazade, D. I. Allakhverdiev, A. I. Gasanov, Ch. K. Salmanova, Azerb. Khim. Zh., 2, 55 (1986). 887. B. M. Beshimov, O. M. Yariev, A. T. Dzhalilov, Uzb. Khim. Zh., 5, 38 (1986). 888. D. Bruan, G. Sei, Makromol. Chem., 187, 1713 (1986). 889. G. B. Butler, J. C. Chen, Polym. Propr., (Am. Chem. Soc, Div. Polym. Chem.), 27, 94 (1986). 890. J. M. Catala, A. Nonn, J. M. Pujol, J. Brossas, Polym. Bull. (Berlin), 15, 311 (1986). 891. K. H. Chung, J. K. Park, Nonmumjip-Sanop Kwahak Kisul Yoneuso, 14, 391 (1986). 892. S. Das, F. Rodriguez, Polym. Mater. Sci. Eng., 54, 32 (1986). 893. P. K. Dhal, J. Macromol. Sci. A: Chem., 23, 181 (1986). 894. D. M. Dibona, R. F. Fibiger, E. F. Gurnee, J. E. Shuetz, J. Appl. Polym. Sci., 31, 1509 (1986). 895. G. I. Dzhardimalieva, V A. Zhorin, I. N. Ivleva, A. D. Pomogailo, N. S. Enikolopyan, Dokl. Akad. Nauk SSSR, 287, 654 (1986). 896. E. E. Ergozhin, N. I. Chugunova, B. R. Tausarova, Z. S. Birimzhanova, Izv. Akad. Nauk Kaz. SSR, Ser. Khim., 6,58 (1986).
897. S. A. Gridchin, M. B. Lachinov, A. V. Kisin, G. V. Shatalov, V. R Zubov, Vysokomol. Soedin., Ser. A, 28, 2191 (1986). 898. A. G. Gzyryan, R. V. Egoyan, O. S. Attaryan, V. A. Danielyan, E. G. Darbinyan, Arm. Khim. Zh., 39, 369 (1986). 899. K. Ito, K. Kodaira, Polym. J. (Tokyo), 18, 667 (1986). 900. A. P. Kiseleva, V. T. Kolesnikov, B. I. Budzan, Vestn. L'vov. Politekh. Inst., 201, 54 (1986). 901. K. Kodaira, K. Ito, Nagoya Kogyo Gijutsu Shikensho Hokoku, 35, 291 (1986). 902. V. A. Kruglova, V. V. Annenkov, S. R. Buzilova, Vysokomol. Soedin., Ser. B, 28, 257 (1986). 903. J. Lebduska, J. Snuparek, K. Kaspar, Chem. Prum., 36, 472 (1986). 904. L. I. Leonenko, S. I. Kudinova, N. N. Chernyshova, E. E. Sirotkina, Izv. Vyssh. Uchebn. Zaved., Khim. Khim. Tekhnol., 29, 92 (1986). 905. E. L. Madruga, J. San Roman, M. A. Lavia, J. Polym. Sci., Polym. Chem. Ed., 24, 1379 (1986). 906. S. G. Mamedova, K. I. Gurbanov, Z. M. Rzaev, Vysokomol. Soedin., Ser. A, 28, 758 (1986). 907. U. M. Mirzaev, M. D. Inoyatov, I. F. Shadrin, Uzb. Khim. Zh., 1, 39 (1986). 908. M. Miyamoto, Y. Sano, Y. Kimura, T. Saegusa, Makromol. Chem., 187, 1807 (1986). 909. M. Miyamoto, Y. Sano, T. Saegusa, Makromol. Chem., 187, 2747 (1986). 910. A. A. Mohamed, F. H. Jebrael, M. Z. Elsabee, Macromolecules, 19, 32 (1986). 911. T. J. Oh, G. Smets, J. Polym. Sci., Polym. Lett., 24, 229 (1986). 912. A. Petit, J. Neel, J. Polym. Sci., Polym. Chem., 24, 883 (1986). 913. Z. M. Rzaev, S. G. Mamedova, N. Sh. Rasulov, U. Kh. Agaev, Azerb. Khim. Zh., 3, 58 (1986). 914. Z. I. Rzaeva, L. V. Medyakova, U. Kh. Agaev, Vysokomol. Soedin., Ser. A, 28, 1089 (1986). 915. M. W. Sabaa, M. G. Mikhael, A. A. Yassin, M. Z. Elsabee, Angew. Makromol. Chem., 139, 95 (1986). 916. B. B. Sadriddinov, M. A. Askarov, 1.1. Ismailov, Uzb. Khim. Zh., 5, 32 (1986). 917. G. Smets, C. Samyn, K. Swaelen, Makromol. Chem., 187, 2853 (1986). 918. J. Stejskal, P. Kratochvil, D. Strakova, O. Prochazka, Macromolecules, 19, 1575 (1986). 919. M. Ueda, T. Suzuki, M. Takahashi, Z. B. Li, K. Koyama, C. U. Pittman, Macromolecules, 19, 558 (1986). 920. M. Ueda, M. Yazawa, T. Suzuki, C. U. Pittman, J. Polym. Sci., Polym. Chem., 24, 3177 (1986). 921. A. Akmalov, A. B. Alovitdinov, Zh. M. Niyazova, Uzb. Khim. Zh., 1, 33 (1987). 922. S. M. A. Borban, I. V. Zadneprovskaya, T. M. Babaev, U. N. Musaev, Vysokomol. Soedin., Ser. A, 29, 39 (1987). 923. A. S. Brown, K. Fujimori, Makromol. Chem., 188, 2177 (1987). 924. K. Budevska, K. Brachkov, O. Todorova, D. Braun, W. K. Czerwinski, Makromol. Chem., 188, 1157 (1987).
925. R N. Gaponik, O. A. Ivashkevich, T. B. Kovaleva, T. N. Andreeva, J. Appl. Polym. Sci., 33, 769 (1987). 926. S. Iwatsuki, M. Yamaxaki, Kenkyu Hokoku-Asahi Garasu Kogyo Gijutsu Shoreikai, 51, 113 (1987). 927. A. Karpatyova, J. Barton, O. Paleta, Makromol. Chem., Rapid Commun., 8, 621 (1987). 928. V. Konsulov, D. Kirova, Z. Grozeva, N. Kirov, Khim. Ind. (Sofia), 59, 216 (1987). 929. D. J. Lin, A. Petit, J. Neel, Makromol. Chim., 188, 1163 (1987). 930. S. Masuda, M. Tanaka, T. Ota, Makromol. Chem., 188, 371 (1987). 931. S. Masuda, M. Tanaka, T. Ota, Polymer, 28, 1945 (1987). 932. L. J. Mathias, S. H. Kusefoglu, A. O. Kress, Macromolecules, 20, 2326 (1987). 933. K. Naruchi, F. Akutsu, M. Miura, Makromol. Chem., Rapid Commun., 8, 281 (1987). 934. M. Patel, J. S. Parmar, M. R. Patel, M. M. Patel, J. Macromol. Sci.-Chem., 24, 1085 (1987). 935. U. Kredel, G. Luft, Angew. Makromol. Chem., 185/186,16 (1991). 936. K. A. Rasheed, A. H. K. Yousufzai, T. Akhtar, Pak. J. Sci. Ind. Res., 30, 230 (1987). 937. Z. M. Rzaev, M. R. Bairamov, S. M. Aliev, S. G. Mamedova, M. D. Ibragimova, R. V. Dzhafarov, S. G. Aliev, Vysokomol. Soedin., Ser. B, 29, 89 (1987). 938. J. San Roman, M. Lopez, E. Madruga, L. Pargada, Polymer, 28, 315 (1987). 939. D. N. Shulz, K. Kitano, J. A. Danik, J. J. Kaladas, Polym. Mater. Sci. Eng., 57, 149 (1987). 940. A. F. Shaaban, M. M. Arief, A. A. Mahmoud, N. N. Messiha, Acta Polym., 38, 492 (1987). 941. A. F. Shaaban, M. M. Arief, A. A. Mahmoud, N. N. Messiha, Polymer, 28, 1423 (1987). 942. Y Tezuka, Y Horie, K. Imai, Polymer, 28, 1025 (1987). 943. S. V. Zlev, L. Ya. Tsarik, G. V. Ratovskii, N. A. Ivanova, D. D. Chuvashev, Vysokomol. Soedin., Ser. A, 29, 2026 (1987). 944. K. Aoki, S. Urano, H. Umemoto, R. Mizuguchi, Polym. Prepr. (Am. Chem. Soc, Div. Polym. Chem.), 29, 423 (1988). 945. J. R. Dharia, C. R Pthak, G. N. Babu, S. K. Gupta, J. Polym. Sci., Part A.: Polym. Chem., 26, 595 (1988). 946. Y Ikeda, Y Takeda, Y. Yasuaki, Mem. Konan Univ., Sci. Ser., 35, 17 (1988). 947. G. B. Kharas, J. Appl. Polym. Sci., 35, 733 (1988). 948. O. Sh. Kurmanaliev, L. M. Sugralina, E. M. Shaikhutdinov, A. V. Omasheva, Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol., 31 98 (1988). 949. S. G. Mamedova, G. A. Yusifov, Z. M. Rzaev, F. B. Rustamov, Vysokomol. Soedin., Ser. A, 30, 316 (1988). 950. T. Oishi, N. Okamoto, M. Fujimoto, J. Macromol. Sci. A: Chem., 25, 1039 (1988). 951. T. Otsu, K. Endo, M. Tanaka, Mem. Fac. Eng., Osaka City Univ., 29, 151 (1988). 952. A. Petit, M. T. Cung, J. Neel, J. Chim. Phys. Phys.-Chim., Biol., 85, 319 (1988). 953. K. T. Potts, D. A. Usifer, Macromolecules, 21,1985 (1988).
954. Z. M. Rzaev, S. G. Mamedova, G. A. Yusifov, F. B. Rustamov, J. Polym. Sri., part A: Polym. Chem., 26, 849 (1988). 955. A. I. Skushnikova, E. S. Domnina, A. I. Pavlova, I. M. Korotaeva, Vysokomol. Soedin., Ser. B, 30, 537 (1988). 956. K. Takeda, M. Akiyama, T. Yamamizu, Kobunshi Ronbunshu, 45, 485 (1988). 957. D. Tulyaganova, F. Kh. Khadzhaeva, D. D. H'yasova, Uzb. Khim. Zh., 3, 28 (1988). 958. M. Ueda, M. Mano, M. Yazawa, J. Polym. ScL, Part A: Polym. Chem., 26, 2295 (1988). 959. K. Urushido, M. Yokoyama, Y. Shiratori, A. Matsumoto, Kobunshi Ronbunshu, 45, 435 (1988). 960. O. M. Yariev, B. M. Beshimov, A. T. Dzhalilov, B. A. Mavlonov, Izv. Vyssh. Uchebn. Zaved., Khim. Khim. Tekhnol., 31, 93 (1988). 961. H. You, D. A. Tirrell, Polym. Prepr. (Am. Chem. Soc, Div. Polym. Chem.), 29, 330 (1988). 962. Y-L. Zheng, M. Galin, J. C. Galin, Polymer, 29,724 (1988). 963. B. A. Zhubanov, O. V. Grinina, N. P. Lyubchenko, Izv. Akad. Nauk Kaz. SSR, Ser. Khim., 1, 48 (1988). 964. A. S. Brar, E. Arunan, G. S. Kapur, Polym. J. (Tokyo), 21, 689 (1989). 965. J. Brown, P. Goddard, K. Petrak, J. Polym. ScL, Part C: Polym. Lett., 27, 515 (1989). 966. D. Braun, E. Manger, Colloid Polym. ScL, 264, 494 (1989). 967. D. Braun, A. E. Pour, W. K. Czerwinski, Colloid Polym. ScL, 267, 1096 (1989). 968. Y Ding, D. Qi, Beijing Daxue Xuebao, Ziran Kexueban, 25, 648 (1989). 969. O. Sh. Kurmanaliev, N. U. Aliev, M. Zh. Burkeev, E. M. Shaikhutdinov, Izv. Akad. Nauk Kaz. SSR, Ser. Khim., 5,75 (1989). 970. K. Nagai, K. Asada, K. Chiba, N. Kuramoto, J. Polym. ScL, Part A: Polym. Chem., 27, 3779 (1989). 971. C. P. R. Nair, G. Clouet, Eur. Polym. J., 25, 251 (1989). 972. V. V. Nikolaenko, A. V. Nekrasov, V. V. Smolyaninov, G. A. Bodun, Vysokomol. Soedin., Ser. A, 31, 780 (1989). 973. T. Oishi, M. Moriwaki, M. Momoi, M. Fujimoto, J. Macronol. Sci. A: Chem, 26, 861 (1989). 974. T. Oishi, K. Saeki, M. Fujimoto, J. Polym. Sci., Part A: Polym. Chem., 27, 1429 (1989). 975. T. Oishi, M. Fujimoto, J. Macromol. Sci. A: Chem., 26, 1611 (1989). 976. S. Packirisamy, A. Hirao, S. Nakahama, J. Polym. ScL, Part A: Polym. Chem., 27, 2811 (1989). 977. V. L. Rao, G. N. Babu, Eur. Polym. J., 25, 605 (1989). 978. T. Sato, K. Morina, H. Tanaka, T. Ota, Eur. Polym. J., 25, 1281 (1989). 979. A. F. Shaaban, A. A. Khalil, N. N. Messiha, J. Appl. Polym. Sci., 37, 2051 (1989). 980. Yu. E. Shapiro, N. A. Budanov, Z. V. Orlova, S. I. Kuchanov, Vysokomol. Soedin., Ser. B, 31, 123 (1989). 981. M. Ueda, K. Kawaguchi, M. Mano, J. Polym. Sci., Part A: Polym. Chem., 27, 737 (1989). 982. M. Ueda, T. Koyama, M. Mano, M. Yazawa, J. Polym. ScL, Part A: Polym. Chem., 27, 751 (1989).
983. F. D. Agaev, Ch. A. Chalbiev, Vysokomol. Soedin., Ser. B, 32, 725 (1990). 984. M. Akashi, E. Yashima, T. Yamashita, N. Miyauchi, S. Sugita, K. Marumo, J. Polym. Sci., Part A: Polym. Chem., 28, 3487 (1990). 985. S. S. S. Al-Diab, H. K. Suh, J. E. Mark, H. Zimmer, J. Polym. Sci., Part A: Polym. Chem., 28, 299 (1990). 986. F. Catalina, C. Peinado, E. L. Madruga, R. Sastre, J. L. Mateo, N. S. Allen, J. Polym. Sci., Part A: Polym. Chem., 28, 967 (1990). 987. H. Chen, Y. Wu, Z. Jin, J. Appl. Polym. Sci., 41,427 (1990). 988. C. Deng, Y Qi, Shiyou Huagong, 19, 739 (1990). 989. A. P. Donya, O. I. Kachurin, Yu. B. Vysotskii, V. M. Murav'eva, Vysokomol. Soedin., Ser. A, 32, 1309 (1990). 990. Z. Florjanczyk, W. Krawiec, K. Such, J. Polym. Sci., Part A: Polym. Chem., 28, 795 (1990). 991. L. Janus, H. Tbal, M. Delporte, J. Morcellet, M. Morcellet, Polym. Bull. (Berlin), 23, 13 (1990). 992. A. Matsumoto, T. Kubota, T. Otsu, Macromolecules, 23, 4508 (1990). 993. K. Nagai, K. Asada, N. Kuramoto, J. Polym. Sci., Part A: Polym. Chem., b, 2845 (1990). 994. T. Oishi, M. Iwahara, M. Fujimoto, J. Macromol. Sci. A: Chem., 27, 843 (1990). 995. T. Otsu, A. Matsumoto, H. Ito, Chem. Express, b, 901 (1990). 996. D. R. Patil, D. J. Smith, J. Polym. Sci., Part A: Polym. Chem., 28, 949 (1990). 997. A. Petit, J. Neel, J. Appl. Polym. ScL, 41, 267 (1990). 998. Y. Shigetomi, T. Kojima, N. Ono, J. Polym. Sci., Part A: Polym. Chem., 28, 3317 (1990). 999. S. Soundararaan, B. S. Reddy, S. Rajadurai, Polymer, 31, 366 (1990). 1000. D. L. Trumbo, Polym. Bull. (Berlin), 24, 215 (1990). 1001. R. Truxa, Makromol. Chem., 191, 1941 (1990). 1002. M. Ueda, H. Mori, H. Ito, J. polym. ScL, Part A: Polym. Chem., 28, 2597 (1990). 1003. K. Urushido, K. Koike, K. M. Hiroharu, S. Kuribayashi, Kobunshi Ronbunshu, 47, 79 (1990). 1004. H. You, D. A. Tirrell, J. Polym. Sci., Part A: Polym. Chem., 28, 3155 (1990). 1005. S. Z. Zhakupova, R. G. Karzhaubaeva, E. E. Ergozhin, Sh. M. Nurymbetova, Dokl. Akad. Nauk SSSR, 314, 885 (1990). 1006. E. E. Ergozhin, B. R. Tausarova, S. A. Shitybaev, Dokl. Akad. Nauk SSSR, 321, 108 (1991). 1007. L. F. Gorbas, P. P. Kisilita, Plast. Massy, 2, 55 (1991). 1008. K. Itoh, T. Harada, H. Nagashima, Bull. Chem. Soc. Jpn., 64, 3746 (1991). 1009. Z. Sedlakova, K. Bouchal, M. Ilavsky, Angew. Makromol. Chem., 201, 33 (1992). 1010. A. F. Miles, J. M. G. Cowie, Eur. Polym. J., b, 165 (1991). 1011. J. Muthiah, L. J. Mathias, J. Polym. Sci., Part A:, b, 29 (1991). 1012. T. Narasimhaswamy, S. C. Sumathi, B. S. R. Reddy, Eur. Polym. J., 27, 255 (1991).
1013. T. Narasimhaswamy, S. C. Sumathi, B. S. R. Reddy, J. Macromol. Sci. A: Chem., 28, 517 (1991). 1014. T. Sato, K. Takahashi, H. Tanaka, T. Ota, Macromolecules, 24, 2330 (1991). 1015. T. Sato, D. Ito, M. Kuki, H. Tanaka, T. Ota, Macromolecules, 24, 2963 (1991). 1016. R. V. Sharipov, E. E. Ergozhin, L. N. Prodius, K. Kh. Tastanov, Izv. Akad. Nauk Kaz. SSR, Ser. Khim., 2, 46 (1991). 1017. S. Soundarrarajan, B. S. R. Reddy, J. Appl. Polym. Sci., 43, 251 (1991). 1018. K. Su, E. E. Remsen, H. M. Thompson, L. G. Sneddon, Macromolecules, 24, 3760 (1991). 1019. P. S. Chung, C. K. Lee, Pollimo, 15, 749 (1991). 1020. D. I. Trumbo, J. Polym. Sci., Part A: Polym. Chem., 29, 357 (1991). 1021. J. Z. Yang, T. Otsu, Chem. Express, 6, 41 (1991). 1022. V. E. Baikov, E. F. Panarin, S. L. Timofeevskii, Vysokomol. Soedin., Ser. B, 34, 3 (1992). 1023. A. S. Brar, Eur. Polym. J., 28, 803 (1992). 1024. A. S. Brar, J. Polym. Sci., Part A: Polym. Chem., 30, 2549 (1992). 1025. B. Charleux, C. Pichot, M. F. Llauro, Makromol. Chem., 193, 187 (1992). 1026. H. Cheng, G. Zhao, D. Yan, J. Polym. Sci., Part A: Polym. Chem., 30, 2181 (1992). 1027. M. C. Fernandez-Monreal, R. Cuervo, E. L. Madruga, J. Polym. Sci., Part A: Polym. Chem., 30, 2313 (1992). 1028. M. Georgieva, T. Arabadzhieva, Dokl. Blug. Akad. Nauk, 45, 81 (1992). 1029. S. Janietz, M. Hahn, W. Jaeger, Acta Polym., 43, 230 (1992). 1030. Z. Janovi, T. T. Matusinovitch, J. Macromol. Sci. A: Pure Appl. Chem., 29, 801 (1992). 1031. S. Kobayashi, J. Kadokawa, Y. Matsumura, I. F. Yen, H. Uyama, Macromol. Rep. A, 29, (Suppl. 3), 243 (1992). 1032. L. K. Kostanski, A. E. Hamielec, Polymer, 33, 3706 (1992). 1033. S. Masuda, J. Macromol. Sci. A: Pure Appl. Chem., 29, 821 (1992). 1034. K. Nagai, K. Okada, J. Kido, J. Polym. Sci., Part A: Polym. Chem., 30, 1187 (1992). 1035. Y. Lu, J. Wu, S. Lin, Gaofenzi Xuebao, 1, 112 (1992). 1036. Y. Nagasaki, S. B. Han, M. Kato, T. Tsuruta, Makromol. Chem., 193, 1633 (1992). 1037. Z. S. Nurkeeva, G. G. Khazrenova, G. A. Mun, Vysokomol. Soedin. Ser. B, 34, 34 (1992). 1038. T. Otsu, A. Matsumoto, K. Shiraishi, N. Amaya, Y. Koiunuma, J. Polym. Sci., Part A: Polym. Chem., 30, 1559 (1992). 1039. T. Otsu, A. Matsumoto, K. Nakamura, J. Appl. Polym. Sci., 45, 1889 (1992). 1040. T. Otsu, M. Yoshioka, Makromol. Chem., 193, 2283 (1992). 1041. Z. Sedlakova, K. Bouchal, M. Ilavsky, Angew. Makromol. Chem., 201, 33 (1992). 1042. K. V. C. Rao, S. K. Nema, V. N. G. Kumar, S. Mathew, Angew. Makromol. Chem., 152, 21 (1987).
1043. K. Takenaka, A. Hirao, S. Nakahama, Makromol. Chem., 193, 1943 (1992). 1044. S. Wen, X. Yin, W. T. K. Stevenson, Polym. Int., 27, 81 (1992). 1045. Y. Shigetomi, N. Ono, H. Kato, M. Oki, Polym. J. (Tokyo), 24, 87 (1992). 1046. G. A. Valieva, A. S. Maksumova, I. I. Ismailov, M. A. Askarov, Izv. Vyssh. Uchebn. Zaved., Khim. Khim. Tekhnol., 35, 109 (1992). 1047. B. Yamada, M. Satake, T. Otsu, J. Macromol. Sci. A: Pure Appl. Chem., 29, 533 (1992). 1048. B. Yamada, M. Satake, T. Otsu, Polym. J. (Tokyo), 24, 563 (1992). 1049. M. Yoshioka, A. Matsumoto, T. Otsu, Macromolecules, 25, 2837 (1992). 1050. D. Zaldivar, C. Peniche, A. Bulay, J. San Romano, Polymer, 33, 4625 (1992). 1051. A. Gallardo, J. San Roman, Polymer, 34, 567 (1993). 1052. V. F. Gromov, Yu. S. Bogachev, E. V. Bune, I. L. Zhuravleva, E. N. Teleshov, Vysokomol. Soedin., Ser. A, 35, 7 (1993). 1053. F. Heatley, R A. Lovell, J. McDonald, Eur. Polym. J., 29, 255 (1993). 1054. T. Oishi, H. Tsotomu, S. Haruyuki, Polym. J. (Tokyo), 25, 781 (1993). 1055. T. Oishi, K. Kagawa, M. Fujimoto, Polymer, 34, 2644 (1993). 1056. T. Otsu, K. Shiraishi, A. Matsumoto, J. Polym. Sci., Part A: Polym. Chem., 31, 2523 (1993). 1057. C. K. Park, C. S. Ha, J. K. Lee, J. Won, J. Appl. Polym. Sci., 50, 1239 (1993). 1058. A. Petit, Eur. Polym. J., 29, 1419 (1993). 1059. T. Sato, M. Ikazaki, M. Seno, H. Tanaka, Makromol. Chem., 194, 637 (1993). 1060. T. Sato, S. Kawasaki, M. Seno, H. Tanaka, K. Kato, Makromol. Chem., 194, 2247 (1993). 1061. S. Soundrarajan, B. S. R. Reddy, Polymer, 34, 2224 (1993). 1062. D. L. Trumbo, Polym. Bull. (Berlin), 31, 629 (1993). 1063. D. Zaldivar, C. Peniche, A. Bulay, J. San Roman, Polym. Sci., Part A: Polym. Chem., 31, 625 (1993). 1064. R. A. Akhmed'yanova, A. G. Liakumovich, S. V. Shulyndin, P. A. Kirpichnikov, G. B. Kamardin, S. V. Mokeeva, Zh. Prikl. Khim. (S.-Peterburg), 67, 514 (1994). 1065. P. Bajaj, M. Goyal, R. B. Chavan, J. Appl. Polym. Sci., 53, 1771 (1994). 1066. A. I. Barabanova, V. F. Gromov, E. V. Bune, Yu. S. Bogachev, N. V. Kozlova, E. N. Teleshov, Vysokomol. Soedin., Ser. A. Ser. B, 36, 901 (1994). 1067. A. S. Brar, S. Charan, J. Appl. Polym. Sci., 53,1813 (1994). 1068. W. -J. Cho, C. -H. Choi, C. -S. Ha, Polym. Sci., Part A: Polym. Chem., 32, 2301 (1994). 1069. P. Durand, A. Margaillan, M. Camail, J. L. Vernet, Polymer, 35, 4392 (1994). 1070. E. K. Fedorov, O. E. Labanov, L. F. Mosalova, V. I. Svergun, S. A. Kedik, Yu. E. Kirsh, Vysokomol. Soedin., Ser. A Ser. B, 36, 1446 (1994). 1071. G. S. Georgiev, I. G. Dakova, Eur. Polym. J., 30, 1417 (1994).
1072. G. S. Georgiev, I. G. Dakova, Macromol. Chem. Phys., 195, 1695 (1994). 1073. E. L. Madruga, M. Fernandez-Garcia, Polymer, 35, 4437 (1994). 1074. A. Miller, Eur. Polym. J., 30, 185 (1994). 1075. U. Rehn, W. Frank, M. Arnold, Plaste Kautsch., 41, 69 (1994). 1076. F. Sanda, T. Takata, T. Endo, Macromolecules, 27, 3982 (1994). 1077. T. Sato, S. Shimooka, M. Seno, H. Tanaka, Macromol. Chem. Phys., 195, 833 (1994). 1078. H. Tanaka, M. Sakaguchi, Y. Kikukawa, T. Sato, Macromol. Chem. Phys., 195, 2083 (1994). 1079. Y. Y Tan, G. O. R. A. van Ekenstein, Eur. Polym. J., 30, 1363 (1994). 1080. G. Bauduin, B. Boutevin, M. Belbachir, R. Meghabar, Macromolecules, 28, 1750 (1995). 1081. M. Camail, H. Essaoudi, A. Margaillan, J. L. Vernet, Eur. Polym. J., 31, 1119(1995). 1082. Y Chen, Z. Han, P. Wu, Qingdao Daxue Xuebao Ziran Kexueban, 8, 86 (1995). 1083. K. Chino, T. Takata, T. Endo, Macromolecules, 28, 5947 (1995). 1084. W. K. Czerwinski, Macromolecules, 28, 5411 (1995). 1085. T. Endo, T. Koizumi, T. Takata, K. Chino, Polym. ScL, Part A: Polym. Chem., 33, 707 (1995). 1086. R. Francis, A. Ajayaghosh, Polymer, 36, 1091 (1995). 1087. G. S. Georgiev, I. G. Dakova, S. J. Simpson, Macromol. Sci. A: Pure Appl. Chem., 32, 497 (1995). 1088. J. Jang, H. Kim, J. Appl. Polym. Sci., 56, 1495 (1995).
1089. K. Kagawa, T. Oishi, K. Matsusaki, M. Fujimoto, Polymer, 36, 941 (1995). 1090. M. Kanamaru, T. Takata, T. Endo, Polym. Sci., Part A: Polym. Chem., 33, 1361 (1995). 1091. S. Kobatake, B. Tamada, S. Aoki, Polymer, 36, 413 (1995). 1092. S. Kobatake, B. Yamada, Macromolecules, 28,4047 (1995). 1093. G. K. Kostov, Al. T. Nikolov, J. Appl. Polym. Sci., 55,1529 (1995). 1094. G. K. Kostov, Al. T. Nikolov, J. Appl. Polym. Sci., 55,1545 (1995). 1095. M. Kumagai, K. Tsuchida, Y Ogino, J. Hansen, H. Ishida, Polymer, 36, 535 (1995). 1096. B. Levenfeld, J. San Roman, Macromolecules, 28, 3650 (1995). 1097. D. L. Murray, H. J. Harwood, M. M. Samy, I. Piirma, Polymer, 36, 3841 (1995). 1098. H. Nakamura, M. Seno, H. Tanaka, T. Sato, Colloid Polym. Sci., 273, 122 (1995). 1099. T. Oishi, K. Kagawa, M. Fujimoto, Polym. Sci., Part A: Polym. Chem., 33, 1341 (1995). 1100. T. Oishi, K. Sase, K. Saeki, S. Yao, K. Ohdan, Polymer, 36, 3935 (1995). 1101. J. Penelle, S. verraver, P. Raucq, J. Marchand-Brynaert, Macromol. Chem. Phys., 196, 857 (1995). 1102. T. Sato, I. Kamiya, M. Seno, H. Tanaka, J. Macromol. Sci. A: Pure Appl. Chem., 32, 415 (1995). 1103. T. Sato, Y Hirose, M. Seno, H. Tanaka, Polym. Sci., Part A: Polym. Chem., 33, 797 (1995). 1104. D. L. Trumbo, Polym. Bull. (Berlin), 34, 27 (1995). 1105. D. L. Trumbo, Polym. Bull. (Berlin), 34, 399 (1995).
Q
a n d
e
V a l u e s
f o r
F r e e
C o p o l y m e r i z a t i o n s M o n o m e r s
a n d
o f
R a d i c a l V i n y l
T e l o g e n s
Robert Z. Greenley* Monsanto Co., 544 Oak Valley Drive, St. Louis, MO 63131, USA
A. Introduction B. Q and e Values for Free Radical Copolymerizations Table 1. Monomers Table 2. Telogens Table 3. Monomers Arranged by Q Values Table 4. Monomers Arranged by e Values C. References A.
11-309 11-310 11-310 11-314 11-314 11-317 11-319
INTRODUCTION
The Alfrey and Price Q and e equation (Al) is well known: (Al) Q and e are measures of the reactivity and polarity, respectively, of a vinyl monomer and r\ = kn/kn, a reactivity ratio. This equation may be arranged to a logarithmic form (A2) which provides a more convenient linear solution: (A2) When monomer 2 is the one to be characterized, its Q and e values may be determined from the slope (—^2) and intercept (InQ 2 ) of the equation. The first requirement for the use of Eq. (A2) is the selection of a small group of common monomers for which Q and e could be independently established. Since, by definition the Q and e scheme is based on styrene (Q=LO and e = — 0.8), the average Q and e values of these primary monomers were calculated using Eqs. (Al) and (A3) (Ref. 1). (A3) utilizing only their reactivity ratios with styrene. The six primary monomers (Group I) - acrylic acid, acrylonitrile, *Retired.
butadiene, methyl acrylate, methacrylonitrile and methyl methacrylate - were chosen because their reactivity ratios had been narrowly defined by several investigators. These primary reactivity ratios were taken from the compilation in the second edition of this Handbook. The Q and e values of a secondary group (Group II) of ten common vinyl monomers were determined using Eq. (A2), with the primary monomer group supplying the Qx and e\ values. The Q and e values were then calculated for a tertiary set (Group III) of reactivity ratios for which a set of reactivity ratios with four or more of the primary and secondary monomers was available. For all groups except Group I, recalculated reactivity ratios (see the preceding chapter) were used when available. Otherwise, reported values were included. The Q and e values developed for the three groups during the first pass through the data were subsequently used to recalculate the Q and e values for Groups II and III. Group I was not redetermined so that the styrene bias of the system could be better maintained. After four iterations, no significant changes were observed. During the iterative process, a number of reactivity ratio citations were dropped due to a lack of fit with the majority of data points. The final Q and e values for these three groups were then used to determine the Q and e values of other monomers with four or more reactivity ratio citations with at least three comonomers (Group IV), and monomers with three citations with three different comonomers (Group V). By replacing r\ in Eq. (A2) with the reciprocal of the chain transfer constant, \/Cs (3), Q and e values of telogens may also be estimated (4) from their coreactivity with vinyl monomers. The Monomer Table lists the monomer group designation, the Q and e values, and the correlation coefficient (r) for the regression. The Number column (n) represents the number of r\ values actually used in the regression. If the monomer is in Group V, the number is understood to be 3. The data are listed alphabetically as well as in increasing values of Q and e.
Recent work by Jenkins (5) has uncovered another approach to characterizing the copolymerization character of vinyl monomers. By deriving data from r\ and T2 values,
he was able to calculate three coefficients which appear to allow a more precise prediction of the actual reactivity ratios.
B. Q AND e VALUES FOR FREE RADICAL COPOLYMERIZATIONS TABLE 1. MONOMERS Monomer
Group
Q
e
n
r
5 6 5 16 5 17 6 4 5
0.98 0.75 0.63 0.97 0.98 0.64 0.91 0.93 0.56 0.68 0.99 0.87 0.38 0.99 0.90 0.92 0.94 0.91 0.65 0.87 0.81
Acenaphthalene Acetylene, phenylAconitate, trimethyl Acrolein Acrolein, methylAcrylamide Acrylamide, Af-methylolAcrylamide, Af-octadecylAcrylamide, N,iV-diethyl Acrylamide, WV-dimethyl-glucitol Acrylate, a-acetoxy-, ethyl Acrylate, a-chloro, ethyl Acrylate, a-chloro-, methyl Acrylate, a-cyano-, methyl Acrylate, oc-phenyl-, methyl Acrylate, benzyl Acrylate, butyl Acrylate, ethyl Acrylate, ferrocenylmethyl Acrylate, glycidyl Acrylate, heptafluorobutyl Acrylate, methyl Acrylate, octadecyl Acrylate, octyl Acrylate, trifluoro-, methyl Acrylate, 2-chloroethyl Acrylate, 2-ethylhexyl Acrylate, 2-nitrobutyl Acrylic acid Acrylic acid, oc-bromoAcrylic anhydride Acrylonitrile Acryloyl chloride AUyI acetate Allyl acrylate AUyI alcohol Allyl chloride Allylbenzene TV-Allylstearamide
IV IV III IV IV IV IV IV IV V V V IV IV IV IV II III IV IV V I IV V V V IV V I V V I IV III V IV III IV V
0.72 0.45 0.25 0.80 1.83 0.23 0.52 0.66 0.48 0.22 0.52 1.00 2.43 4.91 5.19 0.33 0.38 0.41 0.15 0.48 0.96 0.45 0.33 0.63 0.048 0.49 0.37 0.69 0.83 3.07 1.46 0.48 1.82 0.24 0.32 0.005 0.026 0.038 0.024
-1.88 0.10 2.27 1.31 0.71 0.54 1.15 1.64 -0.31 0.61 0.77 -1.03 0.35 0.91 0.96 1.13 0.85 0.55 0.51 1.28 1.34 0.64 1.26 2.01 1.20 1.03 0.24 1.09 0.88 1.37 0.31 1.23 1.92 -1.07 -0.99 -1.48 - 0.60 0.40 -0.41
Benzothiazole, vinylmercaptoBicyclo[2.2.1]hept-2-ene-5,6-dicarboxamine, TV-benzylButadiene Butadiene-1-carboxylate, ethyl Butadiene, 1,4-dicarboxylate, diethyl Butadiene, 2,3-dichloroButadiene, 2,3-dimethylButadiene, hexafluoroButadiene, 2-chloroButadiene, 2-fluoroButene-1 Butene-2 Carbamate, TV-vinyl-, ethyl Carbamate, TV,TV-diethyl-, vinyl Carbazole, TV-vinylCarbon monoxide
IV IV I V V V V IV II III IV IV V IV III V
0.36 0.01 1.70 1.67 1.94 9.08 1.42 0.82 10.52 1.88 0.007 0.002 0.037 0.028 0.26 0.013
- 0.44 -0.36 -0.50 1.26 1.39 0.14 -0.43 0.58 1.20 0.63 -0.06 -0.29 -1.12 -1.11 -1.29 1.68
4 4 8 5 20 12 4 4 7 5 4
0.97 0.99 0.55 0.95 0.37 0.98 0.99 0.37
6 8 5 12 4 4 6 24
4 10 6 5 6 4 12
0.90 0.85 0.96 0.98 0.93 0.60 0.62 0.95 0.47 0.82 0.99 0.99 0.93 0.58 0.93 0.98 0.77 0.08 0.44 0.91 0.95 0.99 0.70
TABLE 1. cont'd Monomer
Group
Q
e
n
r
Citraconimide, N-methylCrotonaldehyde Crotonicacid 4-Cyclopentene-l,3-dione
IV IV III IV
0.87 0.023 0.017 0.42
1.58 0.84 0.89 2.43
4 5 6 4
0.94 0.82 0.98 0.96
Diallyl melamine Diallyl phthalate Diallycyanamide AW-Divinylaniline
V IV IV II
0.059 0.031 0.14 0.26
-1.57 -0.26 2.41 -0.68
20 4 5
0.99 0.50 0.96 0.78
Ethylene Ethylene, 1,1-diphenylEthylene, chlorotrifluoroEthylene, tetrachloroEthylene, tetrafluoroEthylene, trichloro-
III IV III III IV III
0.016 0.17 0.026 0.001 0.032 0.010
0.05 -1.71 1.56 1.24 1.63 1.29
6 5 5 7 4 11
0.52 0.84 0.99 0.99 0.99 0.94
Fumarate, diethyl Fumarate, diisopropyl Fumaronitrile
IV IV IV
0.25 0.11 0.29
2.26 2.58 2.73
10 8 5
0.91 0.84 0.96
Hexatriene, tetrachloroHexene-1
IV V
1.83 0.035
0.94 0.92
6
0.98 0.69
Imidazole, 1-vinylImidazole, l-vinyl-2-methylIndene Isobutylene Isobutylene, 3-chloroIsoprene Isoprene, 3-acetoxyIsopropenyl acetate Isopropenyl methyl ketone Isopropenyl, 3-(l-cyclohexenyl), acetate Isopropenylisocyanate Itaconate, dibutyl Itaconate, diethyl Itaconate, dimethyl Itaconicacid
V IV IV III IV II V IV III V III V V III IV
0.11 0.14 0.13 0.023 0.17 1.99 1.91 0.023 1.03 0.57 0.18 0.82 1.04 0.73 0.78
-0.68 -0.98 -0.71 -1.20 -0.86 -0.55 -0.11 - 0.94 0.64 -0.66 -1.05 0.57 0.88 0.57 1.07
Maleate, diethyl Maleic anhydride Maleimide Maleimide, 2,3-dimethyl-iV-(2-methacryloxyethyl)Maleimide, 7V-(2-hydroxyethyl)Maleimide, AK2-chlorophenyl)Maleimide, A^-(4-chlorophenyl)Maleimide, Af-butylMaleimide, N-phenylMethacrylamide Methacrylamide, Af-phenylMethacrylamide, 1-deoxy-D-glucital Methacrylate, 2-chloro-2,3,3,3-tetrafluoropropyl Methacrylate, 2,2,6,6-tetra-methyl-4-piperidinyl Methacrylate, 2,3-epithio-propyl Methacrylate, benzyl Methacrylate, butyl Methacrylate, ethyl Methacrylate, ferrocenylmethyl Methacrylate, glycidyl Methacrylate, isobutyl Methacrylate, isopropyl Methacrylate, methyl Methacrylate, phenyl Methacrylate, sulfolanyl
IV IV V V V IV V V IV IV V V V IV IV IV III III IV III III IV I IV V
0.053 0.86 0.94 2.54 1.26 2.29 2.98 0.88 2.81 0.40 0.40 0.15 2.09 0.52 1.04 0.88 0.82 0.76 0.22 0.96 0.82 0.97 0.78 1.25 1.18
1.08 3.69 2.86 1.64 1.07 2.87 2.75 3.70 3.24 -0.05 0.19 -0.16 0.62 -1.09 0.29 0.35 0.28 0.17 0.65 0.20 0.27 0.10 0.40 0.79 0.95
6 8 7 4 11 4 6 8 8 5 12 25
5 4 8
4 4 10 10 7 7 9 5 4 7
0.98 0.93 0.45 0.99 0.98 0.86 0.10 0.98 0.78 0.98 0.94 0.88 0.98 0.90 0.99 0.87 0.98 0.99 0.98 0.68 0.96 0.99 0.92 0.99 0.29 0.70 0.19 0.56 0.68 0.84 0.97 0.68 0.62 0.85 0.92 0.76 0.46 0.91 0.95
References page 11-319
TABLE 1. cont'd Monomer
Group
Q
e
n
r
8 5 4
Methacrylate, 2-naphthyl Methacrylate, 2-(N,Ar-dimethyl-carbamoyloxy)ethyl Methacrylate, 2-(sulfonic acid)ethyl Methacrylate, 2-acetoxyethyl Methacrylate, 2-bromoethyl Methacrylate, 2-chloroethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxypropyl Methacrylic acid Methacrylic anhydride Methacrylonitrile Methacryloyl chloride Methacryloylacetone Methylenebutyrolactone 2-Methyleneglutaronitrile
IV IV IV V IV IV IV IV III IV I V V V IV
1.04 1.14 1.09 0.60 1.18 1.04 1.78 4.38 0.98 3.00 0.86 2.04 5.47 2.48 0.41
-0.09 0.84 0.25 0.51 0.74 0.31 -0.39 1.86 0.62 0.56 0.68 1.54 -0.76 0.83 1.25
4 7 7 7 23 5
0.46 0.74 0.52 0.80 0.96 0.79 0.67 0.81 0.73 0.93
6
0.94 0.79 0.90 0.83
Norbornadiene
III
0.051
-1.48
7
0.90
Oct-1-ene, 6,6-dimethyl-4,8-dioxaspiro(2.5)Oxazolidone, N-vinylOxazoline, 2,-2-isopropenyl-4,4-dimethylOxazoline, 2-isopropenyl-2Oxazoline, 2-,4-acryloxymethyl-2,4-dimethylOxazoline, 2-,4-methacryloxymethyl-2,4-dimethyl-
V III IV IV IV IV
0.25 0.087 0.87 0.59 0.97 0.44
0.61 -1.70 0.34 - 0.64 -0.51 - 0.70
6 4 7 4 4
0.82 0.95 0.65 0.54 0.71 0.99
Pentadiene, trans-1,3Phosphonate, a-carbomethoxyvinyl-, diethyl Phosphonate, isopropenyl-, dimethyl Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl-, diethyl Phosphonate, vinyl-, dimethyl Phosphonic acid, a-phenyl-vinylPhthalimide, iV-Cmethacryloyloxy)Propene, 3,3,3-trichloroPropene, 1-chloro-, cisPropene, 1-chloro-, transPropene, 2-chloroPropene, 2-chloro-3-hydroxyPropene, 2,3-dichloroPropenyl, 2-chloro-, acetate Propenyl, 2-methyl-, acetate Propylene Pyridazinone, 3-(2-vinyl)-6-methylPyridazinone, 3-(2-vmyl)-6-methyl-4,5-dihydroPyridine, 2-methyl-5-vinylPyridine, 2-vinylPyridine, 2-vinyl-5-ethylPyridine, 4-vinylPyrrolidone, l-benzyl-3-methylene-5-methyl-
IV V V V V V IV V V V V V V IV IV V V V V III II IV III V
1.28 0.14 0.032 0.044 0.27 0.24 0.65 1.89 0.030 0.003 0.006 0.073 0.091 0.12 0.20 0.040 0.009 0.57 0.18 1.32 1.41 1.29 2.47 1.50
-0.13 —0.04 0.96 1.64 - 0.40 - 0.25 0.52 0.96 1.00 -0.46 -0.16 -0.16 -0.95 -0.40 -0.85 - 2.08 -1.69 0.24 -0.32 -0.66 -0.42 -0.91 0.84 -0.59
Quinoline, 2-vinyl-
IV
1.04
-0.09
Silane, 7-methacryloxypropyl-trimethoxy Styrene Styrene, 2,4,6-trimethylStyrene, 2,5-dichloroStyrene, 3-tri-«-butylstannylStyrene, a-methoxyStyrene, a-methylStyrene, m-bromoStyrene, m-chloroStyrene, m-methylStyrene, m-nitroStyrene,/7-bromoStyrene,/7-chloro-
V I IV II IV IV III IV IV V IV IV III
1.08 1.00 0.15 1.50 0.014 0.39 0.97 1.25 2.46 1.57 2.66 1.30 1.33
0.07 -0.80 -0.58 0.94 -0.61 -1.02 -0.81 -0.27 - 0.90 -0.03 1.57 -0.68 -0.64
8
5
4 5 7
9 12 4 7
4
0.54 0.96 0.98 0.89 0.54 0.53 0.76 0.74 0.99 0.84 0.28 0.99 0.99 0.67 0.61 0.97 0.84 0.58 0.35 0.95 0.97 0.94 0.86 0.98 0.46 0.35
4 12 4 5 15 4 4 7 7 12
0.41 0.96 0.51 0.77 0.98 0.98 0.87 0.06 0.85 0.99 0.92
TABLE 1. cont'd Monomer
Group
Q
e
n
r
7 5 6 5
0.74 0.75 0.99 0.98 0.65 0.51 0.91 0.87 0.96
Styrene, p-chloromethylStyrene, p-cyanoStyrene, p-methoxyStyrene,/?-methylStyrene, p-\-(2-hydroxybutyl)Styrene,/7-l-(2-hydroxypropyl)Styrene,/?-2-(2-hydroxypropyl)Styrene, pentachloroSuccinimide, iV-vinyl-
IV IV III III V IV IV V III
1.39 2.93 1.53 1.10 0.70 1.08 1.15 0.20 0.19
-0.38 -0.38 -1.40 -0.63 -0.97 -0.35 -0.49 0.79 -1.42
Tetrazole, 1-vinylTetrazole, 2-methyl-5-(4/-vinyl)phenylTetrazole, 2-methyl-5-vinylTetrazole, 2-phenyl-5-(4/-vinyl)phenylTetrazole, 5-phenyl-2-(4/-vinyl)phenylToluenesulfonamide, A^methyl-vinylTriallyl citrate Triallyl cyanurate Triallyl isocyanurate
V V V V V V IV V V
0.13 0.86 0.55 0.84 1.11 0.18 0.054 0.14 0.035
-0.14 0.51 - 0.46 -0.52 0.53 -0.53 0.26 2.41 -0.23
Urea, N-vinyl-iV'-ethyl-
V
0.17
-1.88
Vinyl acetate Vinyl benzoate Vinyl bromide Vinyl butyl ether Vinyl butylsulfonate Vinyl butyrate Vinyl chloride Vinyl chloroacetate Vinyl chloromethyl ketone Vinyl cinnamate Vinyl cymantrene Vinyl dichloroacetate Vinyl dodecyl ether Vinyl ether Vinyl ethyl ether Vinyl ethyl oxalate Vinyl ethyl sulfide Vinyl ethyl sulfoxide Vinyl fluoride Vinyl formate Vinyl hendecanoate Vinyl isobutyl ether Vinyl isobutyl sulfide Vinyl isopropyl ketone Vinyl isothiocyanate Vinyl laurate Vinyl-m-cresyl ether Vinyl methyl ketone Vinyl methyl sulfide Vinyl methyl sulfoxide Vinyl -cresyl ether Vinyl octadecyl ether Vinyl octyl ether Vinyl p-cresyl ether Vinyl pelargonate Vinyl phenyl ether Vinyl phenyl ketone Vinyl phenyl sulfide Vinyl propionate Vinyl stearate Vinyl tert-butyl sulfide Vinyl thiolacetate
II III IV IV IV IV II IV IV IV IV V IV IV III IV IV IV IV III III IV IV V IV V V II IV V V IV IV V IV IV IV IV IV III IV IV
0.026 0.030 0.038 0.038 0.16 0.024 0.056 0.039 16.00 0.18 0.39 0.059 0.041 0.029 0.018 0.056 0.27 0.065 0.008 0.043 0.056 0.030 0.49 0.58 0.59 0.011 0.016 0.66 0.42 0.60 0.010 0.024 0.020 0.015 0.046 0.046 1.16 0.33 0.027 0.043 0.046 0.27
-0.88 -0.89 -0.23 -1.50 1.06 -0.89 0.16 -1.61 1.78 0.76 -0.57 -1.38 -1.69 -1.16 -1.80 - 0.65 -1.31 0.05 0.72 -1.19 -0.84 -1.27 - 0.95 -1.16 0.37 -0.54 - 6.33 1.05 -1.66 -1.79 -8.53 -1.93 -1.57 -6.86 -1.22 -2.16 1.02 -0.99 -0.68 -0.97 - 2.20 -0.52
4 4 8
4
0.39 0.49 0.85 0.97 0.53 0.78 0.50 0.17 0.35 0.98
49 9 10 10 4 8 38 5 4 4 4 6 4 8 4 6 4 8 5 5 7 7 4 8 5 4 4 4 9 5 5 7 7 4 5
0.87 0.95 0.94 0.87 0.97 0.91 0.37 0.98 0.97 0.99 0.88 0.95 0.83 0.80 0.90 0.53 0.96 0.21 0.71 0.99 0.82 0.98 0.99 0.44 0.77 0.81 0.99 0.98 0.99 0.46 0.97 0.87 0.98 0.99 0.79 0.95 0.95 0.96 0.82 0.85 0.72 0.85
References page II - 319
TABLE 1. cont'd Monomer
Group
Vinyl 4-chlorocyclohexyl ketone Vinyl 2-chloroethyl ether Vinyl-tris(trimethoxysiloxy)silane /?-Vinylbenzylethylcarbinol /?-Vinylbenzylmethylcarbinol 9-Vinylanthracene Vinyl AW-diethylcarbamate p-Vinylbenzoic acid Af-Vinylcaprolactam Vinylene carbonate Vinylferrocene Vinylhydroquinone Vinylhydroquinone dibenzoate Vinylidene chloride Vinylidene cyanide Vinylisocyanate JV-Vinylpyrrolidone Vinyltriethoxysilane Vinyltrimethylsilane
IV IV IV V V IV IV V IV III IV V IV II IV III II V V
Q 0.66 0.019 0.022 0.69 1.70 0.14 0.028 5.17 0.14 0.004 0.31 4.30 1.73 0.31 14.22 0.14 0.088 0.021 0.027
e - 0.82 -1.64 -0.12 -0.98 -1.27 0.82 -1.10 1.08 -1.18 - 0.49 -1.34 2.26 0.84 0.34 1.92 -0.95 -1.62 0.82 0.19
n
9 5 5 4 4 9 6 5 40 9 6 12
r 0.50 0.96 0.75 0.67 0.98 0.90 0.95 0.95 0.72 0.73 0.91 0.87 0.87 0.68 0.82 0.98 0.95 0.61 0.58
TABLE 2. TELOGENS Telogen
Temp. (0C)
Acetone
60 80 60 80 60 80 60 80 60 80 60 60 60 80 60 80 60 80 60 60 60 60 60 60 60 80 60 80 60 60
Benzene -, chloro-,ethyl-,methylBenzoyl peroxide Butanol Butanone Cyclohexane 1,2-Dichloroethane Ethyl acetate Mercaptan, alkylMercaptoacetate, alkylMethane, dichloro-, nitro-, tetrabromoMethane, tetrachloro-, trichloroMethanol Triethylamine
Q ( x 104) 0.11 0.32 0.05 0.07 0.07 0.13 0.95 0.91 0.16 0.34 36 0.53 0.82 1.40 0.11 0.14 0.62 1.1 0.07 14500 15100 0.10 3.26 7300 3.64 5.15 1.18 1.24 0.18 28.8
e
No.
r
0.35 0.45 -1.21 -0.61 0.08 -0.06 -1.02 -0.61 -0.95 -0.87 -1.89 -0.57 0.53 1.00 -0.64 -1.41 1.34 2.07 -0.87 2.44 3.27 -0.68 -1.50 2.90 3.21 3.41 0.47 0.70 -0.93 -2.39
5 5 16 9 7 5 8 7 12 11 4 6 4 7 6 7 3 6 11 11 4 4 4 8 13 9 8 10 5 7
0.80 0.68 0.94 0.72 0.30 0.30 0.84 0.86 0.93 0.94 0.93 0.63 0.60 0.80 0.86 0.77 0.96 0.96 0.97 0.99 0.99 0.82 0.92 0.99 0.99 0.99 0.95 0.82 0.76 0.99
TABLE 3. MONOMERS ARRANGED BY Q VALUES Monomer Ethylene, tetrachloroButene-2 Propene, 1-chloro-, cis-
Q
e
0.001 0.002 0.003
1.24 - 0.29 - 0.46
Monomer Vinylene carbonate Allyl alcohol Propene, 1-chloro-, trans-
Q
e
0.004 0.005 0.006
- 0.49 - 1.48 -0.16
TABLE 3.
cont'd
Monomer Butene-1 Vinyl fluoride Propylene Bicyclo[2.2.1]hept-2-ene5,6 dicarboxamine, N-benzylEthylene, trichloroVinyl o-cresyl ether Vinyl laurate Carbon monoxide Styrene, 3-tri-rc-butylstannylVinyl p-cresyl ether Ethylene Vinyl m-cresyl ether Crotonic acid Vinyl ethyl ether Vinyl 2-chloroethyl ether Vinyl octyl ether Vinyltriethoxysilane Vinyl-tris(trimethoxysiloxy)silane Crotonaldehyde Isobutylene Isopropenyl acetate N-Allylstearamide Vinyl butyrate Vinyl octadecyl ether AUyI chloride Ethylene, chlorotrifluoroVinyl acetate Vinyl propionate Vinyltrimethylsilane Carbamate, MN-diethyl-, vinyl Vinyl WV-diethylcarbamate Vinyl ether Propene, 3,3,3-trichloroVinyl benzoate Vinyl isobutyl ether Diallyl phthalate Ethylene, tetrafluoroPhosphonate, isopropenyl-, dimethyl Hexene-1 Triallyl isocyanurate Carbamate, AT-vinyl-, ethyl Allylbenzene Vinyl bromide Vinyl butyl ether Vinyl chloroacetate Propenyl, 2-methyl-, acetate Vinyl dodecyl ether Vinyl formate Vinyl stearate Phosphonate, vinyl-, bis(2-chloroethyl) Vinyl pelargonate Vinyl phenyl ether Vinyl tert-butyl sulfide Acrylate, trifluoro-, methyl Norbornadiene Maleate, diethyl Triallyl citrate Vinyl chloride Vinyl ethyl oxalate Vinyl hendecanoate Diallyl melamine Vinyl dichloroacetate Vinyl ethyl sulfoxide Propene, 2-chloro-
Q
e
0.007 0.008 0.009
-0.06 0.72 -1.69
0.010 0.010 0.010 0.011 0.013 0.014 0.015 0.016 0.016 0.017 0.018 0.019 0.020 0.021 0.022 0.023 0.023 0.023 0.024 0.024 0.024 0.026 0.026 0.026 0.027 0.027 0.028 0.028 0.029 0.030 0.030 0.030 0.031 0.032 0.032 0.035 0.035 0.037 0.038 0.038 0.038 0.039 0.040 0.041 0.043 0.043 0.044 0.046 0.046 0.046 0.048 0.051 0.053 0.054 0.056 0.056 0.056 0.059 0.059 0.065 0.073
- 0.36 1.29 - 8.53 - 0.54 1.68 -0.61 - 6.86 0.05 - 6.33 0.89 -1.80 -1.64 -1.57 0.82 - 0.12 0.84 -1.20 - 0.94 -0.41 - 0.89 -1.93 - 0.60 1.56 - 0.88 - 0.68 0.19 -1.11 -1.10 -1.16 1.00 - 0.89 -1.27 -0.26 1.63 0.96 0.92 - 0.23 -1.12 0.40 - 0.23 -1.50 -1.61 - 2.08 -1.69 -1.19 - 0.97 1.64 - 1.22 - 2.16 - 2.20 1.20 -1.48 1.08 - 0.26 0.16 - 0.65 - 0.84 -1.57 -1.38 0.05 -0.16
Monomer Oxazolidone, N-vinylN-Vinylpyrrolidone Propene, 2-chloro-3-hydroxyFumarate, diisopropyl Imidazole, 1-vinylPropene, 2,3-dichloroIndene Tetrazole, 1-vinylN-Vinylcaprolactam Diallylcyanamide Imidazole, l-vinyl-2-methylPhosphonate, a-carbomethoxyvinyl-diethyl Triallyl cyanurate 9-Vinylanthracene Vinylisocyanate Acrylate, ferrocenylmethyl Methacrylamide, 1-deoxy-D-glucitol Styrene, 2,4,6-trimethylVinyl butylsulfonate Ethylene, 1,1 -diphenylIsobutylene, 3-chloroUrea, TV-vinyl-TV'ethylIsopropenylisocyanate Pyridazinone, 3-(2-vinyl)-6-methyl4,5-dihydroToluenesulfonamide, iVyV-methyl-vinylVinyl cinnamate Succinimide, N-vinylPropenyl, 2-chloro-, acetate Styrene, pentachloro1-Acrylamido-1-deoxy-D-glucitol Methacrylate, ferrocenylmethyl Acrylamide AHyI acetate Phosphonate, vinyl-, dimethyl Aconitate, trimethyl Fumarate, diethyl Oct-1-ene, 6,6-dimethyl-4,8-dioxaspiro(2,5)Carbazole, N-vinylAW-Divinylaniline Phosphonate, vinyl-, diethyl Vinyl ethyl sulfide Vinyl thiolacetate Fumaronitrile Vinylferrocene Vinylidene chloride Allyl acrylate Acrylate, benzyl Acrylate, octadecyl Vinyl phenyl sulfide Benzothiazole, vinylmercaptoAcrylate, 2-ethylhexyl Acrylate, butyl Styrene, a-methoxyVinyl cymantrene Methacrylamide Methacrylamide, N-phenylAcrylamide, A^Af-dimethylAcrylate, ethyl 2-Methyleneglutaronitrile 4-Cyclopentene-l,3-dione Vinyl methyl sulfide Oxazoline, 2-,4-methacryloxymethyl2,4-dimethylAcetylene, phenyl-
Q
e
0.087 0.088 0.091 0.11 0.11 0.12 0.13 0.13 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.15 0.15 0.15 0.16 0.17 0.17 0.17 0.18 0.18
-1.70 -1.62 -0.95 2.58 -0.68 -0.40 -0.71 -0.14 -1.18 2.41 -0.98 —0.04 2.41 0.82 —0.95 0.51 —0.16 -0.58 1.06 -1.71 -0.86 -1.88 —1.05 -0.32
0.18 0.18 0.19 0.20 0.20 0.22 0.22 0.23 0.24 0.24 0.25 0.25 0.25 0.26 0.26 0.27 0.27 0.27 0.29 0.31 0.31 0.32 0.33 0.33 0.33 0.36 0.37 0.38 0.39 0.39 0.40 0.40 0.41 0.41 0.41 0.42 0.42 0.44
—0.53 0.76 -1.42 - 0.85 0.79 0.61 - 0.65 0.54 -1.07 - 0.25 2.27 2.26 0.61 -1.29 - 0.68 - 0.40 -1.31 - 0.52 2.73 -1.34 0.34 - 0.99 1.13 1.26 - 0.99 — 0.44 0.24 0.85 - 1.02 - 0.57 - 0.05 0.19 -0.26 0.55 1.25 2.43 -1.66 — 0.70
0.45
0.10
References page 11-319
TABLE 3.
cont'd
Monomer Acrylate, methyl Acrylamide, N,N-diethy\ Acrylate, glycidyl Acrylonitrile Acrylate, 2-chloroethyl Vinyl isobutyl sulfide Acrylamide, Af-methylolAcrylate, a-acetoxy-, ethyl Methacrylate, 2,2,6,6-tetramethyl4-piperidinyl Tetrazole, 2-methyl-5-vinylIsopropenyl, 3-(l-cyclohexenyl)acetate Pyridazinone, 3-(2-vinyl)-6-methylVinyl isopropyl ketone Oxazoline, 2-isopropenyl-2Vinyl isothiocyanate Methacrylate, 2-acetoxyethyl Vinyl methyl sulfoxide Acrylate, octyl Phosphonic acid, a-phenylAcrylamide, Af-octadecylVinyl methyl ketone Vinyl 4-chlorocyclohexyl ketone Acrylate, 2-nitrobutyl p-Vinylbenzylethylcarbinol Styrene, p-1 -(2-hydroxybutyl)Acenaphthalene Itaconate, dimethyl Methacrylate, ethyl Itaconic acid Methacrylate, methyl Acrolein Butadiene, hexafluoroItaconate, dibutyl Methacrylate, butyl Methacrylate, isobutyl Acrylic acid Tetrazole, 2-phenyl-5-(4'-vinyl)-phenylMaleic anhydride Methacrylonitrile Tetrazole, 2-methyl-5-(4/-vinyl)-phenylCitraconimide, TV-methylOxazoline, 2-, 2-isopropenyl-4,4-dimethylMaleimide, A^-butylMethacrylate, benzyl Maleimide Acrylate, heptafluorobutyl Methacrylate, isopropyl Oxazoline, 2-,4-acryloxymethyl-2,4-dimethylStyrene, a-methylMethacrylic acid Acrylate, a-chloro-, ethyl Styrene Isopropenyl methyl ketone Itaconate, diethyl Methacrylate, 2-naphthyl Methacrylate, 2,3-epithiopropyl Methacrylate, 2-chloroethyl Quinoline, 2-vinylSilane, y-methacryloxypropyl-trimethoxy Styrene, /?-l-(2-hydroxypropyl)Methacrylate, 2-(sulfonic acid)ethyl Styrene, p-methyl-
Q
e
0.45 0.48 0.48 0.48 0.49 0.49 0.52 0.52 0.52
0.64 - 0.31 1.28 1.23 1.03 - 0.95 1.15 0.77 -1.09
0.55 0.57 0.57 0.58 0.59 0.59 0.60 0.60 0.63 0.65 0.66 0.66 0.66 0.69 0.69 0.70 0.72 0.73 0.76 0.78 0.78 0.80 0.82 0.82 0.82 0.82 0.83 0.84 0.86 0.86 0.86 0.87 0.87 0.88 0.88 0.94 0.96 0.97 0.97 0.97 0.98 1.00 1.00 1.03 1.04 1.04 1.04 1.04 1.04 1.08 1.08 1.09 1.10
- 0.46 —0.66 0.24 —1.16 - 0.64 0.37 0.51 -1.79 2.01 0.52 1.64 1.05 - 0.82 1.09 - 0.98 - 0.97 -1.88 0.57 0.17 1.07 0.40 1.31 0.58 0.57 0.28 0.27 0.88 -0.52 3.69 0.68 0.51 1.58 0.34 3.70 0.35 2.86 0.20 0.10 -0.51 -0.81 0.62 -1.03 -0.80 0.64 0.88 -0.09 0.29 0.31 -0.09 0.07 - 0.35 0.25 - 0.63
Monomer Tetrazole, 5-phenyl-2-(4'-vinyl)-phenylMethacrylate, 2-(N,N-dimethylcarbamoyloxy)ethyl Styrene, /?-2-(2-hydroxypropyl)Vinyl phenyl ketone Methacrylate, sulfolanyl Methacrylate, 2-bromoethyl Methacrylate, phenyl Styrene, m-bromoMaleimide, A^-(2-hydroxyethyl)Pentadiene, trans-1,3Pyridine, 2-vinyl-5-ethylStyrene, p-bromoPyridine, 2-methyl-5-vinylStyrene, /?-chloroStyrene, /?-chloromethylPyridine, 2-vinylButadiene, 2,3-dimethylAcrylic anhydride Pyrrolidone, l-benzyl-3-methylene-5-methylStyrene, 2,5-dichloroStyrene, p-methoxyStyrene, m-methylButadiene-1-carboxylate, ethyl Butadiene p-Vinylbenzylmethylcarbinol Vinylhydroquinone dibenzoate Methacrylate, 2-hydroxyethyl Acryloyl chloride Acrolein, methylHexatriene, tetrachloroButadiene, 2-fluoroPhthalimide, AHmethacryloyloxy)Isoprene, 3-acetoxyButadiene, 1,4-dicarboxylate, diethyl Isoprene Methacryloyl chloride Methacrylate, 2-chloro2,3,3,3-tetrafluoropropyl Styrene, m-nitroMaleimide, Ar-(2-chlorophenyl)Acrylate, a-chloro-, methyl Styrene, ra-chloroPyridine, 4-vinylMethylenebutyrolactone Maleimide, 2,3-dimethylAf-(2-methacryloxyethyl)Styrene, o-chloroMaleimide, JV-phenylStyrene, /?-cyanoMaleimide, A^-(4-chlorophenyl)Methacrylic anhydride Acrylic acid, a-bromoVinylhydroquinone Methacrylate, 2-hydroxypropyl Acrylate, a-cyano-, methyl /7-Vinylbenzoic acid Acrylate, a-phenyl-, methyl Methacryloylacetone Butadiene, 2,3-dichloroButadiene, 2-chloroVinylidene cyanide Vinyl chloromethyl ketone
Q
e
1.11 1.14
0.53 0.84
1.15 1.16 1.18 1.18 1.25 1.25 1.26 1.28 1.29 1.30 1.32 1.33 1.39 1.41 1.42 1.46 1.50 1.50 1.53 1.57 1.67 1.70 1.70 1.73 1.78 1.82 1.83 1.83 1.88 1.89 1.91 1.94 1.99 2.04
- 0.49 1.02 0.95 0.74 0.79 -0.27 1.07 -0.13 - 0.91 - 0.68 -0.66 — 0.64 - 0.38 -0.42 -0.43 0.31 -0.59 0.94 —1.40 -0.03 1.26 -0.50 —1.27 0.84 -0.39 1.92 0.71 0.94 0.63 0.96 —0.11 1.39 -0.55 1.54
2.09 2.19 2.29 2.43 2.46 2.47 2.48 2.54
0.62 0.20 2.87 0.35 - 0.90 0.84 0.83 1.64
2.66 2.81 2.93 2.98 3.00 3.07 4.30 4.38 4.91 5.17 5.19 5.47 9.08 10.52 14.22 16.00
1.57 3.24 - 0.38 2.75 0.56 1.37 2.26 1.86 0.91 1.08 0.96 - 0.76 0.14 1.20 1.92 1.78
TABLE 4. MONOMERS ARRANGED BY e VALUES Monomer Vinyl ethyl sulfoxide Ethylene Silane, y-methacryloxypropyl-trimethoxy Acetylene, phenylMethacrylate, isopropyl Butadiene, 2,3-dichloroVinyl chloride Methacrylate, ethyl Vinyltrimethylsilane Methacrylamide, N-phenylMethacrylate, glycidyl Styrene, ra-nitroAcrylate, 2-ethylhexyl Pyridazinone, 3-(2-vinyl)-6-methylMethacrylate, 2-(sulfonic acid)ethyl Methacrylate, isobutyl Methacrylate, butyl Methacrylate, 2,3-epithiopropyl Methacrylate, 2-chloroethyl Acrylic anhydride Vinylidene chloride Oxazoline, 2-,2-isopropenyl-4,4-dimethylMethacrylate, benzyl Acrylate, a-chloro-, methyl Vinyl isothiocyanate Allylbenzene Methacrylate, methyl Acrylate, ferrocenylmethyl Methacrylate, 2-acetoxyethyl Tetrazole, 2-methyl-5-(4'-vinyl)-phenylPhosphonic acid, oc-phenylvinylTetrazole, 5-phenyl-2-(4'-vinyl)-phenylAcrylamide Acrylate, ethyl Methacrylic anhydride Itaconate, dimethyl Itaconate, dibutyl Butadiene, hexafluoro1-Acrylamideo-l-deoxy-D-glucitol Oct-1-ene, 6,6-dimethyl-4,8-dioxaspiro(2.5)Methacrylic acid Butadiene, 2-fluoroAcrylate, methyl Isopropenyl methyl ketone Methacrylonitrile Acrolein, methylVinyl fluoride Methacrylate, 2-bromoethyl Vinyl cinnamate Acrylate, oc-acetoxy-, ethyl Styrene, pentachloroMethacrylate, phenyl Vinyltriethoxysilane 9-Vinylanthracene Methylenebutyrolactone Vinylhydroquinone dibenzoate Crotonaldehyde Methacrylate, 2-(ATv/V-dimethylcarbamoyloxy)ethyl Pyridine, 4-vinylAcrylate, butyl Acrylic acid Itaconate, diethyl Crotonic acid Acrylate, a-cyano-, methyl
Q
e
Monomer
0.065 0.016 1.08 0.45 0.97 9.08 0.056 0.76 0.027 0.40 0.96 2.19 0.37 0.57 1.09 0.82 0.82 1.04 1.04 1.46 0.31 0.87 0.88 2.43 0.59 0.038 0.78 0.15 0.60 0.86 0.65 1.11 0.23 0.41 3.00 0.73 0.82 0.82 0.22 0.25 0.98 1.88 0.45 1.03 0.86 1.83 0.008 1.18 0.18 0.52 0.20 1.25 0.021 0.14 2.48 1.73 0.023 1.14
0.05 0.05 0.07 0.10 0.10 0.14 0.16 0.17 0.19 0.19 0.20 0.20 0.24 0.24 0.25 0.27 0.28 0.29 0.31 0.31 0.34 0.34 0.35 0.35 0.37 0.40 0.40 0.51 0.51 0.51 0.52 0.53 0.54 0.55 0.56 0.57 0.57 0.58 0.61 0.61 0.62 0.63 0.64 0.64 0.68 0.71 0.72 0.74 0.76 0.77 0.79 0.79 0.82 0.82 0.83 0.84 0.84 0.84
2.47 0.38 0.83 1.04 0.017 4.91
0.84 0.85 0.88 0.88 0.89 0.91
Hexene-1 Styrene, 2,5-dichloroHexatriene, tetrachloroMethacrylate, sulfolanyl Phosphonate, isopropenyl-, dimethyl Phthalimide, AHmethacryloyloxy)Acrylate, a-phenyl-, methyl Propene, 3,3,3-trichloroVinyl phenyl ketone Acrylate, 2-chloroethyl Vinyl methyl ketone Vinyl butylsulfonate Itaconic acid Maleimide, A^-(2-hydroxyethyl)/?-Vinylbenzoic acid Maleate, diethyl Acrylate, 2-nitrobutyl Acrylate, benzyl Acrylamide, Af-methylolAcrylate, trifluoro-, methyl Butadiene, 2-chloroAcrylonitrile Ethylene, tetrachloro2-Methyleneglutaronitrile Acrylate, octadecyl Butadiene-1-carboxylate, ethyl Acrylate, glycidyl Ethylene, trichloroAcrolein Acrylate, heptafluorobutyl Acrylic acid, a-bromoButadiene, 1,4-dicarboxylate, diethyl Methacryloyl chloride Ethylene, chlorotrifluoroStyrene, ochloroCitraconimide, N-methylEthylene, tetrafluoroPhosphonate, vinyl-, bis(2-chloro-ethyl) Acrylamide, N-octadecylMaleimide, 2,3-dimethyl-Af(2-methacryloxyethyl)Carbon monoxide Vinyl chloromethyl ketone Methacrylate, 2-hydroxypropyl Vinylidene cyanide Acryloyl chloride Acrylate, octyl Methacrylate, 2-chloro2,3,3,3-tetrafluoropropyl Vinylhydroquinone Fumarate, diethyl Aconitate, trimethyl Fumarate, diisopropyl Triallyl cyanurate Diallylcyanamide 4-Cyclopentene-l,3-dione Fumaronitrile Maleimide, AT-(4-chlorophenyl)Maleimide Maleimide, N-(2-chlorophenyl)Maleimide, Af-phenylMaleic anhydride Maleimide, N-butylStyrene, m-methylPhosphonate, a-carbomethoxyvinyl-, diethyl
Q
e
0.035 1.50 1.83 1.18 0.032 1.89 5.19 0.030 1.16 0.49 0.66 0.16 0.78 1.26 5.17 0.053 0.69 0.33 0.52 0.048 10.52 0.48 0.001 0.41 0.33 1.67 0.48 0.010 0.80 0.96 3.07 1.94 2.04 0.026 2.66 0.87 0.032 0.044 0.66
0.92 0.94 0.94 0.95 0.96 0.96 0.96 1.00 1.02 1.03 1.05 1.06 1.07 1.07 1.08 1.08 1.09 1.13 1.15 1.20 1.20 1.23 1.24 1.25 1.26 1.26 1.28 1.29 1.31 1.34 1.37 1.39 1.54 1.56 1.57 1.58 1.63 1.64 1.64
2.54 0.013 16.00 4.38 14.22 1.82 0.63 0.62
1.64 1.68 1.78 1.86 1.92 1.92 2.01 2.09
4.30 0.25 0.25 0.11 0.14 0.14 0.42 0.29 2.98 0.94 2.29 2.81 0.86 0.88 1.57 0.14
2.26 2.26 2.27 2.58 2.41 2.41 2.43 2.73 2.75 2.86 2.87 3.24 3.69 3.70 -0.03 —0.04
References page 11-319
TABLE 4. cont'd Monomer Methacrylamide Butene-1 Methacrylate, 2-naphthyl Quinoline, 2-vinylIsoprene, 3-acetoxyVinyl-tris(trimethoxysiloxy )silane Pentadiene, trans-1,3Tetrazole, 1-vinylPropene, 1-chloro-, transPropene, 2-chloroMethacrylamide, 1-deoxy-D-glucitol Triallyl isocyanurate Vinyl bromide Phosphonate, vinyl-, dimethyl Triallyl citrate Diallyl phthalate Acrylamide, WV-dimethylStyrene, m-bromoButene-2 Acrylamide, MA^-diethyl Pyridazinone, 3-(2-vinyl)-6-methylStyrene, /?-l-(2-hydroxypropyl)Bicyclo[2.2.1]hept-2-ene5,6 dicarboxamine, Af-benzylStyrene, /?-chloromethylStyrene, /?-cyanoMethacrylate, 2-hydroxyethyl Propene, 2,3-dichloroPhosphonate, vinyl-, diethyl N-Allylstearamide Pyridine, 2-vinylButadiene, 2,3-dimethylBenzothiazole, vinylmercaptoTetrazole, 2-methyl-5-vinylPropene, 1-chloro-, cisVinylene carbonate Styrene, p-2-(2-hydroxypropyl)Butadiene Oxazoline, 2,4-acryloxymethyl-2,4-dimethylVinyl thiolacetate Tetrazole, 2-phenyl-5-(4/-vinyl)-phenylToluenesulfonamide, iVVV-methyl-vinylVinyl laurate Isoprene Vinyl cymantrene Styrene, 2,4,6-trimethylPyrrolidone, l-benzyl-3-methylene-5-methylAUyI chloride Styrene, 3-tri-n-butylstannylStyrene, /?-methylOxazoline, 2-isopropenyl-2Styrene, /?-chloroVinyl ethyl oxalate Methacrylate, ferrocenylmethyl Isopropenyl, 3-(l-cyclohexenyl)-acetate Pyridine, 2-methyl-5-vinylVinyl propionate Imidazole, 1-vinylMN-Divinylaniline Styrene, p-bromoOxazoline, 2-,4-methacryloxymethyl2,4-dimethylIndene Methacryloylacetone Styrene Styrene, a-methyl-
Q
e
0.40 0.007 1.04 1.04 1.91 0.022 1.28 0.13 0.006 0.073 0.15 0.035 0.038 0.24 0.054 0.031 0.41 1.25 0.002 0.48 0.18 1.08
- 0.05 -0.06 -0.09 -0.09 —0.11 -0.12 -0.13 -0.14 -0.16 - 0.16 —0.16 - 0.23 - 0.23 - 0.25 - 0.26 -0.26 -0.26 -0.27 - 0.29 -0.31 -0.32 - 0.35
0.01 1.39 2.93 1.78 0.12 0.27 0.024 1.41 1.42 0.36 0.55 0.003 0.004 1.15 1.70 0.97 0.27 0.84 0.18 0.011 1.99 0.39 0.15 1.50 0.026 0.014 1.10 0.59 1.33 0.056 0.22 0.57 1.32 0.027 0.11 0.26 1.30 0.44
— 0.36 - 0.38 - 0.38 -0.39 -0.40 - 0.40 -0.41 - 0.42 -0.43 — 0.44 - 0.46 - 0.46 - 0.49 - 0.49 -0.50 -0.51 - 0.52 -0.52 - 0.53 -0.54 -0.55 - 0.57 -0.58 —0.59 -0.60 -0.61 - 0.63 —0.64 - 0.64 - 0.65 - 0.65 —0.66 -0.66 - 0.68 -0.68 - 0.68 - 0.68 - 0.70
0.13 5.47 1.00 0.97
-0.71 - 0.76 -0.80 -0.81
Monomer Vinyl 4-chlorocyclohexyl ketone Vinyl hendecanoate Propenyl, 2-chloro-, acetate Isobutylene, 3-chloroVinyl acetate Vinyl butyrate Vinyl benzoate Styrene, m-chloroPyridine, 2-vinyl-5-ethylIsopropenyl acetate Vinylisocyanate Vinyl isobutyl sulfide Propene, 2-chloro-3-hydroxyVinyl stearate Styrene, p-1 (2-hydroxybutyl)/7-Vinylbenzylethylcarbinol Imidazole, l-vinyl-2-methylVinyl phenyl sulfide AHyI acrylate Styrene, oe-methoxyAcrylate, a-chloro-, ethyl Isopropenylisocyanate Allyl acetate Methacrylate, 2,2,6,6-tetramethyl-piperidinyl Vinyl AW-diethylcarbamate Carbamate, AW-diethyl-, vinyl Carbamate, N-vinyl-, ethyl Vinyl ether Vinyl isopropyl ketone N- Vinylcaprolactam Vinyl formate Isobutylene Vinyl pelargonate Vinyl isobutyl ether /7-Vinylbenzylmethylcarbinol Carbazole, N-vinylVinyl ethyl sulfide Vinylferrocene Vinyl dichloroacetate Styrene, p-methoxySuccinimide, N-vinylAllyl alcohol Norbornadiene Vinyl butyl ether Vinyl octyl ether Diallyl melamine Vinyl chloroacetate N-Vinylpyrrolidone Vinyl 2-chloroethyl ether Vinyl methyl sulfide Vinyl dodecyl ether Propylene Oxazolidone, TV-vinylEthylene, 1,1-diphenylVinyl methyl sulfoxide Vinyl ethyl ether Urea, Af-vinyl-Af'ethylAcenaphthalene Vinyl octadecyl ether Propenyl, 2-methyl-, acetate Vinyl phenyl ether Vinyl terf-butyl sulfide Vinyl m-cresyl ether Vinyl /?-cresyl ether Vinyl o-cresyl ether
Q
e
0.66 0.056 0.20 0.17 0.026 0.024 0.030 2.46 1.29 0.023 0.14 0.49 0.091 0.043 0.70 0.69 0.14 0.33 0.32 0.39 1.00 0.18 0.24 0.52 0.028 0.028 0.037 0.029 0.58 0.14 0.043 0.023 0.046 0.030 1.70 0.26 0.27 0.31 0.059 1.53 0.19 0.005 0.051 0.038 0.020 0.059 0.039 0.088 0.019 0.42 0.041 0.009 0.087 0.17 0.60 0.018 0.17 0.72 0.024 0.040 0.046 0.046 0.016 0.015 0.010
- 0.82 - 0.84 - 0.85 -0.86 - 0.88 - 0.89 - 0.89 - 0.90 - 0.91 - 0.94 —0.95 - 0.95 -0.95 - 0.97 - 0.97 - 0.98 -0.98 - 0.99 - 0.99 -1.02 -1.03 —1.05 -1.07 -1.09 -1.10 -1.11 -1.12 -1.16 —1.16 -1.18 -1.19 -1.20 -1.22 -1.27 —1.27 -1.29 -1.31 —1.34 -1.38 -1.40 —1.42 -1.48 -1.48 -1.50 -1.57 -1.57 -1.61 -1.62 -1.64 -1.66 -1.69 -1.69 -1.70 -1.71 -1.79 -1.80 -1.88 -1.88 -1.93 - 2.08 -2.16 - 2.20 - 6.33 - 6.86 - 8.53
C. REFERENCES 1. T. Alfrey, C. C. Price, J. Polym. ScL, 2, 101 (1947). 2. R. Z. Greenley, J. Macromol. Sci. A: Chem., 9, 505 (1975). 3. L. J. Young, in: J. Brandrup, E. H. Immergut (Eds.), "Polymer Handbook", 2nd ed., Wiley, New York, 1975.
4. R. Z. Greenley, J. Macromol. Sci. A: Chem., 11, 933 (1977). 5. A. D. Jenkins, J. Polym. Sci.: Part A: Polym. Chem., 34, 3495 (1996).
P a t t e r n s f o r
t h e
o f
R e a c t i v i t y
P r e d i c t i o n
R a t i o s i n
a n d
o f
( U , V )
M o n o m e r
T r a n s f e r
R a d i c a l
P a r a m e t e r s R e a c t i v i t y
C o n s t a n t s
P o l y m e r i z a t i o n
A u b r e y D . Jenkins, Jitka Jenkins School of Chemistry, Physics and Environmental Science, University of Sussex, Brighton, Sussex, BN1 9QJ, UK
A. B. C. D.
Introduction Example Transfer Constants Tables of Parameters Table 1. Monomers Table 2. Transfer Agents E. References
A.
11-321 II-322 II-322 II-323 II-323 II-326 II-327
INTRODUCTION
The relation between monomer reactivity ratios and the Alfrey-Price Q-e parameters is explained in the introduction to the tables of monomer reactivity ratios and Q-e values, compiled by Robert Z. Greenley and published in the present volume (1,2). Although very widely used, the Q-e scheme is well known to have serious limitations (3), which have prompted several attempts to improve upon it. One such endeavour was the "Patterns of Reactivity" scheme, first described as long ago as 1959 (4-7), when the Q-e scheme was only about ten years old; despite the indisputably more satisfactory basis of this procedure, it did not achieve popularity but recent revisions have greatly improved both its accessibility and its accuracy (3,8,9). In the Q-e scheme, four parameters (Qi, Q2, e\, e2, two for each monomer) are necessary for the prediction of a monomer reactivity ratio (e.g. r\2 = &11/&12, where subscript 1 refers to the radical and subscript 2 to the monomer) but the same four parameters also facilitate the prediction of the partner monomer reactivity ratio (?2\ — k22/k2\) because identical Q and e parameters are used to characterise both a given monomer and its derived radical. This device is certainly economical on input data but it introduces an approximation of very doubtful validity. In the "Patterns" scheme (to use the abbreviated title), different parameters are designated for the monomer and its conjugate radical. Hence, while four input parameters are
again necessary for the calculation of a single monomer reactivity ratio, eight are required to calculate both r\2 and r2\. The reward for the greater input of data is a substantial increase in the precision of the result; furthermore, all four parameters for each monomer/radical conjugate pair are experimentally determined from polymerization data, specifically monomer reactivity ratios from Greenley's tabulation, so no arbitrary assignment is involved, as it is with the Q-e scheme. The fundamental equation for the calculation of a reactivity ratio, r\2, is given below. log rn = log ris - U2TTi - V2.
(Al)
Here, the symbol S denotes the monomer styrene, and log ris is the counterpart of Q\ in the Q-e scheme. The counterpart of ei is the polarity parameter TTI; this is usually almost exactly equal to the Hammett a parameter for the substituent(s) present on the oc-carbon atom of the radical derived from monomer 1 but it is best calculated (8) from monomer reactivity ratio data according to Eq. (A2). TT1 = 0.385 log[(r 1A )/0.377(n s )]
(A2)
Here, the symbol A denotes the monomer acrylonitrile. It is truly an astonishing fact that the Hammett a parameter, derived originally from studies of the dissociation of substituted benzoic acids, is equal in value to a simple quantity derived from a knowledge of the monomer reactivity ratios for the reactions of a monomer 1 with (separately) acrylonitrile and styrene. The values of U2 and V2, the respective counterparts of the Q-e scheme's e2 and Q2, are determined by reference to data for the (separate) copolymerizations of monomer 2 with the members of a Basic Monomer Set. These are five monomers for which reliable data exist in the literature: styrene (S); methyl methacrylate (MM); methyl acrylate
(MA); methacrylonitrile (MAN); and acrylonitrile (A). Ideally, monomer reactivity ratios should be known for the copolymerization of the monomer of interest (labelled 2 in this case) with each of these five reference monomers. If the reference monomer is monomer 1 in this context, a plot is made of [log r 12 — log ris] against TT\; the slope of the resulting straight line is — Ui and the intercept on the ordinate axis is — V2, in conformity with Eq. (Al). If data for reactions with all five members of the Basic Monomer Set are not available, use can be made of such data as exists, always provided that styrene and acrylonitrile are among the monomers included. This condition ensures that the data are spread over a wide range of radical polarity, represented by TT\, because styrene has a very low value (zero), while acrylonitrile has one of the highest values known (0.701). In Table 1, each monomer is designated either as Basic or assigned to a category according to the number of members of the Basic Monomer Set for which data have been employed in the determination of its U2 and V2; for category 5, all five Basic monomers were involved, and so on down to category 2, where data for only styrene and acrylonitrile are available. Clearly, the higher the category number, the more reliable the w2 and V2 values. The procedure described thus far is known as the Patterns U, V Scheme (3). For Group 2 monomers, there is no need to make a plot because the use of just two data points permits algebraic solutions to be found. In fact, it can be shown (3) that the following relations hold.
(A3) Substitution in Eq. (Al) leads to the following relationships (A4, A5), giving the two monomer reactivity ratios for the copolymerization of any two monomers, 1 and 2.
(A4)
(A5) Application of Eqs. (A3-A5) corresponds to the Patterns A, S Scheme (4), so-called, because data for reaction with only acrylonitrile and styrene are involved. According to the Patterns A,S Scheme, it is possible to calculate the two monomer reactivity ratios for copolymerization of monomers 1 and 2, if each of them has separately been copolymerized with acrylonitrile and styrene. (The two monomer reactivity ratios for copolymerization of acrylonitrile and styrene are also required. These are taken to be: rAS = 0.04, r SA = 0.38 (3).)
The TT, w, and v values listed in the table below have been derived as explained above, with the Patterns U,V Scheme being used for the monomers in categories 3 - 5 and the Patterns A,S Scheme for those in category 2. The r\$ values are mean values from the figures supplied in Greenley's table, making due allowance for the consistency of the data. B. EXAMPLE Suppose one wants to evaluate the monomer reactivity ratios for the copolymerization of 2-chlorobutadiene (CB) and 2-vinylpyridine (VP). To use the Patterns U,V Scheme for this purpose, it is first necessary to consult Greenley's table of monomer reactivity ratios for data characterizing the copolymerizations of each of these monomers with as many members of the Basic Monomer Set as possible. In fact, in both cases, values exist for reactions with styrene, methyl methacrylate, methyl acrylate and acrylonitrile, but not methacrylonitrile. The TT values for the four useful basic monomers are, respectively, 0.000, 0.339, 0.423 and 0.701. The relevant monomer reactivity ratios are listed in the table below. MONOMER REACTIVITY RATIOS FOR 2-CHLOROBUTADIENE AND 2-VINYLPYRIDINE AND MEMBERS OF THE BASIC MONOMER SET Monomer reactivity ratio
2-Chlorobutadiene
2-Vinylpyridine
rxs rXA rs,x rA,x
6.91 5.18 0.038 0.05
1.26 0.44 0.53 0.10
r MM ,x r MA ,x
0.08 0.06
0.35 0.25
X = 2-chlorobutadiene or 2-vinylpyridine.
Plots of [log r 12 — log ris] against TT\, where 2 = CB or VP, are linear with slopes and intercepts that provide the following u and v values (9). For CB, u = - 2.18, v = 1.44, and for VP, u = - 0.982 and v = 0.323. All the data are now available for substitution in Eq. (Al), first for CB = monomer 1 and VP = monomer 2, and secondly with the monomers' roles reversed, to obtain values of r\i and rj\. The results are rn = 4.26 and r2\ =0.04. The Patterns A,S Scheme can be applied by simply substituting the appropriate monomer reactivity ratio data in Eqs. (A4) and (A5), giving ri2 = 4.71 and r 2 i = 0 . 0 5 . The corresponding experimental results are ri2 = 5.19 and 7*21 =0.06, while the Q = e scheme predicts that ri2 = 1.07 and r2i =0.07. C
TRANSFERCONSTANTS
Transfer constants can be predicted by exactly parallel reasoning (3). It is necessary only to realise that whereas the rate constant for the propagation step of a radical with its own parent monomer appears in the numerator of a monomer reactivity ratio (Vi2 = &11A12X where both rate
constants refer to propagation reactions, it figures in the denominator of a transfer constant because (C 2) 1 = kn/kn, where k\2 represents a transfer reaction between the radical derived from a monomer (species 1) and a transfer agent (species 2); the equations for calculating transfer constants are thus easily obtained from the equations above by replacing log rn by - l o g (C2)1. The only formal difference between the two cases is that, for transfer, there is no symmetrical counterpart of the equations representing reaction of a radical of type 2 with a transfer agent of type 1. Thus, the equivalent of Eq. (Al), for transfer is Eq. (A6), and this enables the Patterns U,V Scheme to be applied to chain transfer. (A6) For use of the Patterns A,S Scheme in transfer, a parallel derivation to that used in copolymerization leads to the following equation, where (C2) s a n d (C 2) A are, respectively, the (known) transfer constants for reaction of the same transfer agent (species 2) with radicals derived from styrene and acrylonitrile (species 1). (A7) Since IT A — 0.701 and r A s = 0 . 0 4 , this equation can be reduced to Eq. (A8) for general use. (A8) The transfer constants used here are taken from two tabulations, one due to Eastmond (10) and one in the Polymer Handbook (11). D.
TABLES OF PARAMETERS
As explained above, each monomer or transfer agent is assigned to a category, designated by Basic or the number 2, 3, 4, or 5, according to the number of members of the
Basic Monomer Set with which this reagent has been reacted to obtain data for the evaluation of w, v and (in the case of monomers) TT. Although it must be true that the higher the category, the more reliable the derived parameters, the difference between Categories 2 and 5 is not so great as might appear at first sight. In all cases, two of the basic monomers involved are styrene, S, (the least polar) and acrylonitrile, A, (the most polar), so the role played by other basic monomers is merely to add intermediate points to what should be a straight line joining the data points for S and A; if the data for these two latter monomers are accurate, intermediate points add little or no value beyond confirmation of the slope and intercept. They do contribute valuable weighting when there are some discrepancies in the data, but parameters have not been recorded here in cases where the discrepancies are large. Where either r\$ or r i A was reported as zero, the value 0.05 has been assigned arbitrarily in order to make it possible to calculate an approximate value for the TT parameter but the values of the u and v parameters are not influenced by this device; entries of this type are printed in italics in Table 1. Sometimes both r\s and n A are reported to be zero; when this happens, TT cannot usefully be estimated but u and v can still be determined, if positive values of r$\ and r A i are available. Nomenclature In the tables below, compounds are listed in alphabetical sequence in accordance with the following rules: The primary listing is based on the root name of the compound and the secondary sequence on the name(s) of the substituent(s) or the esterifying moiety. For example, the compounds, p-methyl styrene, N-vinyl carbazole, and ethyl acrylate, will be found listed under Styrene, p-methyl, Carbazole, N-vinyl, and Acrylate, ethyl, respectively. In deciding on the appropriate order of names, all prefixes (alphanumeric, Greek or whatever) and spaces are ignored, and reliance is placed solely on the alphabetical priority of the strictly chemical part of the name. In styrene, p-methyl, for example, the prefix p- plays no part in determining the place of this name in the list; this is governed by the m in methyl.
TABLE 1. MONOMERS Monomer Acenaphthalene Acetylene, phenyl Aconitate, trimethyl Acrolein Acrolein, methyl Acrylamide Acrylamide, iV-methylol Acrylamide, N-octadecyl Acrylate, benzyl Acrylate, butyl Acrylate, 2-chloroethyl Acrylate, oc-chloro-, methyl
Category
rls
r1A
rA1
4 5 2 5 4 3 4 3 3 3 4 3
0.33 0.33
2.56 0.33
0.27 0.60 0.70 0.48 0.54 0.20 0.18 0.12 0.30
1.11 3.10 1.10 2.43 1.40 0.72 0.97 0.87 1.76
0.02 0.27 4.24 0.78 0.15 0.90 0.60 1.03 1.49 1.11 1.03 O.fe
rSi
log(ri S )
n
3.81 0.32 1.026 0.23 0.26 1.20 0.03 2.08 0.49 0.77 0.53 0.25
-0.4815 -0.4815
0.506 0.159
-0.5686 -0.2219 -0.1549 -0.3188 -0.2676 -0.6990 -0.7447 -0.9208 -0.5229
0.397 0.436 0.237 0.432 0.321 0.376 0.443 0.492 0.457
u
v
1.33 -1.88 -2.88 -2.75 -1.73 -1.82 -3.94 -1.56 -2.68 -2.22 -2.38 -1.55
-0.46 0.37 -0.01 0.59 0.77 -0.07 1.18 -0.35 0.28 0.12 0.25 0.64
References page II - 327
TABLE 1. cont'd Monomer
Category
Acrylate, a-cyano-, methyl Acrylate, 3,4-epoxyhexahydrobenzyl Acrylate, P-ethoxy-, ethyl Acrylate, ethyl Acrylate, methyl Acrylate, octadecyl Acrylate, octyl Acrylate, 2-nitrobutyl Acrylate, a-phenyl-, methyl Acrylate, di-zinc Acrylonitrile Acryloyl chloride Allyl acetate AUyI chloride Aniline, N,N-divinyl Benzothiazole, vinylmercaptoButadiene Butadiene-1-carboxylic acid Butadiene- 1-carboxylate, ethyl Butadiene-1,4-dicarboxylic acid Butadiene, 1,4-dicarboxylate-, diethyl Butadiene, 2-chloroButadiene, 2-fluoroButadiene, 2-trimethylsilyloxyCarbazole, TV-vinyl Cinnamonitrile Citraconimide, TV-methylCrotonaldehyde Crotonate, a-acetyl-, methyl Crotonate, a-carboethoxy-, ethyl Crotonate, a-chloro-, ethyl Crotonate, a-cyano-, ethyl Crotonate, ethyl Crotonate, u-methoxy-, methyl Crotonate, OL-methyl-, methyl Crotonicacid Diallyl phthalate Ethylene Ethylene, tetrachloroEthylene, trichloroEthylene, diphenylFumarate, diethyl Fumarate, diisopropyl Hexatriene, tetrachloroImidazole, yV-vinyl Isoprene Isopropenyl isocyanate Isopropenyl methyl ketone Itaconicacid Itaconic anhydride Maleate, diethyl Maleic anhydride Maleimide, N-(2-chlorophenyl)Methacrylamide, /V-phenylMethacrylate, benzyl Methacrylate, 2-bromoethyl Methacrylate, butyl Methacrylate, isobutyl
rls
rlA
rAl
rSi
log(ri S )
n
u
0.61 1.97
0.68 0.39
0.01 0.25
0.05 0.27
-0.2147 0.2945
0.180 -0.110
-1.09 -1.95
1.20 0.57
0.17 0.18 0.26 0.125 0.12 1.28 0.90 0.04 0.02
0.87 0.85 1.20 0.84 1.76 6.70 0.24 1.00 1.00
-0.7696 -0.7447 -0.5850 -2.0000 -0.9208 0.1072 -0.0458 -1.3980 -1.6990
0.436 0.421 0.417 0.482 0.610 0.438 -0.060 0.701 0.815
0.04 0.033 0.42 1.40 5.55 0.3 0.52
0.04 0.05 0.18 0.29 7.5 3.2 4.00
2.42 0.80 1.42 3.15 1.98 0.67 0.08 0.41 1.00 1.20 6.57 2.80 0.246 0.19 0.06 0.12 0.3 0.20
-1.3980 -1.482 -0.3768 0.1461 0.7443 -0.5229 -0.2840
0.162 0.231 0.020 -0.100 0.213 0.559 0.502
-0.16 -1.99 -2.34 -3.01 -3.01 -2.39 -2.13 -1.39 -2.60 -3.50 -0.37 -0.39 -0.08 -0.38 -0.30 -2.00 -2.57 -2.18
-1.67 0.08 0.16 0.24 0.41 0.44 1.20 -0.04 0.42 1.09 -1.97 -1.53 -0.73 -0.38 0.41 0.94 0.92 0.82
2
0.55
2.79
0.29
0.09
-0.2596
0.433
-2.73
1.05
4 3 2
6.91 1.67 1.20
5.18 0.60 0.07
0.05 0.077 0.036
0.038 0.22 0.64
0.113 -0.0095 -0.324
-2.18 -1.32 -0.21
1.44 0.51 0.19
0.05 0.24 0.07
0.36 0.60 0.01
-0.25 -2.74 -2.77 -2.33 -2.72 -2.51
-0.58 -0.41 0.59 -1.17 -0.43 -0.92
0.02
0.06
0.04
-0.71 0.59 -1.43 -1.26
5 2 2 3 B 3 2 3 5 2 B 4 3 3 2 3 5 2 2 2
4 2 3 2 2 2 2 2 2 2 2 2 4 3 3 4 5 3 5 4 3 4 3 2 3 2 3 4 3 3 3 3 4 4
46.98 0.81 0.75 0.61 0.39 0.35 0.06 1.10 0.38 0.10 90 36 5.38 2.6 0.57 0.115 0.12 0.15
0.39 8.46 0.53 25 8.68 18.7
5.82 2.55 0.145 14.7 2.7 8.24
0.05
9.53 11.4 25.2 1.00
5.13 0.26 27 18.4
0.02
0.05
2.97
30.7
0.076 0.05
0.0385 0.05
0.06 0.055 0.85 0.68 1.84 0.096 0.48 0.12 0.55 0.04 0.011 0.021 0.88 0.47 0.41 0.53 0.42
0.05 0.20 4.01 0.832 0.45 0.1 0.95 0.86 4.83 0.05 0.05 1.078 0.71 0.96 2.38 0.98 1.05
21 3.5 7 463 64.5 0.05 9 16 0.234 3.39 0.03 0.24 0.33 0.59 0.034 16 6 0.956 0.381 0.2 0.31 0.291 0.217
20 23.5 14.88 195 14.6 0.335 0.33 0.4 0.123 8.38 0.458 7.48 0.38 0.26 0.031 7.03 0.36 0.0245 1.24 0.52 0.32 0.6 0.54
0.8395 0.2227 0.0792
v
-1.3010 -0.6198 -1.1549
0.491 0.315 -0.164
-1.6990
0.345
-1.3980
0.199
-2.38 -4.35 -1.96 -0.19
-1.699
0.315
-0.55
-1.49
-1.301 -1.12 -1.301
0.048 0.162
-2.03 -0.77 -1.57 - 2.60 -2.87 - 0.74 -4.05 -4.31 -2.39 -1.44 -0.32 0.14 -1.91 -2.50 -2.06 -2.51 -5.20 -4.23 -1.26 -1.40 -1.97 -1.49 -1.43
-1.30 -1.35 -1.23 - 2.36 -1.20 0.23 0.56 0.17 0.86 -0.92 0.34 -0.87 0.42 0.54 1.51 -0.83 1.22 1.32 -0.08 0.26 0.47 0.26 0.27
-1.222 -1.26 -0.0706 -0.1675 0.2648 -1.0177 -0.3188 -0.9208 -0.2596 -1.398 -1.959 -1.688 -0.0555 -0.3279 -0.3872 -0.2757 -0.3768
0.131 0.377 0.421 0.195 -0.074 0.170 0.276 0.491 0.526 0.199 0.416 0.826 0.126 0.281 0.455 0.267 0.315
TABLE 1. cont'd Monomer Methacrylate, 2-chloroethyl Methacrylate, ferrocenylmethyl Methacrylate, glycidyl Methacrylate, 2-hydroxyethyl Methacrylate, methyl Methacrylate, 3,5-dimethyladamantyl Methacrylate, 2,2,6,6-tetramethyl4-piperidinylMethacrylate, phenyl Methacrylic acid Methacrylonitrile Methacryloylacetone Methylenebutyrolactone Naphthalene, 1-vinylOct-l-ene,6,6-dimethyl4,8-dioxaspiro(2,5)Oxazoline, 2,2-isopropenylOxazoline, 2,2-isopropenyl4,4-dimethylPentadienoate, rra^-4-ethoxy2,4-,ethyl Phthalimide, N-vinylPropene, 3,3,3-trichloroPyridazinone, 3-(2-vinyl)-6-methylPyridazinone, 3-(2-vinyl)-6-methyl4,5-dihydroPyridine, 2-methyl-5-vinylPyridine, 2-vinylPyridine, 2-vinyl-5-ethylPyridine, 4-vinylSilane, 3-methacryloxypropyl, trimethoxyStyrene Styrene,/7-acetoxyStyrene, 3-tri-rc-butylstannylStyrene, 2,5-dichloroStyrene, p-chloromethylStyrene, p-1 -(2-hydroxypropyl)Styrene, a-methoxy Styrene, a-methyl Styrene, p-methyl Succinimide, N-vinyl Tetrazole, 1-vinylTetrazole, 5-phenyl-2(4 '-vinyl)-phenylToluenesulfonamide, N,N-methyl-vinylTriallyl citrate Vinyl acetate Vinyl benzoate Vinylbenzoic acid, pVinyl benzyl methyl carbinol Vinyl bromide Vinyl isobutyl ether Vinyl butyl sulfide Vinyl isobutyl sulfide Vinyl tert-butyl sulfide Vinyl chloride Vinyl chloroacetate Vinyl dichloroacetate
Category
rls
r1A
rA1
3 2 3 3 B 3
0.3 0.01 0.5 0.64 0.46 0.63
1.30 0.82 1.32 1 1.32 1.30
2
0.30
3 4 B 2 3 2 2
0.51 0.524 0.33 1.66 0.7 2.02 0.271
4 4
0.64 0.68
2
12.2
rSi
log(ri S )
n
u
v
0.14 0.15 0.14 0.2 0.138 0.19
0.37 3.6 0.415 0.48 0.5 0.89
-0.5229 -2 -0.301 -0.1938 -0.3372 -0.2007
0.406 0.898 0.325 0.238 0.339 0.283
-1.39 -0.03 -1.32 -1.45 -1.18 -1.04
0.42 -0.56 0.34 0.34 0.23 0.10
0.02
0.63
-0.5229
0.806
0.14
0.20
0.46 0.2 1.67 3.74 1.10 0.451 1.484
0.36 0.04 0.43 0.01 0.09 0.107 0.985
0.25 0.24 0.38 0.067 0.09 0.699 1.93
-0.2924 -0.2807 -0.4815 0.2202 -0.1549 0.3054 -0.567
0.146 0.002 0.432 0.297 0.237 -0.089 0.446
-2.22 -0.95 -2.08 -0.82 -1.98 -0.83 -1.58
0.62 0.39 0.44 1.17 0.88 0.16 -0.29
0.52 1.83
0.13 0.24
0.67 0.55
-0.1938 -0.1675
0.127 0.327
-0.95 -1.51
0.19 0.31
5.40
0.01
0.04
1.0864
0.025
-1.14
1.40
14
2 2 3
0.07 0.05 0.85
0.24 0.10 0.19
0.43 12.2 0.32
6.27 6.9 0.90
-1.155 -1.301 -0.0706
0.367 0.277 -0.089
-0.33 -2.35 -1.36
-0.80 -0.84 0.09
3
0.13
0.02
0.74
5.92
-0.8861
-0.151
-0.73
-0.57
4 4 4 4 2
0.85 1.26 1.09 0.69 0.868
0.31 0.44 0.43 0.375 3.79
0.16 0.10 0.04 0.10 0.094
0.70 0.53 0.74 0.52 0.425
-0.0706 0.1004 0.03743 -0.1612 -0.0615
-0.007 -0.014 0.006 0.06 0.408
-1.04 -0.98 -0.20 -0.94 -1.06
0.28 0.32 0.12 0.30 0.37
B 2 2 4 2 3
1.00 1.26 0.03 0.40 1.12 0.91
0.38 0.40 0.001 0.08 0.56 0.53
0.04 0.07 4.88 0.24 0.067 0.10
1.00 0.86 18.5 0.236 0.62 0.97
0 0.1004 -1.5229 -0.3979 0.0492 -0.041
0 -0.030 -0.407 -0.107 0.046 0.071
0.00 -0.44 -1.17 -1.98 -0.62 -0.60
0.00 0.07 -1.27 0.67 0.21 0.16
5 3 4 4 2 2
0.07 0.60 0.993 0.033 0.184 2.2
0.05 0.143 0.33 0.516 0.314 1.4
0.06 0.047 0.05 0.116 0.54 0.32
2.51 1.1 0.891 7.71 3.85 0.48
-1.1549 -0.2219 -0.0031 -1.4815 -0.7352 0.3424
0.105 -0.077 -0.021 0.623 0.251 0.088
0.41 -0.04 -0.20 0.75 -0.78 -1.75
-0.49 -0.03 0.08 -1.02 -0.59 0.32
3
0.05
0.04
0.42
5.6
-1.301
-0.40
-0.66
2 5 3 3 3 3 3 2 4 2 4 2 2
0.076 0.02 0.06 1.03 0.94 0.054 0.32 0.05 0.05 0.158 0.055 0.03 0.28
0.05 0.05 0.019 1.63 0.54 0.06 0.40 0.041 0.027 0.05 0.045 0.09 0.04
1.76 4.78 5.03 0.06 0.11 2.52 0.49 0.086 0.074 0.09 3.29 0.34 3.85
-0.49 -0.44 -0.86 -1.03 -0.66 -0.82 0.41 0.14 0.18 0.41 -0.90 1.04 -0.98
-1.30 -1.56 -1.45 0.50 0.18 -1.27 -1.41 -0.43 -0.36 -0.64 -1.16 -1.65 -1.30
20 48 31.56 0.282 0.98 16.6 24.5 2.69 2.38 4.36 18.7 45 20
-1.12 -1.699 -1.222 0.0124 -0.027 -1.268 -0.495 -1.3.01 -1301 -0.8013 -1.26 -1.523 -0.553
0.126 0.092 0.315 -0.031 0.238 0.069 0.179 0.200 0.128 0.059 -0.029 0.128 0.345 -0.162
References page 11-327
TABLE 1. cont'd Monomer
Category
Vinyl 2-chloroethyl ether Vinyl chloromethyl ketone Vinyl cymantrene Vinyl dodecyl ether Vinylene carbonate Vinyl ethyl ether Vinyl ethyl oxalate Vinyl ethyl sulfide Vinyl ethyl sulfoxide Vinylferrocene Vinyl hendecanoate Vinylidene chloride Vinyl isocyanate Vinyl isothiocyanate Vinyl methyl ketone Vinyl phenyl ether Vinyl phenyl sulfide Vinyl stearate Vinyltriethoxysilane Vinyl-tris(trimethoxysiloxy) silane Vinyltrimethylsilane
ri S
r1A
rA1
rSi
0.07 0.507 0.096
0.05 0.88 0.05
1.09 0.064 0.446 0.82 14.9 0.69 1.34 0.075 1.63 0.173 1.88 0.64 0.19 0.36 0.61 2.50 0.11 4.64 6.59 3.90
160 0.127 2.32 41.5 70 100 5.62 5.38 7.82 3.57 24.89 1.79 8.13 0.725 0.29 1.70 3.8 15.96 20.86 25
-0.740 -1.000 -0.7696 -1.301 -0.9686 -1.097 -0.3615 -0.495 -2.000 -0.854 -1.301 -1.301 -2.301
4.08
10.32
-1.301
4 3 2 2 3 4 3 3 3 3 3 5 3 3 2 3 3 3 2 3
0.05 0.05
0.08 0.06
0.182 0.10 0.17 0.05 0.1075 0.08 0.435 0.32 0.01 0.14 0.05 0.05 0.005
0.055 0.05 0.158 0.09 0.32 0.16 1.40 1.57 0.23 0.03 0.078 0.41 0.075
3
0.05
0.10
log(riS)
n
u
v
-1.155 -0.295 -1.018
0.105 0.255 0.053
-0.038 0.046 0.149 0.260 0.346 0.277 0.357 0.427 0.685 -0.090 0.236 0.513 0.616
1.18 -1.58 -0.97 0.44 -1.03 1.11 -1.11 0.66 -1.02 -0.12 -0.34 -1.34 0.29 -1.56 -2.46 -2.23 0.20 -1.19 -1.28 -0.84
-2.CX 0.9' -0.3 -1.6: -1.9: -2.Ol -0.7 -0.7' -0.9' -0.51 -1.3. -0.2< -0.91 0.1! 0.5< -0.31 -0.5! -LL -1.3: -1.4
0.29 -1.301
0.252 0.192
0.277
-1.41
-1.1:
TABLE 2. TRANSFER AGENT Transfer agent Acetaldehyde Acetamide, N,N-dimethylAcetic acid Acetone Acetonitrile Allyl chloride Aluminium, hydrodiisobutyl Aluminium, triethyl Aluminium, triisobutyl Aniline Aniline, WV-dimethylAnthracene Benzene Benzene, bromoBenzene, tert-butylBenzene, chloroBenzene, ethyl/7-Benzoquinone Borane, tributyl Butanone Butyl alcohol sec-Butyl alcohol tert-Butyl alcohol Butyl mercaptan Butyric acid, 4-hydroxy-y-lactone Cadmium, dibutyl Carbonic acid, cyclic ethylene ester Carbon tetrabromide, Carbon tetrachloride, Chloroform Copper(II) chloride Cumene Cyclohexane
Category 3 2 3 4 2 2 3 4 2 4 4 3 4 3 3 4 4 3 3 3 3 3 3 4 2 2 2 3 5 3 3
Cs 0.00085 0.00046 0.000222 0.000032 0.000044 0.00151 27.5 12.5 28.5 0.0020 0.0053 2 0.000003 0.000178 0.000005 0.000041 0.00007 227 0.00348 0.0005 0.00016 0.000056 0.00003 21.99 0.00004 0.117 0.000024 See methane, tetrabromoSee methane, tetrachloro0.00005 10300 0.00009 0.000005
CA
U
V
0.0047 0.0005 0.000081 0.000113 0.0002 0.000595 0.394 0.059 28 0.0050 0.0547 1.8 0.000246 0.000136 0.000193 0.000079 0.003573 1.3 0.647 0.000643 0.001542 0.009755 0.000044 0.409 0.00007 5.5 0.000013
-0.93 -1.94 -2.61 -1.28 -1.06 -2.57 -4.60 -5.46 -2.01 -1.43 -0.55 -2.29 0.80 -2.07 0.26 -1.49 0.49 -5.19 1.29 -1.82 -0.57 1.23 -1.75 -4.42 -1.66 0.39 - 2.36
-3.12 -3.34 -3.80 -4.59 -4.36 -2.82 1.21 0.79 1.45 -2.70 -2.20 -0.01 -5.65 -4.73 - 5.20 -4.51 -4.28 2.29 -2.95 -3.55 -4.05 -4.62 -4.62 1.23 -4.39 -0.93 - 4.63
0.000577 67.19 0.004141 0.000206
-0.49 -4.61 0.38 0.25
-4.17 4.33 -4.07 -4.63
TABLE 2. cont'd Transfer agent Dimethyl sulfoxide Diphenylamine-T Ethane, 1,2-dichloroEthane, 1,1,2,2-tetrachloroEther, dodecyl vinyl Ethyl acetate Formamide, WV-dimethyloc-D-Glucoside, methyl, 6-deoxy-6-mercaptooc-D-Glucoside, methyl-, di-O-benzyla-D-Glucoside, methyl-, 2,3,4,6-tetra-O-acetyla-D-Glucoside, methyl-, 6-(p-toluene sulfonyl)a-D-Glucoside, methyl-, 6-O-triphenylmethylP-D-Glucoside, methyl-, 6-deoxy-6-dipropylaminoGlycerol Heptanol, dodecafluoroIndium, triethyl Iron(III) chloride Isobutyl alcohol Isobutyronitrile Lead, tetraethyl Mercury, diethyl Methane, dichloroMethane, tetrabromoMethane, tetrachloroMethane, nitroMethanol Octadiene, 2,6-dimethylOxime, acroleinOxime, crotonaldehydeOxime, ethyl isopropenyl ketoneOxime, methacroleinOxime, methylacroleinOxime, methyl isopropenyl ketoneOxime, methyl vinyl ketonePentanol, octafluoroSilane, tetraethyl Stibine, tributyl Tin, tetrabutyl Toluene Triethylamine Tripropylamine Zinc, diethyl
E. 1. 2. 3. 4.
Category
Cs
CA
U
V
3 3 3 3 2 3 2 2
0.00005 0.00009 0.0002 0.00108 0.000372 0.00155 0.0001 5.5
0.000029 0.07 0.000147 0.000311 0.000495 0.000254 0.000278 0.13
-2.32 2.18 -2.17 -2.73 -1.82 -3.07 -1.36 -4.31
-4.44 -4.57 -3.82 -3.39 -3.43 -3.28 -4.00 0.74
2
0.0062
0.009
-1.76
-2.21
2
0.0002
0.003
-0.32
-3.70
2
0.0002
0.001
-1.00
-3.70
2
0.0021
0.008
-1.17
-2.68
2
0.0022
0.11
0.43
-2.66
2 3 3 3 3 2 2 3 2 4 3 3 3 3 3 3 3 3 3 3 3 3 4 3 3 5 4 4 2
0.002864 0.001333 1.76 536 0.00005 0.00027 0.000124 0.000034 0.000015 2.2 0.01 0.001 0.000074 0.0002 1.08 0.15 0.43 1.3 0.04 0.11 0.27 0.001136 0.000812 0.0058 0.000371 0.000012 0.00071 0.00242 0.366
-2.12 -3.20 -3.25 -5.44 0.41 -1.95 1.28 1.35 -0.13 - 4.04 -4.85 -2.30 -2.23 1.37 0.53 -0.35 -1.45 -0.77 1.03 -0.30 -1.06 -3.10 -1.30 2.78 -0.06 0.26 1.85 1.32 -1.08
-2.54 -2.85 -0.08 2.43 -4.54 -3.57 -3.91 -4.60 -4.82 0.37 -2.09 -3.09 -4.18 -3.79 -0.02 -1.06 -0.37 0.13 -1.25 -0.90 -0.67 -2.93 -3.02 -3.27 -3.69 -4.84 -3.04 -2.89 -0.44
0.00235 0.00019 0.222 3.33 0.002406 0.00029 0.0243 0.00722 0.000306 0.085 0.000099 0.0006 0.00005 0.045 62.6 2.05 1.03 9.41 5.35 1.71 1.20 0.00019 0.0021 11.1 0.00808 0.00032 0.304 0.428 1.6
REFERENCES
R. Z. Greenley, "Polymer Handbook", this volume, p. 181. R. Z. Greenley, "Polymer Handbook", this volume, p. 309. A. D. Jenkins, J. Polymer ScL, 34, 3495 (1996). C. H. Bamford, A. D. Jenkins, R. Johnston, Transactions. Farad. Soc, 55, 418 (1959). 5. C. H. Bamford, A. D. Jenkins, J. Polymer ScL, 53,149 (1961). 6. C. H. Bamford, A. D. Jenkins, Transactions. Farad. Soc, 58, 530 (1962).
7. A. D. Jenkins, Eur. Polymer J., 1, 177 (1965). 8. A. D. Jenkins, Macromol. Chem. Phys. Rapid Commun., 17, 275 (1996). 9. A. D. Jenkins, J. Jenkins, Macromol. Chem. Phys., Macromol. Symp., I l l , 159 (1996). 10. G. C. Eastmond, Comprehensive Chemical Kinetics, (C. H. Bamford, C. F. H. Tipper (Eds.)), 14A, 105 (1976). 11. A. Ueda, S. Nagai, "Polymer Handbook", this volume, p. 97.
C o p o l y m e r i z a t i o n M e t a l l o c e n e - C a t a l y z e d
P a r a m e t e r s
o f
C o p o l y m e r i z a t i o n s
G e r h a r d F i n k , W o l f JCirgen R i c h t e r Max-Planck-lnstitut fur Kohlenforschung, Kaiser-Wilhelm-Platz 1, D-45466 Mulheim an der Ruhr, FR Germany
A. Introduction 11-329 B. A Brief Theoretical Outline of Copolymerization Reactions 11-329 1. First-Order Markov Model II-330 2. Second-Order Markov Model II-330 C. Calculation of the Copolymerization Parameters 11-331 1. First-Order Markov Model 11-331 1.1. Copolymerization Parameters Deduced from the Mayo-Lewis Equation 11-331 1.2. Determination of Copolymerization from the Sequence Distribution (Triad Distribution) Parameters 11-331 2. Second-Order Markov Model M-332 3. Example M-332 D. Table of Copolymerization Parameters II-333 E. List of Catalysts/Cocatalysts Used II-336 F. References II-336 A.
the copolymerization behavior, and, in particular, determination of copolymerization parameters requires correct modeling, i.e. adequate Markov-statistics. B. A BRIEF THEORETICAL OUTLINE OF COPOLYMERIZATION REACTIONS
Various mathematical models have been applied to copolymerization reactions induced by Ziegler-catalysts. Wall (1) assumed the velocity of the monomer addition Mi and M 2 to be independent of the previously integrated monomeric unit (zero-order Markov model):
R = Polymer chain This scheme gives rise to the following equation for a copolymerization reaction:
INTRODUCTION
In contrast to radical and ionic polymerization reactions in which the incoming monomer always adds to the end of the growing chain
Mayo and Lewis (2) extended this model by including the influence of the last built-in monomer into the chain during the subsequent step (first-order Markov model):
the most distinct feature of Ziegler-Natta-catalysis is the attachment of a monomer molecule to a highly structured catalyst complex (which may be homogeneously solvated or heterogeneously fixed to a surface) and its insertion between the catalyst complex and the growing chain:
Since the structural features of the catalyst - in particular the steric bulk of ligands, the bite angle of metallocenes, the configuration and conformation on the one hand, and the increasing space-filling demand of the growing chain and of the various monomers on the other do influence the addition of the monomers, elucidation of
This results in the so-called Mayo-Lewis equation,
with ri = k\\/k\2 and r 2 = £22/^21 • Taking the effect of
the last two built-in monomers into account, Merz, et al (3) developed a second-order Markov model. This 'penultimate model' necessarily results in a more complex kinetic scheme:
with P n + P 1 2 = 1 and P 21 + P22 = 1 The proportion of the Mi and M 2 units (1Pi or 1 P 2 ) in the copolymer is also determined by reactivity probabilities: With m = km/km, r2\ = £211/^212, ^22 = &222A221 and 7*12 = k \22/k 121, the following copolymerization equation is obtained:
with x= [Mi]/[M2]. Expanding this model even further to the influence of the last three monomeric units, Ham (4) proposed a third-order Markov model. However, due to the many parameters involved, it has been of little practical use. Thus, most authors restrict themselves to first- or secondorder Markov models when dealing with Ziegler-Nattacatalysis for copolymerization, and this is elaborated below.
1 1 giving Pi - P 2 i/(Pi 2 +P21) and P2 = Pi2/ (Pn+Pn). All the potential sequence distributions can thus be calculated. Consider, for example, the triad distributions:
1. First-Order Markov Model
The Mayo-Lewis equation describes the composition of a copolymer as a function of the composition of the monomer mixture and their respective copolymerization parameters. These parameters not only determine the composition of the resulting copolymer, but also its microstructure, e.g. the distribution of the sequence length. A knowledge of the ratio of the starting monomers and their copolymerization parameters enables the sequence length distribution to be calculated. The reactivity probabilities Ptj are defined (5,6) that give the probability of the monomer j adding to the polymer chain with the terminating monomer /:
The triad distribution allows the calculation of the true copolymerization parameters. For a given polymer, the triad distribution is deduced from experimental 13C-NMR spectra (7) (see below). 2. Second-Order Markov Model
The kinetic scheme for this model gives rise to eight reaction probabilities Pijk that result from the probability of the monomer k adding to the polymer chain with the terminating monomers ij. The reactivity probability P m is
given for instance as
1. First-Order Markov Model
with P1n +Pm = 1, Pm + Piii = 1, ^122+^121 = 1, ^211+^212 = 1. The triad distribution is calculated in a manner analogous to the first-order Markov model:
7.7. Copolymerization Parameters Deduced from the Mayo-Lewis Equation The Mayo-Lewis equation calculates the composition of the copolymer formed as a function of the ratio of the monomer concentration at a given time. At arbitrary intervals these values are generally inaccessible; thus a sufficiently small interval (a small percent of the total conversion) is taken and the relative change of the monomer concentration d[M 2]/d[Mi] is assumed to be the composition of the copolymer ([mi], [1112]) itself according to
l
Pij is the frequency of the diad //, and is calculated as follows:
It is advisable to keep the monomer ratio [M2]/[Mi] constant during polymerization by constantly feeding both monomers, or at least the most reactive monomer. To determine the copolymerization parameters the experiments are run with varying ratios of the starting monomers, and their compositions are subsequently measured. The data obtained can be analyzed by linear or nonlinear methods. Linear Methods: Mayo and Lewis (2), Fineman and Ross (8), Kelen and Tudos (9) Nonlinear Methods: Behnken (10), Tidwell and Mortimer (11), Braunet al. (12) Independent of the analytical methods the copolymerization parameters derived from the Mayo-Lewis equation have some major drawbacks, but do enable a part of the information contained in each copolymerization experiment to be extracted, namely the integral composition of the copolymer. A series of experiments is necessary to obtain the copolymerization parameters. Furthermore, using this approach it cannot be decided whether the application of the first-order Markov model is valid or not. One may even obtain a nearly perfect Fineman-Ross plot, where other methods show that a first-order Markov model cannot be applied.
It results in
and
7.2. Determination of Copolymerization Parameters from the Sequence Distribution (Triad Distribution)
Once the copolymerization parameters of a catalyst system with a given ratio of monomers are known, the composition of the copolymer and all its sequence distributions result, e.g., the complete microstructure of the copolymer is revealed. These parameters characterize any catalyst system and enable different systems to be compared. The major practical problem is the choice of the adequate statistical model.
As mentioned above, a knowledge of the copolymerization parameters enables all the sequence distributions to be calculated. Or inversely, experimentally determined sequence distributions yield the copolymerization parameters. In the simplest case, intensities of appropriate single sequences can be compared. The results are even more reliable, if the determination of the copolymerization parameters is based on the maximal accessible information on the microstructure of the copolymer. To derive the rparameters from the overall triad distribution is the safest way (13). This may be done by calculating a triad distribution based on a first-order Markov model and optimizing by variation of the reaction probabilities Ptj until the best fit between calculated and experimental data
The
diad
frequency
C. CALCULATION OF THE COPOLYMERIZATION PARAMETERS
References page II - 336
is reached. Based on the optimized reaction probabilities the copolymerization parameters r\ and r2 are calculated according to the following equations:
This, procedure for determining the copolymerization parameters is superior to the Mayo-Lewis approach. While the latter requires several experiments, using the above approach, all the information can be obtained from one experiment. To determine the copolymerization parameters from the triad distribution, six variables are available, five of which are independent. The system is over-determined and thus allows critical evaluation.
Randall (7) found a way to avoid this problem by creating a "collective assignment method". Here the complete triad distribution results from combining the experimental spectral information with the relation between different n-ades. In the first step the 13C-NMR spectrum of an ethene/oc-olefin copolymer is split into several spectral areas given by signal overlap. The 13C-NMR spectra of ethene/propene copolymers, for example, are divided into eight appropriate spectral areas A to H, as shown in Fig. 1. The integrals Tx of different spectral areas are expressed by the number of contributing triads ending up in the complete triad distribution by appropriately combining several TVdata. Randall exemplified this method in detail for ethene/propene-, ethene/1-butene-, and ethene/1-hexenecopolymerizations (7). The resulting triad distribution allows the composition of the copolymer
2. Second-Order Markov Model The second-order Markov model gives four copolymerization parameters, which are gained from the sequence distribution (full triad distribution) with a high degree of reliability. The calculated triad distribution from the second-order Markov model is optimized by varying the reaction probabilities P^ until the best fit is reached. The four copolymerization parameters are calculated from reaction probabilities P^ as follows (13-15):
and the average sequence length:
to be calculated. 3. Example
The second-order Markov model results in four copolymerization parameters from six variables based on triad distribution. A higher degree of determination clearly is desirable to justify this copolymerization model. However, the complete distribution is not obtained from 13C-NMR spectra of ethene/oc-olefin copolymers. The full triad distribution does not exhaust the full information of the spectra, since some peaks exhibit tetrad or even pentad sensitivity. Cheng (16,17) suggested that all recorded peaks of a 13C-NMR spectrum should be included to calculate the copolymerization parameters. Arbitrarily chosen reaction probabilities give rise to a polymer chain built at random, and its 13C-NMR spectrum is calculated. This spectrum is superimposed on the experimental one and optimized by varying the starting values, until the minimal difference is reached. Since the 13C-NMR spectra of ethene/oc-olefin copolymers display many overlapping peaks, the quality of the spectra simulation very much influences the success of this method.
To demonstrate which model describes the experimental results best, the following table from a recent publication by Fink is reproduced (15). It is based on ethene/1-octene copolymerization experiments using a homogeneous metallocene/MAO catalyst.
area C area B
area D area F area H area E area G
area A
ppm Figure 1. 13C-NMR spectrum of an ethene/propene copolymer.
COMPARISON BETWEEN THE EXPERIMENTAL MEASURED TRIAD DISTRIBUTION AND THE CALCULATED TRIAD DISTRIBUTION ACCORDING TO THE FIRST- (M1) AND THE SECOND-ORDER (M2) MARKOVIAN-STATISTIC OF THE ETHYLENE (E)/1 -OCTADECENE (O) COPOLYMERIZATION0 [O]/[E] in solution 0.28
1.39
1.41
2.84
7.14
14.18
Model
EEE
EEO+ OEE
OEO
OOO
EOO + OOE
EOE
Exp. Ml M2 Exp. Ml M2 Exp. Ml M2 Exp. Ml M2 Exp. Ml M2 Exp. Ml M2
0.976 0.980 0.976 0.878 0.878 0.878 0.883 0.883 0.882 0.795 0.798 0.795 0.878 0.738 0.731 0.718 0.733 0.718
0.014 0.004 0.014 0.077 0.078 0.078 0.074 0.074 0.072 0.118 0.124 0.117 0.143 0.158 0.143 0.112 0.153 0.111
0.000 0.000 0.001 0.004 0.002 0.003 0.005 0.002 0.003 0.011 0.005 0.010 0.020 0.008 0.019 0.046 0.008 0.045
0.000 0.011 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.006 0.000 0.006 0.011 0.001 0.011 0.010 0.005 0.010
0.001 0.004 0.001 0.004 0.004 0.004 0.005 0.006 0.006 0.008 0.010 0.008 0.011 0.014 0.011 0.030 0.035 0.031
0.008 0.000 0.008 0.038 0.038 0.039 0.033 0.035 0.036 0.063 0.062 0.064 0.084 0.080 0.085 0.084 0.066 0.085
Rb ( x 106)
50 0.22 0 0.3 0 6.27 20 0.64 90 0.27 610 0.60
T p = 60 0C, Kat: iPr(CpFlu)ZrCl2 and MAO, [Zr] = 7.56 x l(r 6 mol/l, Al/Zr = 9800. b R is the sum of the least squares divided by the number of measured values.
Second-order Markov statistics is only applicable when there is a sufficiently high comonomer concentration in solution, and enables the formation of a-olefin/ a-olefin dual-blocks. Now the insertion of another a-olefin unit into this dual-block sequence is preferred to that into in a single-block. The complete triad distribution is gained by this procedure and it has to be performed over a wide range of the monomer/comonomer ratio in solution.
If the experimentally determined triad distribution is compared with the calculated values based on a first-order or alternatively on a second-order Markov model (Mi or M 2 of the table), both models give a reasonable good fit up to a monomer/comonomer ratio in solution of 1.5. Beyond a ratio of 3, however, the second-order Markov model proves to be the better approximation as indicated by the sum of the error squares divided by the number of experimental values (R of the table). D.
TABLE OF COPOLYMERIZATION PARAMETERS
Monomer/ comonomer
r\
r2
Ethene/propene 6.26 6.61 18.6 2.57 2.90 15.7 16.1 20.6 12.43 5.1 1.3 5.60 4.23 25.42 13.75 16.53 19.61 24
0.11 0.06 0.032 0.39 0.28 0.009 0.025 0.074 0.08 0.14 0.2 0.13 0.12 0.18 0.0085
r\\
r2\
r2i
ru
3.4 4.1
2.2 3.9
0.270 0.153
0.153 0.065
Cat./ cocat. 19 28 24 24 2 24 25 1 7 35 29 24 19 24 28 13 12 7 11 4
Remarks
Aa
B^ B B B B B
r Po i y (0C) 25 25 25 50 36 50 50 50 50 50 120-220 0 25 40 40 40 40 40 40 50
Model tested
Analytical method*
Refs.
Ml; M2 Ml; M2 Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml
C.T.A. C.T.A. R-R. E-R. R-R. See Ref. 20 See Ref. 20 See Ref. 20 See Ref. 20 See Ref. 20 R-R. R-R. R-R. See Ref. 24 See Ref. 24 See Ref. 24 See Ref. 24 See Ref. 24 See Ref. 24 R-R.
13 13 18 18 19 20 20 20 20 20 21 22 22 23 23 23 23 23 23 25
*C.T.A. - Complete Triad Analysis (7); D.A. - Diad Analysis (28); R-R. - Pineman-Ross (8); K.-T. - Kelen-Tiidos (9); M.-L. - Mayo-Lewis (2).
References page II - 336
Monomer/ comonomer
r\ 19.5 50 48 24 250 60 3.9 4.4 5.5
ri
20.2 2.5 42.28 43.35 61.56 99.43 4.71 6.36 8.16 10.6 10.1 7.5 10.1 18.9 19.5 10.7
Remarks
B B B
Model tested
Analytical method
Refs.
50 50 50 50 50 50 40 60 40
Ml Ml Ml Ml Ml Ml Ml Ml Ml
E-R. E-R. E-R. E-R. E-R. E-R. see ref. 24 see ref. 24 see ref. 24
25 25 25 25 25 25 26 26 26
Tp0Iy (0C)
2.9 6.8
0.21 0.085
0.041 0.017
19 28 24 24 24 37 37 37
25 25 30 50 70 30 50 70
Ml; M2 Ml; M2 Ml Ml Ml Ml Ml Ml
C.T.A. C.T.A. E-R. E-R. E-R. E-R. E-R. E-R.
13 13 27 27 27 27 27 27
3.2 10.3
2.6 6.4
0.150 0.111
0.065 0.022
19 28
25 25
Ml; M2 Ml; M2
C.T.A. C.T.A.
13 13
0.034 0.024 0.022
26 26 6 6 24 24 12 12 6 6 6 6 19 19 19
60 60 60 60 60 60 60 60 20 40 60 70 25 40 60
Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml; M2 Ml; M2 Ml; M2
E-R. D. A. E-R. D. A. E-R. D. A. E-R. D. A. E-R. E-R. E-R. E-R. C.T.A. C.T.A. C.T.A.
29 29 29 29 29 29 29 29 30 30 30 30 15 15 15
85 85 60 60 60 60 0 20 40 60 40 60 40 40 40 40
Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml
D.A. D.A. E-R. D.A. E-R. D.A. C.T.A. C.T.A. C.T.A. C.T.A. see ref. 24 see ref. 24 C.T.A. C.T.A. C.T.A. C.T.A.
31 31 29 29 29 29 32 32 32 32 26 26 33 33 33 33
4.58 6.60 8.85
0.130 0.109 0.098
0.55 0.035 0 0.03 0 0.23 0.18 0.14 0.11 0.03 0.07 0.118 0.014 0.013 0.076
Ethene/ 1-octadecene
Cat/ cocat.
3.6 7.9
0.027 0 0.003 0 0.013 0 0.005 0 0.004 0.005 0.005 0.005
Ethene/ 1-dodecene
Ethene/styrene Ethene/2-allylnorbornane
r\i
3 8 6 27 10 9 37 37 24
5.93 7.95 10.08 Ethene/ 1-octene
rii
0.05 0.03 0.04 0.17 0.10 0.21
Ethene/ 1-hexene 32.67 44.75 62.31 74.60 31.00 36.00 88.00 86.70 55 54 52 79
rn
0.015 0.007 0.015 0.029 0.002 0.12 0.12 0.11
Ethene/ 1-butene 19.4 23.6 29.2 5.4 6.6 6.8
/*n
6 5 26 26 6 6 32 32 32 32 24 24 32 28 30 31 7.2 12.0
5.0 5.7
11.2 14.7 38.45
6.3 8.4 18.58
B B
2.9 0.3
0.057 0.036
19 28
28 28
Ml; M2 Ml; M2
C.T.A. C.T.A.
34 34
1.6 0.4 0.085
0.044 0.035 0.041
28 28 60 40
Ml; M2 Ml; M2 Ml; M2 Ml
C.T.A. C.T.A. C.T.A. E-R.
34 34 15 35,46
35 35
Ml Ml
E-R. K.-T.
36 36
23.4
0.015
19 28 19 5
43.7 42.6
0.038 0.027
6 6
Monomer/ comonomer Ethene/ cyclopentene
Ethene/ norbornene
ri\
rii
Model tested
Analytical method
-10 0 10 20 0 25
Ml Ml Ml Ml Ml Ml
R-R. R-R. R-R. R-R. R-R. R-R.
39 39 39 39 40 40
28 34 19 23 23 25 25 25 25 6 24 28 19 23 23 22
30 30 30 30 0 -25 0 25 50 25 25 30 30 0 30 30
Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml
R-R. R-R. R-R. R-R. R-R. R-R. R-R. R-R. R-R. R-R. R-R. R-R. R-R. R-R. R-R. R-R.
37 37 37 37 37 38 38 38 38 38 38 40 40 40 40 40
15 16 17 14 19 20 21 22 33 5
70 70 70 70 70 70 70 70 70 70
Ml Ml Ml Ml Ml M2 M2 M2 M2 M2
K.-T. K.-T. K.-T. K.-T. K.-T. C.T.A. C.T.A. C.T.A. C.T.A. C.T.A.
41 41 41 41 41 41 41 41 41 41
28 19
30 30
Ml Ml
M.-L. M.-L.
43 43
23 18 38
50 50 50
Ml Ml Ml
R-R. R-R. R-R.
40,42 40,42 40,42
28 19
30 30
Ml Ml
M.-L. M.-L.
43 43
23 28 30 31 32
50 40 40 40 40
Ml Ml Ml Ml Ml
R-R. D.A. D.A. D.A. D.A.
40 44 44 44 44
28
60
Ml
K.-T.
45
ri
80 120 250 300 1.9 2.2
<0.05 <0.02 <0.02 <0.07 <1 <1
24 24 24 24 25 25
n.d.c n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. <2 0.06 0.05 0.05 0
2.66 3.44 2.93 2.61 1.85 1.5 1.9 2.2 3.2 20 6.6 2.6 3.4 2.0 3.0 3.1
ru
Cat./ /*i2 cocat.
r\
Remarks
TV0Iy (0C)
Refs.
Ethene/norbornene 0.88 1.14 1.1 0.83 1.3
0.05 0.1 0.026 0.29 0.03 1.2 2.2 2.2 5.2 2.2
Ethene/5-phenyl-2-norbornene 7.8 0.1 7.0 0.05 Ethene/dimethanooctahydronaphthalene 7.8 0.1 7.0 0.05 7.1 0.04 Ethene/phenyldimethanooctahydronaphthalene 11.5 0.05 7.1 0.03 Ethene/trimethanododecahydroanthracene 15.6 0.06 Propene/1-octene 3.3 0.39 3.6 0.32 2.6 0.37 2.4 0.48 Propene/cyclopentene 40 0.001
3.6 2.7 8.9 18.2 54
0 0 0 0 0
0 0 0 0 0
Cd C C C C
°High pressure copolymerization (100-150 MPa). fc [Monomer]/[Comonomer] ratio varied. The cited r-values hold only for a selected ratio of [Ethene]/[Propene]. c Not determined. d Alternating copolymerization, hence, rn = r 22 = 0.
References page II - 336
E. LIST OF CATALYSTS/COCATALYSTS USED 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38
[Cp] 2 TiCl 2 [Cp] 2 TiMe 2 [Cp] 2TiPh 2 [Cp] 2 Ti = CH 2 Me 2 Si[Me 4 CpNt-Bu]TiCl 2 [Cp] 2 ZrCl 2 [Cp] 2 ZrCl 2 ([Cp] 2 ZrCl 2 )O [MeCp] 2 ZrCl 2 [C 5 Me 4 J 2 ZrCl 2 [n-Bu-Cp] 2 ZrCl 2 [lnd] 2 ZrCl 2 [lnd] 2 ZrBenzyl 2 MeCH[Cp] 2 ZrCl 2 Me 2 C[Cplnd]ZrCl 2 Me 2 C[MeCpIiId]ZrCl 2 Me 2 C[3-t-BuCplnd]ZrCl 2 Ph 2 C[Cplnd]ZrCl 2 Me 2 C[CpFIu]ZrCl 2 Me 2 C[3-MeCpFlu]ZrCl 2 Me 2 C[3-PropCpFlu]ZrCl 2 Me 2 C[3-t-BuCpFlu]ZrCl 2 Ph 2 C[CpFIu]ZrCl 2 C 2 H 4 [IiId] 2 ZrCl 2 C 2 H 4 [lndH4] 2 ZrCl 2 Me 2 Si[Cp] 2 ZrCl 2 Me 2 Si[Cp] 2 ZrCl 2 Me 2 Si[lnd] 2 ZrCl 2 Modified silylbridged [lndH4] 2 ZrCl 2 Me 2 Si[2-Melnd] 2 ZrCl 2 Me 2 Si[Benz(e)lnd] 2 ZrCl 2 Me 2 Si[2-MeBenz(e)lnd] 2 ZrCl 2 Me 2 Si[3-t-BuCpFlu]ZrCl 2 Ph 2 Si[IiId] 2 ZrCl 2 [Cp] 2 HfCl 2 Me 2 C[CpFIu]HfCl 2 C 2 H 4 [IiId] 2 HfCl 2 Ph 2 C[CpFIu]HfCl 2
MAO AlMe 3 MAO: AlMe 3 AlMe 2 Cl MAO MAO MAO: AlMe 3 MAO: AlMe 3 MAO: AlMe 3 MAO: AlMe 3 MAO MAO MAO MAO MAO MAO MAO MAO MAO MAO MAO MAO MAO MAO MAO MAO MAO: AlMe 3 MAO MAO MAO MAO MAO MAO MAO MAO MAO MAO MAO
(1:1 mixture) (Tebbe reagent)
( 1 : 1 mixture) ( 1 : 1 mixture) ( 1 : 1 mixture) ( 1 : 1 mixture)
( 1 : 1 mixture)
F. REFERENCES 1. F. T. Wall, J. Am. Chem. Soc, 63, 1862 (1941). 2. F. R. Mayo, F. M. Lewis, J. Am. Chem. Soc, 66, 1594 (1944). 3. E. Merz, T. Alfrey, and G. Goldfinger, J. Polym. ScL, 1, 75 (1946). 4. G. E. Ham, J. Polym. ScL, 45, 169 (1960). 5. F. P. Price, J. Chem. Phys., 36, 209 (1962). 6. K. Ito, Y. Yamashita, J. Polym. ScL, Part A: Gen. Pap., 3, 2165 (1965). 7. J. C. Randall, J. Macromol. ScL, C: Rev. Macromol. Chem. Phys., 29, 201 (1989). 8. M. Fineman, S. D. Ross, J. Polym. ScL, 5, 269 (1950). 9. T. Kelen, F. Tiidos, J. Macromol. ScL, A: Chem., 9, 1 (1975). 10. D. W. Behnken, J. Polym. ScL, Part A: Gen. Pap., 2, 645 (1964). 11. RW. Tidwell, G. A. Mortimer, J. Polym. ScL, Part A: Gen. Pap., 3, 369 (1965). 12. D. Braun, W. Brendlein, G. Mott, Eur. Polym. J., 9, 1007 (1973).
13. N. Herfert, P. Montag, G. Fink, Makromol. Chem., 194, 3167 (1993). 14. J. Koivumaki, G. Fink, Macromolecules, 27, 6254 (1994). 15. P. Muhlenbrock, G. Fink, Z. Naturforsch., B: Chem. ScL, 50, 423 (1995). 16. H. N. Cheng, J. Chem. Inf. Comput. ScL, 27, 8 (1987). 17. H. N. Cheng, J. Appl. Polym. ScL: Appl. Polym. Symp., 43, 129 (1989). 18. H. Drogemuller, K. Heiland, W. Kaminsky, in: W. Kaminsky, H. Sinn (Eds.), "Transition Metals and Organometallics as Catalysts for Olefin Polymerization", Springer, Heidelberg, 1988, p. 302. 19. V. Busico, L. Mevo, G. Palumbo, A. Zambelli, Makromol. Chem., 184, 2193 (1983). 20. J. C. W. Chien, D. He, J. Polym. ScL, Part A: Polym. Chem., 29, (1991). 21. C. Bergemann, R. Cropp, G. Luft, J. MoI. Catal., 102, 1 (1995).
22. A. Zambelli, A. Grassi, M. Galimberti, R. Mazzocchi, F. Piemontesi, Macromol. Chem., Rapid Commun., 12, 523 (1991). 23. C. Lethinen, B. Lofgren, Eur. Polym. J., 33, 115 (1997). .24. M. Kakugo, Y. Naito, K. Mizunuma, T. Miyatake, Macromolecules, 15, 1150(1982). 25. J. A. Ewen, in: T. Keii, K. Soga (Eds.), Cataytic Polymerization of Olefins, Stud. Surf. Sci. Catal., 25, 271 Elsevier, Amsterdam (1986). 26. P. Starck, C. Lethinen, B. Lofgren, Angew. Makromol. Chem., 249, 115 (1997). 27. K. Heiland, W. Kaminsky, Makromol. Chem., 193,601 (1992). 28. K. Soga, T. Uozumi, Makromol. Chem., 193, 823 (1992). 29. R. Quijada, J. Dupont, M. S. L. Miranda, R. B. Scipioni, G. B. Galland, Macromol. Chem. Phys., 196, 3991 (1995). 30. W. Kaminsky, in: T. Keii, K. Soga, Catalytic Polymerization of Olefins, Stud. Surf. Sci. Catal, 25, 293, Elsevier, Amsterdam (1986). 31. K. Soga, T. Uozumi, S. Nakamura, T. Toneri, T. Teranishi, T. Sano, T. Arai, Macromol. Chem. Phys., 197, 4237 (1996). 32. J. Suhm, M. J. Schneider, R. Mulhaupt, J. Polym. Sci., Part A: Polym. Phys., 35, 735 (1997). 33. M. J. Schneider, J. Suhm, R. Mulhaupt, M.-H. Prosenc, H.-H. Brintzinger, Macromolecules, 30, 3164 (1997). 34. J. Koivumaki, G. Fink, J. V. Seppala, Macromolecules, 27, 6254 (1994).
35. F. G. Sernetz, R. Mulhaupt, R. M. Waymouth, Macromol. Chem. Phys., 197, 1071 (1996). 36. S. Marathe, T. P. Mohandas, S. Sivaram, Macromolecules, 28, 7318 (1995). 37. W. Kaminsky, A. Noll, Polym. Bull. (Berlin), 31, 175 (1993). 38. W. Kaminsky, A. Bark, M. Arndt, Makromol. Chem., Makromol. Symp., 47, 83 (1991). 39. W. Kaminsky, R. Spiehl, Makromol. Chem., 190, 515 (1989). 40. W. Kaminsky, Macromol. Chem. Phys., 197, 3907 (1996). 41. D. Ruchatz, G. Fink, Macromolecules, 31,4681 (1998) and the two preceeding papers by the same authors on pages 4669 and 4674 (1998). 42. W. Kaminsky, R. Engehausen, J. Kopf, Angew. Chem., 107, 2469 (1995), Angew. Chem. Int. Ed. Engl., 34, 2273 (1995). 43. W. Kaminsky, A. Noll, in: G. Fink, R. Mulhaupt, H.-H. Brinzinger (Eds.), Ziegler Catalysts, Springer, Berlin, 1995, p. 149. 44. M. J. Schneider, R. Mulhaupt, Macromol. Chem. Phys., 198, 1121 (1997). 45. M. Arnold, O. Henschke, F. Koller, Macromol. Rep., A33,219 (1996). 46. L. Oliva, P. Longo, L. Izzo, M. DiSerio, Macromolecules, 30, (1997).
R a t e s
o f
P o l y m e r i z a t i o n
A v e r a g e
M o l e c u l a r
W e i g h t
a n d
D e p o l y m e r i z a t i o n ,
W e i g h t s ,
D i s t r i b u t i o n s
o f
a n d
M o l e c u l a r
P o l y m e r s
L. H . Peebles, Jr. Chemistry Division, Naval Research Laboratory, Washington, DC, USA
A. Introduction 11-339 B. Reference Tables for the Calculation of Rates of Polymerization, Average Molecular Weights, and Molecular Weight Distributions of Polymers for Various Types of Polymerization 11-340 Table 1. Addition Polymerization with Termination 11-341 Table 2. Addition Polymerization - "Living" Polymers with Partial Deactivation II-344 Table 3. Linear Condensation Polymerization without Ring Formation II-346 Table 4. Equilibrium Polymerization II-347 Table 5. Nonlinear Polymerization Systems II-348 Table 6. Degradation of Polymers - May be Accompanied by Crosslinking II-350 Table 7. Influence of Reactor Conditions and Design on the Molecular Weight Distribution II-352 C. Some Distribution Functions and Their Properties II-352 1. Normal Distribution Function (Gaussian Distribution) II-353 2. Logarithmic Normal Distribution Function II-353 3. Generalized Exponential Distribution II-354 4. Poisson Distribution II-354 D. Molecular Weight Distribution in Condensation Polymers: The Stockmayer Distribution Function II-354 E. References II-356
A.
INTRODUCTION
An attempt is made to present a systematic guide to the literature dealing with rates of polymerization, average molecular weights, and molecular weight distributions of polymers for various types of polymerization. This chapter is based on a review of molecular weight distributions (1) in which many of the equations are given in detail along with
graphs showing the interrelationship among various distributions; here, we present only references to the literature. In addition, sections have been added on the effects of degradation and reactor design on the reaction rates and the molecular weight distributions. Literature references beyond (312) are those that have been added since the third edition of Polymer Handbook. The theoretical description of the molecular weight distribution of a polymer and its rate of polymerization is dependent on the assumed mechanism of polymerization and on the mathematical simplifications used to obtain analytical expressions. As the number of distinct reactions is increased, such as the various transfer reactions, the mathematical expressions can become quite complex and unwieldy. In general, the equations for the rate of polymerization are the most difficult to describe, the distribution equations are somewhat easier, and the average molecular weights the simplest. In condensation polymerization, many of the distribution formulas are derived by considering the statistics or the probability of a given reaction instead of the kinetics of the reactions. Depending on which assumptions are made, quite different average molecular weights are derived, despite the rigor of the derivation. The emphasis in this section is, therefore, on the distribution functions and their averages; the rates of polymerization are given only if they have been explicitly derived. This chapter is divided into several tables and sections, each treating various types of polymerization. The Stockmayer distribution function for condensation polymers is given in detail because of its general applicability and usefulness. Some general distribution functions are given in Section C. For all the other expressions, the reader must refer to the original literature. Many of the simpler functions are adequately described in textbooks of polymer chemistry. Flory (2), Bamford et al. (3), Odian (4), Billmeyer (5), and Kuechler (6) give extended descriptions of many systems. Bagdasarian (7) gives an extended discussion of methods of determining absolute values of propagation and termination constants, the influence of cage effects on the rate of initiation, and the influence
of retardation, inhibition, and diffusion-controlled termination on the rate of polymerization. A review of the various ways of deriving molecular weight distributions and the moments of a distribution is given by Chappelear and Simon (8). Section B presents a series of tables describing the main assumption or conditions imposed on the theoretical models and references to the articles where the corresponding equations may be found. Tables 1 and 2 present rate equations and the distribution formulas for addition polymerization by a variety of mechanisms. No distinction is made among free radical, cationic, anionic, or coordinationtype polymerization. While Table 1 treats those cases where termination reactions predominate and where steady-state assumptions are usually made, Table 2 treats those cases where termination reactions either do not exist, or may be considered as side reactions, having a minor to major control over the molecular weight distribution. The sequence length distributions for addition-type copolymers are omitted. However, see Kuechler (6) for an extended discussion of copolymerization distributions. Table 3 contains distribution formulas for linear condensation polymers in which the polymer is assumed to be perfectly linear and to contain no rings. Table 4 treats equilibrium polymerization. Table 5 describes nonlinear systems. Table 6 treats those cases where polymers are degraded (or altered) by the application of heat, light, or ionizing radiation. In the latter case, the polymer may undergo scission, crosslinking, or both reactions simultaneously. Several references on crosslinking are included here but not in Table 5. Finally, Table 7 is concerned with the influence of reactor design on molecular weight distribution; the kinetic equations for addition polymerization (with and without termination) and condensation polymerization are considered. Section C lists a number of distribution functions and their properties. Among them is the generalized exponential function which is a good approximation to many real systems (Eq. C29). Section D presents the Stockmayer distribution function for condensation polymerization wherein molecules of various types of kind A react with molecules of various types of kind B. B. REFERENCE TABLES FOR THE CALCULATION OF RATES OF POLYMERIZATION, AVERAGE MOLECULAR WEIGHTS, AND MOLECULAR WEIGHT DISTRIBUTIONS OF POLYMERS FOR VARIOUS TYPES OF POLYMERIZATION
The following symbols are used in this chapter. Rv: rate of polymerization; R^: rate of depolymerization; R\: active, growing polymer containing one monomer unit; R^ and Q*: active, growing polymer chains containing n monomer units; Pr: molecular weight distribution; U1: rate constant for initiation; kv\ rate constant for propagation; /: initiator concentration; M: monomer concentration; Mn and Mw: number-average and weight-average molecular weights,
respectively; 1° and 2° represent first and second order, respectively. No distinction is made among free radical, cationic, anionic, or coordination-type polymerizations. The rate of initiation may be held constant (const) throughout the polymerization, or it may depend on some function of the catalyst and monomer concentrations, or it may be instantaneous (instant), in which case only the total number of initiating species need be known. The rate of propagation is normally only the consumption of monomer; in some cases, the rate of propagation through terminal or pendant double bonds is also considered. Transfer reactions may occur to initiator, momomer, solvent, or polymer. Termination of active species may occur by a first-order deactivation, by second-order combination (comb) or disproportionation (disprop), or not at all ("living" polymers). Confusion exists over the meaning of the transfer-tocatalyst reaction. In free radical systems, it means transfer of the active species to the initiator by a second-order mechanism. In ionic polymerization, it means the expulsion of an active fragment from a growing chain by a first-order mechanism to form dead polymer and an active initiator fragment. The first-order mechanism is called here the "catalyst expulsion reaction" (cat ex). The nomenclature of distribution functions can be quite confusing. In this work, the Flory distribution (Eq. C41) is also known as the Schulz-Flory distribution, the "most probable" distribution, and the exponential distribution. The Schulz distribution (Eq. C36) is also known as the Schulz-Zimm distribution or the generalized Poisson distribution; at large values of k it approximates the Poisson distribution (Eq. C48). The Pearson Type III distribution is a variation of the Schulz distribution. If an addition polymer is made at constant monomer concentration, no transfer reactions occur, termination is only by second-order combination, and the distribution of the polymer is described by the Schulz distribution with k — 2. This distribution is sometimes called the self-convolution distribution or the convoluted exponential distribution. In a uniform distribution, all molcules have the same size - it is monodisperse. A rectangular or box distribution has no molecules below ra, an equal number (or weight) of molecules between r a and Tb, and no molecules whose size is above r\>. In Table 5, systems are treated where branching reactions, ring formation, or gel formation may occur. See also Table 6 for crosslinking reactions during degradation. The symbol RA/ means a monomer containing/reactive A units. The problem of calculating the species distribution of polyfunctional condensation polymers where branched, cyclic, and crosslinked species can be formed is exceedingly complex. Most treatments apply the restriction that ring formation does not occur prior to the gel point, which obviously is incorrect. The restriction is invoked because of the transition from the pre-gel condition, where all unreacted functional groups can react without steric limitations to a condition containing rings in which some of the unreacted groups are sterically unable to react with all of the remaining unreacted groups. The problem is
further compounded because each different reacting monomer will have various degrees of steric hindrance. Therefore, a general treatment must ignore this aspect. An examination of the Stockmayer distribution function in Section D shows that in-depth calculations are required even for simple oligomer species. A number of attempts have been made to provide simpler expressions for the number or weight of individual species and the average
molecular weights before and after the gel point. These include the theory of stochastic processes (271), stochastic graph theory (272), the theory of cascade processes which is based on probability generating functions (151), the use of link distribution functions (273), the recursive nature of branching processes and elementary probability laws (274), Monte Carlo methods (275), graph theory (276), and a kinetic approach (277).
TABLE 1. ADDITION POLYMERIZATION WITH TERMINATION References Set
Initiation
Monomer
Transfer
Termination
Rp
Pr
Mn,M^
1.1. INVARIANT MONOMER CONCENTRATION 1.1.1 1.1.2 1.1.3 1.1.4 1.1.5
Const Const Const Const Const
None Monomer, solvent Monomer, solvent Activator None
2° Disprop or comb 2° Disprop 2° Disprop and comb 2° Comb 2° With catalyst; redox system
1.1.6
Const Const Const Const, redox Const, initiation by activator kxM2
2-4 2,3,10-12 3 13 14
1-4 1-3 1,3 13 -
1-4 1-3 1,3 13 14
Const
2° Term
15
-
15
1.1.7
Instant
Const
Dimer, Monomer Initiator None
2° Term; 1° or 2° reactivation
16
-
16
1.2. VARYING MONOMER CONCENTRATION, NO TRANSFER-TO-MONOMER REACTION 1.2.1 1.2.2 1.2.3 1.2.4
Const Const Photosensitized Const
Varies Varies Varies Varies
None Solvent None None
2° Comb or disprop 2° Comb and disprop 2° Disprop 2° Disprop and comb pseudo 1° with scavenger
3 3 39 17 (rate of scavenger
1,3 1,3 1,3 1,3 39 disappearance)
1.3. VARYING MONOMER CONCENTRATION, TRANSFER-TO-MONOMER REACTION OCCURS 1.3.1 1.3.2 1.3.3 1.3.4 .3.5
Const Const k{M2 kxMl Instant
Varies Varies Varies Varies Varies
Monomer, solvent Monomer, solvent Monomer Monomer, initiator Monomer
2° Disprop or comb 2° Disprop and comb 2° Comb and disprop 2° Disprop; degradative chain transfer Non-steady state conditions, term by comb or disprop
3,18 3,4 20 313
1,3,18 1,3,4 313
1 19 1,3,4 20 313
1.4. 1° TERMINATION OR DEACTIVATION, STEADY-STATE KINETICS 1.4.1 1.4.2 1.4.3 1.4.4 1.4.5 1.4.6
Const kiMI k-xM2 kiMI k-M1 kiMI
Const Const Const Varies Varies Const
Monomer Monomer, solvent Monomer Solvent None None
1° Deactivation 1° Deactivation 1° Deactivation 1° Plus solvent term 1° Deactivation Deactivation by init. expulsion
4 1,4 1,4 4 1.4,21,22 1,4,21,22 4 1,4 1,4 4,23 1,4 1,4 4,23 1,4 1,4 21 1,21 1,21
1.5. TERMINATION BY 2° REACTION WITH MONOMER, STEADY-STATE KINETICS 1.5.1 1.5.2 1.5.3 1.6. 1.6.1 1.6.2 1.6.3
Const kiMI Const
Varies Varies Const
None Monomer Monomer
2° With monomer 2° With monomer 2° With monomer
None Monomer Monomer
2° Disprop 2° Disprop 2° Comb; two active chains couple to form a chain with two active ends
4,23 23 4
1,4 1 1,4
1,4 1 1,4
3 3
1,3 18 1,3
1,3 18 1,3
TWO ACTIVE ENDS PER CHAIN Const Const Const
Const Const Const
1.7. SLOW EXHAUSTION OF INITIATOR, NONSTEADY-STATE KINETICS 1.7.1 1.7.2
kj kj
Const Varies
None None
2° Disprop* or comb 2° Comb
25*,26 27
-
1,25*,26 27
*Data belong together.
References page II - 356
TABLE 1. cont'd References Set
Initiation
Monomer
Transfer
Termination
Rp
Pr
Afn, Mw
1.8. DEAD-END POLYMERIZATION, RAPID DECAY OF INITIATOR, MONOMER CONCENTRATION INVARIANT 1.8.1 1.8.2
kj kj2
Const Const
Monomer, solvent None
2° Disprop or comb 2° Disprop or comb
28 28
1,28 1,28
1,28 1,28
30 30 31
-
1,19* 1 -
40 41
-
-
1,2,3,4,10 32,33 239
34
1,35
239
239
315 -
316
316
37*
1,36
27 42 240 241
240 241
242
242
242
243
243
243
317
-
317
-
1,38
1.9. DEAD-END POLYMERIZATION, SLOW DECAY OF INITIATOR, MONOMER CONCENTRATION VARIES 1.9.1 1.9.2 1.9.3
kj kj kJM
Varies Varies Varies
Monomer, solvent Monomer, solvent None
1.9.4 1.9.5
Instant Redox
Varies Varies
Monomer None
2° Disprop * or comb 2° Comb 1° Term, bimolecular monomer addition. /* and R) do not terminate 1° Term, or 2° with monomer 2° Term
1.10. COPOLYMERIZATION: TWO DIFFERENT MONOMERS PRESENT 1.10.1
Const
Const
Monomer
2° Disprop or comb
1.10.2
Const
Varies
None
1.10.3
Const
Const
None
1.10.4 1.10.5
Const Varies
Const Varies
None Agent
Diffusion controlled and inversely proportional to viscosity Rate const for term is known as fn(conc). Comparison of cross term parameter ^ Alternating copolymerization Various; Monte Carlo calculations; initiation and term influences composition
314
1.11. DIFFUSION-CONTROLLED TERMINATION (see also 1.10.2 and 5.1.4) 1.11.1
Const
Varies
None or solvent*
1.11.2 1.11.3 1.11.4 1.11.5
kj Const kj kj
Varies Varies Varies Varies
None None Monomer None
1.11.6
k[
Varies
None
1.11.7
k{
Varies
Monomer, solvent
1.11.8
kj or none
Varies
Monomer, solvent
1.11.9
Const
Const
Solvent
2° Disprop or comb* and diffusion controlled 2° Comb, Rt = ktMn,n > 1 2° Process 2° Disprop and diffusion controlled 2° Disprop and comb, diffusion controlled 2° Disprop, term rate for long chains depends on entanglement density 2° Disprop, term rate for long chains depends on entanglement density 2° Comb, and disprop term depends on free volume or free volume plus entanglement, CaIc. of gel point kt^m) = ko(nm)~a. Term by comb and disprop.
27
318
1.12. PRIMARY RADICAL TERMINATION 1.12.1
Const
Varies
Monomer
1.12.2
Const
Const
None or init. and monomer*
2° Comb and disprop and primary radicals 2° Term and primary radicals
38 33,43-45
- 44,45,15*
1.13. MIXED SPECIES PROPAGATION 1.13.1
Const
Varies
Monomer
1.13.2
Const
Const
None
1.13.3
Const
Varies
None
*Data belong together.
Propagation, transfer and termination rates depend on species type, i.e. free radical and cationic occurring simultaneously Zwitter-ion polymerization; distance between ions varies as r 3/2 , equilibrium between free and solvated ions; 1° term Bifunctional initiator, term by comb
46 244
46 244
244
47
-
47
319
-
319
TABLE 1. cont'd References Set
Initiation
Monomer
Transfer
Termination
Rv
Pr
Mn,Mw
1.14. EMULSION POLYMERIZATION (see also Tables 2 and 7) 1.14.1
Const
Const within particles
None
1.14.2
Const
None
1.14.3
Const
1.14.4
Const
Const within particles Const within particles Const within particles
1.14.5
Const
1.14.6
Slow and const
1.14.7
Const
1.14.8
None Monomer
Const within Monomer particles varies outside Const None None
Const
Const within particles Const
1.14.9
Varies
Varies
Minimize
1.14.10
Const
Const within particles
Monomer, agent
1.14.11
Const
Monomer, agent
1.14.12
Varies
Const within particles Varies
1.14.13
Const
Const
None
1.14.14
Const
Const
None
None
Monomer
General theory; particles act as independent units; 2° term within particles; number of particles remain constant; number of radicals per particle General theory; Slow-term rate within particles Inst. term within particles; number of particles varies Normal 2° term within particles; rapid interchange between phases of small-sized radicals; number of radicals per particle Rapid exchange between phases of small-sized radicals; term in aq phase and in particles Slow 2° comb; calcn. of number of radicals per particle Const number of particles; term by 2° comb Inst term on entering a particle; const number of particles Adjust initiation and term rates while minimizing transfer to obtain "monodisperse" polymer Instant 2° term when a free radical enters a particle containing two growing chains and reacts with one of them. No term by disprop or comb within particles Same as case 1.14.10 but plus term by disprop or particle by comb Varying rate of entry, desorption of oligometic radicals, term by comb and disprop, Monte Carlo simulation model Any number of chains per particle, 1° term, 2° term by disprop or by comb. Use of Markov chains See 1.14.13. Copolymerization, chain composition distribution
48-54
-
53
55
-
55
56
-
-
-
59
59
60
-
60
-
-
61
72
72
72
245
245
245
245
245
245
-
320
-
-
321
-
322
62
62
62
63
-
63
-
-
68
-
68
69
-
69
57
58
1.15. HETEROGENEOUS POLYMERIZATION 1.15.1
k[MI, I varies
Varies
Monomer
1.15.2
Instant
Varies
None
1.15.3
Const
Const
None
1.15.4
Const
Const
None
Polymerization in monomer rich and monomer poor phases; 2° disprop Term by precipitation onto growing solid particle 2° Comb, 1° occlusion onto particle surfaces, and primary radical term 2° Term in liquid phase, 1° radical precipitation, propagation and 2° term at solid-liquid interface
64 65
1.16. INHIBITION AND RETARDATION 1.16.1
Const
Varies
None
1.16.2
Const
Const
Inhibitor
1.16.3
Const
Const
Retarder
2° Term, 2° addition to inhibitor 2° Term, inhibitor term, inhibitor coupling 2° Term, retarder reinitiation and term
3,66,67,73
References page II - 356
TABLE 1. cont'd References Set
Initiation
Monomer
Transfer
1.16.4
Const
Const
Retarder
1.16.5
Const
Const
Retarder
1.16.6 1.16.7 1.16.8 1.16.9
Const Const Const kj
Const Varies Const Const
Retarder None Inhibitor Inhibitor
1.17.
Termination 2° Term, retarder reinitiation, term and coupling 2° Term, rate of transfer equals rate of reinitiation 2° Term, copolymerization of retarder Pseudo 1° with scavenger 2° Disprop, 2° reaction with inhibitor 2° with inhibitor or with monomer to assess the efficiency of initiation
^p
Pr
Mn, Mw
3,12,70 71,74 10
-
-
-
-
11 17 75 246
-
11 75 -
-
-
247
-
323
-
324
324
324
-
325
-
POLYFUNCTIONAL INITIATOR WITH VARIOUS THERMAL STABILITIES
1.17.1
k\Ml On raising the temp., other peroxide groups can initiate
1.18.
Const
None
2° disproportionate
PERIODIC MODULATION OF TERMINATION OR INITIATION
1.18.1
Const
Varies
None
1.18.2
Varies
Varies
None
1.18.3
Varies
Varies
None
Periodic modulation of term by disprop by addition of an inhibitor or by magnetic or electric fields Periodic modulation of initiation, term by comb and/or disprop, computer calculation Periodic modulation of initiation, term by comb. Calcn. of MWD by generating functions
TABLE 2. ADDITION POLYMERIZATION - "LIVING" POLYMERS WITH PARTIAL DEACTIVATION References Set 2.1.
Initiation
Monomer
Transfer
Termination
kpMI
Varies
None
None
2.1.2
kpMIt
Varies
None
None; initiator added at a constant rate
None
None
2.2.1 2.3. 2.3.1 2.3.2 2.3.3
2.3.4 2.3.5 2.3.6
2A. 2.4.1 2.4.2
Pr
Mn^Mw
103
1,2,101, 102 -
1,2,101, 102 103
102, 104
1,102
1,102
THE POISSON DISTRIBUTION: Jc1 = kp
2.1.1
2.2.
Rp
2,101,102
THE GOLD DISTRIBUTION: Zt1 + kp kiMI
Varies
PARTIAL DEACTIVATION BYA 1° PROCESS OR A 2° PROCESS WITH AN IMPURITY Instant Instant Instant initiator has two active sites Instant Instant Instant
Varies Varies Varies
None None None
1° or 2° Rate of term//?p = const. Rate of term//?p = const.
Varies Varies Const
None None None
Rate of term independent of Rp 1° at infinite time Probability that a chain will terminate rather than propagate is kt/kvM
105 1,106 1,106 - 1,106,107 1,106,107 1,107 1,107
1,106 108,109 -
-
1,106 108,109 248
MULTIPLE PROPAGATING SPECIES: R*n CAN TRANSFORM INTO Ql, ETC. Instant kiMI
Const Varies
None None
None, two propagating species None, two propagating species
1, 77-79
76 1,77,78 80
76 1,77-80
TABLE 2. cont'd References Set
Initiation
Monomer
Transfer
2.4.3 2.4.4
Instant Activated monomer addition
Varies Varies; volume also varies
None None
Termination None, multiple propagating species None; two prop constants kp can increase
Rp
Pr
Mn, M ^
249 -
249 326 327
249 326 327
82,83 84
1,81 81
1,81 83
2.5. SIMULTANEOUS POLYMERIZATION AND DEPOLYMERIZATION 2.5.1 2.5.2 2.5.3
kiMI kiMI JcpM2
Const Varies Varies
None None None
None None None
2.6. THE kp VARIES WITH CHAIN LENGTH (see also 2.4.4, 3.3, and 3.4) 2.6.1
2.6.2 2.6.3 2.6.4 2.6.5
kiMI Varies None None (a) all propagation constants (kT) are different 1,85,86 (b) ki : ki : k2 : k3 :~-kn=m : (m - 1) : (m - 2) : (m - 3) : • • • 1,85 (C) * i ^ * 2 - - - ^ m = W i = ••• = *» 1.85 1,85 (d)*i^*i^*2=*m 1,85 Instant, kx = k2 • • • = km,km+l, etc.= 0 86 86 86 Instant, kp is a linear decreasing function of r 86 86 86 Const Varies None None; kv for monomer, dimer, and 328 328 trimer different from remaining molecules Rate constants can vary with extent of conversion; determination of rate constants from Pr and the use of generating functions; termination by monomolecular decay, disprop and/or comb. 329 -
2.7. DEACTIVATION BY TRANSFER TO MONOMER 2.7.1 2.7.2 2.7.3
kxMI Instant Instant
Varies Varies Varies
Monomer Monomer Monomer
None None None, two active ends per initiator
1,87 1,74,90 1,91
1,87 1,74,87,88 1,89,90 1,74,90 1,91,92 1,91
2.8. DEACTIVATION BY SLOW 1° TERMINATION 2.8.1 2.8.2
Instant Instant
Varies Varies
None Monomer
Slow 1° Slow 1°, at infinite time
1,74 1,74
-
1,74 1,74
None 1° term None
67 250
250
1,93 67 250
95
2.9. DEACTIVATION BY INITIATOR EXPULSION REACTION 2.9.1 2.9.2 2.9.3
Instant kiMI Instant
Varies Varies Varies
None Monomer Monomer
2.10. DEACTIVATION BY DEGRADATIVE CHAIN TRANSFER 2.10.1 2.11. 2.11.1
kiMI
Varies
Degradative transfer to polymer
None
94
-
Varies
None
None
-
96
None; diffusion of monomer through solid polymer 2° Term with monomer; diffusion of monomer through solid polymer Sorption and desorption of chains from the surface; slow 1° term which depends on chain length
97
-
97
98
-
98
-
99
99
100
-
100
COPOLYMERIZATION Instant
2.12. HETEROGENEOUS POLYMERIZATION 2.12.1
Instant
Varies
None
2.12.2
Instant
Varies
None
2.12.3
Const
Const
None
2.13. SPONTANEOUS POLYMERIZATION 2.13.1
Const
Const
None
Vinyl compound and activator form monomer; monomer both initiates and propagates; no term
References page II - 356
TABLE 2. cont'd References Set 2.14.
Initiation
Rev 2° with monomer
k[MI
2.15.2
kM
Const
Monomer
No termination; dead species in equilibrium with living species, irreversible propagation
251
252
Numerical method for calc. of MWD with mono- or polyfunctional transfer agent. Latter leads to branching.
-
330
3-State mechanism consisting of two successive equilibria Equilibrium between dormant aggregated polymer and "living" polymer
-
-
331
332
-
-
-
-
334
-
-
335
SLOW EQUILIBRIA
Varies
Varies
None
POLYMER MICROSTRUCTURE
2.17.1
Varies
Varies
None
2.17.2
NA
NA
NA
TABLE 3.
LINEAR CONDENSATION POLYMERIZATION WITHOUT RING FORMATION
3.7
251
-
2.16.2
3.6
251
-
None
3.5
Mn,Mw
No termination. Transfer creates dead polymer and active initiator
Varies
3.1 3.2 3.3 3.4
Pr
Agent const varies Agent
Varies
Set
Rp
Const or varies Varies
2.16.1
2.17.
Termination
DEACTIVATION BY TRANSFER TO AGENT
2.15.1
2.16.
Transfer
REVERSIBLE INITIATION AND REACTIVATION
2.14.1
2.15.
Monomer
None; concentration of head-to-head and tail-to-tail, sequence length distributions, various dyad and triad fractions Block copolymers
Conditions Condensation of bifunctional monomer AB; the Flory distribution. See Eq. (C41) Bifunctional monomer AA reacting with bifunctional monomer BB; the nylon case of hexamethylene diamine and adipic acid Deviations from the principle of equal reactivity; the "substitution effect" Rate of condensation varies 3.4.1 Rate of condensation proportional to chain size 3.4.2 Condensation requires rotation into colinear orientation prior to reaction 3.4.3 The order of reaction varies with conversion, or a catalytic influence of unreacted A or B groups, or both effects occurring simultaneously Other simple linear condensation cases 3.5.1 AA reacting with BC. BC is an anhydride; within a given molecule, B must react before C 3.5.2 AA reacting with BC. BC is an unsymmetrical acid or glycol; B reacts only with A at a different rate from that of C reacting with A 3.5.3 AB reacting with C and itself. B and C react only with A; C is a terminator or capping material 3.5.4 AA reacting with BB and C; the nylon case again with acetic acid as terminator 3.5.5 AA reacting with BC; A and B react with C 3.5.6 AB reacts with CC or DD kinetics 3.5.7 AA and A reacting with BB and B Further polymerization of polymers with an initial geometric distribution 3.6.1 Further polymerization of AB when the initial distribution is geometric 3.6.2 Further polymerization of AB when the initial distribution is a superposition of two geometric distributions 3.6.3 Further polymerization of AA with BB when the initial distribution of both is geometric Copolymerization of condensation polymers 3.7.1 AB reacting with CD; AB and CD can be hydroxy acids or similar materials 3.7.2 AA reacting with BB and CC. A reacts with B and C only and vice versa; BB and CC can be adipic and sebacic acids 3.7.3 AA and BB reacting with CC and DD; A and B react only with C and D and vice versa 3.7.4 AA reacting with BC and DD; A reacts only with B, C, and D 3.7.5 AA and DD reacting with BC; A and B react only with C and D and vice versa 3.7.6 AA reacting with BC-BC, the latter can be a dianhydride; B must react before C
References 1,2,110 1,24,111 1,112,253,254 1,113,114,134 255 256 1,111 1,111 1,111 1,111 1,111 115 336 1,116 1,116 1,116 1,111 111,257 111 111 111 258,259
TABLE 3. cont'd Set 3.8
3.9 3.10 3.11
Conditions Coupled polymers 3.8.1 AB polymerized to extent of conversion a, then coupled with CC 3.8.2 AB polymerized to extent of conversion a, then coupled with CD. A and B can react with C or D 3.8.3 AA and BB polymerized to extent of conversion a, then coupled with an excess of CC. A and B to react completely on coupling 3.8.4 Poisson-distribution polymer of AA coupled with BC 3.8.5 Monomer AB polymerized to extent of conversion a, then coupled with excess CC to extent of conversion 7, then recoupled with excess DD 3.8.6 Particularly narrow distributions via coupling reaction I. AA and BB (great excess)—^BBAABB, then remove excess BB. CC and BBAABB (great excess)—> BBAABBCCBBAABB, then remove excess BBAABB, and continue in like manner II. AA and 2BC^CBAABC then CBAABC and 2DE^EDCBAABCDE, etc III. AB and CD^ABCD then ABCD and EF^ABCDEF, etc 3.8.7 Blocks of polymers of known distribution are coupled together I. A series of Poisson-type-polymers coupled together II. Poisson-type-polymers coupled to "most probable"-type polymers III. A series of "most probable"-type polymers coupled together AB reacts with CC or CD; rate of reaction of A dependent upon whether or not B has reacted Segmented block copolymers; distribution of block sizes Reacted sequences in homopolymers
TABLE 4. Set 4.1
References
1,117 1,117 1,117 119 119 119
120,118 115 260-262 263, 264
EQUILIBRIUM POLYMERIZATION Conditions
References
The "most probable" distribution of Flory has been derived for condensation polymerization when all reactions are assumed to have the same probability, regardless of chain length, and whether or not exchange reactions occur: P r + P5 = P r + s - i + P t ,
4.2
1,117,118 1,117
Eq. C41
i
Here, P1- can be a byproduct such as water, or a polymer molecule whose size is smaller than r + s. The same distribution results when random scission occurs to infinitely long chains. See also (265) for multifunctional monomers. The theoretical equilibrium molecular weight distribution for the system
2,121 122
rM = Pr
4.3 4.4 4.5 4.6 4.7 4.8 4.9 4.10 4.11 4.12 4.13 4.14 4.15 4.16 4.17
depends upon the thermodynamic definition of the final product. If the change in Gibbs free energy of formation and polymerization is a linear function of molecular size r, then two cases can be considered: 4.2.1 The monomer is polymerized to a pure perfectly ordered state (solid); this gives the "most probable" distribution 4.2.2 The monomer is polymerized to a pure randomly ordered state (liquid); a completely different distribution results If the free-energy change upon disordering of the pure polymer is independent of the molecular weight distribution, a new distribution arises Thermodynamics of living equilibrium polymers Given an initial distribution, find the distribution as a function of time when chain ends react at random with all monomer units Initiation, propagation, and termination reactions are all equilibrium reactions; an initiator is required Initiation, propagation, and termination reactions are all equilibrium reactions; the system is self-initiating Equilibrium initiation and equilibrium propagation with a multifunctional initiator Equilibrium initiation and equilibrium propagation; no termination; nonequilibrium solution. The catalyst can form an active species with any polymer molecule, and the total number of moles of the system is kept constant (constant pressure and volume if all polymer molecules are ideal gases) Addition polymerization, instantaneous initiation, no transfer, no termination, monomer concentration held constant, active species in equilibrium with inactive species Addition polymerization, rate of initiation equals k\MC, no transfer, no termination, two active species in equilibrium, monomer concentration varies Addition polymerization, instantaneous initiation, no transfer, no termination, active species in equilibrium with inactive species, monomer concentration varies Poly(phosphate) equilibria Instantaneous initiation, polymerization and depolymerization, 1° termination Instantaneous initiation, polymerization and depolymerization, degradative transfer to monomer Copolymerization: bimolecular addition of one monomer, equilibrium addition of other monomer Copolymerization: equilibrium growth with monomer A or B adding to a chain with a terminal group of either A or B. Three cases: 2° reaction with initiator; 1° formation of active radical; 2° reaction with another monomer
Eq. C41 123 124 125 126 127 127 128,266 129 130 77 78 77 131 132 133 230 267
References page II - 356
TABLE 4. cont'd Set 4.18 4.19 4.20
Conditions Equilibrium copolymerization of two or more comonomers Polycondensation where groups have different equilibrium constants Equilibrium copolymerization initiated by polymer chains with active sites: average mol. wts, grafting ratio, grafting efficiency, grafting success, branching distribution, frequency of grafts
References 268 269,270 337
TABLE 5. NONLINEAR POLYMERIZATION SYSTEMS Set
Conditions
Vinyl polymerization; self-grafting 5.1.1 General case; molecular weight averages for grafted and ungrafted polymer 5.1.2 Constant rate of initiation, monomer concentration invariant, transfer to monomer and to polymer, termination by 2° disproportionation 5.1.3 Constant rate of initiation, monomer concentration varies, transfer to polymer, termination by 2° combination 5.1.4 Constant rate of initiation, monomer concentration can vary, transfer to monomer and to polymer, termination by 2° disproportionation and/or combination 5.1.5 Instantaneous initiation, monomer varies, either no transfer occurs or transfer to monomer, solvent, or polymer is allowed; termination by coupling and varies with chain length 5.2 Vinyl polymerization; grafting onto a performed polymer whose initial distribution is either (i) of constant length or (ii) a geometric distribution 5.3 Vinyl polymerization; all segments of the backbone chains have equal probability to be grafted 5.4 Vinyl polymerization; terminal double-bond polymerization, monomer concentration varies, transfer to monomer and to polymer, terminal double bond polymerization 5.4.1 Termination predominantly by transfer, constant rate of initiation; batch or continuous polymerization 5.4.2 Termination by disproportionation, constant rate of initiation, includes transfer to solvent 5.4.3 Termination by combination, constant rate of initiation, amount of short and long chain branching, transfer to a tertiary site 5.4.4 Termination by combination, initiator and monomer concentration vary, transfer to monomer and to polymer 5.4.5 Termination by combination, initiator and monomer concentration vary, transfer to monomer and to polymer, characterization following saponification and reacetylation 5.5 Vinyl polymerization; long-chain branching. 5.5.1 constant rate of initiation, monomer concentration invariant, transfer to monomer and to polymer, termination by 2° disproportionation 5.5.2 "Living polymer". Instantaneous initiation, P-hydride or p-methyl elimination to form a terminal double bond, transfer with agent to form a saturated end 5.6 Vinyl polymerizaton; "living" branched polymer; polyfunctional initiator RA/; rate of initiation equals rate of propagation, no transfer, no termination 5.7 Vinyl polymerization; Rp, in a diffusion controlled gelling system; termination by disproportionation or combination, no transfer 5.8 Vinyl polymerization; branching density as a function of conversion; branches formed by polymerization through a vinyl group (diene polymers) or by transfer-to-polymer reaction 5.8.1 Batch polymerization 5.8.2 Continuous polymerization 5.9 Vinyl polymerization 5.9.1 Branching density as a function of conversion of (1) long-chain branching, (2) short-chain branching (backbiting), (3) very short chain branching (radical migration) 5.9.2 Copolymerization with divinyl, no ring formation prior to gelation 5.9.3 Copolymerization with divinyl; ring formation permitted; Monte Carlo calculations for crosslinking density, weight fraction of gel; chain-length distribution between crosslinks 5.9.4 Circuits in a network, elastically active chains 5.10a Emulsion polymerization; branch density 5.10b Emulsion polymerization; Monte Carlo calculations; can account for desorption of oligomers, chain-length dependence of kinetic parameters, chain transfer to monomer and solvent, polymerization through terminal double bonds and long-chain branching 5.11 Cyclopolymerization: the concentration of pendent double bonds per molecule 5.12 Gelation condition in a system when cyclopolymerization also occurs; transfer to monomer reaction occurs. Molecular weight given 5.13 General theory of gelation for poly addition- and poly condensation-type polymers 5.14 The general distribution function for various molecules of type A reacting with various molecules of type B; A can only react with B 5.14.1 All functional groups have equal reactivity, independent of position within the molecule or the size of the molecule. Ring formation excluded
References
5.1
278 1,3,18 135 279 280 18 136 1,137-139 338 338,339 340 341 1,140 355 141 142 1,2 1,138 143 274,281 342,343 282,283 144,344 345 145-149 150 151 Section D 276
TABLE 5. cont'd Set
5.15
Conditions
References
5.14.2 Monomers of type RA/ (/can vary) can only react with monomers of type RBg (g can vary) where the various B's can have different reactivities. No ring formation 5.14.3 Monomers of type RA/ and RB g where/and g can vary, the reactivity of a given B can depend on whether or not an adjacent B on the same molecule has reacted. No ring formation 5.14.4 Monomers of type RA/ and RB g where/and g can vary; no ring formation; calculation of higher distribution moments Crosslinking or coupling of a polymer with a known primary distribution (see also Table 6) 5.15.1 General case. No ring formation prior to gelation 5.15.2 All primary chains have the same size; no ring formation prior to gelation
5.16
5.15.3 Primary chains of the Poisson type, (Eq. C48); no ring formation prior to gelation 5.15.4 Primary chains of the Schulz type, (Eq. C36); no ring formation prior to gelation 5.15.5 Primary chains of the "most probable" type; ring formation allowed prior to gelation 5.15.6 Formation of star-type polymers Homopolymer of ARB r _i. A can react only with B; the B's may have different reactivities. Formation of rings excluded prior to gelation 5.16.1 All B groups have the same reactivity 5.16.2 Let B groups have different reactivities 5.16.3 A controversy over the statistical approach
5.17 5.18
5.19
5.20 5.21 5.22
5.23
5.24
Copolymer of ARB/_i and AB; A can react only with B; formation of rings excluded prior to gelation Homopolymer of RA/; formation of rings excluded prior to gelation 5.18.1 All A's equally reactive
284 285 346 1,152-155, 286 1,2,152, 155-157 155,157 286 287 288 1,2,158,265, 289 1,159,160 161,162,163, 164 1,2,158 1,2,121,158, 165,166, 265,274, 277,281, 290-292 167,273,293
5.18.2 Reactivity of A depends on number of A's previously reacted Various copolymers 5.19.1 Copolymer of RA/ and AA; formation of rings excluded prior to gelation 1,2,165 5.19.2 Copolymer of RA/, AA, and BB; A can react only with B; formation of rings excluded prior to gelation; all branch points completely reacted. See set 5.16.3 for a controversy 1,168,169 5.19.3 A mixture of self-condensing monomers RjA g , RiA/j, etc., no ring formation 277,294,295 5.19.4 A stoichiometric mixture of RA/ and RB/ of the same functionality/, indistinguishable reactivity, no ring formation. Note that different authors get different equations for Mn and Mw 277 5.19.5 A stoichiometric mixture of RA/, RA g ,.. .and RBzn R B / . . . , / , g, h, i being different functionalities, indistinguishable reactivities, no ring formation 277,294 5.19.6 A copolymer of RA/ and BB; no ring formation prior to gelation 274,281,290 5.19.7 A copolymer of RA^, AA, and B'B" where B' has a different reaction rate from B"; no rings prior to gelation 293 5.19.8 Copolymer of RA/, AA, and BB where the A's in RA/ can have different rates of reaction 293 Polymers of RA/B g 5.20.1 Homopolymer of RA/B g ; A can only react with B; formation of rings excluded prior to gelation 170,265 5.20.2 A mixture of monomers RA/B g , where/, g = 0,1, 2 , . . . , stoichiometry not required 295 Branching without gelation; copolymer of RA/ and AB. A can react only with B 1,171 Gelation conditions; formation of rings excluded prior to gelation 5.22.1 AA reacting with B/C g . A can react with B and C, but with different velocities. B cannot react with C 1,172 5.22.2 AA, BB, and C reacting with DDE and FF; A, B, and C individually can react with D, E, and F, but with different velocities 1,172 5.22.3 AAB, RC4, and GC reacting with DE and F. DE is an anhydride or similar material. D must react first and may have a different velocity from E. A, B, C. and G may react with different velocities 1,172 5.22.4 AB and CD reacting with EEF and GG. AB and CD are anhydrides or similar materials, where A must react before B and C must react before D. A, B, C, and D may react with different velocities 1,172 5.22.5 AA and BC reacting with DDE and FG. BC is an anhydride, B reacting first, and FG is like an unsymmetrical glycol 1,172 Ring formation in linear polymers 5.23.1 Homopolymer of type AA 1,173,174 5.23.2 Homopolymer of type AA. Formation of catenanes 296 5.23.3 Homopolymer of type AB 1,173,175 5.23.4 Copolymer of type AABB 1,173,176 5.23.5 Distribution for chain fraction 1,2 5.23.6 Copolymer of AA with BC. BC can be an anhydride; within a given molecule, B must react before C; A single cyclic oligomer is permitted to form 297 5.23.7 Ring-chain equilibrium constant, Rp of rings, cut-off point of monomer cone below which only cyclics formed 347 Crosslinking of a polymer with a known distribution; rings are permitted prior to gelation 153
References page II - 356
TABLE 5. cont'd Set
Conditions
References
5.25 5.26
Gelation conditions for RA/ when rings are permitted prior to gelation Homopolymer of RA/. Ring formation permitted prior to gelation
5.27 5.28 5.29 5.30
Copolymer of RA/ and BB when rings are permitted prior to gelation Gelation condition for RA/, AA, and BB when rings are permitted prior to gelation Monte Carlo calculations on small amounts of crosslinking Monte Carlo calculations for RA3, the reactivity of an A group depends on the number of previously reacted groups on that monomer, no ring formation prior to gelation Monte Carlo calculations for vinyl and divinyl copolymerization Grafting of reactive polymers of the type AA, AAB, BB, and BBA where rings can form prior to gelation; M w and the gel point Star type molecules prepared by anionic polymerization and different precursors (see also 5.19.1, 5.21 and 5.27)
5.31 5.32 5.33
1,177 1,178,179, 298 180 1,181 299 275 300 348 349
TABLE 6. DEGRADATION OF POLYMERS - MAY BE ACCOMPANIED BY CROSSLINKING References Set
Initiation
Mass
Initial distribution
Transfer
Termination
Rd
Pr
Mn, M^
6.1. RANDOM SCISSION ONLY 6.1.1 6.1.2
Proportional to time Const Proportional to time Const
6.1.3
Random at all bonds Random at chain ends Random at all chains Random Random Random
6.1.4 6.1.5 6.1.6 6.1.7 6.1.8 6.1.9 6.1.10 6.1.11 6.1.12
Random Random at normal and weak bonds Gaussian about the midpoint Central
None None
None None
-
183-186 183-187
182-184 183,184,188
Const
Arbitrary Infinite or uniform Uniform
None
None
-
189
189
Const
Uniform
None
None
-
190
Const
Uniform
None
None
-
191
191
Const Const Const
Rectangular Flory Schulz
None None None
None None None
-
184 184,188 187,301
Const Const
Poisson Uniform
None None
None None
-
184,187 184,187 184,187, 301 187 -
Const
Schulz
None
None
301
301
Const
Schulz
None
None
301
301
192
6.2. UNZIPPING-TYPE REACTION 6.2.1 6.2.2 6.2.3 6.2.4 6.2.5 6.2.6 6.2.7 6.2.8 6.2.9 6.2.10 6.2.11 6.2.12
1° end 1° end 1° end 1° end 1° end 1° end 1° end; various rates of initiation Random scission only Random scission only 1° end and random scission
Varies Varies Varies Varies Varies Varies Varies; monomer radicals may evaporate Varies
Uniform Uniform Schulz Schulz Schulz (k = 2) Schulz (k = 2) Flory
None Polymer None None None None None
1° 2° Disprop 1° 2° Disprop 1° 2° Comb 1° or 2° Disprop
193 194 193 195 196 196 197
-
193 194 193 195 196 196 -
Uniform
Polymer
2° Disprop
194
-
194
Varies
Schulz
None
2° Disprop
198
-
198
Varies
Unspecified
None
1° and 2° Process
1° end and random scission 1° end and random scission
Varies
Flory
Polymer
Varies
Flory
Polymer
1° and 2° Disprop 2° Comb
199 (all molecules must terminate) 200 (some molecules can completely disappear) 201 201 201
-
201
TABLE 6. cont'd References Initial Distribution
Set
Initiation
Mass
6.2.13
1° end and random scission
Varies
6.2.14
1° end and random scission
Varies
Uniform
Polymer
6.2.15
1° end and random scission
Polymer
6.2.16
1° end and random scission
6.2.17
Unzipping reactions
Varies; units Uniform other than monomer may evaporate Varies; units Flory other than monomer may evaporate Varies Various
Flory
Transfer Polymer
Termination
Ra
Pr
Mn, M^
1° and 2° Process; comparison of random scission, weak link, and transfer theories. Comparison of various term mechanisms 2° Disprop
202 203
-
203
204
-
-
205
-
205
polymer
1° and 2° Disprop or 2° comb
206
206
206
Various
Various, a review
207
153 208 302 303 209
153 208 282 302 303 210 209
153 208 302
211 208
211 208
211 28
211
211
211
29
-
29
-
-
350
153
153
153
182
182
182
182,212, 213 -
182
182
182
-
153
153
153
6.3. RANDOM SCISSION AND CROSSLINKING 6.3.1
Proportional to time
Const
Arbitrary
None
Unspecified term, with and without ring formation
6.3.2
Varies with depth of penetration
Const
Flory
None
6.3.3
Proportional to time
Const
Arbitrary
None
6.3.4
Proportional to time Proportional to time
Const
Arbitrary
None
Const
Schulz
None
Const
Various
Unspecified
1° and 2° Disprop without ring formation End-linking (grafting) rather than crosslinking; without ring formation End-linking; with ring formation Unspecified term, without ring formation Various initial distributions
6.3.5 6.3.6
Proportional to time
210
6.4. CROSS LINKING ONLY 6.4.1 6.4.2 6.4.3 6.4.4 6.4.5
Proportional time Proportional time Proportional time Proportional time Proportional time
to
Const
Arbitrary
None
to
Const
Uniform
None
to
Const
Schulz
None
to
Const
Beasley (140)
None
to
Const
Arbitrary
None
Ring formation prohibited Ring formation prohibited Ring formation prohibited Ring formation prohibited Ring formation permitted
6.5. RANDOM SCISSION FOLLOWED BY UNZIPPING 6.5.1 6.5.2
Random macromolecular fragmentation to form defective groups which subsequently initiates depolymerization Random macromolecular fragmentation to form defective groups which subsequently initiates depolymerization with bimolecular kinetic chain termination
351 352
References page 11-356
TABLE 7. INFLUENCE OF REACTOR CONDITIONS AND DESIGN ON THE MOLECULAR WEIGHT DISTRIBUTION Set 7.1 7.2
7.3 7.4 7.5 7.6a 7.6b 7.7 7.8 7.9 7.10 7.11 7.12 7.13 7.14 7.15 7.16 7.17
Conditions Comparison of 1° term, 2° term with monomer, 2° disprop, 2° comb, and no term for 1° and 2° self-initiation and initiation by light in a CFSTR°: Rv, Pr and Mn are given Emulsion polymerization 7.2.1 Emulsion polymerization in a CFSTR. Instantaneous 2° termination 7.2.2 Emulsion polymerization in isothermal BR a ; 1° init, termination with initiator, four stages of polymerization Effect of inadequate stirring in a CFSTR; comparison with BR and normal CFSTR. Term, by 2° or no term. Rp, P r M n ' s Control of MWD a by use of temperature variation; term by 2° disprop or 2° comb. M n 's Effect of expanding drop of monomer in a catalyst solution on MWD of "living" polymers Effect of inadequate mixing by a laminar shear model on MWD of "living" polymers Effect of different flow lines spending different times in the reactor on the MWD of "living" polymers; the bimodal MWD changes with reactor length Effect of varying rate of addition of initiator and/or monomer, transfer agent, or terminator, in a BR, neglecting change in volume Effect of varying the rate of addition of an instantaneous initiator on MWD of "living" polymers Effect of back mixing on MWD of "living" polymers prepared in BR, semi-BR, and CFSTR See also Table 3, set 3.6: Further polymerization of polymers with an initial geometric distribution Linear condensation of a multifunctional monomer in a BR "Living" polymer, inst. initiation, no transfer, no termination in a TR a , monomer varies Effect of mixing in a BR Condensation polymerization when monomer is R times more reactive with monomer or with polymer molecules, CFSTR, and references to BRs Effect of recycling a portion of a TR; chain-stopper control Production of monodisperse particles Reversible polymerization with multifunctional monomers. Comparison of MWD from CFSTR with BR
References
214 215 304 216 217 218 219 353 220 103,221 222 305 306,307 308 309,310 311 312 354
a
CFSTR: Continuous-flow, stirred tank reactor; BR: batch reactor; TR: tube reactor; MWD: molecular weight distribution.
C. SOME DISTRIBUTION FUNCTIONS AND THEIR PROPERTIES
The frequency function, F(r), is the fraction of molecules of size r. Furthermore, F(r) is normalized
Thus, by the definitions of F(r) and W(r) (C5) The weight-average degree of polymerization is
(Cl) (C6) The weight fraction of molecules of size r is
(C2)
Averages of any distribution are defined by
The z and z + 1 averages are defined by Eq. (C3) with / set equal to 3 and 4. There is no need to restrict averages of a distribution to positive integers - any useful average can be defined; such as the (—5/2) average. If the intrinsic viscosity of a polymer is related to the degree of polymerization through the equation (C7) where rv is the viscosity-average degree of polymerization, it is related to the frequency function by
(C3)
The number-average degree of polymerization is defined by
(C4)
(C8) As a approaches unity, rv approaches r w . In principle, a distribution function can be determined if sufficient averages of the distribution can be determined. In practice, only the number, weight, and perhaps z averages can be found, which are insufficient to define any distribution without making further assumptions.
The degree of polymerization is a useful concept as long as one is describing polymers made with a single monomer or with monomers of equal molecular weight. When considering copolymers, one must work with the actual molecular weight of the reacted unit. This is done in condensation polymerization. The molecular weight distribution of addition copolymers is not included here because of the extreme complexity of these systems. When performing the summation of a distribution equation to find an average of the distribution, use is frequently made of the following sums:
Values of F(r) and J^ F(r) Ar are found in many statistical tables (223). 2. Logarithmic Normal Distribution Function Under the assumption that the weight distribution of the logarithm of molecular size is normally distributed, we can replace r in the normal distribution function by In r and f by lnrm (C15)
(C9) where
(C16)
or in the alternate form (C17) n is an integer where (C18)
and (C19)
Here r m is the median value of the distribution, that is, onehalf of the values of r are less than r m . (C20) (C21) (C22)
1. Normal Distribution Function (Gaussian Distribution)
(C23) (ClO) (CU)
(C24) Note that (C25)
(C12)
(C26)
(C13)
The logarithmic normal distribution sometimes is given in a "generalized" form (224)
(C14)
(C27) References page II - 356
but Honig (225) has shown that (C28) Thus, the normalized Lansing-Kramer function (s = 0) (226) is identical to the normalized Wesslau function (s = - l ) ( 2 2 7 ) . The generalized logarithmic normal distribution is skewed to large values of r, but Kotliar (237, 238) shows that this distribution is not a good representation of a polymer after either low- or high-molecular weight material is removed or degradation has occurred.
(b) The Weibull (231) or Tung (232) distribution is obtained by setting m = 1 + k and k > 0. This distribution is usually seen in the form
(C40)
Kotliar (233) shows that evaluation of y and k by the Tung method can lead to erroneous values of fw/fn. (c) The Flory distribution, as noted above, occurs when Jc = m = 1, provided that In/? can be replaced by - ( I — /?), i.e. p & 1. The Flory distribution is also written as:
3. Generalized Exponential Distribution (1,228)
(C41) (C29)
(C42)
(C30)
(C43)
(C31)
(C44)
(C32) (C33)
and with the approximation In p = p — 1
(C34)
(C45)
and (C35) where a is defined by equation (C7). The variance of a distribution
For high molecular weights p « 1, hence
4. Poisson Distribution Hence, the preferred measure distribution breadth is fw/rn. (a) The distribution function (229) is obtained by setting m = This distribution is equivalent distribution
of the molecular weight
(C37) The distribution reduces to the "most probable" distribution where k = 1. The cumulative number or weight fraction of the Schulz distribution may be computed from
(C38)
(C39)
(CAl)
(C48) (C49)
of Schulz (9) and Zimm 1 and requiring that k > 0. to the Pearson Type III
(C36)
(C46)
(C50) (C51) D. MOLECULAR WEIGHT DISTRIBUTION IN CONDENSATION POLYMERS: THE STOCKMAYER DISTRIBUTION FUNCTION Stockmayer (234) has presented a generalized distribution formula for a variety of monomers containing end groups of type A which can only react with a variety of monomers containing end groups of type B. In the original mixture there are A \, A 2, A 3 , . . . , A,-,... moles of reactants bearing respectively,/1,/2,/3,...,/,-,... functional groups of type A each, together with Bi, B2, • • •, Bj,... moles of reactants of functionalities gi, g2, • • -gj,- • • in groups of type B. all functional groups of a given type are equally reactive and ring formation does not occur appreciably; which obviously is not true near the gel point. The system reacts until a fraction a of the A groups and a fraction /3 of the B groups
have reacted. Further
If each species / has an effective molecular weight Af1-, which is lower than the original molecular weight by the term Wo / ; / 2 , where Wo is the molecular weight of the byproduct, then
Now N{mn, Hj) represents the number of moles of that species which consists of mi, ra2, . . . , m f , . . . monomer units of the A type combined with n 1, ^ 2 , . . . , rij units of the B type.
(D5)
The number of molecules of the end of the reaction is,
(Dl) where
neglecting byproduct, (D6)
The number-average molecular weight is (D2) (D7) The weight-average molecular weight is
An example will illustrate the use of Eq. (Dl). Suppose we have the monomers acetic acid (CH3COOH, A1, /1 = 1) and adipic acid (HOOC(CH 2 ) 4 COOH, A 2 , /2 = 2) reacting with ethylene glycol (HOCH 2 CH 2 OH, B i , gi = 2)
and
glycerol
(HOCH2CHOHCH2OH,
B 2 , g2 = 3) (all hydroxyl groups of the glycerol are considered equally reactive). What is the number of molecules which contain exactly 1 acetic acid unit, 4 adipic acid units, 3 glycol units, and 2 glycerol units? It is W{1,4,3,2} and
(D8) where
(D3) (D9)
where
(D4)
Simpler expressions for M n and M w are given by Ziegel et al. (235) for the case when only bifunctional B monomers are present. The gel point is (DlO) Extensive computations of N{mi,rij} for the Z1 = IJ2 = 2 , / 4 , and g2 = 2 have appeared (236).
case
References page 11-356
E. REFERENCES • 1. L. H. Peebles, Jr., "Molecular Weight Distributions in Polymers", Interscience, New York, 1971. 2. P. J. Flory, "Principles of Polymer Chemistry", Cornell University Press, Ithaca, N.Y, 1953. 3. C. H. Bamford, W. G. Barb, A. D. Jenkins, P F. Onyon, "The Kinetics of Vinyl Polymerization by Radical Mechanisms", Academic Press, New York, 1958. 4. G. Odian, "Principles of Polymerization", McGraw-Hill, New York, 1970; 2nd ed., Wiley-Inter science, New York, 1981. 5. F. W. Billmeyer, Jr., "Textbook of Polymer Science", 2nd ed., Interscience, New York, 1971; 3rd ed., 1984. 6. L. Kuechler, "Polymerisationskinetik", Springer, Berlin, 1951. 7. Kh. S. Bagdasarian, "Theory of Free Radical Polymerization", Israel Program for Scientific Translations, Jerusalem, 1968. 8. D. C. Chappelear, R. H. M. Simon. "Addition and Condensation Polymerization Processes", in: N. Platzer (Ed.), Adv. in Chem., 91, Am. Chem. Soc, Washington, DC, 1969, p. 1. 9. G. V. Schulz, Z. Physik, Chem. B, 43, 25 (1939). 10. G. M. Burnett, L. D. Loan, Trans. Faraday Soc, 51, 214 (1955). 11. L. H. Peebles, Jr., J. T. Clarke, W. H. Stockmayer, J. Am. Chem. Soc, 82, 4780 (1960). 12. J. L. Kice, J. Am. Chem. Soc, 76, 6274 (1954). 13. L. H. Peebles, Jr., J. Appl. Polym. ScL, 17, 113 (1973). 14. S. Saccubai, M. Santappa, Makromol. Chem., 117, 50 (1968). 15. W. A. Pryor, J. H. Coco, Macromolecules, 3, 300 (1970). 16. L. S. Bresler, V. A. Grechanovsky, A. Muzsay, I. Ya. Poddubnyi, Makromol. Chem., 133, 111 (1970). 17. C. H. Bamford, A. D. Jenkins, R. Johnson, Trans. Faraday Soc, 58, 1212 (1962). 18. C. H. Bamford, H. Tompa, Trans. Faraday Soc, 50, 1097 (1954). 19. M. Litt, J. Polym. Sci. A-2, 8, 2105 (1970). 20. M. Litt, F. R. Eirich, J. Polym. Sci., 45, 379 (1960). 21. P. H. Plesch, Ed., "The Chemistry of Cationic Polymerization", MacMillan Co., New York, 1963. 22. A. A. Korotkov, S. R Mitsengendler, V. N. Krasulina, J. Polym. Sci., 53, 217 (1961). 23. D. O. Jordan, A. R. Mathieson, J. Chem. Soc, 1952, 2358. (Note: equation 13 et seq. contain errors owing to an integration error.) 24. H. E. Grethlein, Ind. Eng. Chem. Fund., 8, 206 (1969). 25. J. C. W. Chien, J. Polym. Sci. A, 1, 1839 (1963). 26. J. C. W. Chien, J. Am. Chem. Soc, 81, 86 (1959). 27. S. Katz, G. M. Saidel, Am. Inst. Chem. Eng. J., 13, 319 (1967). 28. C. H. Bamford, Polymer, 6, 63 (1965). 29. M. Inokuti, J. Chem. Phys., 38, 2999 (1963). 30. A. V. Tobolsky, J. Am. Chem. Soc, 80, 5927 (1958); A. V. Tobolsky, C. E. Rogers, R. D. Brinkman, ibid., 82, 1277 (1960).
31. C B . Wooster, Macromolecules, 1, 324 (1968). 32. K. F. O'Driscoll, R. Knorr, Macromolecules, 1, 367 1968). 33. J. C. Bevington, "Radical Polymerization", Academic Press, New York, 1961. 34. W. H. Ray, T. L. Douglas, E. W. Goodsolve, Macromolecules, 4, 166 (1971). 35. W. H. Stockmayer, J. Chem. Phys., 13, 199 (1945). 36. K. Ito, J. Polym. Sci. A-2, 7, 241 (1969). 37. S. W. Benson, A. M. North, J. Am. Chem. Soc, 84, 935 (1962). 38. S. Okamura, T. Manabe, Polymer, 2, 83 (1961). 39. K. Venkatarao, M. Santappa, J. Polym. Sci. A-I, 8, 1785, 3429 (1970). 40. S. Kohjiya, Y. Imanishi, T Higashimura, J. Polym. Sci. A-I, 9, 747 (1971). 41. K. R O'Driscoll, S. A. McArdle, J. Polym. Sci., 40, 557 (1959). 42. K. Ito, J. Polym. Sci., A-I, 7, 827, 2995 (1969). 43. C. H. Bamford, A. D. Jenkins, R. Johnson, Trans. Faraday Soc, 55, 1451 (1959). 44. K. Ito, J. Polym. Sci. A-I, 7, 2247, 3387 (1969); 8, 1823 (1970); 10, 1481 (1972); K. Ito, T. Matsuda, J. Appl. Polym. Sci., 14, 311 (1970). 45. T. Nagabhushanam, M. Santappa, J. Polym. Sci. A-I, 10, 1511 (1972). 46. J. F. Westlake, R. Y. Hunag, J. Polym. Sci. A-I, 10, 1429, 1442 (1972). 47. M. A. Markevich, Ye. V. Kochetov, N. S. Yenikolopyan, Vysokomol. Soedin. A, 13,1013 (1971); Polym. Sci., USSR, 13, 1153 (1971). 48. R. N. Haward, J. Polym. Sci., 4, 273 (1949). 49. W. V. Smith, R. H. Ewart, J. Chem. Phys., 16, 592 (1948). 50. W. H. Stockmayer, J. Polym. Sci., 24, 314 (1957). 51. J. T. O'Toole, J. Appl. Polym. Sci., 9, 1291 (1965). 52. A. G. Parts, D. E. Moore, J. G. Watterson, Makromol. Chem., 89, 156 (1965). 53. J. L. Gardon, J. Polym. Sci. A-I, 6, 623 (1968). 54. L. M. Pisman, S. I. Kuchanov, Polym. Sci., USSR, 13, 1187 (1971); Vysokomol. Soedin. A, 13, 1055 (1971). 55. J. L. Gardon, J. Polym. Sci. A-I, 6, 665 (1968). 56. J. L. Gardon, J. Polym. Sci. A-I, 9, 2763 (1971). 57. P. Harriot, J. Polym. Sci. A-I, 9, 1153 (1971). 58. M. Litt, R. Patsiga, V. Stannett, J. Polym. Sci. A-I, 8, 3607 (1970). 59. S. Katz, R. Shinnar, G. M. Saidel, "Addition and Condensation Polymerization Processes", N. Platzer, Ed., Adv. in Chem. Ser., 91, Am. Chem. Soc, Washington, DC, 1969, p. 145. 60. G. M. Saidel, S. Katz, J. Polym. Sci. C, 149 (1969). 61. J. G. Watterson, J. G. Parts, Markromol. Chem., 146, 1 (1971). 62. A. H. Abdeh-Alim, A. E. Hamielec, J. Appl. Polym. Sci., 16, 783 (1972). 63. M, Iguchi, J. Polym. Sci. A-I, 8, 1013 (1970).
64. O. G. Lewis, R, M. King, Jr., "Addition and Condensation Polymerization Processes", N. Platzer, Ed., in Adv. in Chem. Ser. 91, Am. Chem. Soc, Washington, DC, 1969, p. 25. 65. R. Wessling, I. R. Harrion, J. Polym. Sci. A-I, 9, 3471 (1971). 66. R D. Barlett, H. Kwart, J. Am. Chem. Soc, 72,1051 (1950). 67. Th. Deleanu, M. Dimonie, J. Polym. Sci. A-I, 8, 95 (1970). 68. I. Kar, B. M. Mandal, S. R. Palit, Makromol. Chem., 127, 196 (1969). 69. W. H. Atkinson, C. H. Bamford, G. C. Eastmond, Trans. Faraday Soc, 66, 1446 (1970). 70. A. D. Jenkins, Trans. Faraday Soc, 54, 1885 (1958). 71. A. D. Jenkins, Trans. Faraday Soc, 54, 1895 (1958). 72. J. P. Bianchi, F. P. Price, B. H. Zimm, J. Polym. Sci., 25, 27 (1957). 73. F. F. Williams, K. Hayashi, K. Ueno, K. Hayashi, S. Okamura, Trans. Faraday Soc, 63, 1501 (1967). 74. P. W. Allen, F. M. Merrett, J. Scanlan, Trans. Faraday Soc, 51, 95 (1955). 75. C. H. Bamford, A. D. Jenkins, R. Johnson, Proc Roy. Soc, (London) A239, 214 (1957). 76. B. D. Coleman, T. G. Fox, J. Am. Chem. Soc, 85, 1241 (1963). 77. M. Szwarc, J. J. Hermans, Polym. Lett. B, 2, 815 (1964). 78. R. V. Figini, Makromol. Chem., 71, 193 (1964). 79. R. V. Figini, Makromol. Chem., 107, 170 (1967). 80. R. V. Figini, Makromol. Chem., 88, 271 (1965). 81. A. Miyake, W. H. Stockmayer, Makromol. Chem., 88, 90 (1965). 82. C. R. Huang, H. H. Wang, J. Polym. Sci. A-I, 10, 791 (1972). 83. V. S. Nanda, S. C. Jain, Eur. Polym. J., 6, 1517 (1970). 84. J. Leonard, Macromolecules, 2, 661 (1969). 85. H. J. R. Maget, J. Polym. Sci. A-2, 1281 (1964). 86. I. Mita, J. Macromol. Sci. Chem. A-5, 883 (1971). 87. W. T. Kyner, J. R. M. Radok, M. Wales. J. Chem. Phys., 30, 363 (1959). 88. V. S. Nanda, Trans. Faraday Soc, 60, 949 (1964). 89. L. H. Peebles, Jr., Polym. Lett., 7,75 (1969). See also Ref. 91. 90. S. C. Jain, V. S. Nanda, Polym. Lett., 8, 843 (1970). 91. L. H. Peebles, Jr., J. Polym. Sci. A-2, 8, 1235 (1970) (Note: Eq. 13 of Ref. 89 should be written x = (r - r)/rl/2\ the figures are correct.) 92. V. S. Nanda, R. K. Jain, Trans. Faraday Soc, 64, 1022 (1968). 93. J. C. W. Chien, J. Polym. Sci. A, 1, 425 (1963). 94. S. Penzek, P. Kubisa, Makromol. Chem., 130, 186 (1969). 95. V. I. Irzhak, N. S. Enikolopyan, Dokl. Akad. Nauk SSSR 185, 862 (1969); Dokl. Phys. Chem., 185, 226 (1969). 96. W. H. Ray, Macromolecules, 4, 162 (1971). 97. W. R. Schmeal, J. R. Street, Am. Inst. Chem. Eng. J., 17, 1188 (1971). 98. D. Singh, R. P. Merrill, Macromolecules, 4, 599 (1971). 99. M. Gordon, R. J. Roe, Polymer, 2, 41 (1961).
100. M. I. Mustafayev, K. V. Aliev, V. A. Kabanov, Vysokomol. Soedin. A, 12, 855 (1970); Polym. Sci., USSR, 12, 968 (1970). 101. P. J. Flory, J. Am. Chem. Soc, 62, 1561 (1940). 102. L. Gold, J. Chem. Phys., 28, 91 (1958). 103. M. Litt, D. H. Richards, Polym. Lett., 5, 867 (1967). 104. L. F. Beste, H. K. Hall, Jr., J. Phys. Chem., 68, 269 (1964). 105. H. N. Friedlander, J. Polym. Sci. A, 2, 3885 (1964). 106. B. D. Coleman, F. Gornick, G. Weiss, J. Chem. Phys., 39, 3233 (1963). 107. T. A. Orofino, F. Wenger, J. Chem. Phys., 35, 532 (1961). 108. R. Chiang, J. J. Hermans, J. Polym. Sci. A-1,4, 2843 (1966). 109. A. Guyot, J. Chim. Phys., 548, 1964. 110. P. J. Flory, J. Am. Chem. Soc, 58, 1877 (1936). 111. L. C. Case, J. Polym. Sci., 29, 455 (1958). 112. G. Challa, Makromol. Chem., 38, 105 (1960). 113. V. S. Nanda, S. C. Jain, J. Chem. Phys., 49, 1318 (1968). 114. A. Ninagawa, I. Ijichi, M. Imoto, Makromol. Chem., 107, 196 (1967). 115. L. C. Case, J. Polym. Sci., 48, 27 (1960). 116. J. J. Hermans, Makromol. Chem., 87, 21 (1965). 117. L. C. Case, J. Polym. Sci., 37, 147 (1959). 118. C. H. Bamford, A. D. Jenkins, Trans. Faraday Soc, 56, 907 (1960). 119. L. C. Case, J. Polym. Sci., 39, 175 (1959). 120. L. C. Case, J. Polym. Sci., 39, 183 (1959). 121. P. J. Flory, Chem. Rev., 39, 137 (1946). 122. W. Kuhn, Chem. Ber., 63, 1503 (1930). 123. J. L. Lundberg, J. Polym. Sci. A, 2, 1121 (1964). 124. F. E. Harries, J. Polym. Sci., 18, 351 (1955). 125. M. Szwarc, Adv. Polym. Sci., 4, 457 (1967). 126. J. J. Hermans, J. Polym. Sci. C, 12, 345 (1966). 127. A. V. Tobolsky, J. Polym. Sci., 25,220 (1957); J. Polym. Sci., 31, 126 (1958); A. V. Tobolsky, A. Eisenberg, J. Am. Chem. Soc, 81, 2302 (1959); J. Am. Chem. Soc, 82, 289 (1960). 128. M. E. Baur, A. Eisenberg, J. Chem. Phys., 42, 85 (1965). 129. F. P. Adams, J. B. Carmichael, R. J. Zeman, J. Polym. Sci. A-I, 5, 741 (1967). 130. C. M. Fonatana in: The Chemistry of Cationic Polymerization, P. H. Plesch (Ed.), Macmillan, New York, 1963. 131. J. R. Van Wazer, "Phosphorus and Its Compounds", Vol. 1, Interscience Publishers, Inc., New York, 1958. 132. T. Saegusa, T. Shiota, S. Matsumoto, H. Fujii, Macromolecules, 5, 34 (1972). 133. R. Z. Greenley, J. C. Stauffer, J. E. Kurz, Macromolecules, 2, 561 (1969). 134. V. S. Nanda, S. C. Jain, J. Polym. Sci. A-I, 8, 1871 (1970). 135. G. M Saidel, S. Katz, J. Polym. Sci. A-2, 6, 1149 (1968). 136. L. H. Tung. T. M. Wiley, Polym. Preprints, 13, 1060 (1972). 137. W. W. Graessley. H. Mittelhauser, R. Maramba, Markromol. Chem., 86, 129 (1965). 138. W. W. Graessley, Am. Inst. Chem. Eng.-Inst. Chem. Eng. Joint Meeting, London, June, 1965, 3, 16. 139. O. Saito, K. Najasubramanian, W. W. Graessley, J Polym. Sci. A-2, 7, 1937 (1969).
140. 141. 142. 143. 144. 145. 146. 147. 148. 149. 150. 151. 152. 153. 154. 155. 156. 157. 158. 159. 160. 161. 162. 163. 164. 165. 166. 167. 168. 169. 170. 171. 172. 173. 174. 175. 176. 177. 178. 179.
J. K. Beasley, J. Am. Chem. Soc, 75, 6123 (1953). K. Fukii, T. Yamade, J. Polym. Sci. A, 2, 3743 (1964). M. Gordon, R. J. Roe, J. Polym. Sci., 21, 57 (1956). A. Rigo, G. Palma, G. Talamini, Markromol. Chem., 153, 219 (1972). L. E. Dannals. J. Polym. Sci. A-I, 8, 2989 (1970). M. Gordon, J. Chem. Phys., 22, 610 (1954). C. Aso, T. Nawata, H. Kamao, Makromol. Chem., 68, 1 (1963). Y. Minoura, M. Mitoh, J. Polym. Sci. A, 3, 2149 (1965). G. B. Butler, M. A. Raymond, J. Polym. Sci. A, 3, 3413 (1965). L. Trassarelli, M. Guaita, T. Macromol. Sci.-Chem. 1, 471 (1966). M. Gordon, R. J. Roe, J. Polym. Sci., 21, 75 (1956). M. Gordon, Proc. Roy. Soc. (London), A268, 240 (1962). W. H. Stockmayer, J. Chem. Phys., 12, 125 (1944). O. Saito, J. Phys. Soc. (Japan), 13, 198 (1958). A. A. Miler, J. Polym. Sci., 42, 441 (1960). G. R. Dobson, M. Gordon, J. Chem. Phys., 43, 705 (1965). P. J. Flory, J. Am. Chem. Soc, 63, 3096 (1941). A. Amemiya, J. Phys. Soc. (Japan), 23, 1394, 1402 (1967). P. J. Flory, J. Am. Chem. Soc, 74, 2718 (1952). E. S. Allen, J. Polym. Sci., 21, 349 (1956). S. Erlander, D. French, J. Polym. Sci., 20, 7 (1956). M. Gordon, M. Judd, Nature, 234, 96 (1971). C. R. Masson, I. B. Smith, S. G. Whiteway, Nature, 234, 97 (1971). C. R. Masson, I. B. Smith, S. G. Whiteway, Can. J. Chem., 48, 1456 (1970). S. G. Whiteway, I. B. Smith, C. R. Masson, Can. J. Chem., 48, 33 (1970). P. J. Flory, J. Am. Chem. Soc, 63, 3091 (1941). W. H. Stockmayer, J. Chem. Phys., 11, 45 (1943). M. Gordon, G. R. Scantlebury, Trans. Faraday Soc, 60, 604 (1964). A. R. Shultz, J. Polym. Sci. A, 3, 4211 (1965). H. L. Berger, A. R. Shultz, J. Polym. Sci. A, 3, 4227 (1965). L. M. Pismen, S. I. Kuchanov, Polym. Sci., USSR 13, 890 (1971); Vysokomol. Soedin. A, 13, 791 (1971). J. R. Schaefgen, R J. Flory, J. Am. Chem. Soc, 70, 2709 (1948). L. C. Case, J. Polym. Sci., 26, 333 (1957). H. Jacobson, W. H. Stockmayer, J. Chem. Phys., 18, 1600 (1950). R J. Flory, J. A. Semlyen, J. Am. Chem. Soc, 88, 3209 (1966). H. Morawetz, N. Goodman, Macromolecules, 3, 699 (1970). M. Gordon, W. B. Temple, Makromol. Chem., 152, 277 (1972). F. E. Harris, J. Chem. Phys., 23, 1518 (1955). C. A. J. Hoeve, J. Polym. Sci., 21, 11 (1956). M. Gordon, G. R. Scantlebury, J. Polym. Sci. C, 16, 3933 (1968).
180. M. Gordon, G. R. Scantlebury, J. Chem. Soc. B, 1967, 1 (1967). 181. R. W. KiIb, J. Phys. Chem., 62, 969 (1958). 182. A. Charlesby, S. H. Pinner, Proc. Roy. Soc (London), A, 249, 367 (1959). 183. D. Mejzler, J. Schmorak, M. Lewin, J. Polym. Sci., 46, 289 (1960). 184. V. S. Nanda, R. K. Pathria, Proc. Roy. Soc. (London), A, 270, 14 (1962). 185. L. Monnerie, J. Neel, J. Chim. Phys., 62, 53 (1965). 186. S. W. Lee, J. Polym. Sci. A-2, 7, 77 (1969). 187. L. Monnerie, J. Neel, J. Chim. Phys., 62, 510 (1965). 188. J. Dump. J. Chim. Phys., 51, 64 (1954). 189. R. Simha, J. Appl. Phys., 12, 569 (1941). 190. B. J. Coyne, J. Polym. Sci. A-2, 5, 633 (1967). 191. E. W. Montroll, R. Simha, J. Chem. Phys., 8, 721 (1940). 192. J. R. MacCallum, Markromol. Chem., 83, 129 (1965). 193. M. Gordon, L. R. Shenton, J. Polym. Sci., 38, 157 (1959). 194. R. Simba, L. A. Wall, J. Phys. Chem., 56, 707 (1952). 195. R. H. Boyd, T. P. Lin, J. Chem. Phys., 45, 773 (1966). 196. M. Gordon, L. R. Shenton, J. Polym. Sci., 38, 179 (1959). 197. M. Gordon, J. Phys. Chem., 64, 19 (1960). 198. R. H. Boyd, T. P. Lin, J. Chem. Phys., 45, 778 (1966). 199. G. G. Cameron, Makromol. Chem., 100, 225 (1967). 200. G. G. Cameron, G. P. Kerr, Makromol. Chem., 115, 268 (1968). 201. R. H. Boyd, J. Chem. Phys., 31, 321 (1959). 202. M. Gordon, Trans. Faraday Soc, 53, 1662 (1957). 203. R. Simha, Trans. Faraday Soc, 54, 1345 (1958). 204. L. A. Wall, S. Strauss, Polym. Preprints, 10, 1472 (1969). 205. L. A. Walls, S. Strauss, J. H. Flynn, D. Mclntyre, J. Phys. Chem., 70, 53 (1966). 206. R. H. Boyd, J. Polym. Sci. A-I, 5, 1573 (1967). 207. M. Gordon, Soc Chem. Ind. (London) Monograph, 13, 163 (1961). 208. O. Saito, J. Phys. Soc. (Japan), 13, 1465 (1958). 209. A. R. Shultz, J. Appl. Polym. Sci., 10, 353 (1966). 210. A. R. Shultz, J. Chem. Phys., 29,200 (1958); J. Phys. Chem., 65, 967 (1961). 211. O. Satio, J. Phys. Soc. (Japan), 13, 1451 (1958). 212. T. Kimura, J. Phys. Soc. (Japan), 17, 1884 (1962). See also ref. 213. 213. D. I. C. Kells, J. E. Guillet, J. Polym. Sci. A-2, 7, 1895 (1969). 214. K. G. Denbigh, Trans. Faraday Soc, 43, 648 (1947). 215. A. W. DeGraft, G. W. Poehlin, J. Polym. Sci. A-2, 9, 1955 (1971). 216. Z. Tadmor. J. A. Biesenberger, Ind. Eng. Chem. Fund., 5,336 (1966). 217. M. E. Sacks, S. Lee, J. A. Biesenberger, Chem. Eng. Sci., 28, 241 (1973). 218. R. V. Figini, G. V. Schulz, Z. Physik, Chem. (Frankfurt), 23, 233 (1960); Makromol. Chem., 41, 1 (1960). 219. M. Litt, J. Polym. Sci., 58, 429 (1962).
220. L. F. Beste, H. K. Hall, Jr., J. Macromol. Chem., 1, 121 (1966). 221. A. Eisenberg, D. A. McQuarrie, J. Polym. Sci. A-I, 4, 737 (1966). 222. T. E. Corrigan, M. J. Dean, J. Macromol. Sci. A: Chem., 2, 645 (1968). 223. "Handbook of Chemistry and Physics", Vol. 34 th Edition et seq. Chemical Rubber Publishing Co., Cleveland. 224. W. F. Espenscheid, M. Kerker, E. Matijevic, J. Phys. Chem., 68, 3093 (1964). 225. E. P. Honig, J. Phys. Chem., 69, 4418 (1965). 226. W. D. Lansing, E. O. Kramer, J. Am. Chem. Soc, 57, 1369 (1935). 227. H. Wesslau, Makromol. Chem., 20, 111 (1956). 228. L. T. Muus, W. H. Stockmayer, quoted by F. W. Billmeyer, Jr., in "Textbook of Polymer Science", Interscience, New York, 1962. 229. B. H. Zimm, J. Chem. Phys., 16, 1099 (1948). 230. M. Matsuda, M. lino, T. Hirayama, T. Miyashita, Macromolecules, 5, 240 (1972). 231. W. Weibull, J. Appl. Mech., 18, 293 (1951). 232. L. H. Tung, J. Polym. Sci., 20, 495 (1956). 233. A. M. Kotliar, J. Polym. Sci. A, 2, 1373 (1964). 234. W. H. Stockmayer, J. Polym. Sci., 9, 69 (1952); 11, 424 (1953). 235. K. D. Siegel, A. W. Fogiel, R. Pariser, Macromolecules, 5,95 (1972). 236. I. Nakamura, R. Yokouchi, T. Ito, D. Miura, K. Fujii, Kobunshi Kagaku, 21, 553 (1964). 237. A. M. Kotliar, J. Polym. Sci. A, 2, 4304 (1964). 238. A. M. Kotliar, J. Polym. Sci. A, 2, 4329 (1964). 239. O. Prochazka, P. Kratochvil, J. Polym. Sci., Polym. Phys., Ed. 22, 501 (1984). 240. T. J. Tulig, M. Tirrell, Macromolecules, 14, 1501 (1981). 241. W. Y. Chiu, G. M. Carratt, D. S. Soong, Macromolecules, 16, 348 (1983). 242. J. N. Cardenas, K. F. O'Driscoll, J. Polym. Sci., Polym. Chem. Ed., 14, 883 (1976). 243. J. N. Cardenas, K. F. O'Driscoll, J. Polym. Sci., Polym. Chem. Ed., 15, 1883 (1977). 244. N. S. Yenikolopyan, F. S. D'yachkovskii, R Ye. Matkovshii, Ye. L. Pechatnikov, Kh. M. A. Brikenshtein, G. A. Furman, S. P. Davtyan, Vysokomol. Soyedin. A, 25, 265 (1983); Polym. Sci., USSR, 25, 303 (1983). 245. G. Lichti, R. G. Gilbert, D. H. Napper, J. Polym. Sci., Polym. Chem. Ed., 18, 1297 (1980). 246. K. Ito, J. Polym. Sci., A-I, 57 (1972). 247. V. A. Ivanov, S. I. Kuchanov, S. S. Ivanchev, Vysokomol. Soyedin. A, 19, 1684 (1977); Polym. Sci., USSR, 19, 1923 (1977). 248. H. Morawetz, Macromolecules, 12, 532 (1979). 249. L. L. Boehm, Z. Phys. Chem. N. F, 88, 297 (1974). 250. S. C. Jain, V S. Nanda, Eur. Polym. J., 13, 137 (1977). 251. M. Szwarc, B. H. Zimm, Macromolecules, 16, 1918 (1983). 252. J. Largo-Cabrerizo, J. Guzman, Macromolecules, 12, 526 (1979).
253. S. I. Kuchanov, Ye. S. Povolotskaya, Vysokomol. Soyedin. A, 24, 2179 (1982); Polym. Sci., USSR, 24, 2499 (1982). 254. S. K. Gupta, A. Kumar, A. Bhargava, Eur. Polym., J., 15,557 (1979). 255. L. H. Peebles, Jr., Macromolecules, 16, 929 (1983). 256. J. W. Stafford, J. Polym. Sci., Polym. Chem. Ed., 21, 1627 (1983). 257. E. Ozizmir, G. Odian, J. Polym. Sci., Polym. Chem. Ed., 18, 2281 (1980). 258. V. I. Kolegov, S. Ya. Frenkel, Vysokomol. Soyedin. A, 18, 1680 (1975); Polym. Sci., USSR, 18, 8 (1975). 259. V. I. Kolegov, Vysokomol. Soyedin. A, 18, 1689 (1976); Polym. Sci., USSR, 18, 1929 (1976). 260. L. H. Peebles, Jr., Macromolecules, 7, 872 (1974). 261. L. H. Peebles, Jr., Macromolecules, 9, 58 (1976). 262. Ye. P. Piskareva, Ye. G. Erenburg, I. Ya Poddubnyi, Vysokomol. Soyedin. A, 20 (1978); Polym. Sci., USSR, 20, 883 (1979). 263. J. J. Gonzalez, K. W. Kehr, Macromolecules, 11,996 (1978). See also Ref. 264. 264. N. A. Plate, A. D. Litmanovich, O. V. Noah, Macromolecules, 12, 1231 (1979). 265. J. L. Spouge, Macromolecules, 16, 121 (1983). 266. D. Y Yan, G. F. Cai, Makromol. Chem., 186, 583 (1985). 267. G. F. Cai, D. Y. Yan, Makromol. Chem., 186, 597 (1985). 268. M. Szwarc, C. L. Perrin, Macromolecules, 18, 528 (1985). 269. Ye. B. Brun, S. I. Kuchanov, Vysokomol. Soyedin. A, 21, 691 (1979); Polym. Sci., USSR, 21, 757 (1979). 270. S. I. Kuchanov, Ye. B. Brun, Vysokomol. Soyedin. A, 21, 700 (1979); Polym. Sci., USSR, 21, 767 (1979). 271. P. Whittle, Proc. Cambridge Phil. Soc, 61,475 (1965); Proc. Roy. Soc. London, Ser. A, 285, 501 (1965). 272. D. W. Matula, L. C. D. Groenweghe, J. R. Van Wazer, J. Chem. Phys., 41, 3105 (1964). 273. P. Luby, J. Phys. Chem., 78, 1083 (1974). 274. C. W. Macosko, D. R. Miller, Macromolecules, 9, 199 (1976). 275. J. Mikes, K. Dusek, Macromolecules, 15, 93 (1982). 276. D. Durand, C. M. Bruneau, Macromolecules, 12, 1216 (1979). 277. J. W. Stafford, J. Polym. Sci., Polym. Chem. Ed., 19, 3219 (1981). 278. R. Collins, M. B. Huglin, R. W. Richards, Eur. Polym. J., 11, 197 (1975). 279. B. L. Gutin, Vysokomol. Soyedin. A, 20,620 (1978); Polym. Sci., USSR, 20, 699 (1979). 280. T. Yasukawa, Y Sasaki, K. Murikami, J. Polym. Sci., Polym. Chem. Ed., 13, 17 (1975). 281. D. R. Miller, C. W. Macosko, Macromolecules, 9, 206 (1976). 282. D. S. Pearson, W. W. Graessley, Macromolecules, 11, 528 (1978). 283. A. Ziabicki, J. Walasek, Macromolecules, 11, 471 (1978). 284. D. Durand, C. M. Bruneau, Polymer, 24, 587 (1983). 285. D. Durand, C. M. Bruneau, Polymer, 24, 592 (1983). 286. V. Vojta, K. Dusek, Brit. Polym. J., 12, 1 (1980).
287. K. Dusek, M. Gordon, S. B. Ross-Murphy, Macromolecules, 11, 236 (1978). 288. T. Kotaka, Bull. Inst. Chem. Res., Kyoto Univ., 55, 135 (1977). 289. V. S. Nanda, J. Macromol. ScL, Phys. B, 18, 685 (1980). 290. M. A. Bibbo, E. M. Valles, Macromolecules, 15, 1293 (1982). 291. D. R. Miller, E. M. Valles, C. W. Macosko, Polym. Eng. ScL, 19, 272 (1979). 292. E. Donoghue, Macromolecules, 15, 1634 (1982). 293. D. R. Miller, C. W. Macosko, Macromolecules, 11, 656 (1978). 294. J. W. Stafford, J. Polym. ScL, Polym. Chem. Ed., 22, 365 (1984). 295. D. Durand, C. M. Bruneau, Brit. Polym. J. 13, 33 (1981). 296. H. Jacobson, Macromolecules, 17, 705 (1984). 297. V. I. Kolegov, T. S. Kozlova, V. M. Artemichev, O. I. Rodionova, Vysokomol. Soyedin. A, 25, 1005 (1983); Polym. ScL, USSR, 25, 1162 (1983). 298. M. Gordon, G. R. Scantlebury, Proc. Roy. Soc. London, Ser. A, 292, 380 (1966). 299. I. I. Romantsova, Yu. A. Taran, O. V. Noa, N. A. Plate, Vysokomol, Soyedin A, 21, 1176 (1979); Polym. ScL, USSR, 21, 1293 (1980). 300. R. Bansil, H. J. Herrmann, D. Stauffer, Macromolecules, 17, 998 (1984). 301. M. Ballauff, B. A. Wolf, Macromolecules, 14, 654 (1981). 302. O. Saito in: M. Dole (Ed.), "The Radiation Chemistry of Macromolecules", vol. 1, Academic Press, New York, 1972, p. 223. 303. J. H. O'Donnell, N. P. Rahman, C. A. Smith, D. J. Winzor Macromolecules, 12, 113 (1979). 304. C. C. Lin, W. Y. Chiu, J. Appl. Polym. ScL, 23, 2049 (1979). 305. A. Kumar, S. K. Gupta, B. Kumar, N. Somu, Polymer, 24, 1180(1983). 306. A. Ya. Malkin, Yu. B. Lavochnik, V. P. Begishev, Polym. Proc. Eng., 1, 71 (1983). 307. A. Ya. Malkin, Yu. B. Lavochnik, V. P Begishev, Vysokomol. Soyedin A, 26, 775 (1984); Polym. ScL, USSR, 26, 868 (1984). 308. H. T. Chen, J. Steenord, Polym. Eng. ScL, 15, 357 (1975). 309. A. Kumar, S. K. Gupta, R. Saraf, Polymer, 21, 1323 (1980). 310. A. Kumar, P. Rajora, N. L. Agarwalla, S. K. Gupta, Polymer, 23, 222 (1982). 311. H. Kilkson, I & EC Fund., 3, 281 (1964). 312. J. Ugelstad, H. R. Mfutakamba, P. C. M0rk, T. Ellington, A. Berge, R. Schmid, L. Holm, A. J0rgedal, F. K. Hansen, K. Justad, J. Polym. ScL, Polym, Symp., 72, 225 (1985). 313. D. Yan, Macromolecules, 22, 2926 (1989). 314. G. Kaszas, T. Foldes-Berezsnich, F. Tiidos, J. Macromol. Sci.-Chem. A, 22, 1571 (1985). 315. K. Fujimori, P. P. Organ, M. J. Costigan, I. A. Craven, J. Macromol. Sci.-Chem. A, 33, 647 (1986).
316. M. N. Galbraith, G. Moad, D. H. Soloman, T. H. Spurling Macromolecules, 20, 675 (1987). 317. K. Ito, Eur. Polym. J., 23, 409 (1987). 318. H.-Kh. Mahabadi, Macromolecules, 24, 606 (1991). 319. B. V. Revnov. E. G. Zotikov, N. G. Podosenova, V. P. Budtov, J. Appl. Chem., 58, 766 (1985); Zh. Prikl. Khim. (Leningrad), 58, 845 (1985). 320. H. Tobita, Y. Takada, M. Nomura, J. Polym. ScL, Polym. Chem. Ed., 33, 441 (1995). 321. G. Storti, G. Polotti, M. Cociani, M. Morbidelli, J. Polym. ScL, Polym. Chem. Ed., 30, 731 (1992). 322. G. Storti, G. Polotti, P. Canu, N. Morbidelli, J. Polym. ScL, Polym. Chem. Ed., 30, 751 (1992). 323. G. Zifferer, O. F. Olaj, Macromol. Theory Simul., 6, 53 (1997). 324. A. N. Nikitin, A. V. Evsseev, Macromol. Reports A, 33 (Suppls. 3-4), 187 (1996). 325. K. W. McLaughlin, D. D. Latham, C. E. Hoyle, M. A. Trapp, J. Phys. Chem., 93, 3643 (1989). 326. R. Szymanski, Makromol. Chem., 191, 933 (1990). 327. R. Szymanski, N. Manolova, I. Rashkov, Makromol. Chem., 194, 941 (1993). 328. D.-Y. Yan. G.-F. Cai, Z.-D. Lan, Makromol Chem., 187, 2179 (1986). 329. N. G. Taganov, Vysokomol. Soyed. A, 29, 1682 (1987); Polym. ScL, USSR, 29, 1847 (1987). 330. I. Ermakov, R. DeClercq, E. Goethals, Macromol. Theory Simul., 3, 427 (1994). 331. D. Yan, H. Dong, P. Ye, Macromolecules, 29, 8057 (1996). 332. M. Fontanille, G. Helary, M. Szware, Macromolecules, 21, 1532 (1988). 333. D. Yan, X. Hu, Polymer, 29, 1858 (1988). 334. X. Hu, D. Yan, Polymer, 31, 1950 (1990). 335. D. Yan, C. Yuan, Makromol. Chem. Rapid Commun., 8, 83 (1987). 336. E. T. Thachil, Polym.-Plast. Technol. Eng., 32, 151 (1993). 337. G.-F. Cai, D.-Y. Yan, Makromol. Chem., 188, 1885 (1987). 338. J. Villermaux, L. Blavier, M. Pons, in: K. H. Richert, W. Geisler, (Eds.), Influence React. Eng. Polym. Prop., [Workshop Proc] Hanser, Munich, 1983, p. 1. 339. P. Lorenzini, M. Pons, J. Villermaux, Chem. Eng. ScL, 47, 3969 (1992). 340. N. G. Taganov, Vysokomol. Soyed. A, 27 732 (1985); Polym. ScL, USSR, 27, 816 (1985). 341. N. G. Taganov, Vysokomol. Soyed. A, 27, 741 (1985); Polym. ScL, USSR, 27, 828 (1985). 342. H. Tobita, Macromolecules, 26, 836; 5427 (1993). 343. H. Tobita, Makromol. Chem. Theory Simul., 2, 761 (1993). 344. H. Tobita, Polymer, 35, 3023 (1994). 345. H. Tobita, Y. Takada, M. Nomura, Macromolecules, 27, 3804 (1994). 346. L.-D. Shiau, Macromolecules, 28, 6273 (1995). 347. L. Rief, H. Hocker, Macromolecules, 17, 952 (1984). 348. L. Nie, R. Narayan, Polym. Preprints, 34, 632 (1993). 349. M. Kosmas, N. Hadjichristidis, Macromolecules, 27, 5216 (1994).
350. J. H. O'Donnell, C. L. Winzor, D. J. Winzor, Macromolecules, 23, 167 (1990). 351. V. S. Papkov, M. N. Il'ina, G. L. Slonimskii, Vysokomol. Soyed. A, 30, 1487 (1988); Polym. ScL, USSR, 30, 1566 (1988). 352. V. S. Papkov, M. N. Il'ina, G. L. Slonimskii, Vysokomol. Soyed. A, 30, 1495 (1988); Polym. ScL, USSR, 30, 1576 (1988).
353. A. Ya. Malkin, Yu. B. Lavochnik, V. P. Begishev, Vysokomol. Soyed. A, 26, 775 (1984); Polym. ScL, USSR, 26, 863 (1984). 354. A. Kumar, J. Appl. Polym. ScL, 34, 1383 (1987). 355. J. B. P. Soares, A. E. Hamielec, Macromol. Theory Simul., 5, 547 (1996).
H e a t s C e i l i n g
a n d
E n t r o p i e s
T e m p e r a t u r e s ,
C o n c e n t r a t i o n s , o f
o f
E q u i l i b r i u m
a n d
H e t e r o c y c l i c
P o l y m e r i z a t i o n , M
o
n
o
m
e
r
P o l y m e r i z a b i l i t y C o m p o u n d s *
J. L e o n a r d Departement de Chimie and CERSIM, Universite Laval, Quebec, Canada
A. Heats of Polymerization 11-365 Table 1. Monomers Giving Polymers Containing Carbon Atoms Only in the Main Chain II-365 1.1. With Acyclic Carbons Only in the Main Chain II-365 1.1.1. Dienes M-365 1.1.2. Monomers Giving Polymers With or Without Aliphatic Side Chains that Contain Only C, H M-365 1.1.3. Monomers Giving Polymers With Aliphatic Side Chains that Contain Heteroatoms II-368 1.1.4. Monomers Giving Polymers With Aromatic Side Chains that Contain Only C, H 11-371 1.1.5. Monomers Giving Polymers With Aromatic Side Chains and that Contain Heteroatoms 11-371 1.2. With Aromatic or Cyclic Carbons in the Main Chain II-372 Table 2. Monomers Giving Polymers Containing Heteroatoms in the Main Chain II-373 2.1. Monomers Giving Polymers Containing O in the Main Chain, Bonded to Carbon Only II-373 2.1.1. Ethers and Acetals M-373 2.1.2. Cyclic Esters II-376
2.2.
Monomers Giving Polymers Containing O in the Main Chain, Bonded to other Heteroatoms (S, Si, P) 2.3. Monomers Giving Polymers Containing S in the Main Chain, Bonded in the Chain to Carbon Only 2.4. Monomers Giving Polymers Containing N in the Main Chain, Bonded in the Chain to Carbon Only 2.5. Monomers Giving Polymers Containing N in the Main Chain, Bonded to other Heteroatoms (P) 2.6. Other Monomers Giving Polymers not Listed Above Table 3. Copolymers B. Entropies of Polymerization Table 4. Monomers Giving Polymers Containing Main Chain Carbon Only 4.1. Main Chain Acyclic Carbon Only 4.1.1. Dienes 4.1.2. Monomers Giving Polymers Without or With Aliphatic Side Chains that Contain Only C, H 4.1.3. Monomers Giving Polymers With Aliphatic Side Chains that Contain Heteroatoms
*Based on the tables compiled for the third edition, by W.K. Buslield, School of Sciences Griffith University, Brisbane, Australia.
11-377
II-378
II-378
II-379 II-379 II-380 11-381
II-382 II-382 II-382
II-382
II-384
4.1.4. Monomers Giving Polymers With Aromatic Side Chains that Contain Only C, H II-385 4.1.5. Monomers Giving Polymers With Aromatic Side Chains that Contain Heteroatoms II-385 4.1.6. Other Monomers Giving Polymers not Listed Above 11-386 4.2. With Aromatic or Cyclic Carbons in the Main Chain 11-386 Table 5. Monomers Giving Polymers Containing Heteroatoms in the Main Chain 11-387 5.1. Monomers Giving Polymers Containing O in the Main Chain, Bonded to Carbon Only II-387 5.1.1. Ethers and Acetals II-387 5.1.2. Cyclic Esters II-390 5.2. Monomers Giving Polymers Containing O in the Main Chain, Bonded to Other Heteroatoms (S, Si, P) 11-391 5.3. Monomers Giving Polymers Containing N in the Main Chain, Bonded in the Chain to Carbon Only 11-391 5.4. Other Monomers Giving Polymers not Listed Above II-392 Table 6. Copolymers II-392 C. Ceiling Temperatures and Equilibrium Monomer Concentrations II-393 1. Equilibria Involving Pure Liquid Monomers II-394 Table 7. Monomers Giving Polymers Containing Main Chain Acyclic Carbon Only II-394 Table 8. Monomers Giving Polymers Containing Heteroatoms in the Main Chain II-395 8.1. Monomers Giving Polymers Containing O in the Main Chain, Bonded to Carbon Only II-395 8.2. Monomers Giving Polymers Containing O in the Main Chain, Bonded to Other Heteroatoms (S, P, Si) II-396 8.3. Monomers Giving Polymers Containing S in the Main
Chain, Bonded in the Chain to Carbon Only 8.4. Monomers Giving Polymers Containing N in the Main Chain, Bonded in the Chain to Carbon Only 8.5. Other Monomers Giving Polymers not Listed Above 2. Equilibria Involving Gaseous Monomers 3. Equilibria Involving Monomers in Solution Table 9. Monomers Giving Polymers Containing Main Chain Carbon Only 9.1. Monomers Giving Polymers Containing Main Chain Acyclic Carbon Only 9.2. Monomers Giving Polymers Containing Main Chain Cyclic Carbon Table 10. Monomers Giving Polymers Containing Heteroatoms in the Main Chain 10.1. Monomers Giving Polymers Containing O in the Main Chain, Bonded to Carbon Only 10.2. Monomers Giving Polymers Containing O in the Main Chain, Bonded to Other Heteroatoms (Si, P) 10.3. Monomers Giving Polymers Containing S in the Main Chain, Bonded in the Chain to Carbon Only 10.4. Monomers Giving Polymers Containing N in the Main Chain, Bonded in the Chain to Carbon Only Table 11. Copolymers 11.1. 1:1 Copolymers 11.2. General Copolymers D. Polymerizability of 5-, 6-, and 7-Membered Heterocyclic Ring Compounds Table 12. 5-Membered Ring Compounds Table 13. 6-Membered Ring Compounds Table 14. 7-Membered Ring Compounds Table 15. Comparison of Polymerizability of Unsubstituted 5-, 6- and 7-Membered Ring Compounds E. Notes F. References
II-396
II-397 II-397 II-397 II-398
II-398 II-398
II-399
II-399
II-399
II-400
II-400
II-400 11-401 11-401 11-401 11-401 II-402 II-403 II-404
II-405 M-406 II-407
A.
HEATS OF POLYMERIZATION
Symbols: The subscripts xx to A// denote the state of the monomer (first letter) and the state of the polymer (second letter), as follows: g c c' 1 s
Gaseous state (hypothetical in case of polymer) Condensed amorphous state Crystalline or partially crystalline state Liquid state In solution; solvent specified in the sixth column (Is denotes polymer dissolved in monomer).
For emulsion polymerization the subscript Ic is used and a note added in the sixth column. In all cases where monomer or polymer is present in solution etc., the value of AH will depend on the composition to some extent. Where the polymer is crystalline, AH will depend on the degree of crystallinity. AH values are in kJ per mol of monomer and are generally the limiting values for high degree of polymerization n [1 kcal = 4.187 kJ]. Where more than one value is available in the literature for given states of monomer and polymer and a given method, only one value is shown in the tables. This corresponds to one of the references indicated N1- refers to the ith note given at the end of the table. Example: C 2 H 4 (g) -> ( 1 / ^ ) ( C 2 H 4 ) J g ) ,
AHgg = -93.5kJ
Precision: generally 0.5-4.0 kj/mol (for details see Ref. 1). Methods of determination: These are summarized below, using the numbering system in Ref. 1. 2 3 4a 4b 5
Combustion of monomer or polymer or both. Reaction calorimetry. Thermodynamic (van't Hoff Equation). Semiempirical rules applied to evaluate heat of formation of polymer or monomer or both. Such rules may be found in Refs. 25,143,223,224,335. Heat capacity and heat of transition (Kirchhoff's equation).
TABLE 1. MONOMERS GJVING POLYMERS CONTAINING CARBON ATOMS ONLY IN THE MAIN CHAIN
Monomer 1.1.
State of monomer
-AZZxx
Temp.
and polymer (xx)
(kj/mol)
(0C)
73 78 73 68 59 70.5 75 71 65.5
25 25 25 61.3 - 70 25 25 74.5 34.6
Method
Solvent/Notes
Refs.
WITH ACYCLIC CARBONS ONLY IN THE MAIN CHAIN
1.1.1. DIENES 1,3-Butadiene
Chloroprene Cyclopentadiene Isoprene
gg gg Ic Ic ss gg Ic Is Is
4b 4b 2 3 3 4b 2 3 3
1:2 Polymerization 1:4 Polymerization Ni Methylene chloride
N2
10 10 45 41 190 10 46 15 47
1.1.2 MONOMERS GIVING POLYMERS WITH OR WITHOUT ALIPHATIC SIDE CHAINS THAT CONTAIN ONLY C, H 1.1.2.1. Olefins (listed by increasing carbon number) Ethylene
Propene
gg gc' gc' gc c'c' c'c gc' gc gc' gc gc' gc gl gg gc7 Ic sc
93.5 108.5 107.5 101.5 173 169 212 209 212 209 211 204 198 86.5 104 84 69
25 25 25 25 -173 -173 173 173 25 25 127 127 227 25 25 25 -78
4b 2 3 2 5 5 5 5 4b 4b 5 5 5 4b 2 4b 3
A#fUS (Polymer) taken as 5.0 Polymer is poly(l-butene), iso Polymer is poly(l-butene), iso Polymer is poly(l-butene), iso Polymer is poly(l-butene), iso Polymer is poly(l-butene), iso Polymer is poly(l-butene), iso Polymer is poly(l-butene), iso Polymer is poly(l-butene), iso Polymer is poly(l-butene), iso
n-Butane
2 2,3 183 2,4 385 385 385 385 385 385 385 385 385 5 3 5 6
Notes page 11-406; References page II - 407
TABLEI.
cont'd
Monomer 1-Butene
2-Butene, cis
2-Butene, trans
Isobutene
1-Pentene
-, 4-methyl
2-Pentene, cis
State of monomer and polymer (xx) gg Ic Ic' Ic Ic' Ic gc' gc gc' gc gl gg Ic cV c'c Ic' Ic gc' gc gc' gc gl gg Ic c'c' c'c Ic' Ic gc' gc gc' gc gl gc Ic ss ss c'c' c'c Ic' Ic Ic' Ic gl gl c'c' c'c Ic' Ic Ic' Ic gc' gc gcf gc gl gg c'c' c'c Ic' Ic Ic' Ic
-AHx x (kj/mol) 86.5 83.5 78 74 83 79 108 103 107 99 94 80 75 63 59 75 71 101 96 99 92 86 75.5 71 57 54 71 67 96 91 96 89 83 72 48 53.5 54 84 81 95 93 99 95 117 113 82 79 93 90 97 95 124 117 122 112 105 80.5 75 72 87 85 91 87
Temp. (0C) 25 25 -173 -173 -73 - 73 25 25 127 127 227 25 25 -173 -173 -73 -73 25 25 127 127 227 25 25 -173 -173 -73 - 73 25 25 127 127 227 25 25 25 -35 -173 -173 -73 -73 25 25 127 227 -173 -173 -73 -73 25 25 127 127 227 227 327 25 -173 -173 -73 -73 25 25
Method 4b 4b 5 5 5 5 4b 4b 5 5 5 4b 4b 5 5 5 5 4b 4b 5 5 5 4b 4b 5 5 5 5 4b 4b 5 5 5 2 2 ? 3 5 5 5 5 2,4b 2,4b 5 5 5 5 5 5 4b 4b 5 5 5 5 5 4b 5 5 5 5 2,4b 2,4b
Solvent/Notes
Isotactic Isotactic Isotactic Isotactic Isotactic Isotactic Isotactic Isotactic Isotactic
polymer polymer polymer polymer polymer polymer polymer polymer polymer
Isotactic Isotactic Isotactic Isotactic Isotactic Isotactic Isotactic Isotactic Isotactic
polymer polymer polymer polymer polymer polymer polymer polymer polymer
Isotactic Isotactic Isotactic Isotactic Isotactic Isotactic Isotactic Isotactic Isotactic
polymer polymer polymer polymer polymer polymer polymer polymer polymer
Low polymer Solvent? low polymer CH 2 Cl 2 , polymer swollen, N 3
Refs. 5 5 385 385 385 385 385 385 385 385 385 5 5 385 385 385 385 385 385 385 385 385 5 5 385 385 385 385 385 385 385 385 385 7 3,8 8 9 386 386 386 386 386 386 386 386 387 387 387 387 387 387 387 387 387 387 387 10 386 386 386 386 386 386
TABLE 1. cont'd Monomer
- , 4-methyl
2-Pentene, trans
-,4-methyl
1-Hexene 1-Heptene
State of monomer and polymer (xx) gl gl Ic' Ic gc' gc gc' gc gl gg c'c' c'c Ic' Ic Ic' Ic gl gl Ic' Ic gc' gc gc' gc gl Ic gg
1.1.2.2. Cycloalkanes (listed by increasing ring size) Cyclopropane Ic -,methylIc -, 1,1-dimethylIc Cyclobutane Ic -,methylIc -, 1,1-dimethylIc Cyclopentane Ic -,methylIc - 1,1-dimethylIc Cyclohexane Ic -,methylIc - , 1,1-dimethylIc Cycloheptane Ic Cyclooctane Ic Cyclononane Ic Cyclodecane Ic Cycloundecane Ic Cyclododecane Ic Cyclotridecane Ic Cyclotetradecane Ic Cyclopentadecane Ic Cyclohexadecane Ic Cycloheptadecane Ic 1.1.2.3. Cycloalkenes Cyclobutene Cyclopentene
11 gl Ic c ;(I)c Ic Ic c'(I)c Ic Ic Ic
-AHx x (kj/mol)
Temp. (0C)
109 105 90 88 118 111 116 114 100 75.5 70 68 83 81 87 83 106 103 86 83 115 107 113 103 97 83 86
127 227 25 25 127 127 227 227 327 25 -173 -173 -73 -73 25 25 127 227 25 25 127 127 227 227 327 25 25
113 105 97.5 105 100 93.5 22 17 13.5 -3 -9 -7.5 21.5 34.5 47 48 45 14 22 7 12 8 8.5
25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25
121 145 17.5 11 16 15 23 19 18 18
25 25 25 -173 -73 25 -173 -73 25 77
Method
Solvent/Notes
5 5 4b 4b 5 5 5 5 5 4b 5 5 5 5 2,4b 2,4b 5 5 4b 4b 5 5 5 5 5 4b 4b
Refs. 386 386 387 387 387 387 387 387 387 10 386 386 386 386 386 386 386 386 387 387 387 387 387 387 387 5 5
2 4b 4b 2 4b 4b 2 4b 4b 2 4b 4b 2 2 2 2 2 2 2 2 2 2 2
11 11 11 12 11 11 12 11 11 12 11 11 12 12 13 13 13 13 13 13 13 13 13
2,4b 2,4b 2 5 5 2,4b 5 5 2,4b 5
ds-Polybutadiene ds-Polybutadiene N 66 cw-Polymer cw-Polymer ds-Polymer frans-Polymer rrans-Polymer fraws-Polymer toms-Polymer
388 388 361 388 388 388 388 388 388 388
Notes page 11-406; References page 11-407
TABLE 1. cont'd Monomer
State of monomer and polymer (xx)
Cyclopentadiene Cyclohexene Cycloheptene
ss ss C7CIII)C C7CIII)C' C7CII)C C7CII)C7 Ic Ic 7 11 c 7 (II)c 7 C7CII)C c 7 (I)c 7 c 7 (I)c Ic 7 Ic 11
Cyclooctene
-AHx^ (kj/mol) 59 1 12 18 18 26 18 29 17 18 6 27 19 30 13 13
-
Temp. ( 0 C)
6
-173 5 -173 -173 -73 -73 25 25 51 -173 -173 -73 -73 25 25 57
Method 3 4a 5 5 5 5 2,4b 2,4b 5 5 5 5 5 2,4b 2,4b 5
Solvent/Notes
Refs.
Butyl chloride, N 7 0 Toluene, N 7 8 7 0 % trans, 30% ds-Polymer, 7 0 % trans, 3 0 % ds-Polymer, 7 0 % trans, 30% ds-Polymer, 7 0 % trans, 30% ds-Polymer, 7 0 % trans, 30% ds-Polymer 7 0 % trans, 3 0 % ds-Polymer 7 0 % trans, 3 0 % ds-Polymer 4 8 % trans, 5 2 % ds-Polymer, 4 8 % trans, 5 2 % ds-Polymer, 4 8 % trans, 5 2 % ds-Polymer, 4 8 % trans, 5 2 % ds-Polymer, 4 8 % trans, 5 2 % ds-Polymer 4 8 % trans, 5 2 % ds-Polymer 4 8 % trans, 5 2 % ds-Polymer
N54 N54 N54 N54
N54 N54 N54 N54
371 389 388 388 388 388 388 388 388 388 388 388 388 388 388 388
1.1.3. MONOMERS GIVING POLYMERS WITH ALIPHATIC SIDE CHAINS THAT CONTAIN HETEROATOMS 1.1.3.1. Acrylic Derivatives Acrolein
Acrylamide
- , N-methylol- , AyV 7 -methylene bisAcrylic acid
- , rc-butyl ester
-,ethyl ester - , ethylhexyl ester - , lauryl ester - , methyl ester
Acrylonitrile
(listed alphabetically) Ic ss ss ss Ic ss? sc sc Ic Ic Ic ss sc sc sc Ic ss ss ss ss ss Ic Ic Ic Ic Ic Ic ss ss Ic7 sc7
1.1.3.2. ^-Substituted Acrylic Derivatives (listed alphabetically) a-Chloroacrylic acid, methyl ester Ic a-Cyanoacrilic acid, methyl ether Ic - , ethyl ester c7c c7c Ic Ic Ic - , allyl ester c7c
c7c c7c Ic
80 57.5 81.5 81.5 79.4 70.5 60 57.5 74.5 82.7 67 77.5 73.5 72 74.5 78 77 79 76 75.5 78 78 80.7 78.2 80.5 78 81.8 84.5 81 76.5 77.5
52.7 42 28 29 47 53 54 41
42 43 62
74.5 74.5 74.5 74.5 90 74.5 74.5 74.5 190 190 74.5 20 74.5 74.5 74.5 74.5 74.5 74.5 74.5 74.5 74.5 74.5 90 90 30 76.8 80 20 74.5 74.5 74.5
80 60 173 -73 25 127 177 -173
-73 -8 -8
3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3
Hexane Water Water Acetone Benzene Hexane
Water Benzene Carbon tetrachloride Hexane Acetone Butanone Benzene Carbon tetrachloride Hexane
Ethyl alcohol Hexane Benzene
15 17 17 17,14 332 17 17 17 332 332 15 36,37 15 15 15 17,37 17 17 17 17 17 34,37 318 318 352 21,34,37 319 36 34 17,21,38,201 17
3 3 5 5 2 5 5 5
319 354 390 390 390 390 390 391
5 5 5
391 391 391
TABLE 1. cont'd Monomer
- , rc-decyl ester
- , allyloxyethyl
Ethacrylic acid, methyl ester Methacrolein Methacrylamide
Methacrylic acid
-, benzoic acid ester
- , benzyl ester -, /i-butyl ester -, rm-butyl ester -, cyclohexyl ester -, 2-ethoxyethyl ester -, ethyl ester -, p(N-piperidyl)ethyl ester -, rc-hexyl ester -, -, -, -, -,
2-hydroxyethyl ester 2-hydroxypropyl ester isobutyl ester isopropyl ester methyl ester
- , methyl ester deuterated
- , n-octyl ester
State of monomer and polymer (xx)
-AH^ (kj/mol)
Temp. (0C)
Ic Ic c'c c'c Ic Ic cc Ic Ic Ic Is Ic ss ss ss ss Ic Ic ss ss ss sc c'c c'c c'c ss 11 Ic Ic Is Is Ic Is Ic Is Ic Ic Is Ic Ic Is Ic Ic Ic Ic Ic Ic
64 68 29 29 69 74 41 43 49 51 31 65.5 56 42.5 39.5 35 42.5 64.5 66 56.5 54 57 55 56 59 57 90 56 57.5 60 54.5 51 53 57.5 62 60 59.5 57.5 57 58.5 60 50 50.5 60 60 56 55.5
25 127 -173 -73 25 127 -173 -73 25 57 87 74.5 74.5 74.5 74.5 74.5 74.5 25 20 25 25 74.5 -173 -73 25 77 227 76.8 74.5 26.9 26.9 76.8 26.9 74.5 26.9 120 74.5 26.9 40 25 26.9 25 25
Ic Is c'c c'c Ic Ic ss ss ss ss
55 57.5 34 36 55 56 54 58.5 57.5 58.5
25 26.9 -173 -73 25 77 130 74.5 74.5 74.5
2 3 5 5 5 3 4a 3 3 3
c'c c'c Ic Ic Ic
33 35 55 57 57
-173 -73 25 77 65
5 5 5 3 3
74.5 130 74.5
Method 2,4b 5 5 5 2,4b 5 5 5 2,4b 5 4a 3 3 3 3 3 3 2 3 3 3 3 5 5 5 2,3 5 3 3 3 3 3 3 3 3 4a 3 3 3 3 3 3 3 3 3 4a 3
Solvent/Notes
Water Chloroform Acetone Benzene Water Water Dimethylformamide, N 7 Methanol, N 5
1,4 Dioxane N6
Emulsion (aq.) Emulsion (aq.) Emulsion (aq.)
o-Dichlorobenzene Acetonitrile Tetrahydrofuran Hexane
Refs. 391 391 392 392 392 392 393 393 393 393 395 15 17 17 17 17 15 206 36 37 203,316 15 394 394 394 394 394 39 34,37,39 14 14 39 14 34 14 40 34,37 14 188 37 14 37 37 34 34 42,43,29 17,34,36,37, 41,201,235 206 14 414 414 414 414 42,29 34 34 34 414 414 414 414 188
Notes page 11-406; References page II - 407
TABLE 1. cont'd Monomer - , phenyl ester - , rc-propyl ester Methacrylonitrile
State of monomer and polymer (xx)
-AZZxx (kj/mol)
Ic Ic Ic ss
51.5 57.5 56.5 64
Ic?
60
Is gc Ic Ic Ic
Temp. (0C)
Method
Solvent/Notes
76.8 74.5 74.5 130
3 3 3 4a
N6
50
3
N6
74 132 71 111.5 96
74.5 25 25 25 74.5
3 2 4b 2 3
Ic Is ss ss ss Ic Ic
88 89.5 90 86.5 86 86 88
74.5 25 74.5 74.5 74.5 74.5 74.5
3 3 3 3 3 3 3
Is Ic ss
77.5 88 91
74.5 20 20
3 2 3
Benzonitrile
Refs. 39 34 15 44,29
LlJJ. Vinyl Ethers Vinyl n-butyl ether 1.1.3.4. Vinyl Alcohol, Ketones, Halogens Vinyl alcohol Methyl vinyl ketone Vinyl chloride
1.1J.5. Vinyl Esters Vinyl acetate
Vinyl propionate Vinyl 2-ethylhexoate 7.7.3.6. Others (listed alphabetically) AUyI chloride Ethylene, nitro - , tetrafluoroFumaric acid, diethyl ester Itaconic acid, dimethyl ester Maleic anhydride Maleimide
- , phenyl a-Methylene pentanolactone Vinyl cyclohexane
Vinylidene chloride
N-Vinyl succinimide
see Acetaldehyde
gg gc7 Ic' Ic ss Is ss ss ss ss ss ss c'c' c'c Ic' Ic Ic' Ic Ic' Ic Ic' Ic' Ic' c'c' c'c Ic' Ic Ic' Ic gc' gc gc' gc Is
155 172 163 ± 1 7 65 60.5 59 67.5 89.5 88.5 87.5 37 38.8 88 68 100 79 105 85 111 86 60 75.5 73 67 56 77 66 81 70 108 97 107 95 54.7
25 25 25 100 26.9 74.5 74.5 74.5 74.5 74.5 55 83 -173 -173 -73 -73 25 25 127 127 76.8 25 74.5 -173 -173 -73 -73 25 25 25 25 127 127 97
2 2 2 3 3 3 3 3 3 3 4a 4a 5 5 5 5 2,4b 2,4b 5 5 3 2 3 5 5 5 5 2 2 2 5 5 5 3
Atffus (Monomer) taken as 20
Acetone Hexane Benzene
Dimethylformamide, tetrahydrofuran
o-Dichlorobenzene Chlorobenzene Dioxane Acetonitrile Dimethylformamide DMF, N 78 , N 75 DMF
216 195 17 18.19,20 10 18 215 17,34,21 35 17 17 17 17,34 34 15 214 214 22 22,23 1 235 14 15 24 24 24 24 440 315 396 396 396 396 396 396 396 396 21 18 15 397 397 397 397 397 397 397 397 397 397 384
TABLE 1. cont'd Monomer
State of monomer and polymer (xx)
-AZZxx (kj/mol)
Temp. (0C)
Method
Solvent/Notes
Refs.
1.1.4. MONOMERS GIVING POLYMERS WITH AROMATIC SIDE CHAINS THAT CONTAIN ONLY C, H (listed alphabetically) Acenaphthalene
Acenaphthylene Biphenyl, p-isopropenylIndene - , 5-methyl- , 6-methyl-, 7-methyl-, 4,6-dimethyl-, 4,7-dimethyl-, 5,6-dimethyl- , 4,5,6,7-tetramethylNaphthalene, 2-isopropenylStyrene
- a-acetoxy - , o-chloro-,p-chloro-, 2,5-dichloro-, ar-ethyl-,a-methyl-
- , a-methyl, p-tert-buty\- , 2,4,6-trimethyl-
ss ss ss ss ss c'c ss ss ss
87.8 84.8 98.5 67 67 82 43 34 58
0 18 26.9 74.5 74.5 26.9 60 -15 - 30
3 3 3 3 3 3 4a 4a 3
ss ss ss ss ss ss ss ss ss gg Ic Ic Ic Is Is ss ss Ic Ic Ic Ic Ic Ic Ic ss ss ss ss ss Ic
58 57.5 58.5 77.5 65 79 75 36.5 38 74.5 70 68.5 73 73 73 66.5 26 68.5 67 69 68 35 34.5 39 33.5 47.7 15 14 29.7 70
- 50 -60 -70 -40 -40 - 40 -40 —5 10 25 25 26.9 127 25 26.9 -60 64 76.8 76.8 76.8 76.8 25 -20 25 -20 22 -10 -10
3 3 3 3 3 3 3 4a 4a 4b 2 3 4a 2 3 3 4a 3 3 3 3 2 4a
26.9
4a 4a 4a 4a 4a 3
Dichloromethane Dichloromethane o-Dichlorobenzene 6>-Dichlorobenzene Benzene Toluene, N 78 , N 75 Tetrahydrofuran Methylene chloride indep. of 7 [ - 7 O 0 to 10°] Methylene chloride Methylene chloride Methylene chloride Methylene chloride Methylene chloride Methylene chloride Methylene chloride Tetrahydrofuran Toluene, N 7 8
320 320 14 15 15 14 399 16 190
175 175,169 175,169 175 175 175 175 16 400 25 26 14,17,27,201,235 28,29 26 14 Methylene chloride 30,190 Toluene, N 7 8 , N 7 5 401 27 27 27 27 31 32,29 N9 123 Tetrahydrofuran 32,29,33,16 Cyclohexane 341 rc-Heptane, N78 402 Toluene, N 7 8 402 Solvent and temp, not stated 381 14
1.1.5. MONOMERS GIVING POLYMERS WITH AROMATIC SIDE CHAINS AND THAT CONTAIN HETEROATOMS 2-Amino-4-alkyl/aryl-amino-6-isopropenyl-1,3,5-triazine, R 1 = H , R 2 = ethyl Is R 1 = H , R i = propyl Is R i = ethyl, R 2 = ethyl , Is R i = p r o p y l , R 2 = propyl Is R i = methyl, R 2 = phenyl Is R i = methyl, R 2 = phenyl Is R i = H, R 2 = p-methoxyphenyl Is R i = H, R 2 = p-methoxyphenyl Is 2-Amino-4-(7V-R. anilino)-6-isopropenyl-1,3,5-triazine R = «-alkyl = «-propyl Ic = w-hexyl Ic = n-octyl Ic = rc-decyl Ic = n-dodecyl Ic = «-tetradecyl Ic = n-hexadecyl Ic R = alkyl = isopropyl Ic = isobutyl Ic = sec-butyl Ic
64.8 63.5 53.9 47.7 50.2 53.1 50.2 46.8 46 43 42 41 41 40 39 44 44 43
170 160 161 153 140 150 160 160
3 3 3 3 3 4a 3 4a
60 60 60 60 60 60 60 60 60 60
3 3 3 3 3 3 3 3 3 3
N65 N65 N65 N65
370 370 370 370 379 379 378 378 403 403 403 403 403 403 403 404 40 404
Notes page 11-406; References page II - 407
TABLE 1.
cont'd
Monomer
State of monomer and polymer (xx)
= n-pentyl = isopentyl = 1-methylbutyl R = benzyl R = chloro R = -4-methoxyR = -4-ethoxy2-Anilo-4-R-6-isopropenyl-1,3,5-triazine R = methoxy R = ethoxy Atropic acid, methyl ester Atroponitrile Benzoic acid, w-methacryloyloxy- , v i n y l ester Carbazole, JV-vinyl2,4-Hexadiyne-l,6-di(R group) R = -SO3C6H4CH3(p) R = -NHC 6 H 3 (NO 2 ) 2 (2,4posn.) R =-SO3C6H4NNC6H5(P) R =-OCONHCH2COOH
Oxazole, 2-isopropenylPyridine - , 2-isopropenyl- , 2-vinyl-
- , 4-vinylSilane, benzyl dimethyl vinyl-
- , dimethyl phenyl vinyl- , trimethyl vinylAWV',N'-Tetraethyl-4-isopropenylphenylphosphonous diamide Thiazole, 2-isopropenyl/7-[bis(Trimethylsilyl)methyl]isopropenylbenzene 1.2.
-AHxx (kj/mol)
Ic Ic Ic Ic Is Is Is
44 43 42 44 11 14 14
Is Is ss ss Ic Ic sc' ss
Temp. ( 0 C)
Method
Solvent/Notes
Refs.
60 60 60 60 170 183 182
3 3 3 3 3 3 3
404 404 404 404 405 406 406
12 12 28 39 59 84.5 63.5 94.9
174 174 -40 50 25 74.5 74.5 0
3 3 4b 4b 2 3 3 3
406 406 149 149 363 34 15 321
c'c' c'c' c'c'
152.6 77.5 138
187 135 140
3 3 3
C'C'
130
137
Toluene, N i 0 Toluene, N i 0
Hexane Dichloromethane
372 373 374
3
375
ss
39.5
20
4a
Tetrahydrofuran
284
ss ss Ic Is sc Ic ss c'c' Ic Ic Ic Ic ss
26 40 71.5 75.5 73.5 78 78 48.2 66.7 67.1 56.5 65.8 27
20 -15 74.5 74.5 74.5 74.5 74.5 -73 25 77 25 25 -55
4a 4a 3 3 3 3 3 2 3 3 3 3 4a
Tetrahydrofuran Toluene, N 7 8
N62 N62 N62 N62 Tetrahydrofuran
284 407 15 15 15 17 17 355 366 366 362 367 408
ss ss
28.5 30
20 — 30
4a 4a
Tetrahydrofuran Tetrahydrofuran
284 409
Benzene Benzene, hexane
WITH AROMATIC OR CYCLIC CARBONS IN THE MAIN CHAIN
— 11,12-Dicyano-2,6-naphtoquinodimethane ll,12-bis(alkylthio) alkyl = butyl = s-butyl = isopropyl = ethyl = methyl —, 7,8-Dicyanoquinodimethane 7,8-bis(butoxycarbonyl)7,8-diacetyl7,8-dibenzoyl7,8-dibutoxycarbonyl7,8-diisobutyryl7,8-dipropionyl7,8-bis(ethylthio)7,8-bis(phenylacetyl)7,8-bis(phenylthio)Norbornylene
5-Trimethylsilyl-2-
ss ss ss ss ss
67 59 65 69 70
30 30 30 30 30
4a 4a 4a 4a 4a
Oligomer, Oligomer, Oligomer, Oligomer, Oligomer,
benzene, benzene, benzene, benzene, benzene,
N78, N78, N78, N78, N78,
ss ss ss ss ss ss ss ss ss c'(II)c c'(I)c c'(I)c Ic c'c cc
26 25 22 26 23 24 23 25 23 56 62 62 65 38 40
60 55 55 55 55 55 60 55 50 -173 -73 25 57 -173 —173
4a 4a 4a 4a 4a 4a 4a 4a 4a 5 5 4b 5 5 5
Chloroform, N 7 8 , N 8 1 Chloroform, N 7 8 , N 8 i Chloroform, N 7 8 , N 8 i Chloroform, N 7 8 , N 8 1 Chloroform, N 7 8 , N 8 1 Chloroform, N 7 8 , N 8 1 Chloroform, N 7 8 , N 8 1 Chloroform, N 7 8 , N 8 1 Chloroform, N 7 8 , N 8 1 55% cis/45% trans Polymer, 55% c/s/45% trans Polymer, 55% cis/45% trans Polymer, 55% cis/45% trans Polymer, Overcooled monomer
N 8o N 8o N 8o N80 N 8o
410 410 410 410 410
N54 N54 N54 N54
411 412 412 412 413 413 411 413 411 415 415 415 415 416 416
TABLE 1.
cont'd State of monomer and polymer (xx)
Monomer
Af-7,7-Triacyanobenzoquinonemethideimine
TABLE 2.
39 46 52 55 22
Temp. (0C) -73 — 73 25 107 55
Method 5 5 4b 5 4a
Solvent/Notes
Overcooled monomer
Toluene N7g, Ng 2
Refs. 416 416 416 416 438
MONOMERS GIVING POLYMERS CONTAINING HETEROATOMS IN THE MAIN CHAIN
Monomer 2.1.
c'c cc Ic Ic ss
-AZZxx (kj/mol)
State of monomer and polymer (xx)
-AH^x (kj/mol)
Temp. (0C)
Method
Solvent/Notes
Refs.
MONOMERS GIVING POLYMERS CONTAINING O IN THE MAIN CHAIN, BONDED TO CARBON ONLY
2.1.1. ETHERS AND ACETALS (listed by increasing ring size of monomer) 2-RINGS (aldehydes and ketones) Acetaldehyde
-, -, -, -, -, -, -, -, -,
bromochlorofluorobromodichlorobromodifluorodibromochlorodibromofluorodichlorofluorodifluorochlorotribromotrichloro-
- , trifluoro-
Acetone
Butanal
4,7-Dioxaoctanal Formaldehyde
Heptanal
Ic Ic' Ic c'c Ic Ic sc' sc' sc' sc' sc' sc' sc' sc' gc' gc' gc Ic' Ic' Ic' Ic' Ic Ic' cc' ss sc' sc' sc' gc Ic sc sc' gg gc Ic Ic sc sc Ic ss gc'
0 25 64.5 25 62.5 25 31 -173 34 -73 36 25 36.0 31.2 43.4 26.0 29.0 56.2 51.0 19.6 71 ± 8 50 65.5 -50 5 1 - 5 0 17 57 38 ± 8 50 34 25 34.5 -50 20 -50 30 -73 25 -173 14.5 -50 33.5 13 39 10 37.8 64.5 45 47 25 50.8 25 54.9 -12 25 10 25 -25 25 20.5 20 35.5 18 21.5 20 15.9 -80 16.7 -80 66 25
gc' c'c' c'c
55 25 2 0 - 1 7 3 10 -173
4b Nn 2 To poly(vinyl alcohol) 2 To poly(vinyl alcohol) 5 5 2,4b 4a Toluene, N74 4a Toluene, N74 4a Toluene, N74 4a Toluene, N74 4a Toluene, N 7 4 4a Toluene, N74 4a Toluene, N74 4a Toluene, N74 4a 4a 4a 5 4a 3 4a 4a 5 5 4a Tetrahydrofuran 4a Pyridine 4a n-Heptane 4a Toluene, N 7 4 4a 4a Dichloromethane 4a Dichloromethane 4a Toluene, N 7 4 4b 4b 4b 3 4a «-Hexane (9 kbar), Ni 2 3 rc-Hexane (1 bar, IM), N i 2 4a N69 4a THF 4a Nn 2 5 5
48 195 195 417 417 417 233 344 344 344 344 344 344 344 50 166 166 418 50 418 166 166 418 418 167 50 166 344 129 322 322 344 234 144,148 48,234 161 161 161 330 330 49,164, 165,132 7,49 419 419
Notes page 11-406; References page II - 407
TABLE 2.
cont'd
Monomer
Hexanal
Octanal 4-Oxapentanal Pentanal 0-Phthalaldehyde Propanal
- 2,2-dichloro-, 2-chloro, 2-methyl-, 2-methyl-
State of monomer and polymer (xx) c'c' c;c Ic(I) Ic 11 c'c' c'c c'c' c'c 11 11 Ic sc Ic Is Ic sc ss c'c' c'c Ic' Ic Ic' Ic Ic' Ic gc Ic ss gc Ic ss gc Ic ss ss ss
-A/^ (kj/mol)
Temp. (0C)
22 -73 8 - 7 3 39 25 33 25 36 97 8 - 1 7 3 7 - 1 7 3 12 -73 1 0 - 7 3 27 25 28 67 14.7 -75 14.2 -75 19.7 -80 20.1 -80 22.7 -75 22.2 -75 22 -70 5 - 1 7 3 2 - 1 7 3 15 -73 12 -73 19 25 14 25 21 57 15 57 50 -65 20.5 -65 1 7 - 6 5 47 - 65 19.5 -65 19.5 -65 46 - 65 16 -65 15.5 -65 16.5 -65 22 -65
Method
Solvent/Notes
Refs.
5 5 3 3 5 5 5 5 5 3 5 4a 4a 4a 4a 4a 4a 4a 5 5 5 5 3 3 5 5 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a
419 419 N 77 419 419 419 420 420 420 420 420 420 N69 330 THF 330 N69 329 329 N69 328 THF 328 Dichloromethane, cyclopolymer 154 421 421 421 421 421 421 421 421 172 172 Tetrahydrofuran 172 172 172 Tetrahydrofuran 172 166 166 Tetrahydrofuran 167,172 Diethyl ether 166 rc-Pentane 166 422 14 168 306 306 51 14,52 14 14
3-RINGS
Cyclohexene oxide Ethylene oxide
Propylene oxide Styrene oxide - , 3-nitro-
Ic gg gc' gc Ic' Ic gg Ic Ic
97 104 140 127.3 102.4 94.5 75.5 101.5 101
25 25 25 25 25 25 25 26.9 26.9
2 4b 3 2 2 2 4b 3 3
gc Ic ss Ic ss ss
81.8 51.4 81 84.5 67.5 83.5
25 25 —9 26.9 -9 26.9
4a 4a 3 3 3 3
gg gc gc Ic Ic Ic
26 50 52.0 24 17 15
20 25 57 100 90 25
4b 4a 4a 4b 4a 4a
4-RINGS
Oxetane - , 3,3-di(chloromethyl)- , 3,3-dimethyl- 3,3-di(phenoxymethyl)-
Chloromethane + chloroethane o-Dichlorobenzene
325 325 53 14 53 14
N60 Ni 4 N 69 , N 78 Nn
54 292 353 198 437 292
N 17 Chloromethane + chloroethane
5-RINGS
1,3-Dioxolane
TABLE 2. cont'd Monomer
-, 4-ethyl- , 4,4-dimethyl-, as-4,5-dimethyl- , tmns-4,5-dimethy\- , 4-isopropyl- , 4-methyltams-7-Oxabicyclo[4.3.0]nonane 7-Oxa-bicyclo[2.2. l]heptane, 2-alkylR= H R = exo-CH3 R = endo-CH3 Tetrahydrofuran
- , 3-methyl-
State of monomer and polymer (xx)
- A / f xx (kj/mol)
Temp. (0C)
Method
Ic Is ss ss ss ss ss Ic Ic Ic Ic Ic Ic Ic
23 6.5 22 27 15 17.5 8 13.0 9.6 12.1 7.5 12.1 13.4 14.0
40 55 0 20 30 70 75 -24 80 80 80 80 -8
4a 4a 4a/3 4a 4a 3 4a 4a 4b 4b 4b 4b 4a
Ic Ic Ic gg gg gc gc Ic' Ic' Ic Ic Ic Ic Ic Is ss Is
44.3 49.7 45.4 21 12 39.5 47.1 29.6 38 18.6 7.5 12.5 15 25.5 23 23 22.6
25 25 25 20 25 25 50 25 25 25 25 50 30 25 40 40 -6
2 2 2 4b 4b 4a 4a 2 2 2 4a 4a 4a 2 4a 4a 4a
gg Is gg sc' sc' sc' sc' sc' c'c' c'c' c'c' c'c'
0 -4 1.5 17.5 26.5 19.5 12.5 21.5 6 11.5 4.5 5.5
20 20 20 40 58 30 30 30 30 58 25 25
4b 4a 4b 4a 3 3 4a 3 3 3 4a 2
Solvent/Notes N 15 Dichloromethane Chloroethane Benzene Dichloromethane Toluene, N 78
N 61
N 17 N 16 Diethyl ether
Refs. 159 219 133,159,220 293 134 220 423 333 335 335 335 335 334 357 308 308 308 55 56 292 353 358 56,57 358 292 130 231 140,208 57,58,211 211 342
6-RINGS
m-Dioxane /j-Dioxane Tetrahydropyran Trioxane
N 78 1,2-Dichloroethane 1,2-Dichloroethane Dichloromethane Nitrobenzene Nitrobenzene N 18 N 19
54,59,60 436 55,56,59 178 212 182,202 182 202 202 212 164 see 202
7-RINGS
1,3-Dioxepane
- 2-butyl -, 4-methyl-, 2-methyll-Oxa-4,5dithiepane
gg gc Ic ss ss ss ss ss ss ss ss Ic ss ss
19.5 20 53.9 25 13.0 25 12 75 13.5 60 14 0 15 -30 7 - 5 9.3 -15 8.8 -15 9 - 1 0 7.5 9 8
26.9 26.9 26.9
4b 4a 4a 4a 4a 4a 4a/3 4a 4a 4a 4a
N 17 Toluene, N 78 Benzene 1,2-Dichloroethane, N 78 Dichloromethane 1,2-Dichloroethane, N 78 1,2-Dichloroethane 1,2-Dichloroethane 1,2-Dichloroethane, N 78
3 3 3
Dioxane Benzene
54 323 323 423 134,87 424 136 424 339 340 424 61 61 61
Notes page 11-406; References page II - 407
TABLE 2. cont'd Monomer Oxepane
State of monomer and polymer (xx)
—AHXX (kj/mol)
Temp. (0C)
Method
Solvent/Notes
Refs.
gc Ic
38.6 -1.7
25 25
4a 4a
ss gg gc Ic sc' c'c' c'c' gc Ic ss ss
8 53.5 62.1 18.3 26 3.5 4 62.2 12.0 13 22
10 20 25 25 30 30 25 5 25 20 60
4a 4b 4a 4a 3 3 2 4a 4a 4a 4a
ss ss ss
16.7 4.6 00
0 0
4a 4a 4a
Dichloromethane Dichloromethane Dichloromethane
343 343 343
ss ss ss ss
13.4 3.8 3.8 0
0 0 0 0
4a 4a 4a 4a
Dichloromethane Dichloromethane Dichloromethane Dichloromethane
343 343 343 343
ss ss ss
11.3 7.5 0
5 5 5
4a 4a 4a
Dichloromethane Dichloromethane Dichloromethane
343 343 343
ss ss ss
10.5 -2 2.9 -2 0 — 2
4a 4a 4a
Dichloromethane Dichloromethane Dichloromethane
343 343 343
Ic Ic' Ic' Ic
75 82 80.5 74
3 3 2/4b 3
368 368 137 368
3 3 3
368 368 368
N 17
323 323
8- AND LARGER RINGS
2-Butyl-l,3,6-trioxocane 1,3-Dioxocane Tetraoxane 1,3,6-Trioxocane
(1,3,6-Trioxocane) n n=l n=2 rc = 3-8 (1,3,6,9-Tetraoxacycloundecane) „ n=\ n=2 n=3 n = 4~S 1,3,6,9,12-Pentaoxacyclotetradecane)n n=\ n=2 n = 3-l 1,3,6,9,12,15-Hexaoxacycloheptadecane) „ n=l n=2 n = 3-5
Toluene, N 78 N 17 Nitrobenzene
N 17 Toluene, N 78 Benzene
425 54 324 324 202 131,202 see 202 324 324 425 134
2.1.2. CYCLIC ESTERS 4-RINGS
P-Propiolactone
25 25 25 127
5-RINGS
y-Butyrolactone
Ic Ic' Ic
-5 7 -6
25 25 77
c'(II)c'(II) c'(II)c c'(II)c'(H) c'(II)c Ic'(I) 11 c'c' c'c c'c' c'c c'c' c'c 11 c'c c'c c'c c'c
7 - 1 7 3 -9 -173 7 25 -8 25 18 117 12 147 21 -173 6 - 1 7 3 21 -73 6 - 7 3 21 25 4 25 17 127 8.6 -173 9.0 -73 10.1 25 8.3 87
6-RINGS
2,2-Dimethyltrimethylene carbonate
p-Dioxanone
Ethylene oxalate
5 5 4b 4b 5 5 5 5 5 5 2 2 5 5 5 2 5
N 54 , N 63 , N 77 N545N63 N 63 , N 77 N 63
426 426 426 426 426 426 427 427 427 427 427 427 427 312 312 312 312
TABLE 2.
cont'd
Monomer Glycollide DL-Lactide L-Lactide 8-Oxo-7-oxabicyclo[2,2,2]octane Pentanolactone
State of monomer and polymer (xx)
-AZJxx (kj/mol)
Temp. (0C)
Method
Solvent/Notes
Refs.
Ic c'c' cc Ic c'c Ic ss ss c'c' gc' Ic' Ic' Ic Ic
20.0 34.0 10.8 31.4 8.7 27.0 25 23 20.9 90.5 34.5 27.5 10.5 9.9
142 25 25 277 25 127 40 105 25 25 25 25 25 77
2 2 2 2 2 2 4a 4a 2 2 2 2 2 3
Ic Ic' Ic ss
17 31 13.7 15
25 25 77 40
3 3 3 4a
Nitrobenzene, N 78
368 368 368 428
ss ss ss
11 8 5
4b 4b 4b
Dichloromethane Dichloromethane Dichloromethane
430 430 430
ss
7
- 5 0 t o - 1 0 4b
Dichloromethane
430
Nitrobenzene, N 78 1,4-Dioxane, N 78 N53 N53 N53
312 364 364 364 311 311 428 429 307 307 307 314 314 314
7-RINGS
e-Caprolactone
Spiroorthoester 2-R-1,4,6-trioxaspiro[4.6] undecane R= H R = CH 3 R = CH3Br
R = Ph
- 30 to 5 - 5 0 to 5 -35 t o - 5
8-AND LARGER RINGS
Heptanolactone Octanolactone Nonanolactone Decanolactone Undecanolactone Dodecanolactone Tridecanolactone Tetradecanolactone Pentadecanolactone
Hexadecanolactone
Ic Ic Ic Ic Ic Ic' Ic Ic c'c c'c' Ic Ic c'c c'c' Ic c'(II)c Ic
16 19 22 24 28 62 27 17 -2 38 6 2 -10 39 -3 -37 0
127 127 127 127 25 25 127 127 25 25 127 127 25 25 97 -73 127
4b 4b 4b 4b 3 3 3 4b 3 3 3 4b 1 1 1 1 4b
N54
368 368 368 368 368 368 368 368 368 368 368 368 313 313 313 313 368
2.2. MONOMERS GIVING POLYMERS CONTAINING O IN THE MAIN CHAIN, BONDED TO OTHER HETEROATOMS (S, Si, P) Cyclotrisiloxane, 1,1,3,3,5,5-hexaethyl
-, hexamethyl Cyclotetrasiloxane, octamethylAW-Diethylamino1,3,2-dioxaphosphorinane 1,3,2-Dioxaphospholan, 2-methoxy-
c'(IH)c'(II) c'(II)c'(II) c'(II)c c'(I)c'(I) c'(I)c 11 Is Ic Ic c'c Ic Ic Is ss ss
4.6 -173 5 - 7 3 -10 -23 10 -23 1 25 14 25 15 170 14.5 25 23.4 77 2.79 25 -13.4 77 -6.4 25 -6.3 -20 15 14
3 3 3 3 3 3 3 3 3 3 3 3 4a
N 54 , N 63 , N 77 N 54 , N 63 , N 77 N 54 , N 63 N 54 , N 63 , N 77 N 54 , N 63 N 63 95% Conversion N 62 N63 N 62 N63 N 58
431 431 431 431 431 431 431 84 365 365 365 365 346
3 4a
Dichloromethane 1,1,2,2-Tetrachloroethane
309 309
Notes page 11-406; References page 11-407
TABLE 2.
cont'd
Monomer 2-Oxo-1,3,2-dioxaphosphorinane - , 2-alkoxyR = methyl R = methyl R = ethyl R = propyl R = trimethyl silyl Sulfur trioxide
State of monomer
—AH^
Temp.
and polymer (xx)
(kj/mol)
(0C)
Ic
-6.28
90
Method 4a
Solvent/Notes N59
Refs. 347
Is 2.9 140 4a Diglyme or DMSO 348 ss 0.8 100 4a Dichloromethane 356 ss -1.0 100 4a Dichloromethane 356 ss -2.4 100 4a Dichloromethane 356 ss -2.7 100 4a Dichloromethane 356 gc' 56 13 4a 86 Ic' 12.5 25 4a 86 2.3. MONOMERS GIVING POLYMERS CONTAINING S IN THE MAIN CHAIN, BONDED IN THE CHAIN TO CARBON ONLY (listed by increasing ring size) (polysulfones listed under Table 3. Copolymers) Carbon disulflde Thiirane
- , 2,2-dimethyl- , c/s-2,3-dimethyl- , frarcs-2,3-dimethyl- , 2-methylThietane Thioacetone Thiolane 1,2-Dithiolane Thiane oDithiane SS(CH2)3CH2 exo-3,4,5-Trithiatricyclo[5.2.2.02'6]decane exo-3,4,5-Trithiatetracyclo[5.5.1.02'6.0812]tridec-10-ene
Ic' gg Ic sc' gg gg gg gg gg Is gg ss gg Ic
23 81 73 ± 4 80 ± 4 70.5 63 5.5 71 80 10.8 7.5 26.5 -2.5 2
2 4b 3 3 4b 4b 4b 4b 4b 4a 4b 4a 4b 3
N20 Various solvents N20 N20 N20 N20 N20 Monomer N20 Ethyl alcohol N20
179 69,70,71 173 173 69,70,71 69,70,71 69,70,71 69,70,71 69,70,71 327 69,70,71 72 69,70,71 14
ss
5.8
40
4a
Toluene, N 7 8
377
ss
6.6
50
4a
Toluene, N 7 8
376
4b
N20
Thiepane
gg
14.5
1,2-Dithiepane SS(CH2)4CH2
lc
10 5
1,2-Dithiocane SS(CH2)5CH2
25 25 20 20 25 25 25 25 25 50-90 25 30 25 26.9
sc
11.5
lc
16
25 26 9
26.9 26 9 -
69,70,71
3
14
3
Dioxane
14
3
14
2.4. MONOMERS GIVING POLYMERS CONTAINING N IN THE MAIN CHAIN, BONDED IN THE CHAIN TO CARBON ONLY (listed by increasing ring size) 2-RINGS
Butylisocyanate
ss
2 4 — 5 5
4a
Dimethylformamide, N 7 8
432
3-RINGS
Ethyleneimine -,Ar-(P-trimethylsilylethyl)(TEI) - , - Z n C l 2 - ( T E I ) 2 (complex)
Ic Ic c'c
96.2 119 264
27 27 27
2 2 2
Ic c'c
115 258
27 27
2 2
ss Ic Ic Ic' c'c' Ic ss ss ss
24 4.5 3.5 12 -5.5 3.5 145 104 60
38 75 43 43 25 25 15 30 50
4a 2/4b 3 3 2/4b 4b 3 3 3
#
360 360 360
4-RINGS
Trimethyleneimine, - , AKP-trimethylsilylethyl)(TMI) - , - , Z n C l 2 - (TMI)2(complex)
360 360
5-RINGS
8-Oxa-6-azabicyclo[3.2.1]octan-7-one 2-Pyrollidinone
- , 1-methylPyrrole
Dimethylsulfoxide, N 7 8
Acetonitrile Acetonitrile Acetonitrile
433 62 135 135 63 64 434 434 434
TABLE 2. cont'd Monomer
State of monomer and polymer (xx)
-AHx^ (kj/mol)
Temp. (0C)
Method
Solvent/Notes
Refs.
6-RINGS
2-Piperidone - , 1-methyl-
Ic c'c' Ic
9 4.5 -2
75 25 25
2/4b 2/4b 4b
62 63 64
Ic Ic Ic Is c'c' Ic Is Is Is Is Ic Is Ic Is Is Is
16.3 16 15.5 16.5 12.5 9.5 12.5 16 16.5 14.5 16 11 16 16.5 14.5 14.5
186 75 200 250 25 25 260 240 240 240 75 200 75 225 240 240
3 2 3 4a 2 4b 4a 3 3 3 4b 4a 4b 4a 3 3
310 62 65,135,138 68,67,66 63 64 194 191 191 171 62 225 62 226 191 191
Ic Ic cV Ic Is Is
22 22 24 16.5 22 21.5
75 230 25 25 240 240
4b 3 2 4b 3 3
62 138,207 63 64 171 171
Ic Ic c'c' c'c' c'c' Ic Is
10.6 32.5 23.5 11.5 -2 ~0 13
186 230 25 25 25 230 290
3 3 2/4b 2/4b 2/4b 3 4a
310 138,189 138 138 138 138,139 139
7-RINGS
8-Caprolactam
-, -, -, -, -, -,
1-methyl 3-methyl 3-ethyl 3-propyl 4-ethyl 5-methyl
-, 7-methyl -, 7-ethyl -, 7-propyl 8-RINGS
2-Oxo-hexamethyleneimine -, 1-methyl-,4-ethyl-, 7-ethyl9-13-RINGS
Q-Dodecalactam 2-Oxo-heptamethyleneimine 2-Oxo-octamethyleneimine 2-Oxo-nonamethyleneimine 2-Oxo-decamethyleneimine 2-Oxo-undecamethyleneimine
2.5. MONOMERS GIVING POLYMERS CONTAINING N IN THE MAIN CHAIN, BONDED TO OTHER HETEROATOMS (P) Phosphonitrile chloride -, cyclic trimer - , cyclic tetramer -, cyclic pentamer - , cyclic hexamer -, cyclic heptamer
gc Ic gc Ic gc Ic gc Ic gc Ic
61 6 68 4 79.5 3.5 88 1.5 96.5 0
230 230 230 230 230 230 230 230 230 230
3 3 3 3 3 3 3 3 3 3
125 125 125 125 125 125 125 125 125 125
25 60
2
Linear polymer (carbyne) Chloroform, N 78 , N 79
187 435
4a
Dichloromethane, N 67
317
2.6. OTHER MONOMERS GIVING POLYMERS NOT LISTED ABOVE Carbon C (graphite) 4,7-bis[Cyano(ethoxycarbonyl) methylene]-4,7-dihydrobenzofuran 4-(2,3-Diphenyl cyclopropenylidene)cyclohexa-2,5-dienone 1,3-Disilacyclobutane, 1,1,3,3-tetramethylSelenium Se 8
c'c7 ss ss Ic Is
-39.5 21.6
21.2-15 73.9 -9.5
25 400
2 4a
359 85 Notes page 11-406; References page II - 407
TABLE 2. cont'd State of monomer and polymer (xx)
Monomer 1-Silacyclobutane, 1,1-dimethyl-, 1-phenyl, 1-methylSulfur, S 6 -,S7 -,S8 -,S8
Ic' Ic Ic Is Is Is Is
-AH101 (kj/mol)
Temp. (0C)
92.7 85.4 91.5 10 4 -19 -13.5
Method
25 25 25 138 138 160 200
Solvent/Notes
2 2 2 2 2 4a 4a
Refs. 359 359 359 380 380 380 73,74
N 72 N 72 Nn
TABLE 3. COPOLYMERS (listed alphabetically under Monomer A) N 2 i
Monomer A
Monomer B
State of monomer and polymer xx
Acrylonitrile
Methacrylic acid, Methyl ester Styrene Vinyl acetate Vinylidene chloride Maleic anhydride
sc ss ss ss sc ss
Allyl chloride bis-(0-Aminophenyl)-2,2' dibenzymidazoleoxide Terephthalic acid -, dichloride - , dimethylether 1,3-Butadiene 1-Butene
Styrene Sulfur dioxide Sulfur dioxide
-, 3-methyl-
Sulfur dioxide
2-Butene, cis
Sulfur dioxide
- , trans
Sulfur dioxide
Cyclohexene Cyclopentene 1,3-Dioxane
Sulfur dioxide Sulfur dioxide 1,3-Dioxolane
Fumaric acid, diethyl ester Fumaroyl chloride Isobutene
Vinyl acetate Styrene Styrene, a-methylSulfur dioxide
1-Hexadecene
Sulfur dioxide
1-Hexene Isopropenyl acetate Maleic acid, diethyl ester Maleic anhydride
Sulfur dioxide Maleic anhydride Vinyl acetate Allyl chloride Isopropenyl acetate Styrene
-AH11x (kj/mol)
74
c'c c'c c'c c'c c'c c'c c'c c'c c'c Ic
24 18 6.5 136 96 83.5 31.5 16.5 5.5
ss ss Ic' Ic ss ss ss ss ss ss ss
44.5 43.5 46 22 42.5 43.5 39.5 40.5 38 45 16
ss? ss ss Ic Ic ss ss ss sc ss? ss sc ss ss
Temp. (0C) 25 30.5 20 20 25 74.5 -173 -73 25 -173 -73 25 -173 -73 25 25
Method 3 3 3 3 3 3
Solvent/Notes Emulsion (aq.)
Emulsion(aq.), N 22
5 5 2 5 5 2 5 5 2 2
Polymer Polymer Polymer Polymer Polymer Polymer Polymer Polymer Polymer
+ + + + + + + + +
H 2 O (c') H2O (c 0 H 2 O (1) HCl (c') HCl (g) HCl (g) CH3OH (c') CH3OH (1) CH3OH (1)
26.9 55 35 25 26.9 25 26.9 25 25 26.9 20
3 4a 4a 4a 3 4a 3 4a 4a 3 4a
Excess B Excess B From B-rich mixture From A-rich mixture Excess B Excess B Excess B Excess B Excess B Excess B Methylene dichloride, N 78 A ^ B A = - H
78 80 71.5 31 39.5 42 40 43.5 74.5
76.8 74.5 74.5 25 0 26.9 30 26.9 76.8
3 3 3 2 4a 3 4a 3 3
Excess B, N 22 Hexane Excess B
83.5 74 74.5 81 82.5
76.8 74.5 76.8 74.5 74.5
3 3 3 s 3
Excess B, N 22
N 23 Chloroform Chloroform Excess B
Benzene Acetonitrile
Refs. 38 76 76,201 76 75 34 445 445 445 445 445 445 445 445 445 45 197 5 77 199,200 199,200 5 5 5 5 78 5 446 79 34 34 82 83 5 80 5 79 79 34 79 34 34
TABLE 3. cont'd
Monomer A
Maleimide Methacrylic acid - , methyl ester
Propene Styrene
- , a-methyl-
Sulfur dioxide
Monomer B Styrene, a-methylVinyl acetate Vinyl rc-butyl ether Styrene Styrene, a-methylMethacrylic acid, methyl ester Acrylonitrile Methacrylic acid Styrene Vinyl acetate Sulfur dioxide Acrylonitrile 1,3-Butadiene Fumaroyl chloride Maleic anhydride Maleimide Methacrylic, acid, methyl ester Vinyl acetate Fumaroyl chloride Maleic anhydride Maleimide Butadiene 1-Butene - , 3-methyl2-Butene, cis - , trans Cyclohexene Cyclopentene 1-Hexadecene 1-Hexene Isobutene
Vinyl acetate
Vinyl rc-butyl ether Vinylidene chloride
B.
Propene Acrylonitrile Fumaric acid, diethyl ester Maleic acid, diethyl ester Maleic anhydride Methacrylic acid, methyl ester Styrene Maleic anhydride Acrylonitrile
State of monomer and polymer xx
—AHXX (kj/mol)
Temp. (0C)
ss sc ss ss ss
72.5 84.5 90 87.5 72
74.5 76.8 74.5 74.5 74.5
3 3 3 3 3
25 25 30.5 25 24 24 26.9 20 25 74.5 74.5 74.5 74.5 24
2 3 3 2 3 3 3 3 2 3 3 3 3 3
35 74.5 74.5 74.5
3 3 3 3
26.9 55 35 25 26.9 25 26.9 25 25 26.9 26.9 30 26.9 25 0 26.9 20 76.8 76.8 76.8
3 4a 4a 4a 3 4a 3 4a 4a 3 3 4a 3 2 4a 3 3 3 3 3
24 35 74.5 25
3 3 3 3
Ic sc ss Ic ss ss sc ss Ic ss ss ss ss ss ss ss ss ss ss ss Ic7 Ic ss ss ss ss ss ss ss ss ss Ic Ic sc ss ss? ss? sc ss ss ss sc
42.5
80 81 82.5 87.5
71.5 72.5 72 44.5 43.5 92 44.5 42.5 43.5 39.5 40.5 38 45 42 40 43.5 31 39.5 42.5 78 83.5 84.5
90
Method
Solvent/Notes Excess B Excess B Benzene Acetonitrile Acetonitrile
Emulsion (aq.)
Excess B
Hexane Benzene Acetonitrile Acetonitrile
Excess A Excess A Acetonitrile Excess A Excess A From A-rich mixture From B-rich mixture Excess A Excess A Excess A Excess A Excess A Excess A Chloroform Chloroform Excess A N24 Excess A Excess A, N22 Excess A, N 2 2 Excess A
Benzene Emulsion (aq.), N 2 2
Refs. 34 79 34 34 34 206 38 76 206 81 81 5 76,201 45, 34 34 34 34 81 81 34 34 34 197 5 77 199 199 5 5 5 5 78 5 5 80 5 82 83 5 76 79 79 79 81 81 34 75
ENTROPIES O F P O L Y M E R I Z A T I O N
Symbols: The subscripts to AS0 denote the state of the monomer (first letter) and the state of the polymer (second letter) as in Section A. The standard state of the monomer is 1 atm for the gaseous state and IM in solution, unless otherwise stated. In all cases where monomer or polymer is present in solution, the value of AS0 will depend to some extent on the composition. Where the polymer is crystalline, AS0 will depend on the degree of crystallinity. AS values are in (J/K) per mol of monomer and are generally the limiting values for high degree of polymerization (1 kcal = 4.187kJ).
Notes page 11-406; References page 11-407
Precision: generally 0.5-8.0 (J/K/mol) Methods of determination: (numbering conforms with that in Section A) 1 Third law or statistical. 4a Thermodynamic (van't Hoff Equation). 4b Semiempirical rules applied to evaluate entropy of monomer or polymer or both.
TABLE 4. MONOMERS GIVING POLYMERS CONTAINING MAIN CHAIN CARBON ONLY
Monomer
State of monomer
-AS^ x
Temp.
and polymer xx
(J/K/mol)
(0C)
Method
Solvent/Notes
Refs.
4.1. MAIN CHAIN ACYCLIC CARBON ONLY 4.1.1. DIENES 1,3-Butadiene Isoprene
Ic Ic Ic
89 84 101
25 25 25
1 1 1
ds-l,4-Polymer
95,96 97 100,101
4.1.2. MONOMERS GIVING POLYMERS WITHOUT OR WITH ALIPHATIC SIDE CHAINS WHICH CONTAIN ONLY C, H 4.1.2.1. Olefins (listed by increasing carbon number) Ethylene
Propene
1-Butene
2-Butene, cis
c'c' c'c gc' gc gg gc gc gc1 gc' gc' gc gc' gc gl gg gc' gc' Ic Ic Ic Ic' Ic' Ic Ic' Ic gg gc' gc Ic Ic Ic' gc' gc gl c'c' c'c Ic' Ic gg Ic gc' gc gc' gc gl
66 59 338 331 142 155 158 172 174 336 325 334 317 311 167 191 205 113 116 116 136 75 69 114 107 166 213 193 113 112 141 204 187 182 21 14 106 99 163 104 201 190 196 179 172
-173 -173 -73 -73 25 25 25 25 25 25 25 127 127 227 25 25 25 25 25 25 25 -173 -173 -73 - 73 25 25 25 25 25 25 127 127 227 -173 -173 -73 - 73 25 25 25 25 127 127 227
1 1 1 1 4b 4b 1 4b 1 1 1 1 1 1 4b 1 1 4b 1 1 1 1 1 1 1 4b 1 1 4b 1 1 1 1 1 1 1 1 1 4b 4b 1 1 1 1 1
Isotactic Isotactic Isotactic Isotactic
poly(-l-butene) poly(-l-butene) poly(-1-butene) poly (-1-butene)
100% Cryst. polymer Isotactic poly (-1-butene) Isotactic poly (-1-butene) Isotactic poly (-1-butene) Isotactic poly (-1-butene) Isotactic poly (-1-butene) Syndiotactic polymer Isotactic polymer Isotactic polymer Atactic polymer 100% Cryst. isotactic Isotactic polymer Isotactic polymer Isotactic polymer Isotactic polymer Isotactic polymer Isotactic polymer Isotactic polymer 100% Cryst. isotactic Isotactic polymer Isotactic polymer Isotactic polymer Isotactic polymer Isotactic polymer Isotactic polymer Isotactic polymer Isotactic Isotactic Isotactic Isotactic Isotactic
polymer polymer polymer polymer polymer
385 385 385 385 2,87 11 88-91 11 88-91 385 385 385 385 385 5 186 207 5 88 88,92 88,92 385 385 385 385 5 88,385 88,385 5 88 88 385 385 385 385 385 385 385 5 5 385 385 385 385 385
TABLE 4.
cont'd
Monomer -, trans
Isobutene
1-Pentene
-, 4-methyl
2-Pentene, cis
-,4-methyl
2-Pentene, trans
-,4-methyl
State of monomer and polymer xx
-ASJ x (J/K/mol)
Temp. (0C)
Method
c'c' c'c Ic' Ic gg Ic gc' gc gc' gc gl gg Ic Ic
17 10 100 93 159 100 195 194 193 175 170 172 112 121
-173 -173 -73 - 73 25 25 25 25 127 127 227 25 25 25
1 1 1 1 4b 4b 1 1 1 1 1 4b 4b 1
c'c' c'c Ic' Ic Ic' Ic gl gl c'c' c'c Ic' Ic gc' Ic' Ic gc' gc gc' gc gl c'c' c'c Ic' Ic Ic' Ic gl gl Ic' Ic gc' gc gc' gc gl c'c' c'c Ic' Ic Ic' Ic gl gl Ic' Ic gc' gc gc'
24 20 117 113 133 124 198 190 28 28 111 111 216 131 131 214 200 209 188 176 20 16 114 111 129 120 195 185 134 134 220 205 215 215 183 18 14 111 102 127 118 194 186 130 130 216 202 214
-173 -173 -73 -73 25 25 127 227 -173 -173 -73 -73 25 25 25 127 127 227 227 327 -173 -173 -73 -73 25 25 127 227 25 25 127 127 227 227 327 -173 -173 -73 -73 25 25 127 227 25 25 127 127 227
1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
Solvent/Notes Isotactic Isotactic Isotactic Isotactic
polymer polymer polymer polymer
Isotactic Isotactic Isotactic Isotactic Isotactic
polymer polymer polymer polymer polymer
Isotactic polymer
Refs. 385 385 385 385 5 5 385 385 385 385 385 5 5 11,93 386 386 386 386 386 386 386 386 387 387 387 387 196 387 387 387 387 387 387 387 386 386 386 386 386 386 386 386 387 387 387 387 387 387 387 386 386 386 386 386 386 386 386 387 387 387 387 387
Notes page 11-406; References page 11-407
TABLE 4. cont'd State of monomer and polymer xx
Monomer
1-Hexene 1-Heptene
-ASJJx (J/K/mol)
Temp. (0C)
Method
Solvent/Notes
Refs.
gc gl Ic gg
194 182 113 168
227 327 25 25
1 1 4b 4b
387 387 5 5
Ic Ic Ic Ic Ic Ic Ic Ic Ic Ic Ic Ic Ic Ic
69 85 93 55 72 75 43 64 66 11 32 36 16 3
25 25 25 25 25 25 25 25 25 25 25 25 25 25
4b 4b 4b 4b 4b 4b 4b 4b 4b 4b 4b 4b 4b 4b
11 87 87 11 87 87 11 87 87 11,87 87 87 11,94 11,94
52 131 17 54 52 47.2 18 56 52 51 17 -7 6 37 56 37 70 36 10 -25 49 8 63 9 9
25 25 -173 -73 25 25 -173 -73 25 77 -65 -173 -173 - 73 -73 25 25 5 1 -173 -173 -73 - 73 25 25 57
4.1.2.2. Cycloalkanes (listed by increasing ring size) Cyclopropane - , methyl- , 1,1-dimethylCyclobutane - , methyl- , 1,1-dimethylCyclopentane - , methyl- , 1,1-dimethylCyclohexane -,methyl- , 1,1-dimethylCycloheptane Cyclooctane Cycloalkenes Cyclobutene
11 gl c'(I)c Ic Ic Ic c'(I)c Ic Ic Ic ss c'(III)c c '(HI)C' c'(II)c c'(II)c' Ic Ic' 11 c'(II)c' c'(1I)C c'(I)C7 c r(I)c Ic' Ic 11
Cyclopentene
Cyclohexene Cycloheptene
Cyclooctene
1,4b 1,4b 1 1 1,4b 1 1 1 1,4b 1 4b 1 1 1 1 4b 4b 1 1 1 1 1 1,4b 1,4b 1
N25 N25
ds-Polybutadiene as-Polybutadiene czs-Polymer ds-Polymer ds-Polymer N66 frans-Porymer Jra^-Polymer tarns-Polymer tarns-Polymer Toluene, N 7 8 70% trans, 30% cis Polymer, N 5 4 70% trans, 30% cis Polymer, N 5 4 70% trans, 30% cis Polymer, N 5 4 70% trans, 30% cis Polymer, N 5 4 70% trans, 30% cis Polymer 70% trans, 30% cis Polymer 70% trans, 30% cis Polymer 48% trans, 52% cis Polymer, N 5 4 48% trans, 52% cis Polymer, N 5 4 48% trans, 52% cis Polymer, N 5 4 48% trans, 52% cis Polymer, N 5 4 48% trans, 52% cis Polymer 48% trans, 52% cis Polymer 48% trans, 52% cis Polymer
388 388 388 388 388 361 388 388 388 388 389 388 388 388 388 388 388 388 388 388 388 388 388 388 388
4.1.3. MONOMERS GIVING POLYMERS WITH ALIPHATIC SIDE CHAINS THAT CONTAIN HETEROATOMS Acrylonitrile - , allylester
- , allylloxyethyl
-,
rc-decylester
Ic' c'c c'c c'c Ic Ic Ic cc Ic Ic Ic c'c c'c
109 -6 1 24 97 85 96 16 29 56 60 4 8
25 -173 -73 -8 -8 25 127 -173 -73 25 57 -173 -73
1 1 1 1 1 1 1 1 1 1 1 1 1
193 391 391 391 391 391 391 393 393 393 393 392 392
TABLE 4. cont'd Monomer
State of monomer and polymer xx
- , ethylester
Ethacrylic acid -methyl ester Ethylene, tetrafluoroMethacrylic acid - , ethyl ester - , methyl ester
- , methyl ester deuterated
Methacrylonitrile a-Methylene pentanolactone Vinylidene chloride
"AS^ x (J/K/mol)
Temp. (0C)
Ic Ic c'c C7C Ic Ic Ic
141 155 3 16 88 104 107
25 127 -173 -73 25 127 177
Is gc' Ic' ss Ic Ic c'c c'c c'c' Ic Ic ss c'c c'c Ic Ic ss ss c'c' c'c Ic' Ic Ic' Ic gc' gc gc' gc
105 87 197 -75.7 112 -75.7 146 80 126 120 117 127 9 -173 24.1 -73 40 -63 105 25 115 77 130 127 1 0 - 1 7 3 26 -73 110 25 118 77 151 127 108.8 83 31 -173 25 -173 97 -73 91 -73 112 25 106 25 201 25 195 25 198 127 191 127
Method
Solvent/Notes
1 1 1 1 1 1 1 4b 1 1 4b 4a 4a 1 1 1 1 1 4a 1 1 1 1 4a 4a 1 1 1 1 1 1 1 1 1 1
Refs. 392 392 390 390 390 390 390
o-Dichlorobenzene
Benzonitrile DMF
395 98,99 98,99 316 40 42,43,102 414 414 102,103 414 414 42,49 414 414 414 414 44,29 315 397 397 213,397 397 397 397 397 397 397 397
4.1.4. MONOMERS GIVING POLYMERS WITH AROMATIC SIDE CHAINS THAT CONTAIN ONLY C, H Acenaphtylene Biphenyl,/7-isopropenylNaphthalene, 2-isopropenylStyrene
- , oc-methyl-
-, a-methyl, p-tert-buly\-
ss ss ss ss gg Ic Ic Ic Ic Ic Ic Ic' Ic ss ss ss ss ss
98 118 122 125 149 90 104 116 104 105 112 111 110 130 51 47 163.3 106.6
60 -20 -5 10 25 -23 25 127 127 25 25 25 -20 -20 -10 -10 22
4a 4a 4a 4a 4b 1 1 1 4a 1 1 1 4a 4a 4a 4a 4a 4a
Toluene, N 78 Tetrahydrofuran Tetrahydrofuran Toluene, N 78
N 26 Isotactic polymer 100% Cryst. isotactic Tetrahydrofuran rc-Heptane, N 78 Toluene, N 78 Cyclohexane Solvent and temp, not stated
399 16 16 400 25 104 104 104 28 88 105 88 32 32,29,16 402 402 341 381
4.1.5. MONOMERS GIVING POLYMERS WITH AROMATIC SIDE CHAINS AND THAT CONTAIN HETEROATOMS a-Acetoxystyrene 2-Amino-4-(Af-alkalino)-6-isopropenyl-1,3,5-triazine alkyl = «-propyl isopropyl isobutyl
ss
83
64
4a
Is Is Is
117 114 114
157 151 154
4a 4a 4a
Toluene, N 78
401 402 403 403
Notes page 11-406; References page 11-407
TABLE 4. cont'd
Monomer
State of monomer and polymer xx
sec-butyl Is 1-methylbutyl Is rc-pentyl Is isopentyl Is rc-hexyl Is n-octyl Is rc-decyl Is rc-dodecyl Is rc-tetradecyl Is n-hexadecyl Is benzyl Is 2-Amino-4-alkyl/aryl-amino-6-isopropenyl-1,3,5-triazine Is Ri = H, R 2 = ethyl Is Ri = H, R 2 = propyl Is Ri = ethyl, R 2 = ethyl Is R 1 = propyl, R 2 = propyl Ri = methyl, R 2 = phenyl Is Ri = H, R 2 = p-methoxyphenyl Is Benzoic acid, rc-methacryloyloxyc'c c'c crc 11 Oxazole, 2-isopropenyl, 4,5-dimethylss Pyridine, 2-isopropenylss Silane, benzyl dimethyl vinylc'c Ic Ic - , dimethyl phenyl vinylIc - , trimethyl vinylIc Thiazole, 2-isopropenylss /7-[bis(Trimethylsilyl)methyl] isopropenylbenzene ss AWV',Ar'-Tetraethyl-4isopropenylphenyl-phosphonous diamide ss
-AS^ x (J/K/mol) 112 111 114 113 112 110 109 109 105 102 113 160.5 153.8 137.5 124.6 131.7 117 -2 5 8 85 96 70 0.7 83.5 107.3 127.5 109.5 69
Temp. (0C) 148 146 150 151 149 143 140 134 132 130 157 150 145 130 125 150 160 -173 -73 25 227 20 20 -73 25 77 25 25 20
Method
Solvent/Notes
Refs.
4a 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a 1,4a 4a 4a 4a 1 1 3 1 1 4a
403 403 403 403 402 402 402 402 402 402 403
Tetrahydrofuran
370 370 370 370 379 378 394 394 363,394 394 284 284 355 366 366 362 367 284
Tetrahydrofuran Tetrahydrofuran
110
-30
4a
Tetrahydrofuran
409
10
-55
4a
Tetrahydrofuran
408
4.1.6. OTHER MONOMERS GIVING POLYMERS NOT LISTED ABOVE
Vinylcyclohexane
4.2.
c'c c'c Ic' Ic Ic' Ic Ic' Ic
28 3 95 75 120 85 136 102
-173 -173 -73 -73 25 25 127 127
1 1 1 1 1 1 1 1
396 396 396 396 396 396 396 396
WITH AROMATIC OR CYCLIC CARBONS IN THE MAIN CHAIN
-11,12-Dicyano-2,6-naphtoquinodimethane ll,12-bis(alkylthio) alkyl = butyl = sec-butyl = isopropyl = ethyl = methyl -7,8-Dicyanoquinodimethane 7,8-bis(butoxycarbonyl)7,8-diacetyl7,8-dibenzoyl7,8-dibutoxycarbonyl7,8-diisobutyryl7,8-dipropionyl7,8-bis(ethylthio)-
ss ss ss ss ss
109 109 116 115 114
30 30 30 30 30
4a 4a 4a 4a 4a
Oligomer, Oligomer, Oligomer, Oligomer, Oligomer,
benzene, benzene, benzene, benzene, benzene,
ss ss ss ss ss ss ss
37 37 38 37 39 37 37
60 55 55 55 55 55 60
4a 4a 4a 4a 4a 4a 4a
Chloroform, Chloroform, Chloroform, Chloroform, Chloroform, Chloroform, Chloroform,
N78, N78, N78, N78, N78, N78, N78,
N78, N78, N78, N78, N78,
N8i N8i N 82 Ngi N8i N8i N8i
N 8o N80 N80 N80 N 8o
410 410 410 410 410 411 412 412 412 413 413 411
TABLE 4. cont'd Monomer 7,8-bis(phenylacetyl)7,8-bis(phenylthio)-4,7-Dihydrobenzofuran 4,7-bis-[cyano(ethoxycarbonyl)methylene] Norbornylene
5-trimethylsilyl-2-
Af,7,7-Tricyanobenzoquinonemethideimine
State of monomer and polymer xx
-ASJ x (J/K/mol)
ss ss
37 34
ss c'(II)c c'(I)c c'(I)c Ic c'c cc c'c cc Ic Ic ss
41 5 50 50 58 4 13 14 48 70 81 38
Temp. (0C) 55 50 60 -173 -73 25 57 -173 —173 -73 — 73 25 107 55
Method
Solvent/Notes
4a 4a
Chloroform, N 78 , N 8 i Chloroform, N 78 , N 81
4a 3 3 4b 3 1 1 1 1 1 1 4a
Chloroform, N 78 55% cis/45% trans 55% cis/45% trans 55% cis/45% trans 55% cis/45% trans
Polymer Polymer Polymer Polymer
Overcooled monomer Overcooled monomer Toluene, N 7 8 , N 8 i
Refs. 413 411 N54 N54 N54 N54
435 415 415 415 415 416 416 416 416 416 416 438
TABLE 5. MONOMERS GIVING POLYMERS CONTAINING HETEROATOMS IN THE MAIN CHAIN
Monomer 5.1.
State of monomer
-AS^ x
Temp.
and polymer xx
(J/K/mol)
(0C)
Method
Solvent/Notes
Refs.
MONOMERS GIVING POLYMERS CONTAINING O IN THE MAIN CHAIN, BONDED TO CARBON ONLY
5.1.1. ETHERS AND ACETALS (listed by increasing ring size of monomer) 2-RINGS (aldehydes and ketones) Acetaldehyde c'c -6 Ic 14 Ic 21 -, bromochlorofluorosc' 122 -, bromodichlorosc' 122 -, bromodifluorosc' 135 -, dibromochlorosc' 116 -, dibromofluorosc' 114 - , dichlorofluorosc' 179 - , difluorochlorosc' 152 - , tribromosc' 100 - , trichlorogc' 190 ± 3 0 Ic' 95 ± 3 0 sc' 134 sc' 117 ss 52 sc' 142 - , trichloro cc' 37 Ic' 69 Ic' 80 Ic' 30 - , trifluorogc 187 Ic 97 sc' 155 sc 142.7 Acetone gc 188 Butanal sc 122 4,7-Dioxaoctanal Ic 67.4 ss 77.0 Formaldehyde gg 124 gc' 174 gc; 169 Heptanal c'c' 25 c'c 1 c'c' 32
-173 -73 25
50 50 13 -50 10 -173 -73 25 57 45 25 25 25 10 -80 -80 25 25 25 -173 -173 -73
1 1 1 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a 1 1 1 1 4a 4a 4a 4a 4b 4a 4a 4a 1 1 4a 1 1 1
Toluene, Toluene, Toluene, Toluene, Toluene, Toluene, Toluene, Toluene,
N74 N74 N74 N74 N74 N74 N74 N 74
Toluene, N 7 4 Pyridine, N 27 Tetrahydrofuran n-Heptane
Dichloromethane Toluene, N 7 4 Dichloromethane rc-Hexane N 69 THF N28
[9 kbar], N n
417 417 417 233 344 344 344 344 344 344 344 50 50 344 50 167 166 418 418 418 418 129 322 344 322 144,148 161 330 330 141,142 106 164,165 419 419 419
Notes page 11-406; References page II - 407
TABLE 5. cont'd Monomer
Hexanal
Octanal 4-Oxapentanal Pentanal oPhthalaldehyde Propanal
-, 2-chloro 2-methyl-, 2,2-dichloro-, 2-methyl-
State of monomer and polymer xx
"AS^ x (J/K/mol)
Temp. (0C) -73 25 25 97 -173 -173 -73 -73 25 67 -75 -75 -80 -80 -75 -75 -70 -173 -173 -73 -73 25 25 57 57 - 65 - 65 - 65 - 65 -65
Method
c'c Ic'(I) Ic 11 c'c' c'c c'c' c'c 11 11 Ic sc Ic Is Ic sc ss c'c' c'c Ic' Ic Ic' Ic Ic' Ic ss ss ss ss ss
4 Hl 101 110 19 16 43 41 117 121 57.8 65.7 81.6 93.6 97.1 107.6 96 8 6 69 67 85 76 90 77 90 69 74 78 94
1 1 1 1 1 1 1 1 1 1 4a 4a 4a 4a 4a 4a 4a 1 1 1 1 1 1 1 1 4a 4a 4a 4a 4a
gc' gc'
174 189
25 25
gc Ic Ic
162.7 68.4 83
25 25 25
4a 4a 1
gc' gc gc gc Ic' Ic Ic Ic Ic Ic ss ss ss ss Ic Ic Ic Ic Ic Ic Ic Ic Ic
205 167 139 147 100 37 67 63 76 18 78 94 22 59 54.8 55.3 55.3 59.4 60.7 53.2 75.3 96.2 96.2
25 25 25 57 25 25 25 40 100 90 0 20 75 30 80 80 80 -24 80 -8 25 25 25
1 1 4a 4a 1 4a 1 4a 4a 4a 4a 4a 4a 4a b4 4b 4b 4a 4b 4a 4b 4b 4b
Solvent/Notes
Refs.
Tetrahydrofuran Tetrahydrofuran Tetrahydrofuran Diethyl ether rc-Pentane
419 419 419 419 420 420 420 420 420 420 330 330 329 329 328 328 154 421 421 421 421 421 421 421 421 172 172 172 166 166
100% Cryst. polymer Estimated for 100% cryst. polymer
210 210
N 17
325 325 107
N 77
N 69 THF N 69 N 69 THF Dichloromethane
3-RINGS
Ethylene oxide Propylene oxide 4-RINGS
Oxetane -, 3,3-dichloromethyl 5-RINGS
1,3-Dioxolane
- , 4,4-dimethyl- , cis 4,5-dimethyl- , trans 4,5-dimethyl- , 4-ethyl- , 4-isopropyl - , 4-methyl7-Oxa-bicyclo[2,2, l]heptane - , 2-exo-methyl- , 2-endo-methyl-
N 60 N 17 N 15 NM N 69 , N 78 Dichloromethane Chloromethane Toluene, N 78 Benzene
177 177 292 353 177 292 177 159 198 398 133,154 213 423 134 335 335 335 333 335 334 308 308 308
TABLE 5. cont'd Monomer £rarcs-7-Oxabicyclo[4.3.0]nonane Tetrahydrofuran
-, 3-methyl-
State of monomer and polymer xx Ic gc' gc gc gc Ic' Ic' Ic Ic Ic Ic Ic Is ss Is
-AS^ x (J/K/mol)
Temp. (0C)
55.7 177 112 139 143 100 81.9 47.6 16 62 41 49 67 87 100.9
25 25 25 50 25 25 25 25 25 50 30 40 40 - 6
1 4a 1 4a 1 1 1 4a 1 4a 4a 4a 4a 4a
20 25 25 25 25 40 25 25
4a 1 1 1 1 4a 4a 4a
Method
Solvent/Notes
N 61
N 17 N 16 Diethyl ether
Refs. 357 140 292 140 353 140 358 358 292 140 130 231 57,58 211 342
6-RINGS
1,3-Dioxane Paraldehyde Trioxane
Is gc' gc' gg gc' ss sc' c'c'
-23 201 159 64 156 41 42 18 ± 1 6
N 78 , Cyclic oligomer Isotactic polymer Syndiotactic polymer 1,2-Dichloroethane Nitrobenzene
436 184 184 141 141 178 182 164
7-RINGS
1,3-Dioxepane
-, 2-butyl - , 2-methyl-,4-methylOxepane l-Oxa-4,5-dithiepane
gc' gc' gc Ic Ic' Ic ss ss ss ss ss ss ss ss gc Ic ss
181 144 131.4 25.1 77 39 48 39 26 43 33 37.2 39 38.8 91.8 -12.4 > 12
25 25 25 25 25 25 -30 60 75 0 -5 -15 - 10 -15 25 25 25
1 1 4a 4a 1 1 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a
ss gc Ic gg c'c' gc Ic ss ss
16 121.7 10.2 51 -3 129.1 8.0 39 13
10 25 25 25 27 25 25 60 20
4a 4a 4a 1 1 4a 4a 4a 4a
Toluene, N 78
N17 Benzene Toluene, N 78
425 324 324 142 131 324 324 134 425
4a 4a 4a 4a 4a 4a 4a 4a
Dichloromethane Dichloromethane Dichloromethane Dichloromethane Dichloromethane Dichloromethane Dichloromethane Dichloromethane
343 343 343 343 343 343 343 343
N 17 Dichloromethane Benzene Toluene, N 78 1,2-Dichloroethane, N 78 1,2-Dichloroethane, N 78 1,2-Dichloroethane 1,1-Dichloromethene, N 78 1,2-Dichloroethane N 17 Benzene
170 170 323 323 170 170 136 134 423 424 424 340 424 339 323 323 61
8-AND LARGER RINGS
2-Butyl-l,3,6-trioxocane 1,3-Dioxocane Tetraoxane 1,3,6-Trioxocane
(1,3,6-Trioxocane) n n=\ n=2 n=3 n= 4 n=5 n—6 rc = 7 n=S
ss ss ss ss ss ss ss ss
34.3 12.6 36.4 43.1 47.7 51.5 54.8 57.8
0 0 0 0 0 0 0 0
N 17
Notes page 11-406; References page II - 407
TABLE 5.
cont'd
Monomer (1,3,6,9-Tetraoxacycloundecane) n n= \ n=2 n=3 n= 4 n=5 n=6 w= 7 n=$ (1,3,6,9,12-Pentaoxacyclotetradecane) n n= l n= 2 n=3 n=4 n= 5 n=6 n=l (1,3,6,9,12,15-Hexaoxacycloheptadecane) „ n=\ n=2 n=3 n=4 n=5
State of monomer and polymer xx
-ASJ x (J/K/mol)
Temp. (0C)
Method
Solvent/Notes
Refs.
ss ss ss ss ss ss ss ss
13.0 20.1 28.9 48.2 52.3 56.9 59.9 62.8
0 0 0 0 0 0 0 0
4a 4a 4a 4a 4a 4a 4a 4a
Dichloromethane Dichloromethane Dichloromethane Dichloromethane Dichloromethane Dichloromethane Dichloromethane Dichloromethane
343 343 343 343 343 343 343 343
ss ss ss ss ss ss ss
8.4 10.0 43.1 49.8 54.4 58.2 61.1
5 5 5 5 5 5 5
4a 4a 4a 4a 4a 4a 4a
Dichloromethane Dichloromethane Dichloromethane Dichloromethane Dichloromethane Dichloromethane Dichloromethane
343 343 343 343 343 343 343
ss ss ss ss ss
8.4 28.1 44.8 50.7 54.8
-2 -2 —2 -2 -2
4a 4a 4a 4a 4a
Dichloromethane Dichloromethane Dichloromethane Dichloromethane Dichloromethane
343 343 343 343 343
Ic Ic' Ic
54 74 51
25 25 127
1 1 1
368 368 368
Ic Ic' Ic
30 65 29
25 25 77
1 1 1
368 368 368
5.1.2. CYCLIC ESTERS 4-RINGS
P-Propiolactone
5-RINGS
y-Butyrolactone
6-RINGS
2,2-Dimetyltrimethylene carbonate
p-Dioxanone
Ethylene oxalate
Glycollide DL-Lactide L-Lactide 8-Oxo-7-oxabicyclo[2,2,2]octane
c'(II)c'(II) c'(II)c c'(II)c'(II) c'(1I)C Ic'(I) 11 c'c' c'c c'c' c'c c'c' c'c 11 c'c c'c c'c Ic c'c' cc Ic c'c Ic ss ss gg Ic'
7.7 -35.3 5.8 -35.2 38.7 24.0 6 -28 9 -25 10 -32 13 -12 -9 -5 15 0.3 -10.5 17.5 -31.3 13.0 41 25 127.7 76.2
-173 -173 25 25 117 147 -173 -173 -73 -73 25 25 127 -173 -73 25 142 25 25 277 25 127 105 40 25 25
1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 4a 4a 4b 4b
N63 N63 N63 N63 N63 N 63
1,4-Dioxane, N 78 Nitrobenzene, N 78 N53 N53
426 426 426 426 426 426 427 427 427 427 427 427 427 312 312 312 312 364 364 364 311 311 429 428 307 307
TABLE 5. cont'd Monomer Pentanolactone
State of monomer and polymer xx
-AS^ x (J/K/mol)
Temp. (0C)
Method
Solvent/Notes
Refs.
Ic' Ic Ic
65 15 13
25 25 77
1 1 1
314 314 314
Ic Ic' Ic
4 54 8
25 25 77
1 1 1
368 368 368
ss ss ss ss
-39.6 -30.7 -20.8 -25.7
7-RINGS
s-Caprolactone Spiroorthoester 2-R-1,4,6-trioxaspiro[4.6] undecane R= H = CH 3 = CH 2 Br = Ph
-10 -25 -20 -30
4a 4a 4a 4a
127 127 127 127 25 25 127 127 25 25 127 127 25 25 97 -73 127
4b 4b 4b 4b 1 1 1 4b 1 1 1 4b 1 1 1 1 4b
Dichloromethane, Dichloromethane, Dichloromethane, Dichloromethane,
N78 N78 N78 N78
430 430 430 430
8-AND LARGER RINGS
Heptanolactone Octanolactone Nonanolactone Decanolactone Undecanolactone Dodecanolactone Tridecanolactone Tetradecanolactone Pentadecanolactone
Hexadecanolactone
Ic Ic Ic Ic Ic Ic7 Ic Ic c'c cV Ic Ic c'c c'c' Ic C7CII)C Ic
1 -5 -12 -18 -24 69 -25 -25 -57 50 -26 -25 —41 86 -23 -109 -21
N54
368 368 368 368 368 368 368 368 368 368 368 368 313 313 313 313 368
5.2. MONOMERS GIVING POLYMERS CONTAINING O IN THE MAIN CHAIN, BONDED TO OTHER HETEROATOMS (S, Si, P) Cyclotrisiloxane, 1,1,3,3,5,5-hexaethyl
hexamethylCyclotetrasiloxane, octamethylAf,7V-Diethylamino1,3,2-dioxaphosphorinane 1,3,2-Dioxaphospholan, 2-methoxy 2-Oxo-1,3,2-dioxaphosphorinane - , 2-alkoxyR = methyl R = methyl R = ethyl R = propyl R = trimethyl silyl Sulfur trioxide
c'(HI)C'(II) c'(H)C7OI) c'(II)c c'(I)c'(I) c'0)c 11 Ic c'c Ic Ic
7 0 -62 9 -22 25 3.03 -51.0 -190 -194.4
-173 -73 -23 -23 25 25 77 25 77 25
1 1 1 1 1 1 1 1 1 1
N54, N63, N77 N54, N63, N77 N54, N63 N54, N63, N77 N54, N63 N63
431 431 431 431 431 431 365 365 365 365
Is ss Ic
-20.9 13.5 -19.3
-20 90
4a 4a 4a
N58 1,1,2,2-Tetrachloroethane N59
346 309 347
Is ss ss ss ss gc'
11.7 2.5 -1.5 -4.5 -6.0 178
140 100 100 100 100 41
4a 4a 4a 4a 4a 4a
Diglyme or DMSO Dichloromethane Dichloromethane Dichloromethane Dichloromethane
348 356 356 356 356 86
5.3. MONOMERS GIVING POLYMERS CONTAINING N IN THE MAIN CHAIN, BONDED IN THE CHAIN TO CARBON ONLY (listed by increasing ring size) 3-RINGS
Ethyleneimine - , MP-trimethylsilyl ethyl)-(TEI)
Ic Ic
51.9 113
27 27
1 1
360 360 Notes page 11-406; References page II - 407
TABLE 5. cont'd State of monomer
-AS^ x
Temp.
and polymer xx
(J/K/mol)
(0C)
Monomer - , - , ZnCl2(TEI)2(complex)
c'c
114
Method
Solvent/Notes
Refs.
27
1
360
360 360
4-RINGS
Trimethyleneimine, iV-(P-trimethylsilyl ethyl)-(TMI) - , ZnCl2(TEI)2(complex)
Ic c'c
83.0 37.2
27 27
1 1
ss c'c'
72 31
38 25
4a l/4b
c'c'
25
25
l/4b
63
c-Caprolactam
Is c'c'
29 -5
250 25
4a 1
68 63
-, 3-methyl-, 5-methyl-, 7-methyl-
Is Is Is
260 200 225
4a 4a 4a
5-RINGS
Bicyclic oxalactam 2-Pyrrolidinone
Dimethylsulfoxide
433 63
6-RINGS
2-Piperidone 7-RINGS
11 16 21
194 225 226
8-RINGS
2-Oxo-hexamethyleneimine c'c' —17 25 1 N. B. Values for 9-13 rings by probably unreliable extrapolation of ASC>C> for 5-8 rings are given in Ref. 138
63
13-RINGS
2-Oxo-undecamethyleneimine 5.4.
Is
16
290
4a
- 15
4a
25 55 200 25 25 25 80 80 160 159 50-90
1 4a 4a 1 1 1 1 1 4a 4a 4a
139
OTHER MONOMERS GIVING POLYMERS NOT LISTED ABOVE
4-(2,3-Diphenyl cyclopropenylidene)cyclohexa-2,5-dienone ss
1,3-Disilacyclobutane, 1,1,3,3-tetramethylTV-Phenylmaleimide Selenium Se g 1-Silacyclobutane, 1,1-dimethyl- , 1-phenyl 1-methylSulfur, S 6 -,S7 -,S8 Thioacetone exo-3,4,5-Trithiatricyclo[5.2.1.02'6]decane exo-3,4,5-Trithiatetracyclo[5.5.1.02'6.08'12]tridec-10-ene
TABLE 6.
69.4
Dichloromethane, N67
317
Ic ss Is Ic' Ic Ic Is Is Is Is Is
18.1 86 - 27 85.4 71.2 57.4 2 -11 -44.7 -31 48.9
ss
31.4
40
4a
Toluene, N 7 6
377
ss
29.3
50
4a
Toluene, N 7 6
376
DMF 9 N 78 From estimated T e
N73 N73 Nn Monomer
359 440 88,111 359 359 359 380 380 380 73,74,111 327
COPOLYMERS (listed alphabetically under Monomer A)
Monomer A Bis-(o-aminophenyl)-2,2' dibenzimidazoleoxide
Monomer B Terephthalic acid
State of monomer and polymer, xx c'c c'c c'c
— A5° x (J/K/mol) 19 -17 -112
Temp. (0C) -173 -73 25
Method 1 1 1
Solvent/Notes Polymer + H 2 O (c') Polymer + H 2 O (c') Polymer + H 2 O (1)
Refs. 445 445 445
TABLE 6. cont'd Monomer A
Monomer B - , dichloride - , dimethylester
1,3-Butadiene 1-Butene
Styrene Sulfur dioxide
-, 3-methyl-
Sulfur dioxide
2-Butene, cis -, trans Cyclopentene 1,3 Dioxane
Sulfur dioxide Sulfur dioxide Sulfur dioxide 1,3 Dioxolane
1-Hexadecene 1-Hexene
Sulfur dioxide Sulfur dioxide
Isobutene Methacrylic acid
Sulfur dioxide Methacrylic acid, methyl ester Sulfur dioxide
State of monomer and polymer, xx
-AS^ x (J/K/mol)
c'c c'c c'c c'c c'c c'c Ic Ic ss Ic Ic ss ss ss ss
-33 -295 -320 -13 -108 -160
Temp. (0C)
Method
Solvent/Notes
1 1 1 1 1 1 1 1 4a 4a 4a 4a 4a 4a 4a
Polymer + HcI (c') Polymer + HcI (g) Polymer + HCl (g) Polymer+ CH 3 OH (c') Polymer+ CH 3 OH(I) Polymer+ CH 3 OH(I)
116 145 162 81 146 140 134 57
-173 -73 25 -173 -73 25 30 25 64 35 25 25 25 102 20
ss Ic ss Ic
139 116 145 134
30 25 60 0
4a 1 4a 4a
Chloroform
Ic sc gc
117 130 172
25 90 25
1 4a 1
Excess B Excess B Excess A Excess B Excess B Excess B Methylene ASBA =
Propene
Ethylene
C.
Refs.
445 445 445 445 445 445 108 109 110 199,200 199,200 5 5 110 dichloride, N 78 , 446 -34
Excess B N 23
Excess B 31 mol% A in copolymer, N 3 0
110 109 110 83 206 109 110 222
CEILING TEMPERATURES A N D EQUILIBRIUM MONOMER CONCENTRATIONS
Most addition polymerization reactions are exothermic and exentropic. The free energy of polymerization per monomer unit therefore becomes less negative as the temperature is raised. At the ceiling temperature Tc, the free energy of polymerization under the prevailing conditions is zero, and above this temperature, polymerization to long-chain polymer is impossible (just as in physical aggregation a liquid cannot form a solid when the temperature is above the melting point). The reverse phenomenon of a floor temperature is also known, e.g., for sulfur. In general a pure liquid monomer which gives an insoluble polymer will have a single well-defined ceiling temperature, given by Tc = AH\C/AS\C. A pure liquid monomer which gives a soluble polymer will have a series of ceiling temperatures corresponding to different percentage conversions of monomer to polymer. The condition for equilibrium is then - A G i + AGic + AG 2 = 0 The partial molar free energy per mol of monomer, AG i and per base mol of polymer, AG 2 are then functions of composition and may be evaluated from an appropriate equation for mixing of monomer and polymer, e.g., the Flory-Huggins equation. For a monomer dissolved in a solvent the situation is more complex and the ceiling temperature at a given monomer concentration (or the equilibrium concentration of monomer at a given temperature) is dependent on the nature of the solvent and the composition of the medium (Refs. 28,29,112,113,114,160). For the case where both monomer and polymer are in solution the variation of Tc with concentration is given to a first approximation by r c =A// s ° s /(A5 s s +RIn[M]) where [M] is the concentration of monomer and A//° s and A5°s refer to the heat and entropy changes in an appropriate standard state. A more general expression may be derived from the free energy condition by insertion of suitable expressions for AG i and AG 2 . These will contain the various interaction parameters appropriate to the polymer-monomer-solvent system. The values of Tc quoted in the table are mostly obtained from experimental values by interpolation or short extrapolation. Some unpolymerizable monomers are included where these are structurally closely related to monomers which do polymerize and where the cause of nonpolymerization appears to be thermodynamic. This is amplified for cyclic monomers in Section D. Section C is divided into three sections 1 Equilibria involving pure liquid monomers (Ic, Ic', Is) 2 Equilibria involving gaseous monomers (gc, gc') 3 Equilibria involving monomers in solution (sc, sc', ss) and copolymerizations For meaning of symbols, see Section A.
Notes page 11-406; References page II - 407
1.
Equilibria Involving Pure Liquid Monomers
TABLE 7. MONOMERS GIVING POLYMERS CONTAINING MAIN CHAIN ACYCLIC CARBON ONLY
Monomer
State of monomer and polymer
2-Amino-4-(7V-alkylanilino)-6-isopropenyl-1,3,5-triazine alkyl = rc-propanyl Ic = n-hexanyl Ic = rc-octanyl Ic = /z-decanyl Ic = n-dodecanyl Ic = rc-tetradecanyl Ic = rc-hexadecanyl Ic = isopropyl Ic = isobutyl Ic = sec-butyl Ic = rc-pentyl Ic = isopentyl Ic = 1-methylbutyl Ic = benzyl Ic 2-Amino-4-alkyl/aryl-amino-6-isopropenyl-1,3,5-triazine Is R 1 = H , R 2 = ethyl Is R i = H , R 2 = propyl Is R i = ethyl, R 2 = ethyl Is R i = propyl, R 2 = propyl Is Ri = methyl, R 2 = phenyl Is R i = H, R 2 =/?-methoxyphenyl 2-Amino-4-(/?-chloroanilino)-6-isopropenyl-1,3-5-triazine Ic 2-Amino-4-methoxy Is -4-ethoxy Is 6-isopropenyl-1 -3,5-triazine 2-Anilo-4-methoxy Is -4-ethoxy Is 6-isopropenyl-1,3,5-triazine Atropic acid, methyl ester Is 1-Butene Ic 2-Butene, cis Ic , trans Ic - , 2-methyl11 - , 2,3-dimethyl11 ot-Cyanoacrilic acid - , allyl ester Ic - , rc-decyl ester Ic - , allyloxyethyl Ic Cyclopentene Ic Ethacrylic acid - , methyl ester Is Ethylene Ic Methacrylic acid - , benzoil acid ester Ic - , methyl ester Ic - , methyl ester deuterated Ic Naphtalene, 2-isopropenyl Is Pentene-1 Ic Pentene-2, cis Ic Pentene-2, trans Ic - , 4-methyl, cis Ic - , 4-methyl, trans Ic Silane, benzyl dimethyl vinylIc - , dimethyl phenyl vinylIc Styrene, a-methylIs Is Is
Tc [0C]
Wt. fraction monomer at equilibrium
157 149 143 140 134 132 130 151 154 148 150 151 146 157
1 1 1 1 1 1 1 1 1 1 1 1 1 1
402 402 402 402 402 402 402 403 403 403 403 403 403 403
181 177 163 161 169 169
1 1 1 1 1 1
370 370 370 370 379 378
170 183 182
1 1 1
404 405 405
174 174
1 1
405 405
—8 247 227 217 -29 -223
1 1 1 1 1 1
Isotactic polymer, N 5 7 Isotactic polymer, N 5 7 Isotactic polymer, N 5 7 Calculated, N 3 1 Calculated, N 3 1
149 385 385 385 143 143
307 217 607 97
1 1 1 1
N57 N57 N57 N66
391 392 393 361
87 367
1 1
N75 Polymer is polybutene-1-iso
395 385
787 102 93 69 317 287 277 317 267 397 197 61 54 170
1 1 1 1 1 1 1 1 1 1 1 1 1 1
N57
394 414 414 400 386 386 386 387 387 366 362 119 341 119
Notes
N43 N57 N57 N57 N57 N57
1 bar 6.57 kbar
Refs.
TABLE 7. cont'd
Monomer Vinylcyclohexane Vinylidenechloride Vinyldimethylbenzylsilane Vinyldimethylphenylsilane Vinyltrimethylsilane
State of monomer and polymer
Tc [ 0 C]
Wt. fraction monomer at equilibrium
Ic Ic Ic Ic Ic
567 387 397 117 327
1 1 1 1 1
Notes N57 N57 N57 N57 N57
Refs. 396 397 367 367 367
N.B. The following compounds are not polymerizable for thermodynamic reasons but can sometimes be copolymerized with other monomers (see Ref. 205): a-trifluoromethyl vinyl acetate, oc-methoxystyrene, 1,1-diphenylethylene, frafts-crotonitrile, trans-stilbene, rrarcs-l,2-di(2-pyridyl)-ethylene, ?raw5-l,2-dibenzoylethylene, /rarcs-l,2-diacetylethylene, oc-stillbazole, methyl 2-terf-butylacrylate, 1-isopropenylnaphthalene, 2,4-dimethyl-a-methyl-styrene.
TABLE 8.
M O N O M E R S G I V I N G POLYMERS C O N T A I N I N G HETEROATOMS I N THE M A I N C H A I N
State of monomer and polymer
Monomer 8.1.
Tc [ 0 C]
Wt. fraction monomer at equilibrium
Notes
Refs.
MONOMERS GIVING POLYMERS CONTAINING O IN THE MAIN CHAIN, BONDED TO CARBON ONLY
Acetaldehyde
—, trichloro- , trifluoro2,2-Dimethyltrimethylene carbonate 4,7-Dioxaoctanal 1,3-Dioxepane
- , 2-phenyl(1,3-Dioxolane) n
n=\
/2=1-8 1,3-Dioxolane, 4,4-dimethyl- , cis 4,5-dimethyl- , trans 4,5-dimethyl- , 4-ethyl- , 4-isopropyl- , 4-methyl- , 4-phenylHeptanal Hexanal L-Lactide Octanal 7-Oxabicyclo[2,2,1 ]heptane - , 2-exo-methyl- , 2-endo-methylfrarcs-7-Oxabicyclo[4,3,0]nonane 4-Oxapentanal 1,2-Oxathiolane-2,2-dioxide Oxepane Oxetane 8-Oxo-7-oxabicyclo[2,2,2]octane
gg Is Is Ic' Ic Ic Ic Ic Is Is Is Is Is Is Is Ic Is
—31 -39 20 58 177 212 227 -38 100 192 144 20 100 165 100 98 60
1 1 1 1 1 1 1 1 0.1 1 1 0.36 0.3 1 1 1
Ic Ic Ic Is Ic Ic Is Ic Is Ic Ic' Ic Ic Ic Ic Ic Ic
-98 -54 -137 -48 -54 -74 -20 -21 20 74 -43 -25 640 -19 320 240 200
1 1 1 4.74 Md/1 1 1 4.47 Md/1 1 1 1 1 1 1 1 1 1 1
Ic Ic Is Is Is Ic Ic Ic7
12 -35 -59 95 41.5 -136 478 180
1 1 1 0.74 1 1 1 1
Atactic polymer (1 bar) Isotactic polymer (1 bar) <10kbar N57 N68 N57 N69 N22 N43 N22
N43 Kn determined for cyclic monomers N57 N57 N57 N56 N57 N57 N56 N57 N57 N57 N57 N 5 7 , calculated N69 N57 N57 N57
N69 N22 N32, N57 N3i N53
115 115 158 233 418 322 426 330 H6 423 398 116 116,219 198 423 353 232 335 335 335 333 333 335 334 334 285 419 420 420 429 330 308 308 308 357 329 329 152 147 323 325 307
Notes page 11-406; References page II - 407
TABLE 8.
cont'd
State of monomer and polymer
Monomer Pentanal Propanal
Spiroorthoester 2-R-1,4,6-trioxaspiro[4,6]undecane R= H = CH 3 = CH2Br = Ph Tetrahydrofuran - , 3-methyl Tri(ethylene terephthalate)
Tc [0C]
Wt. fraction monomer at equilibrium
Ic Is Is Ic' Ic
-42 -31 —39 -48 -83
1 1 1 1 1
Ic Ic Ic Ic Is Is Is Is
172 254 498 258 80 129 4 297
1 1 1 1 1 1 1 0.014
Notes
Refs.
N69 Atactic polymer Isotactic polymer N 57 N 57
328 115 115 421 421
N68 N 68 N68 N68 1 bar 12.5 kbar
430 430 430 430 58,130 146 342 see 174
N.B. The following compounds are not polymerizable for thermodynamic reasons but can sometimes be copolymerized with other monomers (see Ref. 205); benzaldehyde (Refs. 297-299), hexafluoroacetone, 1,1-dimethylpropanal; also numerous cyclic ethers - see Section D. 8.2.
MONOMERS GIVING POLYMERS CONTAINING O IN THE MAIN CHAIN, BONDED TO OTHER HETEROATOMS (S, Si, P)
Sulfur trioxide Sodium metaphosphate Na„(OPO 2 ) n n=3
Ic' Is
800
0.043
n=4 n= 5 Siloxanes (RiR 2 SiO) n Ri, R 2 Me, H /z = 3-5
Is Is
800 800
0.026 0.008
Is
0
0.045
n = 6-18 /i=19-oo n = 3-oo
Is Is Is
0 0 0
0.034 0.046 0.125
/2 = 3-5
Is
110
0.100
n = 6-18 /i=19-oo rc = 3-oo n = 4-40
Is Is Is Is
110 110 110 110
0.036 0.047 0.183
n = 4-30
Is
145
Me, Et
n = 3-5
Is
110
0.170
Me, Pr
n= «= /i = n=
Is Is Is Is
110 110 110 110
0.049 0.039 0.258 0.270
Me, CF 3 (CH 2 ) 2
/i = 3-8 n = 3-5
Is Is
110 110
0.310 0.711
Et, Et
n = 6-18 n =19-oo n = 3-00 n= 3
Is Is Is Ic
110 110 110 247
0.089 0.027 0.827 1
Me, Me
8.3.
6-18 19-oo 3-oo 3-5
30.4
1
86 Kn determined for cyclic monomers, n = 3-l
300,301 300,301 300,301
Kn determined for cyclic monomers, n — 4-15
176 176 176 176
Kn determined for cyclic monomers, n = 4-40
Kn determined for values of n indicated Kn determined for values of n indicated Kn determined for cyclic monomers, n — 4-20
Kn determined for cyclic monomers, n = 4 - 8 Kn determined for cyclic monomers, n — 4-20
Calculated
176 176 176 176 180 180 176 176 176 176 176 176 176 176 176 176 431
MONOMERS GIVING POLYMERS CONTAINING S IN THE MAIN CHAIN, BONDED IN THE CHAIN TO CARBON ONLY
Thiacetone Thioacetophenone
Ic Is Is
95 -52 approx. 40
1 1 1
N 55
148 327 288
N.B. Isothiocyanates (Ref. 295) are not polymerizable for thermodynamic reasons, but can be copolymerized with thiiranes; carbon disulfide (Ref. 296) can also be copolymerized with thianes
TABLE 8. cont'd State of monomer and polymer
Monomer 8.4.
n=l
n=2 n=3 /i = 4 n=5 n=>6 - , 3-methyl- , 3-ethyl- , 3-propyl- , 4-ethyl- , 5-methyl- , 7-methyl- , 7-ethyl- , 7-propyl2,5-Dioxopiperazine 2-Oxo-hexamethylenimine -,4-ethyl- , 7-ethyl- , 8-propyl2-Oxo-undecamethylenimine 2-Piperidone 2-Pyrrolidone
Notes
Refs.
Is Is Is Is Is Is Is Is Is Is Is Is Is Is Is Is Is Is Is Is Is Is Is Ic Is
220 225 277 277 277 277 277 277 225 240 240 240 172 225 240 240 171 240 240 240 240 290 60 76 70
0.055 0.067 0.084 0.0078 0.0052 0.0056 0.0048 0.0076 0.086 0.1 0.1 0.35 0.18 0.107 0.1 0.1 1 0.03 0.06 0.02 0.32 1 1
68 192 See 181 Cyclic monomer See 181 Cyclic monomer See 181 Cyclic monomer See 181 Cyclic monomer See 181 Cyclic monomer See 181 192,194 191 191 171 225,302 226,302 191,302 191,302 From calorimetric data 437 302 171 171 302 139 118 N 75 383 Tc varies with the accelerator, N 75 439
OTHER MONOMERS GIVING POLYMERS NOT LISTED ABOVE
Norbornene 5-trimethylsilyl-2Selenium Se 8 Sulfur S 8
2.
Wt. fraction monomer at equilibrium
MONOMERS GIVING POLYxMERS CONTAINING N IN THE MAIN CHAIN, BONDED IN THE CHAIN TO CARBON ONLY
(s-Caprolactam),,
8.5.
Tc [0C]
Ic Ic Is Is
777 417 83 159
1 1 1 1
Is
157
1
55% cis/45% trans polymer, N57 N32 N33 Effect of pressure N33
415 416 85 73,,111 145 380
Equilibria Involving Gaseous Monomers (listed alphabetically)
Monomer
State of monomer and polymer xx
Tc (0C)
gc' gc gc gc gc gc gc gc'
98 73 -220 149 288 87 560 119
Acetaldehyde, trichloro- , trifluoroAcetone 1,3-Dioxepane 1,3-Dioxocane 1,3-Dioxolane Ethylene, tetrafluoroFormaldehyde Methacrylic acid - , ethyl ester - , methyl ester Oxepane Oxetane Sulfur trioxide
gs gs gc gc gc'
Tetrahydrofuran 1,3,6-Trioxocane
gc gc
173 164 135 319 27.0 0.0 83 243
Equilibrium pressure (mbar)
Notes
1013 1013 Estimated, N 3 6 1013 1013 1013 128 1013 1013 1013 1013 1013 372 40.8 1013 1013
N34 N28 N35 N35
Refs. 50 129 144 323 324 292 23,120 49,164,165 40 43 323 325 86 86 292 324
Notes page 11-406; References page II - 407
3.
Equilibria Involving Monomers in Solution
TABLE 9. MONOMERS GIVING POLYMERS CONTAINING MAIN CHAIN CARBON ONLY Monomer
State of monomer and polymer xx
Tc (0C)
M (mol/i)
Solvent/Notes
Refs.
9.1. MONOMERS GIVING POLYMERS CONTAINING MAIN CHAIN ACYCLIC CARBON ONLY Acrylonitrile Atropic acid - , methyl ester -, ethyl ester - , n-propyl ester - , n-butyl ester -,/?-methyl-, methyl ester Atroponitrile Biphenyl, p-isopropenylCyclohexene Cyclooctene Isobutylene Methacrylamide, N-butyl- , Af-phenylMethacrylic acid, methyl ester - , o-methyl phenyl ester - , phenyl ester - , o-tert-buiy\ phenyl ester - , cKseobutylphenyl ester - , o-chlorophenyl ester -, 2,6-diisopropylphenyl ester - , 2,6-dimethyl phenyl ester - , o-ethylphenyl ester - , o-isopropylphenyl ester - , o-methoxyphenyl ester - , 0-methoxycarbonylphenyl ester - , onitrophenyl ester - , ophenylphenyl ester -, 0-propylphenyl ester 2,4,6-tribromophenyl ester 2,4,6-trichlorophenyl ester 2,4,6-trimethylphenyl ester Methacrylonitrile Methyl-a-/?-chlorobenzylacrylate a-Methylene pentanolactone Methyl-a-p-methoxybenzylacrylate Methylphenylitaconate Naphthalene, 2-isopropenylOxazole, - , 2-isopropenyl-4,5-dimethylPyridine, 2-isopropenylStyrene - , a, acetoxy - , a-methyl- , - , o-methoxyAWA^Af'-TetraethyMisopropenylphenylphosphorous diamide Thiazole, 2-isopropenyl/?-[Bis(Trimethylsilyl)methyl] isopropenylbenzene
25 ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss
-40 -67 -72 -80 —37 50 0 -23 20 88 122 125 155.5 135 140 146 81 100 139 33 77 118 112 145 112 108 100 118 92 104 69 145 85 83 55 95 120 0
ss ss ss ss ss ss ss ss ss ss
0 0 150 150 47 0 53 58 -25 10
ss ss
0 1.2
3 x 1 ~8 1.0 1.0 1.0 1.0 1.0 1.0 0.515 5 1.2 0.651 0.611 0.82 0.611 0.64 0.64 0.64 0.64 0.64 0.64 0.64 0.64 0.64 0.64 0.64 0.64 0.64 0.64 0.64 0.64 0.64 0.27 5 1 0.324 5 2,22 0.284 0.0025 0.043 9.1 x 10 ~4 6.5 x l O " 4 1.0 0.76 1.8 1.8 ~2 1.0 0.010 1.0
Estimated from AG]c>
193
Toluene Toluene Toluene Toluene Toluene Toluene Tetrahydrofuran Toluene Benzene, N 38 Supercritical CO 2 Ethyl benzoate Ethyl benzoate o-Dichlorobenzene Ethyl benzoate /?-Xylene Benzene or/?-xylene, N75 /?-Xylene Benzene or p-xylene, N 75 Benzene or/?-xylene, N 75 Benzene or /?-xylene, N75 /?-Xylene Benzene or p-xylene, N 75 Benzene or/?-xylene, N 75 Benzene or p-xylene, N 75 Benzene or p-xylene, N75 Benzene or/?-xylene, N 75 Benzene or/?-xylene, N 75 Benzene or p-xylene, N 75 Benzene or p-xylene, N 75 Benzene or/?-xylene, N 75 Benzene or /?-xylene, N 75 Benzonitrile Toluene DMF DMF Toluene Dichlorobenzene Tetrahydrofuran
149 150 150 150 150 149 16 389 229,230 441 326 326 42 326 345 442 345 442 442 442 345 442 442 442 442 442 442 442 442 442 442 44 443 315 315 443 444 16
Tetrahydrofuran Tetrahydrofuran Benzene Cyclohexane Toluene Tetrahydrofuran, N 37 rc-Heptane Toluene Methylene chloride Tetrahydrofuran
284 284 28 28 401 16,32,33 402 402 155 408
Tetrahydrofuran Tetrahydrofuran
284 409
TABLE 9. cont'd State of monomer and polymer xx
Monomer 9.2.
Tc (0C)
M (mol/1)
Solvent/Notes
Refs.
MONOMERS GIVING POLYMERS CONTAINING MAIN CHAIN CYCLIC CARBON
- , 7,8-Dycyanoquinodimethane 7,8-bis(butoxycarbonyl) 7,8-Diacetyl7,8-Dibenzoyl7,8-Dibutoxycarbonyl
ss ss ss ss ss ss ss ss ss ss ss ss
93 442 87 415 88 301 93 442 79 422 67 481
0.014 1.0 0.018 1.0 0.069 1.0 0.014 1.0 0.014 1.0 0.014 1.1
Chloroform, Chloroform, Chloroform, Chloroform, Chloroform, Chloroform, Chloroform, Chloroform, Chloroform, Chloroform, Chloroform, Chloroform,
N75 N43 N75 N43 N75 N43 N75 N43 N75 N43 N75 N43
411 411 412 412 412 412 412 411 411 411 411 411
TABLE 10. MONOMERS GIVING POLYMERS CONTAINING HETEROATOMS IN THE MAIN CHAIN State of monomer and polymer xx
Monomer 10.1.
Tc (0C)
M (mol/1)
Solvent/Notes
Refs.
MONOMERS GIVING POLYMERS CONTAINING O IN THE MAIN CHAIN, BONDED TO CARBON ONLY
Acetaldehyde - , bromochlorofluoro- , bromodichloro- , bromodifluoro- , dibromochloro- , dibromofluoro- , dichlorofluoro- , chlorodifluoro- , tribromo- , trichloro-
- , trifluoroButanal
4,7-Dioxaoctanal 1,3-Dioxepane
- , 2-butyl - , 2-methyl- , 4-methyl(1,3-Dioxolane)n
n=l
n=l-8
sc sc' sc' sc' sc sc' sc sc' sc sc' sc' ss sc' sc' sc' sc' sc' sc sc sc sc ss ss ss ss ss ss ss ss ss ss ss ss Is
~ - 80 23 —17 48 -40 -19 52 41 70 63 -75 11 12.5 35 18 9 81 9 -18 12 27 -56 78 27 32 -51 -37 -40 -33 1 -8 20 20 60
Is
145
ss
60
6 1 1 1 1 1 1 1 1 1 1 1.0 (0.1) 1.0 1 1 1 1 ~2 1.0 1.0 1 1.0 1.0 1.0 1.0 1 1.0 1 1.0 1.0 2.0 1.0 2.0 10.0
Toluene, N 22 Toluene Toluene Toluene Toluene Toluene Methyl cyclohexane Toluene Methyl cyclohexane Toluene Toluene Tetrahydrofuran Pyridine, N 3 9 , N 4 0 /i-Heptane Methyl cyclohexane Toluene Toluene Dichloromethane Toluene, isotactic polymer n-Hexane [8kbar], Ni 2 n-Hexane [10 kbar], N12 THF Benzene Dichloromethane 1,2-Dichloroethane, N 5 7 1,2-Dichloroethane, N 5 7 1,2-Dichloroethane 1,2-Dichloroethane, N 5 7 1,2-Dichloroethane Dichloromethane Benzene, N 4 i 1,3-Dioxane, N41 Chloroethane A few percent dichloromethane present A few percent dichloromethane present Dichloroethane, N 42
228 233 344 344 337 344 336 344 336 344 338 167 50 166 336 344 344 322 227 161 161 330 116,134 136 424 424 340 424 339 133,159 134,159 159 293 198 198 232
Notes page 11-406; References page 11-407
TABLE 10. cont'd
Monomer Formaldehyde L-Lactide Octanal frans-8-Oxabicyclo[4,3,0]nonane mms-2-Oxabicyclo[3,3,0]octane Oxa-4,5 -dithiepane Oxepane Pentanal o-Phthalaldehyde Propanal, 2-chloro-, 2-methyl- , 2,2-dichloro- , 2-methyl-
Tetrahydrofuran Tetraoxane
Trioxane
1,3,6-Trioxocane - , 2-Butyl10.2.
sc' sc' ss sc ss
30 25 284 -59 -51
ss ss ss sc ss ss ss ss ss ss ss ss ss sc' sc' sc' sc' sc' sc' sc' sc' sc' ss ss ss
0 25 30 -68 -43 -54 -24 approx. 5 -36.6 -63 -61.6 25 20 50 25 25 50 30 30 30 25 25 297 330 220
M (mol/l) 0.06 0.004 1.0 1 1 0.63 < 0.005 0.08 1 1.0 1.0 1.0 (0.25) 1.0 1.0 1.0 4.45 2.8 < 0.008 0.12 0.10 0.20 0.13 0.05 0.19 1.5 2.5 1.0 1.0 1.0
Solvent/Notes
Refs.
Dichloromethane Nitrobenzene 1,4-Dioxane THF Dichloromethane
122 182 429 330 357
Dichloromethane Benzene Dichloromethane THF Dichloromethane, cyclopolymer Tetrahydrofuran Tetrahydrofuran Dichloromethane, N 2 2 , N40 rc-Pentane Tetrahydrofuran Diethyl ether Benzene, N 3 7 , N 4 4 Diethyl ether 1,2-Dichloroethane Dichloromethane Nitrobenzene 1,2-Dichloroethane 1,2-Dichloroethane Benzene Nitrobenzene, N 45 Nitrobenzene, N 4 5 Dichloromethane Benzene, N 4 5 Toluene, N 57 Toluene, N 5 7
357 61 236 328 154 172 172 153 166 172 166 231 211 178 182 182 178 178 178 178 182 182 134 425 425
ss ss ss
157 -33 -37
0.1 1 1
ss ss ss ss
0 110 110 110
(0.2) 0.3 (0.4) (0.9)
1,1,2,2-Tetrachloroethane 1,2-Dichloroethane 1,2-Dichloroethane
Toluene, N 4 6 Toluene, N 47 Toluene, N 4 6 Cyclohexanone, N 4 6
309 339 340
176 217,218 176 176
MONOMERS GIVING POLYMERS CONTAINING S IN THE MAIN CHAIN, BONDED IN THE CHAIN TO CARBON ONLY
1,3-Dithiolane, 2-phenylimino-4-methylexo-3,4,5-Trithiatetracyclo[5,5,l,02'6.0812]tridec-10-ene exo-3,4,5-Trithiatricyclo5.2.1.026]decane
10.4.
Tc (0C)
MONOMERS GIVING POLYMERS CONTAINING O IN THE MAIN CHAIN, BONDED TO OTHER HETEROATOMS (Si, P)
1,3,2-Dioxaphospholan, 2-methoxy1,3-Dioxepane, 4-methyl- , 2-methylSiloxanes (RiR 2 SiO) n R1, R2 H, Me Me, Me Me, Et Me, CF 3 (CH 2 ) 2 10.3.
State of monomer and polymer xx
ss
65
2.7
Benzene
290
ss ss
25 90
2.37 3.72
Toluene, N 7 6 Toluene, N 7 6
376 376
ss ss
10 70
3.8 6.0
Toluene, N 7 6 Toluene, N 7 6
377 377
MONOMERS GIVING POLYMERS CONTAINING N IN THE MAIN CHAIN, BONDED IN THE CHAIN TO CARBON ONLY
Bicyclic oxalactam n-Hexyl isocyanate Pyrrole N,7,7-Tricyanobenzoquinone methide imine
ss sc ss ss
60 —22 77 74
1.0 2 0.017 0.14
Dimethylsulfoxide Dimethylformamide Acetonitrile Toluene, N 7 5 , N 8 i
433 127 434 438
Next Page
TABLE 11. COPOLYMERS Monomer A
Monomer B
State of monomer and polymer
Ta (0C)
[A][B] (mol 2 /I 2 )
Solvent/Notes
Refs.
11.1. 1:1 COPOLYMERS Allyl acetate Allyl alcohol Allyl ethyl ether Allyl formate 1-Butene -, 2-ethyl-, 3-methyl2-Butene, cis -,trans 2-Butene, (50% cis) - , 2-methylCycloheptene Cyclohexene 1,3-Cyclooctadiene Cyclopentene Ethene Ethene oxide Formaldehyde 2-Heptene (88% m ) 1-Hexadecene 1-Hexene -,2-ethylIsobutene 1-Pentene -,2-methyl-, 4,4-dimethyl-, 2,4,4-trimethyl2-Pentene (50% cis) -, 4-methyl4-Pentenoic acid Propene Propene oxide 3-Propenyl phenyl ether Styrene Tetrafluoroethene Vinyl chloride
Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Carbon monoxide Carbon dioxide Sulfur dioxide Carbon monoxide Carbon dioxide Carbon monoxide Carbon dioxide Sulfur dioxide Sulfur dioxide
Sulfur dioxide Sulfur dioxide Carbon monoxide Carbon dioxide Carbon monoxide Carbon dioxide Carbon monoxide
sc sc gg gg gg gg gg
45 76 68 45 64 <-80 36 46 38 34.6 <—80 11 24 37 103 150 (-35) -(50) >135 350 (—127) 220 (-58) 190 (-47) - 1 5 0 (46) -38 69 30 60 <-80 5 63 -34 14 <-80 8.5 <-80 66 90 140 (-39) - 1 2 0 (39) 490 (-129) 180 (-49) 590 (—136)
Carbon Carbon Carbon Carbon Carbon Carbon
gg gg gg gg gg gg
190 (-36) -190 (53) 280 (-74) 30 ( - 2 ) 230 (-55) -45(18)
N 64 N 64 N 64 N 64 N 64 N 64
369 369 369 369 369 369
Is
225
N50
192,194
Sulfur Sulfur Sulfur Sulfur Sulfur Sulfur Sulfur Sulfur
dioxide dioxide dioxide dioxide dioxide dioxide dioxide dioxide
dioixde monoxide monoxide dioxide monoxide dioxide
ss sc ss sc ss sc ss ss ss ss ss ss ss gg gg sc' gg gg gg gg ss sc ss ss sc ss ss sc ss
27 27 27 27 27 27 27 27 27 27 27 10 27 27
33 27 1.15 27 27 27 27 27 32 27 27
Excess B Excess B Excess B Excess B Excess B All compositions Excess B Excess B, N 48 Excess B, N 48 Excess B, N 49 All compositions Excess B Excess B Excess B (1,2 addition) Excess B N 64 N 64 Excess B N 64 N64 N 64 N 64 Excess B, N 49 Excess B Chloroform Excess B All compositions Excess B Excess B Excess B Excess B All compositions N 49 All compositions Excess B Excess B N 64 N 64 N 64 N 64 N 64
110 110 110 110 110 110 110,199 110 110 110 110 124 110 156 110 369 369 110 369 369 369 369 110 110 80 110 110 110 110 110 110 110 110 110 110 110 369 369 369 369 369
11.2. GENERAL COPOLYMERS 8-Caprolactam a
e-Caprolactam, 3-methyl-
Values in parentheses are for AGJ98 in (kJ/mol).
D.
POLYMERIZABILITY OF 5-, 6- AND 7-MEMBERED HETEROCYCLIC RING COMPOUNDS
The free energy of polymerization is generally negative for 3-, 4-, 8-, and higher-membered ring compounds. With heterocyclic rings there is generally an ionic mechanism available which allows these compounds to polymerize. With 5-, 6- and 7-membered ring compounds the sign of AG, and hence the polymerizability, is critically dependent on the nature of the ring and on the extent and position of substitution. Substitution generally makes AG less negative (more positive) and reduces polymerizability in the thermodynamic sense. Tables 12-14 summarize the polymerizability of 5-, 6- and 7-membered rings, respectively, as a function of the nature of the ring and extent of substitution. Table 15 provides a comparison of polymerizability of unsubstituted 5-, 6-, and 7-membered rings.
Notes page 11-406; References page II - 407
Previous Page
TABLE 11. COPOLYMERS Monomer A
Monomer B
State of monomer and polymer
Ta (0C)
[A][B] (mol 2 /I 2 )
Solvent/Notes
Refs.
11.1. 1:1 COPOLYMERS Allyl acetate Allyl alcohol Allyl ethyl ether Allyl formate 1-Butene -, 2-ethyl-, 3-methyl2-Butene, cis -,trans 2-Butene, (50% cis) - , 2-methylCycloheptene Cyclohexene 1,3-Cyclooctadiene Cyclopentene Ethene Ethene oxide Formaldehyde 2-Heptene (88% m ) 1-Hexadecene 1-Hexene -,2-ethylIsobutene 1-Pentene -,2-methyl-, 4,4-dimethyl-, 2,4,4-trimethyl2-Pentene (50% cis) -, 4-methyl4-Pentenoic acid Propene Propene oxide 3-Propenyl phenyl ether Styrene Tetrafluoroethene Vinyl chloride
Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Carbon monoxide Carbon dioxide Sulfur dioxide Carbon monoxide Carbon dioxide Carbon monoxide Carbon dioxide Sulfur dioxide Sulfur dioxide
Sulfur dioxide Sulfur dioxide Carbon monoxide Carbon dioxide Carbon monoxide Carbon dioxide Carbon monoxide
sc sc gg gg gg gg gg
45 76 68 45 64 <-80 36 46 38 34.6 <—80 11 24 37 103 150 (-35) -(50) >135 350 (—127) 220 (-58) 190 (-47) - 1 5 0 (46) -38 69 30 60 <-80 5 63 -34 14 <-80 8.5 <-80 66 90 140 (-39) - 1 2 0 (39) 490 (-129) 180 (-49) 590 (—136)
Carbon Carbon Carbon Carbon Carbon Carbon
gg gg gg gg gg gg
190 (-36) -190 (53) 280 (-74) 30 ( - 2 ) 230 (-55) -45(18)
N 64 N 64 N 64 N 64 N 64 N 64
369 369 369 369 369 369
Is
225
N50
192,194
Sulfur Sulfur Sulfur Sulfur Sulfur Sulfur Sulfur Sulfur
dioxide dioxide dioxide dioxide dioxide dioxide dioxide dioxide
dioixde monoxide monoxide dioxide monoxide dioxide
ss sc ss sc ss sc ss ss ss ss ss ss ss gg gg sc' gg gg gg gg ss sc ss ss sc ss ss sc ss
27 27 27 27 27 27 27 27 27 27 27 10 27 27
33 27 1.15 27 27 27 27 27 32 27 27
Excess B Excess B Excess B Excess B Excess B All compositions Excess B Excess B, N 48 Excess B, N 48 Excess B, N 49 All compositions Excess B Excess B Excess B (1,2 addition) Excess B N 64 N 64 Excess B N 64 N64 N 64 N 64 Excess B, N 49 Excess B Chloroform Excess B All compositions Excess B Excess B Excess B Excess B All compositions N 49 All compositions Excess B Excess B N 64 N 64 N 64 N 64 N 64
110 110 110 110 110 110 110,199 110 110 110 110 124 110 156 110 369 369 110 369 369 369 369 110 110 80 110 110 110 110 110 110 110 110 110 110 110 369 369 369 369 369
11.2. GENERAL COPOLYMERS 8-Caprolactam a
e-Caprolactam, 3-methyl-
Values in parentheses are for AGJ98 in (kJ/mol).
D.
POLYMERIZABILITY OF 5-, 6- AND 7-MEMBERED HETEROCYCLIC RING COMPOUNDS
The free energy of polymerization is generally negative for 3-, 4-, 8-, and higher-membered ring compounds. With heterocyclic rings there is generally an ionic mechanism available which allows these compounds to polymerize. With 5-, 6- and 7-membered ring compounds the sign of AG, and hence the polymerizability, is critically dependent on the nature of the ring and on the extent and position of substitution. Substitution generally makes AG less negative (more positive) and reduces polymerizability in the thermodynamic sense. Tables 12-14 summarize the polymerizability of 5-, 6- and 7-membered rings, respectively, as a function of the nature of the ring and extent of substitution. Table 15 provides a comparison of polymerizability of unsubstituted 5-, 6-, and 7-membered rings.
Notes page 11-406; References page II - 407
TABLE 12. 5-MEMBERED RING COMPOUNDS Ring
Polymerized
Not polymerized
C2N2O
Refs. 237
R = Me, Ph
376
C2S3
377
238,239,433
C3NO R = Me, Ph etc.
239,240
C3NS
C3N2
239 R = Me, MeCO
C3OS
152
C3O2 R = Me, CH2Cl, Ph
R1 R1 R1 R1 R1
= R 2 = R 3 =H = R 2 = R 3 =Me = R 2 = R 3 = CH 2 Ph = R 3 = CH2Ph5R2= H = R 2 = CH 2 Ph 5 R 3 = H
R = Me, Ph
R = Me, CH2Cl
116,133,134, 159,177. 239,241-244, 285-287, 350,351,349, 398,423
331
C3S2
245,246,290
C4N
239,240,243
240,247-249
C4O
51,58,117, 130,140,146, 239,243,250-256, 291,303,304 R' = H,R = H R' = H, R = endo - Me R' = H, R = e x o - M e R' = endo - Me, R = exo - Me
R' = exo-Me R = exo-Me
TABLE 12. cont'd Ring
Polymerized
Not polymerized
Refs. 357
(trans)
(cis)
(trans)
(cis)
(trans)
(cis)
357
357
357 {trans)
(cis)
185,256
C4S
TABLE 13. 6-MEMBERED RING COMPOUNDS Ring
Polymerized
Not polymerized
Refs.
C3N2O
239
C3N3
239
C3O2P
346
R=H
347 348
R = OCH 3
C3O3
141,178,184,257
C3S3
148,258,259,260
C 4 NO
185,239,240
C 4 NS
240
C4N2
239,240,261 R = Me,Ph
Notes page 11-406; References page II - 407
TABLE 13. cont'd Ring
Polymerized
Not polymerized
Refs.
C4OS
152
C4O2
116,136,239,243,262,426,436
239,243,262,263,428,429 R = Me, Ph
R = Me 1 Ph
427
382 246,265
C4S2 C5N
R = H, Et, Ph
118,209,239,240,243,266
153,239,243,264,226-270,283
C5O
331
185,256
C5S
431
Si 3 O 3
TABLE 14. 7-MEMBERED RING COMPOUNDS Ring
Polymerized
Not polymerized
Refs.
C 4 OS 2
61
C5NS
240
C5N2
239,240
TABLE 14. Ring
cont'd Polymerized
Not polymerized
Refs.
C5O2
116,136,170,241, 262,271,423,424
C5S2
246
C6N
63,68,240, 249,272-279 R= 3555-
Me, 4 - Me, R = H, Me Me, 5 - Et, n - propyl, 5-z-propyl Cyclohexyl
R = Me, Ph, CH 2 OH, EtSCH 2
R = Ph, PhCH 2 n - Heptyl
6 - Me, 7 - Me
240,243,276, 277,280,305 C6O
153,239,243, 281,282
C6S
256
TABLE 15. COMPARISON OF POLYMERIZABILITY (+ OR - ) OF UNSUBSTITUTED 5-, 6- AND 7-MEMBERED RING COMPOUNDS0 T^pe of ring
Name of 5-ring
1,3-CnNO
2-Oxazolidinone
1,3-CnN2
2-Imidazolidinone
1,2-CnOS
1,2-Oxathiolane-2,2-dioxide
1,3-CnO2
1,3-Dioxolane
5-Ring
6-Ring
7-Ring
Ethylene carbonate 1,2-CnS2
1,2-Dithiolane
CnN
Pyrrolidine 2-Pyrrolidinone Succinimide
Notes page 11-406; References page II - 407
TABLE 15. cont'd Type of ring
Name of 5-ring
5-Ring
6-Ring
7-Ring
2-Pyrrolidinethione CnO
Tetrahydrofuran (oxolane) Oxolane-2-one (y-butyrolactone) Oxolane-2,5-dione(succinic anhydride)
CnS a
Thiolan-2-one (y -thiobutyrolactone)
The formulae denote rings of any size. Thus in the first line 1,3C4NO is drawn as
and represents
E. NOTES Ni N2 N3 N4
Corrected for end-group effects. Is assumed. Partial allowance for unreacted monomer. Semi-empirical values for a number of other olefins are given in Ref. 143. N5 Value given is for dilute solution. Values determined for complete range of composition; maximum (14.4) at 50 mol% monomer. N 6 No allowance for unreacted monomer. N 7 Strongly dependent on both monomer concentration and temperature. N 9 Corrected for enthalpy of glassy state. N i 0 - AS s s assumed to be 120.3 J/Kmol. N n Zero heat not necessarily in conflict with observed polymerizability below — 40 0 C. Additional loss of free energy may be provided by the crystallization of the polymer. N12 Polymer largely insoluble and remains in suspension. N13 After correction for species in vapour other than formaldehyde. N14 In the presence of a few per cent methylene chloride. N15 From measurements in methylene chloride, benzene and 1,4-dioxane. N i6 From measurements in benzene. N n From measurements on vapor-solid equilibrium. N i8 From measurements in both methylene chloride and nitrobenzene. NI 9 From measurements in 1,2-dichloroethane. N 20 Value calculated by the compiler of this table from data in Ref. cited. N21 Numerical values for heats of copolymerization are listed only for those systems yielding 1:1 copolymers. The values refer to the copolymerization of 0.5 mol of each monomer. In all other cases listed the copolymers have a range of composition; details of the corresponding heats of copolymerization are given in the Ref. cited.
N 22 N 23 N 24 N 25 N 26 N 27 N 28 N 29
N 30 N 31 N 32 N 33 N34 N35
Where no solvent is specified in the seventh column, the symbol AH ss denotes that the measured heat is for a liquid mixture of monomers going to a solution of copolymers. AH\c denotes the heat change for pure liquid monomers going to condensed amorphous polymer. (This symbolism differs from that in Ref. 1.) The states of monomer and/or polymer are not stated in Ref. but are likely to be the ones given. Value calculated from measurements on mixtures containing excess B. Value calculated from measurements on mixtures containing excess A. Value in Ref. 11 corrected using entropy of monomer in Ref. 94. From measurements in both benzene and cyclohexane. Standard state: mol fraction of monomer = 0.1. After correction for species in vapor other than formaldehyde. Numerical values for entropies of polymerizaiton listed are for systems yielding 1:1 copolymers. The values refer to the copolymerization of 0.5 mol of each monomer. The symbolism and standard states are the same as used for the heats of copolymerization (see N 2 i). Value of A5° for the composition of polymer indicated. No allowance for free energy of mixing of polymer and monomer. Floor temperature (hypothetical for supercooled liquid). Floor temperature. Calculated value. Not measurable experimentally because of side reactions. Small amount of vapor dissolved in the polymer: approximately gc.
N 36 Hypothetical value for acetone as a gas at 1013 mbar pressure. N 37 Decreases with increasing polymer concentration (Ref. 112,160,289). N 38 Recognised that polymerization over WCl 6/EtAlCl 2/ EtOH yields an equilibrium mixture of unsaturated cyclic rings (CsH 14)«. Species up to n = 15 have been identified and higher cyclic polymers are also likely to be present. No firm equilibrium data exist as yet. N 3 9 dr c /dP=19deg/kbar. N 40 Value in [M] column is the mol fraction of monomer. N41 Decreases with increasing polymer concentration in methylene chloride, in benzene and in 1,4-dioxane (Ref. 159). N42 Kn values determined for cyclic monomers, n = 1-8. N43 Extrapolated value. N 4 4 For equilibrium concentrations of linear oligomeric species see Ref. 294. N45 Note the substantial discrepancy between the two sets of results with nitrobenzene as solvent. N 46 Value in [M] column is the volume fraction of cyclic monomer (rings of all sizes). N47 Concentration of rings, rc = 13-oo, taking mol. wt. = 74 (value for n— 1); Kn determined for cyclic monomers, n — 3-400. N48 Corrected for isomerization effect. N 49 Uncorrected for isomerization effect. N 50 Equilibrium concentrations of A and B lower than expected from values for homopolymerizations. N51 Polymer is -{CONHN(COMe)f. N 5 2 Polymer is 4CH 2 CH 2 N(COR)J-. N53 cis and trans forms of polymer. N 5 4 c'(I)^(IIXc(III) refer to crystal forms I, II, III of monomer. N 5 5 Standard state is IM, calculated from data in Ref. 148. N56 Polymer dissolved in monomer; equilibrium concentration in mol/L. N 5 7 Tc calculated from AH?JAS°lc or A#S°S/ASS°S. N5g Valid in concentration range 2.3 to 4.6 M. N59 Corrected for monomer-polymer interactions; required temperature variable interaction parameter. N6O Data from Ref. 292, with corrections for monomer adsorbed in polymer. N 6 i Ic data from Ref. 231 combined with vaporization data.
N 62 Calorimetry in solution with adjustments for solution enthalpies. N63 With heat capacity adjustment for T change: may apply to N 62N64 From group method calculations; AG° (298K) value given in brackets in kJ/mol; Tc refers to standard state conditions, PA = PB = I atm. N65 AHP by method 4a in close agreement. N66 Ring opening polymerization giving 78% trans polymer. N 67 Polymer is N 68 Calculated from solution values with experimentally determined data. N 69 Calculated from solution data utilizing monomerpolymer interaction parameters, see Ref. 130. N 70 Mixture of 1,2 and 1,4 polymerization. N71 Includes adjustment for the presence of small concentrations of other cyclics; Sn 7^ S 8 . N 72 Calculations based on standard enthalpies of formation of Sn and AHP (S 8 ). N73 Calculation based on standard entropies of Sn and AS P (S 8 ). N 7 4 Values apply in temperature range below the appropriate ceiling temperature, see Section C, Table 10, under "Monomers Giving Polymers Containing O in the Main Chain, Bonded to C Only." N 7 5 Obtained by extrapolation of kinetic data. N 7 6 Ring opening at S-C bond. N 7 7 c'(I), C7CII) refer to crystal forms I, II of polymer. N 7 8 Average Temperature
N 7 9 Polymer is
N8o Polymer is
N 8 i Polymer is
N82 Polymer is
F. REFERENCES 1. E S . Dainton, K. J. Ivin, in: H. A. Skinner (Ed.) "Experimental Thermochemistry", vol. II, Interscience, New York, 1962, p. 251. 2. R. S. Jessup, J. Chem. Phys., 16, 661 (1948). 3. J. W. Richardson, G. S. Parks, J. Am. Chem. Soc, 61, 3545 (1939). 4. F. A. Quinn, L. Mandelkern, J. Am. Chem. Soc, 80, 3178 (1958).
5. F. S. Dainton, J. Diaper, K. J. Ivin, D. R. Sheard, Trans. Faraday Soc, 53, 1269 (1957)., 6. C. M. Fontana, G. A. Kidder, J. Am. Chem. Soc, 70, 3745 (1948). 7. G. S. Parks, H. P. Mosher, J. Polym. Sci. A, 1, 1979 (1963). 8. A. G. Evans, M. Polanyi, Nature, 152, 738 (1943).
9. R. H. Biddulph, R H. Plesch, R R Rutherford, Polymer, 1, 521 (1960). 10. D. E. Roberts, J. Res. Natl. Bur. Std. 44, 221 (1950). 11. R S . Dainton, T. R. E. Devlin, R A. Small, Trans. Faraday Soc, 51, 1710 (1955). 12. S. Kaarsemaker, J. Coops, Rec. Trav. Chim, 71, 261 (1952). 13. H. van Kamp, J. Coops, W. A. Lambregts, B. J. Visser, H. Dekker, Rec. Trav. Chim, 79, 1226 (1960). 14. F. S. Dainton, K. J. Ivin, D. A. G. Walmsley, Trans. Faraday Soc, 56, 1784 (1960). 15. R. M. Joshi, Makromol. Chem., 55, 35 (1962). 16. H. Hopff, H. Luessi, Makromol. Chem., 62, 31 (1963). 17. R. M. Joshi, J. Polym. ScL, 56, 313 (1962). 18. G. C. Sinke, D. R. Stull, J. Phys. Chem., 62, 397 (1958). 19. J. R. Lacher, E. E. Merz, E. Bohmfalk, J. D. Park, J. Phys. Chem., 60, 492 (1956). 20. J. R. Lacher, H. B. Gottlieb, J. D. Park, Trans. Faraday Soc, 58, 2348 (1962). 21. L. K. J. Tong, W. O. Kenyon, J. Am. Chem. Soc, 69, 2245 (1947). 22. W. M. D. Bryant, J. Polym. ScL, 56, 277 (1962). 23. C. R. Patrick, Tetrahedron, 4, 26 (1958). 24. R. M. Joshi, Makromol. Chem., 62, 140 (1963). 25. F. S. Dainton, K. J. Ivin, Trans. Faraday Soc, 46, 331 (1950). 26. D. E. Roberts, W. W. Walton, R. S. Jessup, J. Res. Natl. Bur. Std., 38, 627 (1947). 27. L. K. J. Tong, W. O. Kenyon, J. Am. Chem. Soc, 69, 1402 (1947). 28. S. Bywater, D. J. Worsfold, J. Polym. ScL, 58, 571 (1962). 29. S. Bywater, Makromol. Chem., 52, 120 (1962). 30. R. H. Biddulph, W. R. Longworth, J. Penfold, R H. Plesch, P. P. Rutherford, Polymer, 1, 521 (1960). 31. D. E. Roberts, R. S. Jessup, J. Res. Natl. Bur. Std., 46, 11 (1951). 32. D. J. Worsfold, S. Bywater, J. Polym. ScL, 26, 299 (1957). 33. H. W. McCormick, J. Polym. ScL, 25, 488 (1957). 34. R. M. Joshi, Makromol. Chem., 66, 114 (1963). 35. W. I. Bengough, Trans. Faraday Soc, 54, 1560 (1958). 36. A. G. Evans, E. Tyrrall, J. Polym. ScL, 2, 387 (1947). 37. K. G. McCurdy, K. J. Laidler, Can. J. Chem., 42, 818 (1964). 38. J. H. Baxendale, G. W. Madaras, J. Polym. ScL, 19, 171 (1956). 39. L. K. J. Tong, W. O. Kenyon, J. Am. Chem. Soc, 68, 1355 (1946). 40. R. E. Cook, K. J. Ivin, Trans. Faraday Soc, 53, 1132 (1957). 41. S. Ekegren, S. Oehrn, K. Granath, R Kinell, Acta Chem. Scand., 4, 126 (1950). 42. S. Bywater, Trans. Faraday Soc, 51, 1267 (1955). 43. K. J. Ivin, Trans. Faraday Soc, 51, 1273 (1955). 44. S. Bywater, Can. J. Chem., 35, 552 (1957). 45. R. A. Nelson, R. S. Jessup, D. E. Roberts, J. Res. Natl. Bur. Std., 48, 275 (1952). 46. R. S. Jessup, A. D. Cummings, J. Res. Natl. Bur. Std., 13,357 (1934). 47. A. A. Korotkov, E. N. Marandzheva, Russ. J. Phys. Chem. (English Transl.), 37, 135 (1963).
48. V. A. Kargin, V. A. Kabanov, V. R Zubov, I. M. Papisov, Dokl. Akad. Nauk SSSR, 134,1098 (1960). Chem. Abst, 55, 8282 (1961). 49. F. S. Dainton, K. J. Ivin, D. A. G. Walmsley, Trans. Faraday Soc, 55, 61 (1959). 50. W. K. Busfield, E. Whalley, Trans. Faraday Soc, 59, 679 (1963). 51. H. C. Raine, R. B. Richards, H. Ryder, Trans. Faraday Soc, 41, 56 (1945). 52. R Gray, A. Williams. Trans. Faraday Soc, 55, 760 (1959). 53. J. B. Rose, J. Chem. Soc, 546 (1946). 54. S. M. Skuratov, A. A. Strepikheev, S. M. Shtekher, A. V. Volokhina, Dokl. Akad. Nauk. SSSR, 117, 263 (1957). 55. S. M. Skuratov, A. A. Strepikheev, M. R Kozina, Dokl. Akad. Nauk. SSSR, 117, 452 (1957). 56. R. C. Cass, S. E. Fletcher, C. T. Mortimer, H. D. Springall, T. R. White, J. Chem. Soc, 1406, (1958). 57. D. Sims, J. Chem. Soc, 864, (1964). 58. C. E. H. Bawn, R. M. Bell, A. Ledwith, Polymer, 6, 95 (1965). 59. A. Snelson, H. A. Skinner, Trans. Faraday Soc, 57, 2125 (1961). 60. S. E. Fletcher, C. T. Mortimer, H. D. Springall, J. Chem. Soc, 580 (1959). 61. E S . Dainton, J. A. Davies, R P. Manning, S. A. Zahir, Trans. Faraday Soc, 53, 813 (1957). 62. A. A. Strepikheev, S. M. Skuratov, O. N. Kachinskaya, R. S. Muramova, E. R Brykina, S. M. Shtekher, Dokl. Akad. Nauk. SSSR, 102, 105 (1955). 63. V. R Kolesov, I. E. Paukov, S. M. Skuratov, Zh. Fiz. Khim., 36, 770 (1962); Russ. J. Phys. Chem., 36, 400 (1962). 64. M. R Kozina, S. M. Skuratov, Dokl. Akad. Nauk. SSSR, 127, 561 (1959). 65. S. M. Skuratov, A. A. Strepikheev, Y. N. Kanarskaya, Kolloidn. Zh., 14, 185 (1952). 66. A. B. Meggy, J. Chem. Soc, 796, (1953). 67. P. F. van Velden, G. M. van der Want, D. Heikens, C. A. Kruissink, R H. Hermans, A. J. Staverman, Rec. Trav. Chim., 74, 1376 (1955). 68. A. V. Tobolsky, A. Eisenberg, J. Am. Chem. Soc, 81, 2302 (1959). 69. H. Mackle, R A. G. O'Hare, Tetrahedron, 19, 961 (1963). 70. S. Sunner, Acta Chem. Scand., 17, 728 (1963). 71. H. Mackle, R. G. Mayrick, Trans. Faraday Soc, 58, 230 (1962). 72. J. A. Barltrop, R M. Hayes, M. Calvin, J. Am. Chem. Soc, 76, 4348 (1954). 73. F. Fairbrother, G. Gee, G. T. Merrall, J. Polym. ScL,16, 459 (1955). 74. A. V. Tobolsky, A. Eisenberg, J. Am. Chem. Soc, 81, 780 (1959). 75. H. Nagao, T. Yamaguchi, J. Chem. Soc Japan, Ind. Eng. Chem. Sect, 59, 1363 (1956). 76. H. Miyama, S. Fujimoto, J. Polym. ScL, 54, S 32 (1961). 77. F. S. Dainton, K. J. Ivin, Proc Roy. Soc. (London) A, 212, 207 (1952). 78. J. E. Hazell, K. J. Ivin, Trans. Faraday Soc, 58, 342 (1962).
79. L. K. J. Tong, W. O. Kenyon, J. Am. Chem. Soc, 71, 1925 (1949). 80. F. S. Dainton, K. J. Mn, D. R. Sheard, Trans. Faraday Soc, 52, 414 (1956). 81. M. Suzuki, H Miyama, S. Fujimoto, J. Polym. ScL, 31, 212 (1958). 82. K. J. Ivin, W. A. Keith, H. Mackle, Trans. Faraday Soc, 55, 262 (1959). 83. R. E. Cook, K. J. Ivin, J. H. O'Donnell, Trans. Faraday Soc, 61, 1881 (1965). 84. W. A. Piccoli, G. G. Haberland, R. L. Merker, J. Am. Chem. Soc, 82, 1883 (1960). 85. A. Eisenberg, A. V. Tobolsky, J. Polym. ScL, 46, 19 (1960). 86. D. C. Abercromby, R. A. Hyne, P. F. Tiley, J. Chem. Soc, 5832 (1963). 87. F. S. Dainton, K. J. Ivin, Quart. Rev., 12, 61 (1958). 88. F. S. Dainton, D. M. Evans, F. E. Hoare, T. P. Melia, Polymer 3, 277, 286 (1962). 89. E. Passaglia, H. K. Kevorkian, J. Appl. Polym. ScL, 7, 119 (1963). 90. R. W. Warfield, M. C. Petree, Makromol. Chem., 51, 113 (1962). 91. B. Wunderlich, J. Chem. Phys. 37, 1203 (1962). 92. E. Passaglia, H. K. Kevorkian, J. Appl. Phys., 34, 90 (1963). 93. G. T. Furukawa, M. L. Reilly, J. Res. Natl. Bur. Std., 56, 285 (1956). 94. H. L. Finke, D. W. Scott, M. E. Gross, J. F. Messerly, G. Waddington, J. Am. Chem. Soc, 78, 5469 (1956). 95. R. B. Scott, C. H. Meyers, R. D. Rands, F. G. Brickwedde, N. Bekkedahl, J. Res. Natl. Bur. Std., 35, 39 (1945). 96. G. T. Furukawa, R. E. McCoskey, J. Res. Natl. Bur. Std., 51, 321 (1953). 97. F. S. Dainton, D. M. Evans, F. E. Hoare, T. P. Melia, Polymer, 3, 297 (1962). 98. G. T. Furukawa, R. E. McCoskey, M. L. Reilly, J. Res. Natl. Bur. Std., 51, 69 (1953). 99. G. T. Furukawa, R. E. McCoskey, G. J. King, J. Res. Natl. Bur. Std., 49, 273 (1952). 100. N. Bekkedahl, L. A. Wood, J. Res. Natl. Bur. Std., 19, 551 (1937). 101. N. Bekkedahl, H. Matheson, J. Res. Natl. Bur. Std., 15, 503 (1953). 102. T. P. Melia, Polymer, 3, 317 (1962). 103. R. W. Warfield, M. C. Petree, J. Polym. ScL A, 1, 1701 (1963). 104. R. H. Boundy, R. F. Boyer, "Styrene", Reinhold, New York, 1952, p. 67. 105. R. W. Warfield, M. C. Petree, J. Polym. ScL, 55, 497 (1961). 106. F. S. Dainton, D. M. Evans, F. E. Hoare, T. P Melia, Polymer, 3, 263 (1962) 107. F. S. Dainton, D. M. Evans, F. E. Hoare, T. P. Melia, Polymer, 3, 271 (1962). 108. R. J. Orr, Polymer, 2, 74 (1961). 109. F. S. Dainton, D. M. Evans, F. E. Hoare, T. R Melia, Polymer, 3, 310 (1962). 110. R. E. Cook, F. S. Dainton, K. J. Mn, J. Polym. ScL, 26, 351 (1957).
111. G. Gee, Chemical Society (London) Special Publication, 15, 67 (1961). 112. A. Vrancken, J. Smid, M. Szwarc, Trans. Faraday Soc, 58, 2036 (1962). 113. A. V. Tobolsky, A. Rembaum, A. Eisenberg, J. Polym. ScL, 45, 347 (1960). 114. K. J. Mn, Pure Appl. Chem., 4, 271 (1962). 115. A. M. North, D. Richardson, Polymer, 6, 333 (1965). 116. A. A. Strepikheev, A. V. Volokhina, Dokl. Akad. Nauk. SSSR, 99, 407 (1954). 117. C. L. Hamermesh, V. E. Haury, J. Org. Chem., 26, 4748 (1961). 118. N. Yoda, A. Miyake, J. Polym. ScL, 43, 117 (1960). 119. J. G. Kilroe, K. E. Weale, J. Chem. Soc, 3849, (1960). 120. H. H. G. Jellinek, H. Kachi, Makromol. Chem., 85,1 (1965). 121. R. B. Whitney, M. Calvin, J. Chem. Phys., 23, 1750 (1955). 122. W. Kern, V. Jaacks, J. Polym. ScL, 48, 399 (1960). 123. B. J. Cottam, J. M. G. Cowie, S. Bywater, Makromol. Chem., 86, 116(1965). 124. J. E. Hazell, K. J. Mn, Trans. Faraday Soc, 58, 176 (1962). 125. J. K. Jacques, M. F. Mole, N. L. Paddock, J. Chem. Soc, 2112, (1965). 126. J. W. C. Crawford, J. Chem. Soc, 2658, (1953). 127. V. E. Shashoua, W. Sweeny, R. E. Tietz, J. Am. Chem. Soc, 82, 866 (1960). 128. R. C. P. Cubbon, Makromol. Chem., 80, 44 (1964). 129. W. K. Busfield, Polymer, 7, 541 (1966). 130. K. J. Mn, J. Leonard, Polymer, 6, 621 (1965). 131. K. Nakatsuka, H. Suga, S. Seki, J. Polym. Sci. B, 7, 361 (1969). 132. J. B. Thompson, W. M. D. Bryant, Am. Chem. Soc. Polym. Preprints, 11, 204 (1970). 133. P. H. Plesch, P. H. Westermann, J. Polym. Sci. C, 16, 3837 (1968). 134. Y. Yamashita, M. Okada, K. Suyama, H. Kasahara, Makromol. Chem., 144, 146 (1968). 135. O. Riedel, P. Wittmer, Makromol. Chem., 97, 1 (1966). 136. R H. Plesch, P. H. Westermann, Polymer, 10, 105 (1969). 137. B. Boerjesson, Y. Nakase, S. Sunner, Acta Chem. Scand., 20, 803 (1966). 138. A. K. Bonetskaya, S. M. Skuratov, Vysokomol. Soedin. A, 11, 532 (1969). 139. H. G. Elias, A. Fritz, Makromol. Chem., 114,31 (1968); 120, 238 (1968). 140. G. A. Clegg, D. R. Gee, T. P. Melia, A. Tyson, Polymer, 9, 501 (1968). 141. G. A. Clegg, T. P. Melia, A. Tyson, Polymer, 9, 75 (1968). 142. G. A. Clegg, T. P. Melia, Makromol. Chem., 123, 184 (1969). 143. R. M. Joshi, B. J. Zwolinski, C. W. Hayes, Macromolecules, 1, 30 (1968). 144. D. R. Waywell, J. Polym. Sci. B, 8, 327 (1970). 145. G. C. Vezzoli, F. Dachille, R. Roy. J. Polym. Sci. A-I, 7, 1557 (1969). 146. M. Rahman, K. E. Weale, Polymer, 11, 122 (1970). 147. F. P. Jones, Ph.D. Thesis, Keele University, 1970.
148. V. C. E. Burnop, K. G. Latham, Polymer, 8, 589 (1967). 149. H. Hopff, H. Luessi, L. Borla, Makromol. Chem., 81, 268 (1965). 150. L. Borla, Promotionsarbeit Nr. 3668, E. T. H. Zuerich (1965). 151. H. Luessi, Makromol. Chem., 103, 68 (1967). 152. S. Hashimoto, T. Yamashita, Kobunshi Kagaku, 27, 400 (1970). 153. H. Sumimoto, T. Nakagawa, J. Polym. Sci. B, 7, 739 (1969). 154. C. Aso, S. Tagami, T. Kunitake, J. Polym. Sci. A-I, 7, 497 (1969). 155. Y.Okamoto, H. Takano, H. Yuki, Polym. J., 1, 403 (1970). 156. T. Yamaguchi, K. Nagi, Kobunshi Kagaku, 26, 809 (1969). 157. J. Stein, P. Wittmer, J. Toelle, Angew. Makromol. Chem., 8, 61 (1969). 158. A. Novak, E. Whalley, Can. J. Chem., 37,1710 (1959). 159. L. I. Kuzub, M. A. Markevich, A. A. Berlin, N. S. Yenikolopyan, Vysokomol. Soedin. A, 10,2007 (1968); Polym. Sci. SSSR, 10, 2332 (1968). 160. K. J. Ivin J. Leonard, Eur. Polym. J., 6, 331 (1970). 161. Y. Ohtsuka, C. Walling, J. Am. Chem. Soc, 88,4167 (1966). 162. C. Walling, T. A. Augurt, J. Am. Chem. Soc, 88, 4163 (1966). 163. G. Natta, G. Mazzanti, P. Corradini, I. W. Bassi, Makromol. Chem., 37, 156 (1960). 164. W. K. Busfield, D. Merigold, Makromol. Chem., 138, 65 (1970). 165. Y. Iwasa, T. Imoto, J. Chem. Soc. Japan, Pure Chem. Sect. (Nippon Kagaku Zasshi), 84, (29 (1963). 166. I. Mita, I. Imai, H. Kambe, Makromol. Chem., 137, 169 (1970). 167. I. Mita, I. Imai, H. Kambe, Makromol. Chem., 137, 143 (1970). 168. V. E. Ostrovskii, V. A. Khodzhemirov, A. P. Barkova, Dokl. Akad. Nauk. SSSR, 191, 1095 (1970). 169. R Caillaud, J. M. Huet, E. Marechal, Bull. Soc. Chim. France, 1473 (1970). 170. G. A. Clegg, T. P. Melia, Polymer, 11, 245 (1970). 171. A. K. Bonetskaya, T. V. Sopova, O. B. Salamatina, S. M. Skuratov, B. P. Fabrichuyi, I. F. Shalavina, V. L. Gol'dfarb, Vysokomol. Soedin. B, 11, 894 (1969). 172. I. Mita, I. Imai, H. Kambe, Makromol. Chem., 137, 155 (1970). 173. A. Nicco, B. Boucheron, Europ. Polym. J., 6, 1477 (1970). 174. G. R. Walker, J. A. Semlyen, Polymer, 11, 472 (1970). 175. E. Marechal, J. Polym. Sci. A-I, 8, 2867 (1970). 176. P. V. Wright, J. A. Semlyen, Polymer, 11, 462 (1970). 177. G. A. Cleg, T. P. Melia, Polymer, 10, 912 (1969). 178. T. Miki, T. Higashimura, S. Okamura, J. Polym. Sci. A-I, 8, 157 (1970). 179. E. G. Butcher, H. Mackle, D. V. McNaIIy, Trans. Faraday Soc, 65, 2331 (1969). 180. J. A. Semlyen, P. V. Wright, Polymer, 10, 543 (1969). 181. J. A. Semlyen, G. R. Walker, Polymer, 10, 597 (1969). 182. A. A. Berlin, K. A. Bogdanova, I. P. Kravchuk, G. P. Rakova, N. S. Yenikolopyan, Dokl. Akad. Nauk. SSSR, 184, 1128 (1969).
183. V. E. Ostrovskii, V. A. Khodzhemirov, S. P. Kostareva, Dokl. Akad. Nauk. SSSR, 184, 103 (1969). 184. G. A. Clegg, T. P. Melia, Makromol. Chem., 123, 194 (1969). 185. G. Nabi, Pak. J. Sci., 20, 29 (1968). 186. D. R. Gee, T. P. Melia, Makromol. Chem., 116, 122 (1968). 187. V. I. Kasatochkin, M. E. Kazakov, Y. P. Kudryavtsev, A. M. Sladkov, V. V. Korshak, Dokl. Akad. Nauk. SSSR, 183, 109 (1968). 188. E. M. Morazova, V. I. Yeliseyeva, M. A. Korshunov, Vysokomol. Soedin. A, 10, 2354 (1968); Polym. Sci. A, SSSR, 10, 2736 (1968). 189. A. K. Bonetskaya, S. M. Skuratov, N. A. Lukina, A. A. Strel'tsova, K. E. Kuznetsova, M. P. Lazareva, Vysokomol. Soedin. B, 10, 75 (1968). 190. H. Cheradame, J. R Vairon, P. Sigwalt, Europ. Polym. J., 4, 13 (1968). 191. O. B. Salamatina, A. K. Bonetskaya, S. M. Skuratov, B. P. Fabrichnyi, I. F. Shalavina, Y L. Gol'dfarb, Vysokomol. Soedin. B, 10, 10 (1968). 192. P., Cefelm, R Schmidt, J. Sebenda, J. Polym. Sci. C, 23,175 (1966). 193. B. V. Lebedev, I. B. Rabonovich, L. Y. Martynenko, Vysokomol. Soedin. A, 9, 1640 (1967). 194. P. Cefelm, A. Frydrychova, J. Labsky, P. Schmidt, J. Sebenda, Coll. Czech Chem. Comm., 32, 2787 (1967). 195. M. Furue, S. Nozakura, S. Murahashi, T. Tanaka, Bull. Chem. Soc. Japan, 40, 2700 (1967). 196. T. P. Melia, A. Tyson, Makromol. Chem., 109, 87 (1967). 197. S. Iwatsuki, S. Amano, Y. Yamashita, Kogyo Kagaku Zassi, 70, 2027 (1967). 198. L. A. Kharitonova, G. V. Rakova, A. A. Shaginyan, N. S. Yenikolopyan, Vysokomol. Soedin. A, 9, 2586 (1967). 199. B. H. G. Brady, J. H. O'Donnell, Trans. Faraday Soc, 64, 29 (1968). 200. B. H. G. Brady, J. H. O'Donnell, Europ. Polym. J., 4, 537 (1968). 201. J. Chiu, Proc 2nd Symp. on Anal. Calorimetry 171, (1970). 202. K. A. Bogdanova, A. K. Bonetskaya, A. A. Berlin, G. V Rakova, N. S. Yenikolopyan, Dokl. Akad. Nauk. SSSR, 197, 618 (1971). 203. F. Delben, V. Crescenzi, Ann. Chim. (Rome), 60,782 (1970). 204. G. Natta, G. Mazzanti, R Corradini, I. W. Bassi, Makromol. Chem., 37, 156 (1968). 205. K. J. Ivin, Thermodynamics of Addition Polymerization Processes, Ch. 16 in: A. D. Jenkins, A. Ledwith, (Eds.), "Reactivity, Mechanism and Structure in Polymer Chemistry", Wiley, New York, 1973. 206. I. B. Rabinovich, L. L Pavlinov, Vysokomol. Soedin. A, 10, 416 (1968). 207. S. M. Skuratov, V. V. Voevodskii, A. A. Strepikheev, Y. N. Kanarskaya, R. S. Muramova, N. V. Fok, Dokl. Akad. Nauk. SSSR, 95, 591 (1954). 208. J. H. S. Green, Quart. Rev. Chem. Soc, 15, 125 (1961). 209. F. Korte, W. Glet, J. Polym. Sci. B, 4, 685 (1966). 210. R. H. Beaumont, B. Clegg, G. Gee, J. B. M. Herbert, D. J. Marks, R. C. Roberts, D. Sims, Polymer, 7, 401 (1966).
211. B. A. Rozenberg, O. M. Chekhuta, Y. B., Lyudvig, A. R. Gantmakher, S. S. Medvedev, Vysokomol. Soedin., 6, 2030 (1964); Polym. Sci. SSSR, 6, 2246 (1964). 212. L. Lesse, M. W. Baumber, Polymer, 6, 269 (1965). 213. R. W. Warfield, M. C. Petree, J. Polym. Sci. A-2, 4, 532 (1966). 214. J. Grodzinsky, A. Katchalsky, D. Vofsi, Makromol. Chem., 44/46, 591 (1961). 215. R. M. Joshi, Indian. J. Chem., 2, 215 (1964). 216. M. F. Shostakovskii, I. F. Bogdanov, J. Appl. Chem. Russ., 15, 249 (1942). 217. J. F. Brown, G. M. J. Slusarczuk, J. Am. Chem. Soc, 87, 931 (1965). 218. P. J. Flory, J. A. Semlyen, J. Am. Chem. Soc, 88, 3209 (1966). 219. M. Kucera, Y. Pichler, Vysokomol. Soedin., 7, 10 (1965); Polym. Sci. SSSR, 7, 9 (1965). 220. G. M. Chil'-Gevorgyan, A. K. Bonetskaya, S. M. Skuratov, N. S. Yenikolopyan, Vysokomol. Soedin. A, 9, 1363 (1967). 221. I. Mita, S. Yabe, I. Imai, H. Kambe, Makromol. Chem., 137, 133 (1970). 222. T. P. Melia, G. A. Clegg, A. Tyson, Makromol. Chem., 112, 84 (1968). 223. O. E. Grikina, V M. Tatevskii, N. F. Stepanov, S. S. Yarovoi, Vestn. Mosk. Univ. Ser. II, 22, 8 (1967). 224. O. E. Grikina, N. F. Stepanov, V. M. Tatevskii, S. S. Yarovoi, Vysokomol. Soedin. A, 13, 575 (1971); Polym. Sci. SSSR, 13, 653 (1971). 225. R Cefelin, D. Doskocilova, A. Frydrychova, J. Sebenda, Coll. Czech. Chem. Comm., 29, 485 (1964). 226. P. Cefelin, A. Frydrychova, P. Schmidt, J. Sebenda, Coll. Czech. Chem. Comm., 32, 1006 (1967). 227. O. Vogl. J. Polym. Sci. A, 2, 4607 (1964). 228. H. Takida, K. Noro, Chemistry of High Polymers, Japan, 21, 452 (1964). 229. E. Wasserman, D. A. Ben-Efraim, R. Wolovsky, J. Am. Chem. Soc, 90, 3286 (1968). 230. N. Calderon, J. Macromol. Sci. Rev. Macromol. Chem. C7, 105 (1972). 231. J. Leonard, D. Maheux, Am. Chem. Soc. Polymer Preprints, 13, 78 (1972). 232. J. M. Andrews, J. A. Semlyen, Polymer, 13, 142 (1972). 233. O. Vogl, personal communication. 234. O. Vogl, W. M. D. Bryant, J. Polym. Sci. A, 2, 4633 (1964). 235. H. Kambe, I. Mita, K. Horie, Proc 2nd Int. Conf. on Thermal Analysis (1969) 1071. 236. T. Saegusa, T. Shiota, S. Matsumoto, H. Fujii, quoted in Macromolecules, 5, 34 (1972). 237. T. Endo, Bull. Chem. Soc. Japan, 44, 870 (1971). 238. T. Kagiya, S. Narisawa, T. Maeda, K. Fukui, Kogyo Kagaku Zasshi, 69, 732 (1969); J. Polym. Sci. B, 4, 441 (1966). 239. H. K. Hall, A. K. Schneider, J. Am. Chem. Soc, 80, 6409 (1958). 240. H. K. Hall, J. Am. Chem. Soc, 80, 6404 (1958). 241. J. W. Hill W. H. Carothers, J. Am. Chem. Soc, 57, 925 (1935).
242. M. Okada, Y Yamashita, Y. Ishii, Makromol. Chem., 80,196 (1964). 243. W. H. Carothers, Collected papers of, G. S. Whitby, H. Mark, (Ed.), Interscience, New York, 1940. 244. I. Maruyama, M. Nakaniwa, T. Saegusa, J. Furukawa, J. Chem. Soc Japan Ind. Chem. Sect., 68, 1149 (1965). 245. R. B. Whitney, M. Calvin, J. Chem. Phys., 23, 1750 (1955). 246. J. G. Affleck, G. Dougherty, J. Org. Chem., 15, 865 (1950). 247. W. O. Ney, W. R. Nummy, C. E. Barnes, USP. 2638463 (1953). 248. W. O. Ney, M. Crowther, USP. 2739959 (1956). 249. M. P. Kozina, S. M. Skuratov, Dokl. Akad. Nauk. SSSR, 127, 561 (1959). 250. H. Meerwein, Angew. Chem., 59, 168 (1947). 251. H. Meerwein, D. Delfs, H. Morschel, Angew. Chem., 72, 927 (1960). 252. M. P. Dreyfuss, R Dreyfuss, J. Polym. Sci. A, 4,2179 (1966). 253. T. Saegusa, S. Matsumoto, J. Macromol. Sci. A: Chem., 4, 873 (1970). 254. J. B. Rose, J. Stuart-Webb, unpublished results quoted in: P H. Plesch, (Ed.), "The Chemistry of Cationic Polymerization", Pergamon, Oxford 1963. 255. R. Chiang, J. H. Rhodes, J. Polym. Sci. B, 7, 643 (1969). 256. C. G. Overberger, J. K. Weise, J. Am. Chem. Soc, 90, 3533 (1968). 257. W. Kern, H. Cherdron, V. Jaacks, Angew. Chem., 73, 177 (1961). 258. E. Gipstein, E. Wellisch, O. L. Sweeting, J. Polym. Sci. B, 1, 237 (1963). 259. J. B. Lando, V Stannett, J. Polym. Sci. B, 2, 375 (1964). 260. O. G. von Ettinghausen, E. Kendrick, Polymer, 7, 469 (1966). 261. A. B. Meggy, J. Chem. Soc, 1444, (1956). 262. H. K. Hall, Am. Chem. Soc Polymer Preprints, 6, 535 (1965). 263. W. Dittrich, R. C. Schulz, Angew. Makromol. Chem., 15, 109 (1971). 264. E. Hollo, Bericht, 61, 895 (1928). 265. A. Schoeberl, G. Wiehler, Ann., 595, 101 (1955). 266. P. A. Small, Trans. Faraday Soc, 51, 1717 (1955). 267. F. Fichter, A. Beisswenger, Ber., 36, 1200 (1903). 268. K. Saotome, Y. Kodaira, Makromol. Chem., 82, 41 (1965). 269. H. Batzer, G. Fritz, Makromol. Chem., 14, 179 (1954). 270. H. D. K. Drew, W. N. Haworth, J. Chem. Soc, 775, (1927). 271. M. H. Palomaa, V Toukola, Ber. 66B, 1629 (1933). 272. D. D. Coffman, N. L. Cox, E. L. Martin, W. E. Mochel, F. J. van Natta, J. Polym. Sci., 3, 85 (1948). 273. W. E. Hanford, R. M. Joyce, J. Polym. Sci., 3, 167 (1948). 274. H. R. Mighton, USR 2647105 (1953). 275. F. N. S. Carver, B. L. Hollingsworth, Makromol. Chem., 95, 135 (1966). 276. A. Schaffler, W. Ziegenbein, Ber., 88, 1374 (1955). 277. W. Ziegenbein, A. Schaffler, R. Kaufhold, Ber., 88, 1906 (1955). 278. L. E. Wolinski, H. R. Mighton, J. Polym. Sci., 49, 217 (1961).
279. M. Imoto, H. Sakurai, T. Kono, J. Polym. Sci., 50, 467 (1961). 280. N. L. Coxx, W. E. Hanford, USR 2276164 (1942); Swiss P. 270546 (1951), 276924 (1952). 281. F. P. Jones, Ph.D. thesis, Univers. of Keele, 1970. 282. R. Gehm, Angew. Makromol. Chem., 18, 159 (1971). 283. T. Saegusa, T. Hodaka, H. Fujii, Polym. J., 2, 670 (1971). 284. K. Yagi, T. Miyazaki, H. Okitsu, F. Toda, Y. Iwakura, J. Polym. Sci. A-I, 10, 1149 (1972). 285. B. Krummenacher, H. G. Elias, Makromol. Chem., 150, 271 (1971). 286. R C. Wollwage, R A. Seib, J. Polym. Sci. A-I, 9, 2877 (1971). 287. C. C. Tu, C. Schuerch, J. Polym. Sci. B, 1, 163 (1963). 288. T. Kunitake, M. Yasumatsu, C. Aso, J. Polym. Sci. A-I, 9, 3678 (1971). 289. I. Mita, H. Okuyama, J. Polym. Sci. A-I, 9, 3437 (1971). 290. G. Belonovskaya, Z. Tchernova, B. Dolgoplosk, Europ. Polym. J., 8, 35 (1972). 291. J. Kops, H. Spanggaard, Makromol. Chem., 151, 21 (1972). 292. W. K. Busfield, R. M. Lee, D. Merigold, Makromol. Chem., 156, 183 (1972). 293. Y. B. Lyudvig, Y. E. Berman, Z. N. Nysenko, V. A. Ponomarenko, S. S. Medvedev, Vysokomol. Soedin. A, 13, 1375 (1971); Polym. Sci. SSSR, 13, 1546 (1971). 294. J. M. Andrews, J. A. Semlyen, Polymer, 12, 642 (1971). 295. V. S. Etlis, G. A. Razuvaev, A. P. Sineokof, Khim. Geterosicl. Soedin., 2, 223 (1967). 296. G. A. Razuvaev, V. S. Etlis, L. N. Gribov, Zh. Obshch. Khim., 33, 1366 (1963). 297. C. Aso, S. Tagami, T. Kunitake, Kobunshi Kagaku, 23, 63 (1966). 298. A. A. Dugaryan, A. V. Agumyan, Vysokomol. Soedin., 5, 1755 (1963). 299. R. Raff, J. L. Cook, B. V. Etting, J. Polym. Sci. A, 3, 3511 (1965). 300. E. Thilo, U. Schuelke, Z. Anorg. Allgem. Chem., 341, 293 (1965). 301. D. R. Cooper, J. A. Semlyen, Polymer, 13, 414 (1972). 302. O. B. Salamatina, A. K. Bonetskaya, S. M. Skuratov, B. P. Fabrichnyi, I. F. Shalavina, Y. L. Gol'dfarb, Vysokomol. Soedin., 7, 485 (1965). 303. K. Weissermel, E. Noelken, Makromol. Chem., 68, 140 (1963). 304. T. Saegusa, M. Matoi, S. Matsumoto, H. Fujii, Macromolecules, 5, 233, 236 (1972). 305. T. Kodaira, J. Stehlicek, J. Sebenda, Eur. Polym. J., 6, 1451 (1970). 306. F. Andruzzi, S. Suradi, G. Pilcher, Makromol. Chem., 183, 2183 (1982). 307. F. Andruzzi, G. Pilcher, J. M. Hacking, S. Cavell, Makromol. Chem., 181, 923 (1980). 308. F. Andruzzi, G. Pilcher, Y. Virmani, P. H. Plesch, Makromol. Chem., 178, 2367 (1977). 309. S. Sosnowski, J. Libiszowski, S. Slomkowski, S. Penczek, Macromol. Chem., Rapid Commun., 5, 239 (1984).
310. T. M. Frunze, V. A. Kolelnikov, M. P. Ivanov, V. V. Kurashev, L. B. Danilevskaya, S. P. Davtyan, V. V. Korshak, Dokl. Akad. Nauk. SSSR (Chem.), 260, 1379 (1981). 311. T. G. Kulagina, B. V. Lebedev, E. G. Kiparisova, E. B. Lyudvig, I. G. Barskaya, Polym. Sci. USSR, 24, 1702 (1982). 312. B. V. Lebedev, T. G. Kulagina, E. B. Lyudvig, T. N. Ovchinnikova; Polym. Sci. USSR, 24, 1695 (1982). 313. A. A. Yevstropov, B. V. Lebedev, E. Kiparisova, Polym. Sci., USSR, 25, 1951 (1983). 314. A. A. Yevstropov, B. V. Lebedev, T. G. Kulagina, N. K. Lebedev, Polym. Sci., USSR, 24, 628 (1982). 315. M. Ueda, M. Takahashi, Y. Imai, C. U. Pitman, Macromolecules, 16, 1300 (1983). 316. G. O. R. Alberda von Ekenstein, Y. Y. Tan, Eur. Polym. J., 18, 1061 (1982). 317. K. Takahashi, K. Ohnishi, K. Takase, Tetrahedron Lett., 25, 73 (1984). 318. T. Malavasic, U. Osredkar, I. Anzur, I. Vizovisk, J. Macromol. Sci. A, Chem., 19, 987 (1983). 319. T. Malavasik, I. Visorisek, U. Osredkar, I. Anzur, J. Polym. Sci., Polym. Symp., 69, 73 (1981). 320. A. M. Soledad, L. M. Leon, J. Polym. Sci., Polym. Lett. Ed., 21, 979 (1983). 321. M. Rodriguez, L. M. Leon, J. Polym. Sci., Polym. Lett. Ed., 21, 881 (1983). 322. W. K. Busfield, I. J. McEwen, Eur. Polym. J., 9, 1143 (1973). 323. W. K. Busfield, R. M. Lee, Makromol. Chem., 169, 199 (1973). 324. W. K. Busfield, R. M. Lee, Makromol. Chem., 176, 2017 (1975). 325. R. M. Lee, Ph.D. Thesis, University of Dundee, 1972. 326. T. Otsu, B. Yamada, T. Mari, M. Inoue, J. Polym. Sci., Polym. Lett. Ed., 14, 283 (1976). 327. R. M. Joshi, Polymer, 20, 394 (1979). 328. K. Hashimoto, H. Sumitomo, S. Ohsawa, J. Polym. Sci., Polym. Chem. Ed., 14, 1221 (1976). 329. K. Hashimoto, H. Sumitomo, S. Ohsawa, J. Polym. Sci., Polym. Chem. Ed., 13, 2775 (1975). 330. K. Hashimoto, H. Sumitomo, S. Ohsawa, J. Polym. Sci., Polym. Chem. Ed., 16, 435 (1978). 331. M. Okada, H. Sumitomo, M. Atsumi, Macromolecules, 17, 1840 (1984). 332. V. R. Pai Verneker, K. N. Santhanalakshimi, J. Polym. Sci., Polym. Chem. Ed., 22, 3217 (1984). 333. M. Okada, K. Mita, H. Sumitomo, Makromol. Chem., 177, 895 (1976). 334. M. Okada, K. Mita, H. Sumitomo, Makromol. Chem., 176, 859 (1975). 335. M. Okada, K. Mita, H. Sumitomo, Makromol. Chem., 177, 2055 (1976). 336. B. Yamada, R. W. Campbell, O. Vogl, J. Polym. Sci., Polym. Chem. Ed., 15, 1123 (1977). 337. D. W. Lipp, O. Vogl, Polym. J., 9, 499 (1977). 338. D. W. Lipp, O. Vogl, Polymer, 18, 1051 (1977). 339. M. Okada, T. Hisada, H. Sumitomo, Makromol. Chem., 179, 959 (1978).
340. M. Okada, K. Yagi, H. Sumitomo, Makromol. Chem., 163, 225 (1973). 341. R. E. Cunningham, Polymer, 19, 729 (1978). 342. L. Garrido, J. Guzman, E. Riande, Macromol., 14, 1132 (1981). 343. Y. Yamashita, J. Mayumi, Y. Kawakami, K. Ito, Macromolecules, 13, 1075 (1980). 344. P. Kubisa, O. Vogl, Polymer, 21, 525 (1980). 345. T. Otsu, B. Yamada, S. Sugiyama, S. Mori, J. Polym. Sci., Polym. Chem. Ed., 18, 2197 (1980). 346. J. Pretula, K. Kaluzynski, S. Penczek, J. Polym. Sci., Polym. Chem. Ed., 22, 1251 (1984). 347. K. Kaluzynski, S. Penczek, Makromol. Chem., 180, 2289 (1979). 348. G. Lapienis, S. Penczek, J. Polym. Sci., J. Polym. Sci., Polym. Chem. Ed., 15, 371 (1977). 349. K. Hatanaka, S. Kanazawa, T. Uryu; J. Polym. Sci., Polym. Chem. Ed., 22, 1987 (1984). 350. K. Kobayashi, H. Sumitomo, Macromolecules, 16, 710 (1983). 351. T. Uryu, Y. Sakamoto, K. Hatanaka, K. Matsuzaki, Macromolecules, 17, 1307 (1984). 352. J. E. Moore, S. H. Schroeter, A.R. Shultz, L. D. Stang, Am. Chem. Soc. Symp. Ser., 25, 90 (1976). 353. J. C. Favier, J. Leonard, Macromolecules, 11, 424 (1978). 354. J. C. Bevington, J. A. L. Jemmett, P. F. Onyon, Polymer, 18, 73 (1977). 355. N. K. Lebedev, B. V. Lebedev, V. S. Khotimskii, S. G. Durgar'yan, Polym. Sci., USSR, 21, 1131 (1980). 356. G. Lapienis, S. Penczek, Macromolecules, 10, 1301 (1977). 357. J. Kops, S. Hvilsted, H. Spanggaard, Pure Appl. Chem., 53, 1777 (1981). 358. B. V. Lebedev, V. Ya Lityagov, Vysokomol. Soedin. A, 19, 2283 (1977). 359. B. V. Lebedev, I. B. Rabinovich, N. K. Lebedev, N. V. Ushakov, Dokl. Phys. Chem., 239, 376 (1978). 360. B. V. Lebedev, I. B. Rabinovich, Dokl. Phys. Chem., 235, 762 (1977). 361. B. V. Lebedev, I. B. Rabinovich, V. Ya Lityagov, Yu. V. Kobshak, V. M. Kuteinikov, Vysokomol. Soedin. A, 18, 2444 (1976). 362. B. V. Lebedev, I. B. Rabinovich, N. K. Lebedev, V. G. Tsvetkov, S. G. Durgar'yan, V. S. Khotimskii, Vysokomol. Soedin. A, 19, 513 (1977). 363. B. V Lebedev, N. K. Lebedev, Ye. G. Kiparisova, K. A. Yesayan, L. K. GoIova, Yu. B. Amerik, Vysokomol. Soedin., 26, 909 (1984). 364. B. V. Lebedev, A. A. Yevstropov, Ye. G. Kiparisova, V. I. Belov, Vysokomol. Soedin. A, 20, 29 (1978). 365. B. V. Lebedev, N. N. Mukhina, T. G. Kulagina, Vysokomol. Soedin. A, 20, 1297 (1978). 366. N. K. Lebedev, B. V. Lebedev, V. S. Khotimiskii, S. G. Durgar'yan, Vysokomol. Soedin. A, 21, 1031 (1979). 367. B. V Lebedev, N. K. Lebedev, V. S. Khotimskii, S. G. Durgar'yan, N. S. Nametkin, Dokl. Phys. Chem., 259, 666 (1981). 368. B. V. Lebedev, A. A. Evstropov, Dokl. Phys. Chem., 264, 334 (1982).
369. M. A. Markevich, L. I. Pavlinov, Yu. A. Lebedev, Dokl. Phys. Chem., 262, 64 (1982). 370. Y. Yuki, H. Kunisada, T. Seo, T. Kakurai, Kobunshu Ronbunshu, 40, 733 (1983). 371. I. M. Barkalov, D. P. Kirukhin, G. A. Kichigina, M. P. Muidinov, Eur. Polym. J., 20, 1013 (1984). 372. G. M. Patel, R. R. Chance, E. A. Turi, Y. R Khanna, J. Am. Chem. Soc, 100, 6644 (1978). 373. A. F. Garito, C. J. Horner, P. S. Kalyanaraman, K. N. Desai, Makromol. Chem., 181, 1605 (1980). 374. G. N. Patel, Macromolecules, 14, 1170 (1981). 375. G. N. Patel A. F. Preziosi, H. R. Bhattacharjee, J. Polym. Sci., Polym. Symp., 71, 247 (1984). 376. T. Baran, A. Duda, S. Penczek, Makromol. Chem., 185,2337 (1984). 377. T. Baran, A. Duda, S. Penczek, J. Polym. Sci., Polym. Chem. Ed., 22, 1085 (1984). 378. Y. Yuki, T. Ouchi, Kobunshu Ronbunshu, 33, 303 (1976). 379. Y. Yuki, T. Ouchi, Kobunshu Ronbunshu, 32, 97 (1975). 380. R. Steudal, S. Passlack-Stephan, G. Holdt, Z. Anorg. AlIg. Chem., 517, 7 (1984). 381. H. Sawada, "Thermodynamics of Polymerization", Marcel Dekker, New York, 1976. 382. H. Uno, T. Endo, M. Okawara, J. Polym. Sci., Polym. Chem. Ed., 23, 63 (1985). 383. T. Fries, J. Belohlavkova, J. Roda, J. Kralicek, Polym. Bull., 12, 87 (1984). 384. M. Morcellet, Thermochim. Acta, 80, 361 (1984). 385. B. V. Lebedev, L. Ya. Tsvetkova, V G. Vasil'ev, V. I. Kleiner, B. A. Krentsel, Vysokomol. Soedin. A, 35, 1941 (1993). 386. B. V Lebedev, N. N. Smirnova, E. G. Kiparisova, D. G. Faminskii, V. G. Vasil'ev, V. F. Vasilenko, Vysokomol. Soedin. A, 35, 1951 (1993). 387. B. V Lebedev, N. N. Smirnova, V. G. Vasil'ev, E. G. Kiparisova, V. I. Kleiner, Vysokomol. Soedin. A, 36, 1413 (1994). 388. N. N. Smirnova, B. V. Lebedev, Vysokomol. Soedin. A, 32, 2536 (1990). 389. P. A. Patton, T. J. McCarthy, Polym. Prep., 26 (1), 160 (1985). 390. T. A. Bykova, Ye. G. Kiparisova, B. V, Lebedev, K. A. Mager, Yu. G. Gololobov, Vysokomol. Soedin. A, 33, 614 (1991). 391. E. G. Kiparisova, T. A. Bykova, B. V. Lebedev, T. I. Guseva, K. A. Mager, Yu. G. Gololobov, Vysokomol. Soedin. A, 35, 615 (1993). 392. T. A. Bykova, E. G. Kiparisova, B. V. Lebedev, N. G. Senchenya, K. A. Mager, Yu. G. Gololobov, Vysokomol. Soedin. A, 35, 13 (1993). 393. T. A. Bykova, Ye. G. Kiparisova, B. V. Lebedev, T. I. Guseva, K. A. Mager, Yu. G. Gololobov, Vysokomol. Soedin. A, 33, 2602 (1991). 394. B. V. Lebedev, N. K. Lebedev, Ye. G. Kiparosiva, K. A. Yesayan, L. G. GoIova, Yu. B. Amerik, Polym. Sci. USSR, 26, 1013 (1984). 395. J. Penelle, J. Collot, G. Rufflard, J. Polym. Sci. A: Polym. Chem., 31, 2407 (1993).
396. B. V. Lebedev, N. N. Smirnova, E. G. Kiparisova, V. G. Vasil'ev, N. Yu. Surkova, V. I. Kleiner, B. A. Krentsel, Vysokomol. Soedin. A, 35, 767 (1993). 397. B. V. Lebedev, T. G. Kulagina, N. N. Smirnova, T. A. Bykova, V. G. Visil'ev, D. F. Grishin, Vysokomol. Soedin. A, 37, 1896 (1995). 398. R. Binet, J. Leonard, Polymer, 14, 355 (1973). 399. S. Iwatsuki, M. Kubo, H. Iwayama, Macromolecules, 26, 7309 (1993). 400. R. E. Cunningham, H. A. Colvin, Polymer, 33, 5073 (1992). 401. M. Ueda, T. Ito, H. Ito, Macromolecules, 23, 2895 (1990). 402. V. Gebauer, K. Burghardt, S. Jaehrig, K. Gehrke, Plaste Kautsch., 38, 372 (1991). 403. H. Kunisada, Y. Yuki, S. Kondo, Macromolecules, 24, 4733 (1991). 404. H. Kunisada, Y. Yuki, S. Kondo, K. Adachi, N. Takahashi, Polymer, 33, 3512 (1992). 405. H. Kunisada, Y. Yuki, Kobunshi Ronbunshu, 43, 895 (1986). 406. Y. Yuki, H. Kunisada, Nippon Kagaku Kaishi, 2, 242 (1985). 407. A. Aboudalle, A. Soum, M. Fontanille, T. E. Hogen-Esch, Polym. Prepr., 27(1), 143 (1986). 408. T. Kase, M. Imahori, T. Kazama, Y. Isono, T. Fujimoto, Macromolecules, 24, 1714 (1991). 409. Y. Nagasaki, N. Yamazaki, K. Takeda, N. Kato, M. Kato, Macromolecules, 27, 3702 (1994). 410. T. Itoh, T. Ario, M. Kido, S. Iwatsuki, Macromolecules, 27, 7035 (1994). 411. S. Iwatsuki, T. Itoh, N. Kusaka, H. Maeno, Macromolecules, 25, 6395 (1992). 412. S. Iwatsuki, T. Itoh, T. Higuchi, K. Enomoto, Macromolecules, 21, 1571 (1988). 413. S. Iwatsuki, T. Itoh, H. Yabunouchi, M. Kubo, Macromolecules, 23, 3450 (1990). 414. N. K. Lebedev, B. V. Lebedev, N. N. Smirnova, V. G. Vasil'ev, N. M. Kozyreva, S. B. Skubina, V V. Korshak, Vysokomol. Soedin. B, 28, 357 (1986). 415. B. V. Lebedev, N. Smirnova, Y. Kiparisova, K. Makovetsky, Makromol. Chem., 193, 1399 (1992). 416. B. Lebedev, N. Smirnova, N. Novosyolova, K. Makovetsky, I. Ostrovskaya, Macromol. Chem. Phys., 195, 1807 (1994). 417. B. V. Lebedev, V. G. Vasil'ev, Ye. G. Kiparisiova, Vysokomol. Soedin. A, 32, 1070 (1990). 418. V. G. Vasil'ev, B. V. Lebedev, Vysokomol. Soedin. A, 33, 818 (1991). 419. V. G. Vasil'ev, B. V. Lebedev, N. V. Novoselova, Vysokomol. Soedin. A, 35, 621 (1993). 420. B. V. Lebedev, V. G. Vasil'ev, N. Novosyolova, Makromol. Chem., 194, 739 (1993).
421. B. V. Lebedev, V. G. Vasil'ev, N. Novosyolova, J. Therm. Anal., 38, 1299 (1992). 422. F. Andruzzi, S. Li, G. Pilcher, F. Heatley, Makromol. Chem., 188, 2643 (1987). 423. H. Kriiger, J. Rubner, W. Wittke, G. Gnauk, Acta Polym., 37, 601 (1986). 424. J. C. W. Chien, Y. G. Cheun, P. Lillya, Macromolecules, 21, 870 (1988). 425. B. Xu, C. P. Lillya, J. C. W. Chien, Macromolecules, 20, 1445 (1987). 426. B. V. Lebedev, T. G. Kulagina, V. I. Telnoy, V. G. Vasil'ev, Macromol. Chem. Phys., 196, 3487 (1995). 427. B. V. Lebedev, T. A. Bykova, E. G. Kiparisova, B. G. Belen'kaya, V. N. Filatova, Vysokomol, Soedin. A, 37, 187 (1995). 428. I. Rangel, M. Richard, A. Ricaard, Macromol. Chem. Phys., 195, 3095 (1994). 429. A. Duda, S. Penczek, Macromolecules, 23, 1636 (1990). 430. S. Chikaoka, T. Takata, T. Endo, Macromolecules, 24, 6557 (1991). 431. B. V. Lebedev, T. G. Kulagina, V. S. Svistunov, V. S. Papkov, A. A. Zhdanov, Polym. Sci. USSR, 26, 2773 (1984). 432. I. C. Eromosele, D. C. Pepper, J. Polym. Sci., Part A: Polym. Chem., 25, 3499 (1987). 433. K. Hashimoto, H. Sumitomo, H. Shinoda, A. Washio, J. Polym. Sci., Part C, Polymer Letters, 27, 307 (1989). 434. S. Cavallero, A. Colligiani, G. Cum, J. Therm. Anal., 38, 2649 (1992). 435. S. Iwatsuki, T. Itoh, K. Enomoto, T. Itoh, E. Yamamoto, T. Myamoto, Macromolecules, 22, 1014 (1989). 436. R. Szymanski, Makromol. Chem., 192, 2961 (1991). 437. T. G. Kulagina, B. V. Lebedev, Fiz, -Chim. Osn. Sint. Perebab. Polim., 99, (1983). 438. S. Iwatsuki, T. Itoh, H. Ito, M. Kubo, Macromolecules, 23, 2423 (1990). 439. T. Fries, J. Belohlavkova, O. Novakova, J. Roda, J. Kralicek, Makromol. Chem., 188, 239 (1987). 440. S. Iwatsuki, M. Kubo, M. Wakita, Y. Matsui, H. Hanoh, Macromolecules, 24, 5009 (1991). 441. G. Deak, T. Pernecker, J. P. Kennedy, Polym. Bull., 33, 259 (1994). 442. B. Yamada, T. Tanaka, T. Otsu, Eur. Polym. J., 25, 117 (1989). 443. E. L. Madruza, J. S. Roman, M. A. Lavia, M. C. Fernandez-Monreal, Eur. Polym. J., 22, 357 (1986). 444. T. Sato, K. Morino, H. Tanaka, T. Ota, Eur. Polym. J., 26, 1279 (1990). 445. N. V. Karyakin, N. G. Shvetsova, G. P. Kamelova, A. L. Rusanov, V. V. Korshak, L. Kh. Plieva, Vysokomol. Soedin. A, 26, 36 (1984). 446. R. Szymanski, Makromol. Chem., 192, 2943 (1991).
A c t i v a t i o n a n d
E n e r g i e s
o f
T e r m i n a t i o n
R a d i c a l
P r o p a g a t i o n i n
F r e e
P o l y m e r i z a t i o n
T. F. M c k e n n a Laboratoire de Chimie et Procedes de Polymerization, Villeurbanne, Cedex, France A . M . Santos Faculdade de Engenharia Quimica de Lorena-Faenquil, Lorena, Sao Paulo, Brazil
A. Introduction B. Tables Table 1. Dienes Table 2. Olefins Table 3. Acrylic Derivatives Table 4. Methacrylic Derivatives Table 5. Vinyl Halogens Table 6. Vinyl Ethers and Vinyl Esters Table 7. Styrene and Derivatives Table 8. Vinyl Heteroaromatics Table 9. Miscellaneous Compounds C. References A.
11-415 11-416 11-416 11-416 11-417 11-418 II-420 11-421 11-421 II-422 II-423 II-424
INTRODUCTION
The conversion of a free radical homopolymerization as a function of time is usually expressed by the following equation:
where x is the conversion, t the time, fep, ku and k& the propagation, termination and initiator decomposition rate constants, respectively, / the initiator efficiency and / the initiator concentration.
It is generally assumed that the temperature dependence of free radical polymerization rate constants can be expressed using the well-known Arrhenius equation:
where Ao is the frequency factor, R the universal gas constant, T the absolute temperature, and E the activation of the reaction in question. Measurement of kp and kt at different temperatures allows one to determine values of the activation energies of the same two reactions, Ep and E1, respectively. If we accept this representation, then the overall activation energy of a homopolymerization can be written as
The value of the activation energy for the initiator decomposition reaction, 2Jd, can often be estimated separately. When data are not available for Ep and Et as separate quantities, the term (Ev —\Et) can be used to model the polymerization reaction. In the following tables, all energies are reported in terms of kJ/mol, and any appropriate remark(s) associated with the data are presented.
B. TABLES TABLE 1. DIENES Monomer
Ep
Butadiene
10.9 38.9 24.3 & 20.9 20.5 35.7
Et
Ev — \Et
8.42
Chloroprene Dimethyl butadiene Isoprene
40.6 37.7 46.0
Refs.
In gas phase In emulsion In gas phase In gas phase Solution polymerization in CCl4; temperature range: 303-333 K For emulsion polymerization, supposing w = 0.5 Thermal and photoinitiation; temperature range: 278-333 K; kp measured by ESR In emulsion In emulsion In emulsion
5.9
38.9 1,3-Hexadiene
Remarks
13 14 16 21 90 91 92 35 45 15
TABLE 2. OLEFINS Monomer
Ev
Acetylene Ethylene
21.4 34.3 18.4 23.9 46.4
Et
£ p -|£ t
1.3
17.8
33.5
29.7 31.0
36.8 29.7 40.0
6.22 10.0 15.2
25.1 20.8 29.7 32.5 36.9 31.4
-1.59 3.13 10.0 4.19 1.05
Refs.
In gas phase In gas phase Calculated using results of Ref. 24 In gas phase High pressure in gas phase (up to 300 NPa); initiated by oxygen; temperature range: 60-250 0 C; conversion found by gravimetry High pressure polymerization (up to 300 MPa); initiated by DTBPO; temperature range: 130-1650C Activation volumes (cal/mol/atm): propagation: — 19.7, termination: 13.0
Estimation for simulation of emulsion copolymerization with vinyl acetate 14.2 31.6
Propene Isoprene
Remarks
30.3
4.2
17.6 ± 0.31
15.3 ± 0.26
30.2 23.4 41.0
6.44
Activation volume = - 26.2£ x 10~6 m3/gmol Activation volume for propagation = — 0.5 cal/mol/atm Activation volumes (cal/mol/atm): propagation: —16.8 ±0.1; termination: 9.2. Optimized from values of industrial runs In gas phase In emulsion
21 21 35 44 73 82 93 94 95 96 97 98 99 100 101 102 103 104 105 106 21 15
TABLE 3. ACRYLIC DERIVATIVES Monomer
Ep
Et
Acrylamide A B C D E
11.7 ± 1.2 16.3 ± 0.8 18.8 ± 1.9 20.5 ±0.8 25.1 ±0.9
11.7 ±0.8 10.9 ± 0.4 10.9 ±0.4 7.9 ±0.4 0±0.8
22 ±0.2 20 ±0.2 11.5 57.8
Ep-\Et 5.8 dz 1.6 10.9 ± 1.3 13.4±0.3 16.9 ±1.0 25.1 ±1.3
6.2 10.46
iVyV-methylene-bis-acrylamide
9.3
Remarks
Refs.
Solution polymerization in H2O/DMSO mixture with potassium persulfate; initiators: H 2 O: DMSO: (A) 100:0 (B) 88:12 (C) 65:35 (D) 38:62 (E) 0:100 pH 1 pH4 Compilation of data, validated for inverse suspension polymerization Compilation from various sources, validated for solution polymerization Aqueous polymerization with temperature range: 293-313 K
68
111 112 113
Acrylic acid 23.4 21.7 14.1 - , sodium salt
(1) 67.5 (2) 72.1
- , chromium salt
33.5
-, zinc salt
13.0
-, butyl ester
8.8 52.3 15.5
0 73.7 38.1
14 ± 6 £ p - ET = 0 9.6 ± 0.56
- , ethyl ester - , methyl ester
41 29.7 19.7 31.8 ±2.5
12.3 22.2 -0 20.1 ±0.8
-, methyl oc-acetoxy ester
35.5
46.8
-, methyl a-butoxy ester
30.5
25.1
Acrylonitrile
17.2 16.2
22.6 15.5
107 108
109 By PLP; temperature range: 288-328 K 110 Thermally induced solid state polymerization; 87 two methods to find Ep: (1) ESR, (2) DSC; temperature range: 60-160 0 C Polymerized with styrene-arsenic sulfide 114 complex initiator in DMF Initiated with an As2S3-styrene complex in 115 DMSO at 363 K 8 At 20% conversion 26 From PLP-GPC; temperature range: 116 (208-266 K); bulk polymerization 109 From PLP; temperature range: (298-353 K); 117 conversion range: (10-80%); bulk polymerization; P = 1 bar. From PLP; conversion = 30% in bulk 118 polymerization By PLP-GPC; bulk polymerization with 119 photoinitiators: benzoin and 2,2dimethoxy-2-phenylacetophenone; temperature range: 298-303 K 109 Gamma ray induced solid state polymerization; temperature range: 243-283 K
40.7 31.8
-, 1,3-hydroxyneopentyl ester
Initiation with APS; temperature range: 309.5-324.5 K; solution polymerization at pH 0 4.38 Precipitation polymerization; temperature range: 313-333 K
5.9 8.5
109 Measured by dilatometry in both benzene 120 and 1,4 dioxane (kp/k®-5 higher in dioxane) By ESR; temperature range: 303-333 K; 121 solution polymerization in 1,1,2-trichloroethane; initiator: 2,2 '-azobis(4-methoxy-2,4dimethylvaleronitrile) (V-70) By ESR; assuming Ed = 109.5; 121 solution polymerization in 1,1,2-trichloroethane; initiator: 2,2 /-azobis(4-methoxy-2, 4-dimethylvaleronitrile (V-70) In water solvent 25 In DMF solvent 32
References page II - 424
TABLE 3. cont'd Monomer
Ep
Et
Ep — \Et
Acrylonitrile {cont'd)
26.8
~0
6.8 21.4
29.6
7.0
Remarks In DMF solvent Estimated from data on solution copolymerization with styrene as azeotrope
42.7
D-Fluoroacrylic acid -, methyl ester
23.9
Polymerization in NaSCN solution with Mn(CsH702)2 as free radical initiator; temperature range: 295-313 K; value estimated from overall activation energy with Ed = 58.6 kJ/mol
9.6
Solution: acrylonitrile; initiator: AIBN; (assume Ed = 128 kJ/mol)
Refs. 37 109 122 123 124
71
TABLE 4. METHACRYLIC DERIVATIVES Monomer
Ep
Et
Methacrylamide
15.5 22.1
16.7
Methacrylic acid
17.7
-, butyl ester - , butyl ester
17.4 18.4 20.4 20.9 21.8 ± 0.27 22.9 ±1.1
4.6 12.7 8.8
Ev -\Et 7.1
16.1 14.1 16.7
23.3 20.4 20.5 ± 0.24 - , i-butyl ester
22.5 ± 0.42 21.5 ± 0.35
-, f-butyl ester
27.7 ± 2.5
-, chloromethyl ester
5.5
-, cyanomethyl ester
~ 8.4
- , dodecyl ester (lauryl ester)
15.5 29.8 21.5 ±0.34 13.7 16.2
- , ethyl ester
23.2
8.9
18.0
21.3
7.1
17.7 16.5
Remarks Solvent: water By PLP; temperature range: (288-328 K); pH 1 By PLP-GPC; 33% monomer in methanol; temperature range: 293-333 K
Refs. 34 110 125
109 Gamma ray initiation 27 Kinetics from calorimetry 55 Temperature range: 35-27°C Quoted in 58 By PLP 131 By PLP-GPC; P = 1000 bars; temperature 141 range: - 10 to 6O0C Temperature range: 25-55°C; by PLP bulk 135 polymerization; photoinitiator: benzoin 126 By PLP-MWD; bulk polymerization; 127 pressure: 1 bar; photoinitiator: benzoin 131 By PLP-MWD; bulk polymerization; 127 pressure: 1 bar; photoinitiator: benzoin Temperature range: 9-66°C; by PLP with 128 benzoinethyl ether as free rapid initiator Ampoule and emulsion polymerization; 78 AIBN initiator Solution: acetonitrile AIBN initiator 87 calculated, assuming Ed of AIBN= 128 kJ/mol from overall activation energy; temperature range: 50-70 0 C Quoted in 58 Bulk polymerization with BPO initiator; 66 temperature range 60-80 0 C; maximum conversion 1% ByPLP 131 135 By PLP-MWD; bulk polymerization; 135 photoinitiator: benzoin Gamma ray initiation; temperature range: 52 — 30 to 55 0 C; kinetics from calorimetry Quoted in 58 Data from bulk and solution (50% DMF); 63 AIBN initiator; kinetics from GLC and gravimetry
TABLE 4. cont'd Monomer Methacrylic acid, ethyl ester {cont'd)
Ev
Et
27.0 22.8 ±0.35 20.46
- 6.6
Ev-\Et 30.4
27.0 22.9 ± 0.46 22.2 16.3 -, hexadecyl ester - , hexyl ester - , methyl ester
20.1 18.0 26.4 18.4 24.3 20.9
18.8 11.9 0 2.1 0-16.7
10.5 ~ 8.4 20.5 18.4 23.2 20.9-12.6
18.8 22.4 22.8
13.2
11.2
22.6 ± 2.5
Tends to 0
22.6 ± 2.5 13.0
19.7 18.2 ± 0.2
3.3 2.9 ± 0.0
18.0 16.7 ± 0.2
23.4 20.4
~ 10.5
15.1
20.9 ±3.3
1.6 ± 0.4
20.1 ±3.6
31.3 21.3 ±0.25 18.2 26.4
11.7
29.1
3.55 22.6 18.9 15.7 18.0 18.2 24.2 18.3 31.3
0 ± 2.5 2.93
2.9 26.9 2.94 21.1 36 -14 ±8 - 1 6 ±15
22.2 ±0.3
Remarks
Refs.
Quoted in 79 ByPLP 131 By PLP; temperature range: 298-328 0 C; 135 bulk polymerization; photoinitiator: benzoin Evaluated for emulsion polymerization 129 By PLP-GPC; bulk polymerization, 127 pressure: 1 bar; photoinitiator: benzoin Bulk polymerization; initiator: AIBN 130 Solution polymerization in benzene; 130 initiator: AIBN Quoted in 58 Quoted in 58 4 7 28 Termination by combination or 30 disproportionation 47 In emulsion 31 Gamma ray induced; temperature range: 48 - 25 to 55 0 C; used a combination of DCS and inhibition with DPPH to find kinetic parameters Polymerization in benzene; DMDM initiator; 49 temperature range: 50-80 0C Bulk polymerization; DBPO initiator; 53 maximum conversion 25%; ESR used to find kinetic parameters Isothermal bulk; polymerization with AIBN 56 initiator; DCS used to follow reaction; value found assuming E& AIBN= 128 kJ/mol Quoted in 58 Bulk polymerization; AIBN initiator 64 temperature range 15-3O 0 C; reaction followed by spatially intermittent polymerization; DP 10000-15000 Bulk polymerization; AIBN initiator; 65 1-butanethiol used as CTA; value assumes Ed AIBN= 128 kJ/mol Solution: benzene; AIBN initiator; kinetic 68 data from molecular weight data; maximum conversion 5% Emulsion data; particle sizes from turbidity; 72 potassium persulfate initiator Solution: benzene; AIBN initiator; kinetic 77 parameters from intermittent illumination Bulk polymerization 85 ByPLP 131 132 133 109 Temperature range: 293-353 K 156 Suspension polymerization 134 Spatially intermittent polymerization/ 164 emulsion polymerization 135 136 137 Solution polymerization in toluene 138 139 1 Bar; temperature range: 323-353 K, 140 low conversion 100 bars 1000 bars 141
References page II - 424
TABLE 4. cont'd Monomer
Ep
Methcrylic acid, methyl ester (cont'd)
22.4
Et
Ev-\Et
Remarks PLP plus GPC for bulk polymerization; temperature range: 272-363 K
22.2 23.9
22.2
nonyl ester octyl ester phenyl ester o-methylphenyl ester 0-ethylphenyl ester 6>-iso-propylphenyl ester /7-methylphenyl ester p-ethylphenyl ester /7-iso-propylphenyl ester /?-te7t-butylphenyl ester ethyl a-Benzoyloxymethyl ester
17.2 15.9
13.0 12.1
- , ethyl a-acetacetoxymethyl ester - , 2-(3-chloro-3-methylcyclobutyl)-2hydroxyethyl ester Methacryloyl fluoride
Methacrylonitrile
10.4
20.9
- , «-Phenyl-a-methylene-p-lactam
TABLE 5.
10.9 9.7 9.2 9.6 12.2 14.4 10.6 9.3 13.2 9.5 11.5 24.55 30.68
48.1 29.7 ±1.5
142 143 144 145
2.9
-, -, -, -, -, -, -, -, -, -, -,
Refs.
37.7
22.8
By PLP-GPC; bulk polymerization; pressure: 1 bar; photoinitiator: 2-hydroxy-2,2-dimethylacetophenone; temperature range: 272-363 K By PLP-GPC; bulk polymerization; 146 pressure: 1 bar; photoinitiator: benzoin; temperature range: 272-363 K Quoted in 58 Quoted in 58 147 147 147 147 147 147 147 147 By ESR, assuming E& = 129; solution 148 polymerization in benzene; initiator: AIBN 149 Polymerization in dioxane using BZ2O2 as 150 initiator Solution: MEK; AIBN initiator; calculated 81 using Ed AIBN = 128 kJ/mol; temperature range: 50-70 0 C 20 By PLP; solution polymerization in 151 benzylactone; temperature range: 283-333K Solution polymerization in n-methyl-2152 pyrrolidone with AIBN (calculated from £ O v assuming Ed of AIBN= 129 kJ/mol)
VINYL HALOGENS
Monomer
Ev
Tetrafluoroethylene
17.4 5.4 30.0 16.0
Vinyl bromide Vinyl chloride
Vinylidene chloride
27.6 104 37.7 ± 5.9
Et 13.6 0.8 16.3 17.6
18.2 167 20.9 ± 10.5
Ep-\Et 10.6 5.0 21.8 7.4 12
20.5 27.2 ±11.1
Remarks
Validated for model of suspension polymerization For suspension polymerization Solvent: hexane Solution: N-methylpyrrolidone; AIBN used as photoinitiator; most runs < 1% conversion
Refs. 46 43 42 17 153 154 9 67
TABLE 6. VINYL ETHERS AND VINYL ESTERS Monomer
Ep
Et
Butyl vinyl ether
Vinyl acetate
E9-\Et 46.4
18.0 30.6 13 18 18 39±3 19.6 ± 2.9
O 21.9 0 <4 0 0
Refs.
Bulk polymerization; initiator DTBPO; assume Ed = 51.5 kJ/mol (Ref. 82) at given conditions; GPC data used to find kinetic parameters
18.0 19.6 13 16-18 0 19.6 ± 2.9 ~ 26.4
20.5 ±0.39 26.4 23.5
Remarks
Bulk polymerization; DBPO and cyclohexyloxyperoxide initiators; ESR used to find kinetics Bulk polymerization; DBPO and cyclohexyloxyperoxide initiators; temperature range: 55-70 0 C; DSC used for kinetics; maximum conversion 20%
11.7 Validated for emulsion copolymerization with ethylene; temperature range: 293-323 K; pressure range: 0-34 bar 14.2 28.1
19.7 ± 2.9 23.7 23.6 24.2 26.4 35.2
0
Temperature range: 293-353 K For emulsion polymerization Emulsion polymerization
4.0 13.4 14.2
Rotating-sector method; bulk polymerization; photoinitiator: benzoin By PLP-MWD; bulk polymerization; photoinitiator: benzoin
27.8
84
1 5 6 18 22 38 53 57
131 133 102 155 109 156 157 158 159 160 155 161
TABLE 7. STYRENE AND DERIVATIVES Monomer Styrene
Ep 49.0 27.2±4.2 26.0 32.5 31.0 & 35.0 54.0 & 59.0 25.0 73.6 29.0
E1
Ep-\Et
11.7±4.2 8.0 9.9
21.3 ±6.3 22.0 27.5 In emulsions In emulsions
2.0
24.0
37.7 9.2 ± 0.5
24.9 ± 0.4
34.1 29.0 ±3.0
Refs.
In emulsion
25.1
29.5 ± 0.1
Remarks
Gamma ray induced; bulk liquid phase polymerization; maximum conversion 10%; temperature range: 19-74 0 C Low conversion; bulk polymerization; ESR spectroscopy used for kinetics Bulk photopolymerization; kinetics from spatially intermittent polymerization technique; temperature range: 15-36 0C DP 2400-2700 AIBN initiator; assume Ed = 128 kJ/mol; bulk polymerization 1-butanethiol as CTA; maximum conversion 0.4% In emulsion; reaction followed by dilatometry
2 3 10 11 15 19 29 36 42 50 51 64
65 70
References page II - 424
Table 7. cont'd Monomer
Ep
Et
Ep-\Et
32.2 32.5
14.5
25.2
17.7 29.6
Remarks Emulsion data; assume N = 0.5, sodium persulfate and sodium bisulfite initiators Bulk polymerization; AIBN initiator; temperature range: 45-100 0 C In emulsion; sodium persulfate initiator
25.2 37.8 ±1.7 39.8 36.1
15.6 18.7
29.5 44.4 29
36.4
37.5 ± 1.6 30.8
10.91
30.0 29.0 32.3
31.5 31.5 31.5 18
9.5 14.2
32.5
/?-Bromostyrene o-Methylstyrene /7-Methylstyrene
32.0 58.2 32.0
a-Methyl styrene Divinylbenzene
29.6 29.6 54.3 35.5
30.5 8.27 8.4 29.8
Ep
Et
By ESR; temperature range: 273-403 K Suspension polymerization; conversion less than 0.8; temperature range: 283-353 K Spatially intermittent polymerization/emulsion polymerization High conversion suspension polymerization Emulsion polymerization; temperature range: 318-338 K ESR; temperature range: 323-363 K By PLP; temperature range: 298-328 K By PLP; temperature range: 293-353 For dp (degree of polymerization) >4 For all chain lengths together Bulk and diluted systems initiated by (p-acetylbenzylidene)triphenylarsonium Measurements by rotating sector method; initiators: AIBN (30-50 0 C), BPO (70-90 °C) Styrene Perdeuterated styrene PLP; temperature range: 303-363 K; in bulk Measurments by ESR; photo and thermal initiation; temperature range: 293-363 0C PLP; temperature range: 261-366 K; bulk polymerization with photoinitiators: benzoin and 2,2-dimethoxy-2phenylacetophenone (DMPA) In emulsion In emulsion
25.4
Searched by EVM
Refs. 76 79 89 132 109 156 162 163 164 165 166 167 168 169 170 171
172 173 174
39 36 36 109 175 176 177 178
TABLE 8. VINYL HETEROAROMATICS Monomer
Ev-\Et
3-Methylene-5,5-dimethyl-2-pyrrolidone
8.2
Methylene-Af-methylpyrrolidone
20.1
N-Vinylcarbazole 2-Vinylpyridine Af-Vinylpyrrolidone (A) (B) (C) (D)
28.9 33.5 29.7 68.0 40.Od= 2.0 31.6 ±3.0 23.0
20.9 6.7 19.0 13.0 9.0 8.0
23.0 26.4 58.5 33.5 ±2.0 27.5 ±3.0 19.0
Remarks Solution polymerization in DMSO with AIBN (calculated from £ov assuming £ d o f AIBN =129 kJ/mol) In bulk and in solution with acetonitrile; AIBN initiator (assume Ed = 128 kJ/mol) Low conversion In various solvents: (A) Water (B) L-Propanol (C) Methanol (D) Ethyl acetate; rates followed by dilatometry
Refs. 179 86 42 40 41 61
Table 8. cont'd Monomer
Ev
E1
E9-±Et 4.8 (1) 12.8 (2) 10.8
65.8 ± 0.1 29.7
Remarks
Refs.
Template polymerization in DMF; AIBN initiator; DSC used to follow reaction Solution polymerization In DMF; assume Ed of AIBN in DMF =142 kJ/mol; reaction followed by DSC in 2 modes: (1) dynamic (2) isothermal Aqueous phase polymerization with potassium peroxydiphosphate Ag + ; temperature range: 293-323 K
6.7
4-Methylene-4H-l,3-benzodioxin-2-one
11.2
Solution polymerization in rc-methyl-2pyrrolidone with AIBN (calculated from Eov assuming Ed of AIBN= 129 kJ/mol)
74 75
180 181 182
TABLE 9. MISCELLANEOUS COMPOUNDS Monomer Acetaldehyde
Ep
Et
Ep-\Et
46.0 ± 6.3
Diethyl fumarate
25.0 ± 2.0
26.5 Diisopropyl fumarate Formaldehyde D-Methylene-y-butyrolactone
16.8 8.4
Vinylferrocene
20.0
16.3 12.1 7.9
N-Vinyl-methylacetamide ot-Ethyl, P-hexafluoroisopropyl itaconate
26.9 18.0
57.4
29.0 21.0 28.5
30.0 24.0 66.1
Diethyl itaconate
Diisopropyl itaconate Di-«-Butyl itaconate (DBI)
0.5 4.35
l,l-bis[(l-adamantyloxy)carbonyl]-2-vinylcyclopropane Diethylene glycol bis-allyl carbonate (DEAC) A^-Acryloyl-2,2-dimethyl-5®-phenyl-l, 3-oxazolidine (ADPO)
87.1 53.6 29
21
Remarks
Refs.
Radiation induced in solid phase; calorimetry used to follow reaction; temperature range: 130-150 0 K Bulk polymerization; AIBN initiator; (assume Ed = 128 kJ/mol) dilatometry used to follow the reaction; temperature range: 60-80 0 C Assuming Ed = 129; by dilatometry; bulk polymerization; initiator: AIBN
54 59
183
184 Quoted in 54 Solution: DMF; AIBN initiator (assume 80 Ed = 128 kJ/mol); E9-E1K 12.1 Note nonclassical kinetics; overall 62 activation energy does not equal Ed + Ep — Et/2\ can approximate Et = that of styrene Solution: methanol; AIBN initiator; 83 maximum conversion 10%; temperature range: 25-75 0C Polymerization in benzene catalyzed by 185 dimethyl 2,2-azobisisobutyrate Polymerization in benzene catalyzed by dimethyl 2,2-azobisisobutyrate 186 (no SnCl4) (0.342 mol/1 SnCl4) Polymerization in benzene catalysed by 187 dimethyl 2,2-azobisisobutyrate Assuming Ed = 129; by ESR; solution 188 polymerization in benzene; initiator: AIBN Assuming Ed = 129.1; By ESR; 188 solution polymerization in benzene; / initiator: 2,2 -azobis(isobutyrate): MAIB Ring-opening solution homopolymerization 189 in benzene; temperature range: 323-343 K; with AIBN (assume £D,AIBN = 123.5 kJ/mol) Rotating sector method; Initiator: BPO 190 Assuming Ed = 124.3; temperature range: 191 323-343 0 C; solution polymerization in benzene; initiator: 2,2'-azobis(isobutyrate): MAIB
References page II - 424
Table 9. cont'd Monomer
Ep
Et
Af-Cyclohexyrmaleimide (CHMIm)
40.9
20.1
Af-Acryloyl-/?-aminobenzoic acid
Ep-\Et
48.3
Remarks By ESR; temperature range: 313-333 K; solution polymerization in benzene; initiator: AIBN Assuming E^= 129; solution polymerization in dioxane; initiator: AIBN
Refs. 192
193
C. REFERENCES 1. G. M. Burnett, H. W. Burnett, Nature, 156, 661 (1945). 2. W. V. Smith, J. Am. Chem. Soc, 70, 3695 (1948). 3. C. H. Bamford and M. J. S. Dewar, Proc. Roy. Soc. (London) A, 192, 369 (1948). 4. M. S. Matheson, E. E. Auer, E. B. Bevilacqua, E. J. Hart, J. Am. Chem. Soc, 71, 497 (1949). 5. M. S. Matheson, E. E. Auer, E. B. Bevilacqua, E. J. Hart, J. Am. Chem. Soc, 71, 2610 (1949). 6. G. Dixon-Lewis, Proc. Roy. Soc (London) A, 198, 501 (1949). 7. M. H. Mackay, H. W. Melville, Trans. Faraday Soc, 45, 323 (1949). 8. H. W. Melville, A. F. Bickel, Trans. Faraday Soc, 45, 1049 (1949). 9. J. D. Burnett, H. W. Melville, Trans. Faraday Soc, 46, 976 (1950). 10. G. M. Burnett, Trans. Faraday Soc, 47, 772 (1950). 11. M. S. Matheson, E. E. Auer, E. B. Bevilacqua, E. J. Hart, J. Am. Chem. Soc, 73, 1700 (1951). 12. M. S. Matheson, E. E. Auer, E. B. Bevilacqua, E. J. Hart, J. Am. Chem. Soc, 73, 5395 (1951). 13. D. H. Volman, J. Chem. Phys., 19, 68 (1951). 14. M. Morton, R P Salatiello, H. Landfield, J. Polym. ScL, 8, 215 (1952). 15. M. Morton, P P Salatiello, H. Landfield, J. Polym. ScL, 8, 279 (1952). 16. D. H. Volman, W. M. Graven, J. Am. Chem. Soc, 75, 3111 (1953). 17. G. M. Burnett, W. W. Wright, Proc Roy. Soc. (London) A, 221, 41 (1954). 18. W. I. Bengough, H. W. Melville, Proc. Roy. Soc. (London) A, 230, 429 (1955). 19. E. Bartholme, H. Gerrens, R. Herbeck, H. Weitz, Z. Electrochem., 60, 334 (1956). 20. N. Grassie, E. Vance, Trans. Faraday Soc, 52, 727 (1956). 21. L. C. Landers, D. H. Volman, J. Am. Chem. Soc, 79, 2996 (1957). 22. W. I. Bengough, Trans. Faraday Soc, 54, 868 (1958). 23. Z. A. Sinitsyna, Kh. S. Bagdasaryan, Zh. Fiz. Khim., 32, 1319 (1958). 24. Z. Laita, Z. Machacek, J. Polym. ScL, 38, 459 (1959). 25. F. S. Dainton, R. S. Eaton, J. Polym. ScL, 39, 313 (1959).
26. W. I. Bengough, H. W. Melville, Proc. Roy. Soc (London) A, 249, 445 (1959). 27. D. H. Grant, N. Grassie, Trans. Faraday Soc, 55, 1042 (1959). 28. P Heyden, H. W. Melville, J. Polym. ScL, 43, 201 (1960). 29. G. Henrici-Olive, S. Olive, Makromol. Chem., 37, 71 (1960). 30. G. V Schulz, G. Henrici-Olive, S. Olive, Z. Physik. Chem. (Frankfurt), 27, 1 (1960). 31. P. E. M. Allen, G. M. Burnett, J. M. Downer, J. R. Majer, Makromol. Chem., 58, 169 (1962). 32. W. Rabel, K. Ueberreiter, Ber. Bunsenges., 67,710 (1963). 33. N. Coleboume, E. Collinson, D. J. Currie, and F. S. Dainton, Trans. Faraday Soc, 59, 1357 (1963). 34. F. S. Dainton, W. D. Sisley, Trans. Faraday Soc, 59, 1369 (1963). 35. M. Morton, W. E. Gibbs, J. Polym. Sci. A, 1, 2679 (1963). 36. K-P Paoletti, F. W. Billmeyer, J. Polym. Sci. A, 2, 2049 (1964). 37. A. F. Revzin, Kh. S. Bagdasaryan, Zh. Fiz. Khim., 38, 1020 (1964). 38. T A . Berezsnich-Foldes, F. Tudos, Vysokomol. Soedin., 6, 1529 (1964). 39. M. Imoto, M. Kinoshita, M. Nishigaki, Makromol. Chem., 86, 2167 (1965). 40. W. I. Bengough, W. Henderson, Trans. Faraday Soc, 61, 141 (1965). 41. V. A. Agasandyan, E. A. Trosman, Kh. S. Bagdasarayan, A. D. Litmanovich, V. Ya. Shtern, Vysokomol. Soedin., 8, 1580 (1966). 42. J. Hughes, A. M. North, Trans. Faraday Soc, 62, 1866 (1966). 43. A. N. Plyusnin, N. M. Chirkov, Teoret. Eksp. Khim., 2, 777 (1966). 44. S. Machi, S. Kise, M. Hagiwara, T. Kagiya, J. Polym. Sci., A-I, 5, 3115 (1967). 45. F. Khrabk, M. Bezdek, V. Hynkova, Z. Pelzbauer, J. Polym. Sci. C, 16, 1345 (1967). 46. E. F. Nosov, Kinet. Katal. 8, 680 (1967). 47. J. P. Fischer, G. V. Schulz, Ber. Bunsenges. Phys. Chem., 74, 1077 (1970). 48. G. Palma, L. Busolini, S. Lora, Eur. Polym. J., 6, 453 (1970).
49. T. Nakaya, H. Wada, M. Tanaka, J. Macromol. Sci., Chem., A: 5, 1043 (1971). 50. S. R Sood, J. W. Hodgins, J. Polym. Sci. A-I, 9, 3383 (1971). 51. S. E. Bresler, E. N. Kazebov, V. N. Fomichev, V. N. Shadrin, Makromol. Chem., 157, 167 (1972). 52. L. Busulini, S. Lora, G. Palma, G. Lunardon, Eur. Polym. J., 8, 455 (1972). 53. S. E. Bresler, E. N. Kazebov, V. N. Shadrin, Makromol. Chem., 175, 2875 (1974). 54. P. P. Kuryukhin, I. M. Barkalov, V. I. Gol'danski, Eur. Polym. J., 10, 309 (1974). 55. S. Lora, G. Palma, L. Busulini, B. Castiletti, Eur. Polym. J., 10, 1223 (1974). 56. T. Malavasic, I. Vizovisek, S. Lapanje, A. Moze, Makromol. Chem., 175, 873 (1974). 57. A. Moze, I. Vizovisek, T. Malavasic, F. Cernec, S. Lapanje, Makromol. Chem., 175, 1507 (1974). 58. N. A. Plate, A. G. Ponomarenko, Polym. Sci. U.S.S.R., 16, 3067 (1974). 59. W. I. Bengough, G. B. Park, R. A. Young, Eur. Polym. J., 11, 305 (1975). 60. C. Chachaty, M. Latimer, A. Forchioni, J. Polym. Sci.: Polym. Chem. Ed., 13, 189 (1975). 61. E. Senogles, R. Thomas, J. Polym. Sci.: Polym. Symp. Ed., 49, 203 (1975). 62. M. H. George, G. E. Hayes, J. Polym. Sci.: Polym. Chem. Ed., 13, 1059 (1975). 63. J. N. Cardenas, K. F. O'Driscoll, J. Polym. Sci.: Polym. Chem. Ed., 15, 2097 (1977). 64. H. K. Mahabadabi, K. F. O'Driscoll, J. Macromol. Sci. Chem. A: 11, 967 (1977). 65. H. K. Mahabadabi, K. F. O'Driscoll, Makromol. Chem., 178, 2629 (1977). 66. H. K. Mahabadabi, K. F. O'Driscoll, Makromol. Chem., 179, 1921 (1978). 67. K. Matsuo, G. W. Nells, R. G. NeIb, W. H. Stockmayer, Macromolecules, 10, 654 (1977). 68. R C. Deb, S. K. Kapoor, Eur. Polym. J., 15, 477 (1979). 69. V. F. Kurenkov, V. A. Myagchenkov, Eur. Polym. J., 16,1229 (1980). 70. S. W. Landsdowne, R. G. Gilbert, D. H. Napper, J. Chem. Soc, Faraday Trans. I, 76, 1344 (1980). 71. CU.Pittman,M.Ueda,K.Iri,Y.Imai,Macromolecules, 13, 1031 (1980). 72. S. K. Soh, J. Appl. Polym. Sci., 25, 2993 (1980). 73. U. Tatsuikami, T. Takahashi, H. Yoshioka, Makromol. Chem., 181, 1097 (1980). 74. G. O. R. Alberda van Ekenstein, Y. Y. Tan. Eur. Polym. J., 17, 838 (1981). 75. G. O. R. Alberda van Ekenstein, D. W. Koetsier, Y. Y. Tan, Eur. Polym. J., 17, 845 (1981). 76. B. Harris, A. E. Hamielec, L. Marten, A. C. S. Symp. Series, 165, 315 (1981). 77. M. Kamachi, D. J. Liaw, S. Nozakura, Polym. J., 13, 41 (1981).
78. M. Ueda, K. Iri. Y. Imai, C. U. Pittman, Macromolecules, 14, 1046 (1981). 79. S. K. Soh, D. C. Sundberg, J. Polym. Sci.: Polym. Chem. Ed., 20, 1345 (1982). 80. M. Ueda, M. Takahashi, Y. Imai, C. U. Pittman, J. Polym. Sci.: Polym. Chem. Ed., 20, 3819 (1982). 81. M. Ueda, M. Takahashi, Y. Imai, C. U. Pittman, J. Polym. Sci.: Polym. Chem. Ed., 20, 3829 (1982). 82. M. Buback, H. Lendle, Makromol. Chem., 184, 193 (1983). 83. J. P. Fischer, S. Rosinger, Makromol. Chem. 184, 1247 (1983). 84. A. Matsumoto, T. Nakana, M. Oiwa, Makromol. Chem.: Rapid Commun., 4, 277 (1983). 85. M. Stickler, Makromol. Chem., 184, 2563 (1983). 86. M. Ueda, M. Takahashi, T. Suzuki, Y. Imai, C. U. Pittman, J. Polym. Sci.: Polym. Chem. Ed., 20, 1139 (1983). 87. M. Ueda, T. Suzuki, Y. Imai, C. U. Pittman, E. Wallace, J. Polym. Sci.: Polym. Chem. Ed., 21, 2997 (1983). 88. V. R. R Verneker, R. Vasanthakumari, J. Polym. Chem. Ed., 21, 1657, 1664 (1983). 89. C. I. Kao, D. B. Gundlach, R. T. Nelson, J. Polym. Sci. Polym. Chem. Ed., 22, 3499 (1984). 90. S. Deibert, F. Banderman, Makromol. Chem. Rapid. Commun., 13, 351 (1992). 91. M. Morton, R R Salatillo, H. Landfield, J. Polym. Sci., 8,215 (1952). 92. M. Kamachi, Polym. Pre., 38, 649 (1997). 93. S. Agrawal, C. D. Han, AlChE J., 21 (3), 449 (1975). 94. C. H. Chen, J. G. Vermeychuk, S. A. Howell, R Elrich, AlChE J, 22, 463 (1976). 95. S. Goto, S. Yamamoto, S. Furui, M. Sugimoto, J. Polym. Sci.: Appl. Polym. Symp., 36, 21 (1981). 96. K. H. Lee, J. P. Marano, in: J. N. Henderson, T. C. Bouton (Eds.), "Polymerization Reactors and Processes", ACS, Symp. Series 104, 1979, p. 221. 97. G. M. Donati, M. Marini, L. Marziano, C. Mazzaferri, M. Spaminaot, E. Langianni, in: J. Wei, C. Georgakis (Eds.), "Chemical Reaction Engineering", ACS Symp. Ser. 196, 1982, p. 579. 98. W. Hollard, R Elrich, Chem. Eng. Commun., 24, 57 (1983). 99. H. Mavridis, C. Kiparissides, Polym. Proc. Engng., 3 (3), 263 (1985). 100. R R Shirodkar, G. O. Tsien, Chem. Engng. Sci., 41 (4), p. 1031 (1986). 101. R J. Scott, A. Penlidis, G. L. Rempel, Polym. Rxn Engng., 3 (2), p. 93 (1995). 102. A. Penlidis, Ph. D. Thesis, McMaster University, 1986. 103. C. Kiparissides, G. Verros, G. Kalfas, M. Koutoudi, C. Kantzia, Chem. Eng. Commun., 121, 193 (1993). 104. L. Marini, C. Georgakis, AlChE J., 30 (3), 410 (1984). 105. A. Brandolin, M. H. Lacunza, R E. Ugrin, N. J. Capiati, Polym React. Engng. 4 (4), 193 (1996). 106. R Lorenzini, M. Pons, J. Villermaux, Chem. Engng. Sci., 47 (15), 3981 (1992). 107. R. A. Scott, N. Peppas, AlChE J., 43 (1), 135 (1997).
108. H. G. Poersch-Panke, A. Avela, K. H. Reichert, Angew. Chemie, 206, 157 (1993). 109. J. Gao, A. Penlidis, J. Macromol Si., Rev. Macromol. Chem. C, 36 (2), 199 (1996). 110. R Pascal, D. H. Napper, R. G. Gilbert, M. C. Piton, M. A. Winnik, Macromolecules, 23 (24), 5161 (1990). 111. J. Hernadez-Barajak, D. J. Hunkler, Polym. Adv. Tech., 6, 509 (1995). 112. N. F. Umoh, P. Harriott, R. Hughes, Chem. Eng. J., 21, 85 (1981). 113. K. C. Gupta, J. Macromol. ScL, Pure & Appl. Chem. A, 31, 805 (1994). 114. B. Chaturvedi, A. K. Srivastava, Indian J. Technol., 31 (12), 851 (1993). 115. B. R Agrawal, A. K. Srivastava, Macromol. Rep. A, 29 (Suppl. 3), 325 (1992). 116. R. A. Lyons, J. Hutovic, M. C. Piton, D. Christie, P. Clay, B. G. Mandrs, S. H. Kable, R. G. Gilbert, Macromolecules 29, 1918 (1996). 117. M. Buback, B. Degener, Makromol Chemie, 194, 2875 (1993). 118. M. Buback, B. Degener, B. Huckstein, Makromol Chemie, Rapid Commun., 10, 311 (1989). 119. S. Beuermann, D. A. Paquet Jr., R. A. Hutchinson, Macromolecules, 29 (12), 4206 (1996). 120. M. T. Iglesias, G. M. Guzman, J. Riande, E., J. Polym. ScL, Part A: Polym. Chem. 32 (13), 2565 (1994). 121. H. Tanaka, S. Yoshida, Macromolecules, 28 (24), 8117 (1995). 122. C. C. Lin, W. Y. Chiu, C. T. Wang, J. Appl. Polym. ScL, 23, 1203 (1979). 123. C. Lin, W. Chiu, C. Wang, J. Appl. Polym. Sci. 23, p. 1203 (1979). 124. N. Jocheska, G. Petrov, A. Jenevski, A., Sedenik, Eur. Polym. J., 32 (2), 209 (1996). 125. S. Beuermann, D. A. Paquet, J. McMinn, R. A. Hutchinson, Macromolecules, 30 (2), 194 (1997). 126. S. Lora, G. Palma, L. Busilini, B. Castelleti, Eur. Polym. J., 10, 1223 (1974). 127. R. A. Hutchinson, D. A. Paquet Jr., J. H. McMinn, R. E. Fuller, Macromolecules, 28, p. 4023 (1995). 128. P. Pascal, M. A. Winnik, D. H. Napper, R. G. Gilbert, Makromol. Chem., Rapid Commun., 14 (3), 213 (1993). 129. J. Cardenas, K. F. O'Driscoll, J. Polym. ScL: Polym. Chem., 15, 2097 (1977). 130. H. H. Catalgil, B. M. Baysal, Eur. Polym. J., 27 (1), 7 (1991). 131. R. A. Hutchinson, D. A. Paquet, J. H. McMinn, S. Beuermann, in 5th International Workshop on Polymer Reaction Engineering, Dechema Monographs, vol. 131, 1995, p. 467. 132. N. Tefera, G. Weickert, K. R. Westerterp, J. Schweer, in 5th International Workshop on Polymer Reaction Engineering, Dechema Monographs, vol. 131, 1995, p. 557. 133. K. Y. Choi, D. N. Butala, Polym. Eng. ScL, 31 (5), 353 (1991). 134. G. Maschio, T. Bello, C. Scali, Chem. Engng. ScL, 47 (9), 2609 (1992). 135. T. P. Davis, K. F. O'Driscoll, M. C. Piton, M. A. Winnick, Macromol., 23, 2113 (1990).
136. G. Polacco, D. Semino, M. Palla, Polym. Eng. ScL, 36 (11), 2088 (1996). 137. J. Congalides, J. Richards, W. H. Ray, AlChE J., 35 (6), 891 (1989). 138. P. E. Baillagou, D. S. Soong, Chem. Engng. Sci., 40 (1), 87 (1985). 139. D. Panke, M. Stickler, W. Wunderlich, Makromol. Chem., 184, 175 (1983). 140. S. Beuermann, Ph.D. Thesis, University of Gottingen 1993. 141. U. Begert, M. Buback, J. Heyne, Macromol. Chem. Rapid Commun., 16, 275 (1995). 142. S. Beuermann, M. Buback, T. R Davis, R. G. Gilbert, R. A. Hutchinson, O. F. Olaj, G. T. Russel, J. Schweer, A. M. van Herk, Macromol. Chem. Phys., 198, 1545 (1997). 143. G. T. Russel, Macromol. Theory Simul., 4, 549 (1995). 144. R. A. Hutchinson, Polym. React. Eng., 1, 521 (1993). 145. U. Berger, S. Beuermann, M. Buback, H. K. Caroline, G. T. Russell, C. Schmaltz, Macromol. Rapid Commun., 16, 425 (1995). 146. R. A. Hutchinson, M. T. Aronson, J. R. Richards, Macromolecules, 26, 6410 (1993). 147. L. Vrhovac, D. Filipovic, M. Misic-Vukovic, J. Vellekovic, Int. J. Chem. Kin., 24 (10), 861 (1992). 148. T. Sato, I. Kamiya, H. Tanaka, T. Ota, Eur. Polym. J., 27 (10), 1087 (1991). 149. T. Sato, N. Morita, H. Tanaka, T. Ota, Macromol. Chem. Phys., 191 (11), 2599(1990). 150. M. Coskun, K. Demirelli, M. A. Ahmetzade, J. Macromol. ScL, Pure Appl. Chem. A, 34 (3), 429 (1997). 151. D. A. Shipp, T. A. Smith, D. H. Soloman, G. Moad, Macromol. Chem. Rapid Commun., 16, 837 (1995). 152. M. Ueda, H. Mori, H. Ito, J. Polym. Sci., Polym. Chem. A, 28 (10), 2597 (1990). 153. J. C. Pinto, Polym. Eng. Sci., 30 (5), 291 (1990). 154. C. Sidiropoulou, C. Kiparissides, J. Macromol. Sci. A: Chem., 27 (3), 257 (1990). 155. T. Pernecker, T. Foldes-Berezsnich, F. Tudos, J. Macromol. ScL A: Chem., 27 (8), 1029 (1990). 156. M. Kamachi, Adv. Polym. Sci., 82, p. 207 (1987). 157. N. Friis, D. Goosney, J. D. Wright, A. E. Hamielec, J. Polym. Sci., 18, 1247 (1974). 158. S. S. Jang, P. H. Liu, Chem. Engng. Sci., 46 (12), 3153 (1991). 159. J. Congalides, J. Richards, W. H. Ray AlChE J., 35 (6), 891 (1989). 160. F. Teymour, Ph.D. Thesis, University of Wisconsin (Madison) (1989). 161. R. A. Hutchinson, J. R. Richards, M. T. Aronson, Macromolecules, 27 (16), 4530 (1994). 162. B. Yamada, M. Kageoka, T. Otsu, Polym. Bull. 29 (3-4), 385 (1992). 163. N. Tefera, G. Weickert, R. Bloodworm, J. Schweer, Macromol. Chem. Phys., 195, 3067. 164. M. Buback, L. H. Garcia-Rubio, R. G. Gilbert, D. H. Napper, J. Guillot, A. E. Hamielec, D. Hill, K. F. O'Driscoll, F. Olaj, J. Shen, D. Soloman, G. Moad, M. Stickler, M. Tirrell,
165. 166. 167. 168. 169. 170. 171. 172. 173. 174.
175. 176. 177. 178. 179.
M. A. Winnick, J. Polym. ScL: Polym. Let., 26, 293 (1988). D. K. Sharma, D. S. Soong, Macromol., 21 (3), (1988) W. Lansdowne, R. G. Gilbert, D. H. Napper, D. F. Sangster, J. Chem. Soc, Faraday Trans., 76, 1344 (1980). S. E. Bresler, E. N. Kazbekov, U. N. Shardin, Makromol. Chem., 157, 167 (1972). T. P. Davis, K. F. O'Driscoll, M. C. Piton, M. A. Winnick, Macromol., 22, 2785 (1990). M. Deady, A. W. H. Mau, G. Moad, T. H. Spurly, Macromol Chem., 194, 1691 (1993). R. Vasishtha, A. K. Srivastava, Polymer, 31 (1), 150 (1990). G. Clouet, P. Chaffanjon, J. Macromol. Sci. A: Chem., 27 (2), 193 (1990). M. Buback, F. D. Kuchta, Macromol. Chem. Phys., 196, 1887 (1995). M. Kamachi, A. Kajiwara, Macromol. Chem. Phys., 198, 787 (1997). M. Buback, R. G. Gilbert, R. A. Hutchinson, B. Klumpermann, F. D. Kuchta, B. A. Manders, K. F. O'Driscoll, G. T. Russell, J. Schweer, Macromol. Chem. Phys., 196, 3267 (1995). S. K. Soh, D. C. Sundberg, J. Polym. Sci.: Polym. Chem., 20, 1345 (1982). O. Chiantore, A. E. Hamielec, Polymer, 26, 608 (1985). J. P. Fisher, Makromol. Chem., 155, 211 (1972). E. Vivaldo-Lima, A. E. Hamielec, R E. Wood, Polym. React. Engng., 2 (2-1), 87 (1994). K. C. Gupta, J. Appl. Polym. Sci., 53 (1), 71 (1994).
180. K. C. Gupta, J. Appl. Polym. Sci., 53 (1), 71 (1994). 181. V. A. Agasandyan, E. A. Trosman, Kh. S. Bagdasar'yan, A. D. Litmovich, V. Ya. Shtern, Vysokomol. Soyed., 8,1580 (1966). 182. M. Ueda, H. Toyota, A. Sane, H. Ito, J. Polym. Sci., Polym. Chem., 131, 1895 (1993). 183. O. Takayuki, Y. Bunichiro, I. Toshihiro, Macromolecules, 24/2, 415 (1991). 184. B. Yamada, E. Yoshikawa, H. Miura, T. Otso, Macromol. Chem. Rapid Commun., 13, 531 (1992). 185. T. Sato, Y. Hirose, M. Seno, H. Tanaka, J. Polym. Sci., Part A: Polym. Chem., 33 (5), 797 (1995). 186. T. Sato, H. Nakamura, H. Tanaka, T. Ota, Makromol. Chem., 192(11), 2659 (1991). 187. T. Sato, Y. Hirose, M. Seno, H. Tanaka, N. Uchiumi, M. Matsumoto, Eur. Polym. J., 30 (3), 347 (1994). 188. T. Sato, S. Inui, H. Tanaka, T. Ota, M. Kamachi, T. Tanaka, J. Polym. Sci., Part A: Polym. Chem., 25, 637 (1987). 189. J. Sugiyama, N. Kanamori, S. Shimada, Macromol., 29, 1943 (1996). 190. V. S. Nikiforenko, Yu. S. Zaitsev, V. V. Zaitseva, Academician R. V. Kucher, S. V. Muravchenko, A. V. Bulavin, L. N. Mikhailova, Doklady Physical Chemistry, 300 (1-3), 455 (1988). 191. M. Seno, T. Takikawa, H. Tanaka, T. Sato, Macromolecules, 28, 4795 (1995). 192. T. Sato, K. Arimoto, H. Tanaka, T. Ota, K. Kato, K. Doiuchi, Macromolecules, 22, 2219 (1989). 193. B. Patel, B. Suthar, R. Patel, Macromolecular Reports, 29 (1), 55 (1992).
Activation Volumes of Polymerization Reactions G. Luft n l stiut fur Chem siche Technoo lgei, Technsiche Hochschuel, Darmsad,t FR Gem r any Yh Oag Research n Istiute for Sovlo t.erm loT*echnoo lgy, Takamas tu, Takamas tu, Japan
A IA trocd uo co tinVo 11e 4 -2 9o B..Rn v t i a t i n u l m e s o f S o m e P o y l m z r i a itn e a c o i t n s 1 1 4 3 2 C .. A c v titia o titin V o u llm e s o ff C n I tih aatn o rP D ep co m p oo s itin114 1514 -35 D A c v a o n V o u m e s o i r o a g a o i t n 3 E Ac cv v ao o nV Vo o u me es so off C Ch ha an n Tre m irao itn 114 -36 F.. A titia titin u llm ii T arn se fn Reactions G. Influence of Pressure on Copolymerization Table 1. Copolymerization Parameters Table 2. Reactivity Ratios of Terpolymerization Table 3. Activation Volumes Table 4. Q, e Values H. References A.
11-436 11-437 II-437 II-438 II-439 II-440 II-440
INTRODUCTION
The activation volume is included in the pressure dependence of the reaction rate constant (1-4): (Al) where k is the reaction rate constant, p is the pressure, T, the temperature K the volume, and Av*, the activation volume (analogous to the activation energy). It is the difference between the partial molar volume of the activated complex, as formed in the transition state theory by the efficient collision of molecules, and those of the initial reactants. The sign of the activation volume depends on the type of the chemical reaction. If new bonds are formed in the transition state, the activated complex is larger than the
* Table 3. Activation Volumes.
initial species, and hence the activation volume is positive. Inversely the activation volume is negative if bonds are stretched and broken. For a rough calculation of the activation volume, we can assume that the formation of new bonds as well as stretching occurs along the axis of a cylinder, whose constant cross section is determined by the van der Waal's radii dmA/2, dmB/2, and dmC/2 of the atoms A, B, C:
(A2) with A A B = (0.10-0.35) dmAB, A B ,c = (1.10-1.35)J m B C ^mB,c (see Refs. 2,5,6), N is the Avogadro number, dmAB, dmBC = bond length (values, see Ref. 7), and d mB c is the interatomic distance at the minimum of potential (sum of van der Waal's radii), d mA / 2 , dmB/2 (see Ref. 8). The stretching of the bonds in the transition state is about 0.01-0.1 nm, whereas the change in the distance dmB£ between the unbonded atoms is usually larger (up to 0.25 nm). If the decomposition of the activated complex causes only small changes in the bond length or in the distance between the atoms, its partial molar volume differs from that of the activated complex only slightly. Hence we can assume
where Av is the excess of the partial molar volume of the reaction products over the partial molar volumes of the initial species. This simplification is valid for reactions in which products of cyclic structure are formed, as in the dimerization of cyclopentadiene, with Ai>* ~ Av = — 30cm 3 /mol (9, 10).
A second term is added to the volume change of the reacting molecules in the transition state if a polar solvent is involved. This term takes into account the change in the packing density of the surrounding solvent molecules due to the arising or disappearing of electrostatic charges between the solvent and the reactant species. This volume change is negative in bimolecular association and positive in unimolecular dissociation and tends therefore to counteract the effect of volume change during the reaction. The activation volume can be determined according to Eq. (Al) from rate measurements at different pressures and constant temperature using a semilog plot of reaction rate constant versus pressure. In this evaluation the value of (QV/dp)T/V can often be neglected, because the compressibility of fluid reactants and compressed gases is generally small at pressures above 100-200MPa. At very high pressures the increase of the reaction rate constant at negative activation volume is retarded by the lower mobility of the molecules due to the increased viscosity. This effect was first measured by Hamann (11) in an examination of the alkaline etherification of ethyl bromide at pressures up to 4000MPa. It was also found in the polymerization of styrene by Nicholson and Norrish (12). In order to obtain the reaction rate as an explicite function of pressure, Eq. (Al) can be integrated, neglecting the compressibility and assuming that the activation volume does not change greatly with pressure (13): (A3) where kp is the reaction rate constant at pressure p and fco is the reaction rate constant at reference pressure po. According to Eq. (A3) the reaction rate constant increases exponentially with pressure if the activation volume is negative and decreases if Ai;* is positive. Eq. (A3) is valid only in the high pressure range (p > 50MPa). At low pressures the compressibility cannot be neglected anymore, and the activation volume changes noticeably with pressure, especially in the neighborhood of the critical point. Simmons and Mason (14) studied the dimerization of chlorotrifluoroethylene at pressures up to 10 MPa. They found that the value of the negative activation volume decreases first with pressure and then increases rapidly. It has a maximum at the critical point and after decreasing again it approaches asymptotically a constant value. The authors describe the pressure dependence of the rate constant, taking account of the partial molar volume of the initial reactants as well as that of the activated complex by the use of suitable equations of state (e.g., Redlich-Kwong or virial coefficient equations). In order to appreciate the influence of pressure on the reaction rate constant one can compare it with the influence of the temperature: an increase in pressure (activation volume Av* = —25cm3/mol) at a temperature of 500C from 0.1 to 450MPa corresponds to a temperature increase (activation energy E = 84kJ/mol) from 50 to 1050C.
Experimentally determined overall activation volumes of some polymerization reactions are listed in Section B. The data were determined from the dependence of the overall rate constant of the polymerization reactions on pressure. The values are more or less negative, hence the rate of polymerization increases with pressure. The overall activation volume is composed of the activation volumes of the different polymerization steps, initiation, or initiator decomposition, chain propagation and chain termination: (A4) where Av* is the activation volume of chain propagation, Av^ is the activation volume of initiation with respect to initiator decomposition, and Ai;* the activation volume of chain termination. The activation volumes of initiator decomposition (values in Section C) are always positive because this reaction is a unimolecular dissociation, in which a bond (e.g., the O-O bond in peroxides and peresters or the N-N bond in azo-compounds) is stretched in the transition state and finally broken. As mentioned before, Ai;^ depends on the solvent. It can significantly be influenced by a change of electrostatic charges, viscosity, and cage effects. The activation volume of initiator decomposition is different when induced decomposition is involved at high concentration of the initiator or when the initiator decomposes in a concerted mechanism. Av^ is small for two-bond scission initiators (15). The activation volume is higher for one-bond scission initiator, bulky molecules, and when more bonds brake simultaneously. The data collected in Section C were obtained in separate measurements, observing the decrease of the initiator concentration with time at different pressures. The disappearance of the initiator can also be measured during polymerization by observing the light absorption at a characteristic waver length or using scavenger techniques. In the chain propagation reaction, the decrease in the distance between the radical and the monomer molecule is greater than the increase in length of the double bond of the monomer. Hence the activation volumes Ai;* listed in Section D are always negative. The data for Ai;* are measured at high pressures by the method of the rotating sector together with Ai;*, the activation volume of chain termination. The activation volumes Ai;* are also negative as shown in Section E. Mostly the termination reactions are diffusioncontrolled. The reactant molecules undergo translational diffusion at first to form a collision pair. It follows the movement of the reactive sites on these molecules into a position favorable to chemical reaction. This process has been considered to be the rate-determining step. The activation volume involved in this so-called segment diffusion is observed. When chain termination is governed by translational diffusion, the activation volume, Ai;*is for viscous flow, is the key parameter for the evaluation of the influence of pressure.
The chain transfer of a radical to the monomer, to a "dead" polymer, or to a modifier molecule is mostly favored by the pressure which means that the activation volumes should be negative, whereas the activation volume of the intramolecular transfer (by "back biting"), which initiates the formation of short side chains, can be negative or positive. The activation volumes of these reactions are determined from the change in short- and long-chain branching or from the change of the average molar mass or degree of polymerization of the formed polymers with pressure. Under the assumption that the monomer and the polymer concentration do not change over a wide range and that the temperature is kept constant, the following relation can be derived from kinetic considerations:
modulus increase with pressure: (A7)
(A5)
where v = chain length. The small negative activation volume of the intramolecular chain transfer shows that this reaction step, which determines the short chain branching, is less favored by high pressures, which means that polymers with high density and crystallinity can be synthesized at high pressures. Similar considerations also show that the composition of copolymers and thus their molecular structure is influenced by the synthesis pressure. The pressure dependence of the copolymerization parameters r\ and r2, which determine the composition of a copolymer, is expressed by the relationship
where VZG is the number of branches and Av *r is the activation volume of the chain transfer reaction. Analogously, the influence of the pressure on the chain transfer to a modifier can be described by the expression
(A8)
(A6) where P is the average degree of polymerization obtained in the presence of a transfer agent and P n o is the average degree of polymerization obtained in the absence of a transfer agent. Because of the mostly negative sign of the activation volumes (listed in Section F), the radical transfer to the modifier molecule is often slightly decreased at high pressures. The activation volume of degradation reactions which can occur at high temperatures should be positive because bond cleavage increases the volume of the activated complex more than the formation of double bonds from single bonds decreases it. The difference in the activation volumes of the various component reactions results in a different influence of the pressure on the rate constants and leads to modified polymers. Because of its larger negative activation volume the chain propagation reaction is more favored by high pressures than the termination. The chain length and consequently the tensile strength as well as the tensile
where Av*n, Av* 22 are the activation volumes of the propagation reaction between a monomer molecule and a radical formed from the same monomer, and Av *12, Ai>*21 are the activation volumes of the propagation reaction between a monomer molecule and a radical formed from the comonomer. Equation (A8) is valid if the composition of the initial reaction mixture does not change appreciably with pressure. According to Eq. (A8), an increase in pressure favors the inclusion of monomers, which in homopolymerization show a large negative activation volume (e.g., substituted olefins). Values of copolymerization parameters obtained at different pressures and activation volumes of some copolymerization reactions are listed in Section G. When r\ and Yi should be calculated for high-pressure copolymerization, following Alfrey and Price, the pressure dependence of Q, e data must be taken into account. Some values of Q and e for high pressures are collected in Section G. The dependence of the e data of two monomers on pressure is given by the equation
(A9)
References page 11-440
B. ACTIVATION VOLUMES (cm3/mol) OF SOME POLYMERIZATION REACTIONS
Monomer Acenaphthylene Acetaldehyde
Acrylic acid anhydride Acrylonitrile AUyI acetate /V-(4-Anilinophenyl)acrylamide
3,3-Bis(chloromethyl)oxetane Butadiene
Butyl acrylate Butyl acrylate
Butyl methacrylate
2-Cyclopropylpropene-l Diallyl cyanamide Diallyl phthalate 3,3-Dichloropropene-l l,l-Dichloro-2-vinylcyclopropane Diethyl fumarate 3,3,3-Difluorochloropropene-l l,l-Difluoro-2-vinylcyclopropane
Maximum pressure (MPa) 390 150 844 844 844 400 200 850 100 200 300 500 1500 500 500 500 500 100 100 100 300 460 700 100 100 100 300 460 >460 140 140 600 500 500 1000 1000 1000 300 1400 1000 1000
Temp. (0C) 60 100-200 -60 - 70 -78 50 50 80 60 60 60 60 60 60 50 70 95 30 30 20 20 20 20 60 30 20 20 20 20 70 20 80 70 70 40 80 20 60 30 50 20
2,3-Dimethyl-l,3-butadiene Ethylene
1,2-Epoxycyclohexane Az-Hexyl methacrylate Indene Isobutyl methacrylate Isoprene
Solvent
AIBN Diethyamine
DMF DMF THF
Toluene
Benzene
Toluene Benzene
Heptane DEE 250 760 200 190
129 50-70 225-235 80
100-210 110-220 250 110-550 175 300 840-1250 450 800 800 100 1400 1400 1400 1400
200-300 190 130-165 170-240 127-197 135-165 60 20 20 64 60 20-30 20-30 20 20
Initiator0
Heptane Benzene Toluene Ethyl acetate
A^*
-5.8 -12.5 -11.1 - 8.0 -6.2 AIBN -14 AIBN -22* BPO -13.4 AIBN -36.1 -31.2 - 22.3 -15.4 -6.4 BF3/diethyl ether -16 -8.8 -13.3 -17.2 ACN -26.3 ACN -26.3 Radiation -21.0 -21.2 - 5.7 -11.4 AIBN -25.6 ACN -17.4 Radiation -21 -21.2 -5.7 -14.4 AIBN -23 Stannic chloirde -15 TBPB -14 AIBN - 9 . 9 to -11.8 AIBN -14.3 DCPC 0 to 8* AIBN -14^ Stannic chlorde - 30 to - 70 -14 DCPC -15 AIBN -15 Stannic chloride -45 BuLi -36 BuLi -48 DTBP - 2 0 to - 2 3 AIBN - 3 to - 6 Peroxide - 20 to - 26 DCPC -10 Enanthylperoxide - 5 8 to - 6 8 Methylinobutylketone -18 TBPO - 1 8 to - 2 2 TBPP -22.6 Oxygen - 1 2 to - 1 8 Diphenyl disulfide -29 DTBP -17.5 BPO -13 Radiation - 24 -17.4 -21.0 AIBN -23.9 Oxygen -11.0 BPO - 7 . 9 to 18.0 HLOI2O -7.9 HLW2O -9.8C
Refs. 16 127 142 51 52 17 150
55 141 91 154 147
128 90 94,95 53 53 54 130 57 56 18 58 59 59,60 133 46,20 19 73 74 151 114 61 79 21 85 79 55 94 22 122 23 24
Monomer
Isopropenylcyclopropane Itaconic acid
Maleic anhydride Maleimide Methyl acrylate
Methyl methacrylate
a-Methylstyrene
Octyl methacrylate Propylene
Sodium allylsulfonate Styrene
Maximum pressure (MPa)
Temp. (0C)
1400 1400 1400 500 500 500 500
20 70 20 40 50 60 70
500 100 180 270 400 700 200 300 100
20-40 50 20 20 20 20 40 40 30
300 550 100 100 100 100 100 100 400 100
20 20 50 50 40 50 60 70 50 50
100 100 100 100 100 350 500 500 500 500 100
50 50 50 50 50 60 50 60 70 80 30
1600 1600 1600 800 400 400 400 900 208
21 48 83 80-100 80 90 100 22
Radiation Radiation Radiation AIBN BPO BPO BPO Radiation Radiation
273 400 100
25 30 30
Radiation Radiation ACN
200 280 400 600 300 100 200
40 40 40 40 50 50 60
Radiation Radiation Radiation Radiation AIBN AIBN AIBN
Initiator0
Solvent Dichloromethane DMF DMF DMF DMF Methanol Benzene
HI/H2O AIBN Stannic chloride AIBN AIBN AIBN AIBN BPO AIBN Radiation
Peroxide Peroxide ACN Radiation Acetone Benzene Benzene Benzene Benzene Benzene Butyraldehyde Carbon tetrachloride Dichloroethane Ethanol Ethyl acetate H-Hexane Trichloromethane
Peroxide AIBN Peroxide Peroxide Peroxide Peroxide AIBN AIBN AIBN AIBN Peroxide Peroxide Peroxide AIBN AIBN AIBN AIBN ACN
H2O
\v* -10.8 -23.0 -15.0 - 23.2 -27.4 -30.8 -32.3 —4.6 - 1 5 to - 25 -17.6 -21.4 -22.9 -3.6 -12.8 -19 -19 -15.6 -21.8 C -23.6 -13.7 -26.0 -21.6 -17 -19 -21 -23 -25 -19 -21 -20 - 24 -19 -22 -18 -14.5 -13.8 -11.8 -10.7 -26.3 -25.6 C -9.6 -9.6 -12.2 -14 -9.0 -10.8 -12.7 - 5 to - 7 -20.5 -18.6 C + 5.8 -20.9 -18 -17.1 -17.6 C -15.8 -50.5 -4.3 -29.5 -21 -20.2 -15
Refs.
158 140
132 122 129 147
25 26 87,153 93,95 27 129 27 27 27 27 62 27 27 27 27 27 27 18 135
99 28 144
145 137 136 126 89 146 146 146 146 64 27 149
References page II - 440
Monomer
Maximum pressure (MPa)
Temp. (0C)
293 265 265 274
60 80 80 25
274
l,l,2,2-Tetrachloro-l,3-butadiene Tetrahydrofuran Vinyl acetate
Vinyl chloride
25
200-500 100 100
60 50 50
100 400 400 100
50 50 50 50
300 100 100 100 100 400 100 400 268 293 440 300 300 100-600 1400 250-540 100 600 400 400 300
25-30 50 50 50 50 60 50 60 60 60 60 30 40 72 25-80 60 30 20 40 40 40
400 500 390 390 390 390 250 200 300 200 400
65 60 40 50 60 70 50 60 60 60 60
Initiator0
Solvent
Emulsion Emulsion with SDS SDS Emulsion with aerosol OT Emulsion Emulsion with nonionic emulsifier Emulsion Acetone Benzene Benzene Benzene Butyraldehyde Butyraldehyde Carbon tetrachloride Chlorobenzene Chloroform Dichloroethene Ethanol Ethyl acetate Isopropyl aldehyde Hexane Propionaldehyde Tetrachloroethylene Toluene Triethylamine Triethylamine Triethylamine Triethylamine
Acetone Butyraldehyde Carbon tetrachloride Trichloroethylene
Benzaldehyde Benzene Benzonitrile Toluene
AIBN BPO Thermal Radiation
Av*
Refs.
-18 -17 -25.8 138 - 18.7C - 17.9C -18.3c
29 125 125
Radiation
AIBN AIBN AIBN Peroxide AIBN AIBN AIBN HClO4 AIBN AIBN AIBN AIBN AIBN AIBN AIBN Peroxide AIBN AIBN BPO BPO Thermal BF3/diethyl ether ACN Radiation AIBN AIBN AIBN AIBN BPO BPO BPO BPO LPO AIBN AIBN AIBN AIBN
138 138 138
-21.6
139 139
-11.1 -25.5 -19.2 -23.0 -18 -25 -22 -19.1
35 27 27 63 30 65 63 27
- 2 0 to - 2 5 -21.9 -21.2 -19.6 -24.3 -6.8 -19.1 -15.5 -16 -17 -17 -18 > —11.5 -17.5 -36 -22 -17.2 -9 -19 -21 -13
155 27 27 27 27 157 27 157 31 29 29 32 33 34 159 55 86 148 62 62 36
-10.5 -16.7 -4.6 -6.8 -8.1 -10.4 -18 -4.1 -20.5 -12.0 -8.2
65 131 143
124 98 131 98 98
a Abbreviation: ACN: l,l'-azobiscyclohexane-l-carbonitrile; AIBN: 2,2/-azobisisobutyronitrile; BPO: benzoyl peroxide; DCPC: dicyclohexyl peroxidicarbonate; DEE: diethyl ehter; DMF: dimethylformamide; DTBP: di-terf-butyl peroxide; LPO: lauroyl peroxide; TBPB: terf-butyl perbenzoate; TBPO: te/Y-butyl peroctoate; THF: tetrahydrofuran; SDS: sodium dodecylsulfate; Aerosol OT: sodium dioctyl sulfosuccinate; TBPP: tert-butyl pervivalate. ^Calculated by other authors. c Cationic polymerization.
C. ACTIVATION VOLUMES OF INITIATOR DECOMPOSITION
Initiator
Solvent
AIBN* Azobis-terf-butanolate Benzoyl peroxide
2,2-Bis(tert-butyl peroxy)butane Decanoyl peroxide Dicyclohexyl peroxydicarbonate Di-rc-propyl peroxydicarbonate Dioctanoyl peroxide Di-tert-butyl peroxide
Pentaphenylethane tert-Amyl perneodecanoate tert-Amyl perpivalate tert-Buty\ cyclohexanecarboxylate tert-Buty\ perbenzoate tert-Butyl perneodecanoate tert-Butyl perpivalate tert-Butyl peroxy-2-ethylhexanoate terf-Butyl phenylperacetate 1-Methyl-l propylpentyl perpivalate 1,1,4-Trimethylpentyl perpivalate 1,1,4-Trimethylpentyl perneodecanoate
Toluene Toluene Octane Acetophenone Allyl acetate Carbon tetrachloride Carbon tetrachloride Iso-dodecane Benzene Iso-dodecane Benzene Iso-dodecane Benzene Iso-dodecane Carbon tetrachloride «-Heptane Cyclohexane Toluene Toluene Toluene Iso-dodecane Iso-dodecane Cumene Cumene Benzene Iso-dodecane Iso-dodecane n-Heptane Benzene Cumene Iso-dodecane Iso-dodecane Iso-dodecane
Absolute pressure (MPa)
Temperature (0C)
Activation volume Av J (cm3/mol)
Refs.
0.1-150 0.1-1000 0.1-630 0.1-650 0.1-550 0.1-300 0.1-300 0.1-200 0.1-300 0.1-300 0.1-300 0.1-300 0.1-300 0.1-730 0.1-300 0.1-730 10-230 0.1-730 0.1-730 0.1-150 100-270 0.1-300 0.1-300 0.1-410 0.1-410 0.1-300 0.1-300 0.1-300 0.1-200 0.1-300 0.1-410 0.1-300 0.1-300 0.1-300
70 62.5 55 80 80 60 70 135-212 <100 95-200 <100 80-200 <100 120 143-230 120 140-200 120 120 60 50 100-200 120-200 80 80 <100 100-200 120-200 65-105 <100 80 120-200 120-200 100-200
13.1 3.8* to 9.4C 4.3 4.8 4.7 9.7 8.6 22.3 3 4.3 4 5.9 15 12.6 13.4 13.3 10.1 6.7 5.4 7 5 7.0 9.4 3.9 10 7 6.1 6.1 1.6 6 1 13 14 9
37 37 104 38 17 39 39 81 78 75 78 75 78 40 75 40 77 40 40 37 37 75 75 101 102 78 75 88 78 78 103 76 76 76
Absolute pressure (MPa)
Temperature (0C)
Activation volume Av* (cm3/mol)
Refs.
0.1-100 0.1-100 -40 50-175 0.1-100 0.1-100 0.1-100 0.1-100
30 30 24 130-200 30 30 30 30
-22.5 -23.2 -39 -25.5 -19 -24.7 -17.9 -23.3
91 90 152 85 87 99 89 86
a
Azobisisobutyronitrile. ^Photometric analysis. c By 12 scavenger technique.
D.
ACTIVATION VOLUMES OF C H A I N PROPAGATION
Monomer
Solvent
Butyl acrylate Butyl methacrylate Ethylene Ethylene Methyl methacrylate Octyl methacrylate Styrene Vinyl acetate
/-Butanol -
a
Initiator ACNa ACN Radiation Diphenyl disulfide ACN ACN ACN ACN
ACN: 1,1 -azocyclohexane-1,1' -dicarbonitrile.
References page 11-440
E. ACTIVATION VOLUMES OF CHAIN TERMINATION
Monomer Butyl acrylate Butyl methacrylate Ethylene Methyl methacrylate Octyl methacrylate Styrene Vinyl acetate a
Solvent -
Initiator ACN" ACN Diphenyl disulfide ACN ACN ACN ACN
Absolute pressure (MPa)
Temperature (0C)
Activation volume Av * (cm3/mol)
0.1-100 0.1-100 50-175 0.1-100 0.1-100 0.1-100 0.1-100
30 30 130-200 30 30 30 30
20.8 17.8 7 25.0 20.8 13.1 16.3
Refs. 91 90 85 87 99 89 86
ACN: 1,1 -azocyclohexane-1,1 '-dicarbonitrile.
F.
A C T I V A T I O N V O L U M E S O F C H A I N TRANSFER REACTIONS
Activation volume (cm3/mol) Monomer Acrylonitrile 3,3-Dichloropropene-l Ethylene
Transfer agent Butyraldehyde 3,3-Dichloropropene-l Acetone Butane Butanone Cyclohexane Cyclopentane Ethanol Ethylbenzene Ethylene Isopropanol Polyethylene - intermolecular intramolecular Propane Toluene Xylene
Methyl methacrylate Styrene
Vinyl acetate Vinyl chloride
Butyraldehyde Butyraldehyde Carbon tetrachloride Isobutyraldehyde Triethylamine Butyraldehyde Butyraldehyde
Absolute pressure (MPa)
Temperature (0C)
0.1-400 0.1 136-238 138-240 136-238 136-238 136-238 138-240 198-240 136-238 138-240 136-238 138-240 136-238 -250 138-240 136-238 110-200 110-200 180-300 138-240 136-238 138-240 136-238 138-240 138-238 0.1-400 0.1-400 600 0.1-400 181-440 0.1-400 0.1-400
50 50 130 130-200 130 130 130 130-200 130-200 130 130-200 130 130-200 130 130-255 130-200 130 100-300 100-300 175-275 130-200 130 130-200 130 130-200 130 50 50 60 50 60 50 50
Av*r
-24.9
-24.5 -21.3 -22.9 -19.3 -20.1 -19.9 -23 -21 -22.9 -30.7 4.7 -33.8
Av* - \v*r -6.6 —8 -1.1 -1.1 -3.2 -2.9 -1.5 -1.5 -4.7 -4.7 -3.1 -3.1 -6.7 -6.7 -6.1 -6.1 3 5 20-24 -3.1 -3.1 4.7 4.7 7.8 7.8 -6.6 -15
-11 -6.6 - 2 to - 3 -3.2 -3.8
Refs. 62 62 41 83 41 41 41 83 83 41 83 41 83 41 96 83 41 82,85 82,85 83,84 83 41 83 41 83 83 67 63,65,68 33 68 42 67 67
G.
INFLUENCE OF PRESSURE ON COPOLYMERIZATION
TABLE 1. COPOLYMERIZATION PARAMETERS Copolymerization parameters Monomer 1
Monomer 2
Acrylonitrile
Ethyl cinnamate
Solvent
Absolute pressure (MPa)
Temperature ( 0 C)
0.1 80 280 0.1 300 0.1 300 0.1 300 0.1 300 0.1 300 0.1 300 0.1 200 400 3.5 60 51 102-204 3.5 3.5 3.5 3.5 60 120 3.5 34 102 204 3.5 3.5 3.5 3.5 118 0.1 288 0.1 300 0.1 200 0.1 300 0.1 300 0.1 300 0.1 320 0.1 300 0.1 600 0.1 300 0.1 300
60
-
Ethyl fumarate Methyl acrylate a-Methylstyrene Styrene Vinyl acetate Butyl acrylate
Styrene
Cyclopentene
Maleic anhydride
Benzene
Ethylene
Vinyl acetate
-
Benzene Isopropyl alcohol AyV-Dimethylformamide tert-Butyl alcohol Vinyl butyrate Vinyl chloride
tert-Butyl -
Vinyl formate tert-Butyl Vinyl isobutyrate tert-Butyl Vinyl pivalate tert-Butyl Vinyl propionate tert-Butyl Maleic anhydride
Acenaphthylene 2-Ethyl-l-hexene 1-Hexene 2-Methyl-2-butene a-Methylstyrene Norbornene Thiophene
Methyl acrylate
a-Methylstyrene Croton aldehyde Methyl vinyl ketone Vinyl-2-pyridine
alcohol
alcohol alcohol alcohol alcohol
Acetic anhydride
60 62 62 120 62 62 62 62 62 62 62 74 62 62 62 62 62 60 70 70 70 70 70 70 50 50 50 50
/*i 2.4 2.8 3.9 5.5 9.20 0.65 0.76 0.05 0.04 0.02 0.05 3.10 3.50 0.20 0.17 0.49 0.21 0.10 0.74 0.94 0.6 0.82 0.80 0.77 0.92 0.74 0.79 0.80 0.696 0.16 0.16 0.21 0.586 0.609 0.645 0.674 0.68 0.07 0.10 0.15 0.11 0.15 0.10 0.10 0.005 0.005 0.03 0.03 0.02 0.20 0.15 0.10 0.08 20 20 0.50 0.60 0.20 0.30
r2 0.17 0.21 0.36 0.15 0.10 0.46 0.43 0.15 0.10 0.65 0.53 0.10 0.05 0.62 0.50 0.049 0.041 0.030 1.51 1.20 0.95 0.99 1.39 1.485 1.13 1.50 1.40 1.37 1.505 2.7 2.1 2.0 1.29 1.49 1.49 1.50 1.26 0.43 0.32 0.015 0.011 0.015 0.010 0.035 0.025 0.04 0.03 0.05 0.03 0 0 0.27 0.23 0.02 0.02 1.80 1.20 1.10 1.05
Refs. 69 69 69 105 105 105 105 105 105 105 105 105 105 105 105 100 100 100 97 97 41 41 116 116 116 116 117 118 120 41 41 41 120 120 120 120 115 43 43 106 106 106 106 106 106 106 106 106 106 106 106 105 105 105 105 105 105 105 105
References page II - 440
TABLE 1. cont'd Copolymerization parameters Monomer 1
Monomer 2
Methyl methacrylate
Acenaphthylene
Styrene
Solvent
Absolute pressure (MPa)
Temperature (0C)
0.1
60
Toluene
Acrylonitrile
Toluene
Methyl acrylate
Toluene
Acrylic acid
-
Acrylonitrile
Toluene
Diethyl fumarate
Benzene
Diethyl maleate
Benzene
Ethyl methacrylate
Benzene
190 390 0.1 10 100 3.4 590 118 0.1 100 250 0.1 10 100 0.1 10 100 0.1 10 100 0.1 10 100 0.1 100 300 3.4 59 118 3.4 59 118 0.1 10 100 0.1 150 200 0.1 200 300 0.1 300 0.1 150 250 0.1 200 400
Methyl methacrylate -
Vinyl acetate
Vinylidene chloride
Methyl acrylate
Toluene
Methylacrylate
Toluene
Vinyl acetate
Benzene
Vinylidene chloride
-
Vinylidene chloride
-
Isopropyl acetate Vinylidene chloride
-
Indene
-
rx
r2
Refs.
0.57
3.1
43
0.60 0.58 1.34 1.46 2.01 2.42 2.36 2.40 0.25 0.27 0.31 0.37 0.43 0.55 0.26 0.29 0.32 6.53 7.08 9.50 0.56 0.62 0.72 0.704 0.710 0.718 1.20 1.12 1.10 0.86 0.82 0.77 44 46 47 2.6 2.5 2.5 0.54-0.55 0.560 0.605-0.70 0.90 0.60 0.025 0.025 0.03 0.475 0.500 0.525
70 62 62 62 60 70 60 60 50 60 62 62 62 62 62 62 60 60 60
60 60
1.9 1.6 0.12 0.37 0.45 0.31 0.31 0.30 0.07 0.08 0.095 0.07 0.13 0.14 0.06 0.09 0.15 0.01 0.02 0.02 0.50 0.55 0.67 0.159 0.163 0.171 0.09 0.11 0.13 0.38 0.39 0.41 0.01 0.01 0.01 0.04 0.04 0.01 0.80-1.135 1.145 0.80-1.165 0.30 0.35 3.2 3.1 3.1 0.205 0.215 0.225
43 43 44 44 44 119 119 119 69 69 69 44 44 44 70 70 70 70 70 70 45 45 45 69 69 69 119 119 119 119 119 119 46 46 46 47 47 47 69,105 69 69,105 105 105 47 47 47 69 69 69
TABLE 2. REACTIVITY RATIOS OF TERPOLYMERIZATION" Pressure (MPa)
ri2
r2\
ri3
r$\
r23
r32
0.1 300
5.5 3.2
0.15 0.10
0.02 0.05
0.65 0.53
0.06 0.15
0.15 0.25
a
Monomers: (i) acrylonitrile; (ii) diethyl fumarate; (iii) styrene.
Refs.
107,108
TABLE 3. ACTIVATION VOLUMES Activation volume (cm3/mol) Monomer 1
Monomer 2
Acrylonitrile
Butyl acrylate Cyclopentene Ethylene
Ethylfumarate Methyl acrylate a-Methylstyrene Styrene Vinyl acetate Styrene Maleic anhydride Vinyl acetate
Ethylene Indene
Vinyl acetate Acrylonitrile
Isoprene Maleic anhydride
Solvent
Benzene Heptane Dioxane Heptane Heptane
Methyl vinyl ketone Methyl methacrylate Vinylidiene chloride Acrylonitrile Heptane 2-Ethyl-l-hexene 2,3-Dimethyl-2-butene 1,1-Diphenyl ethylene 1-Hexane Cyclohexene 2-Methyl-2-butene a-Methylstyrene Norbornene Thiophene trans-Stilbene
Absolute pressure (MPa) 0.1-300 0.1-300 0.1-300 0.1-300 0.1-300 0.1-300 0.1 -0.1-600 2.5-60 110-190
0.1-300 0.1-300 0.1-300 0.1-200 0.1-300 0.1-300 0.1-300 0.1-300 0.1-320 0.1-300
Temperature ( 0 C) 50 50 50 50 50 50 60 60 62 240 50 50 50 50 50 70 70 70 70 70 70 70 70 70 60
Av*
Av*n - Av\2
Av^2 - Av^1
-5.0 -1.5 ~0 -8.5 -1.1 0
3.7 ~0 3.7 1.9 6.3 1.0
9.3 -11.3
2.7 11.9
0 0 2.5 0
-4.3 -3.6 -1.0 0
- 2 6 . 4 to - 3 7 . 4
-36 -17.5 -18.0 -24.0 -20.1 - 17.8 to - 19.1 —27.0 -36 -25 - 5 0 to - 6 0 -18 -23 -25 -35 -28 -26 -25
-
-
C O P O L Y M E R I Z A T I O N O F MALEIC A N H Y D R I D E W I T H M O N O - A N D POLY-SUBSTITUTED OLEFINS Substitution mono-
di-(l,2)
gem-
tritetra-
Methyl acrylate
a-Methylstyrene Croton aldehyde Maleic anhydride Methyl vinyl ketone Vinyl-2-pyridine
Comonomer
Refs. 107 105 105 105 105 105 100 100 97 72 48 48 49 48 71 50 106 106 106 106 121 106 106 106 106 106
160
Activation volume (cmVmol)
= CH(Pr) = CH(Bu) = CH(z-Pr) = CH(i-Bu) = CH(J-Bu) = CH(Ph) CH(Me) = CH(Et) CH(Me) = CH(Z-Pr) CH(Me) = CH(J-Bu) CH(Z-Pr) = CH(Z-Pr) CH(Ph) = CH(Ph) = C(Me)(Pr) = C(Me)(Z-Pr) = (MeXf-Bu) = C(Me)(CH2J-Bu) = C(Me)(Ph) = C(Et)(Et) = C(Et)(Bu) = (Ph)(Ph) CH(Me) = C(Me)(Me) CH(Et) = C(Me)(Me) C(Me)(Me) = C(Me)(Me)
0.1-300 0.1-300
50 50
0.1-300 0.1-300
50 50
-16.6 -18.0 -17.0 -17.5 -31 -18.5 -19.0 - 20.0 -35 -18.5 -25.0 -31 -33 -60 -46 -35 -34 -36 -50 - 25 - 31 -25
1.0 0
0.7 0
-1.9 -3.7
1.9 ~0
- 1 8 to - 2 5
105 105 71 105 105
References page II - 440
TABLE 3. cont'd Activation volume (cm3/mol) Monomer 1
Monomer 2
Methyl methylacrylate Styrene
Methyl acrylate
TABLE 4.
Solvent
Absolute pressure (MPa)
Temperature (0C)
3.4-118
62
Diethyl fumarate Methyl acrylate Methyl methacrylate Vinyl-2-pyridine
Av*
Av*n - bv\2
Sv*22 - Av*21
0.9 - 1 8 to - 13.8 to - 1 8 to - 2 3 . 5 to
-25 - 14.5 -25 -26
-2.2
1.8
0
Refs. 119 71,105 71 71 71
Q, e VALUES
Qa Monomer
At 0.1 MPa
Acrylic acid Acrylonitrile rt-Butyl acrylate rc-Butyl methacrylate Crotonaldehyde Diethyl fumarate Diethyl maleate Ethylene Ethyl methacrylate Indene Isobutylene Isopropenyl acetate Methylacrylate Methyl methacrylate oc-Methylstyrene Methyl vinyl ketone Propylene Styrene Vinyl acetate Vinyl chloride Vinyl pivalate 2-Vinylpyridine Vinylidene chloride
0.53(0.83)^ 0.53(0.50) 0.40(0.30) 0.62 (0.66) 0.015(0.02) 0.20 (0.03) 0.03(0.04) 0.015(0.013) 0.62(0.57) 0.30(0.36) 0.025 (0.029) 0.08 (0.02) 0.44(0.44) 0.63(0.74) 1.40(1.00) 1.07 (0.65) 0.010 (0.008) 1.20(1.00) 0.06 (0.03) 0.0450(0.056) 0.023 (-) 1.05(1.03) 0.27(0.26)
ea At 300 MPa 0.45 0.62 0.40 0.70 0.015 0.25 0.03 0.05 0.66 0.28 0.022 0.12 0.44 0.63 1.65 1.03 0.015 1.35 0.05 0.045 0.046 0.95 0.24
At 0.1 MPa +0.91(0.88)* +0.90(1.20) +0.35(0.74) - 0.08 (0.34) +0.80(0.84) +1.35 (2.17) +0.62(1.40) -0.15 (-0.15) 0.00(0.35) -1.10 (-1.03) -1.72 (-1.06) -1.30 ( - 0.34) +0.60(0.60) -0.20(0.38) -1.30 (-1.27) +0.95 (1.11) -1.50 ( - 2.20) -1.10(-0.80) - 0.20 ( - 0.22) +0.16(0.20) -0.19 (-) -0.60(-0.50) +0.42(0.40)
At 300 MPa +0.64 +0.95 +0.35 - 0.54 +0.80 +1.25 +0.40 -0.02 -0.35 -1.05 -1.25 -1.60 +0.60 -0.05 -1.40 +1.15 -1.05 -1.22 - 0.35 +0.19 -0.02 -0.50 +0.43
Refs. 108 105 105 92 105 105,109,25 109 110 92 111,108 112 105 105 108,25 105 105 112 105,108,92 105,108,110 112,41 113 105 108
a Reference monomer is methyl acrylate (105). ^Values in parentheses refer to the values of styrene.
H.
REFERENCES
1. M. G. Evans, M. Polanyi, Trans. Faraday Soc, 32, 1333 (1936). 2. S. D. Hamann, in: R. S. Bradley (Ed.), "High Pressure Physics and Chemistry", London, 1963. 3. M. G. Gonikberg., "Chemical Equilibrium and Reaction Rates at High Pressures", 2nd. ed., Khmiya, Moscow, 1969, Td. Y. Ogo., "Kouatsu Kouatsu Kagaku", Nikkan Kogyo Shinbunsha, Tokyo, 1972. 4. G. Luft, Dissertation, Darmstadt 1967. 5. A. E. Steam, H. Eyring, Chem. Rev., 29, 509 (1941). 6. G. Luft, Chem. Ing. Tech., 41, 712 (1969). 7. Landolt-Boernstein, "Zahlenwerte und Funktionen aus Physik und Chemie", Berlin, 1951. 8. W. Kleinpaul, Z. Physik. Chem. (Frankfurt), 29, 201 (1961); 30, 262 (1961).
9. B. Raistrick, R. H. Sapiro, D. M. Newitt, J. Chem. Soc. (London), 1761 (1939). 10. M. G. Gonikberg, L. F. Vereshchagin, Zh. Fiz. Khim., 23, 1447 (1949). 11. S. D. Hamann, Trans. Faraday Soc, 54, 507 (1958). 12. A. E. Nicholson, R. G. W. Norrish, Disc. Faraday Soc, 22, 104 (1956). 13. R. Steiner, G. Luft, Chem. Eng. Sci., 22, 537 (1967). 14. G. M. Simmons, D. M. Mason, Chem. Eng. Sci., 27, 89 (1972). 15. R. C. Neumann, Jr., Ace Chem. Res., 5, 381 (1972). 16. M. N. Romanii, K. E. Weale, Trans. Faraday Soc, 62, 2264 (1966). 17. C. Walling, J. Pellon, J. Am. Chem. Soc, 79, 4782 (1957).
18. R. L. Hemmings, K. E. Weale, "Chemical Reactions at High Pressures", Spon, London, 1967. 19. A. L. Shriers, B. F. Dodge, R. H. Bretton, "Free Radical Polymerization of Ethylene at High Pressures", paper presented on the A.I.Ch.E./London, 1965, Chem. Eng. Symp. Ser., 2, 10 (1965). 20. R. O. Symcox, P. Ehrilich, J. Am. Chem. Soc, 84, 531 (1962). 21. D. Lierse, G. Luft, unpublished. 22. T. YaIa, G. Jenner, in: H. KeIm (Ed.), "High Pressure Chemistry", Reidel, Dordrecht, 1977, p. 376. 23. G. Jenner, Thesis, Strasbourg, 1966 and Bull. Soc. Chim. France, 1, 344 (1967). 24. H. Abdi, G. Jenner, C. Brun, Makromol. Chem., 164, 149 (1973). 25. J. A. Lamb, K. E. Weale, Symp. Phys. Chem. High Pressures, 229 (1963) (Soc. Chem. Ind., London). 26. A. A. Zharov, N. S. Enikolopyan, Zh. Fiz. Khim., 38, 2727 (1964). 27. H. Asai, T. Imoto, J. Chem. Soc. (Japan), 66, 863 (1963); Nirrou Kagaku Zasshi, 84, 863 (1963). 28. D. W. Brown, L. A. Wall, J. Phys. Chem., 67, 1016 (1963). 29. A. C. Toohey, K. E. Weale, Trans. Faraday Soc, 58, 2439, 2446 (1962). 30. H. Asai, T. Imoto, J. Chem. Soc. (Japan), 66, 871 (1963). 31. K. Salahuddin, K. E. Weale, in: K. E. Weale (Ed.), "Chemical Reactions at High Pressures", Spon, London, 1967. 32. A. E. Nicholson, R. G. W. Norrish, Disc. Faraday Soc, 22, 104 (1956). 33. C. Walling, J. Pellon, J. Am. Chem. Soc, 79, 4776 (1957). 34. P. P. Kobeko, E. U. Kuvshinskii, A. S. Semonova, Zh. Fiz. Khim., 24, 345 (1950). 35. F. M. Merrett, R. G. W. Norrish, Proc Roy. Soc (London) A, 206, 309 (1951). 36. V. M. Zhulin, M. G. Gonikberg, R. F. Barkova, Izv. Akad. Nauk. SSSR, 432 (1965). 37. A. H. Ewald, Disc Faraday Soc, 22, 138 (1956). 38. C. Walling, J. Pellon, J. Am. Chem. Soc, 79, 4786 (1957). 39. A. H. Ewald, Disc. Faraday Soc, 22, 146 (1956). 40. C. Walling, G. Metzger, J. Am. Chem. Soc, 81, 5365 (1959). 41. P. Ehrlich, G. Mortimer in Adv. Polymer ScL, 7 (3), 420 (1970). 42. A. C. Toohey, K. E. Weale, Trans. Faraday Soc, 58, 2446 (1962). 43. M. N. Romani, K. E. Weale, Thesis, London University 1964. 44. R. D. Burkhart, N. L. Zutti, J. Polym. ScL, 57, 793 (1962). 45. H. Asai, T. Imoto, J. Chem. Soc (Japan), 85, 155 (1964). 46. Ibid., 85, 152 (1964). 47. B. S. Maulik, K. E. Weale, in: K. E. Weale (Ed.), "Chemical Reactions at High Pressures", Spon, London, 1967. 48. T. YaIa, G. Jenner, Communication 10, Meeting EHPRG, Strasbourg, 1972. 49. T YaIa, Thesis 3, Cycle, Strasbourg, 1972. 50. G. Jenner, J. Rimmelin, unpublished.
51. J. P. J. Higgins, K. E. Weale, J. Polym. Sci. A-I, 8, 1705 (1970). 52. R. I. Baikova, V. M. Zhulin, M. G. Gonikberg, Izv. Akad. Nauk SSSR, Ser. Khim., 154 (1966). 53. V. M. Zhulin, A. R. Volchek, M. G. Gonikberg, A. S. Shashkow, S. V. Zotova, Vysokomol. Soedin., 7A, 1513 (1972). 54. J. P. J. Higgins, K. E. Weale, unpublished. 55. S. A. Mehdi, K. E. Weale, unpublished. 56. A. R. Volchek, V. M. Zhulin, A. S. Shashkov, O. M. Nefedov, A. A. Ivashenko, Vysokomol. Soedin., A14, 2258 (1973). 57. V. M. Zhulin, N. V. Klimentova, M. G. Gonikberg, V. V. Korshak, A. P. Suprun, Vysokomol. Soedin., HA, 101 (1969). 58. V. M. Zhulin, A. P. Suprun, G. P. Lopatina, T. A. Soboleva, A. S. Shashkov, M. G. Gonikberg, G. P. Shakhovskoi, Vysokomol. Soedin., 13A, 2518 (1971). 59. V. M. Zhulin, M. G. Gonikberg, A. R. Volchok, O. M. Nefedov, A. S. Shashkov, Vysokomol. Soedin., 9A, 2153 (1971). 60. A. R. Volchek, V M. Zhulin, A. S. Shashkov, O. M. Nefedov, A. A. Ivashenko, Vysokomol. Soedin., A14, 2258 (1973). 61. G. Luft, H. Bitsch, unpublished. 62. V. M. Zhulin, Thesis for Doctor of Science degree, Moscow (1971). 63. V. M. Zhulin, M. G. Gonikberg, V N. Zagorbinina, Izv. Akad. Nauk, SSSR, Ser. Khim., 827 (1966). 64. V. M. Zhulin, R. I. Baikova, M. G. Gonikberg, G. P. Shakhovskoi, Vysokomol. Soedin., 13, 1071 (1971). 65. V. M. Zhulin, M. G. Gonikberg, V. N. Zagorbinina, Izv. Akad. Nauk, SSSR, Ser. Khim., 997 (1966). 66. M. G. Gonikberg, R. I. Baikova, V. M. Zhulin, Izv. Akad. Nauk, SSSR, 1164(1962). 67. V. M. Zhulin, M. G. Gonikberg, A. L. Goff, V N. Zagorbinina, Vysokomol. Soedin., HA, 777 (1969). 68. V. M. Zhulin, M. G. Gonikberg, V. N. Zagorbinina, Dokl. Akad. Nauk SSSR, 163, 106 (1965). 69. W. F. Dellsperger, K. E. Weale, ACS Polym. Preprints, 11, 645 (1970). 70. H. Asai, J. Chem. Soc (Japan), 85, 247 (1964). 71. J. A. Lamb, Thesis, London University, 1961. 72. H. Bitsch, G. Luft, Angew. Makromol. Chem., 32, 17 (1973). 73. Th. J. van der Molen, Preprint IUPAC Symp. on Macromolecular Chemistry, Budapest, 1969. 74. Th. J. van der Molen, International Symp. on Macromolecules, Helsinki, 1972. 75. G. Luft, P. Mehrling, H. Seidl, Angew. Makromol. Chem., 73, 85 (1978). 76. P. Mehrling, G. Luft, B. Giese, H. Seidl, Chem. Ber., 118, 240 (1985). 77. M. Buback, H. Lendle, Z. Naturforsch., 34A, 1482 (1979). 78. R. Halle, Plastic Compound., 73 (1980). 79. M. Buback, H. Lendle, Makromol. Chem., 184, 193 (1983). 80. M. Buback, Z. Naturforsch., 39A, 399 (1984). 81. G. Luft, P. -Ch. Lim, S. Pavlakis, J. Macromol. Sci. Chem. A, 22(9), 1183(1985).
82. G. Luft, R. Kampf, H. Seidl, Angew. Makromol. Chem., 108, 203 (1982). 83. K. Yamamoto, J. Macromol. Sci. Chem. A, 17 (3), 415 (1982). 84. K. Yamamoto, M. Sugimoto, J. Macromol. Sci. Chem. A, 13 (8), 1067 (1979). 85. R-Ch. Lim, G. Luft, Makromol. Chem., 184, 849 (1983). 86. M. Yokawa, Y. Ogo, Makromol. Chem., 177, 429 (1976). 87. R Ehrlich, G. A. Mortimer, Adv. Polym. Sci., 7, 386 (1970). 88. M. Buback, H. Lendle, Z. Naturforsch, 36A, 1371 (1981). 89. Y. Ogo, M. Yokawa, T. Imoto, Makromol. Chem., 171, 123 (1973). 90. M. Yokawa, Y Ogo, T. Imoto, Makromol. Chem., 175, 2903 (1974). 91. M. Yokawa, Y Ogo, T. Imoto, Makromol. Chem., 175, 2913 (1974). 92. H. Asai, T. Imoto, Nippon Kagaku Zasshi, 85, 149 (1964). 93. T. Sasuga, M. Takehisa, J. Makromol. Sci. Chem. A, 12 (9), 1307 (1978). 94. T. Sasuga, M. Takehisa, J. Makromol. Sci. Chem. A, 12 (9), 1333 (1978). 95. T. Sasuga, S. Kawanishi, M. Takehisa, J. Makromol. Sci. Chem. A, 14 (4), 605 (1980). 96. M. Buback, Ch.-R. Choe, E.-U. Franck, Makromol. Chem., 185, 1685 (1984). 97. F. de Kok, D. Heikens, A. L. German, Proc. 4th Int. Conf. High Pressure, Kyoto 1974, Phys. Soc. Japan. 98. Y Ogo, M. Yoshikawa, S. Ontani, T. Imoto, J. Polym. Sci. Chem., 16, 1413 (1978). 99. M. Yokawa, I. Yoshida, Y Ogo, Makromol. Chem., 178,443 (1977). 100. M. Yokawa, Y. Ogo, T. Imoto, Makromol. Chem., 163, 135 (1973). 101. R. C. Neumann, J. V. Behar, J. Am. Chem. Soc, 91, 6024 (1969). 102. R. C. Neumann, J. V. Behar, Tetrahedron Lett., 3281 (1968). 103. R. C. Neumann, J. V. Behar, J. Am. Chem. Soc, 89, 4549 (1967). 104. R. C. Neumann, R. J. Bussey, J. Am. Chem. Soc, 92, 2440 (1970). 105. G. Jenner, S. Aieche, J. Polym. Sci. Chem., 16, 1017 (1978). 106. M. Kellou, G. Jenner, Makromol. Chem., 180, 1687 (1979). 107. S. Aieche, G. Jenner, Polymer, 19, 1236 (1978). 108. W. Dellsperger, K. Weale, Am. Chem. Soc, Polym. Prepr., 11, 645 (1970). 109. H. Asai, Nippon Kagaku Zasshi, 85, 247 (1964). 110. R. van der Meer, E. H. M. van Gorp, A. German, J. Polym. Sci., Polym. Chem. Ed., 15, 1489 (1977). 111. T. Yala-Lutokanu, G. Jenner, A. Deluzarche, Bull. Soc Chim. France, 609 (1974). 112. K. Hamanoue, Rev. Phys. Chem. Japan, 38, 120 (1968). 113. R. van der Meer, A. German, 15th Meeting EHPRG, Darmstadt, Germany (1977). 114. G. Luft, W. Henning, M. Dorn, Angew. Makromol. Chem. (in press). 115. J. Schrijver, J. L. Ammerdorffer, A. L. German, J. Polym. Sci. Chem., 20, 2693 (1982).
116. R. van der Meer, M. W. A. M. Aarts, A. L. German, J> Polym. Sci. Chem., 18, 1347 (1980). 117. R. van der Meer, A. L. German, J. Polym. Sci. Chem., 17, 571 (1979). 118. R. van der Meer, A. L. German, D. Heikens, J. Polym. Sci. Chem., 15, 1765 (1977). 119. J. Schrijver, A. L. German, J. Polym. Sci. Chem., 21, 341 (1983). 120. R. van der Meer, E. H. M. van Gorp, A. L. German, J. Polym. Sci. Chem., 15, 1498 (1977). 121. G. Jenner, M. Kellou, M. Papadopoulos, Angew. Chem. Suppl., 929 (1982). 122. T. Bartnik, B. Baranowski, Polym. J. Chem., 53 (3), 741 (1979) 124. A. Crosato-Arnaldi, G. B. Guarise, G. Talamini, Polymer, 10, 385 (1969). 125. G. B. Gualise, Polymer, 7, 497 (1966). 126. G. B. Gualise, G. Palma, E. Siviero, G. Talamini, ibid., 11, 613 (1970). 127. T. Imoto, Mem. Fac Eng., Osaka City Univ., 3, 217 (1961). 128. T. Imoto, H. Asai, Nippon Kagaku Zasshi, 85, 149 (1964). 129. T. Imoto, H. Asai, ibid., 85, 347 (1964). 130. T. Imoto, T. Nakajima, Kogyo Kagaku Zasshi, 69, 520 (1966). 131. T. Imoto, Y. Ogo, Y Hashimoto, ibid., 70, 1952 (1967). 132. G. Jenner, M. Kellou, Abstracts, 15th Annual Meeting of European High Pressure Research Group, Darmstadt, 1977, p. 12. 133. A. R. Khalilpour, G. Jenner, A. Deluzarche, Bull. Soc Chim. Fr., 3-4 (2), 583 (1976). 134. G. Luft, R Lim, M. Yokawa, Makromol. Chem., 184, 207 (1983). 135. T. Mitani, Y. Ogo, T. Imoto, Rev. Phys. Chem. Soc Japan, 42, 25 (1972). 136. R W. Moore, F. W. Ayscough, J. G. Clouston, J. Polym. Sci., Polym. Chem. Ed., 15, 1291 (1977). 137. R W. Moore, J. G. Clouston, R. R Chaplin, ibid., 19, 1659 (1981). 138. R W. Moore, J. G. Clouston, R. R Chaplin, ibid., 21, 2491 (1983). 139. R W. Moore, J. G. Clouston, R. R Chaplin, ibid., 21, 2503 (1983). 140. H. Nakomoto, Y. Ogo, T. Imoto, Makromol. Chem., I l l , 104 (1968). 141. J. Osugi, K. Hamanoue, E. Hirayama, Nippon Kagaku Zasshi, 87, 1032 (1966). 142. J. Osugi, T. Mizukami, ibid., 87, 1157 (1966). 143. J. Osugi, K. Hamanoue, ibid., 90, 544 (1969). 144. J. Osugi, K. Hamanoue, ibid., 90, 549 (1969). 145. T. Sasuga, N. Morishita, A. Udagawa, Y Kusama, M. Takehisa, J. Polym. Sci., Polym. Chem. Ed., 14, 2527 (1976). 146. T. Sasuga, S. Kawanishi, J. Phys. Chem., 83, 3290 (1979). 147. T. Sasuga, S. Kawanishi, M. Takehisa, J. Macromol. ScLChem. A, 14 (4), 605 (1980). 148. T. Sasuga, S. Kawanishi, M. Takehisa, Macromolecules, 16, 545 (1983).
149. T. Sano, Y. Ogo, T. Imoto, Kobunshi Ronbunshu., 32, 338 (1975). 150. Y. Tanaka, K. Noguchi, T. Shibata, A. Okada, Macromolecules, 11, 1017 (1978). 151. O. N. Tsvetkov, T. N. Tsvetkova, V. N. Monastyrskii, Plast. Massy, 9, 9 (1975). 152. T. Wada, T. Watanabe, M. Takehisa, J. Polym. ScL, Polym. Chem. Ed., 10, 2639 (1972). 153. M. Yokawa, Y. Ogo, T. Imoto, Makromol. Chem., 175, 179 (1974). 154. M. Yokawa, Y. Ogo, T. Imoto, Makromol. Chem., 175, 2913 (1974).
155. A. A. Zharov, Al. Al. Berlin, N. S. Enikolopyan, J. Polym. ScL, Part C, 16, 2313 (1967). 156. V. A. Zhorin, A. A. Zharov, Yu. V. Kissin, N. S. Enikolopyan, Dokl. Akad. Nauk SSSR, 219, 674 (1974). 157. V. M. Zhulin, M. G. Gonikberg, Dokl. Akad. Nauk, SSSR, 163, 106 (1965). 158. V. M. Zhulin, A. R. Volchek, M. G. Gonikberg, A. S. Shashkov, S. V. Zotova, ibid., 14A, 1484 (1972). 159. V. M. Zhulin, Z. G. Makarova, N. V. Klimentova, A. P. Suprun, A. N. Akopyan, G. P. Shakhovskoi, ibid., 24A, 2621 (1982). 160. G. Jenner, M. Kellou, Tetrahedron, 37, 1153-60 (1981).
A c t i v a t i o n S t e r e o c o n t r o l
E n t h a l p i e s i n
F r e e
a n d
E n t r o p i e s
R a d i c a l
o f
P o l y m e r i z a t i o n s
H a n s - G . Elias Michigan Molecular Institute, 1910 West St. Andrews Rd., Midland, Ml 48640, USA
A. Introduction B. Tables Table 1. Ratios of Some /-ads for Different Mechanisms Table 2. Ratios of Rate Constants for Markov First Order Mechanisms Table 3. AH^. - AHf/s and A S ^ - ASf/s of Free Radical Polymerizations in Different Solvents Table 4. Activation Enthalpy Differences (AH\ - AHl) Calculated from Various Literature Data Table 5. Activation Entropy Differences (ASl-ASl) Calculated from Various Literature Data Table 6. Calculated Compensation Temperatures T0 and Compensation Enthalpies AAHQ for Various Monomers and Modes of Addition, Assuming Markov First Order Trials C. References A.
il-445
II-446 II-446
II-447
(b) The last monomeric unit of the chain, but not the last diad, controls the propagation step. The probabilities for the formation of isotactic and syndiotactic diads are thus different (pi / ps). The process is Bernoullian (zeroth order Markov statistics) with respect to the formation of diads. Consequently, the probability of forming an isotactic diad at an existing isotactic diad equals the probability of forming an isotactic diad at an existing syndiotactic diad (P1J1 = ps/{), and, by analogy, Ps/s = Pi/s• It follows for the diads (6,8)
II-448
II-449
(A3) and for the triads (A4) (A5)
II-449 II-450
INTRODUCTION
In free radical polymerization, the tacticity of the resulting polymer depends on the propagation step, i.e., on stereocontrol by the propagating end. The following simple cases exist: (a) The last monomeric unit does not control the stereospecificity of the propagation step. Isotactic (i) and syndiotactic (s) additions thus exhibit the same conditional probabilities (px — ps). The mole fractions x of the resulting isotactic and syndiotactic diads are equal (x\ = xs). If all steps occur at random, the four conditional probabilities for the formation of triads are equal Q)^1 = p-x/s = ps/-x = /? s / s ), and so are the conditional probabilities for the formation of tetrads, pentads, etc. The resulting polymer is a true atactic polymer. It follows that (Al) (A2)
where xa is the mole fraction of isotactic triads and xss is the mole fraction of syndiotactic triads. ;cht is the mole fraction of heterotactic triads, regardless of whether formed by the formation of an isotactic unit at a syndiotactic one (conditional probability ps/i) or vice versa (conditional probability p i / s ). (c) The last two monomeric units of the chain, i.e., the last monomeric diad, regulate the stereocontrol of the propagation step. The four conditional probabilities do not equal each other (P1J1 ^ pi/s ^ ps/i ^ ps/s)- The mole fractions of isotactic (JCH), syndiotactic (xss) and heterotactic triads (jcht) are thus given by (8,11) (A6) (A7) This process corresponds to a Markov trial of first order. (d) Second order Markov statistics are present if the last two diads (i.e., the last triad or the last three monomeric
units) control the propagation step. In this case (A8) (A9) (AlO) (All) In order to distinguish between Markov second order and Markov first order mechanisms, at least tetrads must be known. The probability of the addition of a 'b' diad (b = i, s) to an existing end 'a' (a = i, s) is given by the corresponding rates R: (A12) with a = i, s or b = i, s, in the Markov first order case, or a = ii, is, si, ss b = ii, is, si, ss, in the Markov second order case. Using these definitions and assuming steady states and the equality of instantaneous and final diad and triad fractions, one can express ratios of all diads, triads, and tetrads in terms of rate constants (Table 1) or ratios of rate constants in terms of diad, triad, etc. fractions (Table 2). The rate constants themselves can be calculated if the rate constants of propagation are known for the corresponding experimental conditions (1). From the temperature dependence of the expressions given in Table 2, differences in activation enthalpies (AHA* — A//g) and differences in activation entropies (AS^ - AS^) can be calculated:
from literature data as very few triad fractions have been reported. For any two modes of addition, the compensation effect between AAH$ and AAS$ (10,12,43) for the polymerization of a given monomer, in different solvents and/or at different monomer/solvent ratios, can be described by (A14) The compensation temperature To has been found to be independent, of the mode of addition (e.g., A = i/i vs. B = i/s) within the limits of error (12,43). However, the compensation enthalpy AAH^ depends on the mode of addition. B. TABLES TABLE 1. RATIOS OF SOME /ADS FOR DIFFERENT MECHANISMS0 Mechanism i-ad Ratio Bernoulli
a
Markov 1st order Markov 2nd order
From Ref. 42.
(AB)
TABLE 2. RATIOS OF RATE CONSTANT FOR MARKOV FIRST ORDER MECHANISMS0
The quantities (AH\ - A # | ) and (AS* - AS^) may reflect activation parameters (2,3), conformation parameters (4,5), or combinations thereof. Table 3 gives the difference AAH^ = AHJ - A # | and AAS^ = AS\ - ASg calculated from the temperature dependence of diad ratios X[/xs. In the case of Bernoulli trials, they represent AHf - AHj and ASf - AS^, respectively. For first order Markov trials, they stand for AHj/{ - AH}/S and ASJ/{ - Asf/s, respectively. In general, both AAH^ and AAS^ depend on the solvent (9,10), and consequently on the monomer/solvent ratio (11,12), but they are nearly independent of monomer conversion. Table 4 gives the differences in activation enthalpies for modes of addition other than s/i vs. i/s, and Table 5 gives the corresponding differences in activation entropies. Only a few of these activation parameters could be calculated
Ratios of rate constants Expressions giving ratios of rate constants
a
From Ref. 43.
TABLE 3.
AHJ/J -
AIfJ1 AND Asjfi - As}/s OF FREE RADICAL POLYMERIZATIONS IN DIFFERENT SOLVENTS*
Monomer (H-additive) Acrylonitrile
Vol.%
30 100 Acrylic acid, isopropyl ester ? ? - , methyl ester ? a-Chloroacrylic acid, methyl ester ? Methacrylonitrile 100 100 - , ( + 1 mol SnCV2 mol monomer) 3:1* - , ( + 1 molSnCVl mol monomer) 2:1* - , ( + 1 molSnCyi mol monomer) 1:1* - , ( + 1 mol SnCl4/2 mol monomer) 1:1* Methacrylic acid 10 20 20 20 -,anhydride ? - , benzyl ester 50 - , j-butyl ester 50 - , f-butyl ester 50 - , p-carboxyphenyl ester ? ? - , cyclohexyl ester 100 - , glycidyl ester 45 50 57 100 - , a-methylbenzyl ester 50 - , methyl ester 9. \d 9Ad 9. ld 9Ad 9.1* 9Ad 9Ad 9Ad 9Ad 9Ad 9Ad 9.1^ 9.1d 9Ad 20 25 25 25 25 25 25 25 28.5 50 100 100 100 100 100 - , - , ( + 8.7 mol ZnCl2A mol MMA) 1.1« - , - , ( + 1 mol ZnCl2A mol MMA) 3.2e - , - , (±0.04 mol ZnCl2A mol MMA) 100 - , - , ( + 1 mol ZnCl2/2 mol MMA) 100 - , - , ( + 1 mol ZnCl2A mol MMA) 100 - , - , ( + 1 mol SnCU/2 mol MMA) 100
Solvent
(J/mol)
Toluene Bulk
3770 ±59 0 0 0 3800 ±190 250 ±50 -4100±71 - 630 ± 54 170±63 251 2350 ± 38 3980 ±92 3850 ±80 7800 ±180 3140±42 13300 ±210 2300 ±130 3430 ±63 2090 ±80 4310 0 1210 ±80 700 ±100 5780 ±42 8600 ±130 9800 ±110 3640 ±59 6280 ± 75 5360 ±75 3480 ±71 3900 ±160 3140 ±88 5100 ±71 3500 ±150 3350 ±96 5317 ± 8 3100 ±67 4860 ±75 5200 ±100 3900 ±110 2810 ±96 2720 ±34 7030 ±75 5860 ±21 9380 ±71 6700 ±46 4980 ±50 5200 ±210 6700 ±29 5650 ±80 2900 ±420 6200 ±110 4480 3800 ±230 2300±54 3560 ±84 2850 ± 71 4100 ±71 2700±190 - 1 3 0 ± 80 - 40 ± 130 800 ± 100
? Toluene Bulk Bulk Toluene Toluene Benzene Benzene 1-Propanol 1-Propanol 2-Propanol Methanol Benzene Toluene Toluene Toluene Dimethylformamide /7-Cetyloxybenzoic acid Bulk Acetone Dimethylformamide Toluene Bulk Toluene Acetone Acetonitrile Benzene Butanone y-Butyrolactone Chloroform Dimethylformamide Dimethyl sulfoxide 1,4-Dioxane Methylene chloride Pyridine Tetrachloroethane Tetrahydrofuran Toluene Paraffin Acetone Carbon tetrachloride Chloroform Dichloroethylene Ethanol ^-Heptane /i-Hexane Toluene Toluene Bulk Bulk Bulk Bulk Bulk Water Ethyl acetate Bulk Bulk Bulk Bulk
(J/mol/K) 2.7 ±0.19 0 -5.9 - 5.9 2.5 ±0.59 3.0 ±0.14 -10.8±0.21 - 0.7 ± 0.18 -0.1±0.18 0.75±0.88 9.76 ± 0.096 - 2 . 2 ±0.32 - 1 . 8 ±0.28 10.5 ±0.63 - 4 . 1 ±0.13 44.4 ±0.63 - 1 . 7 ±3.8 2.0 ±0.22 - 2.6 ± 0.29 2.09 - 6.87 - 5 . 0 ±0.20 9.5 ±0.36 5.0 ±0.15 14.2 ±0.042 17.5 ±0.28 2.2 ±0.22 10.2 ± 0.23 7.3 ±0.26 2.3 ±0.23 4.2 ±0.46 1.4 ±0.27 7.5 ±0.23 3.4 ±0.46 2.5 ±0.28 7.4 ±0.30 2.0 ±0.22 7.7 ±0.22 7.2 ±0.29 4.4 ±0.33 0.8 ±0.26 1.6 ±0.13 9.0 ±0.23 5.36 ±0.067 16.0 ±0.21 8.4 ±0.13 3.6 ±0.14 3.69 ±0.059 8.50 ±0.092 3.9 ±0.26 1.3 ±1.3 9 ±3.8 4.2 -0.04 ±0.63 -1.8±0.16 3.3 ±0.24 2.2 ± 0.20 5.2 ± 0.2 1.13±0.054 - 9.80 ± 0.67 - 6.7 ± 0.46 - 8.2 ± 0.33
Remarks a a
a
c
IR IR IR IR IR IR IR a
-
a
a
-
Refs. 10,14 13 15 15 16 17 18 18 18 18 18 19 19 19 19 20 21 10,22 10,22 23 10,23 10,24 10,25 10,25 10,25 10,25 10,22 12 12 12 12 12 12 12 12 12 12 12 12 12 12 27 9 9 9 9 9 9 9 10,26 21 27 1 25 28 12 10,29 10,29 10,29 27 27 27
*In all cases, except those marked by IR (infrared) (see Remarks column), diad fractions were determined via NMR. References page 11-450
TABLE 3. cont'd Monomer ( +additive)
Vol.%
- , - , ( + 1 mol SnCVl mol MMA) - , L-menthyl ester - , phenetyl ester Trifluorochloroethylene Vinyl bromide Vinyl bromide N-Vinyl carbazole
? ? ? 10 33.3 33.3 100 100 100 100 50d 50 J 50d 100 100 100 ? 100 ?
Vinyl chloride
- P , p-d2 Vinyl formate
Vinyl trichloroacetate
a c e
100 50 50 0.4*" 100 ? 6.5 100 100 ? ? ? ?
Solvent
(J/mol)
Bulk Toluene Toluene Carbon tetrachloride Bulk n-Butyl acetate o-Dichlorobenzene Bulk Bulk Dimethylacetamide Dimethylformamide Dimethylsulfoxide Hexamethylphosphoric triamide Hexane/nonane Methylene dichloride Toluene Cyclohexane Water/ethanol Water Bulk Bulk Bulk Bulk Acetone Chloroform Dimethylformamide Bulk Bulk Bulk w-Butyl acetate Bulk w-Butyl acetate
420 ± 13 960 ± 46 5600 ± 1700 0 710 250 1930 ± 5 4 2140 ±17 1270 ± 3 0 - 4600 ±300 - 2850 ± 100 -3300 ±500 -3400 ±200
-14.07 ± 0.054 0.3 ± 0.18 4.6 ±4.6 -5.8 2.5 2.1 5.3 ±0.17 5.99 ±0.080 2.72 - 20 ± 1 -13.5 ± 0.4 -15.4 ±1.4 -14.7 ±0.7
-1500 ±200 -2650 ±100 -3650 ±1000 1300 ± 8 4 5000 ±1000 1500 ±630 2900 ±160 2260 ± 5 0 1090 ± 2 0 -2650 ± 4 340 ±25 290 ± 5 0 250 ±38 1050 ± 5 4 880 ±25 2830 1800 1590 880
-10.5 ±0.7 -11.7 ±0.4 -16.0 ±0.8 2.5 ±0.42 18 ±4.2 2.9 ±2.0 6.78 ±0.067 5.7 ±0.14 1.9 -6.28 ±0.04 0.21 ±0.80 0.08 ±0.16 0.5 ±0.12 3.3 ±0.17 3.4 ±0.080 84 4.6 4.2 2.1
Data directly from literature, mechanistic assumptions unknown. Literature data, calculated under the assumption of Bernoulli statistics. mol/1.
TABLE 4.
(J/moI/K)
Remarks -
a
a a a
a
IR a
a a a
Refs. 27 30 21 31 32 32 34 34 44 45 45 45 45 45 45 45 36 35 35 37 34 44 34 41 41 41 38 41 32 32 32 32
b
Solvent/monomer molar ratio. mol%. f g/ml. d
ACTIVATION ENTHALPY DIFFERENCE (AH* - AHj|) CALCULATED FROM VARIOUS LITERATURE DATA
\H\ - AHI (J/mol) A = i/i B = i/s
Monomer
Solvent
Glycidyl methacrylate
Acetone Bulk Dimethylformamide Toluene Methanol 1-Propanol 2-Propanol
33000 ±2300 25000 ± 1400 14000 ±1500 27000 ±1800
Bulk Bulk Bulk Ethyl acetate 70% ZnCl2/H2O Acetone Bulk Chloroform Dimethylformamide Water Water/methanol Bulk
2800 ±120 - 1 3 ±110 -20±160 2300±230 700±240 670 ±25 2850 ±84 1700 ±180 0±150 423 3600 ±63 3180 ± 46
Methacrylic acid (20 vol.%) Methyl methacrylate/ZnCl2 9.34/0.369 (mol/mol) 2.00/1.00 (mol/mol) 1.00/1.00 (mol/mol) 3.19/3.19 (mol/mol) 1.10/9.6 (mol/mol) Vinyl formate
Vinyl chloride Vinyl chloride, P, P-d2
A = s/i B = i/i
A = i/i B = s/s
-
-
-
-
38000 ± 2500 20000 ±1800 33000 ±2600
6500 ± 750 300 ±160 5556 ± 8
-130 ±110 -100 ±75 -21±110 1800±180 2200±180 -1060 ±88 -1700 ±100 -3200 ±190 -250 ±190 1210 -1230 ±54 540 ± 46
2430 ±59 - 4 2 ±88 -29±130 2600±170 1400±150 -419 ± 4 650 ±25 -520 ±46 -180 ±200 170 4420 ±29 2860 ±21
A = i/s B = s/s 420 ± 80 -1240 ±75 150 ±29 -340 ±59 - 2 9 ±29 -8±17 370±63 700±92 -1060 ±92 -1900 ±130 -300 ±190 -180 ±200 980 830 ±84 - 330 ± 29
A = s/i B = s/s
Refs.
7100 ±110 9300 ±140 580 ±33 10000 ±1000 3300 ±110 4010 ±96 8000 ±220
25 25 25 25 19 19 19
2310 ±54 -140 ±75 -46±130 4480±54 3550±38 -2150 ±92 -900 ±130 -3700 ±1250 -440 ±230 2500 5600 ±140 2320 ± 25
29 27 27 29 29 41 41 41 41 35 35 39
TABLE 5. ACTIVATION ENTROPY DIFFERENCES (As| - ASj[) CALCULATED FROM VARIOUS LITERATURE DATA AS* - ASJ (J/mol/K)
Monomer
Solvent
A = i/i B = i/s
Glycidyl methacrylate
Acetone Bulk Dimethylformamide Toluene Methanol 1-Propanol 2-Propanol
85 ±8.8 54 ± 4.2 32 ±7.1 75±7.5
Methacrylic acid (20 vol.%) Methyl methacrylate/ZnCl2 9.34/0.369 (mol/mol) 2.00/1.00 (mol/mol) 1.00/1.00 (mol/mol) 3.19/3.19 (mol/mol) 1.10/9.6 (mol/mol) Vinyl formate
Vinyl chloride Vinyl chloride, P, P-d2
Bulk Bulk Bulk Ethyl acetate 70% ZnCl2 in water Acetone Bulk Chloroform Dimethylformamide Water Water/methanol Bulk
4.0±0.34 -7.0±0.46 - 5 . 2 ±0.63 1.4 ±0.88 3.1 ±0.71 5.1 ±0.25 11.1 ±0.25 7.7 ±0.54 4.6 ±0.46 -1.3 11.7 ±0.25 8.3 ±0.17
A = s/i B = i/i
A = i/i B = s/s
A = i/s B = s/s
A = s/i B = s/s
-
-
-
125 ±8.4 72 ±8.0 100±ll
- 1 . 3 ± 2.3 -15.8 ±0.54 -1.84 ±0.04
2.3 ± 0.25 - 3 . 4 ±0.25 .0.7 ±0.13
10.3 ±0.42 16.1 ±0.54 5.8 ±0.13 17 ±3.9 - 1 . 1 ± 0.13 - 0 . 9 ±0.38 11.1 ±0.75
25 25 25 25 19 19 19
-2.9±0.29 -2.8±0.29 -1.7 ±0.38 3.9 ±0.71 5.2±0.54 - 5 . 6 ±0.29 - 7 . 6 ±0.25 -13.0 ±0.63 - 3 . 9 ±0.59 4.6 - 4 . 1 ±0.21 2.1 ±0.17
1.8±0.17 -8.0±0.38 - 6 . 0 ±0.46 1.8 ±0.63 -1.5±0.42 -0.75 ±0.04 2.55 ±0.080 - 1 . 1 ±0.13 - 0 . 3 ±0.13 4.5 15.3 ±0.54 7.03 ±0.080
-2.2±0.17 -1.5±0.13 - 0 . 8 ±0.21 0.4 ±0.25 1.6±0.25 - 5 . 8 ±0.29 - 8 . 6 ±0.34 -13.9 ±0.59 - 4 . 3 ±0.39 3.8 3.6 ±0.34 -1.30 ±0.08
—1.1 ±0.13 -10.8±0.29 -7.7 ±0.42 5.7 ±0.13 3.8±0.13 - 9 . 3 ±0.29 - 5 . 0 ±0.38 -13.9 ±0.75 - 3 . 9 ±0.71 6.8 20.6 ±0.54 4.98 ±0.08
29 27 27 29 29 41 41 41 41 35 35 39
Refs.
TABLE 6. CALCULATED COMPENSATION TEMPERATURES T0 AND COMPENSATION ENTHALPIES AAH* FOR VARIOUS MONOMERS AND MODES OF ADDITION, ASSUMING MARKOV FIRST ORDER TRIALS Modes of addition M o n o m e r
A
Acrylonitrile Methacrylic acid, in alcohols
s/i s/i i/i s/i i/i s/i i/s s/i s/i s/i s/i s/i s/i s/i i/i s/i i/i s/i i/s s/i i/i s/i i/i s/i i/s s/i s/i s/i s/i i/i s/i i/i s/i
- , /-butyl ester - , rc-butyl ester - , /7-carboxyphenyl ester - , glycidyl ester - , hexyl ester - , methyl ester
- , - , ( + ZnCl2)
- , /-propyl ester - , rc-propyl ester Vinyl acetate Vinyl chloride
B
T0 (K) i/s i/s i/i i/i s/s i/s s/s s/s i/s i/s i/s i/s s/s i/s i/s i/i s/s i/s s/s s/s i/s i/i s/s i/s s/s s/s i/s i/s i/s i/s i/i s/s i/s
1400 455 294 ±26 323 ± 5 403 ±140 323 ±10 302 ±74 333 ±23 294 ± 3 236 ± 4 481 345 ± 15 373 ±11 303 ±11 315 ± 49 310 ±20 323 ±124 362 ±15 338 ±51 334 ±54 314 ± 39 321 ± 9 331 ±24 336 ±21 304 ±10 328 ±42 230 ± 54 248 ± 41 1100 283 ±25 282±6 235 ±28 305 ±124
AAHJ (J/mol) 0 2780 6300 ±1260 -2300 ±510 6600 ±200 4480 ±21 - 1 8 0 ±63 4250 ±25 3304 ± 4 3576 ± 8 3308 3800 ± 200 3500 ±120 3260 ± 29 120 ± 160 2600 ±130 1440 ±84 1470 ±50 1400 ±92 4010 ±75 1650 ± 67 540 ±33 1930 ±42 2250 ±50 243 ± 4 2530 ±80 3420 ± 67 3300 ± 176 -2050 820 ±130 -75±17 900 ±160 - 2 2 0 ±420 References page 11-450
TABLE 6. cont'd Modes of addition M o n o m e r
Vinyl formate
N-Vinyl carbazole Vinyl chloroacetate Vinyl trifluoroacetate
A i/s s/i i/i s/i i/i s/i i/s s/i s/i s/i s/i
B
T0 (K) s/s s/s i/s i/i s/s i/s s/s s/s i/s i/s i/s
248 ± 9 219 ± 1 0 362 ± 2 3 315 ± 1 6 323 ± 2 7 330 ± 9 5 320 ± 1 8 316 ± 5 - 243 300 340
AA/fJ (J/mol) - 1 3 ±33 1130 ± 5 9 -1400 ±130 850 ± 8 0 -200 ±25 -290 ±42 970 ± 9 6 740 ± 2 1 288 419 167
"Based on data in Tables 3-5; see also Refs. 40,43.
REFERENCES
1. H. -G. Elias, Makromol. Chem. 137, 277 (1970). 2. J. W. L. Fordham, J. Polym. ScL, 39, 321 (1959). 3. C. E. H. Bawn, W. H. Janes, A. M. North, J. Polym. Sci. C 4, 427 (1963). 4. H. Fischer, Kolloid-Z., 206, 131 (1965). 5. P. L. Luisi, R. M. Mazo, J. Polym. Sci. A-2, 7, 775 (1969). 6. F. A. Bovey, G. V. D. Tiers, J. Polym. Sci., 44, 173 (1960). 7. T. G. Fox, H. W. Schnecko, Polymer 3, 575 (1962). 8. F. A. Bovey, "Polymer Conformation and Configuration", Academic Press, New York, 1969. 9. H. Watanabe, Y. Sono, Kogyo Kagaku Zasshi, 65, 273 (1962). 10. H. -G. Elias, P. Goeldi, V. S. Kamat, Makromol. Chem., 117, 269 (1968). 11. E. L. Miller, SPE Trans., 3, 1 (1963). 12. P. Goeldi, H. -G. Elias, Makromol. Chem., 153, 81 (1972). 13. G. Svegliado, G. Talamini, G. Vidotto, J. Polym. Sci. A-I, 5, 2875 (1967). 14. H. Murano, R. Yamadera, J. Polym. Sci. B, 5, 333 (1967). 15. C. Schuerch, W. Fowells, F. P. Hood, F. A. Bovey, cited in Ref. 36. 16. K. Matsuzaki, T. Uryu, K. Ito, Makromol. Chem., 126, 292 (1969). 17. K. Matsuzaki, T. Uryu, J. Polym. Sci. B, 4, 255 (1966). 18. H. Hirai, T. Ikegami, S. Makishima, J. Polym. Sci. A-1,7,2059 (1969). 19. J. B. Lando, J. Semen, B. Farmer, Polym. Preprints, 10, 586 (1969). 20. W. L. Miller, W. S. Brey, G. B. Butler, J. Polym. Sci., 54, 329 (1961). 21. K. Yokota, Y. Ishi, Kogyo Kagaku Zasshi, 69, 1966 (1966). 22. K. Matsuzaki, A. Ishida, N. Tateno, T. Asakura, A. Hasegawa, T. Tameda, Kogyo Kagaku Zasshi, 68, 852 (1965). 23. Y. B. Amerik, I. I. Konstantinov, B. A. Krentsel, IUPAC, International Symposium, Macromolecular Chemistry, Tokyo, 1966, Preprint 1.1.09. 24. K. Matsuzaki, A. Ishida, N. Tateno, IUPAC, International Symposium, Macromolecular Chemistry, Prague, 1965, Preprint 265.
25. Y. Iwakura, F. Toda, T. Ito, K. Aoshima, Makromol. Chem., 104, 26 (1967). 26. Y Kato, A. Nishioka, Bull. Chem. Soc. Japan, 37, 1614 (1964). 27. S. Okuzawa, H. Hirai, S. Makishima, J. Polym. Sci. A-I, 7, 1039 (1969). 28. F. A. Bovey, J. Polym. Sci., 46, 59 (1960). 29. T. Otsu, B. Yamada, M. Imoto, J. Macromol. Chem., 1, 61 (1966). 30. H. Sobue, K. Matsuzaki, S. Nakano, J. Polym. Sci. A, 2, 3339 (1964). 31. EA. Bovey, G. V. D. Tiers, Fortschr. Hochpolym. -Forschg., 3, 139 (1963). 32. M. Uoi, M. Sumi, S. Nozakura, S. Murahashi, cited in Ref. 33. 33. S. Murahashi, in: IUPAC, International Symposium, Makromol. Chem., 3, 435 (1967) ( = Pure Appl. Chem., 15, nos. 3-4 (1967)). 34. G. Talamini, G. Yidotto, Markromol. Chem., 100, 48 (1967). 35. J. Bargon, K. H. Hellwege, U. Johnsen, Makromol. Chem., 95, 187 (1966). 36. F. A. Bovey, F. D. Hood, E. W. Anderson, R. L. Kornegay, J. Phys. Chem., 71, 312 (1967). 37. H. U. Pohl, D. O. Hummel, Makromol. Chem., 113, 203 (1968). 38. K. C. Ramey, D. C. Lini, G. Statton, J. Polym. Sci. A-I, 5, 257 (1967). 39. L. Cavalli, G. C. Borsini, G. Carraro, G. Confalonieri, J. Polym. Sci. A-I, 8, 801 (1970). 40. H. -G. Elias, P Goeldi, Makromol. Chem., 144, 85 (1971). 41. H. -G. Elias, M. Riva, P. Goeldi, Makromol. Chem., 145, 163 (1971). 42. B. L. Johnson, H. -G. Elias, Makromol. Chem., 155, 121 (1972). 43. H. -G. Elias, P. Geoldi, B. L. Johnson, Adv. Chem. Ser., 128, 21 (1973). 44. R. E. Cais, W. L. Brown, Macromolecules, 13, 801 (1980). 45. D. R. Torrell, F. Evers, Makromol. Chem., 183, 863 (1982).
P r o d u c t s
o f
T h e r m a l
D e g r a d a t i o n
o f
P o l y m e r s
John Liggat Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, Scotland A. Introduction B. Tables Table 1. Main-Chain Acyclic Carbon Polymers Table 2. Main-Chain Carbocyclic Polymers Table 3. Main-Chain Heteroatom Polymers Table 4. Main-Chain Heterocyclic Polymers Table 5. Cellulose and Its Derivatives C. References A.
11-451 11-451 11-451 II-464 II-465 II-473 II-475 II-475
INTRODUCTION
Polymer degradation is a complex phenomenon, and the nature of the chemistry occurring during thermal decomposition can be difficult to determine precisely. The observed products of degradation can be the result of a mixture of primary, secondary or even tertiary decomposition processes, and as a consequence, the distribution of products will depend on such factors as sample thickness and melt viscosity, in addition to the more obvious factors such as temperature, atmosphere and the chemical structure of the polymer itself. It is often overlooked that abnormal structures (terminal unsaturation, head-to-head structures, peroxide links etc.) can also markedly effect polymer stability and product distribution. Products are of three types. Firstly, there are the volatile small molecules (typically of the size of monomer or smaller) which are fairly readily separated and character-
ized. Secondly, there are the larger molecules that represent fragments of the chain. These species are volatile at the degradation temperature but condense outwith the degradation zone. Generally produced as a complex spectrum of oligomers, these fragments are more difficult to separate and characterize in detail, particularly as internal rearrangements of the backbone often occur before and during fragmentation. In many cases, identification is limited to key functionalities but the advent of sophisticated chromatographic and mass spectrometric techniques is leading to increasingly detailed analyses. In particular, the smaller fragments such as dimer and trimer are in principle more readily fully characterized than the larger fragments; nevertheless there often remains some uncertainty, particularly in relation to end groups. The most intractable product is the third type, the residue, which is often (but not always) insoluble, and characterization may again be limited to identification of key functionalities. Naturally, most of the information in the literature relates to the easily identified low molecular weight species, and the data in this section reflects this. In addition, most thermal degradation studies focus on inert rather than oxidizing environments. Following the lead of the previous author, Norman Grassie, the vast majority of the entries included here are concerned with products of the first two types from purely thermal degradation processes under inert atmospheres.
B. TABLES TABLE 1. MAIN-CHAIN ACYCLIC CARBON POLYMERS Polymer
Temperature range (0C)
Degradation products
Refs.
1.1. UNSATURATEDPOLYMERS Poly(acetylene)
650
Poly(butadiene)
325-475 20°C/min to 15% weight loss
Methane (0.87 moles relative to benzene= 1), ethylene (0.47), ethane 82 (0.26), propylene (0.27), propane (0.047), 1,3-butadiene (0.19), cyclopentadiene (0.086), cyclopentene (0.063), benzene (1.0), toluene (0.18), m-xylene (0.091), /?-xylene (0.015), styrene (0.041), o-xylene (0.013), methylstyrene (0.010), frans-p-methylstyrene (0.011), indane (0.0074), indene (0.036), methylindene (0.0072), naphthalene (0.052), 2-methylnaphthalene (0.015), 1-methylnaphthalene (0.018), biphenyl (0.0091), fluorene (1.0), anthracene (0.005) 14.1% of products are volatile at 25°C including 1.5% of monomer 16 among other saturated and unsaturated hydrocarbons; 85.9% of products are larger fragments involatile at 250C Effect of cisltrans ratio; increasing trans content gives more cyclopentene 83 and 1,3-cyclohexadiene and less 4-vinyl-l-cyclohexene and 1,3-butadiene
TABLE 1. cont'd Polymer Poly(butadiene-co-acrylonitrile) (70/30) 25-100 mol% butadiene
Poly(butadiene)-£/ewd-poly(styrene) (0-100wt.%) Poly(butadiene-co-sytrene) (75/25) Poly(chloroprene)
Poly(chloroprene)-fc/em/ poly(methyl methacrylate) Poly(isoprene), synthetic 97% c/s-1,4; 3%, 3,4
natural rubber
Temperature range (0C) 310-400 350-400
Ambient to 500 327-430
chlorinated rubber-blendpoly(vinyl chloride) Poly(perfluoro-4-chloro-l,6-heptadiene)
14.5% of products are volatile at 25°C, consisting of saturated hydrocarbons Main product is structurally modified chain fragments; ammonia and hydrogen cyanide increasing with acrylonitrile content to approximately 4% each by weight of copolymer containing mole 75% acrylonitrile; traces of hydrogen and hydrocarbons up to C 7 Volatile products as for individual polymers
Refs. 10 98
84
160-350
11.8% of products are volatile at 25°C; 1.9% butadiene with 10,16 other saturated and unsaturated hydrocarbons Hydrogen chloride 19 HCl (90% of theoretical), ethylene, chloroprene (trace), chloroprene 85 dimers and other modified chain fragments HCl (trace), methane, ethylene, propylene (trace) 85 Methyl methacrylate, HCl, CO 2 , CO, 86 methyl chloride, methanol. 3.4% isoprene, 8.8% dipentene, small amounts of p-menthene. 2,16,31 In helium; methane (0.04 wt.%), ethylene (0.08), ethane (0.03), 87 propylene (0.15), propane (0.06), isobutylene (0.09), butenes (0.07), methyl butene (0.09), isoprene (29), toluene (0.02), 2,3-dimethyl cyclopentene (1.2), octene (0.05), 2,4-dimethyl cyclohexene (0.16), m-xylene (0.33), l-methyl-4-ethyl cyclohexene (0.18), l,5-dimethyl-5-vinyl cyclohexene (2.5), dipentene (60), C n H i 8 (0.2), C 12 H 18 (0.2), C 15 H 24 (3.5), C 16 H 26 (1.8) 3.9% isoprene, 13.2% dipentene, small amounts of /?-menthene 2,16,31 Dipentene main product at 4500C, optimum yields of isoprene in 32 range 675-8000C, e.g., 58% at 7500C and 13mbar Monomer, dimers (l,7,7-trimethyl-2,2,l-bicyclohept-2-ene, 259 2,5,6-trimethyl 1,3,6-heptatriene, dipentene/d,l-limonene), trimers 3.0% Isoprene, 15.6% dipentene, small amounts of/?-menthene 2,16,31 Styrene, isoprene, dipentene larger chain fragments of both 88 polymers, traces of ethylene, ethane, and propane HCl (almost quantitative), CH 4, C 2 H 4 , and H 2 are minor products 89 formed in the later stages of reaction HCl 90
320-400
Completely volatilized - products unknown.
335-450
Continuous spectrum of saturated and unsaturated hydrocarbons 13,16 from C 2 -C90; lower temperature favors larger fragments Continuous spectrum of saturated and unsaturated hydrocarbons 243 C 1 -C 1 5 ; trace of hydrogen In air; CO 2 , H2O, ethene, propene, propane, cyclopropane, butene, 91 butane, pentene, pentane, hexene, hexane, heptene, heptane, octene, octane, methanol, ethanol, furan, tetrahydrofuran, formaldehyde, acetaldehyde, propanal, acrolein, butanal, isobutanal, pentanal, acetone, methyl vinyl ketone, methyl ethyl ketone, 2-pentanone, 2-hexanone, 2-heptanone, formic acid, acetic acid, propionic acid, acrylic acid, butyric acid, isovaleric acid, hydroxyvaleric acid, crotonic acid, caproic acid, butyrolactone, valerolactone CO, H2O, ethene, series of ketones with general structure 270 R_[_CO-CH 2 -CH 2 -] n -CO-R / where R, R' = - C H 3 , -CH 2 -CH 3 or -CH=CH 2 Broad spectrum of saturated and unsaturated hydrocarbons, ethyl esters 243 and carboxylic acids; ethanol, ethylene, CO2, CO and small amounts of ketene and ethyl acrylate Acetic acid, ketene, CO 2 , ethylene, saturated and usaturated 92 hydrocarbons, chain fragment fraction containing some vinyl acetate units Acetic acid > 99% 93 18.1% monomer together with methane, isobutane, and C 5 and 16 higher saturated and unsaturated hydrocarbons As temperature is increased the yields of fragments smaller than 28 monomer increase at the expense of larger fragments
377 170-400 400-500 Ambient to 500 287-400 384
287-400 450-800 500
gutta percha Poly(isoprene)-&/ew
Degradation products
287-400 Ambient to 500 Ambient to 500
49
1.2. POLY(ALKENES) Poly(ethylene) - , low density
Ambient to 500 264-289
Poly(ethylene-co-carbon monoxide) Alternating copolymer
500
Poly(ethylene-c0-ethyl acrylate) 18:1 mole ratio
Ambient to 500
Poly(ethylene-c0-vinyl acetate) (12-33 mol% vinyl acetate) (38.5% (wt.%) of ester groups) Poly(isobutene)
Ambient to 500 260-290 288-425 Up to 1200
TABLE 1. cont'd Polymer
Temperature range (0C) 325 345 365 300-320
Poly(isopropenylcyclohexane)
400-900
Poly(isopropenylcyclohexane-co-amethylstyrene) (92/8 and 33/67)
400-900
Poly(4-methyl-l-pentene)
291-341
Poly(propylene)
328-410 400-1200 360-400
120-280
200-356 Poly (propylene)-£/end-poly (methyl methacrylate)
Poly(vinylcyclohexane)
Ambient to 500
335-391 360-380
Poly(chlorotrifluoro-ethylene)
Ambient to 500
Degradation products
Refs.
At 4.9% weight loss, products are isobutene (64.3%), CH4 (13.6%), 29 neopentane (10.3%); remainder C2-C12 hydrocarbons At 15.7% weight loss, products are isobutene (78.9%), CH4 (5.9%), 29 neopentane (4.7%); remainder C 2-C12 hydrocarbons At 46.8% weight loss, products are isobutene (81.6%), CH4 (3.9%), 29 neopentane (3.1%); remainder C2-C12 hydrocarbons Two types of f-butyl ended and two types of isopropyl ended terminal 249 monoolefins in range 2-mers to 12-mers Methylenecyclohexane and/or methyl-1-cyclohexene, ethylcyclohexane, 94 toluene, isopropenylcyclohexane, isomer of isopropenylcyclohexane, ethyl benzene, isopropylcyclohexadiene, pentadienylcyclohexane (5 isomers), dicyclohexylpropane, 3-cyclohexenyl-l-cyclohexylpentadiene, dicyclohexylhexadiene Methylenecyclohexane and/or methyl-1-cyclohexane, benzene, toluene, 94 isopropenylcyclohexane, ethylbenzene (92/8 only), decalin (92/8 only), cumene (33/67 only), oc-methylstyrene, styrene, (33/67 only), pentadienylcyclohexane (92/8 only), indene and methyleneindene (33/67 only), naphthalene, dicyclohexylhexadiene (92/8 only). The following from the 33/67 copolymer only: 2-methylnaphthalene, 1-methylnaphthalene, biphenyl, methylstilbene, a-methylstilbene, anthracene/phenanthrene, dihydropyrene After 22 hours at 341°C, 20% residue, 71% saturated and 43 chain fragments; 9% of products volatile at 25°C, comprising isobutene (56%), propane (34%), traces of monomer, and hydrocarbons Saturated and hydrocarbons from C2 upwards, monomer yield 0.17% 13 As temperature is raised, yield of small fragments increases at 28 expense of large fragments At 4000C, chain fragments with 7.05 wt.% of volatile products 95 comprising principally, methane 0.057 wt.%, ethane 0.13, propane 0.078, propene 0.83, isobutene 0.16, butane 0.004, 2-methyl-l-butene 0.010, 1-pentene 0.008, pentane 1.62, 2-pentene (cis and trans) 0.015, 2-methyl pentane 0.074, 2-methyl-1-pentene 1.19, 2,4-dimethylpentane 0.032, 2,4-di-methyl-1-pentene 0.089, 4-methylheptane 0.24, 2,4-dimethyl-l-heptene 2.20, 4,6-dimethylnonane (threo form) 0.042 (erythro form) 0.052, 2,4,6-trimethyl-l-nonene (threo form) 0.055 (erythro form) 0.066 In air; ethene, ethane, propene, propane, isobutene, butane, isobutane, 96 pentadiene, 2-methyl-1-pentene, 2,4-dimethyl-1-pentene, 5-methyl-l-heptene, dimethylbenzene, methanol, ethanol, 2-methyl-2-propene-l-ol, 2-methyl furan, 2,5-dimethylfuran, formaldehyde, acetaldehyde, acrolein, propanal, methacrolein, 2-methyl propanal, butanal, 2-vinyl crotonaldehyde, 3-methyl pentanal, 3-methyl hexanal, octanal, nonanal, decanal, ethenone, acetone, 3-buten-2-one, 2-butanone, l-hydroxy-2-propanone, 1-cyclopropylethanone, 3-methyl-2-buten-2-one, 3-penten-2-one, 2-pentanone, 2,3-butanedione Under 254 nm radiation; additional methane and ethylene are formed 97 compared with the thermal reaction Poly (methyl methacrylate) stabilized by blending with polypropylene; 99 pre-irradiation with 2537 A radiation at ambient temperature reduces amount of methyl methacrylate formed on subsequent thermal degradation; missing methyl methacrylate units appear in a chain fragment fraction Small amounts of cyclohexane, cyclohexane, methylcyclohexene, methyl 2,3 cyclohexane, vinylcyclohexene, vinylcyclohexane, ethylcyclohexane with larger chain fragments Cyclohexane (main product), cyclohexene, vinylcyclohexane, vinylcyclo 100 hexane oligomers, methane, ethane, ethylene, propane, propylene, butane, butylene, hydrogen Monomer, traces of dichlorodifluoroethene, chloropentafluoropropene, 261 trichlorotrifluoroethane
References page II - 475
TABLE 1. cont'd Polymer
Temperature range (0C)
Degradation products
Refs.
1.3. POLY(ACRYLICS), POLY(METHACRYLICS) Poly(acrylic acid)
- , methyl ester
Ambient to 500
292-399
Up to 980
50 - , ethyl ester
300-500 50 Ambient to 500
- , w-propyl ester
300-500
- , isopropyl ester
250-500
- , n-butyl ester
300-500 50
- , tert-butyl ester -, 2-ethyl hexyl ester - , benzyl ester
>160 300-500 260-300
-, 1,1,5-trihydroperfluoroamyl ester
300-315
- , 2,2,2-trichloroethyl ester
319
- , oc-bromo-, methyl ester - , a-chloro-, methyl ester - , a-chloro-, .sec-butyl ester -, a-cyano-, methyl ester - , a-phenyl-, methyl ester Poly (acrylic acid, magnesium salt)
110-150 600 600 190 > 180 210-280 Ambient to 500
Poly(acrylic acid, calcium salt)
Ambient to 500
CO, CO 2 , H 2 O, CH 4 , acetone, ketene, ethene, propylene, 1-butene, 297 methyl vinyl ketone, benzene, acrylic acid, toluene, xylene, short chain fragments such as dimer to octamer with unsaturated and anhydride functionalities 26% of products are volatile at 25°C, mainly methyl alcohol and 2,3 carbon dioxide with traces of monomer and methyl methacrylate and C 4-C 6 oxygenated compounds (74% of products are large chain fragments involatile at 250C) Methanol (1.9%), methyl formate (trace), methyl acetate (1.4%), methyl 101 acrylate (19.0%), methyl methacrylate (1.9%), saturated ester (2.1%), dimethyl glutarate (7.5%), methyl 4-methoxycarbonyl-pent-4-enoate (11.6%), trimethyl pentane 1,3,5-tricarboxylate (0.6%) methyl 4,6-di-methoxycarbonylhept-6-enoate (53%), saturated and tetramers (1.0%) Irradiated with high-pressure mercury lamp; methanol, formaldehyde, 102 methyl acetate, methyl formate, CO 2 , CO, H 2 , CH 4 Major products, carbon dioxide, ethylene, ethanol, and chain fragments; 103 minor products, ethane, ethyl acrylate, and ethyl methacrylate Irradiated with high-pressure mercury lamp; CO, CO 2 , ethanol, acetalde- 104 hyde, ethane, ethyl formate, acetal, ethyl propionate Ethylene, carbon dioxide, trace of ketene, ethanol (major product), 243 various ethyl esters (see Ref.) Major products carbon dioxide, propene, propanol, and chain fragments; 103 minor products, propane, carbon monoxide, hydrogen, rc-propyl acrylate, and w-propyl methacrylate Major products carbon dioxide, propene; minor products isopropanol 105 with trace carbon monoxide Major products carbon dioxide, 1-butene, butanol, and chain fragments; 103 minor products, butane, /i-butyl acrylate, and n-butyl methacrylate Irradiated with high-pressure mercury lamp. CO, CO 2 rc-butanol, 104 butyraldehyde, «-butene, n-butyl formate, n-butyl valerate (after prolonged exposure) 86% isobutylene, 11% water, 3% carbon dioxide 4 Carbon dioxide, 2-ethyl-l-hexene, 2-ethyl-l-hexanol 103 Major products are benzyl alcohol, chain fragments, partially crosslinked 1 residue; minor products are CO 2 , toluene, CO, CH 4 , H 2 CO 2 , benzyl alcohol, and low polymers 106 Oligomers, 1,1,5-trihydroperfluoroamyl alcohol, monomer, 1,1,5-trihydro- 107 perfluoroamyl methacrylate 2,2,2-Trichloroethanol (80%), monomer (9%), 1,1-dichloroethene, 263 2-chloroethanal, 2,2-dichloroethanal, 1,1-dichloropropane, 1,1,1 -trichloroethane, 2,2,2-trichloroethylethanoate, 2,2,2-trichloroethyl chloromethanoate, 2,2,2-trichloroethylpropanoate, 2,2,2-trichloroethylmethacrylate, 2,2,2-trichloroethyl chloroethanoate, 2,2,2-trichloroethyl-2-chloroacrylate Methylbromide, hydrogen bromide 5 CO 2 , propene, methyl bromide, vinyl bromide 305 CO 2 , propene, methyl chloride, monomer 306 sec-Butyl chloride, butylene, hydrogen chloride 7 Yellows and some monomer formed 6 Monomer is the sole product 8 CO, CH 4 , CO 2 , acetone, ketene, ethene, propene, 1-butene, benzene, 312 toluene, xylene, cyclopentene, methyl ethyl ketone, diethyl ketone, methyl-«-propyl ketone, di-w-propyl ketone, methyl vinyl ketone, methyl isopropenyl ketone, methyl isopropyl ketone, ethyl vinyl ketone, trace amounts of methyl-w-butyl ketone, cyclopentanone, cyclohexanone, acrolein, ethanal and butanal, chain fragments, some monomer CO, CH 4 , CO 2 , acetone, ketene, ethene, propene, 1-butene, benzene, 312 toluene, mesitylene, xylene, methyl ethyl ketone, diethyl ketone, methyl-H-propyl ketone, methyl-fl-butyl ketone, ethyl vinyl ketone, methyl propenyl ketone (trace), ethyl propyl ketone (trace), 3-methyl-cyclopentanone, cyclohexanone (trace), cyclohexa-2-enone,
TABLE 1. cont'd Polymer
Temperature range (0C)
Poly (acrylic acid, sodium salt)
Ambient to 500
Poly(acrylic acid, potassium salt)
Ambient to 500
Poly(methyl acrylate-co-methyl methacrylate) (mole ratios 112/1-2/1)
Ambient to 500
Poly (methyl acrylate-co-acryloyl chloride) 6, 15, 41, 83 mol% AC
Ambient to 500
Poly (methyl acrylate-co-2-bromoethyl methyacrylate) (10-82 mol% methyl acrylate) Poly(methyl acry\ate)-blendpoly((2-bromoethyl methacrylate) (50/50, w/w) Poly(/i-butyl acrylate-co-methyl methacrylate) (3.9-93.4 mol% butyl acrylate)
Ambient to 500
Ambient to 500
313-332
165
Poly(terf-butyl acrylate-co-glycidyl methacrylate) (34/66) Poly(methyl-oc-chloroacrylatec0-2,2,2-trifluoroethyl methacrylate) (70/30) Poly(methyl-a-chloroacrylate-co-2,2,2trifluoroethyl methacrylate) (70/30) Poly(acrylonitrile)
0-700 Ambient
Ambient <200 250-280
280-450 250-350 235 - , a-chloro - , a-phenyl Poly (aery lonitrile-co-2-bromoethyl methacrylate (50/50, mol/mol) Poly(acrylonitrile-co-methyl methacrylate)( 1/410-1/8)
150-200 Ambient to 500 Ambient to 500 Below 310 310-500 220-280
Degradation products
Refs.
2-methyl-cyclohexanone, l-methyl-cyclohexa-l-ene-3-one (trace), acrolein, mesityl oxide, ethanal, propanal, butanal, chain fragments, some monomer CO, CH 4 , CO 2, ketene, 1-butene, propene, acetone, methyl ethyl ketone, 303 methyl isopropyl ketone, methyl-fi-propyl ketone, diethyl ketone, methyl propenyl ketone, 3-hexanone, toluene, 2-hexanone, 1,3-cyclopentadiene, cyclopentanone, 2-methyl cyclopentanone, mesityl oxide, xylenes, benzene, propionaldehyde, acrolein, acetaldehyde, ethene, short chain fragments, traces of monomer CO, CH4, CO2, ketene, 1-butene, propene, acetone, methyl ethyl ketone, 303 methyl rc-propyl ketone, 1,4-cyclohexadiene, toluene, 1-methyl-1,3-cyclohexadiene, 2-hexanone, cyclopentene, 1-methyl cyclopentene, mesityl oxide, xylenes, benzene, ethene, cyclopentanone, 1,3-cyclopentadiene, diethyl ketone, short chain fragments, traces of monomer Monomers, CO2, chain fragments larger than monomer, H2; 108,109 more stable than poly(methyl methacrylate); rapid decrease in molecular weight; products of phtodegradation at 170° by 254 nm radiation are qualitatively similar Acrylic acid, HCl, H2O, CO, CO 2, acryloyl chloride, methyl acrylate, 262 methyl acrylate chain fragments, anhydride and y-lactone structures, chloro-methane, methyl methacrylate, methanol, 3,5-(6-chloro-2-pyrone) and fragments thereof, C6, C9, C12, C15 fragments. Relative yields depend upon copolymer composition CO 2, ketene, methyl bromide, acetaldehyde, methyl acrylate, methanol, 110 1,2-dibromoethane, methyl methacrylate, 2-bromoethanol, ethyl methacrylate, CH 4 , CO, H 2 modified chain fragments CO2, ketene (minor), methyl bromide, vinyl bromide (minor), acetalde111 hyde, methanol, methyl methacrylate, methyl acrylate, 1,2-dibromoethane, 2-bromoethyl methacrylate 1-Butene, carbon dioxide, butanol methyl methacrylate, butyl acrylate, 112 and butyl methacrylate; small quantities of methane, ethane, propane, butane, ethylene, propene, cis, and trans 2-butene, hydrogen, and carbon monoxide increase with butyl acrylate content of the copolymer Under 2537 A radiation; methyl methacrylate with smaller quantities of 113 n-butyl acrylate, n-butanol, n-butyraldehyde, hydrogen, carbon monoxide, and methane; a chain fragment fraction increases with rc-butyl acrylate content CO, CO 2, propene, ethanal, isobutene, acrolein, allyl alcohol 114 Gamma Radiolysis; CH 4 , CO, ethylene, ethane, CH 3 OH, CHF3, HCl, C 3 H 6 , CO 2 , C 2 H 3 F, CH 3 Cl, methyl formate, CH 3 CH 2 Cl, CHF3, CH 3 CF 3 , C H 2 = C ( C H 3 ) C O O C H 2 C F 3 Gamma Radiolysis; CH 4 , CO, ethylene, ethane, CH 3 OH, HCl, C 3 H 6 , CO 2 , CH 3 Cl, methyl formate, CH 3 CH 2 Cl, CH 2 Cl 2 , CHCl3 Colours through yellow, orange, red, and black 12% of products are volatile at 25°C, consisting of hydrogen cyanide, acrylonitrile, and vinyl acetonitrile; 88% of products are involatile at room temperature Five major volatile products are cyanogen, HCN, acrylonitrile, acetonitrile, vinyl acetonitrile; involatile residue remains NH 3 , HCN HCN, hydrogenated acrylonitrile, dimer and trimer, acetonitrile, methacrylonitrile Hydrogen chloride Hydrogen chloride and small amount of HCN at higher temperatures High yields of monomer Ethylene, CO 2 , vinyl bromide acetaldehyde, 1,2-dibromoethane Propane, isobutene, CO 2 , HCN, isocyanic acid, yellow-chain fragment fraction Only methyl methacrylate from 410/1 and 40/1 (molar ratio) copolymers; methyl methacrylate and small amounts of acrylonitrile from 16/1 and 8/1 copolymers; rapid decrease in the molecular weight of all copolymers
115
115 9 10,11
12 116 117 118 119 119 120 121 121
References page II - 475
TABLE 1. cont'd Polymer
Temperature range (0C) 160
Poly(acrylonitrile-c0-methyl vinyl ketone) Poly(acrylonitrile-co-styrene) (0/100-50/50, mol/mol)
(1.86-96.62 mol% acrylonitrile)
Poly(acrylonitrile-co vinyl acetate) (7.5 wt.% vinyl acetate) Poly(acrylonitrile-co-methyl acrylate-co-vinyl bromide) (methyl acrylate, 10 wt.%; vinyl bromide, 5 wt.%) Poly(a-chloroacrylonitrile-co methyl methacrylate) (0-50 mol% a-chloroacrylonitrile) Poly (aciylonitrile)-We/idpoly(methyl methacrylate) (50/50, w/w) Poly(acryloyl chloride) Poly(methacrylic acid)
292
500
260 180-320
> 150 Ambient Up to 320 320-500 Ambient to 500 200 900
- , methyl ester
- , ethyl ester - , rc-propyl ester - , iso-propyl ester - , fz-butyl ester - , wo-butyl ester - , s^c-butyl ester - , tert-butyl ester
-, -, -, -, -, -, -, -,
n-amyl ester wo-amyl ester 1,2-dimethylpropyl ester neopentyl ester 3,3-dimethylbutyl ester 1,3-dimethylbutyl ester 2-bromoethyl ester 2-sulfoethyl ester
- , 2-chloroethyl ester
170-300 246-400 160 100-400 250 245 250 250 250 170 250 250 180-200 < 180 250 250 250 250 250 250 Ambient to 500 50-600 600 600 268
Degradation products Photodegradation by 254 nm radiation gives methyl methacrylate from 410/1 to 8/1 copolymers with a 8/1 copolymer; rapid decrease in the molecular weight of all copolymers Production of water from poly(methyl vinyl ketone) accelerated by copolymerization with acrylonitrile Acrylonitrile causes increase in rate of chain scission; proportion of acrylonitrile among degradation products greater than from pure polyacrylonitrile; chain fragments increase with acrylonitrile content of copolymer; styrene, acrylonitrile, toluene, benzene, four dimers, and four trimers Hydrocyanic acid, acetonitrile, acrylonitrile, propionitrile, toluene, ethyl benzene, styrene, methane, ethylene, ethane, C 3 hydrocarbons, but-1-ene, prop-l-ene-3-nitrile, isopropylnitrile, benzene HCN, hydrogenated acrylonitrile, dimer and trimer, acetonitrile, methacrylonitrile, acetic acid CH3Br, HBr, H 2 O, CO 2 , CH 3 OH, NH 3 , HCN, hydrogenated acrylonitrile, dimer and trimer, acetonitrile, methacrylonitrile, naphthyridine fragments Hydrogen chloride, methyl methacrylate, oc-chloroacrylonitrile
Refs. 121
122 123
124
117 117
125
Under 254 nm radiation. HCl, CO 2 , methyl chloride, methyl formate, 126 methanol, methyl methacrylate, CO, CH 4, H 2 NH 3 , HCN, MMA 127 Chain-fragment fraction and small amounts of CO, CO 2 , methanol, CH 4 Acrylic acid, HCl, H 2 O, CO, acryloyl chloride, 3,5-(6-chloro-2-pyrone) 262 and fragments thereof, C6, C9, Cj 2 , C15 fragments Almost quantitative yields of H 2 O, traces of monomer, residue of 33 poly(methacrylic anhydride) CO 2 , propene, butenes, pentenes, pentadienes, hexene, hexadienes, 128 hexatrienes, benzene, toluene, heptene, heptatriene, methacrylic acid, xylene, octatriene, octadienyne, nonatriene, hexadienoic acid, decatriene, decatetraene, decapentaene, undecatriene, methylbenzoic acids, trimethylbenzoic acid 100% monomer 34, 35 As temperature is raised fragmentation increases to give complex 2 series of products and monomer yields correspondingly decreases 100% monomer under 253.7nm radiation 36 Under 254 nm radiation; 100% monomer 129 Monomer 37 Monomer, ethanol, ethanoic acid 300 Monomer 37 Monomer 37 40% monomer and traces of 1-butene 38 100% monomer under 253.7nm radiation 38 Monomer 37 Monomer and small amount of olefin by cracking of side chain 37 High yields of isobutylene and water, 1% monomer, trace of methacrylic 39 acid, residue of poly(methacrylic anhydride) 100% monomer under 253.7 nm radiation Monomer 37 Monomer 37 Monomer and small amount of olefin by side chain cracking 37 Monomer 37 Monomer 37 Monomer and small amount of olefin by side chain cracking 37 2-Bromoethyl methacrylate (>95%), CO 2 (< 1%), vinyl bromide (< 1%) 130 CO, CO 2 , H 2 O, SO 2 , ethene 290 CO, CO 2 , propene, acetaldehyde, methyl bromide, butene, 305 vinyl bromide, ethyl bromide, methyl methacrylate CO 2 , propene, acetaldehyde, vinyl chloride, ethyl chloride, monomer 306 Monomer (99%), traces of acetaldehyde, methyl methacrylate, 268 1,2-dichloroethane, ethylene methacrylate
TABLE 1. cont'd Polymer
Temperature range (0C)
Degradation products
Refs.
Poly(methacrylic acid), 2-fluoroethyl ester - , 2,2-dichloroethyl ester
600
CO 2, vinyl fluoride, acetaldehyde,
242
- , 2-methoxyethyl ester
Ambient to 300 Ambient to 500
Monomer (90.7%), chloroacetaldehyde (8%), 1,1,2-trichloroethane (0.5%), 268 2,2-dichloroethanol, methacrylic acid (0.1%), 2-chloroethylene methacrylate (0.1%) Monomer, CO 2 309 Monomer, CO 2 , CO, CH4, ethene, formaldehyde, isobutene, methyl 309 vinyl ether, methanol CO 2 , propene, acetaldehyde, methyl bromide, butene, ethyl bromide, 305 bromocyclopropane or 2-bromopropane 2-Hydroxyethyl methacrylate (20% at 5000C), ethylene dimethacrylate 131 (6%at 500°C)(main products), ethylene glycol, 3-methyl-5-hydroxy6-valerolactone (probably), 1,2-di-iospropenyl-oxyethane (probably), CO, CO2, methane, ethylene, ethane, propane, H2O Gamma radiolysis; CH4, CO, ethylene, ethane, CH3OH, CH3F, C 3 H 6 , 115 CO 2 , C 2 H 3 F, methyl formate, CH3CHFOH, CHF3, CF3CH3, CF3OH, CH2 = C(CH3)-COOCH2CF3 CO 2 , vinylidene fluoride, trifluoroacetaldehyde, trifluorethanol, 310 monomer CO 2 , propene, vinyl chloride, vinylidene chloride 306 1,1-Dichloroethene, chloroform, methyl methacrylate, methacrylic acid, 300 2,2,2-trichloroethanol, 2,2,2-trichloroethyl acrylate, 2,2,2-trichloroethyl methacrylate, 2,2-dichloroethyl methacrylate, CH2 = C(CH3)-COOCHI=CCl2 or CH2 = C(CH3)-COOCCl = CHCl CO 2 , trifluoracetaldehyde, acetaldehyde, 1,1,1,3,3,3-hexafluoropropane, 310 hexafluoro-isopropylformate CO 2 , SO 2 , phenol, bisphenol S, hydroquinone, fragments of backbone, 248 benzene sulfonic acid CO 2 , CH4, CO, H 2 , propene, isobutene, dimethyl ketene, acrolein, 283 diallyl ether, allyl methacrylate monomer and dimer, chain fragments including anhydride structures from side-group cyclization and an aliphatic ketone in the vicinity of unsaturation Monomer, some CO2 314 CO, CO 2 , dimethyl ketene, isobutene, propene, acrolein, allyl alcohol, 302 glycidyl methacrylate, glycidol, short chain fragments with some unsaturation Isocyanic acid, NH 3 , HCN, isobutene, CO2 (trace), methacrylonitrile 132 (trace) Ethylene, butene-1, isobutene, acetylene, CO 2 , CH4, CO, acetone, 133 isopropylaldehyde, methacrolein, butyraldehyde, methyl ethyl ketone, benzene (trace), methyl isopropyl ketones, methyl isopropenyl ketone, diethyl ketone, methyl rc-propenyl ketone, cyclopentanone, methyl cyclopentanone, dimethyl cyclopentanone, dimethyl cyclopentenone and traces of toluene, di-isopropyl ketone, mesitylene, mesityl oxide CO2, dimethyl ketene trace amounts of CO, CH4, isobutene, butene-1, 134 ethylene, acetylene, benzene toluene isobutyraldehyde, methyl ethyl ketone, methyl isopropenyl ketone, diethyl ketone, methyl isopropenyl ketone, di-isopropyl ketone, cyclopentanone, 2-methyl cyclopentanone, 2,5-dimethyl-cyclopentanone, 2,5-dimethylcyclopent-3-ene-l-one, methacrolein, butyraldehyde Monomer 194 Monomer, phthalic anhydride, diethylene glycol, C 2 H 4 , propylene, CO2 194 CO 2 , alkenes, CH4, CO, propanal methanol (major), acetone, 2-methyl 135 propanal, methacrolein, butanal, methyl ethyl ketone, methyl isopropyl ketone, methyl isopropenyl ketone, methyl methacrylate (major), methyl prop-2-enyl ketone, toluene, di-isopropyl ketone, cyclopentanone, 2-methyl cyclopentanone, 2,5-dimethyl cyclopentanone, 2,5-di-methyl cyclopent-3-enone. Relative yields depend upon salt and copolymer composition Methyl methacrylate, 2-bromoethyl methacrylate, traces of vinyl bromide 130 and CO2
- , 2,3-dibromopropyl ester
600
-, 2-hydroxyethyl ester
375-500
- , 2,2,2-trifluoroethyl ester
Ambient 600
- , 2,2,2-trichloroethyl ester
600 240
- , hexafluoroisopropyl ester
600
- , bisphenol S ester
464
- , allyl ester
Ambient to 500
- , phenyl ester - , glycidyl ester
Ambient to 500 Ambient to 500
- , ammonium salt
Ambient to 500
- , Li, Na, K, and Co salts
Ambient to 500
- , Mg, Ca, Sr, and Ba salts
Ambient to 500
Poly[a-co-(diethylene glycol phthalate)dimethacrylate] Poly(methyl methacrylate-co-alkali (metal methacrylates) (Li, Na, K) (0-100 mol%)
300 400 Ambient to 500
Poly (methyl methacrylate-co2-bromoethyl methacrylate) (50/50, mol/mol) Poly(methyl methacrylateco-methacrylamide)
Ambient to 500 Up to 340
fluoroacetaldehyde
> 35 mol% methacrylamide. MMA, methanol, NH3, H 2 O
310
146
References page 11-475
TABLE 1. cont'd Polymer
Temperature range (0C) >340
Poly(methyl methacrylate-comethacrylic acid)
Poly(methyl methacrylate-co2-chloroethylmethacrylate) 22 mol% CEMA Poly (methyl methacrylateco2,2,2-trichloroethyl methacrylate) 24 mol% TCEMA Poly (methyl methacrylatecomethyl-oc-chloroacrylate) 38 mol% MCA Poly(methyl methacrylatec6>-2-bromoethyl methacrylate) 22 mol% BEMA Poly (methyl methacrylateco-2,3-dibromopropyl methacrylate) 16 mol% DBPMA Poly (methyl methacrylateco-methyl-a-bromoacrylate) 22 mol% MBA Poly(methyl methacrylateco-chlorotrifluoroethylene) 7.7 mol% MMA 77.7 and 85.7 mol% MMA Poly(methyl methacrylateco-2-sulfoethyl methacrylate) 20, 40, 60 mol% MMA Poly(methyl methacrylateco-4-vinylpyridine) 22, 35, 46, 56 mol% 4vinyl pyridine Poly (methyl methacrylatecophenyl methacrylate) 9, 18, 47, 88 mol% PMA
<300 >300 900
600
Degradation products Methacrylamide; chain fragments and small amounts of CH4, CO2, CO, HCN, methacrylonitrile and isobutene < 10 mol% methacrylamide. Degradation becomes progressively more like that of PMMA Water and methanol Methyl methacrylate, CO2, CO, CH4 (50/50 and 75/25); CO2, propene, butenes, pentenes, pentadienes, hexene, hexadienes, hexatrienes, benzene, methyl isobutyrate, methyl methacrylate, toluene, heptene, heptatriene, methyl pentenoate, methacrylic acid, xylene, octatriene, octadienyne, nonatriene, hexadienoic acid, decatriene, decatetraene, decapentaene, undecatriene, methylbenzoic acids CO2, propene, acetaldehyde, vinyl chloride, ethyl chloride, methyl methacrylate
Refs. 146 146 136 128
306
600
CO2, propene, vinyl chloride, vinylidene chloride, dichloroacetaldehyde, methyl methacrylate
306
600
CO2, propene, methyl chloride, methyl methacrylate
306
600
CO2, propene, acetaldehyde, methyl bromide, butene, vinyl bromide, methyl methacrylate
305
600
CO, CO 2 , ethene, propene, methyl bromide, butene, vinyl bromide, ethyl bromide, 1-bromopropene, 2-bromopropene, cyclopropyl bromide, methyl methacrylate
305
600
CO 2 , acetaldehyde, methyl bromide, butene, vinyl bromide, unidentified alkenyl bromides, methyl methacrylate
305
Ambient to 500
HCl, CO 2 , CH3Cl, C 2 F 3 Cl (monomer), C3F5Cl, C 2 F 3 Cl 3 , methyl methacrylate, chain fragments possibly with some lactonization
281
Ambient to 500 50-600
HCl, CO 2 , CH3Cl, C 2 F 3 Cl (monomer), methyl methacrylate CO, CO2, H2O, SO2, ethene, methanol, methyl methacrylate (only 60 and 80 mol% methyl methacrylate copolymers)
281 290
Ambient to 500
4-vinyl pyridine, methyl methacrylate, traces of pyridine and 4-methyl pyridine
260
Ambient to 500
CO 2 , isobutene, ketene, formaldehyde, methanol, methyl methacrylate, phenyl methacrylate, chain fragments including six-membered anhydride ring structures. Product distribution varies with copolymer composition with non-monomer products most pronounced at low PMA contents CH4, CO, CO 2 , propene, isobutene, dimethyl ketene, acrolein, allyl alcohol, glycidol, glycidyl methyl ether, methyl methacrylate, glycidyl methacrylate, chain fragments. Distribution varies with copolymer composition CO, CH4, CO 2 , ethene, propene, isobutene, aziridine, methanol, methyl methacrylate, a-methylstyrene, 2-phenyl-2-butene, l-r-butylamino-2-isopropenylamino-ethane, 2-r-butylaminoethyl-ethylisopropenylamine, 2-aminoethyl-2-?-butylaminoethylisopropenylamine, oligomers - principally butylaziridine based
314
Poly(methyl methacrylatecoglycidyl methacrylate)
Ambient to 500
Poly (methyl methacrylate -/?/6>c£-j-butylaziridine) ABA type copolymer with MW 12000 butylaziridine (B) and MW 16000 MMA (A) Poly(methyl methacrylate-co-styrene)
Ambient to 600
Poly (methyl methacrylate-covinyl acetate) (5-40 mol% vinyl acetate)
Ambient to 500
260-340
286
287
Methyl methacrylate, styrene and oligomers of styrene; formation of 137 oligomers of styrene strongly inhibited by presence of methyl methacrylate units Acetic acid, methyl methacrylate, methyl acetate, chain fragment fraction, 92 ketene, CO2
TABLE 1. cont'd Polymer
Temperature range (0C)
Poly(methyl methacrylate-co-vinyl bromide) (6-75 mol% vinyl bromide)
Ambient to 500
Poly(2-bromoethyl methacrylateco-styrene) (50/50, mol/mol) Poly(methyl methacrylate)-blendammonium polyphosphate
Ambient to 500 Ambient to 450
Poly (methyl methacrylate)-&/e/2
Ambient to 500
Poly(methyl methacrylate)-&/endpoly (vinyl acetate) (10/1-1/1, w/w) Poly(methyl methacrylate)-£/era/poly(vinyl bromide) (50/50, mol/mol) Poly(methyl methacry\ate)-blendpoly(vinyl chloride) Poly(methacrylamide)
Ambient to 500
Poly(methacrylonitrile)
Ambient to 500 Ambient to 500 Up to 340 Above 340 Ambient to 500 < 200 220-270 Ambient to 500
Poly(methacrylonitrile-c0styrene) 10:1 mole ratio
Ambient to 500
Poly(methacrylonitrileco-styrene) 1:1 mole ratio
Ambient to 500
Poly(methacrylonitrileco-styrene) 1:10 mole ratio
Ambient to 500
1.4.
Degradation products
Refs.
Methyl methacrylate, methyl bromide, methanol, CO2, methanol, HBr, CO, H2 and other unidentified minor products. Relative amounts depend upon copolymer composition Styrene, 2-bromoethyl methacrylate, modified chain fragement fraction. Minor products; ethylene, CO 2, HBr, vinyl bromide, acetaldehyde H2O and NH3 from ammonium polyphosphate. Methyl methacrylate (major product), CO, CO2, methanol, dimethyl ether, hydrocarbons, high boiling chain fragments Polymers degrade separately without interaction to give same products as polymers degraded separately; copolymers and mixtures of the same molar compositions can be distinguished by degradation behavior Methyl methacrylate, acetic acid, methyl acetate, methanol, CO2, butene, benzene, ketene Methyl methacrylate, HBr, CO, CO 2 and other unidentified products
138
139 140
141
142 143
Major products: HCl, methyl methacrylate; minor products: CO 2 , 144,145 methyl chloride, benzene NH 3 and H 2 O 146 Chain fragments (50%) in which a high proportion of amide groups have 146 been converted to cyclic imides; small amounts of CO 2, CH 4, HCN NH 3 , HCN, isobutene, CO 2 (trace), methacrylonitrile (trace) 132 Non-volatile material, coloration through yellow, orange, and red 40 50-100% monomer depending upon pretreatment and purity of polymer 40 Ethene, propene, isobutene, HCN, CO 2 (from benzoyl peroxide end 277 groups), methacrylonitrile (major product), 2-cyanobutane, 2-cyanopentene, CH 4 Ethene, isobutene, HCN, methacrylonitrile, styrene, toluene, 279 a-methylstyrene, p-methylstyrene, 2-phenylbutene, 4-cyano2,4-dimethylpentene, 4-phenyl-2-methylbutene, 3-phenyl2-propenenitrile, chain fragments Ethene, isobutene, HCN, methacrylonitrile, styrene, toluene, 279 a-methylstyrene, 4-phenylbutene, 4-phenyl-2-methylbutene, 3-phenyl-2-propenenitrile, chain fragments Ethene, isobutene, HCN, methacrylonitrile, styrene, toluene, 279 a-methylstyrene, p-methylstyrene, 4-phenylbutene, allylbenzene, 4-phenyl-2-methylbutene, 3-phenyl-2-propenenitrile, chain fragments
POLY(VINYLS)
Poly(tert-butyl-Af-vinyl carbamate) Poly(chlorotrifluoroethylene) (KEL-F)
185-220 347-418
Poly(l,l-dichloro-2,2-difluoroethylene) Poly(perfluoroheptene) Poly(perfluoropropylene) Poly(tetrafluoroethylene)
240 210-270 280-400 504-538 1200 600-700
Poly(trifluoroethylene) Poly(vinyl acetate)
380-800 213-235 300 280-350
Poly (vinyl acetate) in presence of zinc bromide Poly(vinyl acetate-comaleic anhydride) alternating copolymer Poly (vinyl acetate-cocrotonic acid) alternating copolymer
Ambient to 500
Equal amounts of CO 2 and isobutylene, in yields ranging from 43 to 60% 196 25% of products volatile at 25°C-monomer with traces of C 3 F 5 Cl 14 and C 3 F4C1 2 ; 72.1% of larger chain fragments involatile at 25°C 20% black involatile residue; 80% monomer 22 100% monomer 49 100% monomer 49 >95% monomer, 2 - 3 % C 3 Fe, no larger fragments (in vacuum) 14 Monomer yield drops, larger fragments appear (in vacuum) 23 At 6.66 mbar pressure; pure monomer; at 1013 mbar pressure, 24 15.9% monomer, 25.7% C 3 F 6 , 58.4% C 4 F 8 High yields of HF and products involatile at 25°C 23 Quantitative yields of acetic acid 71 Small amounts of aromatics including benzene 71 Acetic acid, benzene, naphthalene, toluene, styrene, ethyl benzene, 147 propenyl benzene, propylbenzene, methylnaphthalene, ethylnaphthalene, propenylnaphthalene, propylnaphthalene, anthracene, methylanthracene, ethylanthracene, propylanthracene Acetic acid produced as low as 1000C 148
Ambient to 500
Acetic acid, CO 2, H 2 O, maleic anhydride, CO
240
Ambient to 500
Ethene, propene, acetic acid, CO 2 , propanoic acid, 2-methylpropanoic acid, butanoic acid, cyclopentanone, some unsaturated cyclic and acyclic aliphatic ketones, some chain fragments containing lactones
241
References page 11-475
TABLE 1. cont'd Polymer Poly (vinyl acetate-comethylvinylidene cyanide) Alternating with 10-15 mol% VA homosequence Poly (vinyl acetate-co-styrene) (5-20 mol% vinyl acetate) Poly(vinyl acetate-co-vinyl alcohol) (50-99 mol% vinyl alcohol) Poly (vinyl acetate-co-vinyl chloride)
0
Temperature range ( C) 285-350
Ambient to 500 0-600 Ambient to 500
180 Poly (vinyl acetate-co-vinyl fluoride) (91:9 to 1:89) (80:20 to 23:77) Poly (vinyl acetate)-blendpoly(styrene) (1/1, w/w) Poly(vinyl acetate-blendpoly (vinyl chloride) Poly (vinyl alcohol)
Poly (vinyl bromide) Poly(vinyl butyrate) Poly(A^-vinylcarbazole)
200-500
Vinyl acetate, acetonitrile, HCN, acetic acid, acetamide, 2-methyl1-aminonaphthalene, 3-cyano-3-pentene Acetic acid, styrene, chain fragment fraction, ketene, CO 2 Acetaldehyde, acetone, benzene, crotonaldehyde, acetic acid
Refs. 266
92 154
Bulk polymer; hydrogen chloride and acetic acid in the proportions of 155 the monomers in the copolymer; at each end of the composition range, incorporation of the comonomer results in a copolymer less stable than the homopolymer; minimum stability at 40-50 mol% vinyl acetate In tritolyl phosphate solution; similar to bulk polymer with minimum in 156 stability at 30-40 mol% vinyl acetate Hydrogen fluoride, acetic acid, hydrocarbons 150
200-500 Ambient to 500
Hydrogen fluoride, HCl, hydrocarbons Products as for individual polymers
Ambient to 500
Ambient to 500
Acetic acid, HCl, and traces of CO 2, ketene, acetyl chloride, CO 157 and CH 4 Quantitative yields of H 2 O 72 Main products H 2 O and C 2 H 5 OH, with aldehydes 73 CH 3 -(CH = CH) n -CHO and ketones C H 3 - ( C H = C H ) n - C O C H 3 where n = 0,1,2, etc. HBr, ethylene, benzene, and other unidentified minor products 143 Butyric acid 74 Below 350°, monomer; above 350°, monomer and low-molecular 175 weight oligomers Monomer (49% of total volatiles at 3000C, 39% at 5000C) ethane, 244 ethene, propene, n-butane, isobutene, cis and trans but-2-ene, 1,3-butadiene, 2-methylbutadiene, trace amounts of C 5 and C 6 hydrocarbons Monomer (83% of total volatiles at 3000C, 67% at 5000C), ethane, 244 ethene, propene, w-butane, isobutene, cis and trans but-2-ene, 1,3- butadiene, 2-methylbutadiene, trace amounts of C 5 and C 6 hydrocarbons Monomer (48% of total volatiles at 3500C, 40% at 500°C), ethane, 244 ethene, propene, /i-butane, isobutene, cis and trans but-2-ene, 1,3-butadiene, 2-methylbutadiene, trace amounts of C 5 and C 6 hydrocarbons Quantitative yields of HCl 75 Saturated and unsaturated, aliphatic and aromatic hydrocarbons are 75 produced with benzene and toluene in high yield In helium; quantitative yield of HCl, remainder residue and 76 hydrocarbons; benzene is major volatile hydrocarbons product Aliphatic hydrocarbons, benzene (major product), toluene, ethylbenzene, 149 o-xylene, monochlorobenzene, styrene, vinyl toluene, p-dichlorobenzene, o-dichlorobenzene, indene, 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene, naphthalene, a-methylnaphthalene, (3-methylnaphthalene; effect of ZnO, SnO 2 , and Al 2 O 3 on the yields of products is also recorded HCl, CO 2 , ethene, ethane, propane, 1-butene, 2-butene, 1-pentene, 267 cyclopentene, n-pentane, 2-methylbutane, 1,3-pentadiene, 2-methyl-1,3-pentadiene, complex series (60 identified) of aromatic and polyaromatic species, including benzene, styrene, methylstyrenes, toluene, o-xylene, m-xylene, /?-xylene, biphenyl, naphthalene, anthracene, phenanthrene, pyrene, etc. (see Ref.) HCl, a-methyl styrene 159
Ambient to 500
HCl, styrene
159
Ambient to 500 Ambient to 500
Products as for individual polymers CO 2 , HCl, benzene, traces of toluene, phenol and other phenolic compounds, bisphenol A, polycarbonate chain fragments
160 291
250 240
300-325 230-410 300-500
Poly(3,6-dichloro N-vinylcarbazole)
300-500
Poly(3,6-dibromo 7V-vinylcarbazole)
350-500
Poly(vinyl chloride)
200-300 400 600 200-800
Ambient to 1000
Poly (vinyl chloride)-&/era/poly(a-methylstyrene) Poly (vinyl chloride)-№ra/poly(styrene) (10/1 to 1/10, w/w) PVC 1:1 blend with bisphenol A polycarbonate
Degradation products
150 158
TABLE 1. cont'd Temperature range (0C)
Polymer PVC 1: 1 blend with poly(dimethylsiloxane) Poly(vinyl fluoride)
Poly(vinylidene chloride) Poly(vinylidene cyanide) Poly(vinylidene
fluoride)
Poly(vinylidene fluorideco-chlorotrifluoroethylene) 80 mol% vinylidene fluoride 3, 10 mol% vinylidene fluoride Poly(vinyltrimethylsilane)
Ambient to 500 372-480 200-500 450
225-275 170 >160 400-530 Ambient to 500 Ambient to 500 Ambient to 500 300-600 in argon
Poly(4-vinyl pyridine) Poly(vinylacetophenone)
Ambient to 500 380
PolytN-acryloyl-N'cyanoacetohydrazide)
600
Degradation products
Refs.
HCl, benzene, traces of toluene, octamethylcyclotetrasiloxane, 292 oligomeric siloxanes High yields of HF and products involatile at 25°C - little carbonization 23 Hydrogen fluoride, C 2 -C9 fractions 150 85% wt. loss, 33 ± 5% volatile products, remainder was oily green liquid; 151 Volatile products: HF (82 mol%), CH4 (5.2), C 2 H 6 (0.6), ethylene (0.8), acetylene (0.03), fluoroethylene (0.07), propene (0.5), C 3 H 5 F (0.4), butane (0.06), butene (1.1), 1,4-butadiene (0.2), 1,3-butadiene (0.7), C 4 H 5 F (0.06), Cyclopentadiene (0.05), benzene (4.5), fluorobenzene (0.3), toluene (1.0), C 6 H 4 (CH 3 )F (0.04), C 6 H 5 C 2 H 5 or C 6 H 4 (CH 3 ) 2 , and styrene (0.9), rc-propylbenzene (0.2), iso-propylbenzene (0.3), C 6 H 5 -C 3 H 5 (0.2), indene (0.3), naphthalene (0.8), fluoronaphthalene (0.3) High yields of HCl 77 Polymer prepared in presence of oxygen; phosgene, formaldehyde, HCl 152 High yields of monomer 78 35% HF and high yields of products involatile at 25°C - some 23 carbonization Monomer, dimer (C 4 F 3 H 3 ), SiF4, (from reaction of HF with glass) 265 HCl, HF, vinylidene fluoride, chlorotrifluoroethylene, dimer (C 4 F 3 H 3 ) 265 HCl, chlorotrifluoroethylene, dichlorodifluoroethene, chloropentafluoropropene, trichlorotrifluoroethane, dimer (C 4 F 3 H 3 ) Tetramethylsilane, trimethylvinylsilane, 2-trimethylsilylpropene, 1,3-tri-methylsilylpropane, 1,3-trimethylsilylpropene, 2,4-trimethylsilylbutene-1,2,4,6-trimethylsilylhexene-1 Monomer, traces of pyridine and 4-methyl pyridine CO, CH4, ethane, 4-acetyl styrene, 4-acetyl toluene, styrene, toluene, 4-vinyl acetaldehyde, a-methylstyrene, a-methyl-4-acetylstyrene, 4-methylstyrene Cyanoactetamide
265 153 260 307 289
1.5. POLY(VINYL KETONES), POLY(VINYL ETHERS) Poly(methyl isopropenyl ketone)
Poly(methyl vinyl ketone) Poly(trifluorovinyl phenyl ether) 1.6.
270-360 Ambient to 500 150-190 270-360 Ambient to 500 275-500
H2O 41 Methyl isopropenyl ketone (50%), modified chain fragments, water, 161 small amounts of CH4 and CO Monomer under 313 nm radiation 42 H2O, 3-methyl-2-cyclohexene-l-one and other six-membered ring ketones 44 Water, modified chain fragments, small amounts of CH4 and CO 161 Maximum of 75% volatilization-products unknown 49
POLY(STYRENES)
Poly(styrene)
300-400 500-1200 300-570
-, (crosslinked) -, (head-to-head)
Ambient to 500 346-450 320 500 under N2
40.6% monomer, 2.0% toluene, 0.1% CO, remainder dimer, trimer, 62,63 and tetramer - monomer yield increases with pressure of nitrogen - 62% at 1013 mbar Small hydrocarbon fragments appear (Ci-C 6 ) - fragmentation is greater 28 the higher the temperature and the greater the pressure of inert gas Pulsed pyrolysis and 40 jig of polymer. Styrene (92.4-99.8% depending 163 upon temperature), benzene, toluene, and ethyl benzene Thin films (1000 A or less), monomer yield about 55% 164 Crosslinking with increasing quantities of divinyl or trivinyl benzene 11,64 progressively decreases the styrene yield-the yield of larger chain fragments and the amount of carbonization also increase Monomer, dimer, trimer, tetramer, pentamer, stilbene 165 Hydrocarbons (Ci-C 4 ) (2.2 relative GC peak intensity), benzene (0.4), 166 toluene (3.3), ethylbenzene (2.0), styrene (20.4), 3-phenyl-1-propene (1.5), 1-pheny!propane (2.3), a-methylstyrene (0.3), 1-phenylbutadiene (1.0), diphenylmethane (0.3), 1,1-diphenylethylene (2.6), 1,2-diphenylethane (1.3), 1,2-diphenylpropane, (0.7), 1,2-diphenyl-l-propene (0.5), 2,3-diphenyl-l-propene (2.2), 3,4-diphenyl-l-butene (0.5), 2,3-diphenylbutadiene (2.0), 1,2-diphenylethylene (6.5), 1,4-diphenylbutane (3.5), 1,4-diphenyl-l-butene (3.8), 1,4-diphenyl-l-pentene (1.3),
References page II - 475
TABLE 1. cont'd Polymer
-, -, -, -,
(poly(divinyl benzene)) (poly(trivinyl benzene)) a-acetoxym-amino-
- , /7-chloro-a-methyl-
-, a-deutero- , p-deutero- , p-fluoro-oc-methyl-
-, /7-methoxy-a-methyl-
-, 3-methyl-, 4-methylPoly(o-propionylstyrene) - , oc-methyl-
-, /?-7VyV-diethylamino-
- , m-A^Af-dimethylamino-
Temperature range (0C)
Degradation products
Refs.
1,3-diphenylpropadiene (2.1), 1,2-diphenylbutadiene (1.8), 1,4-diphenylbutadiene (1.9), 1,3,4-triphenylbutene (0.6), 1,2,5-triphenylpentane (1.5), 1,2,5-triphenyl-l-pentene (4.6), 2,3,6-triphenyl-l-hexene and 2,5,6-triphenyl-l-hexene (8.9), 1,4,5-triphenyl-l-pentene (4.4) Ambient to 600 Styrene, 1,2-diphenylethene, 1,2-diphenylpropane, 1,4-diphenylbutane, 271 1,4-diphenyl-1 -butene, 1,4-diphenylpentane, 4,5-diphenyl-1,8-octadiene, 2,3,6-triphenyl-l-hexene, 1,4,5-triphenyl- 1-pentene 385-450 Volatile products include toluene, benzene, styrene, and xylene 11,64 470-500 Mixture of aliphatic and aromatic hydrocarbons 11,64 270 Acetic acid (99%), mixture of a-acetoxystyrene and acetophenone (1%) 167 340-500 Gaseous fraction CO2, CH4, C 2 H 6 , C 3 H 6 , C 3 H 8 ; liquid fraction 65 m-aminostyrene, m-toluidine; gum fraction mainly dimer and trimer; crosslinked residue remains 320-500 Monomer yield rises from 41% (32O0C) to 61%(500°C); minor product is 66 m-toluidine, with traces of aniline, m-ethylaniline, oc-methylm-aminostyrene, H 2 , CO2, CH4; remainder comprises chain fragments and residue Ambient Gamma radiolysis: CH4 (12.9 relative mass spec, ion current), C 2 H 6 168 (21.8), C 3 H 6 (13.6), C 3 H 8 (10.5), C 4 Hi 0 (61), HCl (4.2), CH3Cl (17.4), C 3 H 4 Cl (20), C 2 H 5 Cl (28.1), C 3 H 7 Cl (3.3), CH2Cl2 (9.9), C 6 H 5 Cl (3.0), p-chlorostyrene (1.5), p-chloro-a-methyl styrene (12.5) 334-387 68.4% monomer, 1.5% a-deuterostyrene, 0.6% a-methylstyrene, 2,13 29.5% larger chain fragments 345-384 39.7% monomer, 1,2% toluene, 0.1% deuterotoluene, 59% larger 2,13 chain fragments Ambient Gamma radiolysis: CH4 (0.4 relative mass spec, ion current), C 3 H 4 168 (3.0), C 3 H 6 (0.6), C 3 H 8 (0.8), C 4 H 4 (3.5), C 4 H 6 (6.0), C 3 H 7 F (3.2), C 4 H 3 F (6.0), C 4 H 9 F (14.5), C 5 H 5 F (9.37), C 6 H 5 F (29), p-fluorotoluene (23), /?-fluorostyrene (6.45), /?-fluoro-a-methyl styrene (175.5), /?-fluoro-isopropyl benzene (11.5) Ambient Gamma radiolysis: CH4 (32 relative mass spec, ion current), H2O (26), 168 C 2 H 4 (35), C 3 H 4 (7.3), C 3 H 6 (15.2), C 3 H 8 (68.7), C 4 H 10 (8.2), CH3OH (24.2), phenol (63.8), methoxybenzene (38.6), p-methoxytoluene (19.6) 309-399 44.4% monomer, 7.3% xylene, 48.3% larger chain fragments 3 200-350 Ratio of monomer to oligomer rises from 40% at 2000C to 95% at 35O0C 79 560 C i - C 4 hydrocarbons, benzene, toluene, ethylbenzene, styrene, 278 ethyltoluene, vinyltoluene, naphthalene, ethylstyrene 385 CO, CH4, ethane, ethene, butane, 2-propionylstyrene, 2-propionyltoluene, 313 styrene, toluene, a-methylstyrene, a-methyl-2-propionylstyrene, various dimeric and trimeric species not fully characterized 200-500 95-100% monomer 28 520-1200 Fragments both larger and smaller than monomer appear in increasing 28 amounts the higher the temperature, particularly CH4, C 2 H 4 , and C 6 H 6 until at 12000C the monomer yield is only 33.9% Ambient Gamma radiolysis: CH4 (1.0 relative mass spec, ion current) C 2 H 6 (1.2), 168 C 3 H 4 (6.7), C 3 H 6 (1.8), C 3 H 8 (2.7), C 4 H 4 (22), C 4 H 10 (9.9), cyclopentadiene (6.1), benzene (72.8), toluene (20), styrene (50.5), oc-methyl styrene (184), isopropyl benzene (10) 400-900 Benzene, toluene, ethylbenzene, cumene, styrene, a-methyl styrene, 169 indene/phenylpropyne, methyl-1,2-dihydronaphthalene, methylene indene, naphthalene, 2-methylnaphthalene, 1-methylnaphthalene, biphenyl, anthracene/phenanthrene, dihydropyrene 350-500 Toluene, styrene, /?-ethylstyrene, 7VyV-diethyl-/?-toluidine, WV-diethyl170 /?-ethylaniline, p-TVyV-diethylaminostyrene, a-methyl-A^Af-diethylaminostyrene, 2-(p-Af,iV-diethylaminophenyl) butane, a-propyl-p-AW-diethylaminostyrene, N-ethyl-p-toluidine, Af-ethyl-p-toluidine, Af-ethyl/?-ethylaniline, Af-ethyl-/?-aminostyrene and closely related compounds 350-500 ra-iVyV-Dimethylaminostyrene, A^TV-dimethyl-m-toluidine, m-xylene, 171 styrene, AUV-dimethyl-m-ethylaniline, toluene, m-methylstyrene, a-methyl-m-A^,A^-dimethylaminostyrene, trans- fi-methy\-m-N,Ndimethylaminostyrene, a-emyl-ra-Af,Af-dimethylaminostyrene, N-methyl-m-toluidine, Af-methyl-ra-ethylaniline, Af-methyl-ra-aminostyrene, oligomers of m-A^Af-dimethylaminostyrene and closely related compounds
TABLE 1. cont'd Polymer
Temperature range (0C)
- , /?-Af,N-dimethylamino-
Poly(/?-(2,4-dichlorobenzyl)styrene)
-, /?-isopropyl-a-methyl- , 2,3,4,5,6-pentafluoro- , a,p,(3-trifluoroPolystyrene (chain brominated on a-position) Poly(styrene-co-methylene) ~ ~ CH-CH 2 -CH 2 -CH-(CH 2 ) „ ~ ~ ' I _ Qi 3 4 d 5 ' ' Poly(styrene-a?-SO2) (1.85 :1) Poly(styrene-c0-methacrylic acid) 18, 44 and 72 mol% MAA Poly(styrene-co-chlorotrifluoroethylene) 7.7, 14, 20 mol% CTFE
500 for 30min
Ambient to 500
Ambient 390-446 333-382 150-300 300-500 Ambient to 500 350 for 4hr
200 Ambient to 500 Ambient to 500
Poly(styrene-co-glycidyl methacrylate) 10, 23, 51, 62, 78, 86 mol% GMA
Ambient to 500
Poly(styrene-cc>-phenyl methacrylate) 10-90 mol% PMA
Ambient to 500
Poly(styrene-co-1,2,2,2,-tetrachloroethyl acrylate) (4.7/1)
310 and 500
Poly(styrene-c-l,2,2,2-tetrachloroethyl methacrylate) (3.8/1)
310 and 500
Poly(styrene-c0-bis-(l,2,2,2-tetrachloroethyl)fumarate) (8.9/1)
310 and 500
Poly(styrene-c6>-bis-(l,2,2,2-tetrachloroethyl) muconate) (7.72/1)
310 and 500
Poly(styrene-co-iV-(2,4,6-tribromophenyl)maleimide) (6.4/1)
310 and 500
Degradation products
Refs.
iV,iV-dimethylaniline (0.2% of original polymer weight), A^Af-dimethylp-toluidine (2.8%), N-methylaniline (0.4%), AyV-dimethyl-/?-ethylaniline (0.4%), N-methyl-/?-toluidine (0.4%), JV-methyl-o-toluidine (0.4%), p-toluidine (0.4%), Af-methyl-p-ethylaniline (0.4%), p-N,JV-dimethylaminostyrene (36.3%), a-methyl-/?-A^,A^-dimethylaminostyrene (0.7%) Benzene, toluene, ethylbenzene, styrene, a-methylstyrene, 1,3-dichlorobenzene, 2,4-dichlorotoluene, monomer (major product), complex series of halogenated and dehalogenated chain fragments (see Ref.) Gamma radiolysis: CH4 (8, relative mass spec, ion current), C 2 H 4 (4.6), C 3 H 4 (7.2), C 3 H 6 (21.2), C3H8 (108), C 4 Hi 0 , (57.4) 63% of the products are volatile at 25°C - contains some monomer 72% monomer, 28% larger chain fragments HBr, trace styrene Styrene, HBr, toluene, benzene HBr, styrene, traces of toluene and benzene, /?-bromostyrene Benzene, toluene, ethylbenzene, styrene (major volatile product), n-propylbenzene (except with n = 2), phenylpropene, butylbenzene (except with n = 0), phenylbutene (with n = 4 and 5 only), amylbenzene ^ wittl n ~ 4 a n c l ^ o m ^ hexylbenzene (with n = 4 and 5 only), chain fragment fraction (major product) At 26.7 mbar pressure; 40% weight loss; main product is 2,4-diphenyl thiophene; at least 11 unidentified minor products CO 2 , H2O, butene, isobutene, dimethyl ketene, styrene, methacrylic acid, succinic-type 5-membered cyclic anhydrides Chlorotrifluoroethylene, styrene, HCl, chloropentafluoropropene, ethene, chloroethene, toluene, a-methylstyrene, dimer and trimer structures with some unsaturation; SiF4 (from reaction of HF with glass). Distribution of products varies with polymer composition CO, CO2, propene, isobutene, dimethyl ketene, acrolein, allyl alcohol, toluene, styrene, a-methylstyrene, ethylbenzene, glycidol, glycidylmethacrylate; product distribution depends on copolymer composition CH4, CO, CO 2 , propene, dimethyl ketene, toluene, styrene, 4-phenylbutene, 4-phenyl-2-methylbutene, phenyl methacrylate, a-methylstyrene, short chain fragments Styrene, benzene, toluene, ethylbenzene, a-methyl styrene, diphenyl, 5,6-benzo-2-methyl-3,5-cyclohexadienone, diphenylethane, 1,3-diphenylpropane, dimers and trimers of styrene, chloroacetaldehyde, dichloroacetaldehyde, trichloroacetaldehyde, trichloropropanal Styrene, benzene, toluene, allylbenzene, a-methylstyrene, indane, isopropenylstyrene, 5,6-benzo-2-methyl-3,5-cyclo-hexadienone, propyl-propenylbenzene, diphenylethane, 1,3-diphenylpropane, dimers and trimers of styrene chloroacetaldehyde, dichloroacetaldehyde, trichloroacetaldehyde, trichloropropanal, benzyl chloride, 2-chloroethylstyrene, 2,2-dichloroethenyl methacrylate, 1,2,2,2-tetrachloroethyl methacrylate Styrene, benzene, toluene, ethylbenzene, allylbenzene, a-methylstyrene, indane, diphenyl propylpropenylbenzene, diphenylethane, 1,3-diphenylpropane, dimers and trimers of styrene, chloroacetaldehyde, dichloroacetaldehyde, trichloroacetaldehyde, benzyl chloride Styrene, benzene, toluene, ethylbenzene, a-methylstyrene, diphenyl, propylpropenylbenzene, diphenylethane, 1,3-diphenylpropane, dimers and trimers of styrene, chloroacetaldehyde, dichloroacetaldehyde, trichloroacetaldehyde, trichloropropanal, benzyl chloride Styrene, benzene, toluene, ethylbenzene, allylbenzene, a-methylstyrene, indane, diphenylethane, 1,3-diphenylpropane, dimers and trimers of styrene, N-(2,4,6-tribromophenyl) maleimide, N-dibromophenyl maleinimide
172
275
168 67 14 271 271 271 173
68 294 261
264
280 174
174
174
174
174
References page II - 475
TABLE 1. cont'd Temperature range (0C)
Polymer Poly(styrene-co-AKpentachlorophenyl)maleimide) (4.9/1)
310 and 500
Poly(styrene) 1:1 (w/w) blend with bisphenol A polycarbonate
Ambient to 500
Poly(vinyl toluene-codivinyl benzene) 10-50% DVB
560
Poly(4-methoxystyrene) 1:1 (w/w) blend with bisphenol A polycarbonate
TABLE 2.
Ambient to 500
Degradation products
Refs.
Styrene, benzene, toluene, ethylbenzene, allylbenzene, oc-methylstyrene, indane, diphenylethane, 1,3-diphenylpropane, dimers and trimers of styrene, pentachlorophenyl isocyanate, Af-pentachlorophenyl formamide, Af-tetrachlorophenyl maleinimide, N-(pentachlorophenyl) maleimide, methyl maleic acid pentachlorophenylimide CO 2 styrene, a-methylstyrene, p-cresol, phenol, /?-ethylphenol, p-vinylphenol, p-isopropylphenol, polystyrene short chain fragments with vinylidene and saturated ends, polycarbonate cyclic dimer and chain fragments, bisphenol A C i - C 4 hydrocarbons, benzene, toluene, ethylbenzene, styrene, ethyltoluene, a-methylstyrene, vinyltoluene, divinylbenzene, naphthalene, ethylstyrene; distribution varies with copolymer composition CO 2, 4-methoxystyrene, a-methyl-4-methoxystyrene, p-cresol and other phenols in small amounts, poly (4-methoxy styrene) dimer and trimer with vinylidene and saturated ends, polycarbonate cyclic dimer and chain fragments, bisphenol A
174
272
278
272
MAIN-CHAIN CARBOCYCLIC POLYMERS
Polymer Poly((E,E)[6.2]paracyclophane-l,5-diene)
Temperature range (0C) 460, 515, 620
Poly(perfluoro-m-phenylene)
700
Poly(perfluoro-p-phenylene) high molecular weight (15000)
700
low molecular weight (3700)
700
Poly(l,4-phenylene)
250-620
- , 2-hydroxy-
300-620
Poly(l,4-phenylene ethylene)
420-465
408-515 436-475 Poy(l,3-phenylene-hexafluorotrimethylene
660 for 30 s
PoIy(1,4-phenylenemethylene)
386-416
Poly a-(ethoxycarbonyl-vinyl)-oo[4-(ethoxycarbonyl-vinyl)-phenyl] (1,4-phenylene-2,4-bis-ethoxycarbonyl1,3-cyclobutylene)
320-360 for 1 h under N 2
Degradation products
Refs.
Primary product is monomer; in addition, a series of secondary products 251 based on ring-opened monomer are formed by H-abstraction (see Ref.); also detected: toluene (not 4600C) and p-xylene Volatiles comprise SiF4 (from silica vessel), CO2, with traces of C6F6 50 and C6F5H; white sublimate on vessel walls; residue contains 1% fluorine Volatiles comprise SiF4 (from silica vessel), CO2, with traces of 50 C-(Fe and C 6 F 5 H; white sublimate on vessel walls; residue contains 1% fluorine Volatiles comprise SiF4 (from silica vessel), CO2, with traces of 50 C 6Fe and CeF5H; no white sublimate; residue contains 33-41% fluorine 79% residue, 10% chain fragments, 11% volatiles comprising H 2 , CH4, 55 H2O, HCl (from catalyst) 60% residue, 24% chain fragments, 16% volatiles comprising CO, CO2 55 H 2 , CH4 3.6% of products are volatile at 25°C and consist of 2.83% xylene, 13,14,80 0.29% toluene, 0.28% methylethyl benzene, 0.14% methylstyrene, 0.06% benzene, products involatile at 250C consist of dimericoctameric fragments Mainly chain fragments (dimer-pentamer); traces of H 2 , monomer 81 H 2 , CH4, C 2 H 4 , C 2 H 6 , toluene, p-xylylene, p-ethyltoluene, p-methyl176 bibenzyl, l,2-di-/?-torylethane, 4,4'-dimethylstilbene C 2 F 4 (21.6% of original weight of polymer), HF (17), 177
C 6 H 6 (8.5%), C 6 H 5 (CF 2 ) 3 C 6 H 5 (7.9%) 7.4% of products are volatile at 25°C; 5.9% toluene, 1.4% benzene, 0.1% xylene Low-molecular-weight polymer and small amount of monomer
13,14 195
TABLE 3. MAIN-CHAIN HETEROATOM POLYMERS Temperature range (0C)
Polymer
Degradation products
Refs.
3.1. POLY(OXIDES) AND POLY(KETONES) Poly(fluoro ethers)
510-540
178
b.
c.
d.
Poly(oxybutylethylene)
321-365
Poly(oxy-2,5-dimethoxy-l,4-phenylene)
100-550
Poly(oxy-2,6-dimethyl-l,4-phenylene)
100-550 400-550
Poly(oxyethylene)
324-363 280
Poly(oxymethylene)
222 100-180
Poly(oxymethyleneoxyethylene) Poly(oxy-2-methylphenylene)
314-338 250-500
Poly(oxy-l,3-phenylene)
300-620
Poly(oxy-l,4-phenylene)
550
Poly(oxy-l,4-phenylene)blend-polystyrene (60: 40) Poly(oxypropylene) atactic isotactic Poly(oxytetramethylene) Poly(oxytrichloromethyl methylene) (Poly(trichloro acetaldehyde))
585 300-360
270-330 275-355 347 Ambient
Mixture of saturated and hydrocarbons (Ci-C 6), aldehydes (C 1 -C 6 XH 2 5 H 2 O 41% residue, 29% fragments, 30% volatiles comprising H 2 , CH4, CO, CO 2 , CH3OH, traces of H 2 O, C 2 H 6 , other hydrocarbons 26% residue, 66% chain fragments, 8% volatiles comprising H 2 , CH4, H2O, CO, CO2 0-Cresol, 2,6-dimethyl phenol, 2,4-dimethyl phenol, 2,4,6-trimethyl phenol, various ketones, dimers, and more complicated structures (see Ref.), various combinations of the monomeric skeletons 9.7% of products volatile at 25°C-3.9% monomer with smaller amounts of CO2, formaldehyde, ethanol, and saturated and C i - C 7 compounds Diethyl ether, ethyl methyl ether, acetaldehyde, formaldehyde, CO 2 , CO, ethene, cyclohex-3-ene-l-one 100% Monomer 100% Formaldehyde; inverse relationship between molecular weight and rate for hydroxyl terminated polymers; acetylation of terminal hydroxy groups inhibits the reaction Major volatile products CH4, C 2 H 6 , C 2 H 4 , C 2 H 2 , HCO 2 C 2 H 5 p-Xylene, phenol, 2-methylphenol, 4-methylphenol, 2,4-dimethylphenol, and a variety of more complex structures (see Ref.) 34% Residue, 53% chain fragments, 13% volatiles comprising H2O, CO, H 2 , CH4, CO 2 , trace of C 6 H 6 Hydroquinone, phenol, benzene, diphenylether, 4,4/-dihydroxydiphenylether, 4-phenoxyphenol. In addition, a broad spectrum of phenyl and phenolic terminated oligomers with up to 10 aromatic units As 5500C plus dibenzofuran and dibenzofuran-containing oligomers Ethylbenzene, styrene, a-methylstyrene, 2-methylphenol, 2,6-dimethylphenol, 2,4-dimethylphenol, 2,4,6-trimethylphenol, 1,3-diphenylpropane, 2,4-diphenyl-1 -butene, 2,4,6-triphenyl-1 -hexene, PPO dimers 12.8% of products volatile at 25°C, including 4.00% acetaldehyde, 2.22% acetone, 1.43% dipropyl ether and 0.75% propylene 20% of products volatile at 25°C, including 6.34% acetaldehyde, 2.39% acetone, 2.19% dipropyl ether, and 2.22% propylene Volatiles comprise a mixture of CH4, C 2 H 6 , C 3 H 8 , C 4 Hi 0 , C 2 H 4 , C 3 H 6 , CH3CHO, C2H5CHO, C3H7CHO Monomer
20 55 55 179
25 252 27 181 20 180 55 255
255 318
25 25 20 182
References page II - 475
TABLE 3. cont'd Polymer
Temperature range (0C)
Poly(oxy- 1,4-phenylenecarbonyl-l,4-phenylene) (Poly(ether ketone), PEK)
390, 490, 530
506 Poly(oxy-1,4-phenyleneoxy-1,4-phenylene -carbonyl-1,4-phenylene) (Poly(ether ether ketone), PEEK) Poly(etherketone-coethersulphone) Mole ratio 1:3, 3:1, 1:1 (random), 1:1 (alternating) 3.2.
506
Degradation products
Refs.
Low MW polymer at 4900C produces benzene, phenol, benzaldehyde, 4-hydroxybenzaldehyde, diphenyl ether, biphenylene, benzophenone, series of -H, -OH and -CHO terminated chain fragments containing < 8 aromatic units and fragments containing dibenzofuran units. High MW polymer at 53O°C as above. Low MW polymer at 3900C produces significant quantities of 4-hydroxy benzaldehyde and benzophenone-4,4 '-diol Phenol, dibenzofuran, benzofuran derivatives, mixtures of oligomers mostly hydroxy terminated Phenol, dibenzofuran, benzofuran derivatives, mixtures of oligomers mostly hydroxy terminated
250
315 315
All polymers have same products with distribution varying with 250 composition. Biphenyl, hydroquinone, 4-phenoxyphenol, benzaldehyde, 4-hydroxybenzaldehyde, diphenyl sulphone, diphenylether, phenol, benzophenone-4,4'-diol. Also two series of chain fragments containing PEK and PES units with -H, -OH and -CHO ends. Analogous fragments with biphenyl units
POLY(ESTERS)
Poly(3-oxybenzoyl) Poly(4-oxybenzoyl) Poly(oxycarbonyl-l,3-phenylenehexafluoroisopropylidene-1,3-phenylene carbonyloxy-1,3-phenylene-hexafluoroisopropylidene-1,3-phenylene) Poly(oxycarbonyl-l-chloroisopropylidene) Poly(oxycarbonylcyclohexylidene) Poly(oxycarbonylcyclopentylidene) Poly(oxycarbonyl-3-pentylidene) Poly(oxyethyleneoxyterephthaloyl) (Poly(ethylene terephthalate))
330 505-565
Monomer, cyclic dimer-heptamer CO, CO 2 , phenol, p-hydroxy phenyl benzoate HF (12%), cyclic structures (see Ref.)
187 197 177
253-384 200-500 200-500 200-300 283-306
HCl and a compound with a glycollidic structure Cyclohexen-1-carboxylic acid, cyclohexanone Cyclopenten-1-carboxylic acid, cyclopentanone, dicyclopentyl glycollide Cw- and trans-2-tthy\ crotonic acid (major products) Acetaldehyde major gaseous product with CO 2 , CO, C 2 H 4 , H2O, CH4, benzene, 2-methyl-dioxolane, terephthalic acid, and more complex chain fragments CO, CH4, CO 2 , ethylene, acetylene, ethane, H2O, propylene, ethanal, acetone, propanal, ethanol, benzene, toluene, ethyl benzene, styrene, /?-vinyl toluene, benzaldehyde, p-ethyl toluene, acetophenone, methyl benzoate, vinyl benzoate, ethyl benzoate, /?-methyl acetophenone, benzoic acid, p-methyl vinyl benzoate, /?-vinyl acetophenone, propyl benzoate, /?-ethyl vinyl benzoate, p-vinyl vinyl benzoate, biphenyl, 1-hydroxy ethyl benzoate, diacetyl benzene, p-acetyl vinyl benzoate, divinyl terephthalate, ethyl vinyl terephthalate, ethyl vinyl terephthalate, /7-acetyl benzoic acid, methyl 1-hydroxyethyl terephthalate, ethylene dibenzoate CO, CH4, CO 2 , ethene, ketene, acetaldehyde, 1,4-dioxane, toluene, benzaldehyde, vinylbenzoate, divinylterephthalate, benzoic acid, terephthaldehydic acid, terephthalic acid, hydroxyethyl methyl terephthalate, short chain fragments CO, CH4 (trace), CO 2 , ethene (trace), formaldehyde, acetaldehyde, 1,3-dioxalane, ethoxyacetaldehyde, 1,4-dioxane, glycidol, diethylether, 1,2-dimethoxyethane, 2-methoxyethanol, 2-ethoxyethanol, -CH2CH2COCH 2 -(ring), HOCH2CH2OCH2CHO, CH3OCH2CH2OC2H5, terephthalic acid, triethylene glycol, tetraethylene glycol, chain fragments CO, CH4 (trace), CO 2 , ethene (trace), formaldehyde, acetaldehyde, 1,3-dioxalane, methoxyacetaldehyde, 1,4-dioxane, 7-membered cyclic ether, methyl benzoate, ethyl benzoate, benzaldehyde,
185 198 198 188 26
900
Ambient to 500
Polyester from terephthaloyl chloride and n = 4 polyethylene glycol
Polyester from terephthaloyl chloride and n = 22 polyethylene glycol
Ambient to 500
-CH 2 CH 2 COCH 2 -(ring), H O C H 2 C H 2 O C H 2 C H O ,
CH3OCH2CH2OC2H5, -(CH 2 CH 2 O) 2 CH 2 CO-(ring), CH2 = CHOCH 2CH 2OCH2CHO, HO(CH 2CH2O) 2C 2H5 , C 2 H 5 (OCH 2 CH 2 ) 3 H, terephthalic acid, triethylene glycol, tetraethylene glycol, chain fragments
192
298
274
274
TABLE 3. cont'd Polymer
Temperature range (0C)
Poly(oxyisophthaloyl-oxy-l,3-phenylene)
330
Poly(oxyisophthaloyl-oxy-l,4-phenylene)
330
Poly(oxy-l-oxohexamethylene) Poly((D)-oxy-l-oxo-3-methyl-trimethylene) (Poly(3-hydroxybutyrate))
220 Ambient to 338
250 400 600 350 Poly((D)-oxy-l-oxotetramethylene) (Poly(4-hydroxybutyrate)) Poly(oxy-l-oxo-2methylethylene) (Poly(l-lactic acid)) Poly(oxy-l-oxo-2,2-dimethyltrimethylene (Poly(a,a-dimethyl-p-propiolactone)) Poly(oxy- 1-oxo-trimethylene) (Poly(p-propiolactone)) Poly(oxyterephthaloyloxy1,2-phenylene) Poly(oxyterephthaloyloxy-l,3-phenylene)
320 500
Poly(oxytetramethyleneoxyterephthaloyl) (Poly(butylene terephthalate))
187 187 184 186
245 245 245 246 257
250-600 180-220
Acrylic acid
189
CO2, benzene, phenol, benzaldehyde, catechol, cyclic dimer
285
Ambient to 500 345
350
Ambient to 500 240-280 200-400 Ambient to 500
Poly(oxydecamethyleneoxyterephthaloyl) Poly(oxyethyleneoxyadipoyl) Poly(oxytetramethyleneoxysebacoyl) Polyester from maleic anhydride, hexolic acid and butanediol; mole ratio 1:1:2.2
Cyclic monomer (10 relative abundance), cyclic dimer (83.5), cyclic trimer (24.5), benzoic acid, isophthalic acid, resorcinol and various fragments of the main chain (see Ref.) Cyclic dimer (17), cyclic trimer (4), m-phthalic acid (26), benzoic acid (7.5), hydroquinone (46), and various fragments of the main chain (see Ref.) Monomer (e-caprolactone) Dimer (41.2 wt.%), crotonic acid (35.3), trimer (12.5), tetramer (2.9), iso-crotonic acid (0.9). Small amounts of CO 2, propene, ketene, acetaldehyde, and P-butyrolactone are formed at higher temperatures due to decomposition of primary products Crotonic acid (64.4% of original polymer), dehydrated dimer (7.2%), dehydrated trimer (1.2%) Crotonic acid (65.4% of original polymer), dehydrated dimer (8.2%), dehydrated trimer (2.1%) Crotonic acid (58.3% of original polymer), dehydrated dimer (9.0%), dehydrated trimer (2.7%) Crotonic acid (trans), dehydrated dimer (trans), dehydrated trimer and tetramer (cisltrans not resolved) Cyclic oligomers (y-butyrolactone and higher homologues)
282
Ambient to 500
Poly(oxyterephthaloyloxy-4,4/diphenylene)
Refs.
CO, CO2, acetaldehyde, acetone, acrylic acid, acetic acid, DL-lactide, meso-lactide, cyclic oligomers up to nonamer, 2,3 pentanedione (?), lactoyl lactic acid (?) Isobutylene and CO2
Ambient to 500
Poly(oxyterephthaloyloxy-l,4-phenylene)
Degradation products
Ambient to 500 Ambient to 500 Ambient to 500 100-440
183
Cyclic dimer (2), cyclic trimer (0.3), terephthalic acid (0.4), benzoic acid 187 (1.5), resorcinol (20) and various fragments of the main chain (see Ref.) CO2, benzene, phenol, benzaldehyde, biphenyl, benzoic acid, 285 3-hydroxyphenylbenzoate, resorcinol, mono and di(3-hydroxyphenyl) terephthalate, terephthalic acid, terephthaldehydic acid, short chain fragments Cyclic dimer (0.1), terephthalic acid (0.5), benzoic acid (6), hydroquinone 187 (40.5), and various fragments of the main chain (see Ref.) Benzene, phenol, benzaldehyde, biphenyl, benzoquinone, 285 4-hydroxyphenylbenzoate, benzoic acid, mono and di(4-hydroxyphenyl) terephthalate, terephthalic acid, terephthaldehydic acid, short chain fragments CO2, benzene, phenol, benzaldehyde, biphenyl, 4-phenylphenol, 285 /?,/?'-dihydroxybiphenyl, 4-hydroxybiphenylbenzoate, di(4-hydroxybiphenyl) terephthalate Butadiene, terephthalic acid, mono-3-butenyl terephthalate, and 190 di-3-butenyl terephthalate Tetrahydrofuran, 1,3-butadiene, CO2, CO, H2O, benzoic acid, tereph191 thalic acid, terephthalic acid mono-3-butenyl, toluene, phenol, benzene CO, CO 2 , butadiene, tetrahydrofuran, toluene, benzene, 1,5-hexadiene, 298 dihydrofuran, 4-vinyl cyclohexene, 1,4-butane diol, benzaldehyde, benzoic acid, terephthaldehydic acid, terephthalic acid, mono-3-butenyl terephthalate, cyclic dimer, short chain fragments CO, CO 2 , 1,9-decadiene, 1,10-decane diol, l-decene-10-ol, benzoic acid, 298 terephthalic acid, mono-decenyl terephthalate Cyclic oligomers, CO, CO2, acetaldehyde, 2-ethylacrolein 269 CO 2 , H2O, butadiene, tetrahydrofuran 299 Tetrahydrofuran, 1-butanol, toluene, maleic anhydride, chlorosuccinic 311 acid isomers, chlorovalerolactone isomers, hydroxypyran, allylpyran, trichlorocylopentadiene, tetrachlorocylopentadiene, pentachlorocylopentadiene, hexachlorocylopentadiene, phthalic anhydride, 1,4-butanediol, 1,4-butanediol dibenzoate, benzoic acid, 4-cyclohexene-l,2-dicarboxylic acid anhydride, benzoic acid butenyl ester, cyclohexadiene carboxylic acid propyl ester, hexolic anhydride,
References page II - 475
TABLE 3. cont'd Polymer
Temperature range (0C)
Degradation products
Refs.
unidentified butenyl ester, compound containing C 5 HCl 5 unit, CH3-CH=CH-CH2-O-CH3, C H 3 - C H = C H - C H 2 - O - C H = CH2,
Polyester from maleic anhydride, phthalic anhydride and butanediol; mol ratio 1:1:2.2
100-440
Unsaturated polyester resins a. Maleic acid-phthalic acid-propylene glycol-styrene
300-800
Cl-CH=CH-O-CH2-CH3 Tetrahydrofuran, 1-butanol, 3-butene-l-ol, toluene, maleic anhydride, 311 phthalic anhydride, 1,4-butanediol, 1,4-butanediol dibenzoate, phthalic acid butenyl ester, various esters containing butenyl, maleate and phthalate units, C H 3 - C H = C H - C H 2 - O - C H 3 , C H 3 - C H = C H - C H 2 - O - C H = CH2
b. Maleic acid-tetrabromophthalic acid-phthalic acid-propylene glycolstyrene c. Maleic acid-phthalic aciddibromoneopentyl glycol-styrene 3.3.
Ethane (above 5000C), propionaldehyde (above 4000C), styrene (major product), phthalic anhydride (major product), benzene (above 5000C), toluene (above 5000C), xylene (above 5000C)
193
Cyclic trimer, tetramer, and pentamer, and various chain fragments Major products: CO 2 , bisphenol A; minor products: CO, CH4, 4-alkyl phenols CO, CO 2 , CH 4 , phenol, diphenyl carbonate, 4-(4-hydroxyphenyl)-2phenyl propane Cyclic dimer, cyclic trimer, bisphenol A, and other chain fragments CO, CH4, CO 2 , H 2 O, phenol, /?-cresol, /?-ethyl phenol, /?-isopropyl phenol, p-vinyl phenol, bisphenol A, cyclic dimer, chain fragments including some ester structures Phenol, /7-cresol CO2, phenol, /?-cresol Cyclic monomer and dimer, and higher cyclic fragments
226 60
304 304 226
HF (3%), cyclic dimer
177
270
Cyclic dimer and trimer, and higher cyclic fragments
226
350
CO 2 , CO, O 2 , H 2 O, phenol, fluorenone, diphenyl carbonate, xanthone, anthraquinone, 2-hydroxyanthraquinone, 2-benzoxyanthraquinone, phenolphthalein, traces of benzoxyphenol and hydroquinone CO2/H2O (possibly desorbed), trimethylene carbonate, cyclic oligomers CO 2 , monomer, oligomer CO, CO 2 , H 2 O (possibly desorbed), a-methylstyrene, chain fragments (85%, w/w)
227
POLY(CARBONATES)
Poly(oxycarbonyloxy-l,3-phenylene) Poly(oxycarbonyloxy-l,4-phenyleneisopropylidene-l,4-phenylene)
270 300-389 200^00 290 Ambient to 500
Poly(oxycarbonyloxy-l,4-phenyleneisopropylidene-1,4-phenylene-oxy-carbonyltetramethylene) Poly(oxycarbonyloxy-l,3-phenylene hexafluorotrimethylene-1,3-phenylene) Poly(oxycarbonyloxy-l,4-phenyleneoxycarbonyloxy-tetramethylene) Poly(oxycarbonyloxy-l,4-phenylenephthalidylidene-l,4-phenylene) Poly(trimethy}ene carbonate) Poly(neopentylene carbonate) Poly(2-phenyl trimethylene carbonate) 3.4.
Ethane (above 6000C), propionaldehyde (above 4000C), styrene (major 193 product), phthalic anhydride (major product), benzene (above (4500C), toluene (above 5000C), xylene (above 4000C) Styrene (major product), phthalic anhydride (major product), benzene 193 (above 5500C), toluene (above 4500C), xylene (above 5000C)
300 375 240
Ambient to 500 Ambient to 500 Ambient to 500
225 226 304
295 296 296
POLY(ANHYDRIDES)
Poly(oxycarbonyl-1,3-phenylenehexafluorotrimethylene-1,3-phenylenecarbonyl) Poly(maleic anhydride-co-frans stilbene) (alternating copolymer)
350 Ambient to 500
Cyclic dimer
177
CO 2 , styrene, maleic anhydride; small amounts benzene, cyclohexadiene, 242 dimethylbutene, ethylcyclobutanol and 4-methoxystyrene; major products (79%) are chain fragments, including aromatic, ketonic and unsaturated structures
3.5. POLY(SULFIDES) AND POLY(SULFONES) Poly(thioacetone) Poly(thioethylene) Poly(thio-l,4-perfluorophenylene)
145 220-260 500
Poly(thiomethylene-1,4phenylene-methylene)
250-350
Main product is cyclic trimer [(CH3) 2CS] 69 Ethylene, H 2 S, ethanethiol 199 73% Residue; remainder, chain fragments, H 2 , SiF 4 (from silica vessel), 51 CO 2 Sulphur, styrene, thiobenzaldehyde, 4-methyl styrene, /?-xylene, 254 4-ethyl toluene, H 2 S, 4-methyl thiobenzaldehyde, stilbene and chain
TABLE 3. cont'd Polymer
Temperature range (0C)
650 Poly(dithiomethylene-1,4phenylene-methylene)
250-350
650 Poly(thio-l,2-phenylene) Poly(thio-l,3-phenylene) Poly(thio-l,4-phenylene)
430 540 460 300-620 325-625 560
Degradation products
Refs.
fragments containing stilbene units, chain fragments containing polymer repeat units with -CH 2 SH, -CH = S and -CH 3 terminal units Toluene, ethylbenzene, p-xylene, 1,4-diethylbenzene, 4-ethyltoluene; series of polycyclic aromatics containing phenanthrene and dihydrophenanthrene Sulphur, styrene, thiobenzaldehyde, 4-methyl styrene, /?-xylene, 4-ethyl toluene, H 2 S, 4-methyl thiobenzaldehyde, stilbene and chain fragments containing stilbene units, chain fragments containing polymer repeat units with -CH 2 SH, - C H = S and -CH 3 terminal units Toluene, ethylbenzene, p-xylene, 1,4-diethylbenzene, 4-ethyltoluene; series of polycyclic aromatics containing phenanthrene and dihydrophenanthrene Cyclic dimer (thianthrene), some cyclic trimer Cyclic oligomers (trimer to heptamer) in decreasing yield 72% Residue; remainder chain fragments, H 2 , dibenzthiophene 38% Residue, 47% chain fragments, 15% volatiles comprising mainly H2S and H 2 Benzene, thiophenol, diphenyl, diphenylsulfide, dibenzothiophene, chlorobenzene (from polymers with terminal chlorine atoms) Cyclic oligomers tetramer to heptamer (pentamer dominates)
254 254
254 258 258 51 59 200 258
Poly(oxy-1,4-phenylene-sulfonyl1,4-phenylene-oxy-1,4-phenyleneisopropylidene-1,4-phenylene) 380
350-450 470 for 2 h 800 Poly(oxy-1,4-phenylene-sulfonyl1,4-phenylene)
470 for 2h 550-600
800 Poy(tris-(oxy-l,4-phenylene)-sulfonyl-l,4phenylene) Poly(oxy-4,4'-diphenylene-oxy-l,4-phenylene sulfonyl-1,4-phenylene) Poly(oxy-l,4-phenylene-sulfony 1-1,4-phenyleneoxy-1,4-phenylenemethylene-1,4-phenylene) Poly(sulfur dioxide-co-1-butene) Poly(sulfur dioxide-co-1-hexene) Poly(sulfur dioxide-co-1-octadecene) Poly(sulfur dioxide-co-bicycloheptene)
700-800 700-800 700-800 700-800
Poly(sulfur dioxide-co-cyclopentene)
700-800
Poly(sulfur dioxide-co-c/s-2-butene)
700-800
Poly(sulfur dioxide-co-methyl methacrylate-co-1-hexene) (24.2/1) Poly(sulfur dioxide-co-methyl methacrylate-co-bicycloheptene) (2.5/1)
700-800 700-800
Phenol with smaller amounts of/7-cresol, /?-ethyl phenol, /?-isopropylphenyl phenol, bisphenol A, diphenyl ether, p-tolyl phenyl ether, p-ethyl diphenyl ether, p-isopropenyl diphenyl ether, isomers of tolyl (ethyl-phenyl)ether In 90min at 4500C, 15% (of initial weight) of gaseous products are formed; SO2 (76% of gaseous products), CO2 (15%), CO (4.5%), CH4 (4.5%) Benzene, toluene, /?-xylene, isopropylbenzene, phenol (main product), diphenyl oxide, diphenyl sulfide SO2, benzene, toluene, styrene, phenol, methylphenol, diphenylether, methyl diphenylether Phenol (main product), diphenyl oxide
201
SO2, diphenylsulfone, phenol, diphenylether, hydroquinone, benzenesulfonic acid, 4-hydroxybenzenesulfonic acid, 4,4/-dihydroxydiphenylether, 4-phenoxyphenol; series of -H and -OH terminated fragments up to trimer, series of compounds containing consecutive diphenylether and dibenzofuran units, fragments containing biphenyl units as a result of SO2 elimination; complex ring structures with sulfonate links SO2, benzene, phenol, diphenyl ether, dibenzofuran Benzene, phenol (major product), diphenyl oxide, p-hydroxydiphenyl, or /?-hydroxydiphenyl oxide Phenol (main product), diphenyl oxide
255
202 203 288 203
288 203 203
Benzene, toluene, /7-xylene, phenol (main product), diphenyl oxide
203
Monomers Monomers Monomers SO2, bicycloheptene, cyclopentadiene, ethylene, methyl cyclohexadiene, benzene, indene, naphthalene, dihydronaphthalenes SO2, cyclopentene, xylenes, ethylbenzene, styrene, indene/decadienes, dihydronaphthalenes, tetralin, napthalene SO 2 , butenes, benzene, toluene, octadienes, xylenes, styrene, indene, naphthalene SO2, hexenes, hexadienes, methyl methacrylate, toluene, naphthalene, dodecadienes SO2, ethylene cyclopentadiene, benzene, methyl methacrylate, bicycloheptene, methylcyclohexa-2,4-diene, ethylbenzene, xylenes, styrene, indene, naphthalene, dihydronaphthalenes
204 204 204 204 204 204 204 204
References page II - 475
TABLE 3. cont'd Polymer
Temperature range (0C)
Degradation products
Refs.
3.6. POLY(AMIDES) Poly(2,5-dimethyl-l,4-piperazinediylisophthaloyl)
475
Poly(2,5-dimethyl-1,4-piperazinediyloxaloyl)
475
Poly(2,5-dimethyl-l,4-piperazinediylterephthaloyl)
475
Poly(iminoisophthaloylimino1,3-phenylene) (Nomex)
300-500 300-500 450-550
PolyOminoisophthaloylimino1,3-perchlorophenylene)
550
Poly(iminoisophthalylimino1,4-phenylene) Poly(iminoisophthaloyl-co-terephthaloylimino-1,4-phenylene) Poly(imino(l-oxohexamethylene) (Nylon 6)
Poly(iminohexamethyleneiminoadipoyl) (Nylon 66)
300-500 250-620 327
310-380 305 305
400
Poly(imino(l-oxoundecamethylene) (Nylon 11)
800
Poly(imino(l-oxododecamethylene) (Nylon 12)
800
Poly(iminoterephthaloylimino1,3-phenylene) Poly(iminoterephthaloylimino1,4-phenylene) (Kevlar)
300-500 300-500 370-450 450-550 527
Poly(2-methylpiperazinediylterephthaloyl)
475
Poly(l,4-piperazinediylterephthaloyl)
475
After 1 h, 5.1% residue, 73.8% chain fragments, 20.5% volatiles comprising mainly CO, H2O, CH4, CO2, H2, with traces of hydrocarbons, pyrazines, pyrroles After Ih, 1% residue, 73.5% chain fragments, comprising mainly CO, with traces of H2, CO2, H2O, hydrocarbons, pyrazines, pyrroles After Ih, 9.4% residue, 3.2% chain fragments 87.4% volatiles comprising mainly CO, H2O, CO2, CH4, NH3, with traces of hydrocarbons, pyrazines, and pyrroles Mixture of H 2 , CO, CO 2 , H2O, HCN, benzene, toluene, benzonitrile CO2, H2O, CO Benzene, HCN, toluene, benzonitrile, H 2 CO, CO 2 , H2O, benzene, benzonitrile, 1,3-dicyanobenzene, 3-cyanobenzoic acid, other trace compounds Water (46 mol%), CO (18), CO2 (31), CH4 (1.2), HCN (1.3), and smaller quantities of, N 2 O, NO, CH3CI, ethylene, acetylene, cyanogen, acetonitrile, acetone, acetic acid, cyanogen chloride, propenenitrile, benzene, toluene, benzonitrile, phenol, chlorobenzene Mixture of H 2 , CO, CO 2 , H2O, HCN, benzene, toluene, benzonitrile
30 47 47 57 205 205 319 206
57
36% residue, 24% chain fragments, 40% volatiles comprising H 2 , CO, 58 CO2, CH 4 Cyclic monomer, acetonitrile, HCN, NH 3, acrylonitrile, 3-cyanopropene, 293 4-cyanobutadiene, 4-cyano-1 -butene, 5-cyano-1,3-pentadiene, 4-pentenal, 5-cyano-l-pentene, 3,5-hexadienal, 5-isocyanato1-pentene, linear dimer H2O, CO 2 , cyclopentanone, traces of saturated and hydrocarbons; 45,46 purification from water and acid polymerization catalysts increases stability and decreases yield of CO2 H2O, CO2, NH 3, cyclic monomer, cyclopentanone, cyclopentylidine207 cyclopentanone, cyclopentylcyclopentanone, hexylamine, hexamethyleneimine, hexamethylenediamine CO 2 , NH3, H2O, cyclic monomer, cyclopentanone, 207 2-cyclopentylidenecyclo pentanone, 2-cyclopentylcyclopentanone, hexylamine, hexamethyleneimine, hexamethylenediamine, 1,2,3,5,6,7-hexahydro dicyclopenta[b,e]pyridine Hexamethylenediamine, aminohexamethylene isocyanate, 247 hexamethylenediamine-monocyclopentanimine, hexamethylenediaminedicyclopentanimine and larger oligomers related to above; cyclopentanone CO 2 , HCN, saturated and olefinic hydrocarbons C5-Cn, 308 saturated and olefinic mononitriles CwH(2n+1)CN and CwH(2n_i)CN, undecalactam, hydrocarbons and nitriles containing amide units CO2, HCN, saturated and olefinic hydrocarbons C 5 - C n , 308 saturated and olefinic mononitriles CnH(2n+1)CN and CnH(2n_!)CN, dodecalactam, hydrocarbons and nitriles containing amide units Mixture of H 2 , CO, CO2, H2O, HCN, benzene, toluene, benzonitrile 57 Mixture of H 2 , CO, CO2, H2O, HCN, benzene, toluene, benzonitrile 57 CO 2 , H2O, CO 205 Benzene, HCN, toluene, benzonitrile, H 2 Cyanobenzene, dicyanobenzene, aniline, 1,4-diaminobenzene, 293 4-cyanoaniline, benzaldehyde, benzene, CO, NH3, CO2, H2O, benzamide, benzoic acid, phenylisocyanate, terephthaldehyde, benzanilide, NH 2 -Ph-NH-CO-Ph, NC-Ph-NH-CO-Ph, NH 2 -Ph-NH-CO-Ph-CN, Ph-NH-CO-Ph-CHO After Ih, 11.3% residue, 46.2% chain fragments, 42.5% volatiles 30 comprising mainly CO, H2O, CO2, CH4, NH3, H 2 , with traces of hydrocarbons, pyrazines, and pyrroles After Ih, 21.1% residue, 45.6% chain fragments, 33.3% volatiles 30 comprising mainly H2O, CO, H 2 , CO2, NH3, with traces of hydrocarbons, pyrazines, and pyrroles
TABLE 3. cont'd Polymer 3.7.
Temperature range (0C)
Degradation products
Refs.
POLY(SILOXANES)
Poly(oxy-dimethylsilylene) (Poly(dimethyl siloxane))
Ambient to 500
470
Poly(oxy-methylphenylsilylene)
Ambient to 500
Poly(oxy-methyl-3,3,3-trifluoropropylsilylene)
400 615 for 30 s
Poly(oxy-phenylbutoxysilylene) Poly(dimethyl siloxane-codiphenyl siloxane)
430-500 Ambient to 500
Poly(dimethyl siloxane-co phenylmethyl siloxane)
Ambient to 500
Poly (dimethyl-1,4-silphenylene)
400 in argon
Predominantly cyclic trimer with smaller amounts of cyclic tetramer and 208 higher cyclics; threshold degradation temperature of about 3000C reduced to 1000C by 5% KOH and CH 4 formed as additional product Distribution of cyclic oligomers, n = 3 (243.9 relative mass spec. 317 intensity), n = 4 (100), n = 5 (35.6), n = 6 (37.6), n = 1 (13.1), n = 8 ( l . l ) , n = 9(0.2) Mixture of all possible stereoisomeric cyclic trimers and tetramers with 209 small amounts of pentamer, benzene, and two more complex oligomers Low-molecular-weight cyclic oligomers, CF 2 = CH-CH 3 , CHF 3 70 Cyclic methyl-(3,3,3-trifluoropropyl)siloxanes, CH 4 , CHF3, CF 2 = CH-CH 3 , CH 2 = CH-CF 3 CO, H 2 and hydrocarbons Complex mixture of cyclic oligomers, which have been individually identified, whose composition varies with the dimethyl/diphenyl ratio; small amounts of benzene Complex mixture of cyclic oligomers, which have been individually identified, whose composition varies with the dimethyl/methyl phenyl ratio; small amounts of benzene Methane, dimethylsilane, benzene, dimethylphenylsilane,
210 211 212
213
214
dimethyldiphenylsilane,
Poly(oxy-methylphenyl1,4-silphenylene-silylene) Poly(oxy-tetramethyl-
Ambient to 500 500 in argon
1,4-silphenylene-silylene)
Benzene, diphenylmethylsilane, triphenylmethylsilane, and higher linear oligomers CH3 CH3
214
Methane, H - S i - O - S i - H , benzene, cyclic trimer of dimethylsiloxane, CH3 Ambient to 500
Poly(oxy-tetramethyl-l,3-silphenylene615 for 30s silylene-hexafluoropropylenephenylene) Poly(oxy-tetramethyl-l,3-silphenylene615 for 30s silylene-tetrafluoroethylenephenylene) Poly(oxy-tetramethyl-l,3-silphenyleneAmbient to 500 siloxane-co-dimethylsiloxane) Poly(boron tri(dimethylsiloxane)), nonlinear 250-350
3.8.
215
CH3
and various higher chain fragments (see Ref.) Cyclic trimer and tetramer of dimethylsiloxane and a complex mixture of higher linear and cyclic oligomers HF (15-18%), methane, methyltrifluorosilane, dimethyldifluorosilane, benzene, toluene, phenyldifluoromethane HF (15-18%), methane, methyltrifluorosilane, dimethyldifluorosilane, benzene, toluene, phenyldifluoromethane Cyclic trimer and tetramer of dimethylsiloxane and a complex mixture of higher linear and cyclic oligomers Molecular weight increases; traces of cyclic products [(CH 3 ) 2 Si0] 3 and [(CH 3 ) 2 Si0] 4
216 210 210 216 15
POLY(URETHANES)
Poly(oxy-2,2-dimethyltrimethylene) oxycarbonyl-Af-imino-1,4-phenylenemethylene1,4-phenylene-A/-iminocarbonyl) Poly(oxy-l,4-phenyleneisopropylidene1,4-phenyleneoxycarbonylimino-l ,4-phenylene methylene-1,4-phenylene-iminocarbonyl) Poly(oxy-l,4-phenyleneisopropylidene1,4-phenylene-oxycarbonyl-A^methylimino1,4-phenylenemethylene-1,4-phenyleneAf-methyliminocarbonyl) Poly(oxy-l,4-phenyleneisopropylidene1,4-phenylene-oxycarbonyl-Af-methyliminohexamethylene-Af-methyliminocarbonyl) Poly((oxy-l,4-phenyleneisopropylidene1,4-phenylene-oxycarbonyl-piperazine1,4-diyl-carbonyl)
350
Various fragments of the main chain (see Ref.)
231
190
4,4/-Diphenylmethane diisocyanate, bisphenol A
231
Bisphenol A, 4,4/-J/V-methyldiphenyl methane and linear and cyclic fragments of the main chain (see Ref.)
231
330
Cyclic monomer and dimer, and various chain fragments
232
330
Cyclic dimer, bisphenol A and various chain fragments
232
References page II - 475
TABLE 3.
cont'd
Polymer
Temperature range (0C)
Poly(oxy-l,3-phenylene-oxycarbonyl320 Af-methylimino-hexamethyleneAf-methyliminocarbonyl) Poly(oxy-l,4-phenyleneoxycarbonyl325 Af-methylimino-1,4-phenylenemethylene1,4-phenylene-A^methyliminocarbonyl) Poly(oxy-l,3-phenylene-oxycarbonyl360 piperazine-1,4-diyl-carbonyl) Poly(oxytetramethylene oxycarbonylAmbient to 500 imino-1,4-phenylenemethylene1,4-phenylene-iminocarbonyl) with 10% (w/w) ammonium Ambient to 500 polyphosphate Poly(oxy-xylylene-oxycarbonylimino300 xylylene-iminocarbonyl) Polyurethane from methylene bis600 (4-phenyl isocyanate) (105 parts) and propoxylated trimethyl propane (100 parts) 250-350 350-500 500-650 Polyurethane from butane diol, phenylphosphonic dichloride, and methylene bis-(4-phenyl isocyanate) Polyester urethane from an ethylene/ propylene glycol/adipic acid polyester, butane diol and methyl bis(4-phenyl isocyanate) Poly(urethane-cocarbonates)
650-800 Ambient to 500 Ambient to 500
330
290
Degradation products
Refs.
Cyclic monomer, dimer and trimer, resorcinol
232
Cyclic dimer, 4,4/-Af-methyldiphenylmethane, hydroquinone, and higher chain fragments (see Ref.)
232
Cyclic dimer and trimer, resorcinol, and various chain fragments (see Ref.) 1,4-Butanediol, methylene bis-(4-phenyl isocyanate), tetrahydrofuran, CO2, H2O, butadiene, HCN, CO
232
Methylene bis-(4-phenyl isocyanate), tetrahydrofuran, H2O, aniline, formaldehyde, CO2 CO 2 , frajis-l,4-cyclohexane-dimethanol, 4-methylene-cyclohexanemethanol, xylylene diamine Methane, CO 2 , ethylene ethane, H2O, propene, propane, ethanol, isobutene, acrolein, propanal, 2-methyl-l-butene, 2-methylpropenal, 2-butanone, benzene, dihydropyran, 2,2,4-trimethyl-l,3-dioxalane CO2, propene, some methane and propanal Methane, ethane, ethene, propane, propene, ethanal, propanal, diminishing quantities of CO2 Methane (max. rate of production at 6000C), ethane, ethene, propene, ethanal, propanal Methane, ethane, ethene, propene, ethanal, propanal CO 2 tetrahydrofuran, dihydrofuran, aniline, /?-toluidine, TV-phenyl pyrrolidine, N-(p-io\y\) pyrrolidine, cyclobutylene phenylphosphonate, butane diol, methylene bis-(4-phenyl isocyanate), 4,4/-methylene dianiline Modified chain fragments, ethylene, propylene, CO2, ethylene oxide, propylene oxide, acetaldehyde, tetrahydrofuran, water, cyclopentanone, ethylene, glycol, propylene glycol, adipic anhydride (trace), aniline (trace) Cyclic monomer, bisphenol A and higher linear and cyclic fragments of the chain (see Ref.)
228 229 230 234 256 256 256 256 235 236
237
Cyclic monomer, resorcinol, and various fragments of the chain (see Ref.)
237
Ethene, propane, propene, isobutane, isobutene, ethylamine, aziridine, 1-r-butyl-perhydro-l,4-diazine, N-t-b\xty\ ethylamine, 1 -?-butyl-4-isopropenyl-1,2,3,4-tetrahydro-1,4-diazine, 1,4-di-(/-butyl)-perhydro-1,4-diazine, oligomers
276
Butadiene, tetrahydrofuran, dihydrofuran, H2O, cyclic ester of phenylphosphonic acid and 1,4-butanediol, phenylphosphonic acid, butane diol Butadiene, tetrahydrofuran, dihydrofuran, H2O, cyclic ester of phenylphosphonic acid and butanediol, phenylphosphonic acid, butane diol, CO2, aniline
233
Cyclic trimer, tetramer, pentamer, hexamer, and higher oligomers, l,l,l-trifluoro-2-chloroethane (due to residual chlorine in the polymer) Cyclic tetramer, trimer and higher oligomers, chlorobenzene (due to residual chlorine in the polymer), phenol, triphenylphosphate
238
3.9. OTHER NITROGEN CONTAINING POLYMERS Poly(£-butyl aziridine)
Ambient to 500
3.10. PHOSPHOROUS CONTAINING POLYMERS Poly(oxytetramethylene oxyphenyl phosphono)
Ambient to 550
Poly(oxytetramethylene oxyphenylAmbient to 500 phosphono) capped with phenylisocyanate)
Poly(bis(trifluoroethoxy)phosphazene)
150-400
Poly(diphenoxyphosphazene)
100-400
233
239
TABLE 3. cont'd Polymer Poly(diphenoxy-phosphazene) (residual chlorine content: <0.05%) Poly(diphenoxy-phosphazene) (residual chlorine content: 2.4%) Poly(diphenoxy-phosphazene) (residual chlorine content: 9.9%)
Temperature range (0C) Ambient to 480 Ambient to 480 Ambient to 480
Degradation products
Refs.
Traces of phenol, phenoxy cyclic trimer and monochlorophenoxy 316 cyclic trimer Phenoxy cyclic trimer and tetramer, monochloropentaphenoxy cyclic 316 trimer, monochloroheptaphenoxy cyclic tetramer, dichlorohexaphenoxy cyclic tetramers Phenoxy cyclic trimer and tetramer, monochloropentaphenoxy cyclic 316 trimer, monochloroheptaphenoxy cyclic tetramer, dichlorohexaphenoxy cyclic tetramers, dichlorotetraphenoxy cyclic trimers, trichloropentaphenoxy cyclic tetramers, HCl
TABLE 4. MAIN-CHAIN HETEROCYCLIC POLYMERS Polymer Phenol-formaldehyde resin PoIy(I-methylene-2-imidazolidinone) (Poly(ethyleneurea formaldehyde))
Temperature range (0C) 250-400 240 Ambient to 600
Poly(7V-phenylmaleimide)
100-400
Poly(5,5/-bibenzimidazole-2,2/-diyl1,4-phenylene)
400-700 570, 700, 1000
Poly(5,5/-bibenzimidazole-2,2/-diyl1,3-phenylene)
599-667
PoIy(1,3,5,7-tetraoxo-2,3,6,7-tetra700 hydro-(lH,5H)-2,6-benzo[l,2-c: 4,5-c']dipyrroldiyl-1,4-phenylene-carbonyl1,4-phenylene) (Poly(pyromellitimide)) Poly(l,3,5,7-tetraoxo-2,3,6,7-tetra700 hydro-(lH,5H)-2,6-benzo[l,2-c:4,5-c']dipyrroldiyl-1,4-phenylene-methylene1,4-phenylene) (Poly(pyromellitimide)) PoIy(1,3,5,7-tetraoxo-2,3,6,7-tetra700 hydro-( 1 H,5H)-2,6-benzo[ 1,2-c: 4,5-c']dipyrroldiyl-1,4-phenylene-oxy1,4-phenylene) (Poly(pyromellitimide)) Poly(l,5-diimino-3,7-dioxo450-500 2,3,6,7-tetrahydro-(lH,5H)-2,6-benzo [1,2-c: 4,5-c'] dipyrroldiyl- 1,3-phenylene) PoIy(1,5-diimino-3,7-dioxo450-500 2,3,6,7-tetrahydro-(lH,5H)-2,6-benzo [1,2-c: 4,5-c']dipyrroldiyl-l,4-phenyleneoxy1,4-phenylene)
Degradation products
Refs.
Volatiles comprise xylene (76%), traces of phenol, cresol, benzene 53 Formaldehyde (trace) 253 Low boiling fraction consists of NH 3 , CO 2 , HCN, CH 4 , CO (trace); 253 IR data also suggests presence of isocyanate, ketamine and carbodiimide or cyanogen compounds; high boiling fraction (77% of total volatiles) consists of chain fragments up to pentamer, including Af-methylethylene urea, corresponding unsaturated compounds and higher homologues; similarly, AUV'-dimethylethylene urea and homologues Aniline, P h - N = C H - C H 2 - C H 3 , Af-phenylsuccinimide, 301 N-phenylmaleimide (trace), P h - N = C H - C H = CH-CO-NH-Ph Phenol, terephthalodinitrile, benzonitrile, 4,4/-diaminodiphenyl, H 2 , CO, 56 NH 3 , HCN, traces of aniline, carbonaceous residue H 2 (700 and 1000°C), NH 3 (570 and 700), N 2 O, HCN, cyanogen (570 217 only), CH 4 , C 2 H 6 , ethylene, acetylene (700 and 1000), acetonitrile (700 and 1000), propene (570 and 700), benzene, toluene, benzonitrile (700 only), ethylbenzene, methylbenzonitrile (700 only) Gaseous products; H 2 , NH 3 , HCN, and CH 4 ; products involatile at 218 ambient temperature after approx. 50% weight loss; benzimidazole (29.8%), benzoxazole (4.9%), 2-methylbenzimidazole (7.3%), 2-phenyl-benzimidazole (24.3%), 2-(3-methylphenyl)benzimidazole (5.3%), 5-(3-aminophenyl)benzimidazole (9.6%), 2-(3-cyanophenyl)benzimidazole (7.8%), 5,5'-bibenzimidazole (4.4%), 2-phenyl-5-(3-aminophenyl)-benzimidazole (4.4%), 2-phenyl-5,5/-bibenzimidazole (1.9%), 2-phenyl-5-(benzoxazolo)benzimidazole (0.3%) H 2 , CO, CH 4 , CO 2 , H 2 O, benzene, benzonitrile, chain fragments, 60% 61 residue H 2 , CO, CH 4 , CO 2 , H 2 O, benzene, toluene, benzonitrile, chain fragments, 60% residue
61
H 2 , CO, CH 4 , CO 2 , H 2 O, benzene, benzonitrile, phenol, chain fragments, 60% residue
61
CO, CO 2 , HCN, NH 3 , H 2 and traces of CH 4 and C 6 H 6 ; NH 3 is the main product at 4400C, CO increases at higher temperatures
219
CO, CO2 HCN, NH3, H2 and traces of CH4 and C6H6; NH3 is the main product at 4400C, CO increases at higher temperatures
References page II - 475
TABLE 4. cont'd Polymer
Temperature range (0C)
Degradation products
Refs.
Poly(triazines)
Poly(perfluoropyridine)
415-505
C 2 F 4 , C 2 F 6 , and smaller amounts of C 3 H 6 and C 3 H 8 and larger chain fragments
48
430-503
C 2 F 4 with traces of CF4, C 3 H 6 , and larger chain fragments
48
305-465 480-660 690-760
Only volatile product is benzonitrile HCN and NH3 H 2 and carbonaceous residue
54 54 54
424-550
Perfluoroethane, perfluoromethane, perfluoroethylene, 220 perfluoropropane, perfluoropropylene, acetal fluoride, carbonyl fluoride
600
Volatiles comprise CO2, CO, SiF4 (all from silica vessel); carbonaceous residue remains
300
CO 2 , CO, NO
52
Poly(parabanic acid)
221
Poly(bismaleimides)
Poly(3-(4-octylphenyl)2,2/-bithiophene) Poly(3-octylthiophene) Poly(3-octyl-2,2'-bithiophene) Poly(3-(4-octylphenyl)thiophene)
350-500
Aliphatic: C 2 - C 6 fractions, maleimide (MI), succinimide (SI) 222 MI-CH 3 , SI-CH 3 , MI-C 2 H 5 , SI-C 2 H 5 , MI-C 3 H 7 , SI-C 3 H 7 , MI-C 4 H 9 , SI-C 4 H 9 , MI-C 5 Hn, SI-C 5 Hn, MI-(CH 2 ) 2 -MI, SI-(CH 2 ) 2 -SI, MI-(CH 2 ) 6 -MI, MI-(CH 2 )S-MI, MI-(CH 2 )I 0 -MI, MI-(CH 2 )I 2 -MI
350-500
Benzene, toluene, aniline, SI, methylaniline, phenylisocyanate, tolylisocyanate, and various other products (see Ref.)
222
350-500
Aniline, phenol, SI, anisidine, phenylisocyanate, and various other products (see Ref.)
222
H 2 S, COS, SO2, CH3SH, CS 2 , S 8 , C i - C 8 alkanes and alkenes, benzene, ethylbenzene, toluene, styrene, octylbenzene, thiophene, methylthiophene, bithiophene C i - C 8 alkanes and alkenes, H 2 S, CS 2 , benzene, toluene C i - C 8 alkanes and alkenes, H 2 S, CS 2 , benzene, toluene C i - C 8 alkanes and alkenes, H 2 S, CS 2 , benzene, toluene
284
800 550-1400 550-1400 550-1400
284 284 284
Next Page
TABLE 5. CELLULOSE AND ITS DERIVATIVES Polymer
Temperature range (0C)
Cellulose
250-397 Ambient to 500
- , a form
330-440
Cellulose (oxidized)
180-331
Cellulose triacetate
250-310 250-900
Ethyl cellulose
C.
230-320 306
Degradation products
Refs.
H 2 O with smaller amounts of CO2 and CO and a tar containing 17,18 principally levoglucosan H 2 , CO, CO2, H2O, furan, furancarboxyaldehyde, methylfurans, acetone, 273 hydroxypropanone, butenal, butanone, butanedione, levoglucosan Fixed gases (not identified), pentene, acetaldehyde, furan, 162 propionaldehyde, acetone, acrolein, 2-methylfuran, butyraldehyde, methyl ethyl ketone, benzene, 2,5-dimethylfuran, methyl vinyl ketone, 2,3-butanedione, toluene, crotonaldehyde, H2O, cyclopentanone, cyclooctatetraene, acetol, pyruvaldehyde, acetic acid, furfural, formic acid, 5-methyl-2-furfural, furfuryl alcohol, butyrolactone, 2-hydroxy-3-methyl-3-cyclopenten-2-one, phenol, o-cresol, m-cresol, p-cresol, 2,5-dimethylphenol, 3,4-dimethylphenol, 5-hydroxymethylfurfural Mainly H 2 O and CO2, smaller amounts of CO, formaldehyde, methanol, acetic acid, ethanol and acetaldehyde, and very little tar Product fraction volatile at 25°C contains acetic acid, CO2, CO, CH4, 18 H 2 , acetaldehyde and acetone; heavier fractions do not contain levoglucosan acetate Main products: acetic acid, water, CO, CH4, H 2 , CO 2 ; minor products: 223 ketene, acetaldehyde, acetone, acetylene, ethylene, ethane, propylene, and C 4 , C 5 and C 6 hydrocarbons Acetic acid, acetyl derivatives of D-glucose 224 H2O, CO, CO2, C 2 H 4 , C 2 H 6 , C2H5OH, CH3CHO, aliphatic 224 compounds, furan derivatives
REFERENCES
1. G. G. Cameron, D. R. Kane, Polymer, 9, 461 (1968). 2. S. Straus, S. L. Madorsky, J. Res. Natl. Bur. Std., 50, 165 (1953). 3. S. L. Madorsky, J. Polym. Sci., 11, 491 (1953). 4. J. R. Schaefgen, I. M. Sarasohn, J. Polym. Sci., 58, 1049 (1962). 5. C. S. Marvel, J. C. Cowan, J. Am. Chem. Soc, 61, 3156 (1939). 6. A. J. Canale, W. E. Goode, J. B. Kinsinger, J. R. Panchak, R. L. Kelso, R. K. Graham, J. Appl. Polym. Sci., 4, 231 (1960). 7. J. W. C. Crawford, D. Plant, J. Chem. Soc, 4492, 1952. 8. G. G. Cameron, G. P. Kerr, J. Polym. Sci. A-I, 7, 3067 (1969). 9. W. J. Burlant, J. L. Parsons, J. Polym. Sci., 22, 249 (1956). 10. S. Straus, S. L. Madorsky, J. Res. Natl. Bur. Std., 61, 77 (1958). 11. S. L. Madorsky, S. Straus, J. Res. Natl. Bur. Std., 63A, 261 (1959). 12. A. R. Monahan, J. Polym. Sci. A-I, 4, 2391 (1966). 13. S. L. Madorsky, S. Straus, J. Res. Natl. Bur. Std., 53, 361 (1954). 14. S. L. Madorsky, S. Straus, J. Res. Natl. Bur. Std., 55, 223 (1955). 15. M. A. Verkhotin, K. A. Andrianov, M. N. Yermakova, S. R. Rafikov, V. V. Rode, Polym. Sci. USSR, 8,2369 (1966). 16. S. L. Madorsky, S. Straus, D. Thompson, L. Williamson, J. Res. Natl. Bur. Std., 42, 499 (1949). 17. S. L. Madorsky, V. E. Hart, S. Straus, J. Res. Natl. Bur. Std., 56, 343 (1956).
18. S. L. Madorsky, V. E. Hart, S. Straus, J. Res. Natl. Bur. Std., 60, 343 (1958). 19. R. F. Schwenker, Jr., L. R. Beck, Textile Res. J., 624, (August, 1960). 20. A. B. Blyumenfel'd, B. M. Kovarskaya, Polym. Sci. USSR, 12, 710 (1970). 21. L. G. Kaufman, R T. Funke, A. A. Volpe, Macromolecules, 3, 358 (1970). 22. J. L. Cotter, G. J. Knight, W. W. Wright, J. Polym. Sci. B, 6, 763 (1968). 23. S. L. Madorsky, V. E. Hart, S. Straus, V. A. Sedlek, J. Res. Natl. Bur. Std., 51, 327 (1953). 24. E. E. Lewis, M. A. Naylor, J. Am. Chem. Soc, 69, 1968 (1947). 25. S. L. Madorksy, S. Straus, J. Polym. Sci., 36, 183 (1959). 26. E. P. Goodings, Soc. Chem. Ind. (London), Monograph, 13, 211 (1961). 27. C. E. Schweitzer, R. N. MacDonald, J. O. Punderson, J. Appl. Polym. Sci., 1, 158 (1959). 28. S. Straus, S. L. Madorsky, J. Res. Natl. Bur. Std., 66A, 401 (1962). 29. Y. Tsuchiya, K. Sumi, J. Polym. Sci. A-I, 7, 813 (1969). 30. S. D. Bruck, Polymer, 7, 231 (1966). 31. S. Straus, S. L. Madorsky, Ind. Eng. Chem., 48, 1212 (1956). 32. B. S. T. Boonstra, G. J. Van Amerongen, Ind. Eng. Chem., 41, 161 (1949). 33. D. H. Grant, N. Grassie, Polymer, 1, 125 (1960). 34. N. Grassie, H. W. Melville, Proc Roy. Soc A, 190, 1 (1949). 35. R D. Zemany, Nature, 171, 391 (1953).
Previous Page
TABLE 5. CELLULOSE AND ITS DERIVATIVES Polymer
Temperature range (0C)
Cellulose
250-397 Ambient to 500
- , a form
330-440
Cellulose (oxidized)
180-331
Cellulose triacetate
250-310 250-900
Ethyl cellulose
C.
230-320 306
Degradation products
Refs.
H 2 O with smaller amounts of CO2 and CO and a tar containing 17,18 principally levoglucosan H 2 , CO, CO2, H2O, furan, furancarboxyaldehyde, methylfurans, acetone, 273 hydroxypropanone, butenal, butanone, butanedione, levoglucosan Fixed gases (not identified), pentene, acetaldehyde, furan, 162 propionaldehyde, acetone, acrolein, 2-methylfuran, butyraldehyde, methyl ethyl ketone, benzene, 2,5-dimethylfuran, methyl vinyl ketone, 2,3-butanedione, toluene, crotonaldehyde, H2O, cyclopentanone, cyclooctatetraene, acetol, pyruvaldehyde, acetic acid, furfural, formic acid, 5-methyl-2-furfural, furfuryl alcohol, butyrolactone, 2-hydroxy-3-methyl-3-cyclopenten-2-one, phenol, o-cresol, m-cresol, p-cresol, 2,5-dimethylphenol, 3,4-dimethylphenol, 5-hydroxymethylfurfural Mainly H 2 O and CO2, smaller amounts of CO, formaldehyde, methanol, acetic acid, ethanol and acetaldehyde, and very little tar Product fraction volatile at 25°C contains acetic acid, CO2, CO, CH4, 18 H 2 , acetaldehyde and acetone; heavier fractions do not contain levoglucosan acetate Main products: acetic acid, water, CO, CH4, H 2 , CO 2 ; minor products: 223 ketene, acetaldehyde, acetone, acetylene, ethylene, ethane, propylene, and C 4 , C 5 and C 6 hydrocarbons Acetic acid, acetyl derivatives of D-glucose 224 H2O, CO, CO2, C 2 H 4 , C 2 H 6 , C2H5OH, CH3CHO, aliphatic 224 compounds, furan derivatives
REFERENCES
1. G. G. Cameron, D. R. Kane, Polymer, 9, 461 (1968). 2. S. Straus, S. L. Madorsky, J. Res. Natl. Bur. Std., 50, 165 (1953). 3. S. L. Madorsky, J. Polym. Sci., 11, 491 (1953). 4. J. R. Schaefgen, I. M. Sarasohn, J. Polym. Sci., 58, 1049 (1962). 5. C. S. Marvel, J. C. Cowan, J. Am. Chem. Soc, 61, 3156 (1939). 6. A. J. Canale, W. E. Goode, J. B. Kinsinger, J. R. Panchak, R. L. Kelso, R. K. Graham, J. Appl. Polym. Sci., 4, 231 (1960). 7. J. W. C. Crawford, D. Plant, J. Chem. Soc, 4492, 1952. 8. G. G. Cameron, G. P. Kerr, J. Polym. Sci. A-I, 7, 3067 (1969). 9. W. J. Burlant, J. L. Parsons, J. Polym. Sci., 22, 249 (1956). 10. S. Straus, S. L. Madorsky, J. Res. Natl. Bur. Std., 61, 77 (1958). 11. S. L. Madorsky, S. Straus, J. Res. Natl. Bur. Std., 63A, 261 (1959). 12. A. R. Monahan, J. Polym. Sci. A-I, 4, 2391 (1966). 13. S. L. Madorsky, S. Straus, J. Res. Natl. Bur. Std., 53, 361 (1954). 14. S. L. Madorsky, S. Straus, J. Res. Natl. Bur. Std., 55, 223 (1955). 15. M. A. Verkhotin, K. A. Andrianov, M. N. Yermakova, S. R. Rafikov, V. V. Rode, Polym. Sci. USSR, 8,2369 (1966). 16. S. L. Madorsky, S. Straus, D. Thompson, L. Williamson, J. Res. Natl. Bur. Std., 42, 499 (1949). 17. S. L. Madorsky, V. E. Hart, S. Straus, J. Res. Natl. Bur. Std., 56, 343 (1956).
18. S. L. Madorsky, V. E. Hart, S. Straus, J. Res. Natl. Bur. Std., 60, 343 (1958). 19. R. F. Schwenker, Jr., L. R. Beck, Textile Res. J., 624, (August, 1960). 20. A. B. Blyumenfel'd, B. M. Kovarskaya, Polym. Sci. USSR, 12, 710 (1970). 21. L. G. Kaufman, R T. Funke, A. A. Volpe, Macromolecules, 3, 358 (1970). 22. J. L. Cotter, G. J. Knight, W. W. Wright, J. Polym. Sci. B, 6, 763 (1968). 23. S. L. Madorsky, V. E. Hart, S. Straus, V. A. Sedlek, J. Res. Natl. Bur. Std., 51, 327 (1953). 24. E. E. Lewis, M. A. Naylor, J. Am. Chem. Soc, 69, 1968 (1947). 25. S. L. Madorksy, S. Straus, J. Polym. Sci., 36, 183 (1959). 26. E. P. Goodings, Soc. Chem. Ind. (London), Monograph, 13, 211 (1961). 27. C. E. Schweitzer, R. N. MacDonald, J. O. Punderson, J. Appl. Polym. Sci., 1, 158 (1959). 28. S. Straus, S. L. Madorsky, J. Res. Natl. Bur. Std., 66A, 401 (1962). 29. Y. Tsuchiya, K. Sumi, J. Polym. Sci. A-I, 7, 813 (1969). 30. S. D. Bruck, Polymer, 7, 231 (1966). 31. S. Straus, S. L. Madorsky, Ind. Eng. Chem., 48, 1212 (1956). 32. B. S. T. Boonstra, G. J. Van Amerongen, Ind. Eng. Chem., 41, 161 (1949). 33. D. H. Grant, N. Grassie, Polymer, 1, 125 (1960). 34. N. Grassie, H. W. Melville, Proc Roy. Soc A, 190, 1 (1949). 35. R D. Zemany, Nature, 171, 391 (1953).
36. R R. E. J. Cowley, H. W. Melville, Proc. Roy. Soc. A, 210, 461 (1952). 37. J. W. C. Crawford, J. Soc. Chem. Ind., 68, 201 (1949). 38. N. Grassie, J. R. MacCallum, J. Polym. ScL, 2, 983 (1964). 39. D. H. Grant, N. Grassie, Polymer, 1, 445 (1960). 40. N. Grassie, I. C. McNeill, J. Chem. Soc, 3929, 1956. 41. C. S. Marvel, E. H. Riddle, J. O. Corner, J. Am. Chem. Soc, 64, 92 (1942). 42. K. F. Wissbrun, J. Am. Chem. Soc, 81, 58 (1959). 43. L. Reginato, Makromol. Chem., 132, 113 (1970). 44. C. S. Marvel, C. L. Levesque, J. Am. Chem. Soc, 60, 280 (1938). 45. S. Straus, L. A. Wall, J. Res. Natl. Bur. Std., 60, 39 (1958). 46. S. Straus, L. A. Wall, J. Res. Natl. Bur. Std., 63A, 269 (1959). 47. S. D. Bruck, Polymer, 6, 483 (1965). 48. L. A. Wall, S. Straus, J. Res. Natl. Bur,. Std., 65A, 227 (1961). 49. S. Straus, L. A. Wall, Soc. Plastics Eng. J., 56, (January 1964). 50. J. L. Cotter, G. J. Knight, J. M. Lancaster, W. W. Wright, J. Appl. Polym. ScL, 12, 2481 (1968). 51. N. S. J. Christopher, J. L. Cotter, G. J. Knight, W. W. Wright, J. Appl. Polym. Sci., 12, 863 (1968). 52. J. L. Cotter, H. Dickinson, G. J. Knight, W. W. Wright, J. Appl. Polym. Sci., 15, 317 (1971). 53. A. A. Berlin, V. V. Yarkina, A. P. Firsov, Polym. Sci. USSR, 10, 2219 (1968). 54. W. Wrasidlo, P. M. Hergenrother, Macromolecules, 3, 548 (1970). 55. G. F. L. Ehlers, K. R. Fisch, W. R. Powell, J. Polym. Sci. A-I, 7, 2931 (1969). 56. V. V. Rode, N. M. Kotsoyeva, G. M. Cherkasova, D. S. Tugushi, G. M. Tseitlin, A. L. Rusanov, V. V. Korshak, Polym. Sci. USSR, 12, 2103 (1970). 57. Ye. P. Krasnov, V. M. Savinov, L. B. Sokolov, V. I. Logunova, V. K. Belyakov, T. A. Polyakova, Polym. Sci. USSR, 8, 413 (1966). 58. G. F. L. Ehlers, K. R. Fisch, W. R. Powell, J. Polym. Sci. A-1, 7, 2969 (1969). 59. G. F. L. Ehlers, K. R. Fisch, W. R. Powell, J. Polym. Sci. A-1, 7, 2955 (1969). 60. A. Davis, J. H. Golden, J. Chem. Soc B, 1, 45 (1968). 61. D. P. Bishop, D. A. Smith, J. Appl. Polym. Sci., 14, 345 (1970). 62. S. L. Madorsky, S. Straus, J. Res. Natl. Bur. Std., 40, 417 (1948). 63. S. L. Madorsky, "Thermal Degradation of Organic Polymers", Wiley, New York, 1964. 64. S. Straus, S. L. Madorsky, J. Res. Natl. Bur. Std., 65A, 243 (1961). 65. R. H. Still, R B. Jones, A. L. Mansell, J. Appl. Polym. Sci., 13, 401 (1969). 66. R. H. Still, P. B. Jones, J. Appl. Polym. Sci., 13, 2033 (1969). 67. L. A. Wall, J. M. Antonucci, S. Straus, M. Tryon, Soc Chem. Ind. (London), Monograph, 13, 295 (1961). 68. D. C. Allport, Polymer, 8, 492 (1967).
69. V. C. E. Burnop, K. G. Latham, Polymer, 8, 589 (1967). 70. S. N. Novikov, Ye. G. Kagan, A. N. Pravednikov, Polym. Sci. USSR, 8, 1114(1966). 71. N. Grassie, Trans. Faraday Soc, 48, 379 (1952). 72. J. B. Gilbert, J. J. Kipling, Fuel, 12, 249 (1962). 73. Y Tsuchiya, K. Sumi, J. Polym. Sci. A-I, 7, 3151 (1969). 74. J. B. Gilbert, J. J. Kipling, B. McEnaney, J. N. Sherwood, Polymer, 3, 1 (1962). 75. R. R. Stromberg, S. Straus, B. G. Achhammer, J. Polym. Sci., 35, 355 (1959). 76. M. M. O'Mara, J. Polym. Sci. A-I, 8, 1887 (1970). 77. F. H. Winslow, W. O. Baker, W. A. Yager, quoted in Ch. V of Ref. 63. 78. H. Gilbert, F. F. Miller, S. J. Averill, R. F. Schmidt, F. D. Stewart, H. L. Trumbull, J. Am. Chem. Soc, 76, 1074 (1954). 79. Y. A. Glagoleva, V. R. Regel, Polym. Sci. USSR, 12, 1078 (1970). 80. P. Brandt, V. H. Dibeler, F. L. Mohler, J. Res. Natl. Bur. Std., 50, 201 (1953). 81. H. H. G. Jellinek, S. N. Lipovac, J. Polym. Sci. A-I, 8, 2517 (1970). 82. J. C. W. Chien, P. C. Uden, Ju-Li Fan, J. Polym. Sci., Chem. Ed., 20, 2159 (1982). 83. S. Tamura, J. K. Gillham, J. Appl. Polym. Sci., 22, 1867 (1978). 84. I. C. McNeill, L. Ackerman, S. N. Gupta, J. Polym. Sci., Chem. Ed., 16, 2169 (1978). 85. D. L. Gardner, I. C. McNeill, Eur. Polym. J., 7, 593 (1971). 86. D. L. Gardner, I. C. McNeill, Eur. Polym. J., 7, 603 (1971). 87. J. C. W. Chien, J. K. Y. Kiang, Eur. Polym. J., 15, 1059 (1979). 88. I. C. McNeil, S. N. Gupta, Polym. Degrad. Stab., 2, 95 (1980). 89. B. Dodson, I. C. McNeill, J. Polym. Sci., Chem. Ed., 12, 2305 (1974). 90. B. Dodson, I. C. McNeill, T. Straiton, J. Polym. Sci., Chem. Ed., 12, 2369 (1974). 91. A. Hoff, S. Jacobson, J. Appl. Polym. Sci., 26, 3409 (1981). 92. I. C. McNeill, A. Jamieson, D. J. Tosh, J. J. McClune, Eur. Polym. J., 12, 305 (1976). 93. G. A. Razuvaev, B. B. Troitskii, L. V. Chochlova, Z. B. Dubova, J. Polym. Sci. (Letters), 11, 521 (1973). 94. R. J. Gritter, E. Gipstein, G. E. Adams, J. Polym. Sci., Chem. Ed., 17, 3959 (1979). 95. Y. Tsuchiya, K. Sumi, J. Polym. ScL A-I, 7, 1599 (1969). 96. A. Hoff, S. Jacobson, J. Appl. Polym. Sci., 29, 465 (1984). 97. N. Grassie, W. B. H. Leeming, Eur. Polym. J., 11, 809 (1975). 98. N. Grassie, A. Heaney, Eur. Polym. J., 10, 415 (1974). 99. N. Grassie, W. B. H. Leeming, Eur. Polym. J., 11, 819 (1975). 100. V. V. Konovalov, A. B. Blyumenfel'd, Ye. F. Zinin, M. S. Akutin, B. M. Kovarskaya, B. V. Andrianov, V. I. Kleiner, Vysokomolkul Soedin. A, 16, 323 (1974). 101. J. K. Haken, D. K. M. Ho, E. Houghton, J. Polym. Sci., Chem. Ed., 12, 1163(1974).
102. L. Ackerman, W. J. McGiIl, J. S. African Chem. Inst., 26, 82 (1973). 103. N. Grassie, J. G. Speakman, T. I. Davis, J. Polym. Sci. A-1,9, 931 (1971). 104. W. J. McGiIl, L. Ackerman, J. Polym. Sci., Chem. Ed., 12, 1541 (1974). 105. N. Grassie, J. G. Speakman, J. Polym. Sci. A-I, 9, 949 (1971). 106. G. G. Cameron, D. R. Kane, Polymer, 9, 461 (1968). 107. Yu. P. Gorelov, R. Ya Khvilivitskii, R. P. Chernovskaya, L. M. Terman, Polym. Sci., USSR, 18, 2309 (1976). 108. N. Grassie, B. J. D. Torrance, J. Polym. Sci. A-I, 6, 3303 (1968). 109. N. Grassie, B. J. D. Torrance, J. B. Colford, J. Polym. Sci. A1, 7, 1425 (1969). 110. N. Grassie, A. Johnston, A. Scotney, Polym. Degrad. Stab., 3, 349 (1980-81). 111. N. Grassie, A. Johnston, A. Scotney, Polym. Degrad. Stab., 3, 365 (1980-81). 112. N. Grassie, J. D. Fortune, Makromol. Chem., 168, 1 (1973). 113. N. Grassie, R. M. Jenkins, Eur. Polym. J., 9, 697 (1973). 114. P. K. Dhal, G. N. Babu, J. Polym. Sci., Chem. Ed., 22, 1817 (1984). 115. G. N. Babu, P. H. Lu, S. L. Hsu, J. C. W. Chien, J. Polym. Sci., Chem. Ed., 22, 195 (1984). 116. N. Grassie, R. McGuchan, Eur. Polym. J., 7, 1091, 1357 (1971). 117. A. Ballistreri, S. Foti, G. Montaudo, S. Pappalardo, E. Scamporrino, Makromol. Chem., 180, 2835 (1979). 118. N. Grassie, E. M. Grant, J. Polym. Sci., C, 16, 591 (1967). 119. N. Grassie, R. McGuchan, Eur. Polym. J., 8, 243 (1972). 120. N. Grassie, A. Johnston, A. Scotney, Polym. Degrad. Stab., 4, 173 (1982). 121. N. Grassie, E. Farish, Eur. Polym. J., 3, 619 (1967). 122. N. Grassie, J. N. Hay, Makromol. Chem., 64, 82 (1963). 123. N. Grassie, D. R. Bain, J. Polym. Sci. A-I, 8, 2653, 2665 (1970). 124. D. Braun, R. Disselhoff, Angew. Makromol. Chem., 23, 103 (1972). 125. N. Grassie, E. M. Grant, Eur. Polym. J., 2, 255 (1966). 126. N. Grassie, A. S. Holmes, Polym. Degrad. Stab., 3, 145 (1981). 127. N. Grassie, I. C. McNeill, J. N. R. Samson, Polym. Degrad. Stab., 1, 17 (1979). 128. R. J. Gritter, M. Seeger, D. E. Johnson, J. Polym. Sci., Chem. Ed., 16, 169 (1978). 129. N. Grassie, A. Scotney, L. Mackinnon, J. Polym. Sci., Chem. Ed., 15, 251 (1977). 130. N. Grassie, A. Johnston, A. Scotney, Eur. Polym. J., 17, 589 (1981). 131. J. Razga, J. Petranek, Eur. Polym. J., 11, 805 (1975). 132. I. C. McNeill, M. Zulfiqar, J. Polym. Sci., Chem. Ed., 16, 2465 (1978). 133. I. C. McNeill, M. Zulfiqar, J. Polym. Sci., Chem. Ed., 16, 3201 (1978). 134. I. C. McNeill, M. Zulfiqar, Polym. Degrad. Stab., 1, 89 (1979).
135. 136. 137. 138. 139. 140. 141. 142. 143. 144. 145. 146. 147. 148. 149. 150. 151. 152. 153. 154. 155. 156. 157. 158. 159. 160. 161. 162. 163. 164. 165. 166. 167.
A. Hamoudi, I. C. McNeill, Eur. Polym. J., 14, 525 (1978). A. Jamieson, I. C. McNeill, Eur. Polym. J., 10, 217 (1974). N. Grassie, E. Farish, Eur. Polym. J., 3, 305 (1967). I. C. McNeill, T. Straiton, P. Anderson, J. Polym. Sci., Chem. Ed., 18, 2085 (1980). N. Grassie, A. Johnston, A. Scotney, Polym. Degrad. Stab., 4, 123 (1982). G. Camino, N. Grassie, I. C. McNeill, J. Polym. Sci., Chem. Ed., 16, 95 (1978). N. Grassie, I. C. McNeill, I. Cooke, J. Polym. Sci., 12, 831 (1968). A. Jamieson, I. C. McNeill, J. Polym. Sci., Chem. Ed., 14, 1839 (1976). I. C. McNeill, T. Straiton, P. Anderson, J. Polym. Sci., Chem. Ed., 18, 2085 (1980). I. C. McNeill, D. Neil, Eur. Polym. J., 6, 569 (1970). A. Guyot, M. Bert, A. Michel, I. C. McNeill, Eur. Polym. J., 7, 471 (1971). N. Grassie, I. C. McNeill, J. N. R. Samson, Eur. Polym. J., 14, 931 (1978). A. Ballistreri, S. Foti, G. Montaudo, E. Scamporrino, J. Polym. Sci., Chem. Ed., 18, 1147 (1980). I. C. McNeill, R. C. McGuiness, Polym. Degrad. Stab., 5, 303 (1983). T. Iida, M. Nakanishi, K. Goto, J. Polym. Sci., Chem. Ed., 12, 737 (1974). D. Raucher, M. Levy, J. Polym. Sci., Chem. Ed., 17, 2675 (1979). D. A. Chatfield, J. Polym. Sci., Chem. Ed., 21, 1681 (1983). D. R. Roberts, A. L. Gatzke, J. Polym. Sci., Chem. Ed., 16, 1211 (1978). M. Blazso, T. Szekely, Eur. Polym. J., 10, 115 (1974). C. Vasile, C. N. Cascaval, P. Barbu, J. Polym. Sci., Chem. Ed., 19, 907 (1981). N. Grassie, I. F. McLaren, I. C. McNeill, Eur. Polym. J., 6, 679 (1970). N. Grassie, I. F. McLaren, I. C. McNeill, Eur. Polym. J., 6, 865 (1970). A. Jamieson, I. C. McNeill, J. Polym. Sci., Chem. Ed., 12, 387 (1974). A. Jamieson, I. C. McNeill, J. Polym. Sci., Chem. Ed., 14, 603 (1976). I. C. McNeill, D. Neil, A. Guyot, M. Bert, A. Michel, Eur. Polym. J., 7, 453 (1971). B. Dodson, I. C. McNeill, J. Polym. Sci., Chem. Ed., 14, 353 (1976). I. C. McNeill, D. Neil, Eur. Polym. J., 7, 115 (1971). F. A. Wodley, J. Appl. Polym. Sci., 15, 835 (1971). N. B. Zaitsev, I. Ya Poddubnyi, Polym. Sci. USSR, 17, 1299 (1975). I. C. McNeill, M. A. J. Mohammed, Eur. Polym. J., 8, 975 (1972). I. Luderwald, O. Vogl, Makromol. Chem., 180, 2295 (1979). Y Sugimura, T. Nagaya, S. Tsuge, Macromolecules, 14, 520 (1981). J. P. Montheard, M. Camps, S. Kawayi, Makromol. Chem., 183, 1191 (1982).
168. G. N. Babu, R H. Lu, S. L. Hsu, J. C. W. Chien, J. Polym. ScL, Chem. Ed., 22, 213 (1984). 169. R. J. Gritter, E. Gipstein, G. E. Adams, J. Polym. ScL, Chem. Ed., 17, 3959 (1979). 170. T. S. Ellis, R. H. Still, J. Appl. Polym. ScL, 23, 2871, 2881 (1979). 171. T. S. Ellis, R. H. Still, J. Appl. Polym. ScL, 23, 2837, 2855 (1979). 172. R. H. Still, M. B. Evans, A. Whitehead, J. Appl. Polym. ScL, 16, 3207 (1972). 173. J. R. MacCallum, K. Paterson, Eur. Polym. J., 10, 477 (1974). 174. F. Hrabak, J. Mitera, V. Kubelka, M. Bezdek, Eur. Polym. J., 14, 219 (1978). 175. J. Y. C. Chu, M. Stolka, J. Polym. ScL, Chem. Ed., 13, 2867 (1975). 176. H. H. G. Jellinek, S. H. Ronel, J. Polym. ScL A-I, 9, 2605 (1971). 177. J. L. Cotter, G. J. Knight, W. W. Wright, Br. Polym. J., 7, 389 (1975). 178. J. L. Cotter, G. J. Knight, W. W. Wright, Br. Polym. J., 7,375 (1975). 179. J. Jachowicz, M. Kryszewski, P. Kowalski, J. Appl. Polym. ScL, 22, 2891 (1978). 180. J. Jachowicz, M. Kryszewski, A. Sobol, Polymer, 20, 995 (1979). 181. N. Grassie, R. S. Roche, Makromol. Chem., 112, 16 (1968). 182. G. H. McCain, J. M. Sanders, J. Appl. Polym. ScL, 18, 3077 (1974). 183. N. A. Nikolayeva, B. G. Belenkii, N. A. Glukhov, Yu. V. Zhuravlev, Yu N. Sazanov, Polym. Sci. USSR, 12, 2978 (1970). 184. S. Iwabuchi, V. Jaacks, W. Kern, Makromol. Chem., 177, 2675 (1976). 185. A. Patterson, G. J. Sutton, B. J. Tighe, J. Polym. Sci., Chem. Ed., 11, 2343 (1973). 186. N. Grassie, E. J. Murray, P A. Holmes, Polym. Degrad. Stab., 6, 47 (1984). 187. S. Foti, M. Giuffrida, P. Maravigna, G. Montaudo, J. Polym. Sci., Chem. Ed., 22, 1201 (1984). 188. D. R. Cooper, R. Molloy, G. J. Sutton, B. J. Tighe, J. Polym. Sci., Chem. Ed., 18, 123 (1980). 189. S. Iwabuchi, V. Jaacks, F. GaKl, W. Kern, Makromol. Chem., 165, 59 (1973). 190. V. Passalacqua, F. Pilati, V. Zamboni, B. Fortunato, P. Manarese, Polymer, 17, 1044 (1976). 191. R. M. Lum, J. Polym. Sci., Chem. Ed., 17, 203 (1979). 192. M. E. Bednas, M. Day, K. Ho, R. Sander, D. M. Wiles, J. Appl. Polym. Sci., 26, 277 (1981). 193. M. Ravey, J. Polym. Sci., Chem. Ed., 21, 1 (1983). 194. R. M. Aseyeva, T. V. Zelenetskaya, O. G. Sel'skaya, A. A. Berlin, Polym. Sci. USSR, 14, 1766 (1972). 195. F. Nakanishi, M. Hasegawa, T. Tasai, Polymer, 16,218 (1975). 196. G. O. Schulz, H. J. Harwood, J. Polym. Sci., Chem. Ed., 12, 1451 (1974). 197. H. H. G. Jellinek, H. Fujiwara, J. Polym. Sci. A-1,10, 1719 (1972).
198. G. P. Norton, B. J. Tighe, R. Molloy, J. Polym. Sci., Chem. Ed., 16, 283 (1978). 199. E. H. Catsiff, M. N. Gillis, R. H. Gobran, J. Polym. ScL A-I, 9, 1271 (1971). 200. V. B. Gavalyan, I. V. Zhieravleva, S-S. A. Pavlova, V. I. Nedel'hin, V. A. Sergeyev, Vysokomol. Soedin., A22, 2121 (1980). 201. A. Davis, Makromol. Chem., 128, 242 (1969). 202. I. I. Levantovaskaya, G. V. Dralyuk, O. A. Mochalova, I. A. Yurkova, M. S. Akutin, B. M. Kovarskaya, Polym. Sci. USSR, 13, 7 (1971). 203. L. I. Danilina, E. N. Teleshov, A. N. Pravednikov, Polym. ScL USSR, 16, 672 (1974). 204. R. J. Gritter, M. Seeger, E. Gipstein, J. Polym. Sci., Chem. Ed., 16, 353 (1978). 205. Yl. P. Krasnov, V. M. Savinov, L. B. Sokolov, V. I. Logunova, V. K. Belyakov, T. A. Polyakova, Vysokomol. Soedin., 8, 380 (1970). 206. D. A. Chatfield, I. N. Einhorn, R. W. Michelson, J. H. Futrell, J. Polym. Sci., Chem. Ed., 17, 1353 (1979). 207. L. H. Peebles, Jr., M. W. Huffman, J. Polym. Sci. A-I, 9, 1807 (1971). 208. N. Grassie, I. G. Macfarlane, Eur. Polym. J., 14, 875 (1978). 209. N. Grassie, I. G. Macfarlane, K. F. Francey, Eur. Polym. J., 15, 415 (1979). 210. J. L. Cotter, G. J. Knight, W. W. Wright, Br. Polym. J., 7, 381 (1975). 211. A. I. Sidnev, Yu. V. Khvashchevskaya, A. F. Moiseyev, I. A. Zubkov, A. N. Pravednikov, Polym. Sci. USSR, 12, 2905 (1970). 212. N. Grassie, K. F. Francey, I. G. Macfarlane, Polym. Degrad. Stab., 2, 67 (1980). 213. N. Grassie, K. F. Francey, Polym. Degrad. Stab., 2, 53 (1980). 214. B. Zelei, M. Blazso, S. Dobos, Eur. Polym. J., 17, 503 (1981). 215. N. Grassie, S. R. Beattie, Polym. Degrad. Stab., 9, 23 (1984). 216. N. Grassie, S. R. Beattie, Polym. Degrad. Stab., 7, 231 (1984). 217. D. A. Chatfield, I. N. Einhorn, J. Polym. Sci., Chem. Ed., 19, 601 (1981). 218. N. R. Lerner, J. Polym. Sci., Chem. Ed., 15, 1145 (1977). 219. R. M. Kromaite, S. V. Lavrov, L. A. Oksentevich, I. V. Vasileva, E. N. Teleshov, A. N. Pravednikov, Polym. ScL USSR, 16, 1006 (1974). 220. V. A. Ponomarenko, V. N. Shilgayev, A. G. Kechina, A. A. Yarosh, S. P. Krukovskii, Polym. ScL USSR, 16, 637 (1974). 221. J. P. Luongo, H. Schonhorn, J. Polym. Sci., Chem. Ed., 13, 1363 (1975). 222. H. D. Stenzenberger, K. U. Heinen, D. O. Hummel, J. Polym. Sci., Chem. Ed., 14, 2911 (1976). 223. A. Scotney, Eur. Polym. J., 8, 163 (1972). 224. W. P. Brown, C. F. H. Tipper, J. Appl. Polym. Sci., 22, 1459 (1978). 225. A. Davis, J. H. Golden, J. Macromol. Sci. Rev. Macromol. Chem. C, 3, 49 (1969).
226. S. Foti, M. Giuffrida, P. Maravigna, G. Montaudo, J. Polym. Sci., Chem. Ed., 21, 1567 (1983). 227. M. S. Lim, B. J. Bulken, E. M. Pearce, J. Polym. Sci., 19, 2773 (1981). 228. N. Grassie, M. Zulfiqar, J. Polym. Sci., Chem. Ed., 16, 1563 (1978). 229. N. Grassie, M. Zulfiqar, in: G. Scott (Ed.), "Developments in Polymer Stabilisation", vol. 1, Applied Science Publishers, London, 1979, p. 197. 230. L. P. Rumao, K. C. Frisch, J. Polym. Sci. A-I, 10, 1499 (1972). 231. S. Foti, P. Maravigna, G. Montaudo, J. Polym. Sci., 19,1679 (1981). 232. S. Foti, M. Giuffrida, P. Maravigna, G. Montaudo, J. Polym. Sci., Chem. Ed., 21, 1583 (1983). 233. N. Grassie, D. H. Mackerron, Polym. Degrad. Stab., 5, 43 (1983). 234. F. Gaboriaud, J. P. Vantelon, J. Polym. Sci., Chem. Ed., 19, 139 (1981). 235. N. Grassie, D. H. Mackerron, Polym. Degrad. Stab., 5, 89 (1983). 236. N. Grassie, M. Zulfiqar, M. I. Guy, J. Polym. Sci., Chem. Ed., 18, 265 (1980). 237. S. Foti, M. Giuffrida, P. Maravigna, G. Montaudo, J. Polym. Sci., Chem. Ed., 21, 1599 (1983). 238. H. R. Allcock, W. J. Cook, Macromolecules, 7, 284 (1974). 239. H. R. Allcock, G. Y. Moore, W. J. Cook, Macromolecules, 7, 571 (1974). 240. I. C. McNeill, A. Ya. Polishchuk, G. E. Zaikov, Polym. Degrad. Stab., 37, 223 (1992). 241. LC. McNeill, S. Ahmed, L Memetea, Polym. Degrad. Stab., 46, 303 (1994). 242. I. C. McNeill, A. Ya. Polishchuk, G. E. Zaikov, Polym. Degrad. Stab., 47, 319 (1995). 243. I. C. McNeill, M. H. Mohammed, Polym. Degrad. Stab., 48, 175 (1995). 244. E. Trebacz, Thermochimica Acta, 143, 51 (1989). 245. H. Morikawa, R. H. Marchessault, Can. J. Chem., 59, 2306 (1981). 246. R. S. Lehrle, R. J. Williams, Macromolecules, 27, 3782 (1994). 247. A. Ballistreri, D. Garozzo, M. Giufrida, G. Montaudo, Macromolecules, 20, 2991 (1987). 248. D.-J. Liaw, K.-F. Teng, Polym. Int., 37, 77 (1995). 249. T. Sawaguchi, T. Takesue, T. Ikemura, M. Seno, Macromol. Chem. Phys., 196, 4139 (1995). 250. G. Montaudo, C. Puglosi, F. Samperi, Macromol. Chem. Phys., 195, 1241 (1994). 251. R. C. White, E. C. Sikabwe, J. Polym. Sci., Chem. Ed., 30, 2781 (1992). 252. M. M. Fares, J. Hacaloglu, S. Suzer, Eur. Polym. J., 30, 845 (1994) 253. G. Camino, M. P. Luda, L. Costa, M. Guaita, Macromol. Chem. Phys., 197, 41 (1996). 254. G. Montaudo, C. Puglisi, J. W. de Leeuw, W. Hartgers, K. Kishore, K. Ganesh, Macromolecules, 29, 6466 (1996).
255. G. Montaudo, C. Puglisi, R. Rapisardi, F. Samperi, Macromol. Chem. Phys., 195, 1225 (1994). 256. F. Gaboriaud, J. P. Vantelon, L Polym. Sci., Chem. Ed., 20, 2063 (1982). 257. R. Abate, A. Ballistreri, G. Montaudo, G. Impallomeni, Macromolecules, 27, 332 (1994). 258. G. Montaudo, C. Puglosi, E. Scamporrino, D. Vitalini, Macromolecules, 19, 2157 (1986). 259. S. Groves, R. Lehrle, Eur. Polym. L, 28, 373 (1992). 260. K. S. Khairou, M. A. Diab, Polym. Degrad. Stab., 44, 17 (1994). 261. K. S. Khairou, M. A. Diab, Polym. Degrad. Stab., 44, 21 (1994). 262. K. S. Khairou, M. A. Diab, Polym. Degrad. Stab., 43, 329 (1993). 263. J. Song, W. Schnabel, Polym. Degrad. Stab., 43, 335 (1994). 264. M. Zulfiqar, A. Paracha, S. Zulfiqar, Polym. Degrad. Stab., 43, 403 (1994). 265. S. Zulfiqar, M. Zulfiqar, M. Rizvi, A. Munir, I. C. McNeill, Polym. Degrad. Stab., 43, 423 (1994). 266. B. Boinon, M. Raihane, J. P. Montheard, Polym. Degrad. Stab., 43, 27 (1994). 267. I. C. McNeill, L. Memetea, Polym. Degrad. Stab., 43, 9 (1994). 268. J. Song, Ch.-H. Fischer, W. Schnabel, Polym. Degrad. Stab., 41, 141 (1993). 269. I. C. McNeill and S. Basan, Polym. Degrad. Stab., 41, 311 (1993). 270. J. C. W. Chien, A. X. Zhao, Polym. Degrad. Stab., 40, 257 (1993). 271. M. Kryszewski, J. Jachowicz, M. Malanga, O. Vogl, Polymer, 23, 271 (1982). 272. A. Rincon, I. C. McNeill, Polym. Degrad. Stab., 40, 343 (1993). 273. S. Soares, G. Camino, S. Levchik, Polym. Degrad. Stab., 49, 275 (1995). 274. M. Bounekhel, I. C. McNeill, Polym. Degrad. Stab., 49, 347 (1995). 275. M. Coskun, K. Demirelli, E. Odzemir, Polym. Degrad. Stab., 47, 251 (1995). 276. S. Zulfiqar, M. Zafar-uz-Zaman, A. Munir, I. C. McNeill, Polym. Degrad. Stab., 47, 59 (1995). 277. I. C. McNeill, T. Mahmood, Polym. Degrad. Stab., 45, 285 (1994). 278. C. N. Cascaval, V. Neagu, Polym. Degrad. Stab., 45, 423 (1994). 279. I. C. McNeill, T. Mahmood, Polym. Degrad. Stab., 46, 195 (1994). 280. S. Zulfiqar, K. Masud, B. Siddique, A. Piracha, Polym. Degrad. Stab., 52, 293 (1996). 281. S. Zulfiqar, M. Rizvi, A. Munir, A. Ghaffar, I. C. McNeill, Polym. Degrad. Stab., 52, 341 (1996). 282. E-D. Kopinke, M. Remmler, K. Mackenzie, M. Moder, O. Wachsen, Polym. Degrad. Stab., 53, 329 (1996). 283. S. Zulfiqar, A. Piracha, K. Masud, Polym. Degrad. Stab., 52, 89 (1996). 284. P. Selsbo, I. Ericsson, Polym. Degrad. Stab., 51, 83 (1996).
285. M. Bounekhel, I. C. McNeill, Polym. Degrad. Stab., 51, 35 (1996). 286. A. Piracha, S. Zulfiqar, Polym. Degrad. Stab., 51, 27 (1996). 287. S. Zulfiqar, M. Zafar-uz-Zaman, A. Munir, I. C. McNeill, Polym. Degrad. Stab., 50, 33 (1996). 288. P. Almen, I. Ericsson, Polym. Degrad. Stab., 50, 223 (1995). 289. N. A. Al-Awadi, M. Z. Elsabee, Polym. Degrad. Stab., 50, 319 (1995). 290. S. L. Hurley, M. L. Mittleman, C. A. Wilkie, Polym. Degrad. Stab., 39, 345 (1993). 291. I. C. McNeill, S. Basan, Polym. Degrad. Stab., 39, 145 (1993). 292. I. C. McNeill, S. Basan, Polym. Degrad. Stab., 39, 139 (1993). 293. H.-J. Dussel, H. Rosen, D. O. Hummel, Makromol. Chem., 177, 2343 (1976). 294. I. C. McNeill, J. J. Liggat, Polym. Degrad. Stab., 36, 291 (1992). 295. I. C. McNeill, A. Rincon, Polym. Degrad. Stab., 24, 59 (1989). 296. I. C. McNeill, A. Rincon, Polym. Degrad. Stab., 24, 171 (1989). 297. I. C. McNeill, S. M. T. Sadeghi, Polym. Degrad. Stab., 29, 233 (1990). 298. I. C. McNeill, M. Bounekhel, Polym. Degrad. Stab., 34, 187 (1991). 299. I. C. McNeill, J. G. Gorman, S. Basan, Polym. Degrad. Stab., 33, 263 (1991). 300. I. Popovic, J. Song, Ch.-H. Fischer, L. Katsikas, G. Hohne, J. Velickovic, W. Schnabel, Polym. Degrad. Stab., 32, 265 (1991). 301. C. T. Vijayakumar, K. Lederer, A. Kramer, Polym. Degrad. Stab., 32, 9 (1991).
302. S. Zulfiqar, M. Zulfiqar, M. Nawaz, I. C. McNeill, J. G. Gorman, Polym. Degrad. Stab., 30, 195 (1990). 303. I. C. McNeill, S. M. T. Sadeghi, Polym. Degrad. Stab., 30, 213 (1990). 304. I. C. McNeill, A. Rincon, Polym. Degrad. Stab., 31, 163 (1990). 305. P. K. Dhal, G. N. Babu, J. C. W. Chien, Polym. Degrad. Stab., 18, 1 (1987). 306. V. L. Rao, P. K. Dhal, G. N. Babu, Polym. Degrad. Stab., 18, 19 (1987). 307. N. A. Weir, K. Whiting, J. Arct, G. McCulloch, Polym. Degrad. Stab., 18, 293 (1987). 308. V. Mailhos-Lefievre, D. Sallot, B. Martel, Polym. Degrad. Stab., 23, 327 (1989). 309. S. Zulfiqar, N. Akthar, M. Zulfiqar, I. C. McNeill, Polym. Degrad. Stab., 23, 299 (1989). 310. P. K. Dhal, G. N. Babu, J. C. W. Chien, Polym. Degrad. Stab., 16, 135 (1986). 311. G. Sivasubramanian, P. Sivasamy, C. T. Vijayakumar, J. K. Fink, Polym. Degrad. Stab., 21, 151 (1988). 312. I. C. McNeill, S. M. T. Sadeghi, Polym. Degrad. Stab., 30, 267 (1990). 313. N. A. Weir, K. Whiting, J. Arct, Polym. Degrad. Stab., 22,17 (1988). 314. S. Zulfiqar, M. Zulfiqar, T. Kausar, I. C. McNeill, Polym. Degrad. Stab., 17, 347 (1987). 315. J. N. Hay, D. J. Kemmish, Polymer, 28, 2047 (1987). 316. S. J. Maynard, T. R. Sharp, J. F. Haw, Macromolecules, 24, 2794 (1991). 317. A. Ballistreri, D. Garozzo, G. Montaudo, Macromolecules, 17, 1312 (1984). 318. J. Jachowicz, M. Kryszewski, M. Mucha, Macromolecules, 17, 1315 (1984). 319. D. A. Chatfield, I. N. Einhorn, R. W. Mickelson, J. H. Futrell, J. Polym. ScL, Chem. Ed., 17, 1367 (1979).
R a d i a t i o n
C h e m i c a l
Y i e l d s :
G
V a l u e s
M . C. Senake Perera Magnetic Resonance Facility, School of Science, Griffith University, Nathan, QId 4111, Australia D a v i d J. T. H i l l Department of Chemistry, University of Queensland, St Lucia, QId 4072, Australia
A. Introduction B. Tables of G values Table 1. Homopolymers 1.1. Polydienes 1.2. Polyolefins 1.3. Polyacrylates 1.4. Poly(methacrylates) 1.5. Poly(styrenes) 1.6. Poly(vinyls) 1.6.1. Acrylamides and Nitriles 1.6.2. Vinyl Monomers 1.7. Miscellaneous Polymers 1.7.1. Cellulose and Derivatives 1.7.2. Poly(siloxanes) 1.7.3. Poly(amino acids) 1.7.4. Polyesters 1.7.5. Polysulfones 1.7.6. Polyketones 1.7.7. Fluoropolymers 1.7.8. Others Table 2. Copolymers 2.1. Copolymers with Ethylene 2.2. Copolymers with Methyl Methacrylate 2.3. Copolymers with Styrene 2.4. Copolymers with Sulfur Dioxide 2.5. Other copolymers Table 3. Polymers Blends Table 4. Composites C. References
11-481 11-481 M-482 M-482 II-482 II-483 II-484 II-485 II-486 II-486 M-486 II-487 II-487 II-487 II-487 II-488 II-488 II-488 II-488 II-489 II-490 II-490 II-490 11-491 11-491 II-492 II-493 II-493 II-493
A.
INTRODUCTION
The G values quoted in the following tables are defined as the radiation chemical yields of individual atomic or molecular events for 100 eV of energy absorbed by the system. G(R) represents the yield of free radicals, G(X) the yield of crosslinks, G(S) the yield of main chain scission, and G(products) the yield of product molecules per 10OeV of absorbed radiation. This table has been compiled from the polymer literature that has been published since the third edition of the "Polymer Handbook" (i.e. 1986-1997). In many cases, the tabulated data are only representative of the total data in the paper, and the original publication should be consulted. B. TABLES OF G VALUES Notes to the Tables General: Unless otherwise stated, the conditions applying are y-rays, vacuum, room temperature (ambient). Symbols/Abbreviations + — vac RT e
cation radical anion radical vacuum room temperature electron beam
d.b. t-v Y X n
double bond trans-vinylene crosslinks crosslinks neutron
TABLE 1. HOMOPOLYMERS Polymer 1.1.
G(R)
G(X)
G(S)
G(products)
Radiation conditions
38.7 (d.b.)
e, 263 K
Refs.
POLYDIENES
Polybutadiene 610 (1,2) 0.0054
2.1 Various
Polyisoprene
0.009 0.5-0.8 Various
NR latex Polychloroprene
77 K 9.3 105 3.36/9.4 5.3
112 (Vinyl) Various 0.34/0.19 90
Various
Various
41 7.2
Poly(2-phenyl butadiene)
1.2.
Comments
3.0
1.6-2.1 Various Various 3.9
e 77K/RT Air, 295 K
Excitation scavenger 1, 2-PBD Radical pairs, isotactic Syndiotactic cis 1,4
64 138 74 97 84 98 104
Effect of pressure Various Review 186 G(Cy) > G(X) 261 G(X) depend on MW G (initiation), 262 G(X) increases G(Cy), G(db) decreases with Crosslinker Vac, 303 K 180 Vac/303 K, ethyl178 ene dichloride 77 K Radical pairs 74 Var cis content 15
94-168 (d.b.), CH 4 , H 2 Various
Various
2.8 (-Cl)
Vac/77, 303 K
186 248 179
RT, vac
235 226
Review +acrylate
POLYOLEFINS
Squalene Poly(butene-l)
1.0
Poly(ethylene)
1.09-1.39 0.63
3.2
4 4.1
4 1.4 15-30 0.25 1.50-2.40
3.0 (H 2 ) 13.9 (-isotactic pentad) 7 (COOH) 9.1 (O 2 ) - 2 (MO
e, air Vac/O2 300K
0.48 8-15
Carries
Air, 300/450K
Pressure effects
1.08-1.69
Various
303-373 K He, 77K O 2 , CCl 4
e pre-irradiated
2.8, 5.8 (C 2 D 4 ) 2.4
Fibers,
89 101 107 172 116 169 30 63 52 147 151
G(S)ZG(X) = 1
1.1-2.8
0.05-2.7 Various gases
1.1 1.5
<0.05 0.48
2.6/0.56 (alkyl) 0.74 G (H) 0.27 G (Y) 1.0
Air
e, N 2 Various compounds e, N 2 Gamma/n
Gamma/alpha, 77 K Vac, molten state 0.2
3.9(H 2 ) 3.5 (damage)
155 70 87 174 163 183
Crystalline region units
228 270
TABLE 1. cont'd Polymer -,LDPE
G(R)
G(X)
G(S)
G(products)
2.5(alkyl) 12.4-15.4 (O 2 ) 4.45 (butanes) Various -1.9(MO
Radiation conditions 77 K O2 air 303 K 298-423 K
Comments
Refs.
G(S)/G(X) = 1.6 +I2 +CH 3 SH antioxidants
Alkanes 77 K
129 164
Various
Air
231 105 184
0.16 (butanes)
Air 77 K 77 K 303 K
3.0 (total) 2.8 (alkyl) Various G(M) -,LLDPE
2.4
-, HDPE
0.4
1.3 2.9-3.6 2.3-4.5(alkyl) 0.3* 0.21
-,HDLPE
5.5
0.3,0.43
Alkanes Y, C = C, (M)
3.7 0.76 (bulk)
- 9 . 6 (f-v)
88 92 177 10 28 32 125 45
Morphology
Monolayer crystals 303 K Air, 77K/RT
1.6* 0.76
Wanning, morphology *G(X/unsat.) 77 K
2.4 (trans) 0.7 (cis) 4-5 (gas) 4.0 2.5 3.8-11.1 Various 2.1
Poly(4-methylpentene-l) polypropylene
Butene-1, hexene-1
Allylic
- , Chlorosulfonated polyisobutylene
Various 3.6
Various Various 0.3,0.6*
4.8, 2.7(dPP) 3.1/0.64 9.4
e 77 K Various temperatures Various Vac/77, 303 K N2/air He, e, 77 K Air/vac O 2 + CCl 4
2.9 (H 2 ) 2.19*
/-Polypropylene
177 96 117 10 27 71
+CCl 4
47 134 75 79 240
119 131 133 78,90,100 186 *G(S)/G(X) Also 373-623 K Also O 2 Decreases with dose *G(S)-G(X)
43 52 129 147 158 159
Various Various 94 (-/-pentad) Various (pentad sequences) 220 (-/-pentad)
Air Air Gamma
118 40 244
e
245
Various gases
Vac/air
Various
293-308 K Vac 77, 300K
Various
Gamma, aq.
H 2 , CO, CO 2 , CH 4 etc.
195-423
170 2 4 185 189 190 233 59 126
1.3. POLYACRYLATES Poly(acrylic acid) 3.6 3.49
Poly(acrylic anhydride) Poly(methyl acrylate)
0.0
0.44
0.47
0.62 1.1*
*G(S)- S(X)
References page II - 493
TABLE 1. cont'd Polymer Poly (methyl bromoacrylate) Poly(methyl a-chloroacrylate)
G(R)
G(X)
G(products)
6.98 5.1
Radiation conditions
Comments
77 K 0.3-0.9 0.8
Poly(methyl a-cyanoacrylate) Poly(methyl oc-fluoroacrylate)
G(S)
1.6 1.0
3.2-7.4 6.0 6.7*
Dose dependent *G(S)-G(X) 77 K 77 K
0.05
Refs. 139 133 24 62 17 133 65
1.4. POLY (METHACRYLATES) Poly(benzyl methacrylate) 0 Poly(f-butyl methacrylate) Poly(cyclohexyl methacrylate) Poly(glycidyl methacrylate) Poly(hexafluoroisopropyl methacrylate) Poly(hexyl methacrylate) Poly(isobutyl methacrylate)
0.29* 0 0.14 1.28* 0.44* 2.4*
e 300K
*G(S)-G(X) Syndiotactic
e e
*G(S)-G(X) *G(S)-G(X) * G(S)-G(X)
Various
9.2
0.1 0.5
Poly(2-methyl heptyl methacrylate) Poly(methacrylic acid)
2.6 0.38* 1.1* 0.8 0.3 3.4 Various
0.2
0.6/2.9 4.8 6.0
0.04
6
Poly(methacrylic anhydride) Poly(methyl methacrylate) 1.1-1.5( + ) 0.7-0.9(-)
7K e e 300K 300K N2 Gamma/e 77/273 K 77 K
Various
77, 303 K
Various
Gamma/e
1.8-2.9 1.9 (DMF) 1.3 (THF) 1.5
SoIn. 77 K
0.5, 1.5( + )
77 K
2.8-4.1
303, 343 K 1.3 1.31 1.9
Aromatic additives Aromatic additives Absorbed on zeolite
77 K
1.63, 1.09 1.4 1.5/0.33 1.2
Gamma/X Various
0.71-1.63 1.9/4.1 1.04/1.11 1.9,4.4 1.5 Various 15.8 (units) 0.34 (H2) 18.6 0.22,0.46,1.08 Various
Si wafers
e/gamma, 303-383K Gamma/n, vac/air 77/273 K Vac/air, 273 K 77 K
Bulk, alcohol
Air
*G(S)-G(X) 4- ethane diol Isotactic
1.5*
Vac, 363 K Deep UV, e, X-ray
73 57 51 53 65 50 131 132 135
e 77 K Gamma/n, vac/air 206 K
0.58 1.42
*G(S)-G(X) *G(S)-G(X) Syndiotactic Syndiotactic Aq. solution
22 192 238 22 22 120 246 65 22 22 192 192 91 176 123 133 185 189 195 176 59 59
139 152 161 176 86
Various radicals
Isotactic
173 146 171 162 17 14 23 33 187 188
TABLE I.cont'd Polymer
G(R)
G(X)
G(S)
G(products)
1.5 1.1 1.7 1.7 1.6 0.99, 0.4 0.77 5.1 (soln.) 0.89 (amorphous solid) 0.48 (crystalline solid) 1.21 (333K) 0.89 (303 K) 0.46(195K) G(damage) = 8.8
1.0
300K N 2 , RT Vac N2 Vac
0.14
Poly(2-naphthyl methacrylate) Poly(2,2,2-trichloroethyl methacrylate)
0.14 0.19 3.7
1.5.
0 0.4
Refs.
Isotactic Syndiotactic
190 192 222 223 224 225 238 249
Protons, gamma e, gamma C5 + , O5 + ions i-PMMA
Morphology effects, racemization Benzene solution
1.7 1.3
300K 300K 77, 300K
1.2, 1.7
258
264 1 238 238 175
Gamma/e, 298-416K
3.7 Poly(ethyl methacrylate) Poly(w-butyl methacrylate) Poly(2-hydroxyethyl methacrylate) Poly(phenyl methacrylate)
Comments
Air, RT
PoIy(I-naphthyl methacrylate)
0.03
Radiation conditions
Dioxane solution Syndiotactic Syndiotactic
0.44
11 192 192 193 238
POLY(STYRENES)
Poly(oc-methyl styrene)
0.3 0.33
e Gamma/e, 77-373K 273-319 K
0.78 0
0.29 0.48,0.89, 0.97, 1.13
303, 353, 373, 383, 393 K
0.105,0.05 Poly(/?-methyl styrene)
0.1
Poly(styrene)
0.45-7.9
77, 298 K Gamma/e, 77-373K 303 K
0.022 0.17
0.022 1.09, 2.12
0.035-0.042 0.043
0.010-0.051 0.0009
0.043-0.027 0.048, 0.021
0.086-0.074 0.2* 0.27, 0.07
0.03/0.2
0.02/0.2
0.043
0.00086 3.9
0.05
0.02
0.1
Air
0.032 (H 2 )
303-373 K 303 K 303-423 K 77 K Air 77 K Gamma/n, vac/air, 206 K
131 38 Benzene solution + Depolymerization
194
197 38 Emulsion polymerization Sheet absorbed on silica gel Includes lit. review * G(S)-G(X) Various doses
Sheet O 2 + CCl 4 373-623K Air
25
48 56 58 60 61 67 73 130 132 135 136 147 157
References page II - 493
TABLE 1. cont'd Polymer
G(R)
G(X) 0.077
G(S)
G(products)
Radiation conditions
Comments
0.055
0.0009 0.094 Various
0.0027 Various
0.018,0.15
0.06,0.07
0.0174 0.0425
0.0012
0.014-0.05
0.105
77 K 313 K Gamma/n, vac/air 77 K Gamma/n/alpha, air 77 K
1.8
0.5
Radical pairs
0.05
Various
24.7-30.4 G(degradation) 0.01 0.03 (H 2 ) H 2 , CH 4 , C 2 H 2 , C3H4, C6H6 Various (-O 2 ) Various Various hydrogen
Warming
Gamma/e, 77-373 K Abs of air Various dose rates
Various sources + Crosslinking agents
Ion beam
Deuterium subs
Vac, various temp.
Variable temp. dose rate Tacticity, crystallinity effect Gamma, X-ray,
0.03-0.05
161 74 81 85 98 112
0.033 (H 2 )
0.03-0.05 6.7-15.2
Refs.
19 6 7 33 38 195 196 228 234
250 257
255
Ne, Ar 1.6.
POLY(VINYLS)
1.6.1. ACRYLAMIDES AND NITRILES Poly(acrylamide)
2.5 0.04
0.88
5 1.33/0.62
Poly(methacrylamide)
0.45/0.52 1.2*
Poly(acrylonitrile)
3.7-4.1
Poly(methacrylonitrile)
0.15-3.0 2.8,4.2 2.2,2.8
303 K
0.59
0.0 0.4-3.3 3.3 gamma 3.6 X 0.5Ne 0.4 Ar
Poly(a-chloroacrylonitrile)
Various
AhYH2O e, O 2 Aq. soln, 304 K Vac/air, 77-393K
1.4
77, 300K 77, 300K Absence of O 2
Aq. soln. Hydrogel
149 103 108 167
* G(S)-GQQ
141
Absorbed on zeolite
53
Various sources
77 K 2.7* 1.1-7.2 3.2 2.1-3.3* 3.1-3.3 3.3*
Vac/air
* G(S)-G(X) Solution + bulk *G(S)-G(X) *G(S)- G(X)
5 198 200 195 255
133 59 99 145 59 62 17
1.6.2. VINYL MONOMERS Poly(r-butyl crotonate) Poly(f-butyl vinyl ether) Poly(ethyl vinyl ether) Poly(isobutyl vinyl ether) Poly(isopropyl vinyl ether)
0.66
0.59 3.6,10.3 0.36,0.50 0.39,1.73 0.86,1.50
273, 273, 273, 273,
348 K 348 K 348 K 348 K
Liquid
54 122 122 122 122
TABLE 1. cont'd Polymer Poly(methyl vinyl ether) Poly(tetrafluoroethylene) Poly(vinyl acetate)
G(R)
G(X)
0.31,0.64 0.5 2.4-4.1
Poly(vinyl alcohol) Poly(vinyl bromide) Poly(vinyl butyral) Poly (vinyl carbazole) Poly (vinyl chloride)
G(S)
1.08 1.02 0.71 0.35
0.6
0.7 (holes) 1.7 2.36 10-11
20-115
G(products)
Radiation conditions
273, 348 K O 2 + CCl4 K 243-273 K 0.9-2.4 gel dose Absence of O 2 O2 Air N2 39-55(HBr) e, N 2 e 77 K Air Various Vac/O2 7.7 (HCl) Vac/O2 (d.b.) 17(HCl) e, N2/vac 0.24 (H2) Vac/O2 8 (HCl) 2.8-3.5(Py + ) 0-1.2 (Phenyl + ) 3.0 (-Cl)
Poly(vinyl imidazole) Poly(vinyl pyrrolidone)
10-54 0.41-0.75
Aq
3.3
77 K 0.01-1.32
Comments
Also 373-623 K
Solution
Underpressure THFsoln. + additives
Refs. 122 147 21 195 236 9 241 168 165 113 115 119 8,44 154 160
G(cation) 247 273 K G(X) Increases 263 with crosslinker 269 +Crosslinker 256 Aq. soln. 12 +Warming 13 Various 205 solutions
1.7. MISCELLANEOUS POLYMERS 1.7.1. CELLULOSE AND DERIVATIVES Cellulose 13-186 7.1
Cellulose acetate
CO, CHO, COOH Vac/air Vac/air Air
Post irrad. H2O incr. G(S)
111 26 156
1.7.2. POLY(SILOXANES) Poly(oxydimethyl diphenylsilylene) Poly(oxydimethyl silylene)
Various Poly(methyl phenyl silane) Poly(cyclohexyl methyl silane)
Various 2.48
N 2 , 303 K
18.5/120
Air
2.7 3.0 2.8 Various
Various
Various
0.01-0.21 1
Poly(dimethyl siloxane) Silicon containing poly(acetylene)
1.8-17.4 1.7 0.3-2.3
Liq. 94 Also blends with 143 PS Effect of 104 pressure 76 80 Liquid 82 186 G(X) increases 265 with crosslinker LET 230 dependence Dose 232 dependence 243 Effect of various 252 pendent groups
1.7.3. POLY (AMINO ACIDS) Poly(alanine) Poly(glycine) Poly(tyrosine) Poly(valine)
2.9 3.6 2.2 < 0.4
3.8-7.0 3.0-3.3 0.12
Various Various Various Various 0.04-0.12 (NH3) Air/N2/N2O Various
Aq. soln.
95 128 95 95 102 95
References page II - 493
TABLE 1. cont'd Polymer
G(R)
G(X)
G(S)
G(products)
Radiation conditions
Comments
Refs.
1.7.4. POLYESTERS Poly(hydroxybutyrate) Poly(L-lactic acid) PoIy(D, L lactic acid)
1.65
Air 77, 300K 77, 300K 77, 300K
2.0,1.5 2.37-1.23 2.4, 1.2
Pressure and temp, effect on G(S) and G(X) Poly(glycolic acid)
1.72,1.47
77, 300K Pressure and temp, effects on G(S) and G(X)
191 201 203 201 274
203 274
1.7.5. POLYSULFONES Bis-A-PSF Hydroquinone PSF Biphenol PSF Bis-S-PSF PES (Polyethersulfone)
0.13 0.13 0.57 0.19 0.14 0.56 0.084 0.084 0.51 0.128 0.24
0.13-1.34
0.11-0.67
Various gases 0.14 (SO2) 0.145 (SO2) 0.136 (SO2) 0.14 (SO2) 0.14(SO2) 0.063 (SO2) 0.06 (SO2) 0.6(SO 2 ) 0.198 (SO2) 0.243 (SO2)
Various temp
207 208 211 207 208 211 207 208 211 207 207
1.7.6. POLYKETONES PEEK
PEEKK
PEEK-Me PEEKK-Me PEK-Ar
0.11 0.004 0.001 1.0e20 spin/kG 0.11 0.12 0.004 0.001 Lle20spin/kG 0.28 0.009 0.001 0.37 0.012 0.001 0.42 0.039 0.005
Vac, 77 K Vac, 300K Air, 300K 77 K
209 211
0.00054 gases
212 209
Vac, 77 K Vac, 300K Air, 300K 77 K Vac, 77 K Vac, 300K Air, 300K Vac, 77 K Vac, 300K Air, 300K Vac, 77 K Vac, 300K Air, 300K
211 209 209 209
1.7.7. FLUOROPOLYMERS Fluoro elastomers Poly(perfluoroethers)
Various
Various
Various
G(S) Poly(tetrafluoroethylene)
2.15 6.0
Various Various Various gases e, argon 9 K G(decomposition) e = 0.2-1.2 G(wt. loss), G(gas)
Review Structure, temp. effects
186 202 259 260
As polymerized 237 sintered, low crystalline Dose rate 267 effects on G(S)
TABLE 1. cont'd Polymer
G(R)
G(X)
G(S)
G(products)
Radiation conditions
0.3 at 373 0.57 at 473 0.89 at 573 1.33 at 673 2.07 at 773 Poly(vinyl Poly(vinylidene
fluoride) fluoride)
0.22 0.37 0.46-0.78 0.6-0.78
0.38-0.86 0.29
Various
Various
Comments
Refs.
+Dose effects 271
0.07 (Polyvinyl) 0.11 (Polyvinyl) 1-4 (HF)
46 46 49 254
293 K +Crosslinker
1.7.8. OTHERS Aromatic polymers Alkyl aromatic poly amides
Various
Aryloxyphosphazenes -[(R-Ph-O)2-PN]n-biphenol 0.6,0.19 -bis phenol 0.6,0.22 -hydroquinone 0.6,0.35 Poly(bis(phenoxy)phosphazene) Poly(bis(4-methyl-phenoxy)phosphazene) Poly(bis(4-r-butyl-phenoxy)phosphazene) Poly(bis(4-cumyl-phenoxy)phosphazene) PoIy(I-(f-butoxycarbonylthio)ethylene) 3.39 Poly(f-butyl isopropenyl ketone) Poly(butylene), l,4-disubstituted(urethane side chain) Poly(epoxide)(Araldite) 0.59 Poly(ether imide) (Ultem) 0.01 Hyaluronic acid
PoIy(I-mercapto ethylene) 2.65 Poly(oxadiazole-2,5-diyl-l,4-phenylenephthalidylidene-1,4-phenylene) Poly (oxycarbonyl-1,1 -dimethy 1-2isopropylidene-ethylene) Poly(oxycarboxyethylene) Poly(oxyethylene)
Various gases
0.22(R = Me) 2.12(R = Et)
G(S)ZG(X) Reduces with increase in methylene 0.26 0.26 77, 300K 77, 300K 77, 300K
0.9 3.5 0.1 0.2
0.7 2.0 0.1 0.2 77 K
0.33 0.139
77 K 77 K
0.00528 5.0-6.7 (O2) 2.0 (H 2 O 2 ) 0-0.1 (peroxide) Vac/air
0.0014
Warming 39
1.9 0.4-11
Poly(oxyethyleneoxyterephthaloyl) 0.023 Poly(oxymethylene) Poly (oxy-l,4-phenylenesulfonyl-l,4-phenelene 0.05 oxy-1,4-phenylene-isopropylidene-1,4phenylene) Poly(oxy-1,4-phenylenesulfony-1,4-phenylene) Poly(oxysebacoyloxy-1,4-phenylene) isopropylidene-1,4-phenylene) Poly(phenylene oxide) 5.7e20 spin/kG 0.6,0.33
Poly(thiopropylene)
pH dependence
77 K Various
0.015/0.067
110 110 210 210 210 273 273 273 273 13 142 93 36 114 253
19 50
14.5,40.5 2.6
N 2 air e, O 2 air 200K
36
0.16,0.04
Warming
1.5
5
Poly(phenylene sulfide) Poly(thiophenylene)
204,211 251
Aq. soln.
57-144
Various
8 0.012
320 (HCHO) 0.04 gas
423 K 300-423 K
29 37 153
0.04 gas
300-423 K Air
153 68
77 K 77, 300K
211 206
77, 300K Gamma/e, vac/air 77 K
206 109
9 0.08H 2 0.015 CH4 0.03H2 0.030/0.15
Dose rate dependence Also e
35 103 83 55
Radical pairs
74
References page 11-493
TABLE 2. COPOLYMERS Copolymers 2.1.
G(R)
G(X)
G(S)
Radiation conditions
Comments
Refs.
303-423 K
+Additives
10 125 89 125 10 127
COPOLYMERS WITH ETHYLENE
Poly(ethylene-co-l-butene)
Various Various
Poly(ethylene-c0-ethyl acrylate) Poly(ethylene-co-hexene)
2.53-3.2
Poly(ethylene-co-propylene)
0.43,0.83
Butyl rubber Halogenated butyl rubber
e, air Various Various
2.92
2.2.
G(products)
0.11,0.35
0.69 1.1 0.9/3.2
1.2 0.33 3.2
0.26
0.16
Various
Various
Various
2.3 (total) 0.19 (allyl) 3.7-4.0
0-0.6
3.9-6.09
Dose dependent
Dose dependent
Various Various Various 8.6-11.0(O 2 ) 5(COOH)
Various gases, O2 Various 0.07-0.62 gel dose Various chain ends Various gases
303-423 K 303 K Air
+Additives 23%, 36% Propylene +Additives
303-423 K Air Air
+Additives
Air
2.0 GPa + variation In terpolymer
293-298 Various
16 182
Review 186 various sources 195
77-398 K 77 K
70 125 10 96 101 116 104
219 Chloro and bromo
220
COPOLYMER WITH METHYL METHACRYLATE
Poly(methyl methacrylate-cobromomethyl methacrylate) Poly(methyl methacrylate-cochlorotrifluoroethylene)
0.2-1.4
0.06-0.1
0.7-1 2.1
139 77 K
65
2.1 Poly(methyl methacrylate-codichlorostyrene) Poly(methyl methacrylate-codimethyl itaconate) Poly(methyl methacrylate-cohexafluoroisopropyl methacrylate) Poly(methyl methacrylate-cohexyl methacrylate) Poly(methyl methacrylate-comethacrylic acid)
50 3.2-3.5* 1.0* 2.0-3.1
0.4 0.53-0.87
77 K
17 59 65 137
22
1.8,2.06
2.0
*G(S)-G(X) * G(S)-G(X)
3.6
273 K
2.9 Poly(methyl methacrylate-comethacrylic acid-styrene) Poly(methyl methacrylate-comethacrylic acid-co-cumyl phenyl methacrylate) Poly(methyl methacrylate-comethacrylic acid-co-2-naphthyl methacrylate) Poly (methyl methacrylate-comethacrylic acid) Poly(methyl methacrylate-co-2 naphthyl methacrylate) Poly(methyl methacrylate-comethacrylonitrile, vinylidene chloride, methyl-a-chloroacrylate, a-chloronitrile ter polymers) Poly(methyl methacrylate-co-methyl bromoacrylate)
137
1.3
77 K
146
1.2
20% MAA 238
1.6
238
133
1.09
238
2.0
238
1.06
238
0.06
1.9-3.1
145
0.41
4.16
139
TABLE 2. cont'd Copolymer
G(R)
Poly(methyl methacrylate-ctf-methyl3.1 oc-chloroacrylate) Poly(methyl methacrylate-co-methyloc-chloroacrylate) Poly(methyl methacrylate-comethyl2-chloroacrylate) Poly(methyl methacrylate-co-methyla-chloroacrylonitrile) Poly(methyl methacrylate-ctf-methyl5.9 a-cyanoacrylate) Poly(methyl methacrylate-co-methyloc-fluoroacrylate) Poly(methyl methacrylate-comethyl fluoroacrylate) Poly(methyl methacrylate-co3-oximino-2-butanone methacrylate) Poly(methyl methacrylate-cotribromophenyl methacrylate) Poly(methyl methacrylate-cotrichloroethyl-alpha-chloroacrylate) Poly(methyl methacrylate-cotrichlorophenyl methacrylate) Poly(methyl methacrylate-cotrifluoroethylene methacrylate) Poly(methyl methacrylate-covinylidene chloride) Poly(methyl methacrylate-covinylidene fluoride) Poly(glycidyl methacrylate-co-ethyl methacrylate) Poly(glycidyl methacrylate-coethyl acrylate) 2.3.
G(X)
0.06
G(S)
G(products)
Comments
Refs.
77 K
14% MCA
133
3.1
24
2.8*
*G(S)-G(X)
6.6
0-0.44
1.0-2.2
14% CAN
133
77 K
20% MCA
133
77 K
65
2.4 > 0.55 0.07-0.19
137 1.4-2.4
0.38-2.2
Various
69
Air
72
3.8 0.05-0.7
17
77 K
Also TFEM
140
0.4-4.4
72
1.9
77 K
2.8-3.4*
65 *G(S)-G(X)
17
1.6
137
1.35-8.5
1.6 1.51-5.5
77 K
0.077 0.04-0.59
Various 0.055 0.0-0.09
Vac
4.3/33
2.8/17
Air
0.3-3.0 Various
Various
313 K 77 K
0.04-0.38
2.18-2.47
Various compositions 246
6.5
65 246
COPOLYMERS WITH STYRENE
Poly(styrene-coacrylates) Poly(styrene-c<9-acrylonitrile) 0.4-2.8 77 K 0.14-4.2 300 K Poly(styrene-co-butadiene)
Poly(styrene-co-cyanoacrylates) Poly(styrene-co-l-mercaptoethylene) Poly(styrene-co-methyl acrylate)
Various CO, CH 4 , CO 2 etc.
Poly(styrene-co-methyl methacrylate)
0.40-2.76 77 K 0.14-1.39 300K 0.18
Poly(styrene-co-methacrylonitrile)
0.31-2.16
0.83 (gases)
Poly(styrene-co-butyl vinyl ketone) Poly(styrene-co-methyl isopropyl ketone) 2.4.
Radiation conditions
77 K Various temperatures Vac 77K/(R), 300 K/(gas)
e e
73 34 Various 215,221 compositions Effect of 104 pressure 3 Block 98 copolymers 73 19 12-80% sty 126 Various compositions 51% sty
216
Various compositions
199
132
239 239
COPOYMERS WITH SULFUR DIOXIDE
Poly(1 -butene-co-sulfur dioxide)
Various gases 12
Poly(2-butene-co-sulfur dioxide) Poly(cyclohexene-co-sulfur dioxide) Poly(4,4-dimethylpentene-co-sulfur dioxide)
Various gases Various gases Various gases
273 -423 K e 273-423 K 273-423 K 273-423 K
31,124,150 131 31,124 31,124 31,124
References page II - 493
TABLE 2. cont'd Copolymer Poly(ethylene-co-sulfur dioxide) Poly(hexene-l-co-sulfur dioxide) Poly(isobutene-co-sulfur dioxide) Poly(3-methyl-l-butene-co-sulfur dioxide) Poly(propylene-co-sulfur dioxide)
G(products)
Radiation conditions
1.8
Various gases Various gases Various gases Various gases
273-423 K 273-423 K 273-423 K 273-423 K
124 31,124 31,124 Poly(31,124, 150
2.2
Various gases
273-423 K
31,124,150
G(R)
G(X)
G(S)
Comments
Refs.
2.5. OTHER COPOLYMERS Poly (butyl methacrylate-col-naphthyl methacrylate) Poly(glutamic acid-co-tyrosine) Poly(glycolic acid-co-1 -lactic acid) Poly(glycidyl methacrylate-co3-chlorostyrene) Poly(hydroxy butyrate-co-valerate)
0.14 0.03-0.5 2.23-2.36 1.49-1.53 1.0
0-0.5
300K 77 K 300K
Various 2.7-3.4
Various gases 1,4-ester
77, 263, 273, 303 K e, gamma
3.2-43.*
Different compositions
77 K 20/150
+ Warming
Air
3.3 0.42 0.6-5.2(HF)
N2 240C
30 (d.b.) 2.3-2.7 1.2
0.9
Various
203
Vac/air/H2O
217
17 13 104 119 106
3.5 (Gas)
Poly(vinyl chloride-coethylglycodimethacrylate) Poly(vinylidene chloride-co-dimethyl itaconate) Poly(vinylidene chloride-co-hexafluoropropylene) Tetrafluoroethylene, perfluoro methyl vinyl ether copolymer 2:1
214
218 *G(S)- G(X)
3.01
1.3
1
144
1.16
Polysulphone-polydimethyl siloxane block copolymer
Various compositions Various compositions
0.42
3.0-0.5 Poly(methacrylonitrile-c0-methyl2-chloroacrylate) Poly (N- vinylpyrrolidone-c0-/-buty I5-vinyl thiocarbonate) Poly(acrylonitrile-co-butadiene) Poly(acrylonitrile-co-chloroprene) Poly(tetrafluoroetnylene-c0hexafluoropropylene) Poly(tetrafluoroethylene-co-propylene)
Benzene soln.
Emulsion 121 polymer + H 2O 116 266 8 *G(S)-G(X)
17
+Additives
166
0.93 (CF4) e 0.31 (COF2) 0.055 (CO2) 0.14 (CF3 OCF3) 1.43 (total gas) 0.34 (acid fluoride) New chain ends 1 (_CF 2 -CF 3 ) 0.09 (-CF 2 -O-CF 3 ) 0.5 (CF2-COOH) 0.2(-CF = CF2)
229
268
Dose and molecular weight effects
272
TABLE 3. POLYMERS BLENDS Polymer Blends
G(X)
Poly (methyl methacrylate)/ Poly (1 -naphthyl(methacrylate) Poly(methyl methacrylate)/ Poly(styrene-co-acrylonitrile) Poly (methyl methacrylate)/styreneacrylonitrile Poly(methyl methacrylate)/Acrylonitrile
G(S)
Comments
Refs.
0.14
Benzene
1
0.025
0.051
50% PMMA
161
0.041 0.034 0.02 0.008 0.042 0.036 0.009 0.01
0.027 0.15 0.21 0.23 0.14 0.25 0.34 0.88
SAN 100 85 50 15 ACNlOO 85 50 15
242
242
TABLE 4. COMPOSITES Polymer Composites
G(products)
Radiation conditions
Refs.
Glass-DGEBA-DDM Color-DGEBA-DDM
H 2 , CO, CO2 H 2 , CO, CO2
77 K, RT 77 K, RT
227 227
C
REFERENCES
1. S. Nishimoto, K. Yamamoti, T. Kagiya, Polym. Photochem., 5, 231 (1984). 2. M. R. Clay, A. Charlesby, Europ. Polym. J., 11, 187 (1975). 3. M. A. El-Azmirly, A. A. Yehia, W. M. Khalifa, N. A. Ghanem, Europ. Polym. J., 11, 499 (1975). 4. A. Chapiro, D. Goldfield-Freilich, J. Perichon, Europ. Polym. J., 11, 515 (1975). 5. A. Chapiro, Z. Mankowski, Europ. Polym. J., 14,15, (1978). 6. C. David, D. Breyens-Volant, Europ. Polym. J., 14, 29 (1978). 7. S. Warty, J. A. Sauer, A. Charlesby, Europ. Polym. J., 15, 445, (1979). 8. G. Palma, M. Gnrenza, C. Pollini, Europ. Polym. J., 16, 333, (1980). 9. A. Chapiro, Z. Mankowski, Europ. Polym. J., 18, 707 (1982). 10. S. Y. Ho, J. H. O'Donnell, Europ. Polym. J., 20, 421 (1984). 11. J. Rosiak, W. Schnabel, Europ. Polym. J., 20, 1159 (1984). 12. A. Chapiro, C. Legris, Europ. Polym. J., 21, 49 (1985). 13. H. Monig, H. Ringsdorf, S. Wessel, Makromol. Chem., 176, 1323 (1975). 14. C. David, F. de Bie, G. Geuskens, Makromol. Chem., 176, 3493 (1975). 15. R. Kaufman, H. Heusinger, Makromol. Chem., 177, 871 (1976). 16. W. Geissler, H. Zott, H. Heusinger, Makromol. Chem., 179, 697 (1978). 17. C-Y. Chen, M. Igbal, C. U. Pitman Jr., Makromol. Chem., 179, 2109 (1978).
18. M. B. Huglin, J. Smith, Makromol. Chem., 180, 2775 (1979). 19. H. Monig, H. Ringsdorf, E. Spirk, Makromol. Chem., 181, 2293 (1980). 20. R. Basheer, M. Dole, Makromol. Chem., 183, 2141 (1982). 21. J. G. Braks, R. Y. M. Huang, Makromol. Chem., 185, 317 (1984). 22. J. H. Lai, J. H. Helbert, Macromolecules, 11, 617 (1978). 23. R. P. Kusy, A. R. Greenburg, Macromolecules, 11, 1051 (1978). 24. J. N. Helbert, C-Y. Chen, C. U. Pittman Jr., G. L. Hagnauer, Macromolecules, 11, 1104 (1978). 25. T. Ikeda, H. S. von Euler-Chelpin, S. Okamura, H. Yamaoka, Macromolecules, 17, 1655 (1984). 26. J. T. Guthrie, Polymer, 16, 134 (1975). 27. T. N. Bowmer, J. H. O'Donnell, Polymer, 18, 1032 (1977). 28. Y. Hori, Z. Fukunaga, S. Shimada, H. Kashiwabara, Polymers, 20, 181 (1979). 29. T. Memetea, V. Stannett, Polymer, 20, 469 (1979). 30. G. Ungar, Polymer, 21, 1278 (1980). 31. T. N. Bowmer, J. H. O'Donnell, Polymer, 22, 71 (1981). 32. M. Dole, Polymer 22, 1458 (1981). 33. W. K. Busfield, J. H. O'Donnell, C. A. Smith, Polymer, 23, 431 (1982). 34. T. Q. Nguyen, H. H. Kausch, K. Jud, M. Dettenmaier, Polymer, 23, 1305 (1982). 35. M. C. Gupta, V. G. Deshmukh, Polymer, 24, 827 (1983). 36. K. R. Schaeffer, R. E. Fornes, R. D. Gilbert, J. D. Memory, Polymer, 25, 54 (1984).
37. L. R Burlak, Y. S. Deyev, G. V. Levit, V. R Pshenitsyna, V. I. Serennkov, N. A. Slovokhotova, F. F. Sukhov, V. S. Tikhomirov, Polymer Science USSR, 21, 2326 (1979). 38. I. K. Chernova, S. S. Leshchenko, V. R Golikov, V. L. Karpov, Polymer Science USSR, 22, 2382 (1980). 39. V. V. Lyashevich, V. V. Korshak, D. R. Tur, V. V. Rode, Polym. Sci. USSR, 22, 2422 (1980). 40. S. G. Kiryushkin, Y. A. Shlyapnikov, Polym. Sci. USSR, 23, 617 (1981). 41. A. R Tyutnev, V. S. Sayenko, Y. D. Pozhidayev, Polym. Sci. USSR, 24, 120 (1982). 42. A. R Tyutnev, V. S. Sayenko, V. S. Tikhomirov, Y. D. Pozhidayev, Polym. Sci. USSR, 25, 113 (1983). 43. N. S. Soboleva, S. S. Leshchenko, V. L. Karpov, Polym. Sci. USSR, 25, 446 (1983). 44. V. I. Dakin, A. V. Danchenko, V. L. Karpov, Polym. Sci. USSR, 26, 2473 (1984). 45. G. N. Patel, J. Polym. Sci. Polym. Phys. Ed., 13, 339 (1975). 46. J. N. Helbert, E. W. Burkhard, E. H. Poindexter, L. Kevan, J. Polym. Sci., Polym. Phys. Ed., 13, 825 (1975). 47. J. C. Randall, Makromol. Chem., Rapid Commun., 4, 149 (1983). 48. K. Sato, A. Rudin, R. Y. M. Huang, J. Polym. Sci., Polym. Chem. Ed., 14, 37 (1976). 49. K. Makuuchi, M. Asano, T. Abe, J. Polym. Sci., Polym. Chem. Ed., 14, 617 (1976). 50. A. C. Ouano, D. E. Johnson, B. Dawson, L. A. Pederson, J. Polym. Sci., Polym. Chem. Ed., 14, 701 (1976). 51. A. Torikai, H. Kato, Z-I. Kuri, J. Polym. Sci., Polym. Chem. Ed., 14, 1065 (1976). 52. V. K. Micinchuk, E. R. Klinshpont, V. V. Vasilenko, J. Polym. Sci., Polym. Chem. Ed., 14, 1419 (1976). 53. J. R Quaegebeur, T. Teguchi, H. LeBail, C. Chachaty, J. Polym. Sci., Polym. Chem. Ed., 14, 2703 (1976). 54. J. H. O'Donnell, N. R Rahman, D. J. Winzor, J. Polym. Sci., Polym. Chem. Ed., 15, 131 (1977). 55. C. Decker, J. Polym. Sci., Polym. Chem. Ed., 15,781 (1977). 56. J. M. Nichol, J. H. O'Donnell, N. R Rahman, D. J. Winzor, J. Polym. Sci., Polym. Chem. Ed., 15, 2919 (1977). 57. A. Torikai, R. Kato, J. Polym. Sci., Polym. Chem. Ed., 16, 1487 (1978). 58. Y. Kasama, A. Udagawa, M. Takehisa, J. Polym. Sci., Polym. Chem. Ed., 16, 2607 (1978). 59. J. Helbert, E. Poindexter, G. Stahl, C-Y. Chen, C. Pittman, J. Polym. Sci., Polym. Chem. Ed., 17, 49 (1979). 60. Y. Shimizu, H. Mitsui, J. Polym. Sci., Polym. Chem. Ed., 17, 2307 (1979). 61. J. H. O'Donnell, N. R Rahman, C. A. Smith D. J. Winzor, J. Polym. Sci., Polym. Chem. Ed., 17, 4081 (1979). 62. C-Y. Chen, C. U. Pittman, Jr., J. N. Helbert, J. Polym. Sci., Polym. Chem. Ed., 18, 169 (1980). 63. H, Mitsui, Y. Shimizu J. Polym. Sci., Polym. Chem. Ed., 18, 1115 (1980). 64. K. Hayashi, M. Tachibana, S. Okamura, J. Polym. Sci., Polym. Chem. Ed., 18, 2785 (1980). 65. C. Pittman, Jr., C-Y. Chen, M. Ueda, J. N. Helbert, J. Kwiatkowski, J. Polym. Sci., Polym. Chem. Ed., 18, 3413 (1980).
66. T. N. Bowmer, J. H. O'Donnell, J. Polym. Sci., Polym. Chem. Ed., 19, 45 (1981). 67. T. N. Bowmer, J. H. O'Donnell, D. J. Winzor, J. Polym. Sci., Polym. Chem. Ed., 19, 1167 (1981). 68. M. C. Gupta, A. K. Srivastava, J. Polym. Sci., Polym. Chem. Ed., 20, 541 (1982). 69. T. N. Bowmer, E. Reichmans, C. W. Wilkins, Jr., M. Y. Hellman, J. Polym. Sci., Polym. Chem. Ed., 20, 2661 (1982). 70. K. Arakawa, T. Seguchi, N. Hayakawa, S. Machi, J. Polym. Sci., Polym. Chem. Ed., 21, 1173 (1983). 71. EJ. Zoepfl, J. Silverman, J. Polym. Sci., Polym. Chem. Ed., 21, 1763 (1983). 72. R H. Lu, G. Babu, J. C. W. Chien, J. Polym. Sci., Polym. Chem. Ed., 23, 1421 (1985). 73. H. Ito, C. Hrusa, H. K. Hall, Jr. A. B. Padias, J. Polym. Sci., Polym. Chem. Ed., 24, 955 (1986). 74. R Hesse, H. Heusinger, Radiat. Phys. Chem., 7, 1 (1975). 75. S. Rafi Ahmad, A. Charlesby, Radiat. Phys. Chem., 8, 497 (1976). 76. R. Folland, A. Charlesby, Radiat. Phys. Chem., 8, 555 (1976). 77. A. Rafi Ahmad, A. Charlesby, Radiat. Phys. Chem., 8, 585 (1976). 78. A. Charlesby, J. Steven, Radiat. Phys. Chem., 8, 719 (1976). 79. M. Dole, V. M. Patel, Radiat. Phys. Chem., 9, 433 (1977). 80. R. Folland, A. Charlesby, Radiat. Phys. Chem., 10, 61 (1977). 81. A. Charlesby, Radiat. Phys. Chem., 10, 177 (1977). 82. C. G. Delides, I. W. Shepherd, Radiat. Phys. Chem., 10, 379 (1977). 83. A. Charlesby, M. Byrne, Radiat. Phys. Chem., 12, 191 (1978). 84. S. G. Burnay, Radiat. Phys. Chem., 13, 171 (1979). 85. Y. Tabata, Radiat. Phys. Chem., 14, 235 (1979). 86. K. Ishigure, S. Egusa, S. Tagawa, Y. Tabata, Radiat. Phys. Chem., 14, 585 (1979). 87. V. Handlos, Radiat. Phys. Chem., 14, 721 (1979). 88. G. N. Patel. Radiat. Phys. Chem., 14, 729 (1979). 89. N. M. Burns, Radiat. Phys. Cehm., 14, 97 (1979). 90. A. Charlesby, R. Folland, Radiat. Phys. Chem., 15, 393 (1980). 91. T. S. Chien, J. K. Thomas, Radiat. Phys. Chem., 15, 429 (1980). 92. N. Gvozdic, M. Dole, Radiat. Phys. Chem., 15, 435 (1980). 93. G. N. Patel, Radiat. Phys. Chem. 15, 637 (1980). 94. G. G. Delides, Radiat. Phys. Chem., 16, 345 (1980). 95. D. J. T. Hill, R. W. Garrett, S. Y. Ho, J. H. O'Donnell, R W. O'Sullivan, P. J. Pomery, Radiat. Phys. Chem., 17,163 (1981). 96. T. Seguchi, S. Hashimoto, K. Arakawa, N. Hayakawa, W. Kawakami, I. Kuriyama, Radiat. Phys. Chem., 17, 195 (1981). 97. H. Okamoto, T. Iwai, Radiat. Phys. Chem., 18, 407 (1981). 98. R. Basheer, M. Dole, Radiat. Phys. Chem., 18, 1053 (1981). 99. H. Yamaoka, K. Nagta, T. Ikeda, S. Okamura, Radiat. Phys. Chem., 18, 1073, (1981).
100. A. Charlesby, B. J. Bridges, Radiat. Phys. Chem., 19, 155 (1982). 101. T. Seguchi, K. Arakawa, N. Hayakawa, Y. Watanabe, I. Kuriyama, Radiat. Phys. Chem., 19, 321 (1982). 102. G. Boguta, A. M. Dancewicz, Radiat. Phys. Chem., 20, 359 (1982). 103. W. Schnabel, O. Denk, V. Grollmann, I. A. Raapand, K. Washino, Radiat. Phys. Chem., 21, 225 (1983). 104. V. K. Milinchuk, E. R. Klinshpont, V. R Kiryukhin, Radiat. Phys. Chem., 21, 519 (1983). 105. M. Dole, Radiat. Phys. Chem., 22, 11 (1983). 106. N. Lin, Radiat. Phys. Chem., 22, 259 (1983). 107. K. Hayakawa, K. Kawase, H. Yamikita, Radiat. Phys. Chem., 22, 929 (1983). 108. Z. -C. Zhang, Q. Li, D. -H. Li, Radiat. Phys. Chem., 22,1064 (1983). 109. G. -L Huang, Z. -F. Chang, Y. -X. Han, Radiat. Phys. Chem., 22, 1067, (1983). 110. S. Yanai, V. T. Stannett, D. R. Squire, G. L. Hagnauer, R. L. Singler, Radiat. Phys. Chem., 23, 489 (1984). 111. W. M. Dziedziela, D. J. Kotynska, Radiat. Phys. Chem., 23, 723 (1984). 112. M. C. Gupta, V. P. Bansod, Radiat. Phys. Chem., 24, 499 (1984). 113. G. Urillo, Radiat. Phys. Chem., 25, 383 (1985). 114. R. Basheer, M. Dole, Radiat. Phys. Chem., 25, 389 (1985). 115. A. H. Zahran, E. A. Hegazy, F. M. Ezz Eldin, Radiat. Phys. Chem., 26, 25 (1985). 116. T. Seguchi, N. Hayakawa, K. Yoshida, N. Tamura, Y. Katsumura, Y. Tabata, Radiat. Phys. Chem., 26, 221 (1985). 117. O. S. Gal, V. M. Markovic, L. J. R. Novakovic, V. T. Stannett, Radiat. Phys. Chem., 26, 325 (1985). 118. E-S. A. Hegazy, A. H. Zahran, Radiat. Phys. Chem., 27,139 (1986). 119. K. Arakawa, T. Seguchi, K. Yoshida, Radiat. Phys. Chem., 27, 157 (1986). 120. M. Kumar, M. H. Rao, K. N. Rao, Radiat. Phys. Chem., 27, 219 (1986). 121. N. Suzuki, J. Okamoto, J. Macromol. Sci. A: Chem., 9 (2), 285 (1975). 122. Y Suzuki, J. M. Rooney, V. Stannett, J. Macromol Sci. A: Chem., 12 (7), 1055 (1978). 123. J. H. O'Donnell, R. D. Sothman, J. Macromol. Sci. A: Chem., 14 (46), 879 (1980). 124. T. N. Bowmer, J. H. O'Donnell, J. Macromol. Sci. A: Chem., 17 (2), 243 (1982). 125. T. N. Bowmer, S. Ho, J. H. O' Donnell, P. W. O'Sullivan, J. Macromol. Sci. A: Chem., 21 (6&7), 745 (1984). 126. W. H. Busfield, J. H. O'Donnell, C. A. Smith, J. Macromol. Sci. A: Chem., 17 (8), 1263 (1982). 127. J. H. O'Donnell, A. K. Whittaker, Brit. Polym. J., 17, 51 (1985). 128. D. J. T. Hill, S. Y Ho, J. H. O'Donnell, P. W. O'Sullivan, R J. Pomery, Polym. Degrad. Stability, 3, 83 (1980-81). 129. T. Kayiga S. Nishimoto, Polym. Degrad. Stability, 12, 261 (1985).
130. M. C. Gupta, B. S. Shaprio, B. P. Kanphade, V. R Bansoo, Polym. Comm., 25, 335 (1984). 131. M. J. Bowden, J. Polym. Sci., Polym. Symp., 49, 221, (1975). 132. J. H. O'Donnell, P. J. Pomery, J. Polym. Sci. Polym. Symp., 55, 269 (1976). 133. J. Helbert, B. Wagner, P. Caplan, E. Poindexter, Polym. Preprints, 16 (1), 708 (1975). 134. N. Gvozdic, M. Dole, Polym. Preprints, 19 (1), 584 (1978). 135. K. Ishigure, S. Egusa, M. Ogawa, S. Tagawa, Y. Tabata, Polym. Preprints, 20 (1), 372 (1979). 136. T. Bowmer, L. Cowen, J. Nichol, J. H. O'Donnell, N. Rahman, C. Smith, D. Winzor, Polym. Preprints, 20 (1), 376 (1979). 137. C. Pittman, C. Chen, M. Ueda, J. Helbert, Polym. Preprints, 20 (2), 602, (1979). 138. M. Golub, R. Cormia, Polym. Preprints, 22 (1), 40 (1981). 139. C. Babu, J. Chien, Polym. Preprints, 23 (2), 85 (1982). 140. E. Wallace, C. Pittman, J. Kwiatkowski, C. Cook, J. Helbert, Polym. Preprints, 24 (1), 157 (1983). 141. D. O'Connor, N. Yang, A. Woodward, Polym. Preprints, 24 (1), 172 (1983). 142. S. MacDonald, H. Ito, C. Willson, J. Moore, H. Gharapetian, J. Guillet, Polym. Preprints, 25 (1), 298 (1984). 143. G. Corfield, D. Astill, D. Clegg, Polym. Preprints, 25 (1), 311 (1984). 144. A. Novembre, T. Bowmer, Polym. Preprints, 25 (1), 324 (1984). 145. E. Wallace, C. Chen, C. Pittman, J. Helbert, J. Kwiatkowski, C. Cook, Polym. Preprints, 25 (1), 326 (1984). 146. P. R. Wunsche, K. Pfeiffer, H-J. Lorkowski, J. Reinhardt, Acta Polymerica, 36, 265 (1985). 147. T. Tagawa, E. Tsuchida, I. Shinohara, M. Hagiwara, T. Kagiya, J. Polym. Sci., Polym. Letters Ed., 13,287 (1975). 148. G. Gasparrini, M. Carenza, G. Palma, J. Polym. Sci., Polym. Letters Ed., 18, 29 (1980) 149. G. Burillo, T. Ogave, J. Polym. Sci., Polym. Letters Ed., 21, 615 (1983). 150. T. N. Bowmer, J. H. O'Donnell, P. R. Wells, Polym. Bull., 2, 103 (1980). 151. J. de Boer, A. J. Pennings, Polym. Bull., 5, 317 (1981). 152. H. Sotobayashi, E Asmussen, K. Thimm, W. Schnabel, H. Betz, D. Einfeld, Polym. Bull., 7, 95 (1982). 153. J. R. Brown, J. H. O'Donnell, J. Appl. Polym. Sci., 19, 405 (1975). 154. W. Szymanski, G. Smietanska, J. Appl. Polym. Sci., 19, 1955 (1975). 155. V. N. Handlos, K. A. Singer, J. Appl. Polym. Sci., 20, 3375 (1976). 156. S. M. AIi, P. G. Clay, J. Appl. Polym. Sci., 23, 2893 (1979). 157. T. N. Bowmer, L. K. Cowen, J. H. O'Donnell, D. J. Winzor, J. Appl. Polym. Sci., 24, 425 (1979). 158. E. A. Hegazy, T. Seguchi, K. Arakawa, S. Machi, J. Appl. Polym. Sci., 26, 1361 (1981). 159. G. Ramanan, M. H. Rao, J. Appl. Polym. Sci., 26, 1439 (1981).
160. E. A. Hegazy, T. Seguchi, S. Machi, J. Appl. Polym. ScL, 26, 2947 (1981). 161. T. Q. Nguyen, H. H. Kausch, J. Appl. Polym. ScL, 29, 455 (1984). 162. P. A. Zagorets, A. G. Shostenko, A. I. Krivonosov, A. M. Dodonov, B. A. Gorelik, M. V. Postrigan, High Energy Chem., 10, 254 (1976). 163. B. K. Pasal'skii, Ya. I. Lavrentovich, V. A. Vonsyatskii, A. M. Kabakchi, High Energy Chem., 10, 316 (1976). 164. A. P. Mal'tseva, V. P. Golikov, S. S. Leshchenko, V. L. Karpov, V. I. Muromtsev, High Energy Chem., 11, 189 (1977). 165. V. I. Dakin, Z. S. Egorova, V. L. Karpov, High Energy Chem., 11, 317 (1977). 166. T. G. Samoilenko, High Energy Chem., 12, 72 (1978). 167. V. N. Khabarov, L. L. Kozlov, G. Panchenkov, High Energy Chem., 15, 382 (1981). 168. A. P. Tyutnev, A. V. Vannikov, V. S. Saenko, S. Likhovidov, E. D. Pozhidaev, High Energy Chem., 16, 386 (1982). 169. P. I. Dubenskov, A. P. Tyutnev, V. S. Shenko, A. V. Vannikov, High Energy Chem., 19, 92, (1985). 170. A. M. Afanas'ev, V. A. Barakova, V. N. Demishev, V. A. Novozhilov, High Energy Chem., 19, 342 (1985). 171. G. S. Zhadanov, A. S. Smolyanskii, V. R. Milinchuk, High Energy Chem., 20, 27 (1986). 172. J. Silverman, F. J. Zoepfl, J. Randall, V. Markovic, in: J. Dobo, P. Hedvig, R. Schiller (Eds.), Proc. Fifth Tihany Symp. Radiation Chem. (Siofok, Hungary, 19-24 Sept, 1982), vol. 2, Akad. Kiado, Budapest, 2, 1983, 895. 173. J. Dobo, P. Hedvig, R. Schiller (Eds.), Proc. Fifth Tihany Symp. Radiation Chem. (Siofok, Hungary, 19-24 Sept, 1982), vol. 2, Akad. Kiado, Budapest, 1983, p. 979. 174. Y. Tabata, Y. Katsumuka, T. Seguchi, N. Hayakawa, K. Yoshida, N. Tamura, Radiat. Process. Plastics and Rubber, 2nd Int. Conf., Canterbury, UK, 28-30 March, 1984, p. 1. 175. J. Rosiak, W. Schnabel, Radiat. Process. Plastics and Rubber, 2nd Int. Conf., Canterbury, UK, 28-30 March, 1984, p. 37. 176. H. Hiroka, IBM J. Res. Develop., 21, 121 (1977) 177. G. Ungar, J. Mater. ScL, 16, 2635 (1981). 178. H. Yamaoka, K. Kato, S. Okamura, Polym. J., 19, 667 (1987). 179. D. J. T. Hill, J. H. O'Donnell, M. C. S. Perera, P. J. Pomery, ACS Symposium Series, 527, 74 (1993) 180. P. F. Barron, J. H. O'Donnell, A. K. Whittaker, Polym. Bull., 14, 339 (1985). 181. A. J. Whittaker, Ph.D. Thesis, University of Queensland, (1986). 182. K. Arakawa, J. Polym. ScL, Polym. Chem. Ed., 25, 1713 (1987). 183. F. Horii, Q. Zhu, R. Kitamaru, H. Yamaoka, Macromolecules, 23, 977 (1990). 184. A. Tidjani, Y. Watanbe J. Polym., ScL, Polym. Chem. Ed., 33, 1455 (1995). 185. D. J. T. Hill, J. H. O'Donnell, C. L. Winzor, D. J. Winzor, Polymer, 31, 538 (1990). 186. G. G. A. Bohm, J. O, Tveekrem, Rubb. Chem. Technol., 55, 575 (1982).
187. L. Dong, D. J. T. Hill, J. H. O'Donnell, T. G. CarswellPomerantz, P. J. Pomery, A. K. Whittaker, K. Hatada, Macromolecules, 28, 3681 (1995). 188. J. A. Moore, J. O. Choi, ACS Symposium series, 475, 156 (1991) 189. D. J. T. Hill, J. H. O'Donnell, R J. Pomery, C. L. Winzor, Radiat. Phys. Chem., 39, 237 (1992). 190. D. J. T. Hill, K. A. Milne, J. H. O'Donnell, P. J. Pomery, ACS Symposium Series, 620, 130 (1996). 191. H. Mitomo, Y. Watanabe, I. Ishigaki, T. Saito, Polym. Degrad. Stab., 5, 11 (1994). 192. L. Dong, D. J. T. Hill, J. H. O'Donnell, P. J. Pomery, K. Hatada, J. Appl. Polym. ScL, 59, 589, (1996). 193. D. J. T. Hill, J. H. O'Donnell, P. J. Pomery, G. Saadat, Radiat. Phys. Chem., 48, 605 (1996). 194. R. W. Garrett, T. Le, D. J. T. Hill, J. H. O'Donnell, P. J. Pomery, in: T. Tabata, I. Mira, T. Nonogaki, (Eds.), "Polymers for Microelectronics Science and Technology", VCH, New York, 1990, p. 47. 195. W. Schnabel, Q. Q. Zin, S. Klaumunzer, ACS Symposium Series, 475, 44 (1991). 196. D. Lopez, G. Burillo, ACS Symposium Series, 475, 262 (1991). 197. R. W. Garrett. D. J. T. Hill, T. T. Le, J. H. O'Donnell, P. J. Pomery, Radiat. Phys. Chem., 39, 215 (1992). 198. D. J. T. Hill, A. P. Lang, J. H. O'Donnell, P. J. Pomery, Polym. Degrad. Stab., 38, 193 (1992). 199. L. Dong, D. J. T. Hill, J. H. O'Donnell, P. J. Pomery, Polym. Degrad. Stab., 48, 71 (1995). 200. L. Dong, D. J. T. Hill, J. H. O'Donnell, P. J. Pomery, Polymer, 36, 2873 (1995). 201. A. Babanalbandi, D. J. T. Hill, J. H. O'Donnell, R J. Pomery, Polym. Degrad. Stab., 50, 297 (1995). 202. J. Pacansky, R. J. Waltman, J. Phys. Chem., 95, 1512 (1991). 203. A. Babanalbandi, D. J. T. Hill, J. H. O'Donnell, P. J. Pomery, Polym. Degrad. Stab., 52, 59 (1996). 204. E. S. A. Hegazy, T. Sasuga, M. Nishii, T. Seguchi, Polymer, 33, 2897 (1992). 205. J. M. Rosiak, ACS Symposium Series, 475, 271 (1991). 206. D. J. T. Hill, D. S. Hunter, D. A. Lewis, J. H. O'Donnell, P. J. Pomery, Radiat. Phys. Chem., 36, 550 (1990). 207. D. J. T. Hill, D. A. Lewis, J. H. O'Donnell, P. J. Pomery, J. L. Hedrick, J. E. McGrath, Polym. Adv. Tech., 2, 15 (1991). 208. D. J. T. Hill, D. A. Lewis, J. H. O'Donnell, P. J. Pomery, Polym. International, 28, 233 (1992). 209. K. Heiland, D. J. T. Hill, J. H. O'Donnell, P. J. Pomery, Polym. Adv., 8, 116(1994). 210. J. L. Hopewell, D. J. T. Hill, J. H. O'Donnell, R J. Pomery, Polym. Degrad. Stab., 293, (1994). 211. K. Heiland, D. J. T. Hill, J. L. Hopewell, D. A. Lewis, J. H. O'Donnell, P. J. Pomery, A. K. Whittaker, Adv. Chem. sen, 249, 637 (1996). 212. L. Dong, K. Heiland, D. J. T. Hill, M. C. S. Perera, in: M. Kitajima, H. Haneda, K. Ishioka, K. Hirata, (Eds.), "Materials Chemistry in Nuclear Environment", National Research Institute of Metals, Tsukuba, Japan, 1996, 61.
213. E. A. Hegazy, T. Sasuga, M. Nishi, T. Seguchi, Polymer, 33, 2897 (1992). 214. D. J. T. Hill, S. Y. Ho, J. H. O'Donnell, P. J. Pomery, Radiat. Phys. Chem., 36, 467 (1990), 215. D. J. T. Hill, A. P. Lang, J. H. O'Donnell, P. J. Pomery, Polym. Degrad. Stab., 38, 205 (1992). 216. R. Kellman, D. J. T. Hill, D. S. Hunter, J. H. O'Donnell, P. J. Pomery, ACS Symposium Series, 475, 119 (1991). 217. T. G. Carswell-Pomerantz, D. J. T. Hill, J. H. O'Donnell, P. J. Pomery, Radiat. Phys. Chem., 45, 737 (1995). 218. T. Bremner, D. J. T. Hill, J. H. O'Donnell, M. C. S. Perera, P J. Pomery, J. Polym. ScL, Polym. Chem. Ed., 34, 971 (1996). 219. D. J. T. Hill, J. H. O'Donnell, M. C. S. Perera, P. J. Pomery, Radiat. Phys. Chem., 40, 127 (1992). 220. D. J. T. Hill, J. H. O'Donnell, M. C. S. Perera, P. J. Pomery, Polymer, 36, 4185 (1995). 221. T. Q. Nguyen, H. H. Kausch, K. Jud, M. Dettnmaier, Polymer, 23, 1305 (1982). 222. H. Kudoh, T. Sasuga, T. Seguchi, ACS Symposium Series, 620, 2 (1996). 223. H. Kudoh, T. Sasuga, T. Seguchi, Y. Katsumura, Polymer, 4663 (1996), 224. H. Kudoh, M. Celina, G. M. Malone, R. J. Kaye, K. T. Gillen, R. L. Clough, Radiat. Phys. Chem., 48, 553 (1996). 225. H. Kudoh, T. Sasuga, T. Seguchi, Y. Katsumura, Polymer, 37, 2903 (1996). 226. W. K. Busfield, G. S. Watson, ACS Symposium Series, 620, 74 (1996). 227. H. Kudoh, N. Kasai, T. Sasuga, T. Seguchi, Radiat. Phys. Chem., 48, 695 (1996). 228. M. Dole, Radiat. Phys. Chem. 37, 65 (1991). 229. J. Pacansky, R. J. Waltman, D. Jebens, Macromolecules, 29, 7699 (1996). 230. S. Seik, H. Shibata, H. Ban, K. Ishigure, S. Tagawa, Radiat. Phys. Chem., 48, 539 (1996). 231. Y. Hama, K. Hamanaka, H. Matsumoto, T. Takano, H. Kudoru M. Sugimoto, T. Seguchi, Radiat. Phys. Chem., 48, 549 (1996). 232. J. Kumagai, K. Oyama, H. Yoshida, T. Ichikawa, Radiat. Phys. Chem., 47, 631 (1996). 233. P Ulanski, E. Bothe, J. M. Rosiak, C. Von Sonntag, J. Chem. Soc, Perkin Trans., 2, 1, 5 (1996). 234. M. B. Lewis, E. H. Lee, J. Nucl. Mater., 203, 224 (1993). 235. Y. S. Soebianto, Y. Katsumura, K. Ishigure, J. Kubo, T. Koizumi, H. Shigekuni, K. Azami, Polym. Degrad. Stab., 42, 29 (1993). 236. G. Lu, H. Chen, D. Liu, Radiat. Phys. Chem., 42,229 (1993). 237. X. Zhong, L. Yu, W. Zhao, Y. Zhang, J. Sun, J. Appl. Polym. ScL, 48, 741 (1993). 238. I. Gitsov, O. Todorova, J. Appl. Polym. ScL, 46,1631 (1992). 239. S. A. M. Hesp, J. E. Guillet, Polym. Microelectron. Proc. Int. Symp., 113, CA 118: 39547, (1989). 240. Q. Zhu, F. Horii, R. Kitamaru, H. Yamaoka, J. Polym. ScL Polym. Chem. ed., 28, 2741 (1990). 241. J. Pacansky, R. J. Waltman, Proc. Water-Borne Higher Solids Coat. Symp., 175, CA: 111: 195538 (1989).
242. A. Daro, F. Zabeau, C. David, Eur. Polym. J., 25, 71 (1989). 243. J. Rosiak, J. Olejniczak, A. Charlesby, Radiat. Phys. Chem., 32, 691 (1988). 244. R F. Barron, W. K. Busfield, J. V. Hanna, J. Polym. ScL, Polym. Lett, ed., 26, 225 (1988). 245. P. F. Barron, W. K. Busfield, J. V. Hanna, Polym. Commun., 29, 70 (1988). 246. D. N. Payne, F. Williams, Polym. Prepr., 28, 303 (1987). 247. A. Torikai, T. Adachi, K. Fueki, J. Polym. ScL, Polym. Chem. Ed., 24, 1413 (1986). 248. P. Peele, Song, Hu, Radiat. Phys. Chem., 42, 121 (1993). 249. L. Yunxia, Y Hang, L. Shuhua, Y Bin, D. Mengxian, J. Bingzhen, Radiat. Phys. Chem., 42, 233 (1993). 250. K. T. Gillen, J. S. Wallace, R. L. Clough, Radiat. Phys. Chem., 41, 101 (1993). 251. B. J. Lyons, L. C. Glover, Radiat. Phys. Chem., 37, 93 (1991). 252. H. Yamaoka, T. Matsuyama, T. Masuda, T. Higashimura, Radiat. Phys. Chem., 37, 111 (1991). 253. D. J. Deeble, G. O. Phillips, E. Bothe, H. P. Schuchmann, C. von Sonntag, Radiat, Phys. Chem., 37 115 (1991). 254. V. S. Ivanov, I. I. Migunova, A. J. Mikhailov, Radiat. Phys. Chem., 37, 119 (1991). 255. W. Schnabel, S. Klaumunzer, Radiat. Phys. Chem., 37, 131 (1991). 256. A. Chapiro, S. Galant, Radiat. Phys. Chem., 37, 505 (1991). 257. Y. Tabata, A. Oshima, K. Takashika, T. Seguchi, Radiat. Phys. Chem., 48, 563 (1996). 258. Y. Lau, J. Guan, H. Yang, S. Li, D. Bin, B. Jiang, CA: 121: 36389, (1992). 259. J. Pacansky, R. J. Waltman, G. Pacansky, Chem. Mater, 5, 1526 (1993). 260. J. Pacansky, R. J. Waltman,, Chem. Mater., 5, 486 (1993). 261. L. Zhang, L. Feng, S. Li, S. Wang, Z. Zhang, CA, 115:184090, (1990). 262. L. Zhang, L. Feng, S. Li, Z. Zhang, CA, 114,102961 (1990). 263. J Shou, Z. Zhu, S. Shi, Y Liu, CA, 111, 195542, (1988). 264. L. Ye, P. Li, Z. Mei, Y Ye, CA, 107: 78430, (1986). 265. X. Chen, X. Tang, H. Guan, Z. Zhang, L. Zhang, S. Li, J. Zhang, Y. Zhang, CA. 107: 78428, (1985). 266. J Sun, S. Zhu, Y. Zhang, CA, 107: 78425, (1986). 267. M. Wang, M. Xu, X. Mao, Y. Liu, CA, 108: 78424 (1986). 268. J. S. Forsythe, D. J. T. Hill, A. L. L. Logothetis, A. K. Whittaker, "Radiothon 96", Australian Institute of Nuclear Science and Engineering, Sydney, 1996. 269. J. Rickards, R. Trejo-Luna, E. Andrade, Radiat. Phys. Chem., 45, 629 (1995). 270. Y. Luo, K. Yang, Y. Chui, CA, 122:82249 (1993). 271. K. Lunkwitz, H. J. Brink, D. Handle, A. Ferse, Radiat. Phys. Chem., 33, 523 (1989). 272. C. Xinfang, Z. Chunshan, Radiat. Phys. Chem., 31, 623 (1988). 273. S. Lora, F. Minto, M. Carenza, G. Palma, A. Faucitanu, Radiat. Phys. Chem., 31, 629 (1988). 274. J. H. Collet, L. Y Lim, P. L. Gould, Polym. Prep., 30, 468 (1989).
S E C T I O N
P H Y S I C A L M
O
N
O
M
E
R
III
P R O P E R T I E S S
A
N
D
S
O
L
O V
E
N
F T
S
P h y s i c a l
P r o p e r t i e s
o f
M o n o m e r s
D a n i e l R. B l o c h Lakeshore Research, 5536 W. Branch Trail, Racine, Wl 53402, USA
A. Introduction B. Tables of Physical Properties Table 1. Acetylenes Table 2. Acid Dichlorides Table 3. Acroleins Table 4. Acrylamides/Methacrylamides 4.1. Acrylamides 4.2. Methacrylamide Table 5. Acrylates/Methacrylates 5.1. Acrylate, Acids/Esters 5.2. Methacrylate, Acids/Esters Table 6. Alcohols 6.1. Alkanediols 6.2. Ether Diols Table 7. AIIyI Functional Table 8. Amines, Difunctional Table 9. Anhydrides 9.1. Monoanhydrides 9.2. Dianhydrides Table 10. Butadienes 10.1. 1,2-Butadienes 10.2. 1,3-Butadienes Table 11. Butenes 11.1. 1-Butenes 11.2. 2-Butenes Table 12. Epoxides 12.1. Monoepoxides 12.2. Diepoxides Table 13. Ethylene Halides Table 14. Fumaric, Acids/Esters Table 15. lsocyanates Table 16. Lactams Table 17. Lactones Table 18. Maleic, Acids/Esters Table 19. Propenes Table 20. Styrenes Table 21. Vinyl Functional 21.1. Aryl 21.2. Esters 21.3. Ethers
111-1 ill-4 III-4 III-4 III-4 III-4 III-4 III-6 III-8 III-8 111-12 111-16 111-16 111-18 111-18 III-20 III-20 III-20 III-24 III-24 III-24 III-24 III-26 III-26 III-26 III-26 III-26 III-28 III-28 III-30 III-30 III-32 IM-32 III-32 III-32 III-34 III-36 III-36 III-36 III-38
21.4. /V-substituted 21.5. Sulfonates
A.
III-38 III-40
INTRODUCTION
This chapter contains some of the principal properties of the more common monomers. The monomers are arranged alphabetically, in groups, with derivatives listed alphabetically within the groups. Compounds are listed under their most commonly used names in polymer chemistry. Therefore, some names are not in agreement with the nomenclature rules of the International Union of Pure and Applied Chemistry. Data are taken from a variety of published literature, including the 3rd edition of the "Polymer Handbook", "The Brandon Worldwide Monomer Reference Guide and Sourcebook", the "Aldrich Catalog Handbook of Fine Chemicals", and "Polysciences Monomers/Polymers, Scientific Polymer Products", "TCI America", "Lancaster and Janssen Chemica" catalogs. Where a range is reported in the literature, the average value is used here for melting points and boiling points. No attempt was made to verify the reported values experimentally. Linear structures are given for most monomers. Molecular formulas are provided when linear structures cannot be unambiguously drawn. Molecular weight is calculated based on the International Atomic Weight values. Boiling point is given in degrees Celsius (0C), at 760mmHg, unless indicated otherwise by the value in mmHg following a slash (/). Melting point is given in degrees Celsius (0C), at 760 mmHg, unless indicated otherwise by the value in mmHg following a slash (/). Refractive index is given at 200C, unless indicated otherwise by the temperature in Celsius following a slash (/). Density is relative to water at 4°C and measured at 200C, unless otherwise indicated by the value following a slash (/). Flash point was determined by the closed-cup method, using a Setaflash apparatus.
RTECS# is the reference to the Registry of Toxic Effects of Chemical Substances. R&S is the reference found in the "Sigma-Aldrich Library of Regulatory & Safety Data", available from Aldrich Chemical Company. FT-NMR is the reference to spectra in the "Aldrich Library of 13C and 1H FT-NMR Spectra", available from the Aldrich Chemical Company. FT-IR is the reference to spectra in the "Aldrich Library of FT-IR Spectra", available from the Aldrich Chemical Company.
Merck Index is the reference to "The Merck Index", Merck & Co., Inc., Whitehouse Station, NJ. Beilstein is the reference to "Beilsteins Handbuch der Organischen Chemie", Springer-Verlag, New York, NY. Fieser is the reference to L. F. Fieser and M. Fieser, "Reagents for Organic Synthesis", John Wiley, New York, NY. Abbreviations: (d) decomposes; (s) sublimes; (aq) aqueous.
B. TABLES OF PHYSICAL PROPERTIES TABLE 1. ACETYLENES Formula RC = CR' Name Acetylene - , Chloro - , Dichloro- , Diphenyl- , Phenyl-
R
CAS Registry Number
R'
-H -Cl -Cl -C 6 H 5 -C 6 H 5
-H -H -Cl -C 6 H 5 -H
74-86-2 501-65-5
MoL wt. 26.04 60.48 94.93 178.23 102.14
Boiling point (0C) -82 -32 60 143
Melting point (0C) - 84(s) -126 -66 170/19
TABLE 2. ACID DICHLORIDES Formula ClC(O)RC(O)Cl Name Adipoyl Azelaoyl Diethylmanoyl Dodecanedioyl Glutaryl Isophthaloyl Malonyl Methylpimeloyl Oxalyl Phthaloyl Pimeloyl Sebacoyl Suberoyl Succinyl Terephthaloyl Thionyl
CAS Registry Number
R -(CH 2 ) 4 -(CH 2 ) 7 -C(CH 2 CH 3 ) 2 -(CH 2 ) 1 0 -(CH 2 ) 3 -C6H4-CH2-(CH 2 ) 2 CH(CH 3 )(CH 2 ) 2 -CO-CO-C6H4-(CH 2 ) 5 -(CH 2 ) 8 -(CH 2 ) 6 -(CH 2 ) 2 -C6H4ClC(S)Cl
111-50-2 123-98-8 54505-72-5 4834-98-4 2873-74-7 99-63-8 1663-67-8 44987-62-4 79-37-8 88-95-9 142-79-0 111-19-3 10027-07-3 543-20-4 100-20-9 7719-09-7
MoI. wt.
Boiling point (0C)
183.03 255.12 197.06 267.20 169.01 203.02 140.95 197.06 126.93 203.02 197.06 239.14 211.09 154.98 203.02 118.97
106/2 166/18 198 140/0.5 217 276 54/19 118/10 61 270 113/5 168/12 162/15 190 266 79
MoI. wt.
Boiling point (0C)
Melting point (0C)
43 -8 12 -2.5 16 80 -105
TABLE 3. ACROLEINS Formula HC(O)CR = CHR' Name Acrolein -, 2-Chloro- , 2-Methyl- , 3-Methyl-, fra/w-(Crotonaldehyde) - , 2-Chloro-3-methyl-
R
CAS Registry Number
R'
-H -Cl -CH 3
-H -H -H
107-02-8
-H -Cl
-CH 3 -CH 3
123-73-9
78-85-3
56.06 90.51 70.09
53 40/30 68
70.09 104.54
148
Melting point (0C) -87 -81 104
TABLE 4. ACRYLAMIDES/METHACRYLAMIDES Name
R
4.1. ACRYLAMIDES H2C=CHC(O)NRR' Acrylamide -H -, Acetyl-, N-C(O)CH3 - , Adamantyl-, N-Ci 0 H 5 -,AlIyI-, N-CH2CH=CH2 - , Benzyl-, N-CH 2 C 6 H 5 - , Butoxymethyl-, N-CH2O(CH2)3CH3 - , terf-Butyl-, N-C(CH 3 ) 3 - , Cyclohexyl-, N-C 6 Hn - , Cystamine-bis-, NJf'-CH 2 CH 2 SSCH 2 CH 2 - , Diacetone-, N-C(CH3)2CH2C(O)CH3 - , Diallyl-, N,N-CH2CH=CH2 - , Di-n-butyl-, N9N-(CH 2 ) 3 CH 3
R' -H -H -H -H -H -H -H -H -H -H -CH2CH=CH2 -(CH 2 ) 3 CH 3
CAS Registry Number
MoI. wt.
79-06-1 1432-45-7 19026-83-6 2555-13-7 13304-62-6 1852-16-0 107-58-4 3066-72-6 60984-57-8 2873-97-4 3085-68-5 2274-13-7
71.08 113.12 205.30 111.14 161.20 157.21 127.19 153.23 260.38 169.23 151.21 183.29
Boiling point (C)
Melting point (0C)
125/25 129 155 120/19 125/0.3
93/0.1 108/3 97/1
70 -9 128 113 123 55
Density (at 200C)
Refractive index (at 200C)
Flash point (°C)
1.000 0.990 0.929
Density (at 200C) 1.259 1.143 1.145 1.069 1.324
R and S
FT-NMR
FT-IR
Fieser 1,11
1(2),2711I
Refractive index (at 200C) 1.4700 1.4680 1.4590 1.4680 1.4720
1.631
1.5190
1(3), 533A
1(2),946B
Refractive index (at 200C)
Flash point (0C) >110 >110 74 >110 107 180 47 >110 None >110 >110 >110 >110 77 180 None
RTECS Number
R and S
WN4900000 WZ1797000 XM515OOOO
1(1), 867J 1(1),869C 1(1),867G 1(1),869E 1(1),867I 1(2),1981H 1(1),867F 1(1),867K 1(1),867D 1(2),1981G 1(1),869A 1(1),869D 1(1),869B 1(1),867H 1(2),1981I 1(2),3197F
Flash point (°C)
RTECS Number
R and S
NT2625000 KI2950000
FT-NMR
FT-IR
11,9428
1(1),1211B 1(1)1212C 1(1),1212A
5,656
1,335
Beilstein
Fieser
1(1),1211A 1(1),1212B
1(1),1211C
FT-NMR
l(l),740D 1(2),352A l(l),740A 1(1),741B 1(1),739C 1(2),351D 1(1),741C 1(1),742B 1(1),741D l(l),740C 1(2),352B 1(2),1227B
FT-IR
-19
AS105000
1(1),515A
1(1),733B
l(l),470D
-16
OZ2625000
1(1),515B
1(1),733C
1(1),471A
0.846 1.478
1.4365
9
GP9625000
1(1),515G
RTECS Number
R and S
AS3325000
1(1),877K
Flash point (°C)
1.122
1.4620
> 110
>110
1(1),472C
FT-NMR 1(1),1221A
2,653 2,709 2,687 2(4),2127 2,634 9,834 2(1),252
l(l),740B
1.4025 1.463 1.4160
Refractive index (at 200C)
Merck
1(1),741A
0.839 1.199 0.847
0.9790
Beilstein
1.548
1.4650 1.4720 1.4290 1.5684 1.4690 1.4680 1.4680 1.4680
Density (at 200C)
Merck
AO9600000
1.449 1.217 1.455 1.409 1.205 1.121 1.172 1.407
Density (at 200C)
RTECS Number
FT-IR 1(1),749B
11,6867 11,7439
11,8844 11,9278
Merck 11,122
13,297
Beilstein
Fieser
1,725
10,2
11,2599
Merck 11,123
1,728
Beilstein 2,400
4(4),664 1(1),887I
1(1),1236A
l(l),750C
17,241 14,263
1(3),2981
AS3450000 AS3460000 AS3475000
2,542 9,805 2,671 2,719 2,694 2,613 9,844
12,291
11,2943
Fieser
TABLE 4.
cont'd
- , Diethyl-, N9N- , 1,2-Dihydroxyethylenebis-,N,N' - , Diisopropyl-, N,N- , 4,4-Dimethoxybutyl-, N- , Dimethyl-, N9N- , 3-(Dimethylamino)propyl-, N-, l,l-Dimethyl-2sulfoethyl-, N-(AMPS) - , Diphenylmethyl-,7V- , Ethylenebis-,WV'- , Ethylhexyl-,iV- , 2-Glycolic acid, N- , 2-Glycolic acid methyl ester, N- , Hexamethylenebis-, N,Nf - , tert-Hexyl-, N- , Hydroxymethyl-, N- (solution) - , Isobornyl-, N-, Isobutoxymethyl-, N-, Isopropyl-, N-, Isopropylidenebis-, N9N1- , 3-Methoxypropyl-, N- , Methyl-, N- , Methylenebis-, N,Nf- , (1-Methoxy) - , (Methoxy)acetoxymethyl-, N- , Morpholinoethyl-, N- , 1-Naphthyl-, N- , Octadecyl-, N- , Octamethylenebis-, NJ*'- , tert-Octyl-, N- , Phthalamidomethyl-, N- , 2,2,2-Trichloro-lhydroxyethyl-, N- , Tri(hydroxymethyl)methyl-, N -, 1,1,3-Trimethylbutyl-, N- , Trimethylenebis-, N,N'- , Triphenylmethyl-, N4.2.
R;
R
Name
Boiling point (0C)
CAS Registry Number
MoI. wt.
2675-94-7 868-63-3
127.19 200.19
93/19 54/0.4 135/0.7 82/21 117/2
Melting point (0C)
-CH 2 CH 3 -CH(OH)CH(OH)-
-CH 2 CH 3 -H
-CH(CHs) 2 -(CH 2 ) 3 CH(OCH 3 ) 2 -CH3 -(CH 2 ) 3 N(CH 3 ) 2
-CH(CH 3 ), -H -CH3 -H
44975-46-4 38486-53-2 2680-03-7 3845-76-9
155.24 187.24 99.13 156.23
-C(CH 3 ) 2 CH 2 SO 3 H
-H
15214-89-8
207.25
-CH(C 6 H 5 ), -CH2CH2-CH 2 CH(CH 2 CH 3 ) (CH 2 ) 3 CH 3 -CH(OH)C(O)OH -CH(OH)C(O)OCH3
-H -H -H
10254-08-7 2956-58-3 91625-16-0
237.30 168.20 183.30
-H -H
6737-24-2 77402-03-0
163.13 173.17
-(CH2)6-
-H
7150-41-6
224.28
135
-CH 2 CH 2 C(CH 3 ), -CH 2 OH
-H -H
51330-07-5 924-42-5
155.24 101.11
100
- C H)H 17
-CH 2 OCH 2 CH(CH 3 ) 2 -CH(CH 3 ), -C(CH3)2-
-H -H -H -H
17159-04-5 16669-59-3 2210-25-5
207.31 157.21 113.16 182.22
-(CH 2 ) 3 OCH 3 -CH3 -CH2-
-H -H -H
107374-86-7 1187-59-3 110-26-9
143.19 85.11 154.17
-C(OCH 3 )C(O)OCH 3
-H
77402-03-0
173.17
-CH 2 CH 2 NC 4 H 8 O -Ci0H7 -(CH 2 ) 17 CH 3 -(CH2)8-
-H -H -H -H
5117-12-4 22302-62-1 1506-54-3 2945-02-0
141.17 197.24 323.56 252.35
-(CH 2 ) 4 C(CH 3 ) 3 -CH 2 NC 8 H 4 O 2 -CH(OH)CCl 3
-H -H -H
4223-03-4 80500-94-3
183.29 230.22 218.47
58 190 170
-C(CH 2 OH) 3
-H
13880-05-2
175.18
139
-C(CH 3 ) 2 CH 2 CH(CH 3 ) 2 -(CH2),-C(C 6 H 5 ),
-H -H -H
25269-93-6 4887-13-2 102548-89-0
169.27 182.22 313.40
156(d)
18
195(d)
178 140
123/0.5 95 74
135
108 90/2
61 210
99/0.3 106/4 >300 73
158/50
125/25
>110 138 75 138
55 112 204
METHACRYLAMIDES H2C=C(CH3)C(O)NRR'
215 76/1.2
Methacrylamide - , Acetyl-, N- , Acetylphenyl-, N- , AlIyI-, N- , 3-Aminopropyl-, N-, hydrochloride - , Benzyl-, N-, Bis(diethylaminoethyl)-, N9N- , Butoxymethyl-, N-
-H -C(O)CH 3 -C 6 H 4 C(O)CH 3 -CH 2 CH=CH 2 -(CH 2 ) 3 NH 2 HC1
-H -H -H -H -H
79-39-0 44810-87-9 58813-69-7 2186-33-6 72607-53-5
85.11 127.14 203.24 125.17 178.66
-CH 2 C 6 H 5 -CH 2 CH 2 N(CH 2 CH 3 ) 2
3219-55-4 76392-05-7
175.23 183.28
122/0.4
-CH 2 O(CH 2 ) 3 CH 3
-H -CH 2 CH 2 N(CH 2 CH 3 ), -H
171.24
105/0.3
-, ^rr-Butyl-, N- , 2-Cyanoethyl-, N- , 2-Cyanoethyl-, N-, methyl-, N
-C(CH 3 ), -CH 2 CH 2 CN -CH 2 CH 2 CN
-H -H -CH3
5153-77-5 28384-61-4 6554-73-0 24854-94-2
142.20 138.17 152.20
163
109 138 138
90/2.2 124 82
113/1
60 46 46
Density (at 200C)
0.962 0.949
Refractive index (at 200C)
1.4730 1.4820
Flash point (0C)
71 > 110
RTECS Number
AU3230000
160
R and S
FT-NMR
1(1),885K
1(1),1233C
1(1),893I
1(1),1244C
l(l),1065K
1(1),1438C
FT-IR
1(3),784B
1(1),915E 1(1),913D
1(1),885J
1.074
1.4130
None
AS3600000
0.970
1.4610
79
AS3630000 AS3675000
1.122
1.5120
Beilstein
4(3),130 4(4), 1268
4(3),526
1(1),883K
AI8967330
Merck
1(1),1276B 1(1),1272B
1(1),781A
l(l),750A
2(4), 1472
4(4),517
AS3678000
1(1),883J
l(l),1230C
AI8967330
1(1),913D
1(1),1272B
> 110
1(1),749D
1.10
UC6475000
1(1),883M
1(1),1231B
1(1),877L
1(1),1221B
27(4),278
2(2),399 1.4702 0.96
1.46
1.4755
122
1(1),749C
Fieser
TABLE 4.
cont'd R
Name -, -, -, -, -, -, -, -, -, -, -, -,
Cyclohexyl-, NDiallyl-, N,NDibenzyl-, N,NDibutyl-, NJf3-Di(butyl)aminopropyl-, NDiethyl-, NJf3-(Diethylamino)propyl-, NDiisopropyl-, NJf2,2-Dimethoxyethyl-, NDimethyl-, NJf2-(Dimethylamino)ethyl-, N3-(Dimethylamino)propyl-, N- , Dodecyl-, N-, Ethylenebis-, NJf'- , 2-Ethylhexyl-, N-, 2-Hydroxyethyl-, N- , Hydroxymethyl-, N- , 4-Hydroxyphenyl-, N- , Isobutoxymethyl-, Af- , Isopropyl-, N-, Methoxymethyl-, N- , Methyl-, N- , Methylenebis-, NJf'- , Methyl-, N-, Phenyl-, N-, Methyl-, N-, 2,2-dimethoxyethyl-, N-, 3-(Af-morpholino)propyl-, A^- , 2-(2-Oxo-l-imidazolidinyl)ethyl-, N- , Phenyl-, N- , Phenyl-, N-, Phenylethyl-, N-, 3-(Trifluoromethyl)phenyl-, A^- , 3-(Trimethylammonium)propyl-, chloride, N- (eq. solution)
TABLE 5.
-C6Hn -CH2CH=CH2 -CH 2 C 6 H 5 -(CH 2 ) 3 CH 3 -(CH2)3N((CH2)3CH3)2 -CH 2 CH 3 -(CH 2 ) 3 N(CH 2 CH 3 ) 2 -CH(CH 3 ) 2 -CH2CH(OCH3)2 -CH 3 -CH 2 CH 2 N(CH 3 ) 2 -(CH 2 ) 3 N(CH 3 ) 2
-H -CH2CH=CH2 -CH 2 C 6 H 5 -(CH 2 ) 3 CH 3 -H -CH 2 CH 3 -H -CH(CH 3 ) 2 -H -CH 3 -H -H
-(CH 2 )nCH 3 -CH 2 CH 2 -CH2CH(CH2CH3)(CH2)3CH3 -CH2CH2OH -CH 2 OH -C 6 H 4 OH -CH2OCH(CH3)2 -CH(CH 3 ), -CH 2 OCH 3 -CH 3 -CH2-CH 3 -CH 3
-H -H -H -H -H -H -H -H -H -H -H -C 6 H 5 -CH2CH(OCH3)2
-(CH 2 ) 3 NC 4 H 4 O -CH 2 CH 2 C 3 H 5 N 2 O
CAS Registry Number 2918-67-4 13169-99-8 57625-30-6 22240-86-4 76392-03-5 5441-99-6 51745-62-1 95984-11-5 6976-91-6 13081-44-2 5205-93-6
MoL wt. 167.25 197.32 265.36 197.32 253.41 141.21 197.30 169.27 173.21 113.16 156.34 170.26
Boiling point (0C)
Melting point (°C) 102
50/1.1 41 81/0.8 125/0.13 82/7 134/10 47 27 66/10 87/1.8 134/2
1191-39-5 6117-25-5 5238-56-2 923-02-4 19243-95-9 4548-27-0 13749-61-6 3644-12-0 3887-02-3 2359-15-1 2918-73-2 95984-81-9
253.43 196.25 197.32 129.16 115.13 177.20 171.24 127.19 129.16 99.13 182.22 238.31 187.24
110/0.3 147/1.2 ca. 100 127/5 112/115 80.03 88/3.5
-H -H
55937-58-1 3089-19-8
212.30 197.24
150/0.08 100
-C 6 H 5 -C 6 H 5 -C 6 H 4 CF 3
-H -CH 2 CH 2 C 6 H 5 -H
1611-83-2 76392-02-4 783-05-1
161.20 266.37 229.20
84 63 95
-(CH 2 ) 3 N(CH 3 ) 3 HC1
-H
51410-72-1
220.74
-22.5
CAS Registry Number
MoL wt.
-H -CH2CH=CH2 -C(O)CH=CH2 -CH 2 C 6 H 5 -C 6 H 4 C 6 H 5 (-(CH2CH2OC6H4)2C(CH3)2 (-CH2CH(OH)CH2OC6H4)2C(CH3)2
79-10-7 999-55-3 2051-76-5 2495-35-4 13026-23-8 64401-02-1 4687-94-9
72.06 112.13 126.11 162.19 226.27 424 484.55
H2C=CBrC(O)OH BrCH=CHC(O)OH H2C=CBrC(O)OCH2CH3 -CH 2 CH 2 Br H2C=C(CH2Br)C(O)OH H2C=C(CH2Br)C(O)OCH2CH3 H2C=C(CH2Br)C(O)OCH3 -CH 2 CH 2 CH(CH 3 )-(CH 2 ) 4 -CH 2 CH=CHCH 2 -
10443-65-9 1609-92-3 4519-46-4 4823-47-6 72707-66-5 17435-72-2 4224-69-5 19485-03-1 1070-70-8
150.97 150.96 164.99 179.03 164.99 193.05 179.02 198.22 198.22 127.16
145/0.08
88/2 72/2
170 -37 154 90 164 50
ACRYLATES/METHACRYLATES
R
Name 5.1.
R'
Boiling point (0C)
Melting point (0C)
139 123 97/35 110/8
13
ACRYLATE, ACIDS/ESIPERS H2C = CHC(O)OR
Acid Allyl ester Anhydride Benzyl ester 4-Biphenylyl ester Bisphenol A ethoxylate diester Bisphenol A diglycidyl ether diester 2-Bromo3-Bromo-, cis2-Bromo-, ethyl ester 2-Bromoethyl ester 2-Bromomethyl2-Bromomethyl-, ethyl ester 2-Bromomethyl-, methyl ester 1,3-Butylene diester 1,4-Butylene diester 2-Butylene-l,4 diester
224
63 63 72/78 52/5 70 86/20 36/1.3 73/0.1 83/0.3 60/23
Density (at 200C)
Refractive index (at 200C)
Flash point (0C)
RTECS Number
R and S
FT-NMR
FT-IR
Merck
Beilstein
Fieser
1.4731
0.940
1.4600 1.4744 1.4790
140
1.5002 1.100 0.97
1.4300 1.46
>110
UC6380000
107 4(3),276
SI1225000 1.4707 1.4740 0.97
1.4560
>110
1.110
1.427 1.053
Density (at 200C)
1.051 0.880
Refractive index (at 20°C)
Flash point (0C)
54 8
1.0573
1.4202 1.4320 1.4487 1.5143
101
1.146 1.180
1.5450 1.5570
> 110 > 110
RTECS Number
R and S
AS4375000
1(1),547A
FT-NMR
1(1),776A
FT-IR
1(1),498B
1.4770
1.388 1.489 1.030 1.051 0.9344
1.478 1.490 1.4500 1.4560 1.4422
78 93 >110
AS4900000 AS5250000 UD3130000
11,124 2,400
Beilstein
2,397
2,402 2(4), 1486
1(1),563H 1(1),563I 1.4774
Merck
1(1),563K
l(l),806C
1(1),516C
1(1),745J
l(l),1031C
1(3),696D 2(4), 170
Fieser
TABLE 5.
Name
cont'd
R
2-(2-Butoxyethoxy)ethyl ester -CH2CH2OCH2CH2O(CH2)3CH3 2-Butoxyethyl ester -CH2CH2O(CH2)SCH3 w-Butyl ester -(CH 2 ) 3 CH 3 s-Butyl ester -CH(CH3)CH2CH3 f-Butyl ester -C(CH 3 ) 3 2-ChloroH2C=CClC(O)OH 2-Chloro-, butyl ester H2C=CC1(O)O(CH2)3CH3 2-Chloro-, ethyl ester H2C=CClC(O)OCH2CH3 2-Chloro-, methyl ester H2C=CClC(O)OCH3 3-Chloro-, cisClCH=CHC(O)OH 3-Chloro-, transClCH=CHC(O)OH 2-Chloroethyl ester -CH2CH2Cl Cinnamyl ester -CH2CH=CHC6H5 Crotyl ester -CH2CH=CHCH3 2-Cyano-, butyl ester H2C=C(CN)C(O)O(CH2)3CH3 2-Cyano-, ethyl ester H2C=C(CN)C(O)OCH2CH3 2-Cyano, isobutyl ester H2C=C(CN)C(O)OCH2CH(CH3)2 2-Cyanoethyl ester -CH2CH2CN Cyclohexyl ester -C 6 H 1 1 Cyclopentyl ester -C 5 H 9 rc-Decyl ester -(CH 2 ) 9 CH 3 2,3-Dibromopropyl ester -CH2CHBrCH2Br 2,3-Dichloropropyl ester -CH2CHCICH2Cl Dicyclopentenyl ester -C1OH13 Dicyclopentenyloxyethyl ester -CH2CH2OC 10H 13 2-(Diethylamino)ethyl ester -CH2CH2N(CH2CH3)2 3-(Diethylamino)propyl ester -(CH 2 ) 3 N(CH 2 CH 3 ) 2 Di(ethylene glycol) diester -CH 2 CH 2 OCH 2 CH 2 Dihydrodicyclopentadienyl estei -C1OH15 2,3-Dihydroxypropyl ester -CH2CH(OH)CH2OH 2-(Dimethylamino) ethyl ester -CH 2 CH 2 N(CH 3 ) 2 3-(Dimethylamino) neopentyl - CH2C(CH3)2CH2N(CH3)2 ester 3-(Dimethylamino) propyl ester -(CH 2 ) 3 N(CH 3 ) 2 Dipentaerythritol pentaester (-CH2)3CCH2OCH2C(CH2OH)(CH2-)2 Di(propylene glycol) diester -CH2CH(CH3)OCH2CH(CH3)Di(trimethylolpropane) tetraester ((-CH2)2C(CH2CH3)CH2)2O Dodecyl ester -(CH 2 ) n CH 3 1H,1H,1 lH-Eicosafluoro-CH 2 (CF 2 ) 9 CHF 2 undecylester 2-(2-Ethoxyethoxy)ethyl ester -(CH2CH2O)2CH2CH3 2-Ethoxyethyl ester -CH2CH2OCH2CH3 Ethyl ester -CH 2 CH 3 Ethylene diester -CH 2 CH 2 2-Ethylhexyl ester -CH2CH(CH2CH3)(CH2)3CH3 Furfuryl ester -CH 2 C 4 H 3 O Glycidyl ester -CH 2 CH(-O-)CH 2 Glycerol propoxylate triester -CH(CH3)CH2OCH(CH2OCH2CH(CH3)-)2 1H,1H,2H,2H-Heptadecafluoro- -CH 2 CH 2 (CF 2 ) 7 CF 3 decyl ester 1H, 1 H-Heptafluorobutyl ester -CH 2 CF 2 CF 2 CF 3 Heptyl ester -(CH 2 ) 6 CH 3 Hexadecyl ester -(CH 2 ) 15CH3 2,2,3,4,4,4-Hexafluorobutyl este:r -CH2CF2CHFCF3 lH-Hexafluoroisoporpyl ester -CH(CF 3 ), Hexanediol diester -(CHa) 6 n-Hexyl ester -(CH 2 ) 5 CH 3 4-Hydroxybutyl ester -(CH 2 ) 4 OH 2-Hydroxyethyl ester -CH2CH2OH 2-Hydroxy-3-phenoxypropyl -CH2CH(OH)CH2OC6H5 ester 2-Hydroxypropyl ester -CH2CH(OH)CH3 Isobornyl ester -C 10 H 18 Isobutyl ester -CH2CH(CH3)2
CAS Registry Number
MoI. wt.
Boiling point (0C)
Melting point (0C)
4074-88-8 12542-30-2 10095-20-2 2439-35-2 20166-73-8
232.28 172.22 128.17 128.17 128.17 106.51 162.62 134.56 120.54 106.51 106.51 134.57 188.23 126.16 153.18 125.13 153.18 125.13 154.21 282.38 212.34 271.94 183.04 202.25 248.32 171.27 185.27 214.22 204.27 146.15 143.19 181.24
18526-07-3 60506-81-2 85136-76-1 94108-97-1 2156-97-0 4998-38-3
157.22 524.53 242.27 466.53 240.39 586.17
7328-17-8 106-74-1 140-88-5 2274-11-5 103-11-7 10525-17-4 106-90-1 52408-84-1 27905-45-9
188.23 144.17 100.12 170.16 184.28 152.15 128.13 428 518.10
250 65/16 99 67/2 217 92/16 115/78
424-64-6 2499-58-3 13402-02-3 54052-90-3 2160-89-6 13048-33-4 2499-95-8 2478-10-6 818-61-1 16969-10-1
254.11 170.25 296.50 236.11 222.09 226.28 156.23 144.17 116.11 222.24
121/743 56/1 170/15 48/12 84 295 190 95/0.1 90/12
-101
999-61-1 5888-33-5 106-63-8
130.15 208.30 128.19
77/15 275 132
-92 -15 -61
7251-90-3 141-32-2 2998-08-5 1663-39-4 26952-44-3 13401-85-9 687-46-7 80-63-7 1609-93-4 2345-61-1 2206-89-5 23916-33-8 6606-65-1 7085-85-0 1069-55-2 106-71-8 3066-71-5 16868-13-6 2156-96-9 19660-16-3 24910-84-7 33791-58-1 65983-31-5 2426-54-2
103/23 63/2 145 59/25 30/25 176(d) 100/42 41/20 52/50
-64 60
61 84 64/20 105/2 38/10 92/6 90/5 81/4 103/8 183 145/0.08 185/50 105/6 58/0.5 105/4 100/0.5 171.27 44/0.1 162 119/5 115/0.1 64/12 53/1.4
-17 -17
<-60 -40 <-60
167 95/0.5 120/1 115/1
49
-72 -90
100/4
-45
Density (at 200C) 0.9821 0.9497 0.894 0.8114 0.8850
Refractive index (at 200C) 1.4394 1.4323 1.4180 1.4140 1.4108
Flash point (0C) 90 39
RTECS Number
R and S
UD3150000
1(1),719E
1(1),974A
1(1),642A
1(1),719F
1(1),974B
1(3),674D
2(3),1228
1(1),563F 1(1),563G
l(l),805C l(l),806A
1(1),516A 1(1),516B
2,400 2,400
FT-NMR
FT-IR
Merck
11,1539
Beilstein
Fieser
2(2),388
17 1.1404 1.189
1.4384 1.4420 33
AS5960000
1.1404 1.0495
1.4384 1.5660
0.986 1.069
1.4420
99 108
1.0690 0.975
1.4433 1.4673
124 29
0.8781 1.7803 1.2603
1.440 1.5520 1.4765
227
1.085 0.9250 0.9180 1.118 1.08
1.5010 1.443 1.441 1.4630 1.509
99 68
AS8225000
> 110
AS9450000
0.943 0.90
1.4380 1.439
58 75
AS8578000
0.928 1.1915
1.4400
68 115
1.101 0.884
1.4488 1.4790 1.4450
3(3),543
AT1500000 AS7350000
1(1),771G
l(l),1073C
1(3),734A
4(3),649
> 110 > 110
2(3), 1230
1.016 0.9819 0.924 1.090 0.8859 1.1125 1.099 1.064
1.4390 1.4282 1.4060 1.4610 1.4360 1.4800 1.4490 1.4610 1.3380
102 65 15 100 79
AS9800000 AT0700000 AT0350000 AT0855000
76
AS9275000
1.418 0.8846 0.8620 1.398 1.330 1.010 0.8882 1.039 1.011 1.160
1.3301 1.4311 1.4470 1.352 1.3190 1.4562 1.4280 1.4520 1.4502 1.5280
31 59 10 > 110 68 > 110 98 89
1.05 0.986 0.8896
1.4448 1.4760 1.4140
65 93 33
1(1),719D 1(1),727M 1(1),719G
1(1),973C 1(1),974C
1(1),638C 1(3),675B 1(3),675A
11,3715
2(3),1232 2(3), 1232 2,399 2(4), 1496 2(3),1229
1(1),1O88C 17(3), 1005
2(4), 1464
AT1430000 AT1450000
1(1),745C 1(1),729E
l(l),1029B
1(1),753L 1(1),753J
l(l),1044C l(l),1044A
1(1),639B l(3),720C l(3),720B
2(3), 1228 2(4), 1470 2(4), 1496
AT1750000 1(1),719H 2(3),1227 AT2100000
6,251
TABLE 5.
cont'd
Name
R
Isodecyl ester -(CH 2 )7CH(CH 3 ) 2 Isooctyl ester -(CH 2 )5CH(CH 3 )2 Isopropoxyethyl ester -CH 2 CH 2 OCH(CH 3 )S Isopropyl ester -CH(CH 3 ) 2 Methallyl ester -CH 2 C(CH 3 )=CH 2 2-(2-Methoxyethoxy) ethyl ester - C H 2 C H 2 O C H 2 C H 2 O C H 3 2-Methoxyethyl ester -CH 2 CH 2 OCH 3 Methyl ester -CH3 2-Methylbutyl ester -CH 2 CH(CH 3 )CH 2 CH 3 2-(A^Morpholino)ethyl ester -CH 2 CH 2 NC 4 H 8 O 1-Naphthyl ester -Ci0H7 2-Naphthyl ester -Ci0H7 Neopentyl ester -CH 2 C(CH 3 ) 3 Neopentyl glycol diester -CH 2 C(CH 3 ) 2 CH 2 Nonyl ester -(CH 2 ) 8 CH 3 Octadecyl ester -(CH 2 ) I 7 CH 3 1H,1H,5H-Octafluoropentyl ester -CH 2 (CF 2 ) 3 CF 2 H rc-Octyl ester -(CH 2 ) 7 CH 3 1H,1H-Pentadecafluorooctyl ester-CH 2 (CF 2 ) 6 CF 3 Pentaerythritol tetraester (-CH 2 ) 4 C Penterythritol triester (-CH 2 ) 3 CCH 2 OH Pentaerythritol stearate diester (-CH 2 ) 2 C(CH 2 OH)CH 2 OC(O)(CH 2 )I 6 CH 3 2,2,3,3,3-Pentafluoropropyl e s t e r -CH 2 CF 2 CF 3 1,5-Pentanediol diester -(CH2)5w-Pentyl ester -(CH 2 ) 4 CH 3 2-Phenoxyethyl ester -CH 2 CH 2 OC 6 H 5 Phenyl ester -C6H5 1,4-Phenylene diester -C6H41,4-Phenylene di(acrylic acid) C 6 H 4 (CH=CHC(O)OH) 2 2-Phenylethyl ester -CH 2 CH 2 C 6 H 5 Trimethyl 2-phosphonoacrylate (CH 3 O) 2 P(O)C(C(O)OCH 3 )=CH 2 Propargyl ester - C H 2 C = CH w-Propyl ester -CH 2 CH 2 CH 3 1,2-Propylene glycol diester -CH 2 CH(CH 3 )1,3-Propylene glycol diester -(CH2)3Tetradecyl ester -(CH 2 )I 3 CH 3 Tetra(ethylene glycol) diester -(CH 2 CH 2 O) 3 CH 2 CH 2 2,2,3,3-Tetrafluoropropyl ester -CH 2 CF 2 CF 2 H Tetrahydrofurfuryl ester -C5H^ S,S'-Thiodi-l,4-phenylene dithiol - S C 6 H 4 S S C 6 H 4 S diester 2,3,3-TrichloroClCH 2 =CC1C(O)OH Tridecyl ester -(CH 2 ) I 2 CH 3 Tri(ethylene glycol) diester -(CH 2 CH 2 O) 2 CH 2 CH 2 2,2,2-Trifluoroethyl ester -CH2CF3 l,l,l-Tri(2-hydroxyethoxy(-CH 2 CH 2 OCH 2 ) 3 CCH 2 CH 3 methyl)propane triester Tri(2-hydroxyethyl) isocyanurate (-CH 2 CH 2 ) 3 C 3 N 3 O 3 triester 3,5,5-Trimethylcyclohexyl ester -C 6 H 8 (CH 3 ) 3 3,5,5-Trimethylhexyl ester -(CH 2 ) 2 CH(CH 3 )CH 2 C(CH 3 ) 3 Trimethylolpropane triester (-CH 2 ) 3 CCH 2 CH 3 Trimethylolpropane ethoxylate ((-CH 2 CH 2 O) X CH 2 ) 3 CCH 2 CH 3 triester Tri(propylene glycol) diester (-CH2(CH3)CH2O)2CH2CH(CH3)Vinyl ester -CH=CH 2
5.2.
CAS Registry Number
MoI. wt.
Boiling point ( 0 C)
25151-33-1 21643-42-5 17831-71-9 7383-71-3 2399-48-6 129283-82-5
212.34 184.25 159.21 114.14 126.16 174.20 130.14 86.09 142.20 185.2 198.22 198.22 142.24 212.25 198.31 324.55 286.12 184.28 454.13 352.34 298.30 510.72 204.10 212.25 142.20 192.21 148.16 218.21 218.21 176.22 194.13 110.11 114.14 184.19 184.19 268.44 302.33 186.11 156.18 386.56
2257-35-4 3076-04-8 1680-21-3 407-47-6 28961-43-5
175.40 254.41 258.30 154.09 428.48
40220-08-4
423.38
86178-38-3 2664-55-3 15625-89-5 28961-43-5
196.29 198.31 296.32 ca. 428
42978-66-5 2177-18-6
300 98.10
>120/l 91
79-41-4 21282-97-3 96-05-9 760-93-0 6498-81-3
86.09 214.22 126.16 154.17 155.20
163 274 60/43 200 190
1330-61-6 29590-42-9 689-12-3 818-67-7 7328-18-9 3121-61-7 96-33-3 19727-38-9 20069-66-3 52684-34-1 4513-36-4 2223-82-7 4813-57-4 376-84-1 2499-59-4 307-98-2 4986-89-4 3524-68-3 92092-01-8 356-86-5 36840-85-4 2998-23-4 48145-04-6 937-41-7 6729-79-9 16323-43-6 3530-36-7 55168-74-6 10477-47-1 925-60-0
121/10 125/20 82/19 51/103 70/50 86/4.6 56/12 80 63/27 67/0.2 212/1 138/0.4 31/3 105/5 76/0.2 160/3 88/41 57/0.05 65/5 >315
Melting point (0C) -100
-75
32
18 15 30
50/100 94/0.3 47/7 103/0.6 87/12 88 >300 104/5 91/0.1 138 43/40 63/0.3 122/0.5 138/0.4 >120/0.3 132 87/9
<-60 64 72
150/10 125/0.2 92 157 97 40/0.1 58/0.8 316 157
-34
<-20
METHACRYLATE, ACIDS/ESTERS (H 2 C=C(CH 3 )C(O)OR)
Acid 2-(Acetoacetoxy)ethyl ester AUyI ester Anhydride 2-(l-Aziridinyl)ethyl ester
-H -CH 2 CH 2 C(O)OCH 2 C(O)CH 3 -CH 2 CH=CH 2 -C(O)C(CH 3 )=CH 2 -CH 2 CH(-NH-)CH 2
16
-20
Density (at 200C)
Refractive index (at 200C)
0.875 0.880 0.9549 0.8932 0.9285 1.0421 1.012 0.956 0.8883 1.0711
1.4420 1.4370 1.4258 1.4060 1.4372 1.4392 1.4272 1.4020 1.4800 1.4728
0.859 1.030 0.875 0.800
1.4530 1.4375
0.8810 1.63 1.190 1.180 1.018 1.32 0.8920 1.104
Flash point (0C)
RTECS Number
106 80
AT2190000 UD3391000
60 7
KL6000000 AT2800000
>37 123
AS8925000
R and S
1(1),719C
FT-NMR
1(1),973B
FT-IR
1(1),638B
Merck
11,5935
190 70
Beilstein
2(3),1232 3,638B
2(4), 1468
1.3467 1.4350 1.3279 1.4870 1.4840
170 > 110
UD3370000
1.3363 1.4551 1.4240 1.5180
> 110
KM0700000
6(3),572
1(2),1775F
1(2), 1050A
l(l),1109B
1(1),1489B
1(1),759E 1(1),745A
l(l),1053B
1(1),743M
l(l),1028C 1(1),999C
1.249
1.4540
105
0.9078
0.8700 1.110 1.317 1.063
1.4130 1.4470 1.4529 1.4468 1.4638 1.3629 1.4580
>110 45 >110
1.099 1.216 1.110
1.4609 1.3506 1.4710
63 12 >110
KM2890000
0.9292 0.875 1.100 1.110
1.455 1.4370 1.4736 1.4720
88 89 >110 86
UD3643625 AT4810000 KM2890000
1(1),729F
1.030 0.942
1.4500 1.4320
AT4690000
1(1),729A
2
1.015 1.122 0.934 1.035
1.432 1.4560 1.4360 1.454
76 106 34 83
OZ2975000
1(1),547B 1(1),791E 1(1),721E 1(1),831C
AS8100000
UD3483000 OZ5700000
1(1),639C
1(1),753I
9,914
1(2),179B
4(4),3638
1(1),639A 17(3),1104 17(3),1104
2(4), 1462
1(3),696C
2(3),1230 l(l),640A 1(1),999C 1(1),638D
1(1),776B l(l),1107C 1(1),977A l(l),1170C
1(1),499C 1(1),641B
11,5849
2,421 2(3), 1290 2(3),1293 6(3),1481
Fieser
17,183
TABLE 5.
cont'd
Benzyl ester Bisphenol A diester Bisphenol A tetraethoxylate diester 2-Bromoethyl ester 1,3-Butylene diester 1,4-Butylene diester 2-Butoxyethyl ester «-Butyl ester s-Butyl ester tert-Butyl ester 7V-te/?-Butyl-2-aminoethyl ester 2-Chloro-2-hydroxypropyl ester 2-Chloroethyl ester Chloromethyl ester Cinnamyl ester Chloride 2-Cyanoethyl ester 1,4-Cyclohexanediol diester Cyclohexyl ester Decanediol diester Decyl ester 2,3-Dibromopropyl ester 2-(Dibutylamino)ethyl ester Dicyclopentenyl ester Dicyclopentenyloxyethyl ester 2-(Diethylamino) ethyl ester 3-(Dimethylamino) propyl ester Di(ethylene glycol) diester 3,4-Dihydroxybutyl ester 2,3-Dihydroxypropyl ester 2-(Dimethylamino) ethyl ester Diurethane diester (isomers) IH, 1H,7H-Dodecafluoroheptyl ester Dodecanediol diester Dodecyl ester 2,3-Epithiopropyl ester 2,3-Epoxybutyl ester 3,4-Epoxybutyl ester 2,3-Epoxyopropyl ester 4-Ethoxybutyl ester 2-Ethoxyethyl ester Ethyl ester Ethyl 2-bromomethyl- ester 2-Ethylbutyl ester 1,2-Ethylene diester 2-Ethylhexyl ester 2-(Ethylthio)ethyl ester Ethyl 2-(trimethoxysilylmethyl-) ester Furfuryl ester Glycerol diester Glycerol triester Glycidyl ester 1H,1H,2H,2H-Heptadecafluorodecyl ester 1H, 1 H-Heptafluorobutyl ester Heptyl ester 1,6-Hexanediol diester 2,2,3,4,4,4-Hexafluorobutyl ester lH-Hexafluoroisopropyl ester Hexyl ester
Boiling point ( 0 C)
CAS Registry Number
MoI. wt.
-CH2C6H5 —C 6 H 4 C(CH 3 ) 2 C 6 H 4 — ((-CH 2 CH 2 O) 2 C 6 H 4 )SC(CHs) 2
2495-37-6 3253-39-2 41637-38-1
176.22 364.44 452.55
-CH 2 CH 2 Br -CH 2 CH 2 CH(CH 3 )-(CHz)4-CH 2 CH 2 O(CH 2 ) 3 CH 3 -(CH 2 ) 3 CH 3 -CH(CH 3 )CH 2 CH 3 -C(CH 3 ) 3 -CH 2 CH 2 NHC(CH 3 ) 3 -CH 2 C(OH)ClCH 3 -CH 2 CH 2 Cl -CH 2 Cl -CH 2 CH=CHC 6 H 5 CH 2 =C(CH 3 )C(O)Cl -CH 2 CH 2 CN -C6HiO-
4513-56-8 1189-08-8 2082-81-7 13532-94-0 97-88-1 2998-18-7 585-07-9 3775-90-4 13159-52-9 1888-94-4 27550-73-8 31736-34-2 920-46-7 4513-53-5 38479-34-4 101-43-9 6701-13-9 3179-47-3 3066-70-4 2397-75-3 31621-69-9 68586-19-6 105-16-8 17577-32-1 2358-84-1 62180-57-8 5919.74.4 2867-47-2 72869-86-4 2261-99-6
193.05 226.28 226.28 186.25 142.20 142.20 142.20 185.27 178.62 148.60 146.57 202.25 104.54 139.16 252.31 168.24 310.44 226.36 285.96 241.38 218.30 262.35 185.28 199.30 242.27 174.20 160.17 157.22 470.57 400.17
69/4 170/2 327 72/0.03 100/1 137/13 150/10 80/10 105/1.5 134/2 110/0.25 140/0.6 187 200 107/23
-CH2CH2-CH 2 CH(CH 2 CH 3 )(CH 2 ) 3 CH 3 -CH 2 CH 2 SCH 2 CH 3 CH 2 =C(CH 2 Si(OCH 3 ) 3 )C(O)OCH 2 CH 3
72829-09-5 142-90-5 3139-91-1 68212-07-7 55750-22-6 106-91-2 76392-24-0 2370-63-0 97-63-2 17435-72-2 5138-86-3 97-90-5 688-84-6 14216-25-2 74976-84-4
338.49 252.42 158.22 156.18 156.18 142.16 186.25 158.20 114.15 193.05 170.25 198.22 198.31 174.26 186.33
142/4 59/1.4 45/0.25 55/0.8 189 85/23 92/35 118 38/0.8 74/16 240 218 102/15 71/10
-CH2C4H3O -CH 2 CH(OH)CH 2 -CH(CH2-), -CH(-O-)CH2 -(CH 2 ) 2 (CF 2 ) 7 CF 3
3454-28-2 1830-78-0 52408-84-1 106-91-2 1996-88-9
166.18 228.25 296.3 142.16 532.20
81/5 120/1 150/0.1 189 120/4
-CH 2 (CF 2 ) 2 CF 3 -(CH 2 ) 6 CH 3 -(CH2)6-CH 2 CF 2 CHFCF 3 -CH(CF 3 ), -(CH 2 ) 5 CH 3
13695-31-3 5459-37-0 6606-59-3 36405-47-7 3063-94-3 142-09-6
268.13 184.28 254.33 250.14 236.11 170.25
R
Name
-C 6 Hn -(CH 2 )IO-(CH 2 ) 9 CH 3 -CH 2 CHBrCH 2 Br -(CH 2 ) 2 N(CH 2 CH 2 CH 2 CH 3 ) 2 -C10H13 -C12HnO -(CH 2 ) 2 N(CH 2 CH 3 ) 2 -(CH 2 ) 3 N(CH 3 ) 2 -CH2CH2OCH2CH2-CH2CH2CH(OH)CH2OH
-CH 2 CH(OH)CH 2 OH -CH 2 CH 2 N(CH 3 ) 2 C23H38N2O8 -CH 2 (CF 2 ) 5 CF 2 H -(CHz)12-(CH 2 )IiCH 3 -CH2CH(-S-)CH2 -CH 2 CH(-O-)CHCH 3 -CH 2 CH 2 CH(-O-)CH 2 -CH2CH(-O-)CH2 -(CH 2 ) 4 OCH 2 CH 3 -CH 2 CH 2 OCH 2 CH 3 -CH 2 CH 3 CH 2 =C(CH 2 Br)C(O)OCH 2 CH 3 -CH2CH(CH2CH3)CH2CH3
Melting point (0C)
232 73 ca. 540 47/2.7 290 133/4 90/3 161 146 132 100/12 95/2 59/7.5 54/20 141/3 95 99/2 50
134 104/14 >315 158 99 88/14
-44
<-60
-30
0.95 -7
<-75 -40
<-18
Density 0
Refractive index (at 20°C)
Flash point (0C)
RTECS Number
R and S
FT-NMR
FT-IR
Merck
Beilstein
(at 20 C) 1.5120
107
1.5320
> 110
1.4520 1.4565 1.4335 1.4230 1.4195 1.4150 1.4420 1.4750
130 113 93 50
1.040
1(2),1931F
1(2),1296C
1(2),316B
1(1),729D
1(1),999A
1(1),639D
1(1),721A
1(1),975C
1(1),641A
1.120 1.010 1.023 0.939 0.894 0.875 0.914 1.190
OZ3675000
50 71 150
OZ3675500 OZ3500000
3
OZ5791000
2(4),1534 2(3),1292 2(3),1286 2(4),1582 4(4),1509 2(4),1533
1.4434 1.070
1.4420 1.4459
0.9626 0.875
1.459 1.4577 1.443
101
1.050 1.064 0.922
1.4474 1.4990 1.4970 1.4442
>110 > 110 85
1.082
1.4580
66
0.933 1.110
1.4400 1.485
70 >150
OZ4200000
1.46 0.868
1.4450
>110
OZ4300000
1(1),732C
82 82
2(3), 1293
6(3),25
6(3), 1942 4(3),676 2(3),1292
1(1),771H
l(l),1074A
1(1),675C 4(3),649
1(1),721D
1(1),976C
1(3),678B 2(3), 1290
0.964 0.917 1.398
1.4422 1.4472 1.4490 1.4223 1.4290 1.4130 1.4790
1.051 0.885
1.4540 1.4380
86 92
0.897
1.4380
59
1.078 1.120
1.4820 1.4720
90 > 115
1.042
1.4490
76
1.345
1.3410
37
0.995 1.348 1.302 0.885
1.4580 1.3610 1.3310 1.432
150 57 14 63
1.038 1.042
1(1),857B
76
OZ4375000
1(1),781F
l(l),1089A
1(1),668D
71 15 87
OZ4550000
1(1),759C 1(1),719J
l(l),1052C 1(1),975B
1(3),723C l(l),640D
OZ4400000 OZ4630000
1(1),729B 1(1),721C
1(1),998B 1(1),976B
2(3),1291 2,423
2(3), 1292 2(3),1289 1(1),642D
1(2),2985A
1(3),686B
1(1),781F
l(l),1089A
17(3), 1248
OZ4375000
1(1),668D 1(1),745F 1(1),745E
l(l),1030B l(l),1030A
Fieser
TABLE 5.
cont'd
R
Name
-(CH 2 ) 4 OH 4-Hydroxybutyl ester 2-Hydroxyethyl ester -CH 2 CH 2 OH 3-(5-Hydroxypentyloxy)-CH 2 CH 2 C(O)O(CH 2 ) 5 OH 3-oxopropyl ester 3-Hydroxypropyl ester -(CH 2 ) 3 OH Isobornyl ester -CioHg Isobutyl ester -CH 2 CH(CHs) 2 2-Isocyanatoethyl ester -CH 2 CH 2 NCO Isodecyl ester -(CH 2 ) 7 CH(CH 3 ) 2 Isopropyl ester -CH(CHs) 2 Methallyl ester -CH 2 C(CH 3 )=CH 2 2-(2-Methoxyethoxy) ethyl ester -(CH 2 CH 2 O) 2 CH 3 2-Methoxyethyl ester -CH 2 CH 2 OCH 3 Methyl ester -CH3 2-Methyl-2-nitropropyl ester -CH 2 C(CH 3 )(NO 2 )CH 3 2-(Methylthio) ethyl ester -CH 2 CH 2 SCH 3 Methyl 2-bromomethyl ester CH 2 =C(CH 2 Br)C(O)OCH 3 Methyl 2-(l-hydroxyethyl-)ester CH 2 =C(CH(OH)CH 3 )C(O)OCH 3 2-Af-Morpholinoethyl ester -CH 2 CH 2 NC 4 H 8 O Neopentylglycol diester -CH2C(CH3)2CH2Nona(ethylene glycol) diester -(CH 2 CH 2 O) 8 CH 2 CH 2 Nona(propylene glycol) diester - ( C H ( C H 3 ) C H 2 O ) 8 C H ( C H 3 ) C H 2 Nonyl ester -(CH 2 ) 8 CH 3 4-Nonylphenyl ester -C 6 H 4 (CH 2 ) 8 CH 3 Octadecyl ester -(CH 2 ) 17 CH 3 «-Octyl ester -(CH 2 ) 7 CH 3 Pentabromophenyl ester -C6Br5 Pentachlorophenyl ester -C6Cl5 1H, 1 H-Pentafluorooctyl ester -CH 2 (CF 2 ) 6 CF 3 Pentaerythritol tetraester C(CH2-), 2,2,3,3,3-Pentafloropropyl ester -CH 2 CF 2 CF 3 Pentyl ester -(CH 2 ) 4 CH 3 2-Phenoxyethyl ester -CH 2 CH 2 OC 6 H 5 Phenyl ester -C6H5 2-Phenylethyl ester -CH 2 CH 2 C 6 H 5 rc-Propyl ester -CH 2 CH 2 CH 3 1,2-Propylene diester -CH 2 CH(CH 3 )1,3-Propylene diester -(CH2),2-Sulfoethyl ester -CH 2 CH 2 SO 3 H 3-Sulfopropyl ester, potassium -(CH 2 ) 3 SO 3 K salt Tetra(ethylene glycol) diester -CH 2 CH 2 (OCH 2 CH 2 ) 3 2,2,3,3-Tetrafluoropropyl ester -CH 2 CF 2 CF 2 H Trimethylsilyl ester -Si(CH 3 ), 2-(Trimethylsilyloxy)ethyl ester -CH 2 CH 2 OSi(CHs) 3 3-(Trimethylsilyloxy)propyl ester -(CH 2 ) 3 OSi(CH 3 ) 3 3-(Tris(trimethylsiryloxy)silyl) -(CH 2 ) 3 Si(OSi(CH 3 ) 3 ) 3 propyl ester Vinyl ester -CH=CH 2
TABLE 6.
MoI. wt.
997-46-6 868-77-9 85099-10-1
158.20 130.14 244.29
105/0.01 250
276-09-3 7534-94-3 97-86-9 30674-80-7 29964-84-9 4655-34-9 816-74-0 45103-58-0 6976-93-8 80-62-6 2177-42-6 14216-23-0 4224-69-5 18020-65-0 2997-88-8 1985-51-9 25852-47-5 25852-49-7 2696-43-7 76391-98-5 32360-05-7 2157-01-9 18967-31-2 16184-61-5 3934-23-4 3253-41-6 45115-53-5 2849-98-1 10595-06-9 2177-70-0 3683-12-3 2210-28-8 1188-09-6
90/9 245 155 211 126/10 125 157 67/1 66/16 100 102/4 38/0.06 36/1.3 91/20 80/0.08 112/1.2
10595-80-9 31098-21-2
144.17 222.33 142.20 155.17 226.36 128.17 140.18 188.22 144.17 100.12 187.20 160.24 179.02 130.14 199.25 240.30 550 560 212.33 288.43 338.58 198.31 556.69 334.41 468.16 408.45 218.12 156.23 206.24 162.19 190.24 128.17 212.25 212.25 194.21 246.33
109-17-1 45102-52-1 13688-56-7 17407-09-9 2530-85-0 17096-07-0
300.37 200.14 158.28 202.33 248.35 422.82
220 124 51/20 65/0.9 190 113/0.2
4245-37-8
112.13
111
Melting point ( 0 C)
-12 -48
-51 -45 -41
-48
>200/l 125/0.03 195/6 105/4
19 132 87
67/5 55/110 73/17 183 115/10 119/11 140 68/1 68/1 (d)
66
295(d)
ALCOHOLS Formula HOROH R
Name 6.1.
Boiling point ( 0 C)
CAS Registry Number
CAS Registry Number
MoI. wt.
Boiling point ( 0 C)
Melting point (0C)
ALKANEDIOLS
1,2-Butane 1,3-Butane 1,4-Butane 1,10-Decane 1,12-Dodecane 1,2-Ethylene
-CH(C2H5)CH2-CH(CH 3 )CH 2 CH 2 -(CH2),-(CHa)10-(CH2)I2-(CH2)2-
584-03-2 107-88-0 110-63-4 112-47-0 5675-51-4 107-21-1
90.12 90.12 90.12 174.28 202.34 62.07
191/747 203 230 170/8 189/12 197
16 73 82 -13
Density (at 200C)
Refractive index (at 200C)
Flash point (0C)
1.073 1.080
1.4520 1.4360
97 >110
1.066 0.9830 0.886 1.096 0.878 0.8847
1.4470 1.4770 1.420
96 107 41 97 >110
1.020 0.993 0.936 1.087 1.040 1.489 1.071
1.4397 1.4310 1.4140 1.450 1.4800 1.4900 1.4520
> 110 65 10 > 110 88 78 43
1.003 1.099 1.010 1.099
1.4530 1.4660 1.4520 1.4660 1.5020 1.4510 1.4373
117 >110 >110 > 110 > 110 196
0.864
1.4430 1.4122
1.5732
1.3482
1.0687
1.5130 1.5184 1.508 1.4450 1.4450
0.98 0.9022
1.3245
1(1),753M
l(l),1045A
OZ4900000
1(1),721B
1(1),976A
FT-IR
Merck
Beilstein
Fieser
1(1),665B
2(3),1287 1(3),677C
OZ5000000
OZ5075000
1(1),719I
11,5849
1(1),975A 1(1),64OC
AS4900000
1(1),745J
2(2),398 2(3),1288
l(l),1031C
2(4),1535
2(3),1290
122
1.4772
82 50 32 76 92 > 110
0.933
1.4360
13
1.113
OZ4725000
FT-NMR
100
1.4630 1.3730 1.4147 1.4280 1.4310 1.4190
1.006 1.005 1.017
Rand S
96 >100 6
1.080 1.250 0.890 0.928 1.045 0.918
Density (at 2O0C)
RTECS Number
Refractive index (at 200C)
1.4380 1.4400 1.4450
1.4310
Flash point (0C)
93 121 >110
>110
l(l),1065F
1(1),1438B
1(1),745B 1(2),2985B 1(2),2985C 1(2),2985D
l(l),1029A 1(3),686C 1(3),687A 1(3),687B
l(l),890D 2(4),1531
OZ4000000
UC0230000
1(2),1116C
2(3),1290
RTECS Number
EK0380000 EK0440000 EK0525000 HD8433713 KW2975000
R and S
1(1),141A 1(1),139L 1(1),139K 1(1),143N 1(1),145A 1(1),139A
FT-NMR
1(1),196C 1(1),195C 1(1),195B l(l),205C l(l),206B
FT-IR
1(1), 130B 1(1), 130D l(l),130A 1(1),136D 1(1),137A 1(1),127D
Merck
11,1566 11,2842 11,3755
Beilstein
1,477 1,477 1,478 l(2),560 1(2),562 1,465
Fieser
15,156
TABLE 6.
cont'd Formula HOROH R
Name 1,7-Heptane 1,16-Hexadiene 1,6-Hexane 1,7-Heptane 1,16-Hexadiene 1,9-Nonane 1,8-Octane 1,5-Pentane 1,2-Propane 1,3-Propane 1,14-Tetradecane 6.2.
ETHERDIOLS
Di(ethylene glycol) Di(propylene glycol) Hexa(ethylene glycol) Penta(ethylene glycol) Tetra(ethylene glycol) Tri(ethylene glycol) Tri(propylene glycol)
TABLE 7.
CAS Registry Number
MoL wt.
Boiling point ( 0 C)
Melting point (0C)
-(CHa)7-(CH2)I6-(CH2)6-(CHa)7-(CH 2 ) 1 6 -(CH2)9-(CH2)S-(CH2)S-CH(CH 3 )CH 2 -(CH2)S-(CH 2 ) 1 4 -CH2CH 2 OCH2CH2-
629-30-1 23079-20-1 629-11-8 629-30-1 23079-20-1 3937-56-2 629-41-4 111-29-5 57-55-6 504-63-2 19812-64-7
132.20 258.45 118.18 132.20 258.45 160.26 146.23 104.15 76.10 76.10 230.39
259 198/3 250 259 198/3 177/15 172/20 242 187 214
-CH(CH3)CH2OCH(CH3)CH2-
111-46-6 110-98-5 2615-15-8 4792-15-8 112-60-7 112-27-6 24800-44-0
106.12 134.18 282.34 238.28 194.23 150.17 192.26
245
-10
217/4 184/2 314 285 273
6
MoL wt.
Boiling point ( 0 C)
-CH 2 CH 2 (OCH 2 CH 2 )S-CH 2 CH 2 (OCH 2 CH 2 ) 4 -CH 2 CH 2 (OCH 2 CH 2 ) 3 -CH 2 CH 2 (OCH 2 CH 2 ) 2 -CH(CH 3 )CH 2 (OCH(CH 3 )CH 2 ) 2 -
18 92 42 18 92 48 60 -60 -27 88
-6 -7
ALLYL FUNCTIONAL Formula CH 2 =CHCH 2 R
Name Acetate -Acetic acid Acetoacetate Alcohol - , 2-Bromo- , 2-Chloro- , 3-Methyl(crotyl alcohol;) -Amine -AT-Aniline -4-Anisole -Benzene Benzyl ether Bromide Butyl ether Butyrate Chloride Chloroacetate Chloroformate Cyanide Cyanoacetate Diallyl amine 2,3-Dibromide 2,3-Dichloride Ether Ethyl ether Fluoride Formate Glycidyl ether Iodide Isocyanate Isopropyl ether 4-(2-Methoxyphenol) Methyl ether -2-Phenol
R -OC(O)CH 3 -CH 2 C(O)OH -OC(O)CH 2 C(O)CH 3 -OH H 2 C=CBrCH 2 OH H 2 C=CClCH 2 OH CH 3 CH=CHCH 2 OH -NH2 -NC6H5 -C 6 H 4 OCH 3 -C6H5 -OCH 2 C 6 H 5 -Br -O(CH 2 ) 3 CH 3 -OC(O)CH 2 CH 2 CH 3 -Cl -OC(O)CH 2 Cl -OC(O)Cl -CN -OC(O)CH 2 CN -NHH 2 =CBrCH 2 Br H 2 C=CClCH 2 Cl -O-OCH 2 CH 3 -F -OC(O)H -O-CH2CH(-O-)CH2 -I -NCO -OCH(CH 3 ) 2 -C 6 H 4 (OCH 3 )OH -OCH3 -C6H4OH
CAS Registry Number 591-87-7 591-80-0 1118-84-9 107-18-6 5976-47-6 6117-91-5 107-11-9 589-09-3 140-67-0 300-57-2 14593-43-2 106-95-6 3739-64-8 2051-78-7 107-05-1 2916-14-5 2937-50-0 109-75-1 13361-32-5 124-02-7 513-31-5 557-40-4 557-31-3 818-92-8 106-92-3 556-569 1476-23-9 97-53-0 627-40-7 1745-81-9
100.12 100.12 142.16 58.08 136.98 92.53 72.12 57.10 133.19 148.21 118.18 148.21 120.98 114.19 128.17 76.09 134.56 120.54 67.09 125.13 97.16 199.88 110.97 98.15 86.13 60.07 86.09 114.14 167.98 83.09 100.16 164.20 72.11 134.18
104 84/12 194/737 97 152 134 122 53 219 215 156 204 70 44/15 45 164/265 109 118 110/20 112 141 94 95 66 -10 84 154 103 88 84 154 46 220
Melting point (0C)
-22 -129
-88
-119
-134
-88
-11
Density (at 20 0 C)
Refractive index (at 20°C)
Flash point (0C)
RTECS Number
0.951
1.4550
>110
MI9804000
0.951
1.4550
102 > 110
MO2100000 MI9804000
1.4500 1.4320 1.4400
129 107 79
1.118 1.023 1.127 1.126 1.125 1.125 1.021
1.4460 1.4410 1.4640 1.4620 1.4590 1.4550 1.4440
143 138 >110 >110 177 166 >110
Density (at 20 0 C)
Refractive index (at 200 C)
0.928 0.981 1.037 0.854 1.6 1.162 0.845 0.761 0.982 0.965 0.892 0.959 1.398 0.783 0.902 0.939 1.159 1.136 0.834 1.065 0.787 1.934 1.211 0.803 0.760
1.4040 1.4283 1.4390 1.4120 1.5 1.4590 1.4270 1.4205 1.5630 1.5210 1.5100 1.5070 1.4690 1.4060 1.4140 1.4135 1.4460 1.4220 1.4050 1.4430 1.4405 1.5470 1.4603 1.4160 1.3880
0.9460 0.962 1.837 0.940 0.7764 1.066 0.978 1.028
1.4330 1.5540 1.4170 1.3946 1.5410 1.5200 1.5450
Flash point (0C)
FT-NMR l(l),204B
1(1),143J 1(1),145E 1(1),143D 1(1),143J 1(1),145E 1(1),143M 1(1),143K 1(1),141I 1(1),139C 1(1),139B 1(1),145C
l(l),205B l(l),204C 1(1),199A 1(1),192C 1(1),192B l(l),207A
ID5950000 UB8785000 MM3670000 RZ2670000 XC2100000 YE4550000 YK6825000
1(1),225D 1(1),225E 1(1),229B 1(1),227K 1(1),227H 1(1),227D 1(1),227F
1(1),341B 1(1),341C 1(1),347A 1(1),346B 1(1),346A 1(1),345A 1(1),345B
RTECS Number
Rand S
>110 0.994 1.036 1.053
R and S
SA0480000 TY2000000 TY2010000
7 89 75 22
AFl760000 SB2800000
54 37 -29 89 81 33 76 -2 14 41 -29 61 31 23 >110 16 81
UD4725000 EM9275000 BA5425000
l(l),202B l(l),204B
FT-NMR
FT-IR 1(1),135C 1(1),137D 1(1),134B 1(1),135C 1(1),137D 1(1),136B 1(1),135D 1(1),132B 1(1),128B 1(1),128A
1(1),223B 1(1),226A 1(1),227A 1(1),226D 1(1),226C 1(1),226B
Merck
Beilstein 1,489
11,4610
11,7073 11,7868 11,9629 1(2),564
11,3109
1,484 1,489 1,489 1,493 1,490 1,481 1,472 1,475
1,468 1(2),537 1,468 1,468 1,468 1,468
11,9585
FT-IR
Merck
Beilstein
1(1),715C 1(1),547H 1(1),787A 1(1),147A
1(1),963C 1(1),778A 1(1),687C l(l),207B
1(1),633B 1(1),499B l(l),1098A 1(1),138B
1(1),183D 1(1),147C 1(1),347A 1(1),1383K 1(1),1243C 1(1),1139E
l(l),208A 1(1),518C 1(2),454B l(2),208B 1(2),24B
1(1),138C 1(1),322B 1(1),1191A l(l),1053B 1(1),946B
1(1),135A 1(1),333B l(l),970B 1(1),133C
1(1),93D
ES5775000 UC7350000
1(1),95I 1(1),219G 1(1),717N 1(1),95E
LQ5775000 EM8050000 AG3690000 UC6650000 UC8200000
1(1),863B 1(1),991F l(l),1013F 1(1),347K l(l),101K
l(l),1206B 1(1),1358C 1(1),1391B l(l),520A
1(1),737A 1(1),843A 1(1),322C 1(1),99C
11,2951 11,3009
4,208 1,201
-7 -21
KN7525000
1(1),219H 1(1),219E
1(1),333C 1(1),332C
1(1),212D 1(1),212C
11,290 11,291
1,438 1,438
57 18 43
RR0875000 VD0450000 NQ8175000
1(1),251C 1(1),95J l(l),1023E
1(1),374A
11,292
1,202
l(l),1404A
1(1),233D 1(1),94A 1(1),872A
SJ4375000
1(1),1283E
1(2),278A
l(l),1091A
11,3855
SJ3850000
1(1),1265H
1(2),245B
l(l),1070D
>110 63 88
BA5075000
BZ8225000 CY2275000 UC7090000
Fieser
1(1),637B 1(1),93C
1(1),687C 11,284
11,2604 11,285 11,3657
11,286
11,287
11,288
Fieser
2,136 2,425 19(3), 1203 1,436 1,439 1,442 4,205 12,170 6,751 5,484 6(3),1459 1,201 1(3),1882 2,272 1,198 2,198 3,12 2,408
4,214 6,961 6,572
13,2
TABLE 7.
cont'd Formula CH 2 =CHCH 2 R
Name
R
Phenyl ether 4-Chloro2,4,6-TribromoPhenyl sulfone Propyl -Succinic anhydride Sulfide 2-Tolyl ether 3-Tolyl ether 4-Tolyl ether -Urea
TABLE 8.
-OC6H5 -OC 6 H 4 Cl -OC 6 H 2 Br 3 -S(O)(O)C 6 H 5 -CH 2 CH 2 CH 3 -C4H3O3 -S-OC 6 H 4 CH 3 -OC 6 H 4 CH 3 -OC 6 H 4 CH 3 -NHC(O)NH 2
Name
R
Butane DecaneDodecaneEthyleneHeptaneHexaneNonaneOctanePentane1,2-Phenylene1,3-Phenylene1,4-PhenylenePropane-
3278-89-5 16212-05-8 1471-03-0 7539-12-0 592-88-1
557-11-9
134.18 168.63 370.88 182.24 100.16 140.1 114.21 148.21 148.21 148.21 100.12
Boiling point (0C)
Melting point (0C)
192 107/12 75 111/0.5 91 260 138 81/2 213 91/10
6
85
CAS Registry Number
MoL wt.
110-60-1 646-25-3 2783-17-7 107-15-3 646-19-5 124-09-4 646-24-2 373-44-4 462-94-2 95-54-5 108-45-2 106-50-3 109-76-2
88.15 172.32 200.37 60.10 130.24 116.21 158.29 144.26 102.18 108.14 108.14 108.14 74.13
CAS Registry Number
MoL wt.
C6H6O5 C6H6O4S C6H4O5
79814-40-7 6953-60-2 6318-55-4
158.11 174.18 156.10
C7H8O3 C 1 2 H 7 NO 3 C9H4O5
7539-12-0 6492-86-0 552-30-7
140.1 213.20 192.13
C10H10O3
24327-08-0
178.19
C 4 HBrO 3 C 1 2 H 5 BrO 3 C 11 H 20 O 4 Si
5926-51-2 21563-29-1 91424-40-7
176.96 277.08 244.37
C12H12O3 C 1 2 H 1 1 NO 5 C10H12O4 C 8 H 4 ClNO 3 C 1 2 H 5 ClO 3 C5H4O3 C8H10O3
32703-79-0 4515-23-5 56-25-7 4743-17-3 4053-08-1 616-02-4 13149-00-3
204.23 249.23 196.20 197.58 232.63 112.08 154.17
-(CHz)4-(CHz)10-(CHz)12-(CHz)2-(CHz)7-(CHz)6-(CHz)9-(CHz)8-(CH2)S-C6H4-C6H4-C6H4-(CHz)3-
Boiling Point(°C) 159 140/12 118 224 204 258/756 225 179 257 283 267 140
Melting Point(°C) 27 62 70 8.5 28 43 37 51 104 65 144 -12
ANHYDRIDES
Name 9.1.
1746-13-0
MoL wt.
AMINES, DIFUNCTIONAL Formula H 2 NRNH 2
TABLE 9.
CAS Registry Number
Formula
Boiling point ( 0 C)
Melting point ( 0 C)
MONOANHYDRIDES
Acetoxysuccinic 5-Acetylmercaptosuccinic Aconitic, cisAcrylic (see Acrylates) Allylsuccinic 4-Amino-1,8-naphthalic 1,2,4-Benzenetricarboxylic (trimellitic) Bicyclo[2.2.2.]oct-5-ene2,3-dicarboxylic, endoBromomaleic 4-Bromo, 1,8-naphthalic 3-(tert-Butyldimethylsilyloxy)glutaric 4-tert-Butylphthalic N-Carboxybenzyloxy-L-aspartic Cantharidin 5-Chloroisotoic 4-Chloro-1,8-naphthalic Citraconic Cyclohexane-1,2-dicarboxylic, cis-
56 83 75 260
6 167 145
215 218 80
213 158/17
73 123 216 300(d) 208 7 33
Density (at 20 0 C)
Refractive index (at 20 0 C)
Flash point (0C)
RTECS Number
R and S
FT-NMR
0.978
1.5200 1.5348
63
DA8575000
1(1),1241M
l(2),207A
1.189 0.767
1.5480 1.3990
>110 _5
WR2400000
1(2),2185B 1(1),219F
1(2), 1580A 1(1),333A
0.887 0.950 0.9564 0.970
1.4889 1.5179 1.5179 1.5168
46
BC4900000
Refractive Index*At 200 C)
0.877
1.4569
0.899
1.4565
0.873
1.4582
Flash Point(°C) 52 155 34 88 81 >110 165 63 >110
0.888
Density (at 200C)
1.4565
Refractive index (at 20 0 C)
34
Flash point (0C)
RTECS Number EJ6800000 HD7175000 JR2200000 KH8575000
1(1),287J
1(1),432C
1(1),939M
l(l),1308B
Rand S
RG8841500 SA0200000 SS7875000 SS7700000 SS8050000 TX6825000
RTECS Number
R and S
FT-NMR 1(1),465A 1(1),469B 1(1),469C 1(1),463B 1(1),468A 1(1),467A 1(1),469A 1(1),468B 1(2),536B 1(2),539A 1(2),542C 1(1),464A
FT-NMR
Merck
Beilstein
6,144
11,14
11,295 1,440 11,296 4,209
FT-IR 1(1),291D 1(1),293D 1(1),294A 1(1),289C 1(1),293A 1(1),292C 1(1),293C 1(1),293B 1(1,292B 1(1),1235C 1(1),1239A 1(1),1242B l(l),290A
FT-IR
Merck 11,7964
11,3752 11,4614
11,1608 11,7255 11,7254 11,7256
Merck
Beilstein 4,264 4,273 4,273 4,230 4,271 4,269 4,272 4,271 4,266 13,6 3,33 13,61 4,261
Beilstein
18(2), 1128 1(1),837E 1(1),837D
1(1),1179B
1QV715C 18,463
1.163 DC2050000
1(2),336A
1(2),1961B 1(2),1959G
1(2),1329C
1(1),835N
1(1),1178B
1(1),839A 1(2),1961A 1(2),2987F
1(1),1182B 1(2), 133OB 1(3),692A
11,9617
18(2),469 18,468
1,(2),334A 1(1),717D 1.905
>110
1(1),719C
RN8575000
1.247
1.4710
101 >110
QL6127295 GE6825000
1(2),1957H 1(2),1959N 1(1),837J 1(1),835G
1(1),1181A 1(1),1175C
Fieser
6,205 6,299 1,438
l(3),2780
l(l),800D
l(l),309G 1(1)3111 1(1),31U l(l),309A 1(1),3HE 1(1),311B 1(1),3HH 1(1),3HF l(l,309K 1(1),1429A 1(1),1431C 1(1),1433D l(l),309D
MOl 180000
l(l),1052B
1(1),269C
YR7875000
Density (at 20 0 C)
FT-IR
1(2),332C 1(2),335D 1(1),718D 1(1),715D
17,435 17,523
19,161 27,265 17,522 17,440
Fieser
4,231
8,393
Fieser
TABLE 9.
cont'd
Name Cyclohexane-1,2-dicarboxylic, transDiacetyl-L-tartaric 3,5-Diacetyltetrahydropyran2,4,6-trione Dichloromaleic 3,6-Dichlorophthalic 4,5-Dichlorophthalic 3,6-Difluorophthalic Diglycolic 2,2-Dimethylglutaric 3,3-Dimethylglutaric 2,3-Dimethylmaleic 2,2-Dimethylsuccinic Diphenic 2,3-Diphenylmaleic 2-Dodecen-1 -ylsuccinic 3,6-Epoxy-l,2,3,6-tetrahydrophthalic, exo3-Ethyl-3-methylglutaric 3-Fluorophthalic 4-Fluorophthalic 2-Foraiamidosuccinic Glutaric l,4,5,6,7,7-Hexachloro-5norbornene2,3-dicarboxylic Hexafluoroglutaric Hexahydro-4-methylphthalic Homophthalic 3 -Hy droxy phthalic Isatoic Isobutenylsuccinic Itaconic Maleic 3-Methylglutaric Af-Methylisatoic Methyl-5-norbornene2,3-dicarboxylic 4-Methylphthalic Methylsuccinic 1,8-Naphthalic 3-Nitro-1,8-naphthalic 4-Nitro-1,8-naphthalic 3-Nitrophthalic 4-Nitrophthalic 5 -Norbornene- endo2,3-dicarboxylic,
Boiling point ( 0 C)
Melting point ( 0 C)
CAS Registry Number
MoI. wt.
C8H10O3
14166-21-3
154.17
146
C8H8O7 C9H8O6
6283-74-5 33524-89-9
216.15 212.16
131 154
C 4 Cl 2 O 3 C 8 H 2 Cl 2 O 3 C 8 H 2 Cl 2 O 3 C8H2F2O3 C4H4O4 C7H10O3 C6H6O3 C6H8O3 Ci 4 H 8 O 3 C 1 6 Hi 0 O 3 C16H26O3 C8H6O4
1122-17-4 4466-59-5 942-06-3 652-40-4 4480-83-5 2938-48-9 4160-82-1 766-39-2 17347-61-4 6050-13-1 4808-48-4 19780-11-1 6118-51-0
166.95 217.01 217.01 184.10 116.07 142.16 142.16 126.11 128.13 224.22 250.26 266.38 166.13
188 186 219 92 36 124 94 30 225 160 42 118(d)
C8H12O3 C 8 H 3 FO 3 C 8 H 3 FO 3 C 5 H 5 NO 4 C5H6C3 C 9 H 2 Cl 6 O 3
6970-57-6 652-39-1 319-03-9 33605-73-1 108-55-4 115-27-5
156.18 166.11 116.11 143.10 114.10 370.83
185/20
C5F6O3 C9H12O3 C9H6O3 C8H4O4 C 8 H 5 NO 3 C8H10O3 C5H4O3 C4H2O3 C6H8O3 C 9 H 7 NO 3 C10H10O3
376-68-1 19438-60-9 703-59-3 37418-88-5 118-48-9 18908-20-8 2170-03-8 108-31-6 4166-53-4 10328-92-4 25134-21-8
222.04 168.19 162.14 164.12 163.13 157.17 112.09 98.06 128.13 117.16 178.19
72
C9H6O3 C5H6O3 Ci 2 H 6 O 3 Ci 2 H 5 NO 5 C 1 2 H 5 NO 5 C 8 H 3 NO 5 C 8 H 3 NO 5 C9H8O3
19438-61-0 4100-80-5 81-84-5 3027-38-1 34087-02-0 641-70-3 5466-84-2 129-64-6
162.14 114.10 198.18 243.17 343.17 193.11 193.11 164.16
295 239
C22H38O3 C12H18O3 C5H4O3
26680-54-6 5617-74-3
350.55 210.27 112.08
251/4 168/10 100/5
C 3 H 3 NO 3 C11H10O3 C10H6O3 C18H10O3
2185-00-4 2959-96-8 36122-35-7 1985-37-1
101.06 190.20 176.16 247.28
C10H8O3 C8H4O3 C 1 3 H 9 NO 5 C7H10O4 C6H2N2O3
1131-15-3 85-44-9 3343-28-0 130221-78-2 4744-5O-7
176.17 148.12 259.22 158.16 150.09
Formula
CVHK)O3
240 175/60 181/25 223 219
180/5
159 79 145 56 237
146/14 114/12 202 181/25
141 200 233(d) 64 71 52 45
91 34 268 248(d) 228 164 118 166
CJS-
Octadecylsuccinic 2-Octen-1 -ylsuccinic 3-Oxabicyclo[3.1.0] hexane2,4-dione 2,5-Oxazolidenedione 2-Phenylglutaric Phenylmaleic 1 -Phenyl-2,3-naphthalenedicarboxylic Phenylsuccinic Phthalic N-Phthaloylglutamic 1 -Propenyloxymethylmaleic Pyrazinedicarboxylic
218/13
191/12 284
62 10 60 120(d) 97 121 259 54 132 199
251 210(d)
Density (at 20 0 C)
Refractive index (at 2O0C)
Flash point (0C)
RTECS Number
ON4025000 1.135
108
177
Rand S
1.654 1.162
1.3240 1.4770
MA3850000 RB9080000
None >110 TI3300000 DM3100000
103 >110
ON3675000 DM3140000
1.232
1.5060
1.220
>110
>110
RB9100000
QK5350000 QK5370000
TI3328000 DT5600000
1.055 1.000
FT-IR
Merck
1(1),1176A
1(1),716A
17,452
1(1),837F 1(1),839L
1(1),1179C 1(1),1174A
1(1),457D
18,162 17(4),6841
1(1),839B 1(2),1959B 1(2),1959C 1(2),1959A 1(1),841C 1(1),839G 1(1),839H 1(1),837K 1(1),835C 1(2),1959L 1(2),1957C 1(1),835K 1(1),837B
1(1),1183C 1(1),1184A 1(1),1181B 1(1),1175A
1(1),722A l(l),720D 1(1),721A 1(1),719A 1(2),335B
1(1),1177A 1(1),1179A
1(1),717A
1(1),1184B
1(1),721B
19(2),181
1(1),839E 1(1),839C
1(1),1183A 1(1),1182C
l(l),720B l(l),720A
1(1),839K 1(1),835I 1(2),1957E 1(2),1959F 1(2),1957F 1(1),835E 1(1),835J 1(1),837I 1(1),839F 1(2),1957G l(l),835O
1(1),1184C 1(1),1176B
1(1),716B
1(2),1957M 1(1),835B 1(2),1959M 1(2),1961C 1(2),1961D 1(2),1959H 1(2),1959I 1(1),835M
1(2),1329B
17(1),231 17(5),11,259 18(11),5,548 17,411 11,2084
17(4),5814 1(2),331D 1(2),332A
1(1),1175B 1(1),1176C l(l),1180C 1(1),1183B 1(1),1178C 1(2),1327B 1(1),1174C
1(1),716D 1(1),718C l(l),720C 1(2),332B 1(1),718C
11,5586
1(1),715B 1(2),335C
1(2), 1330C l(2),1330A 1(1),1177C
Fieser
17,434 5,195 17,483 17,483 17(5), 11,259 19,153 17,418 17,419 17,445 17,417 17,526 17,532
1(1),719D 1(2),1328B 1(2),1328C 1(2),1328A
1(2),334B 1(2),334C 1(1),717C
11,1801
17,489 18,94 27,264 17(4),5927 17,442 17,432 17,415 27,265 17(2),461
11,254
5,422
17,492 17,414 17,521 17,523 17,524 17,486 17,486 17(2),461 1,713
1.4694
>110 17,442
1(1),835F l(l),907M 1(2),1957D
TI3150000 MA3900000 1.100
Beilstein
1(1),835H
1(1),839I
>110
FT-NMR
1.4610
1(2), 1957 J l(2),2017M
27,245 17,494 17,510
1(2),331C
1(2),1327A 1(2)1391A
1(2),332D
11,7346
17,492 17,469 21(3),5370
>110 27,681
1,882
TABLE 9.
cont'd
Name
2,3-Pyridenedicarboxylic 3,4-Pyridinedicarboxylic Succinic 4-Sulfo-1,8-naphthalic Tetrabromophthalic Tetrachlorophthalic Tetrafluorophthalic 1,2,3,6-Tetrahydrophthalic, cis3,4,5,6-Tetrahydrophthalic 3,3-Tetramethy leneglutaric Tetrapropenylsuccinic (isomers) Trimellitic 2-(Triphenylphosphoranylidene)succinic 9.2.
TABLE 10.
699-98-9 4664-08-8 108-30-5 71501-16-1 632-79-1 117-08-8 652-12-0 935-79-5 2426-02-0 5662-95-3 26544-38-7 1204-28-0 906-65-0
149.11 149.11 100.07 316.34 463.72 285.90 220.08 152.15 152.15 168.19 266.38 210.57 360.35
C10H2O6 C17H6O7
89-32-7 2421-28-5
218.12
C12H8O6
1719-83-1
C16H6O6
2420-87-3
C8H4O6 C9H6O6
4415-87-6 6053-68-5
196.11 210.14
>300 225(d)
23911-26-4 23911-25-3 1107-00-2
357.32 256.22 444.25
183 190(d) 244
C14H4O6
81-30-1
268.18
>300
C24H8O6 C8H4O7
128-69-8 25774-69-0
392.32 212.11
>300 223
CAS Registry Number
MoI. wt.
C 7 H 3 NO 3 C 7 H 3 NO 3 C4H4O3 C12H6O6S C 8 Br 4 O 3 C 8 Cl 4 O 3 C8F4O3 C8H8O3 C8H8O3 C9H12O3 C16H26O3 C 9 H 3 ClO 4 C22H17O3P
126
371
186/15 150/3
138 76 119 275 256 95 98 72 65 67 167(d)
C14H19N3O8 C10H12N2O6 C19H6F6O6
397
283 220
322.23 >300 248.19 300 294.22
BUTADIENES
Name
Formula
Boiling point ( 0 C)
Melting point (0C)
1,2-BUTADIENES
1,2-Butadiene - , 4-Bromo- , 4-Chloro- , 4-Hydroxy- , 4-Iodo- , 3-Methyl10.2.
Melting point ( 0 C)
MoI. wt.
DIANHYDRIDES
Benzene-1,2,4,5-tetracarboxylic Benzophenone3 3 ',4,4'-tetracarboxylic Bicyclo[2.2.2.]oct-7-ene2,3,5,6-tetracarboxylic Biphenylene-3,3',4,4'tetracarboxylic Cyclobutanetetracarboxylic Cyclopentane-1,2,3,4tetracarboxylic, cis,cisDiethylenetriaminepentaacetic Ethylenediaminetetraacetic 4,4'-(HeXaSuOrOiSOPrOPyUdBnC) diphthalic Naphthalene-1,4,5,8-tetracarboxylic Pery lene-3,4,9,10-tetracarboxylic Tetrahydrofuran-2,3,4,5-tetracarboxylic
10.1.
Boiling point ( 0 C)
CAS Registry Number
Formula
H 2 C=C=CHCH 3 H 2 C=C=CHCH 2 Br H 2 C=C=CHCH 2 Cl H 2 C=C=CHCH 2 OH H 2 C=C=CHCH 2 I H 2 C=C=C(CH 3 ),
590-19-2
H 2 C=CHCH=CH 2 H 2 C=CBrCH=CH 2 HCCl=CHCH=CH 2 HCCl=C(CH 3 )CH=CH 2 HCC1=CHC(CH 3 )=CH 2 H 2 C=CClCH=CH 2 H 2 C=CC1C(CH 3 )=CH 2
106-99-0
598-25-4
54.09 133.00 88.54 70.09 179.99 68.12
11 110 88 127 130 41
54.09 133.00 88.54 102.57 102.57 88.54 102.57 122.98 122.98
-4 42/165 68 107 100 59 93 63/105 98
-136
-148
1,3-BUTADIENES
1,3-Butadiene - , 2-Bromo- , 1-Chloro- , l-Chloro-2-methyl- , l-Chloro-3-Methyl- , 2-Chloro- , 2-Chloro-3-methyl- , 1,2-Dichloro- , 2,3-Dichloro-
HCCI=CCICH=CH2
H 2 C=CClCCl = CH 2
126-99-8
-109
Density (at 2O0C)
Refractive index (at 200 C)
Flash point (0C)
RTECS Number
WN0875000 TI3350000 TI3450000 GW5775000 1.005
1.4790
>110
WN1300000
DB9300000 162
QK3695000
Density (at 2O0C)
Refractive index (at 20 0 C)
0.652 1.4255 0.9891 0.9164 1.7129 0.694
1.4205/1.3 1.5248 1.4775 1.4759 1.5709 1.4190
0.650/- 6 1.397 0.961 0.9710 0.9543 0.9583 0.9593 1.1991 1.1829
1.4292/ - 2 5 1.4988 1.4709 1.4792 1.4719 1.4583 1.4686 1.4960 1.4890
Flash point (0C)
RTECS Number
R and S 1(2),2547K 1(2),2547L 1(1),835A l(2),2203F 1(2),1959E 1(2),1959D 1(1),835L 1(1),837M 1(1),839J 1(2),1981E
FT-NMR 1(3),336A 1(3),336B 1(1),1174B
1(2),1329A 1(1),1177B 1(1),1182A
1(2),1353B l(2),1680C
1(2),1959K 1(21),1957L
FT-IR 1(2),795B 1(1),715A l(2),501D 1(2),333D 1(2),333C
11,8841
l(l),1180B
1(1),837G
l(l),1180A
1(1),841B 1(1),841A 1(2),1957N
1(1),1185A 1(2),1327C
1(1),717B 1(1),719B 1(1),721C
Fieser
27,261 27,261 17,407
4,468
1(2),351B l(2),550D
19,196
1(1),716C
1(2),1961F
1(2),336B
1(2),1961G
1(2),336C
FT-NMR
Beilstein
17,485 17,484 15,300 17(5),ll,260 17,462 17,461 17,237 17(5),ll,105
1(2),335A 1(2),333B
1(1),837H
Rand S
Merck
FT-IR
19,196
Merck
Beilstein
1(4),975
-23
EI9275000
EI9625000
1(1),27B
1(1),35C
1(1),27D
1(1),36B
1,252
l(l),30C
11,1500
1,249
Fieser
TABLE 10.
cont'd
Name -, -, -, -, -, -,
Formula
2,3-Dimethyl2-FluoroHexachloroHexafluoro2-Iodo2-Methyl-
TABLE 11.
CAS Registry Number
MoI. wt.
H 2 C=CHCH 2 CH 3 H 2 C=CHCH 2 CH 2 Br H 2 C=C(CH 3 )CH(CH 3 ), H 2 C=CHC(CH 3 ) 2 CH 3 H 2 C=C(CH 3 )CH 2 CH 3 H 2 C=CHCH 2 (CH 3 ) 2
106-98-9 5162-44-7 563-78-0 558-37-2 563-46-2 563-45-1
56.11 135.01 84.16 84.16 70.14 70.14
-6 99 56 41 31 20
-158 -115 -137 -168
CH 3 CH=CHCH 3 CH 3 CH=CHCH 3 H 2 C(OH)CH = CHCH 2 (OH) (CH 3 ) 2 C = C(CH 3 ) 2 (CH 3 ) 2 C=CHCH 3
590-18-1 624-64-6 6117-80-2 563-79-1 513-35-9
56.11 56.11 88.11 84.16 70.14
4 1 131/12 73 36
-139 -105 7 -75 -134
CAS Registry Number
MoL wt.
106-92-3 7144-65-2 2426-08-6 7665-72-7 3101-60-8 2212-05-7 286-20-4 286-62-4 285-67-6 3132-64-7 106-89-8 503-09-3 21490-63-1 2404-44-6 2855-19-8 7320-37-8 1436-34-6 3146-39-2 7390-81-0 4436-24-2 5455-98-1 3234-28-4 75-21-8 2461-15-6 5380-87-0 556-52-5
114.14 266.28 130.19 130.19 206.29 184.62 98.15 126.20 84.12 136.98 92.53 76.07 72.11 156.27 184.32 240.43 100.16 110.16 268.49 134.18 203.20 212.38 44.05 186.30 154.17 74.08
CCI2=CCICCI = CCI2
87-68-3 685-63-2
68 12 215 7 112 34
-76 -20 -132 -146
Boiling point ( 0 C)
Melting point (°C)
1-BUTENES -185
2-BUTENES
TABLE 12.
12.1.
Melting point (0C)
78-79-5
513-81-5
Formula
2-Butene, cis2-Butene, trans1,4-Dihydroxy-, cis2,3-Dimethyl2-Methyl-
Name
Boiling point (0C)
82.15 72.08 260.76 162.03 179.99 68.12
H 2 C=C(CH 3 )C(CHs)=CH 2 H 2 C=CFCH=CH 2 CF 2 =CFCF=CF 2 H 2 C=CICH=CH 2 H 2 C=C(CH 3 )CH=CH 2
1-Butene - , 4-Bromo- , 2,3-Dimethyl- , 3,3-Dimethyl- , 2-Methyl- , 3-Methyl11.2.
MoI. wt.
BUTENES
Name 11.1.
CAS Registry Number
EPOXIDES
Formula
Boiling point ( 0 C)
Melting point (0C)
MONOEPOXIDES CH 2 (-O-)CHR
Allylglycidyl ether 2-Biphenylyl glycidyl ether n-Butyl glycidyl ether r-Butyl glycidyl ether 4-f-Butylphenyl glycidyl ether 4-Chlorophenyl glycidyl ether Cyclohexene oxide Cyclooctene oxide Cyclopentene oxide Epibromohydrin Epichlorohydrin Epifluorohydrin 1,2-Epoxybutane, trans1,2-Epoxydecane 1,2-Epoxydodecane 1,2-Epoxyhexadecane 1,2-Epoxyhexane 2,3-Epoxynorbornane, exo1,2-Epoxyoctadecane 2,3-Epoxypropyl benzene iV-(2,3-Epoxypropyl)phthalimide 1,2-Epoxytetradecane Ethylene oxide 2-Ethylhexyl glycidyl ether Furfuryl glycidyl ether Glycidol
-CH 2 OCH 2 CH=CH 2 -CH 2 OC 6 H 4 C 6 H 5 -CH 2 O(CH 2 ) 3 CH 3 -CH 2 OC(CH 3 ) 3 -CH 2 OC 6 H 4 C(CHs) 3 -CH 2 OC 6 H 4 Cl C6H10O C8H14O C5H8O -CH 2 Br -CH 2 Cl -CH2F CH 3 CH(-O-)CHCH 3 -(CH 2 ) 7 CH 3 -(CH 2 ) 9 CH 3 -(CH 2 ) 13 CH 3 -(CH 2 ) 3 CH 3 C7H10O -(CH 2 ) 1 5 CH 3 -CH2C6H5 -CH 2 NC 8 H 4 O 2 -(CH 2 ) n CH 3 -H -CH 2 OCH 2 CH(CH 2 CH 3 )(CH 2 ) 3 CH 3 -CH 2 OCH 2 C 4 H 3 O -CH 2 OH
154 120/0.1 165 151 166/4
31
32 129 55/5 102 135 116 85 54 94/15 124/15 176/12 119 137/0.5 99/17
54 -40 -57
21 123 34 99
95/10.4 10.7 61/0.3 103/11 61/15
-111
Density (at 200C) 0.726 0.843 1.665 1.553/-20 1.4220
Density (at 200C)
Refractive index (at 200C) 1.4390 1.400 1.5550 1.378/-20 1.5616 1.4220
Refractive index (at 200C)
1.330 0.684 0.653 0.650 0.627/0
1.3962 1.4625 1.3890 1.3760 1.3780 1.3640
1.070 0.708 0.662
1.3931/-25 1.3848/-25 1.4780 1.4120 1.3870
Density (at 20°C)
Refractive index (at 200C)
Flash point (0C)
RTECS Number
-22
1(1),32A
l(l),150A
l(l),102A
-54
NT4037000
1(1),27E
1(1),36C
l(l),30D
RTECS Number
Rand S
FT-NMR
Flash point (0C)
1(1),15C 1(1),97E 1(1),23I 1(1),23B 1(1),23G 1(1),23A
9 -18 -29 <-35 -57
37 126 -17 -46
Flash point (0C)
EM4970000
RTECS Number
RR0875000
0.910 0.917 1.038 0.970
1.4190 1.4170 1.5150 1.5450 1.4520
TX4200000 RR0475000 TX4250000 TX5600000 RN7175000
0.964 1.601 1.183 1.067 0.804 0.840 0.844 0.846 0.831
1.4340 1.4820 1.4380 1.3680 1.3730 1.4290 1.4360 1.4460 1.4060
56 43 102 107 27 56 10 56 34 4 -27 78 105 93 16 10 >110 82
1.4408 1.3597/7 1.4340 1.4810 1.4330
1(1),37A
l(l),105H
57
0.845 0.891/4 0.891 1.122 1.117
1(1),27F
FT-IR
EJ0700000
1.4330
1.5230
FT-NMR
None
0.962
1.020
R and S
RN8935000 TX4115000 TX4900000 TZ3325000 EK3855000 JR2450000 ML9450000 MO3630000 RB7176000 DA0178000 TI4950000
>110 97 102 81
KX2450000 TZ33OOOOO LU1423000 UB4375000
1(1),19A 1(1),19B 1(1),153A 1(1),25H 1(1),25D
Rand S
1(1),251C 1(1),1253D 1(1),249K 1(1),251A 1(1),1253A 1(1),1253B 1(1),251L 1(1),251M 1(1),251K 1(1),247L 1(1),247I 1(1),247H 1(1),245F 1(1),245J 1(1),245K 1(1),247A 1(1),245H 1(1),253D 1(1),247B 1(1),1251D l(2),2083B 1(1),245L 1(1),245A 1(1), 251B 1 (2),2319J 1(1),249B
FT-IR
Merck 11,3228
11,5087
Merck
11,1513 1(1),136C 1(1),31B 1(1),29B l(l),30C 1(1),29A
1(1),221A 1(1),35B 1(1),34A
FT-NMR
1(1),374A 1(2),225A 1(1),373A 1(1),373B 1(2),224A 1(2),224B 1(1),376C 1(1),377A 1(1),376B l(l),370B 1(1),369B 1(1),369A 1(1),364C 1(1),365C 1(1),366A 1(1),366C 1(1),378B 1(1),367A l(2),220C 1(2),1461C 1(1),366B 1(1),373C 1(3),17C l(l),370C
Beilstein
Fieser
1(3),991
1,276
1,250
10,195
1,252
Beilstein
Fieser
1(1),94B 1(1),22A 1(1),25B 1(1),21B 1(1),21C
1,203 1(D,84 1(3),816 1,217 1,211 1,213
1,205 1,205
1(1),146C 1(1),25A 1(1),21D'
11,1514 11,1514 1(2),567 1,218 1,211
Beilstein
Fieser
FT-IR
11,644 11,644
Merck
1(1),233D l(l),1065C 1(1),232C l(l),1065B l(l),1064E) 1(1),235A 1(1),235B 1(1),234D 1(1),232A 1(1),231D 11,3563 1(1),231C 1(1),229B l(l),230A l(l),230B l(l),230D 1(1),229A 1(1),235D 1(1),231B l(2),408A l(2),230C
17(3),988 17(3),988
17,21 17,21 17,21 17,6 17(3),49 17,18 17(3),136 17,20 17,86 17(3), 140 17,51
11,3758
17(3), 139 17,4
11,4385
17(5),347 17,104
1(1),232D 1(1),232B
5,290
8,150
TABLE 12.
cont'd
Name
Formula
3-Glycidoxypropyl trimethoxy- -CH 2 O(CH 2 )SSi(OCHs) 3 silane (R)-(-)-Glycidyl Butyrate -CH 2 OC(O)CH 2 CH 2 CH 3 Glycidyl isopropyl ether -CH 2 OCH(CH 3 ) 2 Glycidyl methacrylate (see Methacrylates) GIy cidy ltrimethy lammonium -CH 2 N(CH 3 ) 3 C1 chloride, (70% aq. solution) Hexafluoropropylene oxide F 2 C(-O-)CFCF 3 4-Methoxyphenyl glycidyl ether -CH 2 OC 6 H 4 OCH 3 a-Pinene oxide CioH^O Propylene oxide -CH3 Styrene oxide -C6Hs Tetracyanoethylene oxide (NC) 2 C(-O-)C(CN) 2 1,1,2,2-Tetrafluoroethyl glycidyl -CH 2 OCF 2 CHF 2 ether Vinylethylene oxide -CH=CH 2
CAS Registry Number
MoI. wt.
Boiling point (0C)
2530-83-8
236.34
120/2
60456-26-0 4016-14-2
144.17 116.16
90/19 131
3033-77-0
151.54
428-59-1 2211-94-1 1686-14-2 75-56-9 96-09-3 3189-43-3 85567-21-1
166.02 180.20 152.24 58.08 120.15 144.09 174.10
102/50 34 194
930-22-3
70.09
65
3130-19-6
366.46
1464-53-5 2425-79-8 27035-39-8 2426-07-5 2386-87-0
86.09 202.25 140.18 142.20 252.31
57/25 158/11 70/0.4 240
2224-15-9
174.20
112/4.5
CAS Registry Number
MoI. wt.
Boiling point ( 0 C)
28.05 106.96 62.50 84.48 116.47 185.86
-104 16/750 -13.4 -24 -29 92
Melting point (0C)
-42 46 -112 -37
143
12.2. DIEPOXIDES CH2(-O-)CHRCH(-O-)CH2 Bis(3,4-epoxycyclohexylmethyl) C 6 H9(-O-)CH 2 OC(O)(CH 2 )4C(O)OCH 2 C 6 H9(-O-) adipate 1,3-Butadiene diepoxide CH 2 (-O-)CHCH(-O-)CH 2 1,4-Butanediol diglycidol ether -CH 2 O(CH 2 ) 4 OCH 2 1,2,5,6-Diepoxycyclooctane CgHi 2 O 2 1,2,7,8-Diepoxyoctane -(CH2)43,4-Epoxycyclohexylmethyl C 6 H9(-O-)CH 2 OC(O)C 6 H 9 (-O-) 3,4-epoxycyclohexanecarboxylate Ethylene glycol digycidyl ether -CH 2 O(CH 2 ) 2 OCH 2 -
TABLE 13.
3
-37
ETHYLENE HALIDES
Name Ethylene - , Bromo- (vinyl bromide) - , Chloro- (vinyl chloride) - , 1-Chloro-1-fluoro- , Chlorotrifluoro- , 1,1-Dibromo- (vinylidene bromide) - , 1,2-Dibromo-, cis1,2-Dibromo-, trans- , 1,1-Dichloro- (vinylidene chloride) - , 1,2-Dichloro-, cis- , 1,2-Dichloro-, trans- , Tetrabromo- , Tetrachloro- , Tetrafluoro- , Tetraiodo- , Tribromo- , Trichloro-
Formula H 2 C=CH 2 BrCH=CH 2 ClCH=CH 2 ClCF=CH 2 ClCF=CF 2 Br 2 C=CH 2 BrCH=CHBr BrCH=CHBr Cl 2 C=CH 2 ClCH=CHCl ClCH=CHCl Br 2 C=CBr 2 Cl 2 C=CCl 2 F 2 C=CF 2 I 2 C=CI 2 Br 2 C=CHBr Cl 2 C=CHCl
74-85-1 593-60-2 75-01-4 79-38-9
75-35-4 156-59-2 156-60-5 127-18-4 116-14-3 513-92-8 79-01-6
Melting point (0C) -169 -139 -154 -169 -157
185.86 185.86 96.94
112 108 31
-53 -6 -122
96.94 96.94 343.66 165.83 100.02 531.64 264.76 131.39
60 48 226 121 -76
-80 -50 56 -22 -142 192
163 87
-85
Density (at 20 0 C)
Refractive index (at 20 0 C)
Flash point ( 0 C)
RTECS Number
Rand S
FT-NMR
FT-IR
1.070
1.4290
>110
VV4025000
1(2),2973B
1(3),667C
1(2),1113D
1.018 0.924
1.4280 1.4100
85 33
TZ35OOOOO
1(1),781E 1(1),249J
l(l),1088B 1(1),372C
l(3),306A
1.129
1.4780
> 110
BQ3480000
0.964 0.830 1.054
1.4690 1.3660 1.5350
>110 66 -35 79
TZ3400000 DA0176000 TK4565000 TZ2975000 CZ9625000
1.380
1.3490
51
0.870
1.4170
-50
EM7350000
1.149
1.4930
> 110
MO 1880550
1.113 1.100 1.138 0.997 1.170
1.4340 1.4610 1.4690 1.4450 1.4980
46 >110 105 98 118
1.118
1.4630
> 110
Density (at 20 0 C)
Refractive index (at 20 0 C)
1.517 0.911
1.4350 1.3700
Flash point ( 0 C)
None - 61
Merck
Beilstein
Fieser
17(5),3,34 17(3),988 18,583
1(1),616B 1(1),249A 1(1),1253C 1(1),253B 1(1),245B 1(1),1251A l(l),1003F
1(2),224C 1(1),377C 1(1),363B 1(2),219C 1(1),1376C
l(l),1065A 1(1),237A 1(1),228B l(l),1063C
1(1),247D
1(1),367C
1(1),233A
EJ8400000 EJ5100000 GX9627000 RG9450000 RN7750000
1(1),251E 1(1),251I 1(1),253E 1(1),251F
1(1),374B 1(1),375C 1(1),378C 1(1),374C
1(1),234A 1(1),234C 1(1),235C 1(1),234B
KH5780000
1(1),251G
1(1),375A
RTECS Number
Rand S
KU5340000 KU8400000 KU9625000
1(1),15A 1(1),95B 1(1),95A
KV0525000
l(l),103I
17(3),20
FT-NMR 1(3),17C 1(1),133A
11,7869
5,152 17,6 17,49
18(5),7,215
17(1),13
11,3621
4,53
19,14
17(3),997
FT-IR
Merck 11,3748
1(1),93A 11,9898
Beilstein 1,180 1,188 1,186
Fieser
1,1274
1(3),646
2.178 2.2464 2.2308 1.213
1.5428 1.550 1.4254
-9
KV9275000
l(l),101B
1(1),142B
1(1),98B
11,9900
1,186
1.284 1.257
1.4481 1.4456
6 6
KV9420000 KV9400000
l(l),101D l(l),101E
1(1),143A 1(1),134B
1(1),98A 1(1),79D
11,86 11,86
1,188 1,188
1.623 1.1507/- 40 2.983 2.708 1.463
1.5060
KX3850000
l(l),103J
11,9126
1,187
11,9151
1,195
11,9552
1,187
None 1.6045/16 1.4760 None
KX4125000
l(l),103K
KX4550000
l(l),103G
l(l),101C 1(1),147C l(l),101B
14,127 12,175
11,552
TABLE 14.
FUMARATE ACIDS/ESTERS Formula ROC(O)CH=CHC(O)OR
Name
CAS Registry Number
R
Acid 2-Bromo2-Chloro2-Chloro-, diethyl ester 2-Chloro-, dimethyl ester Di-n-amyl ester Diethyl ester Diisoamyl ester Diisobutyl ester Diisopropyl ester 2,3-DimethylDimethyl ester Dinitrile- (fumaronitrile) Diphenyl ester Di-/z-propyl ester 2-Methyl- (mesaconic acid) 2-Methyl-, diethyl ester
-H HOC(O)CBr=CHC(O)OH HOC(O)CCl=CHC(O)OH CH3CH2OC(O)CCI=CHC(O)OCH2CH3 CH3OC(O)CCI=CHC(O)OCH3 -(CH 2 ) 4 CH 3 -CH 2 CH 3 -CH 2 CH 2 CH(CH 3 ) 2 -CH 2 CH(CH 3 ) 2 -CH(CH 3 ) 2 HOC(O)C(CH3)=C(CH3)C(O)OH -CH 3 NCCH=CHCN -C6H5 -CH 2 CH 2 CH 3 HOC(O)C(CH3) = CHC(O)OH CH3CH2OC(O)C(CH3)=CHC(O)CH2CH3
2-Methyl-, dimethyl ester
CH3OC(O)C(CH3)=CHC(O)OCH3
TABLE 15.
623-91-6
624-49-7 764-42-1
498-24-8
116.07 194.98 150.52 206.63 178.57 256.33 172.18 256.33 228.29 200.24 144.13 144.13 78.07 268.27 200.24 130.10
Boiling point (0C)
200(d) 136/19 224 162/7 217 166/11 170/160 226 192 186 219/14 110/5 205(d) 186.21 158.16
Melting point (0C) 299(s) 186 193
2
241 103 96 162 204 229 204
ISOCYANATES Formula OCNRNCO
Name
110-17-8
MoI. wt.
R
1,3-Benzene diisocyanate -C6H41,4-Benzene diisocyanate -C6H41,3-Bis(isopropyl)benzene -C(CH 3 ) 2 C 6 H 4 C(CH 3 ) 2 a,oc'-diisocyanate 1,4-Bis(isopropyl)benzene -C(CH 3 ) 2 C 6 H 4 C(CH 3 ) 2 a,a'-diisocyanate 1,4-Butene diisocyanate -(CH2)4a-Chlorotoluene -C 6 H 3 (CH 2 Cl)2,4-diisocyanate 1,4-Cyclohexylene diisocyanate, - C 6 H 1 0 trans1,12-Dodecane diisocyanate -(CH 2 ) 1 2 1,6-Hexane diisocyanate -(CH 2 ) 6 Isopherone diisocyanate -C 1 0 H 1 S(isomers) / 4,4 -Methylenebis(cyclohexyl -(C 6 H 1 0 )CH 2 (C 6 H 1 0 )isocyanate) (isomers) 4,4'-Methylenebis(2,6-di-C 6 H 2 (CH 2 CH 3 ) 2 CH 2 C 6 H 2 (CH 2 CH 3 ) 2 ethylphenyl isocyanate) 4,4/-Methylenebis(phenyliso-C6H4CH2C6H4cyanate) 2-Methylpentane 1,5-diisocyanate-CH2CH(CH3)(CH2)3 1,8-Octane diisocyanate -(CH 2 )g2,4-Toluene diisocyanate -C 6 H 3 (CH 3 )-
CAS Registry Number
MoI. wt.
Boiling point (0C)
Melting point (0C)
123-61-5 104-49-4 2778-42-9
160.13 160.13 244.30
121/25 260 157/10
2778-41-8
244.30
150/3
4538-37-8 51979-57-8
140.14 208.60
102/14 153/11
72
7517-76-2
166.18
13879-35-1 822-06-0 4098-71-9
252.36 168.20 222.29
168/3 255 158/15
60
5124-30-1
262.35
105442-35-1
362.48
101-68-8
250.26
200/5
43
34813-62-2 10124-86-4 584-84-9
168.20 196.25 174.16
156/15 120/10
21
50 98 -10
56
Density (at 20 0 C)
Refractive index (at 20 0 C)
1.1880 1.290 0.9681 1.052 0.9655 0.9760
1.4571
0.9416
1.4349
1.0129 1.466
1.4439
Density (at 20 0 C)
1.4496 1.4410 1.4479 1.4432
Flash point ( 0 C)
94
1.0453
1.4488
1.0914
1.4512
Refractive index (at 20 0 C)
Flash point (0C) >110 >110 153
1.05
RTECS Number
R and S
LS9625000
1(1),553A
1(1),787B
l(l),502D
EM5950000
1(1),725M
1(1),993C
1(1),645A
2,742
EM6125000 LT2300000
1(1),725L 1(1),993A
1(1),993B l(l),1360B
1(1),644D 1(1),844A
2,741 2(l),302
OX5075000
1(1),553C
1(1),788A
l(l),503B
RTECS Number
Rand S
NR0150000 CZ6150000 CY8480000
FT-NMR
FT-NMR
FT-IR
FT-IR
Merck 11,4200
11,5806
Merck
Beilstein
Fieser
2,737
5,319
2,763
Beilstein
Fieser
13,50 13,105
1(2),2165G 1(2),2165H
>93 1.105 1.362
1.5960
106 >110
l(l),1023F 1(2),2169H
l(l),1404B 1(2),1572A
4(3),578 13(4),245
GU9642500
l(l),1025A
l(l),1406A
13(3),12
l(l),1405A l(l),1404C l(l),1405C
4(3),624 4(2),711
1(3),1432D
0.940 1.040 1.049
1.4590 1.4520 1.4840
>110 140 >110
MO1740000 NQ9370000
l(l),1023H l(l),1023G l(l),1023J
1.066
1.4970
>110
NQ9250000
l(l),1025B 1(2),2169K
1.180 1.049 1.007 1.214
>110 1.4550 1.4550 1.5680
>110 > 110 > 110
NQ9350000
1(2),1572C 1(1),871A
1(2),2163D l(l),1023I
CZ630000
13(4),33
13(3),461
l(l),1405B
1(2),2169F
11,9456
1(2),478B
4(3),614 13,138
1,117
TABLE 16.
LACTAMS
Name
Formula
y-Butyrolactam (2-pyrrolidinone) s-Caprolactam 12-Dodecanolactam 7-Heptanolactam P-Propiolactam 5-Valerolactam
-C(O)(CH 2 ) 3 NH-C(O)(CH 2 ) 5 NH-C(O)(CH 2 ) n N H -C(O)(CH 2 ) 6 NH-C(O)CH 2 CH 2 NH-C(O)(CH 2 ) 4 NH-
TABLE 17.
Formula
y-Butyrolactone 8-Caprolactone p-Propiolactone 5-Valerolactone
-C(O)(CH 2 )^O-C(O)(CH 2 ) 5 O-C(O)(CH 2 ) 2 O-C(O)(CH 2 ) 4 O-
616-45-5 105-60-2 947-04-6 673-66-5 930-21-2 675-20-7
85.11 113.16 197.32 127.19 71.08 99.13
CAS Registry Number
MoI. wt.
Boiling point (0C)
96-48-0 502-44-3 57-57-8 542-28-9
86.09 114.14 72.06 100.12
204 97/15 162 59/0.5
MoI. wt.
Boiling point (°C)
245 137/10 149/10 106/15 256
Melting point (0C) 24 69 151 36 75 39
Melting point (0C) -45 -33
MALEATE ACIDS/ESTERS Formula ROC(O)CH=CHC(O)OR
Name
R
Acid 2-Chloro2-Chloro-, diethyl ester 2-Chloro-, dimethyl ester Diallyl ester Di-n-amyl ester Di-«-butyl ester 2,3-DichloroDiethyl ester 2,3-DihydroxyDiisoamyl ester Dimethyl ester Diphenyl ester Di-n-propyl ester 2-Methyl-, cis- (citraconic acid) 2-Methyl-, diethyl ester, cis2-Methyl-, dimethyl ester, cis-
TABLE 19.
MoI. wt.
LACTONES
Name
TABLE 18.
Boiling point (0C)
CAS Registry Number
-H HOC(O)CCl=CHC(O)OH CH3CH2OC(O)CCI=CHC(O)OCH2CH3 CH3OC(O)CCI=CHC(O)OCH3 -CH 2 CH=CH 2 -(CH 2 ) 4 CH 3 -(CH 2 ) 3 CH 3 HOC(O)CC1=CC1C(O)OH -CH 2 CH 3 HOC(O)C(OH)=C(OH)C(O)OH -CH 2 CH 2 CH(CH 3 ) 2 -CH 3 -C6H5 -CH 2 CH 2 CH 3 HOC(O)C(CH3 )=CHC(O)OH CH3CH2OC(O)C(CH3)=CHC(O)OCH2CH3 CH3OC(O)C(CH3)=CHC(O)OCH3
CAS Registry Number 110-16-7
999-21-3 105-76-0 141-05-9
624-48-6
498-23-7
116.07 150.52 206.63 178.57 196.20 256.33 228.29 184.97 172.18 148.07 156.33 144.13 268.27 200.24 130.10 186.21
Melting point (0C) 141 110
235 107 110/4 161/10 281
-47
225
120 -10 155
157/13 204 226/15 126/12
93 90
230 158.16
211
PROPENES
Name Propene - , 1-Bromo-, cis- , 1-Bromo-, trans- , 2-Bromo- , 1-Chloro-, cis- , 1-Chloro-, trans- , 2-Chloro- , l-Chloro-2-methyl(isocrotyl chloride) - , 3-Chloro-2-methyl(methallyl chloride) - , 1,1-Dichloro-
Formula
CAS Registry Number
MoI. wt.
Boiling point (0C)
Melting point (0C)
-48 58 64 48 33 37 22.5 68
-185
557-98-2 513-37-1
42.08 120.98 120.98 120.98 76.53 76.53 76.53 90.55
H 2 C=C(CH 3 )CH 2 Cl
563-47-3
90.55
71
-80
Cl 2 C=CHCH 3
563-58-6
110.97
76
H 2 C=CHCH 3 BrCH=CHCH3 BrCH=CHCH3 H 2 C=CBrCH 3 ClCH=CHCH3 ClCH=CHCH3 H 2 C=CClCH 3 C1CH=C(CH3)2
115-07-1 590-13-6 590-15-8 557-93-7
-125 -135 -99 -139
Density (at 2O0C) 1.120
Density (at 200C) 1.120 1.030 1.146 1.079
Density (at 200C)
Refractive index (at 2O0C) 1.4870
Refractive index (at 200 C) 1.4360 1.4630 1.4120 1.4580
Refractive index (at 2O0C)
Flash point (0C) >110
RTECS Number
Rand S
>110
UY5715000 CM3675000 CL6940000 CN4810000
> 110
TO0110000
1(1),923B 1(1),927G 1(1),929A 1(1),927M 1(1),923A 1(1),927E
RTECS Number
Rand S
Flash point (0C) 98 109 70 100
Flash point (0C)
1.590
LU3500000 MO8400000 RQ7350000
l(l),803J 1(1),819E l(l),803A 1(1),815A
FT-NMR 1(1),1285B 1(1),1293B 1(1),1296A 1(1),1295B 1(1),1285A 1(1),1292C
FT-NMR
FT-IR 1(1),788D 1(1),792B 1(1),794A 1(1),793C
Merck 11,8027 11,1762
1(1),1127A 1(1),1161C
1(1),697D 1(1),699B
1(1),1152A
l(l),704D
Merck 11,1596 11,7832
RTECS Number
Rand S
OM9625000
l(l),5510
1(1),787A
FT-NMR
FT-IR l(l),503A
21,236 21(2),216
Merck 11,5585
Beilstein 17,234 17(2),290 17(l),130 17,235
Beilstein
Fieser 1,101 1,957
Fieser
2,748
1.1741 1.277 1.073 0.9741 0.988
1.4690 1.4475 1.4452
>110
ON0700000
1(1),725K
1(1),993A
2(3), 1926
>110
ON0875000
1(1),725J
1(1),992C
2(3),1925
1.064
1.4410
93
ON1225000
1(1),725I
1(1),992B
0.9714 1.152
1.4459 1.4410
1.0245
1.4433
1.0491
1.4468 1.9491
1(1),644C
Fieser
21,242 21(3),3141 21,238
1(1),791D
FT-IR
Beilstein
11,3113 2,751
91
EM6300000
1(1),725H
1(1),992A
1(1),644B 2,751
GE6650000
Density (at 2O0C)
Refractive index (at 2O0C)
1(1),553B
1(1),787C
l(l),503C
11,2323 2,768
1.4473
Flash point (0C)
RTECS Number
R and S
FT-NMR
FT-IR
Merck 11,7862
Beilstein 1,196 l(3),710 1(4),754 1,200
1(1),15B 1(1),95F 1(1),95C 1(1),95H
1(1),134C
1(1),96B
UC7200000 UC8045000
1(1),95D 1(1),97I
1(1),133B 1(1),137C
1(1),96A 1(1),97A
11,2147
1,198 1,209
-12
UC8050000
1(1),97J
1(1),138A
1(1),96D
11,2148
1,209
0
UC8290000
l(l),101G
1(1),144A
1(3),138D
1.423 1.408 1.362 0.9347 0.9351 0.899 0.920
1.4545 1.4530 1.436 1.4055 1.4054 1.3939 1.4225
-34 -15 4
-34 -1
0.917
1.4278
1.169
1.4450
UC6740000
UC7085000
1(1),134A
1,199
Fieser
4,236
TABLE 19.
cont'd
Name
Formula
-, -, -, -, -, -, -,
CICH=CClCH 3 F 2 C=CFCF 3 H 2 C=C(CH 3 ) 2 Cl 2 C=CClCH 3 Cl 2 C=CHCH 2 Cl
1,2-DichloroHexafluoro2-Methyl- (isobutylene) 1,1,2-Trichloro1,1,3-Trichloro1,2,3-Trichloro3,3,3-Trichloro-
TABLE 20.
CAS Registry Number
116-15-4 115-11-7
CICH=CCICH2CI
H 2 C=CHCCl 3
MoI. wt.
Boiling point (0C)
110.97 150.02 56.11 145.42 145.42 145.42 145.42
77 -28 -7 118 131 142 114
MoI. wt.
Boiling point (0C)
Melting point (0C)
-153 -140
STYRENES Formula CH 2 =CHR
Name Styrene - , 4-Acetoxy- , 2-Amino- , 4-Amino- , 4-Benzyloxy-3-methoxy- , 3,5-Bis(trifluoromethyl)a-Bromop-Bromo- , 2-Bromo- , 3-Bromo- , 4-Bromo- , 4-terf-Butyl- , 4-Carboxya-Chloro(3-Chloro- , 2-Chloro- , 3-Chloro - , 3-Chloromethyl (3-vinylbenzyl chloride) - , 4-Chloro- , 4-Chloromethyl- , 4-Chloro-a-Methyl- , 2-Cyano- , 3-Cyano - , 4-Cyano- , 2,5-Dichloro- , 2,6-Dichloro- , 3,4-Dichloro- , a,p-Difluoro- , 1,2-Difluoro- , 2,6-Difluoro- , 1,3-Diisopropenyl benzene - , 3,4-Dimethoxy- , a,2-dimethyl- , 2,4-Dimethyl- , 2,5-Dimethyl- , Divinyl-, (isomers) - , 4-Ethoxy- , 2-Ethyl- , 4-Ethyl- , 3-Iodo- , 2-Fluoro- , 3-Fluoro- , 4-Fluoro- , 2-Hydroxy- , 3-Hydroxy- , 4-Hydroxy- , 4-Isopropyl-
R -C6H5 -C 6 H 4 OC(O)CH 3 -C6H4NH2 -C6H4NH2 -C 6 H 3 (OCH 3 )OCH 2 C 6 H 5 -C 6 H 4 (CF 3 ) 2 H 2 C=CBrC 6 H 5 HCBr=CHC 6 H 5 -C 6 H 4 Br -C 6 H 4 Br -C6H4Br -C 6 H 4 C(CH 3 ), -C6H4CO2H H 2 C=CClC 6 H 5 HCCl=CHC 6 H 5 -C 6 H 4 Cl -C 6 H 4 Cl -C 6 H 4 CH 2 Cl -C 6 H 4 Cl -C 6 H 4 CH 2 Cl H 2 C=C(CH 3 )C 6 H 4 Cl -C6H4CN -C 6 H 4 CN -C 6 H 4 CN -C6H3Cl2 -C6H3Cl2 -C6H3Cl2 HCF=CFC 6 H 5 -C6H3F2 -C6H3F2 C 6 H 4 (C(CH 3 )=CH 2 ) 2 -C6H3(OCH3), H 2 C=C(CH 3 )C 6 H 4 CH 3 -C6H3(CH3), -C6H3(CH3), C 6 H 4 (CH=CH 2 ) 2 -C 6 H 4 OCH 2 CH 3 -C 6 H 4 CH 2 CH 3 -C 6 H 4 CH 2 CH 3 -C6H4I -C6H4F -C6H4F -C6H4F -C6H4OH -C6H4OH -C 6 H 4 OH -C 6 H 4 CH(CH 3 ),
CAS Registry Number 100-42-5 2628-16-2 3867-18-3 1520-21-4 55708-65-1 349-59-7 98-81-7 103-64-0 2039-88-5 2039-86-3 2039-82-9 1746-23-2 1075-49-6
2039-87-4 2039-85-2 57458-41-0 1073-67-2 1592-20-7 1712-70-5 5338-96-5 3435-51-6 1123-84-8 28469-92-3 2039-83-0 366-37-0 3748-13-8 6380-23-0 26444-18-8 2234-20-0 2039-89-6 1321-74-0 5459-40-5 7564-63-8 3454-07-7 394-46-7 350-51-6 405-99-2
2055-40-5
104.15 162.19 119.18 119.18 240.30 240.15 183.05 183.05 183.05 183.05 183.05 160.26 148.16 138.60 138.60 138.60 138.60 152.62
145 260 104/8 249 51 60/20 69/4 111/20 210 74/3 212 219
138.60 152.62 152.62 129.16 129.16 129.16 173.04 173.04 173.04 140.03 140.03 140.03 158.25 164.20 132.21 132.21 132.21 130.19 148.21 132.21 132.21 233.05 122.14 122.14 122.14 120.15 120.15 120.15 146.22
192 229
199 199 188 62/6 229
53/0.15 83/2.6 92/3 74/3 88/8 76/3 88/60 90/45 59/51 231 120/10 54/11 70/11 71/10 59/1 191 193 67/15 30/4 30/14 108/15 115 204
Melting point (0C) -30 7 23 7 -44 7 -53 4.5 -37 143 -23
-63
-16
-15
-64 -35
-127 -50 73
29 73.5 -45
Density (at 20 0 C) 1.1818
1.382 1.403 1.414 1.369
Density (at 20 0 C) 0.9059 1.060 1.608 1.014
Refractive index (at 20 0 C)
1.4827 1.4950 1.5020 1.4827
Refractive index (at 2O0C) 1.5470 1.5380
R and S
UD0350000 UD0890000
l(l),105A 1(1),23F
UD1928500
l(l),103H
RTECS Number
R and S
WL3675000 SL3784000
1(1),1139A 1(2),1927F
1(2),23A 1(2),1287C
1(1),945B
1(1),1237M 1(1),1213A l(l),1203F l(l),1203H l(l),1203L l(l),1205D l(l),1205H
1(2),197C 1(2),155A
l(l),1053A
1(2),136C 1(2),138A 1(2),139C 1(2),141A
l(l),1017B l(l),1018A 1(3),195B l(l),1019C
1(2),1789D
l(2),1076A
1(2),194D
l(l),1203K l(l),1205C
1(2),137C 1(2),139B
l(l),1017D l(l),1018C
l(l),1205F
1(2), 140B
l(l),1019B
l(l),1205G
1(2), 140C
l(l),1018D
l(l),1205J
1(2),141C
l(l),1019D
1(1X12051 1(1),1139L 1(1),1243D
1(2),141B 1(2),26B l(2),208C
1(1),947C l(l),1053D
1(1),1141D 1(1),1141E 1(1),1141B 1(1), 1243 A
1(2),27C 1(2),28A
l(l),1203J l(l),1205B l(l),1205E
1(2),137B 1(2), 139 A 1(2), 140A
FT-NMR
FT-IR
48
Flash PQint ( 0 C) 31 87
1(3),143C 1(3),28B 1(1),148A
Merck
FT-NMR
1.1016/18 1.1095/15 1.080 1.090 1.074
1.5612 1.5648 1.5648 1.5613
1.155 1.083 1.065
1.5662 1.5740 1.5550 1.5756 1.5630 1.575 1.5740
11,5024
1(3),142A
FT-IR
Beilstein
l(3),707
Merck 11,8830
Beilstein 5,474 6(3),2387
>110 122 87 102 85 67 75 80
58 62 105
WL3840000 WL385OOOO
WL4160000
60 104 74
5(4), 1386 5,477 5,477 5(3X1176 5(3),1176 5(2),367 5(3X1254 9(3),2755
5(2),367
104
71
1.5061 1.130 0.925 1.109 0.894 0.906 0.904 0.914 0.990 0.8955 0.8925
Fieser
1(3),697 1,207
12,1187
1.6267 1.4250 1.5880 1.6070 1.5927 1.5891 1.5940 1.5260
1.267
RTECS Number
1.4471
1.334 1.410 1.427 1.460 1.406 1.400 0.875
1.083
Flash point ( 0 C)
1.025 1.025 1.024 1.0609/18 1.0468/35
1.4990 1.5570 1.5710 1.5150 1.5390 1.5391 1.5470 1.5498 1.5351 1.5376 1.6390 1.5200 1.5175 1.5156 1.5783/27 1.5804/31
0.885
1.5289
30 91 >110 43 60 63 64 87
35 29 26
CY8535OOO
WL4450000 WL4460000 CZ9370000
6,954 5,491 5,491
1(3),984B
l(l),1081B l(l),1019A
6,561
5(3),1171 5(3),1171
Fieser
TABLE 20.
cont'd Formula CH 2 =CHR R
Name - , 2-Methoxy- , 3-Methoxy- , 4-Methoxy- , 2-Methoxy-4-hydroxya-Methyl- , 2-Methyl- , 3-Methyl- , 4-Methyl- , P-Nitro- , 2-Nitro- , 3-Nitro- , 4-Nitro- , Pentabromo- , Pentafluoro- , 4-Phenoxy- , 4-Phenyl- , 4-Sulfonic acid, sodium salt - , 2-Trifluoromethyl- , 3-Trifluoromethyl- , 4-Trifluoromethyl- , 2,4,6-Trimethyl-
TABLE 21.
Boiling point (0C)
Melting point (0C)
61.3 144/2 204 224 167 171 170 172 250
29
586-39-0 100-13-0 53097-59-9 653-34-9 4973-29-9 2350-89-2 2695-37-6 395-45-9 402-24-4 402-50-6 769-25-5
134.18 134.18 134.18 150.18 118.18 118.18 118.18 118.18 149.15 149.15 149.15 149.15 498.66 194.10 196.25 180.25 206.20 172.15 172.15 172.15 146.24
Formula
CAS Registry Number
MoI. wt.
Boiling point (0C)
Melting point (0C)
-CI4HQ
2444-68-0
204.27
62/10
65
-C10H7 -C5H4N -C5H4N -C5H4N -C9H6N
827-54-3 100-69-6 1121-55-7 100-43-6 772-03-2
154.21 105.14 105.14 105.14 155.20
80/29 68/15 63/15 71/0.5
108-05-4
86.09
72
56860-96-9 769-78-8 5309-70-6 15484-80-7 123-20-6 872-36-6 2549-51-1 15721-27-4 5130-24-5 3098-92-8 14861-06-4 4704-31-8 2146-71-6 94-04-2 692-45-5 1917-10-8 693-38-9 3050-69-9
212.25 148.16 165.0 204.27 114.14 86.05 120.54 182.61 106.51 174.20 112.13 198.31 226.36 170.25 72.06 138.12 282.47 142.20 168.15
135/9 203 50/10 111/2 116 162 134
-C 6 H 4 OCH 3 -C 6 H 4 OCH 3 -C 6 H 4 OCH 3 -C 6 H 3 OCH 3 (OH) H 2 C=C(CH 3 )C 6 H 5 -C6H4CH3 -C6H4CH3 -C6H4CH3 HC(NO 2 )=CHC 6 H 5 -C6H4NO2 -C6H4NO2 -C6H4NO2 -C6Br5 -C6F5 -C6H4OC6H5 -C6H4C6H5 -C 6 H 4 SO 3 Na -C6H4CF3 -C6H4CF3 -C6H4CF3 -C6H2(CH3),
90/3.5 120/10
-24 -69 -82 -34 58 13 -5 25 188
139 71 120 225 61/40 55/12 65/40 209
ARYLH 2 C=CHR
9-Anthracene Benzene (see Styrene) 2-Naphthalene 2-Pyridine 3-Pyridine 4-Pyridine 2-Quinoline 21.2.
612-15-7 626-20-0 637-69-4 7786-61-0 98-83-9 611-15-4 100-80-1 622-97-9
MoI. wt.
VINYLFUNCTIONAL
Name 21.1.
CAS Registry Number
61
ESTERS H 2 C=CHOC(O)R
Acetate Acrylate (see Acrylates) AUyI adipate Benzoate Bromoacetate 4-tert-Buty\ benzoate Butyrate Carbonate Chloroacetate 2-Chlorobenzoate Chloroformate Cinnamate Crotonate Decanoate Dodecanoate 2-Ethylhexanoate Formate 2-Furoate Hexadecanoate (palmitate) Hexanoate (caproate) Maleate
-CH3 -(CH 2 ) 4 C(O)OCH 2 CH=CH 2 -C6H5 -CH 2 Br -C 6 H 4 C(CH 3 ) 3 -(CH 2 ) 2 CH 3 -OCH=CH 2 -CH 2 Cl -C 6 H 4 Cl -Cl -CH=CHC 6 H 5 -CH 2 CH=CHCH 3 -(CH 2 ) 8 CH 3 -(CH 2 ) K)CH3 -CH(CH 2 CH 3 )(CH 2 ) 3 CH 3 -H -C4H3O -(CH 2 ) 14 CH 3 -(CH 2 ) 4 CH 3 -CH=CHC(O)OCH=CH 2
68/735 125/7 133 146/50 140/10 128/20 46 182/10 165/2 160/10 94/10
-93
22
-90 14 24
Density (at 20 0 C)
Refractive index (at 200 C)
Flash point (0C)
1.0049 0.9999 0.994 1.110 0.909 0.917 0.890 0.897
1.5388 1.5540 1.5620 1.5820 1.5380 1.544 1.5408 1.5412
1.070
1.5840 1.6016
107
1.4455
34
72 >110 45 58 52 45
RTECS Number
SL8205000 WL5075300 WL5075900 WL5075800 WL5076000
R and S
FT-NMR
FT-IR
Merck
Beilstein
l(l),1241O
l(2),207C
l(l),1052C
1(1),1139B 1(1),1139K 1(1),1139M 1(1),1139N
1(2),2437C
1(1),945C 1(1),947A 1(3),869B 1(1),947B
6,561 6(3),4981 5,484 5(1),233 5,485 5,485
1(1),1334D
5,478
1(2),26C
Fieser
1(2),27A
1.406
1.175 1.161 1.165 0.906
1.4700 1.4655 1.4660 1.5320
1(1),1555D WL5470000
42
75
l(l),1205N l(l),1205K
1(2),687C
1(1),1145G l(2),2207I l(l),1207C l(l),1207K l(l),1209F 1(1),1141G
1(2),142A 1(2),35B 1(2),1598C 1(2), 143 A 1(2),138C 1(2),148A
l(l),1020B l(l),1020A
5(4), 1367 5(3),1197 5(4), 1369 5,500
1(1),951D
1(3),871A
Density (at 20 0 C)
0.975 0.975 1.340
Refractive index (at 20 0 C)
1.5490 1.5530 1.5500
Flash point (0C)
RTECS Number
47
UU1040000
52 128
UU1045000
R and S
1.3950
-6
1.5290
82
0.999 0.9022 1.355 1.19 1.22 1.253 1.07 0.940 0.886 0.8639 0.875 0.9651
1.5180 1.411 1.4210 1.4440
>110 20 72
1.4100
-4
1.4480 1.4350 1.4387 1.4256 1.4757
27 104 136 65
0.8602 0.8837
1.4444 1.4159
Merck
Beilstein
1(2),51A
1(1),963B
1(1),1151G 1(2),2495G
1(2),46A 1(3),242C
1(1),959C 1(2),734A
20,256
1(2),738D 1(2),853D
20(2),170 20,425
1(1),632D
11,9896
2(1),63
12,565
1(1),963A 9(1),65
DI1050000
9(4), 1885 2(4),792
l(2),1903L
1(2),1248C
1(1),697E
1(1),933A
1(1),644A
1(1),863A
l(l),1206A
1(1),736D
3(3),28
GQ5850000
1(1),721H
1(1),978C
1(1),642B
2(3),1263 2(3),843
MO7875000 LR0525000
1(1),719A
1(1),793A l(l),1206A
1(1),637C 1(1),736C
2(4), 1005 3(3),28
FG3325000
Fieser
1(3),248B
AK0875000 1(1),715A
1.070
FT-IR
1(1),1153I
1(2),2499B 0.934
FT-NMR
13,342
8,530
8,530
TABLE 21.
cont'd
Name
Maleate, monoester Methacrylate (see Methacrylates) Neodecanoate Nonate Octadecanoate (stearate) 9-Octadecenoate (oleate) Octanoate Pentafluoropropionate Pentanoate Pivalate Propionate Sebacate Succinate Tetradecanoate (myristate) Thioacetate Trichloroacetate Trifluoroacetate 1-Trifluoromethyl acetate Trithiocarbonate Undecanoate Versatate 21.3.
MoI. wt.
Boiling point (0C)
-CH=CHC(O)OH
19896-47-0
142.11
80/1
-C9H19 -(CH 2 ) 7 CH 3 -(CH 2 ) i 6 CH 3 -(CH2)7CH=CH(CH2)7CH3 -(CH 2 ) 6 CH 3 -CF2CF3 -(CH 2 ) 3 CH 3 -C(CH 3 ) 3 -CH 2 CH 3 -(CH 2 ) 8 C(O)OCH=CH 2 -CH 2 CH 2 C(O)OCH=CH 2 -(CH 2 ) I 2 CH 3 H 2 C=CHSC(O)CH 3 -CCl 3 -CF3 H 2 C=C(CF 3 )OC(O)CH 3 H 2 C=CHSC(S)SCH=CH 2 -(CH 2 ) 9 CH 3 -C(CH 3 ) 2 (CH 2 ) 5 CH 3
51000-52-3 6280-03-1 111-63-7 3896-58-0 818-44-0
198.31 184.28 310.51 308.49 170.25 190.08 128.17 128.17 100.12 254.33 170.16 254.41 102.15 189.43 140.06 154.09 134.24 212.33 198.31
216 133/50 181/2 145 79/7 58/560 132 112 95 142/3 50/3 152/3 115 38/5 42 86
109-53-5 37769-62-3 926-65-8 26256-87-1 1663-35-0 107-25-5 930-02-9 1623-05-8 766-94-9 6230-62-2 764-47-6
84.12 144.21 100.16 100.16 100.16 106.55 106.55 126.20 141.00 132.16 70.09 212.38 72.11 156.27 100.12 276.76 268.47 116.16 88.11 114.19 100.16 156.27 86.13 190.24 102.13 58.08 296.54 266.04 120.15 148.21 86.13
67 70/20 94 87 75 109 109 147 128 196 28 118 33 177 139 210 173/5 189 143 112 82 175 83 242 108 5 178/5 36 154 211 65
2235-00-9 1484-13-5 13162-05-5 3485-84-5 88-12-0 3195-78-6
139.20 193.25 71.08 173.17 1-11.14 99.10
128/21 154/3 210
36 65 -16 85
166
-36
5873-43-8 3377-92-2 105-38-4 10355-50-7 13416-90-5 5809-91-6 10340-63-3 7062-87-5 433-28-3 2247-91-8 930-35-8 49863-74-3
Melting point (0C)
32 36
-81
15
48 125/8 60/1
ETHERS H 2 C=CHOR
Allyl Butoxyethyl /i-Butyl 2-Butyl tert-Butyl 1 -Chloroethyl 2-Chloroethyl Cyclohexyl 1,2-Dichloroethyl Di(ethylene glycol) Divinyl Dodecyl Ethyl 2-Ethylhexyl Glycidyl Hexachlorodivinyl Hexadecyl 4-Hydroxybutyl 2-Hydroxyethyl Isoamyl Isobutyl Isooctyl Isopropyl 2-(2-Methoxyethoxy)ethyl 2-Methoxyethyl Methyl Octadecyl Perfluoropropyl Phenyl 1-Phenylethyl Propyl 21.4.
CAS Registry Number
Formula
-CH 2 CH=CH 2 -CH 2 CH 2 O(CH 2 ) 3 CH 3 -(CH 2 ) 3 CH 3 -CH(CH 2 CH 3 )CH 3 -C(CH 3 ) 3 -CHClCH 3 -CH 2 CH 2 Cl -C6Hn -CHClCH 2 Cl -CH 2 CH 2 OCH 2 CH 2 OH -CH=CH 2 -(CH 2 ) 11CH3 -CH 2 CH 3 -CH 2 CH(CH 2 CH 3 )(CH 2 ) 3 CH 3 -CH2CH(-O-)CH2 (Cl 2 C=CCl) 2 O -(CH 2 )I 5 CH 3 -(CH 2 ) 4 OH -CH 2 CH 2 OH -CH 2 CH 2 CH(CH 3 ) 2 -CH 2 CH(CH 3 ) 2 -(CH 2 ) 5 CH(CH 3 ) 2 -CH(CH 3 ) 2 -(CH 2 CH 2 O) 2 CH 3 -CH 2 CH 2 OCH 3 -CH3 -(CH 2 )I 7 CH 3 F 2 C=CFOCF 2 CF 2 CF 3 -C6H5 -CH(C 6 H 5 )CH 3 -CH 2 CH 2 CH 3
3917-15-5 4223-11-4 111-34-2 4181-12-8 926-02-3 110-75-8 110-75-8 2182-55-0 929-37-3 109-93-3 765-14-0 109-92-2 103-44-6 3678-15-7 822-28-6 17832-28-9 764-48-7
-92
-70 -109
-101 -12 -116 -85
16 -33
-112 -140 -83 -123 27
-50
^-SUBSTITUTED H 2 C=CHR
-Caprolactam -Carbazole -Formamide -Phthalimide -Pyrolidone -N-Methylacetamide
-NC 6 H10O -NCi2H8 -NHC(O)H -NC8H4O2 -NC4H6O -N(CH 3 )C(O)CH 3
Density (at 20 0 C)
Refractive index (at 20 0 C)
Flash point ( 0 C)
0.882 0.8689 0.904
1.4360 1.4291
0.8719
1.4256
0.866 0.9173
1.4050 1.4030
10 6
1.3170 1.3410
-31 2 > 110
RTECS Number
83
R and S
FT-NMR
FT-IR
Merck
Beilstein
Fieser
2(3),1290 2(4),1045
1(1),719B
>110 >110
2(3),532
UF8575000
0.87
1.203 1.212
0.8 0.866 0.774 0.762 1.048 1.048 0.891 1.197 0.986 0.773 0.817 0.754 0.816 1.006 1.654
1.4109 1.4220 1.410 1.4558 1.3980 1.4380 1.4380 1.4540 1.4558/17 1.4480 1.3989 1.4382 1.3770 1.4280 1.4326
0.939 0.982 0.7826 0.7645
1.4440 1.4360 1.4072 1.3950
0.7534 0.990 0.8967 0.7511/0 0.821 1.53
1.3840 1.4390 1.4072 1.3730/0 1.440
<20 46 -9 -17 16 16 35 83 -30 >110 -45 52 35
1(1),745G
l(l),1030C
1(1),697F
1(1),933B
KH7175000 KN5950000
1(1),219C
1(1),332B
1(1),213D
KN6300000 KN6300000
1(1),221C 1(1),221C
1(1),336A 1(1),336A
1(1),213B 1(1),213B
1(1),219B
1(1),332A
1(1),212B
19(3),1598
1(4),2387
KM5495500
KO0710000 KO0175000
2(4),466
l(3),704B
11,2139 11,2139
1(3), 1863 1(2),473 1(2),473 6(3), 18 1(4),2398 1(4),2398
1,433 1(3),1864 17(5),8,12
85 48
KM5495000
-13
KO1300000
1(1),219D
1(3),278A
1(3),1862
KO2300000 RG0300000
1(1),219A
1(3),277C
1(3), 1857 l(4),2057
1(4),2518 l(2),520
-32 17 -56 177
1.5226 1.3908
1.029
11,235
-26
1(3),1859
101
1.014
1.4940
102
1.040 0.9600
1.5120 1.4835
94 60
FE6350000
1(2),2425E
1(3),161C
UY6107000 AC6475000
1(1),923K 1(1),891K
1(1),1288A 1(1),1242C
2(3),3207 20(2),282 21(1),363 l(l),790B 1(1),759C
4(3),442
1,697
TABLE 21.
cont'd
Name 21.5.
Formula
CAS Registry Number
MoL wt.
Boiling point (0C)
108.10 178.23 164.21 136.16 192.26 178.23 164.21 152.20 122.13 184.21 152.20
100/0.5 131/17 117/15 76/5 146/15 124/15 78/5 70/4 91/15 45/2 110/18
SULFONATES H 2 C=CHSO 3 R
Ethylene sulfonic acid n-Amy\ ester n-Butyl ester Ethyl ester n-Hexyl ester Isoamyl ester Isobutyl ester Isopropyl ester Methyl ester Phenyl ester rc-Propyl ester
-H -(CH 2 ) 4 CH 3 -(CH 2 ) 3 CH 3 -CH 2 CH 3 -(CH 2 ) 5 CH 3 -(CH 2 ) 2 CH(CH 3 ) 2 -CH 2 CH(CH 3 ) 2 -CH(CH 3 ) 2 -CH3 -C6H5 -CH 2 CH 2 CH 3
1562-34-1
Melting point (0C)
Density (at 200C)
1.4003 1.087 1.122 1.183 1.050 1.082 1.190 1.132 1.248 1.165 1.156
Refractive index (at 200C)
1.4493 1.4412 1.4416 1.431 1.4430 1.4415 1.426 1.4321 1.4316 1.426 1.4368
Flash point (0C)
>110
RTECS Number
Rand S
1(2),2219A
FT-NMR
l(2),1605A
FT-IR
1(3),1437A
Merck
Beilstein
6(3),651
Fieser
13,241
I s o r e f r a c t i v e
a n d
l s o p y c n i c
S o l v e n t
P a i r s
H a n s - G . Elias Michigan Molecular Institute, 1910 West St. Andrews Rd., Midland, Ml 48640, USA
A.
INTRODUCTION
Isorefractive solvents are solvents having the same refractive index, and isopycnic solvents are those that have the same density. The determination of molar masses by non-colligative methods such as light scattering and ultracentrifugation will lead only to apparent molar masses if solvent mixtures are used whose components are not isorefractive. The observed increases or decreases of these apparent molar masses depend in sign and magnitude on both the preferential solvation and the refractive index increment
of solvent 2 in solvent 1 at a fixed polymer concentration. The effect disappears if isorefractive solvent pairs are used. A similar effect may be observed in ultracentrifugal experiments with non-isopycnic solvent pairs. To suppress these effects, isopycnic-isorefractive solvent pairs should be used. A table of isorefractive and isopycnic solvent pairs was prepared (for 25°C), starting with 392 commonly used solvents. A solvent pair was classified as isorefractive and isopycnic if the components had differences no greater than ±0.002 in refractive index and ± 0.015 g/ml in density. The miscibility of the components was not checked.
B. TABLE OF ISOREFRACTIVE AND ISOPYCNIC SOLVENT PAIRS Refractive index Solvent 1
Solvent 2
Acetone Ethyl formate
Ethanol Methyl acetate Propionitrile 2-Methylpentane n-Hexane 2,3-Dimethylbutane 3 -Methy lpentane n-Hexane 3 -Methy lpentane 3 -Methy lpentane 2-Chloropropane Butyraldehyde Butyronitrile n-Butyl ethyl ether 2-Methylhexane rc-Butyl ethyl ether Ethyl propionate Isobutyl formate 1 -Chloropropane f-Butanol Isobutyl formate 1 -Chloropropane rc-Heptane 3-Methylhexane
2,2-Dimethylbutane 2-Methylpentane
2,3 -Dimethy lbutane fl-Hexane Isopropyl acetate 2-Butanone Butyraldehyde n-Propyl ether 2,4-Dimethylpentane Acetaldehyde diethyl acetal n-Propyl acetate
Butyronitrile Ethyl propionate 2-Methylhexane
Density (g/ml)
1
2
1
2
1.357 1.358 1.359 1.366 1.369 1.369 1.369 1.372 1.372 1.372 1.375 1.377 1.378 1.379 1.379 1.379 1.382 1.382 1.382 1.382 1.382 1.382 1.382 1.382
1.359 1.360 1.363 1.369 1.372 1.372 1.374 1.372 1.374 1.374 1.376 1.378 1.382 1.380 1.382 1.380 1.382 1.383 1.386 1.385 1.383 1.386 1.385 1.386
0.788 0.916 0.786 0.644 0.649 0.649 0.649 0.657 0.657 0.655 0.868 0.801 0.799 0.753 0.799 0.753 0.883 0.883 0.883 0.786 0.888 0.888 0.674 0.674
0.786 0.935 0.777 0.649 0.655 0.657 0.660 0.655 0.660 0.660 0.865 0.799 0.786 0.746 0.786 0.746 0.888 0.881 0.890 0.781 0.881 0.890 0.680 0.683
Refractive index Solvent 1
Solvent 2
n-Propanol
3-Methyl-2-butanone 2-Pentanone 1-Chloropropane s-Butyl acetate fl-Butylformate n-Propylamine 3-Methylhexane 2,3,3-Trimethylbutane 2,2,4-Trimethylpentane 2,3-Dimethylpentane 2,3,3-Trimethylbutane 2,4-Trimethylpentane 2,3 -Dimethy lpentane Butyl formate 2-Pentanone 3-Pentanone Diisopropylamine s-Butylamine 2,2,4-Trimethylpentane 2,3 -Dimethy lpentane Methyl butyrate /z-Dodecane Methyl butyrate w-Butyl acetate 2,3-Dimethylpentane 5-Butylamine 3-Pentanone 4-Methyl-2-pentanone 2-Methyl-1 -propanol 4-Methyl-2-pentanone 2-Methyl-1 -propanol rc-Butyl acetate 2-Chlorobutane 2-Chlorobutane 2-Chlorobutane 2-Methyl-1 -propanol Valeronitrile 2-Butanol 2-Hexanone 1-Butanol Methacrylonitrile 3-Methyl-2-pentanone Valeronitrile 2-Butanol 2-Hexanone Butanol Methacrylonitrile 3-Methyl-2-pentanone 2,2,5-Trimethylhexane Butanol Methacrylonitrile 3-Methyl-2-pentanone 2,4-Dimethyl-3-pentanone Butanol
Isobutyl formate
Diethylamine n-Heptane
3-Methylhexane
1-Chloropropane 3-Methyl-2-butanone ft-Propylamine 2,3,3-Trimethylbutane 5-Butyl acetate /z-Butyl formate Isobutyl acetate 2,2,4-Trimethylpentane Diisopropylamine 2-Pentanone
3-Pentanone Methyl butyrate 2-Chloro-2-methyl-propane n-Butyl acetate 4-Methyl-2-pentanone
2-Methyl-1 -propanol
Octane 2-Butanol
2-Hexanone
Density (g/ml)
1
2
1
2
1.383 1.383 1.383 1.383 1.383 1.384 1.385 1.385 1.385 1.385 1.386 1.386 1.386 1.386 1.386 1.386 1.386 1.386 1.387 1.387 1.387 1.387 1.388 1.388 1.389 1.390 1.390 1.390 1.390 1.390 1.390 1.391 1.391 1.392 1.392 1.394 1.394 1.394 1.394 1.394 1.394 1.394 1.394 1.394 1.394 1.394 1.394 1.394 1.395 1.395 1.395 1.395 1.395 1.395
1.386 1.387 1.386 1.387 1.387 1.386 1.386 1.387 1.389 1.389 1.387 1.389 1.389 1.387 1.390 1.390 1.390 1.390 1.389 1.389 1.391 1.391 1.391 1.392 1.389 1.390 1.390 1.394 1.394 1.394 1.394 1.392 1.395 1.395 1.395 1.394 1.395 1.395 1.395 1.397 1.398 1.398 1.395 1.395 1.395 1.397 1.398 1.398 1.397 1.397 1.398 1.398 1.399 1.397
0.806 0.806 0.881 0.881 0.881 0.702 0.680 0.680 0.680 0.680 0.683 0.683 0.683 0.890 0.807 0.807 0.713 0.713 0.686 0.686 0.868 0.888 0.871 0.871 0.687 0.712 0.802 0.802 0.802 0.810 0.810 0.875 0.875 0.872 0.877 0.797 0.797 0.797 0.797 0.797 0.797 0.797 0.798 0.798 0.798 0.798 0.798 0.798 0.698 0.803 0.803 0.803 0.803 0.810
0.807 0.804 0.890 0.868 0.888 0.713 0.683 0.686 0.687 0.691 0.686 0.687 0.691 0.888 0.802 0.810 0.712 0.720 0.683 0.691 0.875 0.775 0.875 0.877 0.691 0.720 0.810 0.797 0.798 0.797 0.798 0.877 0.868 0.868 0.868 0.798 0.795 0.803 0.810 0.812 0.795 0.808 0.795 0.803 0.810 0.812 0.795 0.808 0.703 0.812 0.795 0.808 0.805 0.812
Refractive index Solvent 1
Valeronitrile
2-Hexanone Isobutylamine 2-Chlorobutane Butyric acid «-Butanol 1 -Chloro-2-methyl-propane
2,5,5-Trimethylhexane Methyl methacrylate Methacrylonitrile 3-Methyl-2-pentanone Triethylamine
n-Butylamine Isobutyl n-butyrate
1-Nitropropane Amyl acetate n-Dodecane 1-Chlorobutane 2,2,3-Trimethylpentane Isovaleric acid Dipropylamine n-Nonane Isoamylacetate 2-Pentanol
2-Methoxybutanol
3-Methyl-l-butanol
Solvent 2 Methacrylonitrile 3-Methyl-2-pentanone 2,4-Dimethyl-3-pentanone Methacrylonitrile 3-Methyl-2-pentanone 2,4-Dimethyl-3-pentanone 3 -Methy 1-2-pentanone Triethylamine fl-Butylamine Isobutyl /i-butyrate 2-Methoxyethanol 3-Methyl-2-pentanone 2,4-Dimethyl-3-pentanone Isobutyl n-Butyrate Amyl acetate 1-Chlorobutane 2,2,3-Trimethylpentane 3-Methyl-2-pentanone 2,4-Dimethyl-3-pentanone 2-Methyl-2-butanol 2,4-Dimethyl-4-pentanone n-Butylamine 2,2,3-Trimethylpentane n-Nonane Dipropylamine rc-Dodecane n-Amyl acetate Isoamyl acetate 1-Chlorobutane Propionic anhydride 1-Chlorobutane Tetrahydrofuran Dipropylamine Cyclopentane Tetrahydrofuran n-Nonane 2-Ethoxyethanol Valeric acid Cyclopentane Methylcyclopentane 2,2,4-Trimethyl-1 -pentene Tributyl borate 2-Methyl-l-butanol 3-Methyl-1 -butanol 4-Heptanone 2-Heptanone 3-Methyl-l-butanol Capronitrile 4-Heptanone 2-Heptanone Pentanol 3-Methyl-2-butanol Capronitrile 4-Heptanone
Density (g/ml)
1
2
1
2
1.395 1.395 1.395 1.395 1.395 1.395 1.395 1.395 1.395 1.395 1.396 1.397 1.397 1.397 1.397 1.397 1.397 1.398 1.398 1.398 1.398 1.399 1.399 1.399 1.399 1.399 1.399 1.399 1.399 1.399 1.400 1.400 1.400 1.400 1.400 1.401 1.402 1.402 1.403 1.403 1.403 1.403 1.404 1.404 1.404 1.404 1.404 1.404 1.404 1.404 1.404 1.404 1.404 1.404
1.398 1.398 1.399 1.398 1.398 1.399 1.398 1.399 1.399 1.399 1.400 1.398 1.399 1.399 1.400 1.400 1.401 1.398 1.399 1.404 1.399 1.399 1.401 1.401 1.401 1.400 1.400 1.403 1.401 1.400 1.400 1.404 1.403 1.404 1.404 1.403 1.405 1.406 1.404 1.407 1.407 1.407 1.404 1.404 1.405 1.406 1.404 1.405 1.405 1.406 1.408 1.408 1.405 1.405
0.810 0.810 0.810 0.795 0.795 0.795 0.810 0.729 0.729 0.868 0.955 0.812 0.812 0.872 0.872 0.872 0.703 0.795 0.795 0.795 0.808 0.723 0.723 0.723 0.723 0.736 0.860 0.860 8.860 0.995 0.871 0.871 0.746 0.746 0.871 0.712 0.923 0.923 0.736 0.736 0.714 0.868 0.804 0.804 0.804 0.804 0.805 0.805 0.805 0.805 0.805 0.805 0.805 0.805
0.795 0.808 0.805 0.795 0.808 0.805 0.808 0.723 0.736 0.860 0.960 0.808 0.805 0.860 0.871 0.881 0.712 0.808 0.805 0.805 0.805 0.736 0.712 0.714 0.736 0.746 0.871 0.868 0.875 1.007 0.881 0.885 0.736 0.740 0.885 0.714 0.926 0.936 0.740 0.744 0.712 0.854 0.805 0.805 0.813 0.811 0.805 0.801 0.813 0.811 0.810 0.815 0.801 0.813
Refractive index Solvent 1
Cyclopentane Capronitrile
4-Heptanone
2-Ethoxyethanol 2-Heptanone
2-Pentanol
2,2,4-Trimethyl-1 -pentene Tributyl borate 1-Pentanol
3-Methyl-2-butanol
4-Methyl-2-pentanol
3-Isopropyl-2-pentanone 2-Methyl-l-butanol Isoamyl isovalerate Amyl ether 2,4-Dimethyldioxane
Solvent 2 2-Heptanone Pentanol 3-Methyl-2-butanol Methylcyclopentane 4-Heptanone 2-Heptanone 2-Pentanol 1-Pentanol 3-Methyl-2-butanol 4-Methyl-2-pentanol 3-Isopropyl-2-pentanone 2-Methyl-l-butanol 2-Heptanone 1-Pentanol 3-Methyl-2-butanol 4-Methyl-2-pentanol 3-Isopropyl-2-pentanone 2-Methyl-1 -butanol Valeric acid 1-Pentanol 3-Methyl-2-butanol 4-Methyl-2-pentanol 3-Isopropyl-2-pentanone 2-Ethoxyethanol 2-Methyl-1 -butanol Amyl ether 1-Pentanol 3-Methyl-2-butanol 4-Methyl-2-pentanol 3-Isopropyl-2-pentanone 2-Methyl-l-butanol Amyl ether n-Decane Isoamyl isovalerate Allyl alcohol 3-Methyl-2-butanol 4-Methyl-2-pentanol 3-Isopropyl-2-pentanone 2-Methyl-1 -butanol Amyl ether 4-Methyl-2-pentanol 3-Isopropyl-2-pentanone 2-Methyl-1 -butanol Amyl ether 3-Isopropyl-2-pentanone 2-Methyl-l-butanol Amyl ether 2-Methyl-1 -butanol Amyl ether Amyl ether Allyl alcohol 2-Octanone Allyl chloride Caproic acid
Density (g/ml)
1
2
1
2
1.404 1.404 1.404 1.404 1.405 1.405 1.405 1.405 1.405 1.405 1.405 1.405 1.405 1.405 1.405 1.405 1.405 1.405 1.405 1.406 1.406 1.406 1.406 1.406 1.406 1.406 1.407 1.407 1.407 1.407 1.407 1.407 1.407 1.407 1.407 1.408 1.408 1.408 1.408 1.408 1.408 1.408 1.408 1.408 1.409 1.409 1.409 1.409 1.409 1.409 1.410 1.410 1.412 1.412
1.406 1.408 1.408 1.407 1.405 1.406 1.407 1.408 1.408 1.409 1.409 1.409 1.406 1.408 1.408 1.409 1.409 1.409 1.406 1.408 1.408 1.409 1.409 1.409 1.409 1.410 1.408 1.408 1.409 1.409 1.409 1.410 1.409 1.410 1.411 1.408 1.409 1.409 1.409 1.410 1.409 1.409 1.409 1.410 1.409 1.409 1.410 1.409 1.410 1.410 1.411 1.414 1.413 1.415
0.805 0.805 0.805 0.740 0.801 0.801 0.801 0.801 0.801 0.801 0.801 0.801 0.813 0.813 0.813 0.813 0.813 0.813 0.926 0.811 0.811 0.811 0.811 0.811 0.811 0.811 0.804 0.804 0.804 0.804 0.804 0.804 0.712 0.854 0.854 0.810 0.810 0.810 0.810 0.810 0.815 0.815 0.815 0.815 0.802 0.802 0.802 0.808 0.808 0.815 0.853 0.799 0.935 0.935
0.811 0.810 0.815 0.744 0.813 0.811 0.804 0.810 0.815 0.802 0.808 0.815 0.811 0.810 0.815 0.802 0.808 0.815 0.936 0.810 0.802 0.802 0.808 0.815 0.815 0.799 0.810 0.815 0.802 0.808 0.815 0.799 0.726 0.853 0.847 0.815 0.802 0.808 0.815 0.799 0.802 0.808 0.815 0.799 0.808 0.815 0.799 0.815 0.799 0.799 0.847 0.814 0.932 0.923
Refractive index Solvent 1
Solvent 2
Diethyl malonate Allyl chloride 2-Octanone
Ethyl cyanoacetate Capric acid 3-Methyl-2-heptanone 1-Hexanol 2-Pentanol Caprylnitrile 2-Heptanol 3-Methyl-2-heptanone 2-Pentanol 1-Hexanol 2-Pentanol Caprylonitrile 2-Heptanol 2-Pentanol Caprylonitrile 2-Heptanol 3-Methyl-2-pentanol 2-Ethyl-l-butanol 2-Heptanol 3-Methyl-2-pentanol 2-Ethyl-l-butanol Allylamine 2-Heptanol 3-Methyl-2-pentanol 1-Heptanol 2-Methyl-2-pentanol 2-Ethyl-l-butanol 1-Heptanol 3-Isopropyl-2-heptanone Methylcyclohexane 2-Ethyl-l-butanol 1-Heptanol 3-Isopropyl-2-heptanone 1-Heptanol 3-Isopropyl-2-heptanone Cyclohexane 3-Isopropyl-2-heptanone 1-Octanol 3-Methyl-2-pentanone Caprylic acid Af-Methylalaninenitrile 3-Methy 1-2-pentanol 1 -Chloro-2-ethylhexane 2-Methyl-7-ethyl-4-undecanone Chloro-f-butanol 1,3-Propanediol Diethyl maleate A^-methylmorpholine 2-Methyl-7-ethyl-4-nonanol 6-Ethyl-2-nonanol 5-Ethyl-2-nonanol 1,3-Propanediol Diethyl maleate Dibutyl sebacate
3-Octanone 3-Methyl-2-heptanone
1-Hexanol
2-Pentanol
Dibutylamine Caprylonitrile
2-Heptanol
Allylamine 3-Methyl-2-pentanol
2-Ethyl-l-butanol Methylcyclohexane 1-Heptanol 3-Isopropyl-2-heptanone 3-Chloro-2-methyl-1 -propene Caprylic acid 1-Octanol 1-Chlorooctane 2-Methyl-7-ethylnonane Butyrolactone
4-n-Propyl-5-ethyldioxane 2-Methyl-7-ethyl-4-undecanone 6-Ethyl-3-octanol Chloro-f-butanol 7V-Methylmorpholine
Density (g/ml)
1
2
1
2
1.412 1.413 1.414 1.414 1.414 1.414 1.414 1.414 1.414 1.415 1.415 1.415 1.415 1.416 1.416 1.416 1.416 1.416 1.416 1.416 1.416 1.416 1.418 1.418 1.418 1.418 1.418 1.418 1.418 1.419 1.420 1.420 1.420 1.420 1.420 1.421 1.422 1.423 1.423 1.425 1.426 1.427 1.428 1.433 1.434 1.434 1.434 1.435 1.435 1.435 1.435 1.436 1.436 1.436
1.415 1.415 1.415 1.416 1.416 1.418 1.418 1.415 1.416 1.416 1.416 1.418 1.418 1.416 1.418 1.418 1.420 1.420 1.418 1.418 1.420 1.419 1.418 1.420 1.422 1.420 1.420 1.422 1.423 1.421 1.420 1.422 1.423 1.420 1.423 1.424 1.423 1.427 1.427 1.426 1.429 1.427 1.430 1.435 1.436 1.438 1.438 1.436 1.438 1.438 1.438 1.438 1.438 1.440
1.051 0.932 0.814 0.814 0.814 0.814 0.814 0.830 0.830 0.818 0.818 0.818 0.818 0.814 0.814 0.814 0.814 0.814 0.826 0.816 0.826 0.756 0.810 0.810 0.810 0.818 0.818 0.818 0.818 0.758 0.823 0.823 0.815 0.829 0.829 0.765 0.818 0.815 0.815 0.917 0.905 0.821 0.867 0.830 1.051 1.051 1.051 0.927 0.832 0.832 0.832 1.059 1.059 0.924
1.056 0.923 0.818 0.814 0.826 0.810 0.818 0.818 0.826 0.814 0.826 0.810 0.818 0.826 0.810 0.818 0.823 0.829 0.818 0.818 0.829 0.758 0.818 0.823 0.818 0.823 0.829 0.818 0.815 0.765 0.829 0.818 0.815 0.818 0.815 0.774 0.815 0.821 0.824 0.905 0.895 0.824 0.872 0.832 1.059 1.049 1.064 0.924 0.829 0.836 0.830 1.049 1.064 0.932
Refractive index Solvent 1
Solvent 2
2-Methyl-7-ethyl-4-nonanol
5-Ethyl-2-nonanol 6-Ethyl-3-octanol Butanethiol 7-Methyl-7-ethyl-4-undecanol Ethyl sulfide 6-Ethyl-3-decanol 6-Ethyl-3-octanol Butanethiol 2-Methyl-7-ethyl-4-undecanol Ethyl sulfide 6-Ethyl-3-decanol Diethyl maleate 2-Methy 1-7-ethy 1-1 -undecanol Ethyl sulfide Butanethiol 6-Ethyl-3-decanol 6-Ethyl-3-decanol 2-Methyl-7-ethyl-4-undecanol Ethyl sulfide Mesityl oxide 2-Methyl-7-ethyl-4-undecanol Ethyl sulfide Mesityl oxide Mesityl oxide Butyl stearate 1 -Chlorotetradecane Ethyl sulfide 2-Butyloctyl-3-aminopropyl ether Butyl stearate 1 -Chlorotetradecane 2-Butyloctyl-3-aminopropyl ether 1 -Chlorotetradecane 2-Butyloctyl-3-aminopropyl ether 2-Butyloctyl-3-aminopropyl ether 1,2-Dichloroethane trans-1,2-Dichloroethylene trans-1,2-Dichloroethylene 2-Butyloctyl-3-aminopropyl ether 1 -Chlorohexadecane Formamide Ethylene glycol diglycidyl ether 3-Lauroxy-1 -propylamine Ethylene glycol diglycidyl ether Cyclohexanone 1 - Amino-2-propanol Tetrahydrofurfuryl alcohol 2-Butylcyclohexanone 2-Propylcyclohexanone 4-Methylcyclohexanone 2,2 '-Dimethyl-2,2 '-dipropyldiethanolamine 4-Methylcyclohexanol 3-Methylcyclohexanol 2,2 '-Dimethyl-2,2 '-dipropyldiethanolamine 1,8-Cineole
5-Ethyl-2-nonanol
1,3-Propanediol Methyl salicylate
6-Ethyl-3-octanol Butanethiol
6-Ethyl-3-decanol
1-Chlorododecane (technical)
2-Methyl-7-ethyl-4-undecanol Mesityl oxide
Butyl stearate Ethyl sulfide 1,3-Butanediol sulfite 1,2-Dichloroethane 1 -Chlorotetradecane Diethylene glycol 2-Butyloctyl-3-aminopropyl ether Formamide 2-Methylmorpholine Dipropylene glycol monoethyl ether 1 - Amino-2-methyl-2-pentanol 3-Methyl-5-ethyl-2,4-heptanediol
2-Propylcyclohexanone
Density (g/ml)
1
2
1
2
1.438 1.438 1.438 1.438 1.438 1.438 1.438 1.438 1.438 1.438 1.438 1.438 1.438 1.438 1.438 1.438 1.440 1.440 1.440 1.440 1.441 1.441 1.441 1.441 1.441 1.441 1.442 1.442 1.442 1.442 1.442 1.442 1.442 1.442 1.444 1.444 1.444 1.445 1.445 1.445 1.445 1.446 1.446 1.446 1.446 1.446 1.449 1.452 1.452 1.452 1.452 1.452 1.452 1.452
1.438 1.438 1.440 1.442 1.442 1.441 1.438 1.440 1.442 1.442 1.441 1.438 1.442 1.442 1.442 1.441 1.441 1.442 1.442 1.442 1.442 1.442 1.442 1.442 1.442 1.445 1.442 1.446 1.442 1.445 1.446 1.445 1.446 1.446 1.444 1.444 1.444 1.446 1.448 1.446 1.447 1.447 1.447 1.448 1.448 1.450 1.453 1.452 1.454 1.456 1.454 1.455 1.456 1.456
0.829 0.829 0.829 0.829 0.829 0.829 0.830 0.830 0.830 0.830 0.830 1.049 0.836 0.836 0.836 0.836 0.837 0.837 0.837 0.837 0.838 0.838 0.838 0.862 0.862 0.862 0.829 0.829 0.850 0.850 0.850 0.850 0.854 0.831 1.231 1.231 1.231 0.857 0.857 1.128 1.128 0.842 1.129 0.951 0.951 1.043 1.050 0.922 0.922 0.922 0.923 0.923 0.923 0.923
0.830 0.836 0.837 0.829 0.831 0.838 0.836 0.837 0.829 0.831 0.838 1.064 0.829 0.831 0.837 0.838 0.838 0.829 0.831 0.850 0.829 0.831 0.850 0.850 0.854 0.858 0.831 0.842 0.854 0.858 0.842 0.858 0.842 0.842 1.245 1.257 1.257 0.842 0.859 1.129 1.134 0.840 1.134 0.943 0.961 1.050 1.047 0.923 0.908 0.922 0.908 0.913 0.922 0.921
Refractive index Solvent 1
Solvent 2
4-Methylcyclohexanol 3 -Methy Icy clohexanol Cyclohexylamine 1-Chloroeicosane (technical) Oleic acid
2,2 '-Dimethyl-2,2 '-dipropyldiethanolamine 2,2 '-Dimethyl-2,2 '-dipropyldiethanolamine 1-Chloroeicosane Oleic acid 2-((3-Ethyl)butylcyclohexanone 2-Butylcyclohexanol 2-(P-Ethyl)hexylcyclohexanone 1 - Aminopropanol Af-(n-Butyl)diethanolamine 4,5-Dichloro-1,3-dioxolane-2-one 2,4-(bis)oc-Phenylethyl)phenylmethyl ether 2-((3-Ethyl)hexylcyclohexanone Cyclohexanol 2-(p-Ethyl)hexylcyclohexanone 2-Ethylcyclohexanol Fluorobenzene Af-(2-Hydroxyethyl)-2-hydroxybutyl amine 1-oc-Pinene mzns-Decahydronaphthalene p-Fluorotoluene frans-Decahydronaphthalene o-Fluorotoluene AT-(2-Hydroxyethyl)-2-hydropropylamine 2-Allyloxy-2-hydroxypropylamine Di(2-Hydroxybutyl)ethanolamine Di(2-Hydroxypropyl)ethanolamine Di(2-Hydroxybutyl)ethanolamine 1 -Methoxy-1 -butene-3-yn n-Dodecyl-4-r-butylphenyl ether n-Dodecylphenyl ether ft-Dodecyl-4-methylphenyl ether rc-Dodecylphenyl ether n-Dodecyl-4-methylphenyl ether n-Dodecylphenyl ether Dioctylbenzene (90% /?; 10% m) p-Cymene Isopropylbenzene f-Butylbenzene (80% p, 15% m, 5% o) n-Propylbenzene 5"-Butylbenzene Hexyl-m-xylene f-Butylbenzene Isopropylethylbenzene (35% p, 60% m, 5% o) Isopropylbenzene f-Butylcumene (80% /?, 15% m, 5% o) n-Propylbenzene 5-Butylbenzene Hexyl-m-xylene (mainly 1,3,5) f-Butylbenzene Isopropylethylbenzene (35% p, 60% m, 5% o) J-Butyltoluene Hexylcumene (90% /7, 5% m, 5% o) Octyltoluene (96% /7, 2% m, 2% o) f-Butylcumene (80% p, 15% m, 5% o)
1,1 ',2,2 '-Tetramethyldiethanolamine Carbon tetrachloride 2-((3-Ethyl)butylcyclohexanone N-(n-Butyl)diethanolamine 2-Butylcyclohexanol N- (3-Oxypropylmorpholine Fluorobenzene D-a-Pinene m-Fluorotoluene 1-oc-Pinene /7-Fluorotoluene Ar-(2-Hydroxyethyl)-2-hydrobutylamine
2-Allyloxy-2-hydroxypropylamine c/s-Decahydronaphthalene
1 -Methoxy-1 -butene-3-yn rc-Dodecyl-4-r-butylphenyl ether Butylbenzene
p-Cymene
Isopropylbenzene
Density (g/ml)
1
2
1
2
1.454 1.455 1.456 1.459 1.459 1.459 1.459 1.459 1.459 1.459 1.461 1.461 1.461 1.462 1.462 1.462 1.463 1.464 1.464 1.465 1.465 1.467 1.467 1.467 1.467 1.467 1.469 1.479 1.479 1.479 1.479 1.480 1.480 1.482 1.487 1.487 1.487 1.487 1.487 1.487 1.487 1.487 1.487 1.488 1.488 1.488 1.488 1.488 1.488 1.488 1.488 1.488 1.488 1.489
1.456 1.456 1.459 1.459 1.461 1.462 1.463 1.459 1.461 1.461 1.462 1.463 1.465 1.463 1.463 1.463 1.467 1.465 1.468 1.467 1.468 1.468 1.468 1.469 1.469 1.469 1.469 1.480 1.482 1.482 1.483 1.482 1.483 1.482 1.487 1.488 1.489 1.490 1.490 1.490 1.490 1.490 1.491 1.489 1.490 1.490 1.490 1.490 1.490 1.491 1.491 1.492 1.492 1.490
0.908 0.913 0.862 0.872 0.887 0.887 0.887 0.973 0.973 1.584 0.892 0.892 0.965 0.898 0.898 1.013 1.020 0.855 0.855 0.994 0.855 0.994 1.027 1.027 1.027 1.027 1.017 0.893 0.893 0.893 0.893 0.902 0.902 0.881 0.856 0.856 0.856 0.856 0.856 0.856 0.856 0.856 0.856 0.853 0.853 0.853 0.853 0.853 0.853 0.853 0.853 0.853 0.853 0.857
0.922 0.922 0.872 0.887 0.892 0.898 0.892 0.965 0.965 1.591 0.898 0.892 0.968 0.892 0.908 1.020 1.027 0.855 0.867 0.995 0.867 0.995 1.042 1.017 1.018 1.042 1.018 0.902 0.881 0.891 0.889 0.891 0.889 0.891 0.856 0.853 0.857 0.856 0.856 0.856 0.860 0.862 0.856 0.857 0.856 0.858 0.858 0.860 0.862 0.856 0.858 0.863 0.866 0.856
Refractive index Solvent 1
/-Butylcumene (80% /?, 15% m, 5% o)
n-Propylbenzene
s-Butylbenzene
Solvent 2 n-Propylbenzene 5-Butylbenzene Hexyl-m-xylene (mainly 1,3,5) f-Butylbenzene Isopropylethylbenzene (35% p, 60% m, 5% o) f-Butylbenzene (80% p, 15% m, 5% o) w-Propylbenzene s-Butylbenzene Hexyl-m-xylene (mainly 1,3,5) f-Butylbenzene Isopropylethylbenzene (35% /?, 60% m, 5% o) f-Butyltoluene (80% p, 15% m, 5% o) Hexylcumene (90% /7, 5% m, 5% ) Octyltoluene (96% p, 2% m, 2% o) Octylcumene (90% /7, 4% m, 6% 0) Dihexylbenzene /7-Xylene 1,3-Diethylbenzene £-Butyl-m-xylene (mainly 1,3,5) Ethylbenzene Octylethylbenzene (80-90% p, 10% m) Isopropyl-m-xylene (mainly 1,3,5) Toluene s-Butylbenzene Hexyl-m-xylene (mainly 1,3,5) f-Butylbenzene Isopropylethylbenzene (35% p, 60% m, 5% o) f-Butyltoluene (80% p, 15% m, 5% p) Hexylcumene (90% p, 5% m, 5% o) Octyltoluene (96% /7, 2% m 2% 0) Octylcumene (90% p, 4% m 6% 0) Dihexylbenzene p-Xylene 1,3-Diethylbenzene f-Butyl-m-xylene (mainly 1,3,5) Ethylbenzene Octylethylbenzene (80-90% p, 10% m) Isopropyl-m-xylene (mainly 1,3,5) Toluene Hexyl-m-xylene (mainly 1,3,5) f-Butylbenzene Isopropylethylbenzene (35% /7, 60% m, 5% 0) f-Butyltoluene (80% /7, 15% m, 5% 0) Hexylcumene (90% p, 5% m, 5% 0) Octyltoluene (96% /?, 2% m, 2% 0) Octylcumene (90% p, 4% m, 6% 0) Dihexylbenzene /7-Xylene 1,3 -Diethy lbenzene f-Butyl-m-xylene (mainly 1,3,5) Ethylbenzene Octylethylbenzene (80-90% p, 10% m)
Density (g/ml)
1
2
1
2
1.489 1.489 1.489 1.489
1.490 1.490 1.490 1.490
0.857 0.857 0.857 0.857
0.858 0.858 0.860 0.862
1.489 1.489 1.490 1.490 1.490 1.490
1.491 1.491 1.490 1.490 1.490 1.490
0.857 0.857 0.856 0.856 0.856 0.856
0.856 0.858 0.858 0.858 0.860 0.862
1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490
1.491 1.491 1.492 1.492 1.492 1.492 1.493 1.493 1.493 1.493 1.493 1.494 1.494 1.490 1.490 1.490 1.491 1.491 1.492 1.492 1.492 1.492 1.493 1.493 1.493 1.493 1.493 1.494 1.494 1.490 1.490 1.491 1.491 1.492 1.492 1.492 1.492 1.493 1.493 1.493 1.493 1.493
0.856 0.856 0.856 0.856 0.856 0.856 0.856 0.856 0.856 0.856 0.856 0.856 0.856 0.858 0.858 0.858 0.858 0.858 0.858 0.858 0.858 0.858 0.858 0.858 0.858 0.858 0.858 0.858 0.858 0.858 0.858 0.858 0.858 0.858 0.858 0.858 0.858 0.858 0.858 0.858 0.858 0.858
0.856 0.858 0.863 0.866 0.869 0.870 0.857 0.860 0.862 0.863 0.866 0.860 0.862 0.858 0.860 0.862 0.856 0.858 0.863 0.866 0.869 0.870 0.857 0.860 0.862 0.863 0.866 0.860 0.862 0.860 0.862 0.856 0.858 0.863 0.866 0.869 0.870 0.857 0.860 0.862 0.863 0.866
Refractive index Solvent 1
Solvent 2
Isopropyl-m-xylene (mainly 1,3,5) Toluene f-Butylbenzene Hexyl-m-xylene (mainly 1,3,5) Isopropylethylbenzene (35% /?, 60% m, 5% o) f-Butyltoluene (80% p, 15% m, 5% o) Hexylcumene (90% /?, 5% m, 5% o) Octyltoluene (96% /?, 2% m, 2% o) Octylcumene (90% /?, 4% m, 6% 0) Dihexylbenzene p-Xylene 1,3-Diethylbenzene f-Butyl-m-xylene (mainly 1,3,5) Ethylbenzene Octylethylbenzene (80-90% /?, 10% m) Isopropyl-m-xylene (mainly 1,3,5) Toluene Isopropylethylbenzene (35% p, 60% m, 5% o) f-Butylbenzene f-Butyltoluene (80% /?, 15% m, 5% ) Hexylcumene (90% /?, 5% m, 5% o) Octyltoluene (96% /?, 2% m, 2% 0) Octylcumene (90% p, 4% m, 6% 0) Dihexylbenzene p-Xylene 1,3-Diethylbenzene f-Butyl-m-xylene (mainly 1,3,5) Ethylbenzene Octylethylbenzene (80-90% /?, 10% m) Isopropyl-m-xylene (mainly 1,3,5) Toluene Isopropylethylbenzene (35% /?, 60% m) Hexylcumene (90% /?, 5% m, 5% o) Octyltoluene (96% /?, 2% m, 2% o) Octylcumene (90% /?, 4% m, 6% o) Dihexylbenzene /7-Xylene 1,3-Diethylbenzene f-Butyl-ra-xylene (mainly 1,3,5) Ethylbenzene Octylethylbenzene (80-90% /?, 10% m) Isopropyl-m-xylene (mainly 1,3,5) Toluene f-Butylethylbenzene (70% p, 25% m, 5% o) m-Xylene Hexylethylbenzene Hexylcumene (90% /?, 5% m, 5% o) f-Butyltoluene (85% p, 10% m) Octyltoluene (96% /?, 2% m, 2% o) Octylcumene (90% p, 4% m, 6% t?) Dihexylbenzene p-Xylene 1,3-Diethylbenzene r-Butyl-w-xylene (mainly 1,3,5) Ethylbenzene Octylethylbenzene (80-90% /?, 10% m) Isopropyl-m-xylene (mainly 1,3,5) Toluene
Density (g/ml)
1
2
1
2
1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.490 1.491 1.491 1.491 1.491 1.491 1.491 1.491 1.491 1.491 1.491 1.491 1.491 1.491 1.491 1.491 1.491 1.491 1.491 1.491 1.491 1.491 1.491 1.491 1.491 1.491
1.494 1.494 1.490 1.491 1.491 1.492 1.492 1.492 1.492 1.493 1.493 1.493 1.493 1.493 1.494 1.494 1.491 1.491 1.492 1.492 1.492 1.492 1.493 1.493 1.493 1.493 1.493 1.494 1.494 1.492 1.492 1.492 1.492 1.493 1.493 1.493 1.493 1.493 1.494 1.494 1.495 1.495 1.495 1.492 1.492 1.492 1.492 1.493 1.493 1.493 1.493 1.493 1.494 1.494
0.858 0.858 0.860 0.860 0.860 0.860 0.860 0.860 0.860 0.860 0.860 0.860 0.860 0.860 0.860 0.860 0.862 0.862 0.862 0.862 0.862 0.862 0.862 0.862 0.862 0.862 0.862 0.862 0.862 0.858 0.858 0.858 0.858 0.858 0.858 0.858 0.858 0.858 0.858 0.858 0.858 0.858 0.858 0.858 0.856 0.856 0.856 0.856 0.856 0.856 0.856 0.856 0.856 0.856
0.860 0.862 0.862 0.856 0.858 0.863 0.866 0.869 0.870 0.857 0.860 0.862 0.863 0.866 0.860 0.862 0.856 0.858 0.863 0.866 0.869 0.870 0.857 0.860 0.862 0.863 0.866 0.860 0.862 0.863 0.866 0.869 0.870 0.857 0.860 0.862 0.863 0.866 0.860 0.862 0.854 0.860 0.868 0.863 0.866 0.869 0.870 0.857 0.860 0.862 0.863 0.866 0.860 0.862
Refractive index Solvent 1
1-Phenyl-l-hydroxyphenyl ether Hexylcumene (90% p, 5% m)
Dihexylbenzene (85% p, 10% m)
Octyltoluene (96% p, 2% m)
Octylcumene (90% /?, 4% m, 6% o)
Solvent 2 f-Butylethylbenzene (70% /?, 25% m, 5% 0) m-Xylene Hexylethylbenzene(70% p, 25% m, 5% o) 1,3-Dimorpholyl-2-propanol Octyltoluene (96% p, 2% m, 2% o) Octylcumene (90% /?, 4% m, 6% #) Dihexylbenzene p-Xylene 1,3-Diethylbenzene f-Butyl-m-xylene (mainly 1,3,5) Ethylbenzene Octylethylbenzene (80-90% /7, 10% m) Isopropyl-m-xylene (mainly 1,3,5) Toluene f-Butylethylbenzene (70% p, 25% m, 5% o) m-Xylene Hexylethylbenzene (70% /?, 25% m, 5% o) 1,4-Diethylbenzene Isopropylbenzene Octylcumene (90% /?, 4% m, 6% 0) /7-Xylene 1,3-Diethylbenzene f-Butyl-m-xylene (mainly 1,3,5) Ethylbenzene Octylethylbenzene (80-90% p, 10% m) Isopropyl-m-xylene (mainly 1,3,5) Toluene m-Xylene Hexylethylbenzene (70% /?, 25% m, 5% o) 1,4-Diethylbenzene Isopropylbenzene Octylcumene (90% p, 4% m, 6% o) Dihexylbenzene (85% p, 10% m, 5% o) /7-Xylene f-Butyl-m-xylene (mainly 1,3,5) Ethylbenzene Octylethylbenzene (80-90% /7, 10% m) Isopropyl-m-xylene (mainly 1,3,5) Toluene r-Butylethylbenzene (70% /?, 25% m, 5% o) m-Xylene Hexylethylbenzene (70% /?, 25% m, 5% o) 1,4-Diethylbenzene Isopropylbenzene p-Xylene 1,3-Diethylbenzene r-Butyl-m-xylene (mainly 1,3,5) Ethylbenzene Octylethylbenzene (80-90% p, 10% m) Isopropyl-m-xylene (mainly 1,3,5) Toluene /-Butylethylbenzene (70% /?, 25% m, 5% o) m-Xylene Hexylethylbenzene (70% /7, 25% m, 5% o)
Density (g/ml)
1
2
1
2
1.491 1.491 1.491 1.491 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492 1.492
1.495 1.495 1.495 1.493 1.492 1.492 1.492 1.493 1.493 1.493 1.493 1.493 1.494 1.494 1.495 1.495 1.495 1.496 1.498 1.492 1.493 1.493 1.493 1.493 1.493 1.494 1.494 1.495 1.495 1.496 1.498 1.492 1.492 1.493 1.493 1.493 1.493 1.494 1.494 1.495 1.495 1.495 1.496 1.498 1.493 1.493 1.493 1.493 1.493 1.494 1.494 1.495 1.495 1.495
0.856 0.856 0.856 1.081 0.863 0.863 0.863 0.863 0.863 0.863 0.863 0.863 0.863 0.863 0.863 0.863 0.863 0.863 0.863 0.870 0.870 0.870 0.870 0.870 0.870 0.870 0.870 0.870 0.870 0.870 0.870 0.866 0.866 0.866 0.866 0.866 0.866 0.866 0.866 0.866 0.866 0.866 0.866 0.866 0.866 0.866 0.866 0.866 0.866 0.866 0.866 0.866 0.866 0.866
0.854 0.860 0.868 1.094 0.866 0.869 0.870 0.857 0.860 0.862 0.863 0.866 0.860 0.862 0.854 0.860 0.868 0.858 0.857 0.869 0.857 0.860 0.862 0.863 0.866 0.860 0.862 0.860 0.868 0.858 0.857 0.869 0.870 0.857 0.862 0.863 0.866 0.860 0.862 0.854 0.860 0.868 0.858 0.857 0.857 0.860 0.862 0.863 0.866 0.860 0.862 0.854 0.860 0.868
Refractive index Solvent 1
Solvent 2
1,4-Diethylbenzene Isopropylbenzene 1,3-Diethylbenzene f-Butyl-m-xylene (mainly 1,3,5) Ethylbenzene Octylethylbenzene (80-90% /?, 10% m) Isopropyl-m-xylene (mainly 1,3,5) Toluene f-Butylethylbenzene (70% p, 25% m, 5% o) p-Xylene m-Xylene Hexylethylbenzene (70% p, 25% m, 5% o) 1,4-Diethylbenzene Mesitylene Isopropylbenzene f-Butyl-m-xylene (mainly 1,3,5) Ethylbenzene Octyltoluene (96% /?, 2% m, 2% o) Octylethylbenzene (80-90% p, 10% m) Isopropyl-m-xylene (mainly 1,3,5) Toluene f-Butylethylbenzene (70% /?, 25% m, 5% o) 1,3-Diethylbenzene m-Xylene 1,4-Diethylbenzene Mesitylene Hexyltoluene (70% p, 25% m, 5% o) Isopropylbenzene Ethylbenzene Octylethylbenzene (80-90% p, 10% m) Isopropyl-m-xylene (mainly 1,3,5) Toluene f-Butylethylbenzene (70% /?, 25% m, 5% o) m-Xylene Hexylethylbenzene (70% /?, 25% m, 5% o) f-Butyl-m-xylene (mainly 1,3,5) 1,4-Diethylbenzene Mesitylene Hexyltoluene (70% p, 25% m, 5% o) Isopropylbenzene Octylethylbenzene (80-90% /?, 10% m) Isopropyl-m-xylene (mainly 1,3,5) Toluene r-Butylethylbenzene (70% p, 25% m, 5% o) m-Xylene Hexylethylbenzene (70% /?, 25% m, 5% 0) 1,4-Diethylbenzene Ethylbenzene Mesitylene Hexyltoluene (70% /?, 25% m, 5% 0) Isopropylbenzene Isopropyl-m-xylene (mainly 1,3,5) Toluene f-Butylethylbenzene (70% /?, 25% m, 5% 0) m-Xylene Hexylethylbenzene (70% /?, 25% m, 5% 0) 1,4-Diethylbenzene Octylethylbenzene (80-90% p, 10% m) Mesitylene
Density (g/ml)
1
2
1
2
1.492 1.492 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.493
1.496 1.498 1.493 1.493 1.493 1.493 1.494 1.494 1.495 1.495 1.495 1.496 1.497 1.498 1.493 1.493 1.493 1.493 1.494 1.494 1.495 1.495 1.496 1.497 1.497 1.498 1.493 1.493 1.494 1.494 1.495 1.495 1.495 1.496 1.497 1.491 1.498 1.493 1.494 1.494 1.495 1.495 1.495 1.496 1.497 1.497 1.498 1.494 1.494 1.495 1.495 1.495 1.496 1.497
0.866 0.866 0.857 0.857 0.857 0.857 0.857 0.857 0.857 0.857 0.857 0.857 0.857 0.857 0.860 0.860 0.860 0.860 0.860 0.860 0.860 0.860 0.860 0.860 0.860 0.860 0.862 0.862 0.862 0.862 0.862 0.862 0.862 0.862 0.862 0.862 0.862 0.863 0.863 0.863 0.863 0.863 0.863 0.863 0.863 0.863 0.863 0.866 0.866 0.866 0.866 0.866 0.866 0.866
0.858 0.857 0.860 0.862 0.863 0.866 0.860 0.862 0.854 0.860 0.868 0.858 0.861 0.857 0.862 0.863 0.866 0.866 0.860 0.862 0.854 0.860 0.858 0.861 0.870 0.860 0.863 0.866 0.860 0.862 0.854 0.860 0.868 0.858 0.861 0.870 0.857 0.866 0.860 0.862 0.854 0.860 0.868 0.858 0.861 0.870 0.857 0.860 0.862 0.854 0.860 0.868 0.858 0.861
Refractive index Solvent 1
Solvent 2
Hexyltoluene (70% /?, 25% ra, 5% o) Isopropylbenzene Toluene Isopropyl-ra-xylene (mainly 1,3,5) f-Butylethylbenzene (70% /?, 25% m, 5% o) ra-Xylene Hexylethylbenzene (70% p, 25% m, 5% o) 1,4-Diethylbenzene Mesitylene Hexyltoluene (70% p, 25% m, 5% o) Benzene J-Butylethylbenzene (70% /?, 25% ra, 5% 6>) Toluene m-Xylene Hexylethylbenzene (70% p, 25% ra, 5% ) 1,4-Diethylbenzene Mesitylene Hexyltoluene (70% /?, 25% m, 5% o) Benzene wi-Xylene /-Butylethylbenzene (70% /?, 25% m) 1,4-Diethylbenzene Mesitylene Hexylethylbenzene (70% p, 25% m, 5% 6>) ra-Xylene 1,4-Diethylbenzene Mesitylene Benzene 1,4-Diethylbenzene Hexylethylbenzene (70% /?, 25% m) Mesitylene Hexyltoluene (70% /?, 25% m, 5% o) Benzene Mesitylene 1,4-Diethylbenzene Hexyltoluene (70% /?, 25% m, 5% o) Ethylbenzene Mesitylene Benzene Hexyltoluene (70% p, 25% m) 1,2-Diethylbenzene Mesitylene Benzene 1,2-Diethylbenzene 1,2-Diethylbenzene Mesitylene oXylene 1,2-Diethylbenzene Phenetole p-Picoline Pyridine Phenetole Cyclohexylethylbenzene Cyclohexylcumene (50% p, 20% m) (60% p, 20% m, 20% a) Chloro-f-butylbenzene Benzyl acetate Cyclohexylethylbenzene (60% p, 20% m) Cyclohexyltoluene Thiophene 2-Furfurol m-Cresol Benzyl alcohol Benzaldehyde ra-Cresol oToluidine ra-Toluidine
Density (g/ml)
1
2
1
2
1.493 1.493 1.494 1.494 1.494 1.494 1.494 1.494 1.494 1.494 1.494 1.494 1.494 1.494 1.494 1.494 1.494 1.495 1.495 1.495 1.495 1.495 1.495 1.495 1.495 1.495 1.495 1.495 1.496 1.496 1.497 1.497 1.497 1.498 1.498 1.498 1.501 1.504 1.505
1.497 1.498 1.494 1.495 1.495 1495 1496 1.497 1.497 1.498 1.495 1.495 1.495 1.496 1.497 1.491 1.498 1.495 1.496 1.497 1.495 1.496 1.497 1.498 1.496 1.497 1.497 1.498 1.497 1.498 1.497 1.498 1.501 1.498 1.501 1.501 1.503 1.505 1.507
0.866 0.866 0.860 0.860 0.860 0.860 0.860 0.860 0.860 0.860 0.862 0.862 0.862 0.862 0.862 0.862 0.862 0.854 0.854 0.854 0.860 0.860 0.860 0.860 0.868 0.868 0.868 0.868 0.858 0.858 0.861 0.870 0.870 0.874 0.874 0.874 0.867 0.953 0.961
0.870 0.857 0.862 0.854 0.860 0.868 0.858 0.861 0.870 0.874 0.854 0.860 0.868 0.858 0.861 0.870 0.874 0.860 0.858 0.861 0.868 0.858 0.861 0.874 0.858 0.861 0.870 0.874 0.861 0.870 0.870 0.874 0.876 0.874 0.876 0.876 0.876 0.961 0.978
1.516 1.518 1.520 1.524 1.538 1.542 1.566
1.520 1.521 1.523 1.526 1.542 1.544 1.570
0.917 1.051 0.923 1.057 1.041 1.037 0.985
0.923 1.039 0.923 1.059 1.037 1.041 0.994
R e f r a c t i v e
I n d i c e s
o f
C o m m o n
S o l v e n t s
H a n s - G . Elias Michigan Molecular Institute, 1910 West St. Andrews Rd., Midland, Ml 48640, USA
A.
INTRODUCTION
Solvents
Measurements which depend on the difference in refractive index between the polymer and the solvent will, in general, give greater accuracy as the refractive index increment between polymer and solvent is increased. The magnitude of the increment may be either positive or negative. Systems involving refractive index increments are those of light scattering and ultracentrifugation when either schlieren or interference optics is used. A table of commonly used solvents, arranged according to increasing refractive index, will be useful in practical work with many different polymers. Data at 25°C, D-line. B. TABLE OF REFRACTIVE INDICES OF COMMON SOLVENTS Solvents
Trifluoroacetic acid Trifluoroethanol Octafluoro-1 -pentanol Dodecafluoro-1 -heptanol Methanol Acetonitrile Ethyl ether Acetone Ethyl formate Ethanol Methyl acetate Propionitrile 2,2-Dimethylbutane Isopropyl ether 2-Methylpentane Formic acid Ethyl acetate Acetic acid Propionaldehyde n-Hexane 2,3-Dimethylbutane 3-Methylpentane 2-Propanol Isopropyl acetate Propyl formate
Refractive index 1.283 1.290 1.316 1.316 1.326 1.342 1.352 1.357 1.358 1.359 1.360 1.363 1.366 1.367 1.369 1.369 1.370 1.370 1.371 1.372 1.372 1.374 1.375 1.375 1.375
2-Chloropropane 2-Butanone Butyraldehyde 2,4-Dimethylpentane Propyl ether Acetaldehyde diethyl acetal Butyl ethyl ether Nitromethane Trifluoropropanol 2-Methylhexane Butyronitrile Propyl acetate Ethyl propionate 2-Methyl-2-propanol Propanol Isobutyl formate Diethyl carbonate Heptane /-Butanol Propionic acid 3-Methylhexane Propylamine 3-Methyl-2-butanone 1-Chloropropane 2,2,3-Trimethylbutane 5-Butyl acetate Butyl formate Isobutyl acetate 2,2,4-Trimethylpentane 2,3-Dimethylpentane Acetic anhydride Diisopropylamine 2-Butylamine 2-Pentanone 3-Pentanone Nitroethane Methyl n-butyrate Butyl acetate 2-Nitropropane 4-Methyl-2-propanone 2-Methyl-1 -propanol Octane
Refractive index 1.376 1.377 1.378 1.379 1.379 1.379 1.380 1.380 1.381 1.382 1.382 1.382 1.382 1.383 1.383 1.383 1.383 1.385 1.385 1.385 1.386 1.386 1.386 1.386 1.387 1.387 1.387 1.388 1.389 1.389 1.389 1.390 1.390 1.390 1.390 1.390 1.391 1.392 1.392 1.394 1.394 1.395
Solvents Isobutylamine Valeronitrile 2-Butanol 2-Hexanone 2-Chlorobutane Butyric acid 2,2,5-Trimethylhexane Dibutyl ether Butanol Acrolein 1 -Chloro-2-methylpropane Methacrylonitrile 3-Methyl-2-pentanone Triethylamine Butylamine 2,4-Dimethyl-3-pentanone Isobutyl ft-butyrate 1-Nitropropane Dodecane Amyl acetate 1-Chlorobutane 2-Methoxyethanol Propionic anhydride 2,2,3-Trimethylpentane 1-Chlorobutane P-Methoxypropionitrile Isovaleric acid Nonane Dipropylamine Isoamyl acetate Cyclopentane 2-Methyl-2-butanol 3-Methyl-l-butanol Tetrahydrofuran Capronitrile 4-Heptanone 2-Ethoxyethanol 2-Heptanone Valeric acid Diisobutylene Methylcyclopentane Isoamyl ether 2-Pentanol Tributyl borate Pentanol 3-Methyl-2-butanol Diethyl oxalate Decane 4-Methyl-2-pentanol 3-Isopropyl-2-pentanone 2-Methyl-1 -butanol Butyric anhydride Amyl ether Isoamyl isovalerate 1-Chloropentane Allyl alcohol
Refractive index 1.395 1.395 1.395 1.395 1.395 1.396 1.397 1.397 1.397 1.397 1.397 1.398 1.398 1.399 1.399 1.399 1.399 1.399 1.400 1.400 1.400 1.400 1.400 1.401 1.401 1.401 1.402 1.403 1.403 1.403 1.404 1.404 1.404 1.404 1.405 1.405 1.405 1.406 1.406 1.407 1.407 1.405 1.407 1.407 1.408 1.408 1.408 1.409 1.409 1.409 1.409 1.409 1.410 1.410 1.410 1.411
Solvents 2,4-Dimethyldioxane Ethyl lactate Diethyl malonate 3-Chloropropene Ethylene glycol diacetate 2-Octanone 3-Octanone 3-Methyl-2-heptanone Caproic acid 4-Methyldioxane 1,2-Propylene glycol monobutyl ether Ethyl cyanoacetate Dibutylamine Hexanol 2-Pentanol 1,1 -Dichloroethane Heptachlorodiethyl ether 3-Methoxypropylamine Caprylonitrile 2-Heptanol Allylamine 1,2-Propylene glycol carbonate 2-Heptanol 3-Methyl-2-pentanol 2-Ethyl-l-butanol 1 -Chloro-2-methyl-1 -propene 1,4-Dioxane Methylcyclopropane 4-Hydroxy-4-methyl-2-pentanone Heptanol 3-Isopropyl-2-heptanone Cyclohexane 2-Bromopropane 3-Chloro-2-methyl-1 -propene Caprylic acid Ethylene carbonate Octanol 3-Methyl-2-heptanol Af,A^Dimethylformamide Sulfuric acid 1-Chlorooctane Triisobutylene Af-Methylalaninenitrile 1,2-Ethanediol 1 -Chloro-2-ethylhexane Ethylcyclohexane 1,2-Propanediol 1-Bromopropane 2-Methyl-7-ethyl-4-nonanone Ethylene glycol monoallyl ether Butyrolactone 2-Methyl-7-ethyl-undecanone 1,2-Dichloroisobutane 1,2-Propylene glycol sulfite Af-Methylmorpholine ChlorcK-butanol
Refractive index 1.412 1.412 1.412 1.413 1.413 1.414 1.414 1.415 1.415 1.415 1.415 1.415 1.416 1.416 1.416 1.416 1.416 1.417 1.418 1.418 1.419 1.419 1.420 1.420 1.420 1.420 1.420 1.421 1.421 1.422 1.423 1.424 1.424 1.425 1.426 1.426 1.427 1.427 1.427 1.427 1.428 1.429 1.429 1.429 1.430 1.431 1.431 1.431 1.433 1.434 1.434 1.435 1.435 1.435 1.436 1.436
Solvents Epichlorohydrin Triethylene glycol monobutyl ether 2-Methyl-7-ethyl-4-nonanol 5-Ethyl-2-nonanol 6-Ethyl-3-octanol 1,3-Propanediol Diethyl maleate Butanethiol Dibutyl sebacate 2-Chloroethanol 6-Ethyl-3-decanol 1 -Chlorododecane 3-Methyl-2,4-pentanediol Dimethyl maleate 2-Methyl-7-ethyl-4-undecanol Ethyl sulfide Mesityl oxide Butyl stearate Cyclohexene Lauryl glycidyl ether Dibutyl maleate 1,3-Butylene glycol sulfite 1,2-Dichloroethane Glycol sulfite Chloroform 1 -Chlorotetradecane Diethylene glycol cis-1,2-Dichloroethylene 2-Butyloctyl-3-aminopropyl ether 2-Methylmorpholine Formamide 3-Lauryl-1 -hydroxypropylamine Ethylene glycol diglycidyl ether 1 -Chlorohexanedecane Cyclohexanone 1 - Amino-2-propanol Diethylene glycol mono-P-hydroxyisopropyl ether 1 - Amino-2-methyl-2-pentanol Tetrahydrofurfuryl alcohol 2-Propylcyclohexanone 2-Aminoethanol 1,4-Butanediol glycidyl ether 4-Chloro-1,3-dioxolane-2-one 1 -Chlorooctadecane 2-Butylcyclohexanone Ethylenediamine 2-((3-Methyl)propylcyclohexanone 4-Methylcyclohexanol 3-Methylcyclohexanol Bis(2-chloroethyl) ether Cyclohexyl methacrylate 1,8-Cineole 2,2/-Dimethyl-2,2/-dipropyl diethanolamine 1,3-Butanediol glycidyl ether
Refractive index 1.436 1.437 1.438 1.438 1.438 1.438 1.438 1.440 1.440 1.440 1.441 1.441 1.441 1.441 1.442 1.442 1.442 1.442 1.443 1.443 1.444 1.444 1.444 1.444 1.444 1.445 1.445 1.445 1.446 1.446 1.446 1.447 1.447 1.448 1.448 1.448 1.448 1.449 1.450 1.452 1.452 1.452 1.452 1.453 1.453 1.454 1.454 1.454 1.455 1.455 1.456 1.456 1.456 1.456
Solvents 1-Chloroeicosane Oleic acid (1,1 ',^'-Tetramethyl) diethanolamine 3-Aminopropanol Carbon tetrachloride 3-Methyl-5-ethyl-2,4-heptanediol 2-((3-Ethyl)butylcyclohexanone 2-Methylcyclohexanol AHrc-ButyOdiethanolamine 4,5-Dichloro-l,3-dioxolane-2-one 2-Butylcyclohexanol N- P-Hydroxypropylmorpholine 2-(P-Ethyl)hexylcyclohexanone 2-Ethylcyclohexanol Fluorobenzene D-a-Pinene L-a-Pinene Cyclohexanol m-Fluorotoluene /?-Fluorotoluene AH2-Hydroxyethyl)-2hydroxybutylamine 4-Chloromethyl-1,3-dioxolane-2-one ^rarcs-Decahydronaphthalene -Fluorotoluene AH2-Hydroxyethyl)-2hydroxypropylamine 3-Allyloxy-2-hydroxypropylamine Di(2-hydroxybutyl)ethanolamine Di(2-hydroxypropyl)ethanolamine D-Limonene 2-(a-Hydroxybutyl)cyclohexanol 1,2,3-Trichloroisobutane Decahydronaphthalene 1,2,3-Propanetriol Trichloroethylene AH p-Hy droxy ethyl)morpholine Dimethyl sulfoxide ds-Decahydronaphthalene 2-(a-Hydroxyethyl)cyclohexanol 1 -Methoxy-1 -butene-3-yn 2-Butylidenecyclohexanone N-( P-Chloroallyl)morpholine rc-Dodecyl-4-f-butyl phenyl ether n-Dodecyl phenyl ether n-Dodecyl 4-methylphenyl ether Af-Hy droxyethyl-1,3-propanediamine Morpholyl A^-(ethylhydroxy)ethylamine 2-Ethylidenecyclohexanone Butylbenzene Dioctylbenzene (90% p, 10% m) p-Cymene Isopropylbenzene Furfuryl alcohol f-Butylcumene (80% p, 15% m, 5% o) n-Propylbenzene
Refractive index 1.459 1.459 1.459 1.459 1.459 1.459 1.461 1.461 1.461 1.462 1.462 1.462 1.463 1.463 1.463 1.464 1.465 1.465 1.465 1.467 1.467 1.467 1.468 1.468 1.468 1.469 1.469 1.469 1.471 1.473 1.473 1.474 1.475 1.474 1.476 1.476 1.479 1.479 1.480 1.481 1.481 1.482 1.482 1.483 1.483 1.485 1.486 1.487 1.487 1.488 1.489 1.489 1.490 1.490
Solvents s-Butylbenzene Hexyl-m-xylene (mainly 1,3,5) J-Butylbenzene Dibutyl phthalate Isopropylethylbenzene (35% /?, 60% m, 5% o) r-Butyltoluene (85% p, 10% m, 5% o) 1-Phenyl-l-hydroxyphenyl ethane Hexylcumene (90% /?, 5% ra, 5% o) Octyltoluene (96% p, 2% m, 2% o) Octylcumene (90% p, 4% m, 6% o) Dihexylbenzene (85% p, 10% m, 5% o) p-Xylene 1,3-Diethylbenzene /-Butyl-ra-xylene (mainly 1,3,5) Ethylbenzene Octylethylbenzene (80-90% p, 10% m) 1,3-Dimorpholyl-2-propanol 1,1,2,2-Tetrachloroethane Isopropyl-ra-xylene (mainly 1,3,5) Toluene Benzyl ethyl ether r-Butylethylbenzene (70% p9 25% m, 5% o) m-Xylene Hexylethylbenzene (70% p, 25% m, 5% o) 1,4-Diethylbenzene 2,3-Dichlorodioxane Mesitylene Hexyltoluene (90% p, 5% m, 5% o) 2-Iodopropane Benzene Propyl benzoate a-Picoline 1,2-Diethylbenzene Pentachloroethane 1-Iodopropane o-Xylene Ethyl benzoate P-Picoline Tetrachloroethylene Phenetole Pyridine Iodoethane Phenyl methallyl ether Anisole
Refractive index 1.490 1.490 1.490 1.490 1.491 1.491 1.491 1.492 1.492 1.493 1.492 1.493 1.493 1.493 1.493 1.493 1.493 1.493 1.494 1.494 1.494 1.495 1.495 1.495 1.496 1.496 1.497 1.497 1.497 1.498 1.498 1.499 1.501 1.501 1.502 1.503 1.503 1.504 1.504 1.505 1.507 1.512 1.514 1.515
Solvents Methyl benzoate Cyclohexylcumene (60% p, 25% m, 15% o) Diallyl phthalate Benzyl acetate Cyclohexylethylbenzene (70% p, 20% m, 20% o) 2-Methyl-4-f-butylphenol Phenyl acetonitrile (Chloro-r-butyl)benzene Methyl salicylate Cyclohexyltoluene (50% p, 20% m, 30% o) Chlorobenzene Furfural Octachlorodiethyl ether Benzonitrile Thiophene Nonachlorodiethyl ether Iodomethane 4-Phenyldioxane 3-Phenyl-1 -propanol Acetophenone Benzyl alcohol 1,2-Dibromoethane 1,2,3,4-Tetrahydronaphthalene m-Cresol P,P-Di(butylxanthogenic acid) diethylester m-Dichlorobenzene Benzaldehyde Styrene Nitrobenzene 6>-Dichlorobenzene Bromobenzene o-Nitroanisole m-Toluidine Benzyl benzoate o-Toluidine 1 -Methoxyphenyl-1 -phenylethane Aniline o-Chloroaniline Bromoform Thiophenol 2,4-Bis(a-phenylethyl)phenylmethyl ether Carbon disulfide 1,1,2,2-Tetrabromoethane Methylene iodide
Refractive index 1.515 1.516 1.517 1.518 1.520 1.521 1.521 1.521 1.522 1.523 1.523 1.524 1.525 1.526 1.526 1.529 1.530 1.530 1.532 1.532 1.538 1.538 1.539 1.542 1.543 1.544 1.544 1.545 1.550 1.551 1.557 1.560 1.566 1.568 1.570 1.571 1.583 1.586 1.587 1.588 1.590 1.628 1.633 1.749
P h y s i c a l
C o n s t a n t s S o l v e n t s
o f f o r
t h e
M o s t
C o m m o n
P o l y m e r s
D a n i e l R. B l o c h Lakeshore Research, Racine, Wl, USA
Values given here have been taken a variety of reference books. Where a range was given, the melting and boiling points given here are average values. Flash point was determined by the closed cup method, using a Setaflash apparatus. The refractive index is reported relative to the
Compound Acetic acid Acetic anhydride Acetone Acetonitrile n-Amyl acetate Aniline Anisole Benzene Benzonitrile Benzyl acetate Benzyl alcohol Biphenyl Bromoform n-Butanol n-Butyl acetate y-Butyrolactone Carbon disulfide Carbon tetrachloride Chlorobenzene 2-Chloroethanol Chloroform 2-Chlorophenol m-Cresol Cyclohexane Cyclohexanol Cyclohexanone Cyclohexyl acetate Cyclopentanol ds-Decahydronaphthalene Diacetone alcohol Di-n-amyl ether 1,2-Dichlorobenzene Di-2-chlorodiethylether 1,2-Dichloroethylene, cis & trans Dichloromethane/methylene chloride l,3,-Dichloro-2,4,6-trifluorobenzene Diethyl ether
CAS Number 64-19-7 108-24-7 67-64-1 75-05-8 628-63-7 62-53-3 100-66-3 71-43-2 100-47-0 140-11-4 100-51-6 92-52-4 75-25-2 71-36-3 123-86-4 96-48-0 75-15-0 56-23-5 108-90-7 107-07-3 67-66-3 95-57-8 108-39-4 110-82-7 108-93-0 108-94-1 622-45-7 96-41-3 493-01-6 123-42-2 693-65-2 95-50-1 111-44-4 540-59-0 75-09-2 2368-53-8 60-29-7
Formula Wt. 60.05 102.09 58.08 41.05 130.19 93.13 108.14 78.11 103.12 150.18 108.14 154.21 252.75 74.12 116.16 86.09 76.14 153.82 112.56 80.51 119.38 128.56 108.14 84.16 100.16 98.15 142.2 86.13 138.25 116.16 158.29 147 143.01 96.94 84.93 200.98 74.12
Melting Pt. (0C) 17 -73 -94 -48 -71 -6 -37 6 -13 -51 -15 71 8.3 -90 -78 -45 -111 -23 -45 -89 -63 8 9 7 22 -47 -19 -43 -69 -17 -47 -57 -97 -116
sodium D line. Boiling points are given at 760 mmHg unless indicated otherwise by the pressure in mmHg following a slash (/). Viscosity is reported at 200C unless indicated at another temperature in Celsius following a slash (/).
Boiling pt. (0C) 118 140 56 82 148 184 154 80 191 206 205 255 151 118 125 205 46 77 132 129 61 176 203 81 161 155 173 140 193 166 188 180 66/15 48-60 40 162 34.6
Density Viscosity at (at 200C) 200C (cps) 1.049 1.082 0.790 0.786 0.876 1.022 0.995 0.874 1.010 1.040 1.045 0.992 2.894 0.810 0.882 1.120 1.266 1.594 1.107 1.201 1.492 1.241 1.034 0.779 0.948 0.947 0.966 0.949 0.896 0.931 0.785 1.306 1.220 1.265 1.325 1.599 0.708
1.21 0.324
0.52 5.8 2.948 5.8 0.969 0.568 20.8 0.979
2.543/15
1.4230
1.4870 1.26
Flash pt. Refractive index (at 200C) (0C) 1.3716 1.3900 1.3588 1.3440 1.4026 1.5860 1.5160 1.5010 1.5280 1.5020 1.5400 1.5960 1.3990 1.3940 1.4360 1.6270 1.4600 1.5240 1.4410 1.4460 1.5580 1.5400 1.4260 1.4650 1.4500 1.4390 1.4530 1.4750 1.4119 1.5510 1.4560 1.4470 1.4240 1.3530
40 54 -17 5 36 70 51 -11 71 102 93 35 98 -33 23 60 63 86 -18 67 46 57 51 57 61 57 65 55 6 76 -40
Compound
CAS Number
Di(ethylene glycol) 111-46-6 Di(ethylene glycol mono-n-butyl 112-34-5 ether Di(ethylene glycol) monoethyl ether 111-90-0 Diisobutyl ketone 108-83-8 Diisopropyl ketone 565-80-0 1,2-Dimethoxyethane/ethylene 110-71-4 glycol dimethyl ether AyV-Dimethylacetamide 127-19-5 Af,Af-Dimethylformamide 68-12-2 Dimethylsulfoxide 67-68-5 1,4-Dioxane 123-91-1 Diphenyl ether 101-84-8 Di(propylene glycol) 110-98-5 Di(propylene glycol) monomethyl 34590-94-8 ether Ethanol 64-17-5 Ethyl acetate 141-78-6 Ethylene glycol diacetate 111-55-7 Ethylene carbonate 96-49-1 Ethylene dichloride 107-06-2 Ethylene gylcol 107-21-1 Ethylene glycol mono-rc-butyl ether 111-76-2 Ethylene glycol diacetate 111-55-7 Ethylene glycol diethyl ether 629-14-1 Ethylene glycol dimethyl ether 110-71-4 Ethylene glycol monoethyl ether 110-80-5 Ethylhexyl acetate 103-09-3 (5)-(-)-Ethyl lactate 687-47-8 Formaldehyde, 37% solution 50-00-0 Formamide 75-12-7 Formic acid, 96% 64-18-6 Furfurol 98-00-0 Glycerine 56-81-5 w-Heptane 142-82-5 Hexachloroethane 67-72-1 Hexafluorobenzene 392-56-3 Hexamethylphosphoric triamide 680-31-9 Hexane 110-54-3 Isobutanol 78-83-1 Isobutyl isobutyrate 97-85-8 Isobutyric acid 79-31-2 Isophorone 78-59-1 Isopropanol 67-63-0 Isopropyl acetate 108-21-4 Isopropylamine 75-31-0 Mesitylene 108-67-8 Mesityl oxide 141-79-7 Methanol 67-56-1 2-Methoxyethanol 109-86-4 Methyl acetate 79-20-9 Methyl ethyl ketone 78-93-3 Methyl isoamyl ketone 110-12-3 Methyl isobutyl ketone 108-10-1 Methyl propyl ketone 107-87-9 N-Methylpyrrolidone 872-50-4 Morpholine 110-91-8 Nitrobenzene 98-95-3 Nitromethane 75-52-5 rc-Octane 111-65-9 rc-Pentanol 71-41-0 Perfluoroacetone 684-16-2 Perfluorotributylamine 311-89-7 Phenol 108-95-2 1,4-Phenylenediamine 106-50-3
Formula Wt.
Viscosity at 200C (cps)
Refractive Flash pt. index (at 2O0C) (0C)
Melting Pt. (0C)
Boiling pt. (°C)
Density (at 200C)
106.12 162.23
-10 -68
245 231
1.118 0.967
1.4460 1.4320
143 100
134.18 142.24 114.19 90.12
-46 -80 -58
202 169 124 85
0.999 0.806 0.806 0.867
1.4270 1.4113 1.4000 1.3790
96 49 15 0
1.4380 1.4310 1.4790 1.4220 1.5790 1.4410 1.4220
70 57 95 12 >110 137 74
1.3600 1.3720 1.4150
1.4130 1.3765 1.4470 1.3704 1.4860 1.4740 1.3870
8 -3 82 160 15 > 110 60 82 20 0 44 77 28 56 154 68 65 160 -1
1.3770 1.4580 1.3750 1.3960 1.3980 1.3930 1.4760 1.3770 1.3770 1.3746 1.4990 1.4450 1.3290 1.4020 1.3610 1.3970 1.4070 1.3960 1.3900 1.4700 1.4540 1.5510 1.3820 1.3980 1.4090
10 105 -23 27 37 55 84 11 16 -32 44 30 11 46 -9 3 41 13 7 86 35 87 35 15 48
1.5425
None 79
87.12 73.1 78.13 88.11 170.21 134.18 148.2
-20 -61 18 12 28
166 153 189 102 259 230 90/12
0.937 0.944 1.101 1.034 1.073 1.023 0.938
46.07 88.11 146.14 88.06 98.96 62.07 118.18 146.14 118.18 90.12 90.12 172.27 118.13 30.03 45.04 46.03 98.1 92.09 100.21 236.74 186.05 179.2 86.18 74.12 144.21 88.11 138.21 60.1 102.13 59.11 120.2 98.15 32.04 76.1 74.08 72.11 114.19 100.16 86.13 99.13 87.12 123.11 61.04 114.23 88.15 166.02 671.1 94.11 108.14
-130 -84 -41 39 -35 -13 -75 -41 -74 -58 -90
78 77 187 244/740 83 197 171/743 187 121 85 135 200 154 97 210 101 170 182/20 98
0.785 0.902 1.128 1.321 1.256 1.113 0.903 1.128 0.842 0.867 0.930 0.870 1.042 1.083 1.134 1.220 1.135 1.261 0.684 2.091 1.612 1.030 0.659 0.803 0.855 0.950 0.923 0.785 0.872 0.694 0.864 0.858 0.791 0.965 0.932 0.805 0.888 0.801 0.802 1.033 0.999 1.196 1.127 0.703 0.811
-26 -15 3 8 -29 20 -91 193 4 7 -95 -108 -81 -47 -8 -89 -73 -101 -45 -53 -98 -85 -98 -87 -80 -78 -24 -7 6 -29 -57 -78 -129 41 144
80 232/740 69 108 148 154 214 82 89 34 163 129 65 125 58 80 145 118 110 82/10 129 211 101 127 138 -26 178 182 267
1.883 1.071
1.26
1.2 0.455
1.4450 1.4310 1.4190 1.4150 1.3923 1.3790 1.4070
0.326
0.423/15
2.256
Compound Piperazine H-Propanol Propyl acetate Propylene carbonate Propylene glycol Propylene glycol mono-n-butyl ether Propylene glycol monomethyl ether Propylene glycol mono-n-propyl ether Propylene glycol mono-f-butyl ether Pyridine 1,1,2,2-Tetrachloroethane Tetrachloroethylene Tetrahydrofuran Tetrahydrofurfuryl alcohol Tetrahydronaphthalene/tetralin Tetramethylene sulfone Tetramethylurea Toluene 1,1,1-Trichloroethane Trichloroethylene Tricresyl phosphate Trifluoroacetic acid Water o-Xylene p-Xylene
CAS Number
Formula Wt.
Melting Pt. (0C)
Boiling pt. (0C)
Density Viscosity at (at 200C) 200C (cps)
1.3840 1.3840 1.4210 1.4320 1.4160
109 15 12 132 107 58
0.922
1.4030
33
140-160
0.885
1.4110
48
144
0.874
1.4130
44
115 147 121 66 178 207 285 177 111 75 87 265/10 72 100 144 138
0.978 1.586 1.623 0.889 1.054 0.973 1.261 0.971 0.865 1.338 1.463 1.143 1.480 0.998 0.870 0.866
1.5100 1.4935 1.5060 1.4070 1.4520 1.5410 1.4840 1.4506 1.4960 1.4366 1.4760 1.5550
20 None None -17 83 77 165 65 4 None None >110 None None 32 27
110-85-0 71-23-8 109-60-4 108-32-7 57-55-6
86.14 60.1 102.13 102.09 76.1 132.2
109 -127 -95 -55 -60
146 97 102 240 187 72/20
0.804 0.888 1.189 1.036 0.885
107-98-2
90.12
-97
119
1569-01-3
118.18
57018-52-7
132.20
110-86-1 79-34-5 127-18-4 109-99-9 97-99-4 119-64-2 126-33-0 632-22-4 108-88-3 71-55-6 79-01-6 1330-78-5 76-05-1 7732-18-5 95-47-6 106-42-3
79.1 167.85 165.83 72.11 102.13 132.21 120.17 116.16 92.14 133.41 131.39 368.37 114.02 18.02 106.17 106.17
-42 -45 -22 -108 -80 -35 27 -1 -93 -35 -85 -15 0 -24 13
Flash pt. Refractive index (at 20°C) (°C)
2.256
0.486
0.59
1.005 0.648
1.3329 1.5050 1.4950
S E C T I O N
P H Y S I C A L
D
A
T
A
O
I V
F
O
L
I
G
O
M
E
R
S
P h y s i c a l
D a t a
o f
O l i g o m e r s
M . Rothe Lehrstuhl Organische Chemie II, University at UIm, UIm, FR Germany
A. Introduction B. Oligomers Containing Main Chain Acyclic Carbon Only Table 1. Oligo(olefins) 1.1. Oligo(methylenes) and Oligo(ethylenes) 1.2. Oligo(perfluoromethylenes) and Oligo(perfluoroethylenes) 1.3. Oligo(isobutenes) 1.4. OligoO -alkenylenes) References Table 2. Oligo(dienes) 2.1. Oligomers of 1,3-Butadiene 2.2. Oligomers of lsoprene 2.3. Oligomers of 1,3-Butadiene Derivatives 2.4. 1,4-Oligo(alkadienes) 2.5. Oligomers of Cyclopentadiene and 1,3-Cyclohexadiene 2.6. Oligomers of Allene References Table 3. Oligo(acetylenes) 3.1. Linear Oligomers of Acetylene 3.2. Polyenyne Oligomers 3.3. Oligomeric oc-co-Diynes 3.4. Oligo(alkynes) 3.5. Cyclic Oligo(alkynes) 3.6. Pericyclynes References Table 4. Oligomers with Aliphatic Side Chains which in Addition Contain Heteroatoms 4.1. Oligomeric Acrylic Derivatives 4.2. Oligomeric Methacrylic Derivatives 4.3. Oligomers of P-Alkyl Substituted Vinyl Derivatives 4.4. Oligo(vinyl) Derivatives References Table 5. Oligo(styrenes) References
IV-2 IV-3 IV-3 IV-3 IV-6 IV-8 IV-9 IV-9 IV-14 IV-14 IV-15 IV-16 IV-16 IV-I 7 IV-17 IV-18 IV-19 IV-19 IV-20 IV-20 IV-20 IV-20 IV-21 IV-21
IV-22 IV-22 IV-24 IV-26 IV-27 IV-28 IV-30 IV-32
C. Oligomers Contaning Heteroatoms in the Main Chain Table 6. Oligomers Containing O in the Main Chain 6.1. Oligo(ethers) and Oligo(acetals) References 6.2. Oligo(carbonates) References 6.3. Oligo(esters) References 6.4. Oligo(urethanes) References Table 7. Oligo(sulfides) and Oligo(selenides) 7.1. Cyclic Oligo(thiomethylenes) and Oligo(Selenomethylenes) 7.2. Cyclic Oligo(thioalkylenes) 7.3. Substituted Cyclic(thioethylenes) 7.4. Cyclic Co-Oligomers of Formaldehyde and Thioformaldehyde 7.5. Cyclic Oligo(ethersulfides) 7.6. Thiacyclophanes References Table 8. Oligomers Containing N in the Main Chain 8.1. Oligo(amides) References 8.2. Oligo(peptides) References 8.3. Oligo(imines) References 8.4. Oligo(ureas) References D. Carbon Chain Oligomers Containing Main Chain Cyclic Units Table 9. Oligocyclopentylenes Table 10. Oligo(spiranes) Table 11. Oligo(xylylenes) 11.1. Linear Oligo(xylenes) 11.2. Cyclic Oligo(xylylenes) Table 12. Oligo(stilbenes)
IV-33 IV-33 IV-33 IV-43 IV-47 IV-47 IV-48 IV-56 IV-58 IV-61 IV-62 IV-62 IV-62 IV-62
IV-62 IV-63 IV-63 IV-63 IV-64 IV-64 IV-70 IV-72 IV-84 IV-88 IV-89 IV-89 IV-90 IV-90 IV-90 IV-90 IV-90 IV-90 IV-90 IV-91
Table Table Table Table Table Table Table
Oligo(benzyls) Oigo(2,5-dimethyl-benzyls) Oligo(2,3,5,6-tetramethyl benzyls) Oligo(p-phenylene oxides) Oligo(p-phenylene sulfides) Oligo(p-phenoxy phenylmethanes) Oligo(diphenylmethanes) References Table 20. Phenol-Formaldehyde and Related Oligomers 20.1. Linear Phenol-Formaldehyde Oligomers 20.2. Oligomeric Phenol Alcohols 20.3. Cyclic Phenol-Formaldehyde Oligomers 20.4. Branched PhenolFormaldehyde Oligomers 20.5. Hydroquinone Oligomers References Table 21. Oligo(phenylenes) 21.1. o-Oligo(phenylenes) 21.2. m-Oligo(phenylenes) 21.3. p-Oligo(phenylenes) 21.4. Oligo(p-quinones) References E. Oligomers Containing Heterocyclic Rings in the Main Chain Table 22. Heterocyclic Oligomers 22.1 Oligo(furan) Derivatives 22.2. Oligo(thiophene) Derivatives 22.3. Oligo(pyrrole) Derivatives 22.4. Oligo(pyridine) Derivatives 22.5. Cyclic Oligo(heterocyclics) References Table 23. Oligo(saccharides) 23.1. Oligomeric Pentoses 23.2. Oligomeric Hexoses 23.3. Oligomeric Amino Sugars References A.
13. 14. 15. 16. 17. 18. 19.
IV-91 IV-91 IV-91 IV-91 IV-91 IV-91 IV-91 IV-91 IV-92 IV-92 IV-93 IV-94 IV-94 IV-95 IV-95 IV-96 IV-96 IV-96 IV-97 IV-98 IV-98 IV-99 IV-99 IV-99 IV-100 IV-100 IV-100 IV-101 IV-101 IV-102 IV-102 IV-102 IV-103 IV-104
INTRODUCTION
Oligomers are defined as the low members of the polymeric-homologous series with molecular weights up to about 1000-2000. They are easily obtained by stepwise synthesis from suitably protected monomer derivatives or by separation from the polymers. As monodisperse oligomers are low molecular compounds of defined molecular weights, they represent ideal model substances for the polymers. By physical studies of a complete series of oligomers, substantial knowledge is gained of the relation between chain length and physical properties. In this way certain physical data of the polymers could be explained for the first time. In chemical aspects, oligomers must, on principle, have the same properties as the related polymers; they are, however, much more accessible to all
studies, owing to their strictly defined and comparatively simpler structure. Homologous oligomers differ sufficiently in their physical properties - due to their low molecular weight so that they can be separated into individual chemicals. They can therefore be used for elucidating the structure of polymers and, in close relation, for the investigation of the mechanisms of polymerization. Oligomers are intermediates in polycondensation and polyaddition reactions and are present in more or less significant amounts in the polymers, due to equilibria between different chains, and between chains and rings. Therefore important conclusions on the structure of the related high polymers can be drawn from isolation and structure determination of oligomers, along with a comparison of the chemical properties of polymers and oligomers. In this way clear evidence can be obtained as regards the type of linkage between the monomer units in the polymer as well as the structure of unknown endgroups. Finally, unequivocal evidence on the mechanism of polymer formation is to be expected from the behavior of oligomers under the conditions of the polyreaction. The following tables give the physical properties of the most important, linear, cyclic, and branched monodisperse oligomers which are significant for polymer chemistry. Derivatives and co-oligomers (such as co-oligo-peptides, -saccharides, and -nucleotides) as well as organosilicon and inorganic oligomers are not included, nor are any low polymers which have not been proved to be strictly monodisperse. Only those literature references are cited that indicate the best methods of synthesis and the most important physical properties of the oligomers concerned (including spectroscopic and conformational data which could not be mentioned in detail in the tables). In the last few decades several reviews on linear and cyclic oligomers have appeared. A small list is giving below. 1. H. Zahn, G. B. Gleitsmann, Angew. Chem., 68, 229 (1956); Angew. Chem., Int. Ed. Engl., 2, 410 (1963). 2. M. Rothe, Makromol. Chem., 35, 183 (1960). 3. M. Rothe, I. Rothe, in: J. Brandrup, H. Immergut (Eds.), "Polymer Handbook", 3rd Ed., Wiley, New York, 1989. 4. J. A. Semlyen, "Cyclic Polymers", Elsevier, London, 1986. 5. S. Penczek, S. Slomkowski, Compr. Polym. Sci., 3, 725 (1989). 6. P. Maravigna, G. Montaudo, Compr. Polym. Sci., 5,63 (1989). 7. V. Percec, C. Pugh, O. Nuyken, S. D. Pask, Compr. Polym. Sci., 6, 281 (1989). 8. C. V. Uglea, 1.1. Negulescu, "Synthesis and Characterization of Oligomers", CRC Press, Boca Raton, 1991. 9. M. Rothe, in: E. W. Fischer, R. C. Schulz, H. Sillescu (Eds.), "Chemistry and Physics of Macromolecules", VCH, Weinheim, 1991. 10. K. Hatada, K. Ute, N. Miyatake, Prog. Polym. Sci., 19, 1067 (1994). 11. J. M. Tour, Trends Polym. Sci., 2, 332 (1994).
B. OLIGOMERS CONTAINING MAIN CHAIN ACYCLIC CARBON ONLY TABLE 1. OLIGO(OLEFINS) 1.1. OLIGO(METHYLENES) AND OLIGO(ETHYLENES) 1.1.1. w-ALKANES H[CH2LH n
MoL wt.
m.p. (0C) -182.6 -183.3 -187.1 -138.4 -129.7 -94.0 -90.5 -56.8 -53.5 -29.7 -25.6 -9.7 -6.0 5.5 10.1 18.1 22.1 28.2 32.0
b.p. (°C/mbar)
d4 (g/cm3)/°C
Refs.
-161.6/1013 -88.5/1013 -42.2/1013 -0.5/1013 36.1/1013 68.7/1013 98.4/1013 125.5/1013 150.8/1013 174.1/1013 195.9/1013 216.3/1013 235.5/1013 253.6/1013 270.7/1013 287.1/1013 302.6/1013 317.4/1013 331.6/1013
0.4240/-164 0.5462/89 0.5824/-45 0.6011/0 0.6263/20 0.6594/20 0.6838/20 0.7026/20 0.1111/20 0.7301/20 0.7402/20 0.7487/20 0.7563/20 0.7627/20 0.7684/20 0.7733/20 0.7767/22 0.7768/28 0.7776/32
21,22,75,84,88,93 21,75,84,88,93 21,22,75,84,88,93 21,22,75,84,88,112,178,192 3,7,13,21,22,30,75,84,88,93,112,178,192,195 3,5,7,21,22,30,75,78,84,88,93,112,178,192,195 3,5,7,13,21,22,30,75,84,88,93,112,178,192 3,5,7,13,21,22,30,78,84,87,88,93,112,178,192,195 1,5,7,13,21,22,30,84,87,88,93,111,112,178,192 1,3,5,7,18,21,22,30,84,87,88,93,111,112,178,192,195 1,3,7,13,21,22,30,77,83,84,87,88,93,111,112 1,7,17,21,22,30,79,84,87,88,93,111,112,178,185,192 1,7,13,21,30,77,83,84,87,88,93,112,205,206 1,7,17,21,30,84,87,88,93,111,112 1,3,7,21,30,77,83,84,87,88,93,112 1,7,11,15,16,19,21,30,78,84,87,88,93,111,112,192 1,3,7,13,14,21,30,75,77,83,84,88,93,111,112,193 1-3,7,11,14,15,17,19,21,30,75,84,88,93,111 1,3,4,7,14,15,19,21,77,83,84,88,93,97,111,121, 198,221,235 1,3-7,11,14,15,17-19,21,22,79,82,88,91,93,107, 110,111,198 1,3,4,10,14,15,19,21,77,83,86,88,93,111,118, 194,198,232 1,3,4,7,11,14,21,78,83,88,91,93,97,111,115,121,198 1,3,4,10,14,21,77,83,86,88,93,121,198 1,3,4,11,14,17,21,83,86,88,91,93,99,182,198,202,204 1,3-5,14,21,77,83,88,93,118,193,198,232 1-4,7,11,14,21,83,85,88,93,198 1-4,8,14,21,77,83,85,88,93,118,198 1,4,11,13-15,17,19,21,83,85,86,88,90,93,99,100, 111,198 1,3,4,11,14,21,77,83,85,88,91,93,118,198 1-4,6,7,11,14,18,21,82,83,85,86,88,93,110,198 1-4,8,77,83,85,86 1,2,4,11,15,16,19,20,83,85,91,95,97,99,109,111, 115,185,198 1,4,5,77,83,91,109,116,119,198,207 1-4,7,11,77,83,85,86,198 1,4,7,8,10,15,19,77,79,83,85,86,88,91,95,118 1,2,4,7,10,13-15,19,77,78,83,85,86,88,90,91 107,109,111,185,191,193,194,198,207,211,221, 223,232,233 75,109,198 75,77,83,198 12,75,77,83 6,7,10,17,18,21,75,77,82,83,86,93,99,110,198 75 76 10,22,77,83,86 3,11,15,19,77,79,80,83,89,91,95,107,110,111,115, 116,118,205 109 77,80,83,91,100,198 100,109,202,204 6,7,11,15,18,21,77,80,82,83,90,93,110,116, 188,193,198 77,80,83,90
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19
16.0 30.1 44.1 58.1 72.2 86.2 100.2 114.2 128.3 142.3 156.3 170.3 184.4 198.4 212.4 226.4 240.5 254.5 268.5
20
282.6
36.7
345.1/1013
0.7550/70
21
296.6
40.4
215/20
0.7583/70
22 23 24 25 26 27 28
310.6 324.6 338.7 352.7 366.7 380.7 394.8
44.4 47.4 51.1 54 57.0 60.0 61.6
222-225/20 234/20 243/20 259/20 262/20 270/20 279-281/20
0.7631/70 0.7641/70 0.7657/70 0.7693/70 0.7704/70 0.7732/70 0.7750/70
29 30 31 32
408.8 422.8 436.9 450.9
64.0 66.0 67.9 70.4
286/20 304/20 302/20 310/20
0.7755/70 0.7795/70 0.7678/100 0.7645/100
33 34 35 36
464.9 478.9 493.0 507.0
71.3 72.9 74.7 76.1
331/20 298.4/4
0.7436/135 0.7783/90
37 38 39 40 41 42 43 44
531.0 535.0 549.1 563.1 577.1 591.2 605.2 619.2
77.2 79.2 80.5 81.5 81.7 82.9 85.5 86.4
45 46 48 50
633.2 647.2 675.3 703.4
87.2 88.0 88.5-89 92.1
52
731.4
94.0
150/10- 4 332/4
420-422/20
0.7812/90 0.7514/135
1.1.1. cont'd MoL wt.
m.p. (0C)
54 56 60
759.5 787.6 843.6
95.0 95.5-96 99.1
61 62 64 65 66 67 69 70 72 80 82 94
857.6 871.7 899.7 913.7 927.8 941.8 969.9 983.9 1012.0 1124.2 1152.2 1320.6
100.3 100.5 102.1 102.1 103.6 104.1 104.7 105.3 103-105 108.0 110.1 113.8
n
96 98 100 102 104 120 122 140 144 150 160 162 168 192 194 198 210 216 240 242 246 258 288 294 384 390
1348.6 1404.7 1432.8 1460.8 1685.3 1965.8 2021.9 2106.1 2246.4 2358.5 2695.2 2779.4 2947.7 3029.8 3368.5 3396.6 3450.6 3621.0 4039.8 4126.0 5386.4 5470.5
b.p. (°C/mbar)
d4 (g/cm3)/°C
250/10" 4
0.7654/135
300/10" 4
0.783/115
110-112 113-114 115.2 115.5-116.5 115-115.5 119.2 116-117 121.0 121 123-123.5 122.2 121-121.5 121.9 127.5 126.9 127.0 127.4 128.4 120-121 128-130 128.8 128.8 130.4 131.3 132
Refs. 2,7,77,80,83,90 106,204 6,7,18,21,77,80,82,83,90,93,104,109,110,187,188, 190,193,198 109 2,7,77,80,83,90,116 2,7,13,22,77,79,80,83,90 109 9,77,80,83,90 9,77,80,83,90 109 6,7,18,21,77,80,82,83,90,93,100,110,116 100,202 18,82,104,109 20,77,80,81,83,89,110,188 15,19,20,77,79,80,83,100,103,107,110, 116-118,188,204 100,202 229 18,22,77,80-83,93,104,110,185 105,108,183,203 106,203,204 82,98,104,200,202 229 82 98,200,202 105,108,183,203,227,248 104,108 229 98,114,177,189,199,200,202,221 98,186,189,200-202,225 224,229 105,108,183,184,197,203,224-227,229,248 224,229 98,200,202,225 189,199 229 105,108,181,183,184,203,224-227,229,249 224,229 98,200,202 108,183,203,224,225,229,248 98,200 105,108,183,203,229,248
Conformation, chain folding: Refs. 108,178 (n = 2-10,12), 179 (n = 9-44), 181,183,184,193,194,202,205-208,211,226,227,248. Crystallization: Refs. 168,177-179,181,183,184,188-190,194,197,199-202,211,224-227,248. Thermal behavior, phase transitions, DSC: Refs. 88,98,107,107,109,119,181,184,186-191,193,197-204,217,221,224-226,246. NMR: Refs. 95,97 (n = 19,22,32), 99 (n = 6,8,10,14,18,24,28), 100,179,187,191,205,206,221,229,246. IR, Raman: Refs. 98,108,116,119,178,182,192-194,200,202,232,248. X-ray: Refs. 100,107,109,112,119,183,184,187,190,191,198,206,223,224,226,233. Electron diffraction: Refs. 187,188. MS: Ref. 195. GPC: Ref. 185.
1.1.2. CYCLOALKANES r [CH2]ni n
MoL wt. 3 4 5 6 7 8
42.1 56.1 70.1 84.2 98.2 112.2
m.p. (0C) -127.5 -90 -93.9 6.6 -8.0 13.5
b.p. (°C/mbar)
d4 (g/cm3)/°C
Refs.
-32.8/1013 12.5/1013 49.3/1013 80.7/1013 118.5/1013 149/1000
0.688/-40 0.7038/0 0.7457/20 0.7784/20 0.8098/20 0.8349/20
23,24,93,94,178 25,93,94,178,232 26,93,94,178,183,195 27-29,93,94,99,111,178,183,195 29,31,93,94,178,195 32-34,93,94,99,178,195,208
1.1.2. cont'd n
MoI. wt.
m.p. (0C)
b.p. (°C/mbar)
d4 (g/cm3)/°C
Refs.
9.7 9.5 -7.3 60.6
69/19 69/16 91/16
0.8534/20 0.8575/20 0.8591/20 0.861/20
128/27 131/15
0.861/20 0.8259/79
147/16 170-171/27
0.8240/78 0.819/79
29,34,93,94,178,208 29,35,36,93,94,99,178,180,208 29,37,93,94,99,208 29,38,39,40,93,94,99,101,111,114,178,180,196, 208,214,215,217,232 29,34,38,40,93,94,99,196,208,217 17,29,38,40,41,93,94,99,180,196,208-210,214, 217,218,220 29,38,40,44,93,94,99,196,208,217 16,38,40-42,93,94,99,111,169,180,196,208,209, 212,214,217,220 40,43,44,93,94 17,40-42,45,93,94,99 40,93,94,99 18,40,41,93,94,99,111 41,94,99,102 38,40,43,48,94,96,99,220 46,48,94,99 38,40,41,45,48,94-99,100,101,111,114,169,196, 202,210,211,213-217,219,228,235,246 47,94 38,40,43,48,94,99,210 41,94,102 38,41,48,94,97,99,102,111,219,222 38,94,99 18,41,42,45,48,90,93,94,99,102 41,48,94,97,99,102,111,169,222 48,92,94,113 41,45,94,97,99,100,101,102,111,114,115,120,196, 211,214,215,217,228,248,256 99 18,41,93,97,99,102,111,115,216,219,222,248,256 42,102 99,100 41,102 222 97,98,100,101,111,114,115,120,196,198,200, 202,207,211,213,217,230,235,248,256 18 41,102 101,120,211,247 97,111,115,234,248,256 98,100,101,120,196,198,200,202,207,211,213, 216,217,228,230,231,235 97,111,115,248,256 101 96,98,100,120,196,198,202,216,217,230,231,235 228 248,256 211,228 219,248,256 98,100,198,200,202,230 219,248,256 177 98 228,248,256 98,100,202,230
9 10 11 12
126.2 140.3 154.3 168.3
13 14
182.4 196.4
24.4 56.2
15 16
210.4 224.4
63.4 60.5
17 18 19 20 21 22 23 24
238.5 252.5 266.5 280.5 294.6 308.6 322.6 336.6
65 72-73 80 61-62 64-65 46.8 53-54 48.8
25 26 27 28 29 30 32 34 36
350.7 364.7 378.7 392.8 406.8 420.8 448.9 476.9 505.0
53-54 44-46 47-48 47-48 54.5-55.5 57-58 65.5-66.5 66-67 70.0
37 40 42 44 45 46 48
519.0 561.1 589.2 617.2 631.2 645.2 673.3
65-66 76-77 75-76 82-82.5 80-81 83.5-85 89.2
50 54 60 64 72
701.4 757.5 841.6 897.7 1009.9
87-88 90-91 96.5
80 84 96 100 104 120 128 144 160 168 192 200 288
1122.2 1178.3 1346.6 1402.7 1683.2 1795.5 2019.9 2294.3 2356.5 2693.2 2805.4 4039.8
107.0
0.8200/77 0.8201/76
177/0.5 177/0.1 222-228/0.8
0.8174/75 0.8259/64
218-219/0.7
0.8120/78
213-214/0.3 215/1.5 230/0.3
0.8243/58 0.8232/64 0.8233/69 0.8261/70 0.8229/76
230-240/0.4
13 C-NMR 103.5-104.5 13
108.8 116.0
120.8
124.3 129.8
C-NMR
Conformation, chain folding: Refs: 94,97,113,178 (n = 3-10,12), 179 (n = 3-96), 180,187,202,207-209,211-213,215-217,219,220,228,230,231,234,235,246,248. Crystallization: Refs. 178,179,217,230,234,248. Thermal behavior, phase transition, DSC: Refs. 96,101,179,196,209,216-221,230,246. NMR: Refs. 95,97,99 (n = 6,8,10-16,18-24,26,28-30,32,36,37,40,44), 100 (n = 24,26,44,48,72,96), 111,114,115,179 (n = 3-96), 180,189,214-219,234,246,248,256. IR, Raman: Refs. 92,96,178,179,200,202,209,220,235. X-ray: Refs. 113,120,179,202,210,211,215,216,218,223,230,256. Electron diffraction: Refs. 230,231. GPC.Ref. 211.
1.2. OLIGO(PERFLUOROMETHYLENES) AND OLIGO (PERFLUOROETHYLENES) 1.2.1. PERFLUORO-w-ALKANES F[CF 2 LF n
MoL wt.
1 2 3 4 5 6 7 8 9 10 11 12 14 16 18 20 24
88.0 138.0 188.0 238.0 288.1 338.1 388.1 438.1 488.1 538.1 588.1 638.1 738.1 838.2 938.2 1038.2 1238.2
m.p. (0C)
b.p. (°C/mbar)
-183.6 -96.6 -147.7 -129.2 -125.4 90.7 93.3 -19.0 -16 36 57 75.3
d4 (g/cm3)/°C
Refs.
1.619/-129 1.590/-78
22,49,63,64,125,130,179 49,50,63,64,125,130,154,179 22,51,52,64,125,130,131,179 22,52-54,64,125,126,129,132,139,144,179,241 22,52,54-56,124,129 22,52,57,58,124-126,134,144,175,179 22,52,56,59,125,128,134,144,175,179 22,52,59,125,134,144,175,179 22,52,59,127 22,52,59,127 22,52,59 22,52,59,127,175,179,250,251 124,127,133,179,240,249 54,59,127,175 124,127,133 124,127,133,175,179,243-245,249,252 175,242,243,245
-128/1005 -78.3/1013 -36.7/1013 -2.2/1013 29.2/1013 57.2/1013 82.2/1013 103.3/1013 125.3/1013 144.2/1013 161/1013 178/1013 IR, Raman spectr. 232/1013 IR, Raman spectr. IR, Raman spectr. IR, Raman spectr.
129.0 164.7 192.0
1.620/20 1.6995/20 1.7333/20 1.776/25 1.799/25 1.770/45 1.745/70 1.670/113.5
1.2.2. PERFLUORO-CYCLOALKANES J-[CH2IfI n 3 4 5 6 7 8 9 10
MoI. wt.
m.p. (0C)
b.p. (°C/mbar)
150.0 200.0 250.0 300.0 350.0 400.0 450.0 500.0
-80 -38.7 10.3 58.2 -37 -55 -56 -44
-31.5/1013 -2/1013 22.5/1013 51 (subl.) 76.2/1013 101.5/1013 124.6/1013 146.5/1013
Refs. 60,61 61,63,144 51,54-56,61,64 51,56,59,64,65,144 51,59 59 59 59
1.2.3. oc,co-DISUBSTITUTED PERFLUORO-rc-ALKANES X-[CF 2 J n -X X
n
MoI. wt.
H
1 2 3 4 5 6 7 8 10 2 4 6 8 10 12 2 4 6 8 10 4 6 8 10 2 4
52.0 102.0 152.0 202.0 252.1 302.1 352.1 402.1 502.1 194.2 294.2 394.3 494.3 594.3 694.3 258.4 358.4 458.5 558.5 658.5 318.1 418.1 518.1 618.2 164.1 264.1
CH3S
CH3SO2
CH3COO
HOCH2
m.p. (0C)
42-43
b.p. (°C/mbar) -51.6/1013 -20°/1013 10-11/1013 43.5/1013 66.5/1013 88.5-89.5/1013 104.2/1013 130.6/1013 153-154/1013 67-70/53 80-83/27 81-84/5 102-106/5 90-94/1 118-122/1
125 151 168 171 187 115-116/133 121-123/67 126-127/33 144-146/33 81-82 69
135-136/36
Refs. 144,145 146 135-137,144 136 135-137,144 136,137 136,137 135-137 135 135 135 135 135 135 135 135 135 135 135 135 135 135 135 135 135
1.2.3. cont'd X
n
MoI. wt.
I
2 4 6 8 10
353.8 453.8 553.8 653.8 753.8
m.p. (0C)
b.p. (°C/mbar)
Refs.
113/1013 149/1013 186/1013 222/1013 258/1013
236 236 236 236 236
1.2.4. a,co-DISUBSTITUTED PERFLUORO-rc-ALKANES WITH DIFFERENT ENDGROUPS X-[CF 2 L-Y X
Y n
H
Cl
H
F
(CF 3 ) 2 CF
I
MoI. wt. 2 3 4 5 6 7 8 9 10 11 12 13 14 2 3 4 5 7 12 4 6
136.5 186.5 236.5 286.5 336.5 386.5 436.5 486.5 536.5 586.5 636.5 686.5 736.5 120.0 170.0 220.0 270.0 370.0 620.0 495.9 596.0
m.p.
b.p. (°C/mbar) -10/1013 21/1013 50/1013 77/1013 100/1013 122.5/1013 144.5/1013 162.5/1013 162.5/1013 177/1013 202/1013 213/1013 227-228/1013 -48.5/1013 -16/986 14/986 46/986 94/986
46 52 78 87 95
df (g/cm3)
1.556 1.607 1.661 1.719 1.738 1.778
72 139/1026 189/1008
Refs. 61 61 61 61 61 61 61 61 61 61 61 61 61 240,252 240 240 240 240 250,251 237 237
1.2.5. SEMIFLUORINATED n-ALKANES F-[CF 2 ] m -[CH 2 ] n -H m
n
MoI. wt.
1 6 7 8 10 10 10 10 12 12 12 12 12 12 12 12 12 12
1 12 7 8
84.0 488.3 468.3 532.3 540.3 632.4 660.4 688.4 648.2 676.2 704.3 732.4 760.4 788.4 816.5 844.5 872.6 800.6
8 10 12 2 4 6 8 10 12 14 16 18 20
m.p. (0C)
b.p. (°C/mbar) -46.7/1013
-13.0 27.0 35 53.0 64 65 71.0 76.0 84 88 92 91 93 94 97 100
Refs. 155,176 138,176 255 138,176 251 138,176 138,176,251,255 138,176,251 138,176,250,251,255 138,176,250,251,255 138,176,250,251,255 138,176,251 138,176,251 138,176,250,251,255 138,176,251 138,176,251 138,176,251 138,176,250,251,255
1.2.6. ANIONIC OLIGOMERS OF PERFLUORO-rc-ALKENES (MAJOR OLIGOMERS, cisltrans MIXTURES) n
Compound
MoI. wt.
b.p. (°C/mbar)
400.1 500.1
95-96/1013 135-138/1012
CF 2 =CF 2 (Refs. 238,239,243): 4 5
1.2.6. cont'd n
Compound
MoI. wt.
b.p. (°C/mbar)
6
600.1
160-165/1013
2
300.1
3
450.1
46-48.5/1013 46-48.5/1013 114.8/1013 110-115/1013 110-115/1013
1.2.7. PERFLUORO-1-ALKENES F-[CF 2 L-CF=CR 2 n
MoL wt.
1 2 3 5 7
150.0 200.0 250.0 350.0 450.1
b.p. at ~ 983 mbar (0C)
nf
-29 1 28-29 81 123
Refs. 240 240 240 240 240
1.2571 1.2782 1.2868
Conformation; Crystallization: Refs. 126,179,242,243-245,251. Phase transition, DSC: Refs. 55,125,138,175,176,179,242,244,245,249,251. NMR: Refs. 134,179,250,251. X-ray: Refs. 65,138,175,176,179,244,245. IR, Raman: Refs. 125-127,133,138,175,176,241,242,245,249,250,255. MS: Ref. 56.
1.3.
OLIGO(ISOBUTENES) m.p. (0C)
Compound MONOMER (mol. wt.
b.p. (°C/1013mbar)
df (g/cm3)
56.1)
Isobutene CH 2 =C(CH 3 ) 2
- 6
DiMERS (mol. wt. 112.2; Refs. 66-70,72,74,122,141,143,147,148,150-152,153) 2,4,4-Trimethyl-l-pentene
-93.6
101.4
0.7150
-106.5
104.9
0.7212
112.3
0.7392
116.3
0.7434
108
0.729
108.4
0.7352
105.0
0.7481
2,4,4-Trimethyl-2-pentene
3,4,4-Trimethyl-2-pentene
2,3,4-Trimethyl-2-pentene -113.4 2,3,4-Trimethyl-1 -pentene
2,3,3-Trimethyl- 1-pentene -69 1,1,3-Trimethyl-cyclopentane
1.3. cont'd m.p. (0C)
Compound
TRiMERS (mol. wt. 168.3, Refs. 71,73,74,123,140,142,143,147-149,151,152) 1,1 -Dineopentylethylene CH2=C[CH2C(CH3)2]2
b.p. (0C/1013 mbar)
178.0/1013
df
(g/cm3)
0.7599
2,2,4,6,6-Pentamethyl-3-heptene 13
(CH 3 ) 3 C-CH=C-CH 2 -C(CH 3 ) 3
C-NMR
CH3 TETRAMERS (mol. wt. 224.4; Refs. 74,141-143,147,151,152) 2,2,6,6,8,8-Hexamethyl-4-methylene-nonane (CH 3 ) 3 C- C H 2 - C - CH 2 - C(CH3)2— C H 2 - C(CH3)3
106-107/11 C-NMR
13
CH2 2,2,4,6,6,8,8-Heptamethyl-4-nonene (CH 3 ) 3 C- C H 2 - C = C H - C(CH 3 ) 2 - C H 2 - C(CH3)3
13
C-NMR
CH3
1.4. x
OLIGO(l-ALKENYLENES) n
2
3 4
5 6 n= 7 8 10
13
Configuration
MoI. wt.
m.p. (0C)
2 cisltrans 108.2 -70 3 cisltrans 162.3 4 cisltrans 216.3 5 cisltrans 270.4 6 cisltrans 324.5 n = 4-13 cisltrans GC Refs. 161,166 /1 = 4-7,10,11 cisltrans 1H-, 13C-NMR Ref. 161 2 cis 136.2 21-23 2 cw 164.3 0 3 cisltrans 246.4 4 cis 328.6 25-27 2 cis 192.3 46 3 cisltrans 288.5 2 c/5 220.4 18.5 3 cisltrans 330.6 2-8 (cisltrans): GPC, b.p., /ig\ IR, UV, MS Refs. 158-160 2 ds 248.4 38.5 2 cis 276.5 38-39 1 cisltrans 166.3 2 cw/ftww 332.6 54-55 trans/trans IR: 970 cm" 1 translcis 970, 725Cm"1 cislcis 725 cm" 1 3 cw/fra/w 498.3 4 cisltrans 665.2 /i = 2-14: MS Refs. 167,168 /i = 2-9: GPC Ref. 160 rc = 2-7: MS Ref. 166
b.p. (°C/mbar)
«J?
150.8/1002 104/15 88-91/0.07 105-110/0.07 162/0.1
51/0.5 {cisltrans) 112/0.5 48/0.001 (cisltrans) 116/0.001 89/0.07 (cisltrans) 130/0.07 122/0.4 (cisltrans) 123-124/0.2 (cisltrans) 100/0.11 150/0.09
220/0.12 255/0.12
Refs. 163,170-172 164,173,174 161,164 161,164 161
1.4972 1.4971
162 40,157,162 157 40 40,157 157 40,157,158 157,158 40,157 40,157 156 156-158,160 156 156 156 156 156
REFERENCES
1. F. Krafft, Chem. Ber., 15, 1687, 1711 (1882); 19, 2218 (1886); 40, 4479 (1907). 2. A. Gascard, Ann. Chim. (Paris) (9), 15, 332 (1921). 3. A. Mueller, Proc. Roy. Soc. (London) A, 120, 437 (1928); 127, 417 (1930); 138, 514 (1932). 4. J. H. Hildebrand, A. Wachter, J. Am. Chem. Soc, 51, 2487 (1929).
5. G. S. Parks, H. M. Huffmann, S. B. Thomas, J. Am. Chem. Soc, 52, 1032 (1930). 6. W. H. Carothers, J. W. Hill, J. E. Kirby, R. A. Jacobsen, J. Am. Chem. Soc, 52, 5279 (1930). 7. W. E. Gramer, K. van Bibber, A. M. King, J. Chem. Soc, 1533 (1931). 8. H. Staudinger, F. Staiger, Chem. Ber., 68, 707 (1935).
9. F. Francis, A. M. King, J. A. V. Willis, J. Chem. Soc, 999 (1937) 10. H. J. Backer, J. Strating, Rec. Trav. Chim. Pays-Bas, 59, 933 (1940); 55, 903 (1936). 11. W. F. Seyer, R. F. Patterson, J. L. Keays, J. Am. Chem. Soc, 66, 179 (1944); W. F. Seyer, Wm. Morris, ibid., 61, 1114 (1939). 12. E. Stenhagen, B. Taegtstroem, J. Am. Chem. Soc, 66, 845 (1944). 13. A. K. Doolittle, R. H. Peterson, J. Am. Chem. Soc, 73, 2145 (1951). 14. A. A. Schaerer, C. J. Busso, A. E. Smith, L. B. Skinner, J. Am. Chem. Soc, 77, 2017 (1955). 15. P. R. Templin, Ind. Eng. Chem., 48, 154 (1956). 16. F. Sondheimer, Y. Amiel, J. Am. Chem. Soc, 79, 5817 (1957). 17. F. Sondheimer, Y. Amiel, R. Wolovsky, J. Am. Chem. Soc, 79, 6263 (1957). 18. F. Sondheimer, R. Wolovsky, D. A. Ben-Efraim, J. Am. Chem. Soc, 83, 1686 (1961). 19. A. Odajima, J. A. Sauer, A. E. Woodward, J. Phys. Chem., 66, 718 (1962). 20. D. W. McCaIl, D. C. Douglass, E. W. Anderson, Ber. Bunsenges. Phys. Chem., 67, 336 (1963); D. C. Douglass, D. W. McCaIl, J. Phys. Chem., 62, 1102 (1958). 21. J. D. Downer, K. J. Beynon, in: "Rodd's Chemistry of Carbon Compounds", vol. I, Part A, 2nd ed., Elsevier, Amsterdam, 1964, p. 367. 22. R. Simha, A. J. Havlik, J. Am. Chem. Soc, 86, 197 (1964). 23. M. Trautz, K. Winkler, J. Prakt. Chem., 104, 37 (1922). 24. R. A. Ruehrwein, T. M. Powell, J. Am. Chem. Soc, 68,1063 (1946). 25. G. B. Heisig, J. Am. Chem. Soc, 63, 1698 (1941). 26. J. G. Aston, H. L. Fink, S. C. Schumann, J. Am. Chem. Soc, 65, 341 (1943). 27. J. G. Aston, G. J. Szasz, H. L. Fink, J. Am. Chem. Soc, 65, 1135 (1943). 28. R. A. Raphael, in: E. R. Rodd (Ed.), "Chemistry of Carbon Compounds", vol. II, Part A, 1st ed., Elsevier, Amsterdam, 1953, p. 124. 29. L. Ruzicka, P. A. Plattner, H. Wild, HeIv. Chim. Acta, 29, 1611 (1946). 30. R. M. Deanesley, L. T. Carleton, J. Phys. Chem., 45, 1104 (1941). 31. R. Willstaetter, T. Kametaka, Chem. Ber., 41, 1480 (1908). 32. N. D. Zelinsky, M. G. Freimann, Chem. Ber., 63, 1485 (1930). 33. L. Ruzicka, H. A. Boekenoogen, HeIv. Chim. Acta, 14, 1319 (1931). 34. L. Ruzicka, P. A. Plattner, H. Wild, HeIv. Chim. Acta, 28, 395 (1945). 35. P. A. Plattner, J. Huelstkamp, HeIv. Chim. Acta, 27, 220 (1944). 36. W. Hueckel, A. Gercke, A. Gross, Chem. Ber., 66, 563 (1933). 37. P. A. Plattner, HeIv. Chim. Acta, 27, 801 (1944).
38. L. Ruzicka, M. Stoll, H. W. Huyser, H. A. Boekenoogen, HeIv. Chim. Acta, 13, 1152 (1930). 39. R. Wolovsky, F. Sondheimer, J. Am. Chem. Soc, 84, 2844 (1962). 40. J. Dale, A. J. Hubert, G. S. D. King, J. Chem. Soc, 73 (1963). 41. F. Sondheimer, Y. Amiel, R. Wolosky, J. Am. Chem. Soc, 81, 4600 (1959). 42. L. Ruzicka, W. Bruegger, C. F. Seidel, H. Schinz, HeIv. Chim. Acta, 11, 496 (1928). 43. L. Ruzicka, G. Giacomello, HeIv. Chim. Acta, 20, 548 (1937). 44. L. Ruzicka, W. Bruegger, M. Pfeiffer, H. Schinz, M. Stoll, HeIv. Chim. Acta, 9, 499 (1926). 45. F. Sondheimer, R. Wolovsky, J. Am. Chem. Soc, 84, 260 (1962). 46. R. Stol, HeIv. Chim. Acta, 16, 493 (1933). 47. A. J. Hubert, J. Dale, J. Chem. Soc, 86 (1963). 48. L. Ruzicka, M. Huerbin, M. Furter, HeIv. Chim. Acta, 17,78 (1934). 49. O. Ruff, Angew. Chem., 46, 739 (1933). 50. E. L. Pace, J. G. Aston, J. Am. Chem. Soc, 70, 566 (1948). 51. J. H. Simons, L, P Block, J. Am. Chem. Soc, 61, 2962 (1939). 52. R. N. Haszeldine, J. Chem. Soc, 3761 (1953) 53. J. A. Brown, W. H. Mears, J. Phys. Chem., 62, 960 (1958). 54. W. B. Burford, R. D. Fowler, J. M. Hamilton, Jr., H. C. Anderson, C. E. Weber, R. G. Sweet, Ind. Eng. Chem., 39, 319 (1947). 55. L. L. Burger, G. H. Cady, J. Am. Chem. Soc, 73, 4243 (1951). 56. F. L. Mohler, E. G. Bloom, J. H. Lengel, C. E. Wise, J. Am. Chem. Soc, 71, 337 (1949). 57. V. E. Stiles, G. H. Cady, J. Am. Chem. Soc, 74, 3771 (1952). 58. R. D. Dunlap, C. J. Murphy, R. G. Bedford, J. Am. Chem. Soc, 80, 83 (1958). 59. R. N. Haszeldine, F Smith, J. Chem. Soc, 3617 (1950); 603 (1951). 60. B. Atkinson, J. Chem. Soc, 2684 (1952). 61. J. D. Park, A. F Benning, F. Downing, J. F. Laucius, R. C. McHarness, Ind. Eng. Chem., 39, 354 (1947). 62. J. R. Lacher, G. W. Tompkin, J. D. Park, J. Am. Chem. Soc, 74, 1693 (1952). 63. G. Bier, R. Schaeff, K.-H. Kahrs, Angew. Chem., 66, 285 (1954). 64. N. Fukuhara, L. A. Bigelow, J. Am. Chem. Soc, 63, 2792 (1941). 65. H. J. Christoffers, E. C. Lingafelter, G. H. Cady, J. Am. Chem. Soc, 69, 2502 (1947). 66. F. C. Whitmore, S. N. Wrenn, J. Am. Chem. Soc, 53, 3136 (1931). 67. C. O. Tongberg, J. D. Pickens, M. R. Fenske, F. C. Whitmore, J. Am. Chem. Soc, 54, 3706 (1932). 68. F. C. Whitmore, K. C. Laughlin, J. Am. Chem. Soc, 54, 4011 (1932). 69. F. C. Whitmore, K. C. Laughlin, J. F. Matuszeski, J. D. Surmatis, J. Am. Chem. Soc, 63, 756 (1941).
70. J. A. Dixon, N. C. Cook, F. C. Whitmore, J. Am. Chem. Soc, 70, 3361 (1948). 71. F. C. Whitmore, C. D. Wilson, J. V. Capinjola, C. O. Tongberg, G. H. Fleming, R. V. McGrew, J. N. Cosby, J. Am. Chem. Soc, 63, 2035 (1941). 72. F. L. Howard, T. W. Mears, A. Fookson, P. Pomerantz, D. B. Brooks, J. Res. Natl. Bur. Std., 38, 365 (1947). 73. P. D. Bartlett, G. L. Fraser, R. B. Woodward, J. Am. Chem. Soc, 63, 495 (1941). 74. M. I. Batuev, A. P. Meshcheriakov, A. D. Matveeva, Izv. Akad. Nauk, SSSR, 75 (1958); Bull. Acad. Sci. USSR, 66 (1958). 75. F. D. Rossini, K. S. Pitzer, R. L. Arnett, R. M. Braun, G. C. Pimental, "Selected Values of Physical and Thermodynamic Properties of Hydrocarbons and Related Compounds", Carnegie Press, Pittsburgh, Pa., 1953. 76. G. L. Clark, H. A. Smith, Ind. Eng. Chem., 23, 700 (1931). 77. P. J. Flory, A. Vrij, J. Am. Chem. Soc, 85, 3548 (1963). 78. R. A. Orwoll, P. J. Flory, J. Am. Chem. Soc, 89, 6814 (1967). 79. R. R. Reinhard, J. A. Dixon, J. Org. Chem., 30,1450 (1965). 80. M. G. Broadhurst, J. Chem. Phys., 36, 2578 (1962). 81. G. Staellberg, S. Staellberg-Stenhagen, E. Stenhagen, Acta Chem. Scand., 6, 313 (1952). 82. W. Heitz, Th. Wirth, R. Peters, G. Strobl, E. W. Fischer, Makromol. Chem., 162, 63 (1972). 83. M. G. Broadhurst, J. Res. Natl. Bur. Std., 66A, 241 (1962). 84. M. Kurata, S. Isida, J. Chem. Phys., 23, 1126 (1955). 85. S. H. Piper, A. C. Chibnall, S. J. Hopkins, A. Pollard, J. A. B. Smith, E. F. Williams, Biochem. J., 25, 2072 (1931). 86. W. M. Mazee, Rec Trav. CMm. Pays-Bas, 67, 197 (1948). 87. H. L. Finke, M. E. Gross, G. Waddington, H. M. Huffmann, J. Am. Chem. Soc, 76, 333 (1954). 88. A. A. Schaerer, G. G. Bayle, W. M. Mazee, Rec Trav. Chim. Pays-Bas, 75, 513 (1956). 89. B. G. Ranby, F. F. Morehead, N. M. Walter, J. Polym. Sci., 44, 349 (1960). 90. G. Egloff, "Physical Constants of Hydrocarbons", VoIs. 1 and 5, A. C. S. Monograph Series, Reinhold, New York, 1953. 91. M. Brini, Bull. Soc Chim. France, 996 (1955). 92. T. Tasumi, T. Shimanouchi, R. F. Schaufele, Polym. J., 6,740 (1971). 93. D. Barton, W. D. Ollis, in: J. F. Stoddart (Ed.), Comprehensive Organic Chemistry, Vol. 1, Pergamon Press, Oxford, 1979, pp. 49-51. 94. J. Dale, J. Chem. Soc, 93 (1963). 95. M. Moeller, H.-J. Cantow, J. K. Krueger, H. Hoecker, Polym. Bull., 5, 125 (1981). 96. H.-R Grossmann, Polym. Bull., 5, 137 (1981). 97. I. Ando, T. Yamanobe, T. Sorita, T. Komoto, H. Sato, K. Deguchi, M. Imanari, Macromolecules, 17, 1955 (1984). 98. K. S. Lee, G. Wegner, Makromol. Chem., Rapid Commun., 6, 203 (1985). 99. H. Fritz, E. Logemann, G. Schill, T. Winkler, Chem. Ber., 109, 1258 (1976).
100. G. Schill, C. Zuercher, H. Fritz, Chem. Ber., I l l , 2901 (1978). 101. H. Hoecker, K. Riebel, Makromol. Chem., 178, 3101 (1977). 102. F. Sondheimer, Y. Amiel, R. Wolovsky, J. Am. Chem. Soc, 79, 4247 (1957). 103. J. D. Hoffman, Macromolecules, 18, 772 (1985). 104. K. Takamizawa, Y. Sasaki, K. Kono, Y. Urabe, Rep. Progr. Polym. Phys. Jpn., 19, 285 (1976). 105. I. Bidd, M. C. Whiting, J. Chem. Soc, Chem. Commun., 543 (1985). 106. O. I. Paynter, D. J. Simmonds, M. C. Whiting, J. Chem. Soc, Chem. Commun., 1165 (1982). 107. P. K. Sullivan, J. J. Weeks, J. Res. Natl. Bur. Std., 74A, 203 (1970); R. G. Sullivan, ibid., 78A, 129 (1974). 108. G. Ungar, I. Stejny, A. Keller, I. Bidd, M. C. Whiting, Science, 229, 386 (1985). 109. K. Takamizawa, Y. Ogawa, I. Oyama, Polym. J., 14, 441 (1982). 110. J. N. Hay, J. Polym. Sci., Polym. Chem. Ed., 14, 2845 (1976). 111. T. Yamanobe, T. Sorita, I. Ando, H. Sato, Makromol. Chem., 186, 2071 (1985). 112. R. G. Snyder, J. Chem. Phys., 47, 1316 (1967). 113. B. A. Newman, H. F. Kay, J. Appl. Phys., 38, 4105 (1967); Acta Cryst. B, 24, 615 (1968). 114. H.-J. Cantow, D. Emeis, W. Gronski, A. Hasenhindl, D. Lausberg, M. Moeller, Y. Shahab, Makromol. Chem., Suppl., 7, 63 (1984). 115. T. Sorita, T. Yamanobe, T. Komoto, I. Ando, H. Sato, K. Deguchi, M. Imaneri, Makromol. Chem., Rapid Commun., 5, 657 (1984). 116. G. R. Strobl, R. Eckel, J. Polym. Sci., Polym. Phys. Ed., 14, 913 (1976). 117. F. Khoury, J. Appl. Phys., 34, 73 (1963). 118. G. T. Davis, J. J. Weeks, G. M. Martin, R. K. Eby, J. Appl. Phys., 45, 4175 (1974). 119. B. Ewen, D. Richter, J. Chem. Phys., 69, 2954 (1978); G. R. Strobl, B. Ewen, E. W. Fischer, W. Piesczek, J. Chem. Phys., 61, 5257, 5265 (1974); W. Piesczek, G. R. Strobl, K. Malzahn, Acta Cryst. B, 30, 1278 (1974); G. R. Strobl, Coll. Polym. Sci., 254, 170 (1976). 120. T. Trzebiatowski, M. Drager, G. R. Strobl, Makromol. Chem., 183, 731 (1982). 121. J. D. Barnes, J. Chem. Phys., 58, 5193 (1973). 122. F. C. Whitmore, J. M. Church, J. Am. Chem. Soc, 54, 3710 (1932). 123. R. J. McCubbin, J. Am. Chem. Soc, 53, 356 (1931); R. J. McCubbin, H. Adkins, ibid., 52, 2547 (1930). 124. J. L. Koenig, F. J. Brerio, J. Chem. Phys., 50, 2823 (1909). 125. M. Campos-Vallette, M. Rey-Lafon, R. Lagnier, Chem. Phys. Lett., 89, 189 (1982). 126. P. Piaggio, P. G. Francese, G. Masetti, G. Dellepiane, J. MoI. Struct., 26, 421 (1975). 127. J. Rabolt, B. Fanconi, Polymer 18, 1258 (1977), Macromolecules 11, 740 (1978). 128. G. D. Oliver, J. W. Grisard, J. Am. Chem. Soc, 73, 1688 (1951).
129. J. H. Simons, R. D. Dunlap, J. Chem. Phys., 18, 335 (1950). 130. J. H. Smith, E. L. Pace, J. Phys. Chem., 73, 2368, 4232 (1969). 131. E. L. Pace, A. C. Plaush, J. Chem. Phys., 47, 38 (1967). 132. J. H. Simons, J. W. Mausteller, J. Chem. Phys., 20, 1516 (1952). 133. G. W. Chantry, E. A. Nicol, R. G. Jones, H. A. Willis, M. E. A. Cudby, Polymer, 18, 37 (1977). 134. J. R. Lyerla Jr., D. L. VanderHart, J. Am. Chem. Soc, 98, 1697 (1976). 135. R. B. Ward, J. Org. Chem., 30, 3009, (1965). 136. K. Matsuo, W. H. Stockmayer, J. Phys. Chem., 85, 3307 (1981). 137. T. W. Bates, W. H. Stockmayer, Macromolecules, 1, 12 (1968). 138. J. F. Rabolt, T. P. Russell, R. J. Twieg, Macromolecules, 17, 2786 (1984). 139. T. W. Bates, Trans. Faraday Soc, 63, 1825 (1967). 140. T. Higashimura, Y. Miyoshi, H. Hasegawa, J. Appl. Polym. Sci., 28, 241 (1983). 141. H. Hasegawa, T. Higashimura, J. Appl. Polym. Sci., 27, 171 (1982). 142. S. A. Francis, E. D. Archer, Anal. Chem., 35, 1363 (1963). 143. H. Schiitz, R. Radeglia, G. Heublein, Acta Polym., 36, 415 (1985). 144. R. N. Haszeldine, J. Chem. Soc, 4259 (1952); R. N. Haszeldine, R. J. Marklow, J. Chem. Soc. 962 (1956). 145. A. L. Henne, M. W. Renoll, J. Am. Chem. Soc, 58, 887 (1936). 146. F. B. Downing, A. F. Benning, R. C. McHarness, United States Patent 2.387.247 (1945), 2.413.695 (1947); through Chem. Abstr., 588 (1946), 2427 (1947). 147. J. P. Kennedy, S. Rengachary, Adv. Polym. Sci., 14,1 (1974). 148. L. Schmerling, V. N. Ipatieff, Adv. Catal., 2, 21 (1950). 149. J. Kriz, M. Marek, Makromol. Chem., 163, 155, 171 (1973). 150. J. B. McKinley, D. R. Stevens, W. E. Baldwin, J. Am. Chem. Soc, 67, 1455 (1945). 151. T. Higashimura, M. Swamoto, Adv. Polym. Sci., 62, 50 (1984). 152. W. O. Haag, Chem. Eng. Progr., 63, 145 (1967). 153. D. H. Rank, E. R. Bordner, J. Chem. Phys., 3, 248 (1935). 154. E. G. Locke, W. R. Brode, A. L. Henne, J. Am. Chem. Soc, 56, 1726 (1934). 155. A. L. Henne, M. W. Renoll, J. Am. Chem. Soc, 58, 889 (1936). 156. R. Wolovsky, Z. Nir, Synthesis, 4, 134 (1972). 157. H. J. Bestmann, H. Pfuller, Angew. Chem., 84, 528 (1972). 158. H. Hocker, R. Musch, Makromol. Chem., 157, 201 1972; 175, 1395 (1974). 159. E. A. Ofstead, E. Asch, H. Hocker, Macromol. Synth., 6, 69 (1977). 160. H. Hocker, W. Reimann, K. Riebel, Z. Szentivany;, Makromol. Chem., 177, 1707 (1976). 161. H. Sato, Y. Tanaka, T. Taketomi, Makromol. Chem., 178, 1993 (1977). 162. D. J. Cram, N. L. Allinger, J. Am. Chem. Soc, 78, 2518 (1956).
163. A. C. Cope, C. L. Stevens, F. A. Hochstein, J. Am. Chem. Soc, 72, 2510 (1950). 164. K. Saito, T. Yamaguchi, K. Tanabe, T. Ogura, M. Yagi, Bull. Chem. Soc Japan, 52, 3192 (1979). 165. H. Kumobayashi, T. Ogura, S. Akutagawa, K. Saito, T. Yamaguchi, K. Tanabe, Chem. Lett., 317 (1976). 166. H. Hocker, W. Reimann, L. Reif, K. Riebel, Makromol. Chem., J. MoI. Catal., 8, 191 (1980). 167. R. Wolovsky, J. Am. Chem. Soc, 92, 2132 (1970). 168. D. A. Ben-Efraim, C. Batich, E. Wasserman, J. Am. Chem. Soc, 92, 2133 (1970). 169. E. Wasserman, D. A. Ben-Efraim, R. Wolovsky, J. Am. Chem. Soc, 90, 3286 (1968). 170. W. Brenner, P. Heimbach, H. Hey, E. W. Mueller, G. Wilke, Ann. Chem., 727, 161 (1969). 171. K. Ziegler, H. Wilms, Ann. Chem., 567,1 (1950); K. Ziegler, H. Sauer, L. Bruns, H. Froitzheim-Kuehlhorn, J. Schneider, Ann. Chem., 589, 122 (1954). 172. A. C. Cope, W. J. Bailey, J. Am. Chem. Soc, 70, 2305 (1948); A. C. Cope, C. L. Stevens, F. A. Hochstein, ibid., 72, 2510 (1950). 173. G. Wilke, Angew. Chem., 69, 397 (1957); G. Wilke, E. W. Mueller, M. Kroener, ibid., 73, 33 (1961); B. Bogdanovic, P. Heimbach, M. Kroener, G. Wilke, E. G. Hoffmann, J. Brandt, Ann. Chem., 727, 143 (1969). 174. H. Breil, R Heimbach, M. Kroener, H. Mueller, G. Wilke, Makromol. Chem., 69, 18 (1963). 175. H. W. Starkweather, Jr., Macromolecules, 19, 1131 (1986). 176. Th. P. Russell, J. F. Rabolt, R. J. Twieg, R. L. Siemens, Macromolecules, 19, 1135 (1986). 177. R. G. Alamo, NATO ASI, Ser. C, 405, 73 (1993); Chem. Abstr., 121, 110078f (1994). 178. N. L. Allinger, Y. H. Yuh, J.-H. Lii, J. Am. Chem. Soc, 111, 8551 (1989); J.-H. Lii, N. L. Allinger, ibid., Ill, 8566, 8576 (1989). 179. B. Wunderlich, M. Moller, J. Grebowicz, H. Baur, Adv. Polym. Sci., 87, 1 (1988). 180. F. A. L. Anet, A. K. Cheng, J. Am. Chem. Soc, 97, 2420 (1975); F. A. L. Anet, A. K. Cheng, J. Wagner, ibid., 94,9250 (1972). 181. J. D. Hoffman, Polymer, 32, 2828 (1991). 182. K. Ishii, M. Nukaga, Y. Hibino, S. Hagiwara, H. Nakayama, Bull. Chem. Soc Jpn., 68, 1323 (1995). 183. A. Keller, G. Ungar, S. I. Organ, Polym. Preprints, 30, 263 (1989); A. Keller, S. J. Organ, G. Ungar, Makromol. Chem., Macromol. Symp., 48/49, 93 (1991); J. Polym. Sci., Polym. Phys., 25, 2409 (1987); J. Polym. Sci., C, Polym. Lett., 26, 259 (1988); G. Ungar, Integr. Fundament. Polym. Sci. TechnoL, Ed. P. J. Lemstra, L. A. Kleintjens, Elsevier, London, 2, 346 (1988). 184. G. Ungar, A. Keller, Polym., 27, 1835 (1986). 185. D. J. Blundell, A. Keller, I. M. Ward, I. J. Grant, J. Polym. Sci., Part B, Polym. Lett., 4, 781 (1966). 186. L. Mandelkern, A. Prasad, R. G. Alamo, G. M. Stack, Macromolecules, 23, 3696 (1990). 187. W. L. Jarrett, L. J. Mathias, R. G. Alamo, L. Mandelkern, D. L. Dorset, Macromolecules, 25, 3468 (1992).
188. D. L. Dorset, R. G. Alamo, L. Mandelkern, Macromolecules, 25, 6284 (1992). 189. R. G. Alamo, L. Mandelkern, G. M. Stack, C. Krohnke, G. Wegner, Macromolecules, 27, 147 (1994). 190. L. Mandelkern, R. G. Alamo, E. L. Sokolov, Y. Li, B. Chu, Macromolecules, 27, 2324 (1994). 191. M. J. Stewart, W. L. Jarrett, L. J. Mathias, R. G. Alamo, L. Mandelkern, Polym. Preprints, 35, 779 (1994). 192. S.-I. Mizushima, T. Simanouti, J. Am. Chem. Soc, 71, 1320 (1949). 193. Y Kim, H. L. Strauss, R. G. Snyder, J. Chem. Phys., 93,7520 (1989). 194. H. Hagemann, H. L. Strauss, R. G. Snyder, Macromolecules, 20, 2810 (1987). 195. R. L. Betts, M. A. Park, E. L. Shirey, E. A. Schweikert, Org. Mass Spectr., 29, 679 (1994). 196. K. Drotloff, M. Moller, Thermochem. Acta, 112, 57 (1987). 197. S. J. Organ, G. Ungar, A. Keller, Macromolecules, 22, 1995 (1989). 198. R. D. Heyding, K. E. Russell, T. L. Varty, D. St.-Cyr, Powder Diffraction, 5, 93 (1990). 199. R. G. Alamo, L. Mandelkern, G. M. Stack, C. Krohnke, G. Wegner, Macromolecules, 26, 2743 (1993). 200. G. Wegner, G. Lieser, Polym. Preprints, 30, 265 (1989). 201. G. M. Stack, L. Mandelkern, C. Krohnke, G. Wegner, Macromolecules, 22, 4351 (1989). 202. K.-S. Lee, G. Wegner, S. L. Hsu, Polymer, 28, 889 (1987). 203. I. Bidd, D. W. Holdup, M. C. Whiting, J. Chem. Soc, Perkin Trans. I, 2455 (1987). 204. E. Igner, O. I. Paynter, D. J. Simmonds, M. C. Whiting, J. Chem. Soc, Perkin Trans. /, 2447 (1987). 205. G. D. Smith, D. Y. Yoon, W. Zhu, M. D. Ediger, Macromolecules, 27, 5563 (1994); G. D. Smith, D. Y Yoon, R. L. Jaffe, ibid., 28, 5897 (1995). 206. G. D. Smith, D. Y Yoon, J. Chem. Phys., 100, 649 (1994). 207. W. Stocker, G. Bar, M. Kunz, M. Moller, S. N. Magonov, H.-J. Cantow, Polym. Bull., 26, 215 (1991). 208. J. Dale, Acta Chem. Scand., 27, 1115, 1130 (1973). 209. G. Borgen, J. Dale, J. Chem. Soc, Chem. Commun., 1340 (1970). 210. P. Groth, Acta Chem. Scand. A, 33, 199 (1979); 30, 155 (1979). 211. K. J. Ihn, M. Tsuji, S. Isoda, A. Kawaguchi, K. Katayama, Y Tanaka, H. Sato, Macromolecules, 23,1781,1788 (1990); K. J. Ihn, M. Tsuji, A. Kawaguchi, K.-I. Katayama, Microscop. Res. Tech., 20,205 (1992); K. J. Ihn, M. Tsuji, S. Isoda, A. Kawaguchi, K. Katayama, Y. Tanaka, H. Sato, Makromol. Chem., 190, 837 (1989). 212. R. Zhang, W. L. Mattice, J. Chem. Phys., 98, 9888 (1993). 213. A. Wawkuschewski, H.-J. Cantow, S. N. Magonov, M. Moller, W. Liang, M.-H. Whangbo, Adv. Mater., 5, 821 (1993). 214. M. Moller, Adv. Polym. ScL, 66, 59 (1985). 215. M. Moller, W. Gronski, H.-J. Cantow, H. Hocker, J. Am. Chem. Soc, 106, 5093 (1984). 216. M. Moller, G. Kogler, D. OeMn, H. Drotloff, Solid-State NMR Polymer, Ed. L. Mathias, Plenum Press, NY, 245 (1991); Chem. Abstr, 116, 23643Oe (1992).
217. H. Drotloff, D. Emeis, R. F. Waldron, M. Moller, Polymer, 28, 1200 (1987). 218. H. Drotloff, H. Rotter, D. Emeis, M. Moller, J. Am. Chem. Soc, 109, 7797 (1987). 219. M. Takenaka, T. Yamanobe, T. Komoto, I. Ando, H. Sato, K. Sato, J. Polym. Sci., Part B, Polym. Phys., 25, 2165 (1987). 220. V. L. Shannon, H. L. Strauss, R. G. Snyder, C. A. Elliger, W. L. Mattice, J. Am. Chem. Soc, 111, 1947 (1989). 221. M. Moller, H.-J. Cantow, H. Drotloff, D. Emeis, K.-S. Lee, G. Wegner, Makromol. Chem., 187, 1237 (1986). 222. G. Schill, N. Schweickert, H. Fritza, W. Vetter, Chem. Ber., 121, 961 (1988). 223. H. M. M. Shearer, V. Vand, Acta Cryst., 9, 379 (1956). 224. E. Boda, G. Ungar, G. M. Brooke, S. Burnett, S. Mohammed, D. Proctor, M. C. Whiting, Macromolecules, 30, 4674 (1977). 225. S. J. Sutton, A. S. Vaughan, D. C. Bassett, Polymer, 25,5735 (1996). 226. G. Ungar, A. Keller, Polymer, 28, 1899 (1987). 227. S. J. Organ, A. Keller, M. Hikosaka, G. Ungar, Polymer, 37, 2517 (1996). 228. P. R. Sundararajan, T. A. Kavassalis, Macromolecules, 30, 5172 (1977). 229. G. M. Brooke, S. Burnett, S. Mohammed, D. Proctor, M. C. Whiting, J. Chem. Soc, Perkin Trans. I, 1635 (1996). 230. G. Lieser, K.-S. Lee, G. Wegner, Colloid Polym. Sci., 266, 419 (1988). 231. D. L. Dorsett, S.-L. Hsu, Polymer, 30, 1596 (1989). 232. G. Zerbi, R Roncone, G. Longhi, S. L. Wunder, J. Chem. Phys., 89, 166 (1988). 233. P. W. Teare, Acta Cryst., 12, 294 (1959). 234. I. Ando, T. Sorita, T. Yamanobe, T. Komoto, H. Sato, K. Deguchi, M. Imanari, Polymer, 26, 1864 (1985). 235. P. Grossmann, R. Arnold, K. R. Burkle, Polymer Bull., 3, 135 (1980). 236. S. Boneva, St. Kotov, Chromatographia, 25, 735 (1988). 237. R. D. Chambers, J. Hutchinson, R. H. Mobbs, W. K. R. Musgrove, Tetrahedron, 20, 497 (1964). 238. D. P. Graham, J. Org. Chem., 31, 955 (1966). 239. R L. Coe, S. F. Sellers, J. C. Tatlow, H. C. Fielding, G. Whittaker, J. Fluorine Chem., 18, 417 (1981). 240. J. D. LaZerte, L. J. Hals, T. S. Reid, G. H. Smith, J. Am. Chem. Soc, 75, 4525 (1953). 241. B. Albinsson, J. Michl, J. Am. Chem. Soc, 117, 6378 (1995). 242. R. J. Twieg, J. R Rabolt, Macromolecules, 21, 1806 (1988); 16, 1361 (1985). 243. R. D. Chambers, A. A. Lindley, H. C. Fielding, J. S. Moilliet, G. Whittaker, J. Chem. Soc, Perkin Trans. I, 1064 (1981). 244. T. Albrecht, H. Elber, R. Jaeger, M. Kimmig, W. Petry, C. Ritter, H. Schwickert, R. Steiner, G. Strobl, B. Stuhn, Progr. Colloid Polym. Sci., 87, 46 (1992). 245. S. Tsubakihara, K. Higashi, S. Taki, K. Matsushige, M. Yasuniwa, Polymer J., 24, 777, 1215 (1992).
246. J. K. Krtiger, J. Albers, M. Moller, H.-J. Cantow, Polym. Bull., 5, 131 (1981). 247. H. Schwickert, G. Strobl, M. Kimmig, J. Chem. Phys., 95, 2800 (1991). 248. K. Hatada, K. Ute, N. Miyatake, Progr. Polym. ScL, 19,1067 (1994). 249. H. Vanni, J. F. Rabolt, J. Polym. Sci., Polym. Phys., 18, 587 (1980). 250. R. J. Twieg, J. F. Rabolt, J. Polym. Sci., Polym. Lett., 21,901 (1983). 251. J. Hopken, C. Pugh, W. Richtering, M. Moller, Makromol. Chem., 189, 911 (1988); J. Hopken, M. Moller, Macromolecules, 25, 2482 (1992).
252. D. S. Young, N. Fukuhara, L. A. Bigelow, J. Am. Chem. Soc, 62, 1171 (1940). 253. W. Brunskill, W. T. Flowers, R. Gregory, R. N. Haszeldine. J. Chem. Soc, Chem. Commun., 1444 (1970). 254. S. P. V. Halasz, F. Kluge, T. Martini, Chem. Ber., 106, 2950 (1973). 255. G. Minoni, G. Zerbi, J. Polym. Sci., Polym. Lett., 22, 533 (1984). 256. T. Takenaka, T. Yamanobe, T. Komoto, I. Ando, H. Sato, Solid State Commun., 61, 563 (1987). 257. W. Dmowski, W. T. Flowers, R. N. Haszeldine, J. Fluorine Chem., 9, 94 (1977).
TABLE 2. OLIGO(DIENES) 2.1. OLIGOMERS OF 1,3-BUTADIENE Oligomers
n
MoI. wt
LINEAR DIMERS
2
108.2
m.p. (0C)
3-Methyl-l-fra«s-4,6-heptatriene CH 2 =CH-CH(CH 3 )-CH=CH-CH=CH 2 1,3,6-Octatriene
b.p. (°C/mbar)
nDl°C
Refs.
117/1013
1.4657/20
13,14,33,35,36,38
129/1013
1.4743/20
33,36
CH2=CH-CH=CH-CH2-CH=CH-CH3
1,3,7-Octatriene
31,32,35,36,39
CH2=CH-CH=CH-CH2-CH2-CH=CH2
trans CW 2,4,6-Octatriene {cisltrans)
124-125/1013 115-117/1013 65-66/53
1.4686/20 1.4594/20
39 39 34,40,41
147-148/1019 230-232/1013
1.5131/27
34,40,41 42,43
CH 3 - C H = C H - C H = C H - C H = C H - C H 3
all-trans A3'3'-Octahydro-diphenyl 3 162.3 Vinylcyclopolyenes p [(CH 2 CH= CHCH 2 ^CH(CH= CH2)CH2]-] 4-Vinyl-l-cyclohexene
52.5
2
108.2
129-130/1013
1.4642/20
1-7,34-37,44,48,49
5
270.4
~ 136/1.3
1.5093/20
37
6
324.5
~ 170/1.3
1.5098/20
37
2
108.2
(*=D 17-Vinyl-all-frarcs-l,5,9,13-cyclooctadecatetraene (X = A)
21-Vinyl-all-fra«s-l,5,9,13,17cyclodocosapentaene (x = 5) 1,2-Divinyl-cyclobutane cis
38/51
trans
1.4563
1,8,48,49
112-113/1013
1.4451/20
8,44,48,49
-70.1 -62
150.8/1002
1.4936/20 1.4933/20
34 -16.8 -9 to-8 19-20
237.5/1013 241.5/1013 244/1013 ~97/l
1.5005/20 1.5078/20 1.5129/20 1.507/20
1,3-10,35-37 1,4,8,9 4 5-7,10-12,35-37 5-7,12,45,46 5,6,12,45-47 6,12,46 37
CYCLOPOLYENES
1,5-Cyclooctadiene cis,cis trans,trans 1,5,9-Cyclododecatriene trans,trans,trans cis,trans,trans cis,cis,trans All-/ra«s-l,5,9,13-cyclohexadecatetraene
2
4
216.4
All-rram-l,5,9,13,17-cycloeicosapentaene
5
270.4
~ 142/1
1.5133/20
37
All-rraiw-l,5,9,13,17,21-cyclotetracosahexaene
6
324.5
~ 176/1
1.5133/20
37
3
108.2
162.3
2.2. OLIGOMERS OF ISOPRENE Oligomers
n
MoI. wt.
2
136.3
2
b.p. (°C/mbar)
nD/° C
Refs.
176/1013
1.4721/25
50,51
136.3
57-58/16
1.4794
2
136.3
54/13
1.4786/20
11,29,30
2
136.3
167/1013
1.4704/25
50
2
136.3
161/1013
1.4570/25
50
3
204.3
78/1.3
1.4963/20
53
3
204.3
70/1.3
1.4786/20
53
4
272.5
160/1.3
1.5013/20
53
frans-l,2-Dimethyl-l,2-divinylcyclobutane
2
136.3
134.5-135/992
1.4541/27
49
trans-1 -Isopropenyl-2-methyl-2- vinylcyclobutane
2
136.3
152.5-153/992
1.4591/27
49
trans-1,2-Diisopropenylcyclobutane
2
136.3
155.1-155.4/987
1.4585/29
49
4-Isopropenyl-l-methyl-1-cyclohexene (dipentene) (D,L)
2
136.3
178/1013
1.4727/18
15-17, 55,62,71
6-Isopropenyl-3-methyl-l-cyclohexene (diprene) (D,L)
2
136.3
173-175/1000
1.4735/20
15,16, 59,71
2,4-Dimethyl-4-vinyl-1 -cyclohexene
2
136.3
162/1000
1.4654/20
11,29,30, 49,55, 58-60,71
1,4-Dimethyl-4-vinyl-1 -cyclohexene
2
136.3
160.5-161.5/988
1.4658/28
11,17,30, 49,53,55, 57-59,71
cis,cis 1,5-Dimethyl-1,5-cyclooctadiene
2
136.3
182.4/988
1.4863/28
49,54, 56-59,71
cis,cis 2,5-Dimethyl-1,5-cyclooctadiene
2
136.3
182.5-184/992
1.4870/27
49,54, 56-59,71
LINEAR OLIGOMERS
2,7-Dimethyl-l-rrayw-3,7-octatriene CH 2 =C(CH 3 )-CH=CH-CH 2 -CH 2 -C(CH 3 )=CH 2 2,6-Dimethyl-l,3,6-Octatriene CH2=C(CH3)-CH=CH-CH2-C(CH3)=CH-CH3 2,7-Dimethyl-l-/ra«5-3,6-octatriene CH 2 =C(CH 3 )-CH=CH-CH 2 -CH=C(CH 3 )-CH 3 2,6-Dimethyl-l-mms-3,7-octatriene CH2=C(CH3)-CH=CH-CH2-CH(CH3)-CH=CH2 3-Methyl-6-methylene-l,7-octadiene CH2=CH-C(CH3)-(CH2)2-C(=CH2)-CH=CH2 2,6,10-Trimethyl-l-/ra^-3,5,10-dodecatetraene CH2=C(CH3)-CH=CH-CH=C(CH3)-(CH2)3-C(CH3)=CH-CH3 7,ll-Dimethyl-3-methylene-l-fran5-6,ll-dodecatriene (P-farnesene) CH 2 =C(CH 3 )-(CH 2 )3-C(CH 3 )=CH-(CH 2 ) 2 -C(=CH 2 )-CH=CH 2 2,6,10,14-Tetramethyl- l-trans-3,6,10,14-hexadecapentaene CH2=C(CH3)CH=CH-[CH2C(CH3)=CHCH2]3=H
6,30,52,27
CYCLIC OLIGOMERS
2.2. cont'd Oligomers
n
MoI. wt.
l,5,10-Trimethyl-d5,rra«5,rraw5-l,5,9-cyclododecatriene
3
204.3
2.3.
b.p. (°C/mbar)
nD/°C
Refs.
1.5120
61
b.p. (°C/mbar)
«/>/°C
Refs.
53/1.2
1.5135/25
63-66
1.5339/25
9,63-66
138/17
OLIGOMERS OF 1,3-BUTADIENE DERIVATIVES
Monomer
Oligomers
m.p. ( 0 C)
n
MoI. wt.
l-Chloro-4-(a-chloro-vinyl)-l-cyclohexene
2
177.1
l,6-Dichloro-l,5-cyclooctadiene
2
177.1
13.8
64/0.33
2,3-Dichloro-l,3-butadiene Hexafluoro-l,3-butadiene
3,4,7,8-Tetrachloro-l,5-cyclooctadiene Cyclic dimer
2 2
246.0 324.1
98-99 40
140-146/4.8 80/1013
63 20,21
2-Cyano-l,3-butadiene
4-Vinyl-l,4-dicyano-l-cyclohexene
2
158.2
55-56
110-112/1.3
69
l-Phenyl-l,3-butadiene
3-Phenyl-4-/ra«s-styryl-l-cyclohexene
2
260.4
189-191/3
67
2-Phenyl-l,3-butadiene
l,4-Diphenyl-4-vinyl-l-cyclohexene
2
260.4
60
220-222/17
68
l,3-Diphenyl-l,3-butadiene
l,3,4-Triphenyl-4-fra7w-styryl-l-cyclohexene
2
412.3
137-138
2-Chloro-l,3-butadiene
2.4.
1,4-OLIGO(ALKADIENES) CH 3 CH 2 - [ C H 2 - C X = C H - C H 2 ] „-CH 2 CH 3
X
n
Configuration
H
1
cis trans M-cis All-trans AU-CiJ
2
CH 3
18,19
3 1 2 3 4
MoI. wt.
b.p. (°C/mbar)
nD/°C
112.2
121.7/985 121.4/985 90-91/23 87-88/23 120-125/2 138-140/1013 92/7 98/0.3 140/0.2
1.4136/20 1.4116/20 1.4455/23 1.4415/24 1.4638/19 1.4224/20 1.4540/20 1.4729/20 1.4878/16
166.3 220.4 126.2 194.3 262.5 330.6
Refs. 87 87 85 85 86 75 75 75 75
2.5.
OLIGOMERS OF CYCLOPENTADIENE AND 1,3-CYCLOHEXADIENE
Oligomers
n
MoI. wt.
Dicyclopentadiene endo exo
2
132.2
m.p. ( 0 C)
b.p. (°C/mbar)
nDl°C
Refs. 84
32
163/1021 170/1017
1.5070/25
22,23,49,70,74 49,70,72
Tricyclopentadiene 3
198.3
68
251/1021
22,23,74,84
4
264.4
207
344/1021
22,23,74,84
2
132.2
170-172/1013
2
160.3
229/1013
Tetracyclopentadiene
/rarcs-Tricyclo[5,3,0,02'6]-3,9-decadiene
Dicyclohexadiene
2.6.
1.5080/25
49,70
22,73,74
OLIGOMERS OF ALLENE
Oligomers
n
DIMERS
2
MoI. wt.
m.p. ( 0 C)
b.p. (°C/mbar)
nD/°C
Refs.
80.1
1,2-Dimethylene-cyclobutane
74/1013
1.4690/20
24-27,77,81,82
1,3-Dimethylene-cyclobutane
69/1013
1.4485/20
77-80
68-69/80
1.4919/25
76,77
68-69/80
1.4919/25
76
TRIMERS
3
120.2
1,2,4-Trimethylene-cyclohexane
1,3,5-Trimethylene-cyclohexane
33.5-35
3-Methylenebicyclo-[4,2,0]-octa-l(6)-ene
1.5-(or l,6-)-Dimethylenespiro-[3,3]heptane
TETRAMERS
4
2,6- + 2,7-Dimethylenebicyclo-[4,4,0]-dec-9,10-ene (P-tetramer)
UV, 1H-NMR, MS
77
IR, UV, 1H-NMR, MS
77
160.3
107-108/17
1.5248/25
24,25,28,60,83
2.6. cont'd Oligomers
n
MoI. wt.
1,3,5,7-Tetramethylene cyclooctane
PENTAMERS
m.p. ( 0 C)
b.p. (°C/mbar) 60/4.7
5
nD/°C 1.5102/25
Refs. 76
200.4
6 '-Methylene-3 ',4',7 ',8 '-tetrahydrospiro[2- and 3-methylene]-cyclobutane-1,2'(1 'H,5 'H)-naphthalene + 7 '-methylene-3 ',4',5 ',6 '-tetrahydrospiro[2- and 3-methylene]cyclobutane-l,2'-(l 'H,8 'H)-naphthalene 73/0.03 1.5307/20
24,88
REFERENCES 1. W. Brenner, R Heimbach, H. Hey, E. W. Mueller, G. Wilke, Ann. Chem., 727, 161 (1969). 2. N. E. Duncan, G. J. Janz, J. Chem. Phys., 20, 1644 (1952). 3. J. C. Hillyer, J. V. Smith, Jr., Ind. Eng. Chem., 45,1133 (1953). 4. K. Ziegler, H. Wilms, Ann. Chem., 567, 1 (1950); K. Ziegler, H. Sauer, L. Bruns, H. Froitzheim-Kuehlhorn, J. Schneider, Ann. Chem., 589, 122 (1954). 5. G. Wilke, Angew. Chem., 69, 397 (1957); G. Wilke, E. W. Mueller, M. Kroener, ibid., 73, 33 (1961); B. Bogdanovic, R Heimbach, M. Kroener, G. Wilke, E. G. Hoffmann, J. Brandt, Ann. Chem., 727, 143 (1969). 6. G. Wilke, Angew. Chem., 75, 10 (1963). 7. G. Pajaro, D. Fiumani, M. Moro, Gazz. Chim. Ital., 92, 1452 (1962); C. 1965, II, 990. 8. E. Vogel, Angew. Chem., 68, 413 (1956); Ann. Chem., 615, 1 (1958). 9. A. C. Cope, W. J. Bailey, J. Am. Chem. Soc, 70, 2305 (1948); A. C. Cope, C. L. Stevens, E A. Hochstein, ibid., 72, 2510 (1950). 10. H. W. B. Reed, J. Chem. Soc, 1931 (1954). 11. G. Wilke, J. Polym. ScL, 38, 45 (1959). 12. H. Breil, R Heimbach, M. Kroener, H. Mueller, G. Wilke, Makromol. Chem., 69, 18 (1963). 13. S. Tanaka, K. Mabuchi, N. Shimazaki, J. Org. Chem., 29,1626 (1964). 14. S. Otsuka, T. Kikuchi, T. Taketomi, J. Am. Chem. Soc, 85, 3709 (1963). 15. T. Wagner-Jauregg, Ann. Chem., 488, 176 (1931). 16. O. Aschan, Ann. Chem., 439, 221 (1924); Chem. Ber., 57, 1959 (1924). 17. C. Walling, J. Paisach, J. Am. Chem. Soc, 80, 5819 (1958). 18. W. Herz, W. Lewis, J. Org. Chem., 23, 1646 (1958). 19. T. L. Jacobs, M. H. Goodrow, J. Org. Chem., 23, 1653 (1958). 20. I. L. Karle, J. Karle, T. B. Owen, R. W. Broge, A. H. Fox, J. L. Hoard, J. Am. Chem. Soc, 86, 2523 (1964).
21. M. Prober, W. T. Miller, Jr., J. Am. Chem. Soc, 71, 598 (1949). 22. K. Alder, G. Stein, Ann. Chem., 485, 223 (1931); 496, 204 (1932); 504, 216 (1933). 23. H. Staudinger, H. A. Bruson, Ann. Chem., 447, 97 (1926). 24. S. V. Lebedev, Zh. Fiz. Khim. Obshch., 45,1357 (1913); C. A., 9, 799 (1915). 25. R. N. Meinert, C. D. Hurd, J. Am. Chem. Soc, 52, 4540 (1930). 26. K. Alder, O. Ackermann, Chem. Ber., 87, 1567 (1954). 27. A. T. Blomquist, J. A. Verdol, J. Am. Chem. Soc, 78, 109 (1956). 28. B. Weinstein, A. H. Fenselau, Tetrahedron Lett., 1463, (1963). 29. J. Itakura, H. Tanaka, Makromol. Chem., 123, 274 (1969). 30. L. I. Zakharkin, Dokl. Akad. Nauk SSSR, 131, 1069 (1960). 31. E. J. Smutny, J. Am. Chem. Soc, 89, 6793 (1967). 32. S. Takahashi, T. Shibano, N. Hagihara, Tetrahedron Lett., 2451, (1967). 33. H. Takahasi, S. Tai, M. Yamaguchi, J. Org. Chem., 30, 1661 (1965). 34. T. Alderson, E. L. Jenner, R. V. Lindsey, Jr., J. Am. Chem. Soc, 87, 5638 (1965). 35. G. R Potapov, V. V. Punegov, U. M. Dzhemilev, Izv. Akad. Nauk SSSR, Ser. Khim., 1468 (1985); Bull. Acad. Sci. USSR, 1342 (1985). 36. H. Mueller, D. Wittenberg, H. Seibt, E. Scharf, Angew. Chem., 77, 318 (1965); D. Wittenberg, Angew. Chem., 75, 1124(1963). 37. A. Miyake, H. Kondo, M. Nishino, Angew. Chem., 83, 851 (1971). 38. T. Saito, Y. Uchida, A. Misono, Bull. Chem. Soc Japan, 37, 105 (1964). 39. G. B. Butler, T. W. Brooks, J. Org. Chem., 28, 2699 (1963). 40. M. Urion, Koll.-Z., 63, 84 (1933); Compt. Rend. Acad. Sci., 196, 353 (1933).
41. 42. 43. 44. 45. 46. 47. 48. 49. 50. 51. 52. 53.
54. 55. 56. 57. 58. 59. 60.
61. 62. 63. 64.
R. Kuhn, Ch. Grundmann, Chem. Ber., 71, 442 (1938). K. Alder, H. F. Rickert, Chem. Ber., 71, 373 (1938). G. B. Kistiakowsky, W. W. Ransom, J. Chem. Phys., 7,725 (1939). H. W. B. Reed, J. Chem. Soc, 685, (1951). H. Nozaki, Y. Nisikawa, M. Kawanisi, R. Noyori, Tetrahedron, 23, 2173 (1967). M. Denecke, H. C. Broecker, Makromol. Chem., 176, 1471 (1975); V. D. Mochel, J. Polym. Sci. A-I, 10, 1009 (1972). H. Takahasi, M. Yamaguchi, J. Org. Chem., 28, 1409 (1963). G. S. Hammond, N. J. Turro, A. Fischer, J. Am. Chem. Soc, 83, 4674 (1961). G. S. Hammond, N. J. Turro, R. S. H. Liu, J. Org. Chem., 28, 3297 (1963). K. Takahashi, G. Hata, A. Miyake, Bull. Chem. Soc. Japan, 46, 600 (1973). A. Josey, J. Org. Chem., 39, 139 (1974). A. Misono, Y. Uchida, K. Furuhata, S. Yoshida, Bull. Chem. Soc. Japan, 42, 2303 (1969). U. M. Dzhemilev, G. M. Latypov, G. A. Tolstikov, O. S. Vostrikova, Izv. Akad. Nauk SSSR, Ser. Khim., 553 (1979); Bull. Akad. Sci. USSR, 509 (1979). U. M. Dzhemilev, G. E. Ivanov, G. A. Tolstikov, Zh. Org. Khim, 11,1636 (1975); J. Org. Chem. USSR, 11,1623 (1975). J. R Candlin, W. H. Janes, J. Chem. Soc. C, 1856 (1968). A. Misono, V. Uchida, M. Hidai, V. Ohsawa, Bull. Chem. Soc. Japan, 39, 2425 (1966). S. Watanabe, K. Suga, H. Vikuchi, Austr. J. Chem., 3,385 (1970). L. L Zakharkin, G. G. Zhigareva, Izv. Akad. Nauk SSSR, 168, (1964); Bull. Akad. Sci. USSR, 149 (1964). J. L. Binder, K. C. Eberly, G. E. P. Smith, Jr., J. Polym. Sci., 38, 229 (1959). S. Lebedev, Zh. Russ. Fiz.-Khim. Obshch., 45, 1249 (1913); C. 1914 I, 1406; J. W. Lebedew, A. A. Ivanov, ibid., 48, 997 (1916); C. 1923 I, 1539. Y. Tanaka, H. Sato, Y. Nakafutami, H. Iwasaki, T. Taketomi, Polym. J., 14, 713 (1982). G. S. Whitby, R. N. Crozier, Can. J. Res., 6, 203 (1932). R. E. Foster, R. S. Schreiber, J. Am. Chem. Soc, 70,2303 (1948). J. G. T. Brown, J. D. Rose, J. L. Simonsen, J. Chem. Soc, 10 (1944).
65. A. C. Cope, W. R. Schmitz, J. Am. Chem. Soc, 72, 3056 (1950). 66. A. L. Klebanskii, M. M. Denisova, Zh. Obshch. Khim. SSSR, 17, 703 (1947); Chem. Abstr. 42, 1215c (1948). 67. K. Alder, J. Haydn, W. Vogt, Chem. Ber., 86, 1302 (1953); C. Liebermann, C. N. Riiber, Chem. Ber., 35, 2696 (1902). 68. K. Alder, J. Haydn, Ann. Chem., 570, 201 (1950). 69. C. S. Marvel, N. O. Brace, J. Am. Chem. Soc, 71, 37 (1949). 70. N. J. Turro, G. S. Hammond, J. Am. Chem. Soc, 84, 2841 (1962). 71. LN. Nazarov, A. I. Kuznetsova, N. V. Kuznetsov, Zh. Obshch. Khim. SSSR, 25, 291 (1955); J. Gen. Chem., 25, 307 (1955). 72. P. D. Bartlett, I. S. Goldstern, J. Am. Chem. Soc, 69, 2553 (1947); P. D. Bartlett, A. Schneider, J. Am. Chem. Soc, 68, 6 (1946); H. A. Bruson, T. W. Riener, J. Am. Chem. Soc, 67, 723, 1178(1945),68,8(1946). 73. K. Alder, G. Stein, Ann. Chem., 496, 197 (1932). 74. K. Alder, G. Stein, Chem. Ber., 67, 613 (1934). 75. C. Pinazzi, D. Reyx, Bull. Soc Chim. France, 3930 (1972). 76. R. E. Benson, R. V. Lindsey, Jr., J. Am. Chem. Soc, 81, 4247 (1959). 77. B. Weinstein, A. H. Fenselau, J. Chem. Soc C, 368 (1967). 78. F. F. Caserio, Jr., S. H. Parker, R. Piccolini, J. D. Roberts, J. Am. Chem. Soc, 80, 5507 (1958). 79. J. K. Williams, W. H. Sharkey, J. Am. Chem. Soc, 81, 4269 (1959). 80. Y. M. Slobodin, A. R Khitrov, Zh. Obshch. Khim., 33, 153 (1963); J. Gen. Chem. USSR, 33, 146 (1963). 81. A. T. Blomquist, J. A. Verdol, J. Am. Chem. Soc, 77, 1806 (1955). 82. Y. M. Slobodin, A. P. Khitrov, Zh. Obshch. Khim., 33, 2819 (1963); J. Gen. Chem. USSR, 33, 2745 (1963). 83. B. Weinstein, A. H. Fenselau, J. Org. Chem., 32, 2278 (1967). 84. H. Staudinger, A. Rheiner, HeIv. Chim. Acta, 7, 23 (1924). 85. C. Pinazzi, D. Reyx, G. Levesque, C. R., Ser. C, 270, 2120 (1970). 86. C. Pinazzi, D. Reyx, C. R. Ser. C, 274, 252 (1972). 87. K. N. Campbell, L. T. Eby, J. Am. Chem. Soc, 63, 2683 (1941). 88. B. Weinstein, A. H. Fenselau, J. Org. Chem., 32, 2988 (1967).
TABLE 3. OLIGO(ACETYLENES)
3.1. LINEAR OLIGOMERS OF ACETYLENE b.p. (°C/mbar)
d (g/cm3)/°C
n
MoI. wt.
nf
Refs.
Vinylacetylene CH2=CH-C = CH
2
52.1
5/1009
0.705/0
Divinylacetylene CH2=CH-C = C-CH=CH2 l,3-Hexadiene-5-yne cisltrans CH2=CH-CH=CH-C= CH
3
78.1
84.5-85/1013
0.772/20
1.5055
1-3
3
78.1
81-82/1013
0.780/28
1.4900
1,2,4-6,25
l,3,7-Octatriene-5-yne CH 2 =CH-CH=CH-C= C-CH=CH2 (E)-: GC; 1H-, 13C-NMR; Ref. 7 (Z)-: GC; 1H-, 13C-NMR; Ref. 7
4
105.1
10/27
0.830/20
1.5834
1,2,7
1,2
3.2.
POLYENYNE OLIGOMERS ( C H 3 ) 3 C - [ O C - C H = C H ] n - C = C-C(CH 3 ) 3
n
MoI. wt.
m.p. (0C)
Refs.
1 2 3 5 7
188.3 238.4 288.4 388.5 488.6
69-72 118-120 155-156 22Od 204 d
26 26 26 26 26
3.3. JC 1
2
3
4
5 6
OLIGOMERIC a,co-DIYNES H[Cs C - ( C H 2 ) ^ - C s C]rtH /i
MoI. wt.
1 2 3 1 2 4 1 2 4 1 2 4 1 2 1 2 4
64.1 126.1 188.2 78.1 154.2 30.4 92.1 182.3 362.5 106.2 210.3 418.6 120.2 238.4 134.2 266.4 530.8
m.p. (0C) -20 to-19 65-66 103-104 99-100 167-168 d -84.8 --5 60-61 21-22 93-94 -27.3 21-22
b.p. (°C/mbar)
wD/°C
63-64/1013
87.5-88.5/1011
1.4381/23
111.5/1013 110-111/0.9
1.4423/20
93-95/253 119-120/0.1
1.4521/18 1.5205/23
162/1013
1.4490/20 1.5119/26
68-71/18 30-31 59-61
Refs. 8 8,9 8 10 11-14 11,12 15 11,12 11,12 16 11,17 11,17 15 11,12 18 11,12 11,12
3.4. OLIGO(ALKYNES) H[C= C-(CH 2 )Jn-C = CH x 1
2 4
5
6
3.5.
n
MoI. wt.
1 2 3 4 6 1 2 1 2 3 7 8
64.1 102.1 140.2 178.2 254.3 78.1 130.2 106.2 186.2 266.4 586.9 667.0
1 2 3 1 2
120.2 214.3 308.5 134.2 242.4
m.p. (0C) -21 to-19 21-21.5 44-45 73-74 112-113.5 46 -3 19 36 55
-27.3 8 33 24
b.p. (°C/mbar)
nD/°C
63-64/1013 1.4833/22
87.5-88.5/1011 61-63/3 93-95/253 111/1.3 167/0.4
1.4381/23
162/1013 113/1.1 170/0.1 68-71/18 131/0.3
1.4490/20 1.4791/26
1.4521/18 1.4775/25 1.4918/25
1.4806/25
Refs. 8 8 8 8 8 10 19 16 9 9 9 9
15 9 9 18 9
CYCLIC OLIGO(ALKYNES) p [ ( C = C ) x - (CH2)y]r\
x
y
n
MoI. wt.
m.p. (0C)
1
4
2 4 2 2 2 2 2
160.2 320.5 188.3 216.4 244.4 272.5 300.5
39 71 100 -3.5 97 38-39 106.5
5 6 7 8 9
b.p. (°C/mbar) 87/0.3 215/0.3 100-110/0.001 110-120/0.001 160-180/4 145-147/0.01 198-202/0.001
Refs. 9,20,21 9,20 9,20 20 20 20 20
3.5.
cont'd
x
y
n
MoI. wt.
m.p. (0C)
2
2
3 4 5 6 7 2 3 4 2 3 4 5 2 3 4 5 6 2 3 4 2 2 2 1 2 2
228.3 304.4 380.5 456.6 532.6 180.2 270.4 360.5 208.3 312.4 416.6 520.7 236.3 354.5 472.7 590.9 709.0 264.4 396.6 528.8 292.4 320.5 348.5 188.3 376.6 284.4
175-180d 170-18Od 165 d ~180d -180d 115-120 (expl.) 174-175 213-214 163 173-174 154-155 155-157 212 125-126 135-136 144-145 144-145 82 135-136 152-154 171 85 142 18 101-102 >200
3
4
5
6
7 8 9 10 3
3.6.
5
b.p. (°C/mbar)
Refs. 14 14 14 14 14 11,12 13 13,22 12,13,17,20,22 13,22 13,22 13,22 11-13,20,22 13,22 13,22 13,22 13,22 12,20,22 22 22 20 20,22 20 23 23 20
PERICYCLYNES p[C=C-C(CH 3 ) 2 ],n
n
MoI. wt.
m.p. (0C)
Refs.
5 6 7 8
330.5 396.6 462.7 528.8
201-202 249-250 173-174 189-190
24 24 24 24
REFERENCES 1. J. A. Nieuwland, W. S. Calcott, F. B. Downing, A. S. Carter, J. Am. Chem. Soc, 53, 4197 (1931). 2. K. K. Georgieff, W. T. Cave, K. G. Blaikie, J. Am. Chem. Soc, 76, 5494 (1954). 3. R. Lespieau, Guillemonat, Koll.-Z., 63, 84 (1933). 4. D. A. Ben-Efraim, F. Sondheimer, Tetrahedron, 25, 2837 (1969). 5. J. H. Van Boom, L. Brandsma, J. F. Arens, Rec. Trav. Chim. Pay-Bas, 85, 952 (1966). 6. F. Sondheimer, D. A. Ben-Efraim, Y. Gaoni, J. Am. Chem. Soc, 83, 1682 (1961). 7. H. Hopf, L. Eisenhuth, V. Lehne, L. Ernst, Chem. Ber., 119, 1105 (1986). 8. D. A. Ben-Efraim, F. Sondheimer, Tetrahedron, 25, 2823 (1969). 9. J. H. Wotiz, R. F. Adams, C. G. Parsons, J. Am. Chem. Soc, 83, 373 (1961). 10. R. A. Raphael, F. Sondheimer, J. Chem. Soc, 120 (1950). 11. Y. Amiel, F. Sondheimer, R. Wolovsky, Proc Chem. Soc, 1957, p. 22.
12. F. Sondheimer, Y. Amiel, R. Wolovsky, J. Am. Chem. Soc, 79, 6263 (1957). 13. F. Sondheimer, Y. Amiel, R. Wolovsky, J. Am. Chem. Soc, 79, 4247 (1957). 14. F. Sondheimer, R. Wolovsky, J. Am. Chem. Soc, 84, 260 (1962). 15. A. L. Henne, K. W. Greenlee, J. Am. Chem. Soc, 67, 484 (1945); R. Lespieau, Journaud, Compt. Rend., 188, 1410 (1929). 16. H. Bader, L. C. Cross, I. M. Heilborn, E. R. H. Jones, J. Chem. Soc, 619 (1949). 17. F. Sondheimer, Y. Amiel, J. Am. Chem. Soc, 79,5817 (1957). 18. W. M. Lauer, W. J. Gensler, J. Am. Chem. Soc, 67, 1171 (1945). 19. F. Sondheimer, Y. Gaoni, J. Am. Chem. Soc, 84,3520 (1962). 20. J. Dale, A. J. Hubert, G. S. D., King, J. Chem. Soc, 73, (1963). 21. D. J. Cram, N. L. Allinger, J. Am. Chem. Soc, 78, 2518 (1956). 22. F. Sondheimer, Y Amiel, R. Wolovsky, J. Am. Chem. Soc, 81, 4600 (1959).
23. G. Eglinton, A. R. Galbraith, J. Chem. Soc, 889 (1959); Chem & Ind., 737 (1956). 24. L. T. Scott, G. J. DeCicco, J. L. Hyun, G. Reinhardt, J. Am. Chem. Soc, 105, 7760 (1983); 107, 6546 (1985).
TABLE 4. 4.1.
25. A. L. Klebanskii, U. A. Dranitzina, I. M. Dobromilskaya, Compt. Rend. Acad. Sci. USSR, 2, 229 (1935); Chem, Abstr., 29, 6205 (1935). 26. F. Wudl, S. P. Bitler, J. Am. Chem. Soc, 108, 4685 (1986).
OLIGOMERS WITH ALIPHATIC SIDE CHAINS WHICH IN ADDITION CONTAIN HETEROATOMS
OLIGOMERIC ACRYLIC DERIVATIVES
4.1.1. O L I G O ( A C R Y L I C ACIDS) 4.1.1.1. H[CH2CH(COOH)JnCH3 n
MoI. wt.
1 2
88.1 160.2
3
232.2
m.p. (0C)
Configuration
-46 128 141 167.5-170.0 160.0-163.0 153.5-154.5
Isotactic (meso) Syndiotactic (racemic) Isotactic (meso) Heterotactic (racemic) Syndiotactic (meso)
b.p. (°C/mbar)
Refs.
153/1012 1-3,11 1-3,11 3,78 3,78 3,78
4.1.1.2. (CH3)2C(COOH)-[CH2CH(COOH)]n-C(COOHXCH3)2 n
MoI. wt.
1 2 3 4
246.3 318.3 390.4 462.5
a
m.p. (0C)
Refs.
30-35 70-80 a 181-183 80-82
4 4 4 5
p-Nitrobenzyl ester.
4.1.2. OLIGO (ACRYLATES) 4.1.2.1. H[CH2CH(COOH)JnCH3 n
MoI. wt.
1 2
102.1 188.2
3
274.3
Configuration
b.p. (°C/mbar)
Isotactic (meso) Syndiotactic (racemic) Isotactic (meso) Heterotactic (racemic) Syndiotactic (meso)
nD/°C
91.5/990 64/0.9 NMR 163/15 160/15 156/15
1.4440 1.4420 1.4407
nf
Refs.
1.3838/20 1.4258
6 3,6,101 3 3,6,78 3,6,78 3,6,78
4.1.2.2. Anionic Oligomers RO[CH2CH(COOR)JnH R
n
MoI. wt.
b.p. (°C/mbar)
CH 3 CH 3 C2H5 C2H5
1 2 1 2
118.1 204.2 146.2 246.3
55-56/27 90/1 75-77/27 82/0.15
Refs. 7 7 7,42,56 7,42,56,62
1.433 1.446
4.1.2.3. Unsaturated Oligomers Oligomers Dialkyl-A2-dihydromuconate (trans) ROOC-CH=CH-CH2CH2COOR Dialkyl-A3-dihydromuconate ROOC-CH2-CH=CH-CH2COOR Dialkyl-oc-methyleneglutarate oligomers
R
n
MoI. wt.
b.p. (°C/mbar)
/if?
CH3 C2H5 CH3 C2H5 CH3
2 2 2 2 1
172.2 200.2 172.2 200.2 172.2
86-88/1.3 80-84/1.3 74-75/1.3 107-108/1.3 59/0.3
1.4497
Refs. 42,44,58,60,61,63 58 42,58,60,63 58,63 7,8,42,44,62
4.1.2.3. cont'd Oligomers
R
n
MoI. wt.
b.p. (°C/mbar)
C2H5
2 3 4 1
258.2 344.3 430.4 200.2
120/0.9 166-168/0.4 180/0.03 52-53/0.2
C H 2 = C ( C O O R ) - [ C H 2 C H ( C O O R ) ] nH
4.1.3.
1.0392
Refs. 8 8 8 42,52,56,62
ANIONIC OLIGOMERS OF ACRYLAMIDE CH 2 =CHCO-[NHCH 2 CH 2 CO] n NH 2
n
MoI. wt.
m.p. (0C)
Refs.
1 2
142.2 213.2
149-150 179-181
110-112 112
4.1.4.
nf
OLIGO(ACRYLONITRILES)
4.1.4.1. H[CH 2 CH(CN)] n H n
MoI. wt.
1 2 3
55.1 108.1 161.2
b.p. (°C/mbar) 97.1/1013 116-118/6.5 195-196/3.5
nD/°C
Refs.
1.3689/15 1.4320/25 1.4609/20
9,45 9,10,45
4.1.4.2. H[CH 2 CH(CN)] n CH 3 na
MoI. wt.
m.p. ( 0 C)
b.p. (°C/mbar)
1 2
69.1 122.2
107-108/1013 106/3 94/3
3
175.2
4
228.3
-71.5 8.8* 55 C 37-39* 53-54J 80-81e 130-132^ 158
(g/cm 3 )
dfl°C
0.773 0.9051 0.8940
nD/°C
Refs.
1.3720/20 1.4191/60 1.4155/60
37 10,11,38,54,80 10,11,38,54,80 10,38,53 10,53 10,53 10 10
a
n = 2-5 (diastereomers): 13C-NMR, Ref. 35. Isotactic (meso). c Syndiotactic (racemic). d Heterotactic (racemic). e Syndiotactic (meso). f Two stereoisomers. b
4.1.4.3. H[CH(CN)CH 2 I n CH 2 CN n
MoI. wt.
1 2 3
94.1 147.2 200.2
4.1.4.4.
b.p. (°C/mbar)
nD/°C
287.4/1013 85/0.01 95/0.01
Refs.
1.4347/20 1.4644/25
9,12 9,12
1,2-Dicyanocyclobutanes
n
Configuration
1
cisltrans cis trans
MoI. wt.
m.p. ( 0 C)
b.p. (°C/mbar)
67-67.5 30.5/31.5
190/20 160/20
#i|f
106.1 1.4628
Refs. 13,42,43,66,81 13,14,79 13,14,79
4.1.4.5. Unsaturated Oligomers Oligomers"
n
MoI. wt.
m.p. ( 0 C)
2,3-Dihydromuconitrile
2
106.1
76
2
106.1
b.p. (°C/mbar)
iff?
Refs. 14,15,82
NCCH2CH=CHCH2CN
1,4-Dicyano-l-butene
42,46,49,67
CN-CH=CH-CH2CH2CN
cis trans 2-Methyleneglutaronitrile CH 2 =C(CN)-CH 2CH 2CN {cisltrans) 2,4,6-Tricyano-l-hexene CH 2 =C(CN)-CH 2 CH(CN)-CH 2CH 2CN l,l,4,4-Tetracyanoethyl-l,4-dicyano-2-butene (NCCH 2 CH 2 ) 2 C(CN)-CH=CH-C(CN)(CH 2 CH 2 CN) 2 l,4-Dicyano-l,3-butadiene
2
106.1
3
159.2
6
318.4
2
104.1
-19 t o - 1 7 -13 to - 1 2 -9.6
99.5-102.5/0.5 84.5-86.5/0.5 65/0.13
1.4677 1.4646 1.4550
49,50,83 49,50 42,44-48,52
152-164/2.5
1.4762
42,45
240
14,45,46 42,51
NC-CH=CH-CH=CH-CH
cis9cis
128-129
83
transjrans
159-161
97
4.2.
OLIGOMERIC METHACRYLIC DERIVATIVES
4.2.1. OLIGO(METHACRYLIC ACIDS) 4.2.1.1. H[CH2C(CH3)(COOH)]M-C(COOH)(CH3)2 n
MoI. wt.
m.p. ( 0 C)
Refs.
2 3 4
260.3 346.4 432.5
Oil 45-48 56-59
19 18,19 19
m.p. ( 0 C)
Refs.
4.2.1.2. Anionic Oligo(methacrylic acids) n
MoI. wt.
CH3O-[CH2C(CH3XCOOH)]
2 3
nH
204.2 290.3
82 160
17 17
4.2.2. OLIGO(METHACRYLATES) 4.2.2.1. Anionic Oligo(methacrylates) R O - [ C H 2 C ( C H 3 ) ( C O O O R ) ] n H R
R
/i
MoI. wt.
CH 3 O
CH 3 O
1 2 3 4 6
132.2 232.3 332.4 432.5 632.8
H-C 4 H 9 O
W-C 4 H 9 O
1 2 3 4
216.3 358.5 500.7 642.9
b.p. (°C/mbar) 147/1013 241/1013 116/0.1 190/0.1
n = 2-10: GPC Ref. 36 59-61/0.13 128-130/0.13 186-90/0.13 246-250/0.4
20 /(g/cm 3 ) 0 C
nf
Refs.
0.7949 1.0540 1.1045 1.12 1.565
1.4053 1.4378 1.4567 1.4681
17,36,41,73 17,36,41 17,36,41 17 17
0.8970 0.9436 0.9736 0.9909
1.4213 1.4400 1.4508 1.4574
74 74 74 74
Isotactic and syndiotactic oligomers, (CH S)3C-[CH2C(CH3)COOCHs]n-H, n = 2-100 (mol. wt. 158.2-10070.0): HPLC, GPC, SFC; DSC (F 8 , r m ) , X-ray (n = 2-5), NMR, MS; Refs. 114-124. Reviews: Refs. 114,115. Properties of specific oligomers: n (isotactic and syndiotactic, resp.) = 2-8,13,14,16,19,21,22-25,27-29,31,36,41,44,45,50,58,80,100. m.p. (0C), (isotactic oligomers): n = 28: 98.5, n = 31: 104.5, n = 36: 109.6, n = 41: 117.3, n = 44: 124.3; Ref. 116.
4.2.2.2. Unsaturated Oligomersa
CH2=C(COOCH3)-[CH2-X-(COOCH3)],,-CH3
X
n
MoL wt.
b.p. (°C/mbar)
nf?
CH 2 CH
1 2 1
188.2 276.3 188.2
107/4 173/4
1.4445 1.4588 IR, MS, 1 H-NMR
C(CH 3 ) a
Refs. 16,20,42,59,65,77 16,20,42,59,65,77 Ref. 65,77 Ref. 75
n = 2-4: 2D-COSY-NMR
4.2.2.3. Cyclic Oligomers Oligomers
R
n
Configuration
MoL wt.
CH 3
2
cis trans
200.2
2,4,6-Trimethyl-6-methoxy-methyl-cyclohexanone-2,4-dicarboxylate CH 3
3
l,3,3,5-Tetramethylcyclohexane-2-one-l,5-dicarboxylate
3
l,2-Dimethylcyclobutane-l,2-dicarboxylates
CH 3
4,6,7-Trimethyl-3-oxo-7-propyl-2-oxabicyclo-[2,2,2]octane-6-carboxylate CH 3 3
b.p. (°C/mbar)
IR, MS, 1H-NMR IR, MS, 1H-NMR
268.3
Refs. 65 65
122/0.13
17,36
128-138/3 128-138/3
64,72 64,72
cis trans
270.1
6-endo 6-exo
268.3
117-119 Oil
64 64
296.4
IR, MS, 1H-NMR
64
52-54
l-Ethyl-4,6,7-trimethyl-3-oxo-7-propyl-2-oxa-bicyclo[2,2,2]octane-6-carboxylate CH 3 4 6-exo
4.2.3.
m.p. ( 0 C)
OLIGO(METHACRYLOYL CHLORIDES)
Oligomers
n
MoL wt.
b.p. (°C/mbar)
Refs.
2-Chloro-2,5-dimethylcyclopentanone-5-carboxylic chloride 2
209.1
111-117/23
40
2,5-Dimethyl-A 2 -cyclopentenone-5-carboxylic acid chloride 2
209.1
111-117/23
40
4.2.4. ANIONIC OLIGOMERS OF METHACRYLAMIDE CH 2 =C(CH 3 )CO-[NHCH 2 CH(CH 3 )CO] n NH 2 /i
MoI. wt
m.p. (0C)
Refs.
170.2 255.3 340.4
118-120 155-158 195
84 84 84
1 2 3 n = 4-9: GPC, MS, Ref. 84
4.2.5.
OLIGO(METHACRYLONITRILES)
4.2.5.1. Anionic Oligo(methacrylonitriles) CH3O[CH2C(CH3)CN]nH n
MoI. wt.
b.p. (°C/mbar)
1 2 3 4 5
99.1 166.2 233.3 300.4 367.5
160.6/1013 92/0.7 165/0.7 235/0.7 300-305/0.7
nDl°C
Refs.
1.4038/20 1.438 1.464 1.478 1.488
113 21,34 21,34 21,34 21,34
Refs.
4.2.5.2. l,2-Dicyano-l,2-dimethyl-cyclobutanes p[CH2C(CH3)(CN)- C(CH3)(CN)CH2]^I n
Configuration
MoI. wt.
m.p. (0C)
b.p. (°C/mbar)
2 2
CW trans
134.2 134.2
107-108 90.3
170/33 120/33
16,66,89 16,66,89
4.2.5.3. Unsaturated Oligomers Oligomers
n
MoI. wt.
a-Methylene-5-methyladiponitrile
2
134.2
3
201.3
m.p. (0C)
b.p. (°C/mbar)
iiff
Refs.
148/33
1.4502
16,42,89
194/1.3
1.4720
16
CH3CH(CN)-CH2CH2C(CN)=CH2
5-Cyano-8-methyl-2-methylene-nonanedinitrile
47-49
C H 2 = C ( C N ) - [ C H 2 C H 2 C H ( C N ) ] 2=CH 3
4.3. OLIGOMERS OF 0 ALKYL-SUBSTITUTED VINYL DERIVATIVES 4.3.1.
OLIGO(ESTERS)
Monomer
R
CH3CH=CHCOOR
Oligomers
n
MoI. wt.
b.p. (°C/mbar)
«ff
Refs.
2 2 2
200.2 228.3 200.2
70-80/96 84/0.75 90-110/13
1.4512
2
252.3
100-102/4
55
2
252.3
90-93/3
55
2-methyl-3-pentene1,3-dicarboxylate {cisltrans) OT3CH=C(COOR)CH(CH3)CH2COOR CH3 C2H5 CH3
W-C3H7CH=CHCOOR
CH3
i-C 3H7CH=CHCOOR
CH3
2-Methyl-4-pentene1,3-dicarboxylate {cisltrans) CH2=CH-CH(COOR)CH(CH3)CH2COOR 2-«-Propyl-3-heptene1,3-dicarboxylate C3H7-CH=C(COOR)CH(CH2COOR)-C3H7 2-Isopropyl-5-methyl4-hexene-1,3-dicarboxylate (CH3)2C=CH-CH(COOR)CH(CH 2COOR)-CH(CH 3) 2
42,55,68,70,71 42,55,56,69 42,70,71
•4.3.2.
OLIGO(CROTONONITRILES)
Oligomers
n
MoI. wt.
b.p. (°C/mbar)
n%
Refs.
l,3-Dicyano-2-methyl-3-pentene(aVfra«s)
2
134.2
81-83/0.3
1.4730
42,52,55-57
l,3,5-Tricyano-2,4,6-trimethylcyclohexane P[CH(CN)-CH(CH 3 )Ig 1
3
201.3
152-155/0.3
1.4950
42,57
l,3,5-Tricyano-2,4-dimethyl-5-heptene
3
CH3CH=C(CN)-CH(CH3)CH2CN
150-160/0.13
42,52
CH3CH=C(CN)-CH(CH3)CH(CN)-CH(CH3)CH2CN
4.4.
OLIGO(VINYL) DERIVATIVES
4.4.1.
OLIGO(VINYL ALCOHOLS) AND OLIGO(VINYL ACETATES) H[CH2CHOR] nCH3
R
n
H
2 3
COCH 3
2
3
4.4.2.
Configuration
2b
Isotactic (meso) Syndiotactic (racemic) Mixture Isotactic Heterotactic Syndiotactic Mixture
3b
b
MoI. wt.
Isotactic (meso) Syndiotactic (racemic) Isotactic (meso) Heterotactic (racemic) Syndiotactic (meso) Isotactic (meso) Syndiotactic (racemic) Mixture Isotactic Heterotactic Syndiotactic Mixture
104.1
m.p. (0C)
b.p. (°C/mbar) 73/4 74/4 120/1.3 120/1.3
1.4327 1.4378
20/1013 201/1013 103-107/27 116-117.5/0.7 115-116/0.7 112-114/0.5 120-122/0.7
1.4172 1.4142 1.4170 1.4342 1.4319 1.4297 1.4320
48-49 67
148.2
nf
87.5-88 188.2
274.3 21-22 32.5-33.5
Refs. 80,86,87 80,86,87 84,85 84,85 84,85 86,88,97 86,88,97 96 84,88 84 84,88 84,96
O L I G O ( V I N Y L CHLORIDES) H[CH2CHCL] n CH 3 a
n
a
Configuration
MoL wt. 141.0
203.5
b.p. (°C/mbar)
nD20
Refs.
40/16 36/16 140-141/1013 102.5/20 103.5/20 104.5/20 102.5-104.5
1.4409 1.4390 1.4409 1.4722 1.4704 1.4686 1.4699
80,90-95,97 80,90-95,97 95 89,94,95 89,94,95 89,94,95 89
Oligomers (CHs) 3 C-[CH 2 CHCl] n -H, n = 1,2,3 (threo-; erythro-), 4 (ribo-; xylo-; arabino-; lyxo-): HPLC, 13C-NMR, Ref. 39. 2,4-Dibromopentanes and 2,4,6-tribromoheptanes: Kerr Effekt, Ref. 98.
4.4.3.
O L I G O ( V I N Y L ALDEHYDES) AND OLIGO(VINYL KETONES)
Monomer
n
MoI. wt.
2-Formyl-2,3-dihydropyran
2
3-Formyl-5,6-dihydropyran
a-Methylacrolein
oc-Ethylacrolein
Acrolein CH 2 =CHCHO
Oligomers
m.p. ( 0 C)
b.p. (C/mbar)
Refs.
112.1
145-148/1013
22-25
2
112.1
77-78/16
26,27
2-Formyl-2,5-dimethyl-2,3-dihydropyran
2
140.2
166/1000
24,28
2-Formyl-2,5-diethyl-2,3-dihydropyran
2
168.2
195/1013
24
-75
4.4.3. cont'd Monomer
Oligomers
n
MoI. wt.
Methyl vinyl ketone
2-Methyl-6-acetyl-5,6-dihydropyran
2
128.2
2
140.2
2-Methyl-l-butene-(3)-one CH 2 =C(CH 3 )COCH 3 Phenyl vinyl ketone
3-Methylene-2,6-heptanedione CH 3 COC(=CH 2 )CH 2 CH 2 COCH 3 2,6-Dimethyl-3,7-dioxo-l-octene CH 3 COCH(CH 3 )CH 2 CH 2 COC(CH 3 )=CH 2 2,4-Dibenzoylpentane
2
168.2
2
280.4
CH2=CH-CO-C6H5
CH3CH(COC6H5)CH2CH(COC6H5)CH3
Isotactic (meso) Syndiotactic (racemic)
4.4.4.
5-7
1
b.p. (C/mbar)
Refs.
68/17
29
91-92/7
46
83-85/23
30,99,100
H-NMR 64-65 62-63
99,100 100/1.3 155/1.3
99,100 99,100
OLIGOMERIC N-VINYL DERIVATIVES Oligomers
n
MoI. wt.
m.p. ( 0 C)
l,3-Bis-[N-pyrrolidone-(2)-yl]-l-butene
2
212.3
75
Monomer N-Vinyl-pyrrolidone
4.4.5.
m.p. ( 0 C)
Ref. 31
OLIGO(VINYL PYRIDINES)
Monomer
2-Vinylpyridine
4-Vinylpyridine
Oligomers
n
Configuration
MoL wt.
2 Isotactic (meso) 226.3 3 Isotactic (meso) 331.4 4 Isotactic (meso) 436.6 n = 2-7: LC, 1 H-, 13C-NMR Refs. 108,109 sym-Tri(4-pyridyl)-cyclohexane 3 315.4
b.p. (° C/mbar)
106-108/0.33 LC, GC, 1 H-, 13C-NMR LC, GC, 1 H-, 13C-NMR m.p. (0C): 228.5
Refs.
102,105-107,109 103,105,107,109 104,103,107,109 32,33
REFERENCES 1. 2. 3. 4. 5. 6. 7. 8. 9. 10.
K. Auwers, J. Thrope, Ann. Chem., 285, 337 (1985). E. Moeller, Chem. Ber., 43, 3250 (1910). H. G. Clark, Makromol. Chem., 86, 107 (1965). H. Kaemmerer, A. Jung, Makromol. Chem., 101, 284 (1967). H. Kaemmerer, N. Oender, Makromol. Chem., I l l , 67 (1968). D. Lim, O. Wichterle, J. Polym. Sci., 29, 579 (1958). B. A. Feit, Eur. Polym. J., 3, 523 (1967). B. A. Feit, Eur. Polym. J., 8, 321 (1972). H. Zahn, P. Schaefer, Chem. Ber., 92, 736 (1959); Makromol. Chem., 30, 225 (1959). T. Takata, M. Taniyama, Kobunshi Kagaku, 16, 693 (1955);T. Takata, H. Ishii, Y. Nishiyama, M. Taniyama,
11.
12. 13. 14. 15. 16.
ibid., 18, 235 (1961); C. 729 (1964); Chem. Abstr., 56, 1591 (1962); T. Takata, I. Hirori, M. Taniyama, J. Polym. Sci. A, 2, 1567 (1964). H. G. Clark, Makromol. Chem., 63, 69 (1963); L. E. Alexander, R. Engmann, H. G. Clark, J. Phys. Chem., 70, 252 (1966). R. C. Houtz, Textile Res. J., 20, 786 (1950). E. C. Coyner, W. S. Hillman, J. Am. Chem. Soc, 71, 324 (1949). N. Takashina, C. C. Price, J. Am. Chem. Soc, 84, 489 (1962). W. Reppe, Ann. Chem., 596, 133 (1956). C. J. Albisetti, D. C. England, M. J. Hogsed, R. M. Joyce, J. Am. Chem. Soc, 78, 472 (1956).
17. Th. Voelker, A. Neumann, U. Baumann, Makromol. Chem., 63,182 (1963); G. Schreyer, Th. Voelker, Makromol. Chem., 63, 202 (1963). 18. H. Kaemmerer, J. S. Shukla, G. Scheuermann, Makromol. Chem., 116, 72 (1968). 19. H. Kaemmerer, J. S. Shukla, Makromol. Chem., 116, 62 (1968). 20. E. Trommsdorf, Angew. Chem., 68, 355 (1956). 21. B. A. Feit, J. Wallach, A. Zilkha, J. Polym. Sci. A, 2, 4743 (1964). 22. K. Alder, A. Rueden, Chem. Ber., 74, 920 (1941). 23. S. Potnis, K. Shorara, R. C. Schulz, W. Kern, Makromol. Chem., 63, 78 (1963). 24. H. Schulz, H. Wagner, Angew. Chem., 62, 105 (1950). 25. S. M. Scherlin, A. J. Berlin, T. A. Sserebrennikowa, F. E. Rabinowitsch, Zh. Obshch. Khim., 8, 22 (1938); C. 1939 I, 1971. 26. R. Hall, Chem. Ind., 1772 (1955). 27. G. Dumas, R Rumpff, C. R. Ser. C, 242, 2574 (1956). 28. G. G. Stoner, J. S. McNulty, J. Am. Chem. Soc, 72, 1531 (1950). 29. K. Alder, H. Offermanns, E. Rueden, Chem. Ber., 74, 905 (1941). 30. H. Staudinger, B. Ritzenthaler, Chem. Ber., 67, 1773 (1934). 31. J. W. Breitenbach, F. Galinovsky, H. Nesvadba, E. Wolf, Naturwissenschaften, 42, 155, 440 (1955). 32. F. Longo, J. W. Bassi, F. Greco, M. Cambini, Tetrahedron Lett., 995 (1964). 33. A. Segre, Tetrahedron Lett., 1001 (1964). 34. B. A. Feit, E. Heller, A. Zilkha, J. Polym. Sci. A-I, 4, 1499 (1966); G. Teichmann, A. Zilkha, Eur. Polym. J., 3, 25 (1967). 35. H. Balard, H. Fritz, J. Meybeck, Makromol. Chem., 178, 2393 (1977). 36. A. Laguerre, J.-P. Busnel, C-M. Bruneau, Makromol. Chem., Rapid Commun., 5, 21 (1984). 37. R. E. Kent, S. M. McElvain, Org. Synth., 25, 61 (1945). 38. V. Janout, P. Cafelin, Coll. Czech. Chem. Commun., 45, 1928 (1980). 39. K.-F. Elgert, R. Kosfeld, Polym. Bull., 175, 244 (1983). 40. W. Fischer, D. Bellus, A. Alder, E. Francotte, A. Roloff, Chimia, 39, 19 (1985). 41. S. Fujishige, Makromol. Chem., 177, 375 (1976); 179, 2251 (1978). 42. V. R Yurev, G. A. Gailyunas, O. T. Kofanova, Usp. Khim., 53, 1352 (1984); Russ, Chem. Rev., 53, 783 (1984). 43. D. M. Gale, J. Org. Chem., 35, 970 (1970). 44. T. Saegusa, Y. Ito, H. Kinoshita, S. Tomita, Bull. Chem. Soc. Japan, 43, 877 (1970). 45. M. M. Baizer, J. D. Anderson, J. Org. Chem., 30, 1357 (1965). 46. J. D. McClure, J. Org. Chem., 35, 3045 (1970). 47. British Patent 1,003,656; Chem. Abstr., 64, 605a (1966). 48. French Patent 1,388,444; Chem. Abstr., 63, 504e (1965). 49. C. M. Langkammer, United States Patent 2,478,285; Chem. Abstr., 44, 2009c (1950).
50. A. Misono, Y. Uchida, M. Hidai, H. Shinobara, Y. Watanabe, Bull. Chem. Soc. Japan, 41, 396 (1968). 51. D. J. Milner, R. Whelan, J. Organomet. Chem., 152, 193 (1978). 52. D. A. White, Synth. React. Inorg. Met.-Org. Chem., 7, 433 (1977). 53. M. Murano, R. Yamadera, J. Polym. Sci., Polym. Lett. Ed., 5, 483 (1967). 54. M. Murano, R. Yamadera, J. Polym. Sci. A-I, 5, 1855 (1967). 55. T. Saegusa, Y Ito, S. Tomita, H. Kinoshita, J. Org. Chem., 35, 670 (1970). 56. D. A. White, M. M. Baizer, J. Chem. Soc, Perkin Trans. I, 2230 (1973). 57. J. Shabtai, E. Ney-Igner, H. Pines, J. Org. Chem., 40, 1158 (1975). 58. G. Oehme, H. Pracejus, J. Prakt. Chem., 322, 798 (1980). 59. M. Stickler, G. Meyerhoff, Makromol. Chem., 181, 131 (1980). 60. M. G. Barlow, M. J. Bryant, R. N. Haszeldine, A. G. Mackie, J. Organomet. Chem., 21, 215 (1970). 61. T. Alderson, E. L. Jenner, R. V. Lindsey, Jr., J. Am. Chem. Soc, 87, 5638 (1965). 62. M. M. Rauhut, H. Currier, United States Patent 3,074,999 (1963); Chem. Abstr., 58, 11224b (1963). 63. E. H. Farmer, J. Chem. Soc, 123, 2531 (1923). 64. K. Yamaguchi, K. Yokota, Y Takada, Makromol. Chem., 182,669 (1981); Makromol. Chem., Rapid Commun., 2,645 (1981). 65. J. Lingnau, M. Stickler, G. Meyerhoff, Eur. Polym. J., 16, 785 (1980). 66. M. Bolte, J. Lemaire, C. R., Ser. C, 288, 403 (1979). 67. H.-F. Piepenbrink, Ann. Chem., 572, 83 (1951). 68. T. Saegusa, Y. Ito, S. Kobayashi, S. Tomita, J. Chem. Soc, Chem. Commun., 273 (1968). 69. J. Shabtai, H. Pines, J. Org. Chem., 30, 3854 (1965). 70. M. Ikeda, T. Hirano, T. Tsuruta, Tetrahedron, 30, 2217 (1974). 71. M. Ikeda, T. Hirano, T. Tsuruta, Tetrahedron Lett., 4477, (1972). 72. L. Lochmann, M. Rodova, J. Petranek, D. Lim, J. Polym. Sci., Polym. Chem. Ed., 12, 2295 (1974). 73. D. Dosococilova, J. Stokr, B. Schneider, M. Pradny, S. Sevcik, Coll. Czech. Chem. Commun., 49, 2275 (1984). 74. J. Trekoval, Coll. Czech. Chem. Commun., 38, 3769 (1973). 75. P. Cacioli, D. G. Hawthorne, S. R. Johns, D. H. Solomon, E. Rizzardo, R. I. Willing, J. Chem. Soc, Chem. Commun., 1355 (1985). 76. W. von E. Doering, C. A. Guyton, J. Am. Chem. Soc, 100, 3229 (1978). 77. K. Naruchi, M. Miura, Polymer, 22, 1716 (1981); K. Naruchi, M. Miura, K. Nagakubo, Nipoon Kagaku Kaishi, 871, (1977); K. Naruchi, O. Yamamoto, M. Miura, K. Nagakubo, ibid., 1974, (1976). 78. D. Lim, B. Obereigner, D. Doskocilova, J. Polym. Sci., Polym. Lett., 3, 893 (1965).
79. J. A. Barltrop, H. A. J. Carless, J. Am. Chem. Soc, 94,1951 (1972). 80. R E. McMohan, W. C. Tincher, J. MoI. Spectr., 15, 180 (1965). 81. S. Hosaka, S. Wakamatsu, Tetrahedron Lett., 219 (1968). 82. R Kurtz, Ann. Chem., 572, 23 (1951). 83. K. Nakagawa, H. Onoue, Tetrahedron Lett., 1433, (1965). 84. D. Lim, E. Votavova, J. Stokr, J. Petranek, J. Polym. Sci., Polym. Lett., 4, 581 (1966). 85. K. Fujii, J. Polym. Sci., Polym. Lett., 3, 375 (1965). 86. J. G. Pritchard, R. L. Vollmer, J. Org. Chem., 28, 1545 (1963). 87. Y. Fujiwara, S. Fujiwara, Bull. Chem. Soc. Japan, 37, 1010 (1964). 88. Y. Fujiwara, S. Fujiwara, K. Fujii, J. Polym. Sci. A-I, 4, 257 (1966). 89. D. Lim, M. Kolinsky, J. Stokr, J. Petranek, J. Polym. Sci., Polym. Lett., 4, 577 (1966). 90. S. Satoh, J. Polym. Sci. A, 2, 5221 (1964). 91. Y. Inoue, I. Ando, A. Nishioka, Polym. J., 3, 246 (1972). 92. T. Shimanouchi, M. Tasumi, Spectrochim. Acta, 17, 755 (1961). 93. T. Shimanouchi, M. Tasumi, Y. Abe, Makromol. Chem., 86, 43 (1965). 94. Y. Abe, M. Tasumi, T. Shimanouchi, S. Satoh, R. Chujo, J. Polym. Sci. A-I, 4, 1413 (1966). 95. R. Lukas, J. Jakes, V. Paleckova, S. Pokorny, M. Kolinsky, J. Polym. Sci., Polym. Chem. Ed., 21, 3093 (1983). 96. J. Stokr, B. Schneider, Coll. Czech. Chem. Commun., 28, 1946 (1963). 97. D. Doskocilova, B. Schneider, Coll. Czech. Chem. Commun., 29, 2290 (1964). 98. A. E. Tonelli, G. Khanarian, R. E. Cais, Macromolecules, 18, 2324 (1985). 99. L. Merle-Aubry, Y. Merle, E. Selegny, C. R., Ser. C, 276, 249 (1973). 100. Y. Merle, L. Merle-Aubry, E. Selegny, C. R., Ser. C, 280, 443 (1975). 101. T. E. Hogen-Esch, C. F. Tien, J. Polym. Sci., Polym. Chem. Ed., 17, 281 (1979). 102. C. F. Tien, T. E. Hogen-Esch, Macromolecules, 9, 871 (1976); C. F. Tien, T. E. Hogen-Esch, J. Am. Chem. Soc, 98, 7109 (1976).
103. C. F. Tien, T. E. Hogen-Esch, J. Polym. Sci., Polym. Lett., 16, 297 (1978). 104. T. E. Hogen-Esch, C. F. Tien, J. Polym. Sci., Polym. Lett., 17, 431 (1979). 105. T. E. Hogen-Esch, C. F. Tien, Macromolecules, 13, 207 (1980). 106. T. E. Hogen-Esch, W. L. Jenkins, Macromolecules, 14, 510 (1981). 107. S. S. Hung, C. Mathis, T. E. Hogen-Esch, Macromolecules, 14, 1802 (1981). 108. S. S. Hung, T. E. Hogen-Esch, J. Polym. Sci., Polym. Chem. Ed., 23, 1203 (1985). 109. W. L. Jenkins, C. F. Tien, T. E. Hogen-Esch, Pure Appl. Chem., 51, 139 (1979). 110. A. Leoni, S. Franco, Macromolecules, 4, 355 (1971). 111. D. S. Breslow, G. E. Hulse, A. S. Matlack, J. Am. Chem. Soc, 79, 3760 (1957). 112. A. Leoni, S. Franco, G. Polla, J. Polym. Sci. A-I, 6, 3187 (1968). 113. D. S. Tarbell, P. Noble, Jr., J. Am. Chem. Soc, 72, 2657 (1950). 114. K. Hatada, K. Ute, T. Kitayama, T. Nishiura, N. Miyatake, Macromol. Chem. Macromol. Symp., 85, 325 (1994). 115. K. Hatada, K. Ute, N. Miyatake, Prog. Polym. Sci., 19,1067 (1994). 116. K. Ute, N. Miyatake, K. Hatada, Polymer, 36, 1415 (1995). 117. T. Kitayama, T. Nishimura, A, Oshima, K. Ute, K. Hatada, Polymer Bull., 32, 215 (1994). 118. K. Ute, N. Miyatake, Y. Osugi, K. Hatada, Polym. J., 25, 1153(1993). 119. K. Ute, N. Miyatake, T. Asada, K. Hatada, Polym. Bull., 28, 561 (1992). 120. K. Ute, N. Miyatake, K. Hatada, J. Macromol. Sci., Pure Appl. Chem. A, 29, 599 (1992). 121. K. Hatada, K. Ute, T. Nishimura, M. Kashiyama, T. Saito, M. Takeuchi, Polymer Bull., 23, 157 (1990). 122. K. Ute, T. Nishimura, K. Hatada, Polym. J., 21, 1027 (1989). 123. K. Ute, T. Nishimura, Y. Matsuura, K. Hatada, Polym. J., 21, 231 (1989). 124. K. Hatada, K. Ute, K. Tanaka, T. Kitayama, Polym. J., 19, 1325 (1987).
TABLE 5. OLIGO(STYRENES) No. Styrene
Monomer
Oligomers
n
MoI. wt.
m.p. (0C)
b.p. (°C/mbar)
ri^
3-Methyl-l-phenylindane (2 stereoisomers)
2
208.3
9.5 25.5
168-169/21 157/16
1.5810 1.5809
Refs. 1-5
5.1. cont'd No.
Monomer
a-Methylstyrene
n
MoI. wt.
1,3-Diphenyl-1 -butene
2
208.3
181-182/27 134-135/1
1,4-Diphenyl-1 -butene
2
208.3
124/1013
1,2-Diphenylcyclobutane
2
208.3
1,3,3-Trimethyl- 1-phenylindane
2
236.4
53
158-160/13
4-Methyl-2,4-diphenyl-2-pentene
2
236.4
52
166-167/20
1.5728
8,11,12
2
296.4
237-240/24
1.5703
9,13
2
266.4
93-94
2
266.4
173
9,14 9,14
a-Methyl-/?-methoxystyrene
a-Methyl-p-aminostyrene
m.p. ( 0 C)
Oligomers
1,3,3-Trimethy 1-4' ,6-diaminophenylindane
b.p. (°C/mbar)
n$ 1.5930
1,3,3-Trimethy 1-1-phenylindane4',6-dicarboxylic acid
2
348.4
297
a-/?-Dimethylstyrene
1,3,3,4',6-Pentamethyl1-phenylindane
2
264.4
40
1-3,6,23
6,23
1.5913
a-Methyl-p-carboxystyren
Refs.
7
8-10
9
142-144/1.1
9,15,16
Next Page
5.1. cont'd No.
Monomer
oc-Ethylstyrene
Oligomers
n
MoI. wt.
m.p. ( 0 C)
b.p. (°C/mbar)
n™
Refs.
l,3-Diethyl-3-methyl1-phenylindane
2
264.4
104-106/0.4
1.5642
17
3,5-Diphenyl-5-methyl-2-heptene
2
264.4
133-135/1.6
1.54345/25
17
a-m-Dimethylstyrene
1,3,3,3 ',7-Pentamethyl1-phenylindane
2
264.4
57
p-Bromostyrene
cw-l,3-Di(p-bromophenyl)-l-butene
2
366.1
67-68
18,19
Stilbene
1,2,3,4-Tetraphenylcyclobutane
2
360.5
164-165
20-22
l,2-Diphenyl-l-/?-tolyethane
2
272.4
42-43
9
20
REFERENCES 1. R E . Spoerri, M. J. Rosen, J. Am. Chem. Soc, 72, 4918 (1950). 2. M. J. Rosen, J. Org. Chem., 18, 1701 (1953). 3. B. B. Corson, J. Dorsky, J. E. Nickels, W. M. Kutz, H. I. Thayer, J. Org. Chem., 19, 17 (1954). 4. M. J. Rosen, Org. Syn. Coll. Vol. IV, 665 (1963). 5. R. Stoemer, H. Kootz, Chem. Ber., 61, 2330 (1928). 6. R. Fittig, E. Erdmann, Ann. Chem., 216, 179 (1883); H. Stobbe, G. Posnjak, Ann. Chem., 371, 287 (1909). 7. I. S. Bengelsdorf, J. Org. Chem., 25, 1468 (1960). 8. E. Bergmann, H. Taubadel, H. Weiss, Chem. Ber., 64, 1493 (1931). 9. J. C. Petropoulos, J. J. Fisher, J. Am. Chem. Soc, 80, 1938 (1958). 10. L. M. Adams, R. J. Lee, F. T. Wadsworth, J. Org. Chem., 24, 1186(1959). 11. F. S. Dainton, R. H. Tomlinson, J. Chem. Soc, 151 (1953).
12. J. M. Van der Zanden, Th. R. Rix, Rec Trav. Chim., 75, 1343 (1956). 13. J. M. Van der Zanden, Th. R. Rix, Rec Trav. Chim., 75, 1166 (1956). 14. J. V Braun, E. Anton, W. Haensel, G. Werner, Ann. Chem., 472, 1 (1929). 15. M. Tiffeneau, Ann. Chim. Phys., 10, p. 145, p. 197 (1907). 16. V. N. Ipatieff, H. Pines, R. C. Oldberg, J. Am. Chem. Soc, 70, 2123 (1948). 17. C. G. Overberger, E. M. Pearce, D. Thanner, J. Am. Chem. Soc, 80, 1761 (1958). 18. G. L. Goemer, J. W. Pearce, J. Am. Chem. Soc, 73,2304 (1951). 19. J. Hukki, Acta Chem. Scand., 3, 279 (1949). 20. D. S. Brackman, P. H. Plesch, J. Chem. Soc, 3563 (1958); Chem. Ind., 255 (1955). 21. M. Pailer, U. Mueller, Monatsh. Chem., 79, 615 (1948). 22. J. D. Fulton, J. D. Dunitz, Nature (London), 160, 161 (1947).
Previous Page
30. J. S. Bradshaw, J. Y. K. Hui, J. Heterocycl. Chem., 11, 649 (1974). 31. J. S. Bradshaw, J. Y. K. Hui, B. L. Baymore, R. M. Izatt, J. J. Christensen, J. Heterocycl. Chem., 10, 1 (1973); J. S. Bradshaw, J. Y. K. Hui, J. Y. Chan, B. L. Haymore, J. J. Christensen, R. M. Izatt, J. Heterocycl. Chem., 11, 45 (1974). 32. J. L. Lambert, D. van Ooteghem, E. J. Goethals, J. Polym. Sci. A-I, 9, 3055 (1971). 33. E. J. Goethals, Adv. Polym. Sci., 23, 103 (1977). 34. A. Noshay, C. C. Price, J. Polym. Sci., 54, 533 (1961). 35. W. van Craeynest, E. J. Goethals, Eur. Polym. J., 12,859.9 (1976). 36. J. R. Dann, P. P. Chiesa, J. W. Gates, J. Org. Chem., 26, 1991 (1961). TABLE 8. OLIGOMERS CONTAINING N IN THE MAIN CHAIN
8.1.1.4. Cyclic Oligo(amides) of C-Methyl-$-Alanines |— [NHCHR1CHR2CO]^n
8.1. OLIGO(AMIDES) 8.1.1.
37. F. Vogtle, F. Ley, Chem. Ber., 116, 3000 (1983). 38. F. Vogtle, L. Schunder, Chem. Ber., 102, 2677 (1969). 39. R. H. Mitchell, V. Boekelheide, J. Am. Chem. Soc, 96, 1547 (1974); V. Boekelheide, J. L. Mondt, Tetrahedron Lett., 1203 (1970). 40. K. Galuszko, Rocz. Chem., 49, 1597 (1975). 41. H. J. J.-B. Martel, M. Rasmussen, Tetrahedron Lett., 3843 (1971). 42. B. V. Gorewit, W. K. Musker, J. Coord. Chem., 5, 67 (1976). 43. R. G. GiIUs, A. B. Lacey, Org. Synth., Coll. Vol. IV, 396 (1963). 44. V. Meyer, Chem. Ber., 19, 3259 (1886). 45. J. D. A. Johnson, J. Chem. Soc, 1530 (1933). 46. H. T. Clarke, J. Chem. Soc, 101, 1806 (1912).
Ri
OLIGO(AMIDES) OF p-AMINO ACIDS (NYLON 3)
R2
CH 3
8.1.1.1. Linear Oligo(amides) of (3-Alanine H[NH(CH 2 ) 2 C0] n 0H n
MoI. wt.
m.p. (d) (0C)
Refs.
1 2 3 4 5 6
89.1 160.2 231.2 302.3 373.4 444.5
206 212 >255 >260 >310 >320
1 2,4,96 3,4,96 4,96 5 5
H
H
CH 3
n
MoL wt.
1 3 1 2 3 4 5 6 7 8 9 10 11
85.1 255.3 85.1 170.2 255.3 340.4 425.5 510.6 595.7 680.8 765.9 851.0 936.0
m.p. (0C)
b.p. (°C/mbar) 100/13
300 98-99/20 255 >350 >350 >350 >350 330-335 338-340 327-330 330 325
Refs. 104,105 91 104 84 84,85,87 84 84 84 84 84 84 84 84
8.1.1.5. Linear Oligo(amides) of C-Dimethyl-(3-Alanines H[NHC(R!) 2 C(R 2 ) 2 CO] n OH 8.1.1.2. Cyclic Oligo(amides) of f3-Alanine r [NH(CH 2 ) 2 CO] n -| n 1 2 3 4 5 6 7 8 9 10 11
MoI. wt.
m.p (0C)
Refs.
71.1 142.2 213.2 284.3 355.4 426.5 497.6 568.8 639.7 710.8 781.8
74-74.5 298-299 >360 353 327 360 341 >360 349 >350 >350
6,104,113 4,8,9,72,84,114,116 4,10,84,88,93,101,114,116 4,10,84,114,116 84,114,116 114,116 114,116 114,116 114,116 116 116
Ri
R2
n
MoI. wt.
m.p. (0C)
H
CH 3
CH 3
H
1 3 6 1 3
117.1 315.4 612.8 117.1 315.4
239 209-212 207.5-210.5 217 182-184
R2
n
CH 3
H
1 3
MoI. wt. 103.1 273.3
m.p. (0C) 188-189 240-241
8.1.1.6. Cyclic Oligo(amides) of C-Dimethyl- p-Alanines
Ri
R2
n
MoI. wt.
m.p. (°C)
H
CH 3
1 3 4 5 6 7 8 9 10 11 12 1 3
99.1 297.4 396.5 495.7 594.8 693.9 793.1 892.3 991.3 1090.5 1189.6 99.1 297.4
255-259.5 270 257 310 290 256 315 252 315 245 16-17 257-258
Refs. 102 92
106 94 94 103 95
n [NHC(R 1 ) 2 C(R 2 ) 2 CO]^- ]
8.1.1.3. Linear Oligo(amides) of C-Methyl- $-Alanines H[NHCHR i CHR 2CO] nOH Ri
Refs.
CH 3
H
b.p. (°C/mbar) 70-73/1.1
112/20
Refs. 107 84,91 84 84 84,91 84 84 84 84 84 84 104,105 91
8.1.2. OLIGO(AMIDES) OF y-AMINOBUTYRIC ACID (NYLON 4)
8.1.3. OLIGO(AMIDES) OF-5-AMINOVALERIC ACID (NYLON 5)
8.1.2.1. Linear Oligo(amides) H[NH(CH2)3CO]«OH
8.1.3.1. Linear Oligo(amides) H[NH(CH2)4CO]«OH
n 1 2 3 4 6 8 10 12 16 20
0
MoL wt.
m.p. ( C)
Refs.
103.1 188.2 273.4 358.4 528.6 698.8 869.0 1039.3 1379.6 1719.4
204-205 186 198-199 202-203 196-198 206-208 199-203 208 207-209 206-208
11 4,7,12 4 4 133 133 133 133 133 133
8.1.2.2. Cyclic Oligo(amides) ^[NH(CH2)SCO]n-]
n 1 2 3 4 6 8 10 12 14
MoI. wt.
m.p. (0C)
85.1 170.2 255.3 340.4 510.6 680.9 851.1 1021.3 1191.5
24 283 242-243 255 303 298 312 301 >355
n
MoL wt.
m.p. (0C)
Refs.
1
117.2
160-162
17
2 3 4
216.3 315.4 414.5
178 184-185.5 196.5-198.5
18 18 18
8.1.3.2. Cyclic Oligo(amides) r—[NH(CH2)4CO]/ri n
MoI. wt.
1
98.1
2 3 4
198.3 297.4 396.5
m.p. (0C)
Refs.
39-40
14,17,19
295-296 329-331 266-267
8,18 18 18
Refs. 13,14 4,10,70,71,73 4,10 4,10,70 10,135 135 135 135 135
8.1.3.3. Cationic Oligo(amides)
R
n
MoI. wt.
m.p. ( C )
Refs.
1 0
234.5 216.5
114 93-94
89 89
1
315.5
138
89
8.1.3.4. Amidino-Oligo(aminovaleric Acids)
8.1.2.3. Anionic Oligo(amides)
n
MoI. wt.
m.p. (0C)
0 1
189.2 274.3
92.5 121
Refs. 15 16
n
MoI. wt.
m.p. (0C)
Refs.
1 2 3
198.3 297.4 396.5
166-168 92-94 112
89,118 89 89
8.1.2.4. Cationic Oligo(amides)
R
n
MoI. wt.
1
206.5
m.p. (0C)
Refs.
8.1.4. OLIGO(AMIDES) OF E-AMINOCAPROIC ACID (NYLON 6) 8.1.4.1. Linear Oligo(amides) H[NH(CH2) 5 CO] n OH
181
71,89,118 n
0 1
188.7 273.5
156 162
89,119 89
8.1.2.5. Amidino-Oligo(aminobutyric Acids)
n 1 2 3
MoI. wt. 170.2 255.3 340.4
m.p. (0C)
Refs.
175-177 175 162-163
89,118,121 89 89
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 17
MoI. wt.
m.p. (0C)
131.2 244.3 357.3 470.6 583.8 697.0 810.1 923.3 1036.5 1149.6 1262.8 1375.9 1489.1 1602.3 1715.3 1941.5
206-208 204-205 208-209 220-221 214-215 212-214 210-211 210-211 208-211 212-213 209-212 211-213 210-211 207-208 207-208 209-211
Refs. 20,21 22-24,136 23-25,69,136 23,24,36 23,69,136 23,24,136 23,69,136 23 26,69 26 26,69 26 69 136 69 69
8.1.4.1.
cont'd 8.1.4.5. Anionic Oligo(amides)
n
m.p. ( 0 C)
MoI. wt.
Refs.
18
2054.9
206-209
136
21 22 25 26 30 34 38
2394.5 2507.5 2847.0 2960.2 3412.8 3865.5 4318.1
212-213 209-211 212-213.5 209-211 210-213 211-214 214-217
69 136 69 136 136 136 136
R
n
MoI. wt.
m.p. ( 0 C)
Refs.
H-C 4 H 9
1 2 3 1 2 3
222.8 335.9 449.1 256.8 369.9 483.1
143 176 189 164.5 179 194-195
122 122 122 122 122 122
0 1 2 3
b.p. (°C/mbar)
155.2 268.5 381.5 494.7
nff
123/21
J?f
1.4898 1.4992
0.76 0.67 0.58
Refs.
32 33 33 33
"PC: solvent, tetrahydrofuran/cyclohexane/water (186:14:10).
n
MoI. wt.
m.p. ( 0 C)
1 2 3
226.3 339.5 452.6
168 120 154
8.1.4.4. Amidino-Oligo(aminocaproic
R
n
MoI. wt.
1 2 3 0 1
262.8 375.9 489.1 244.8 357.9
8.1.4.7. End-group Protected
8.1.4.3. Arnidino-Oligo(aminocaproic Acids)
m.p. ( 0 C)
Refs.
112 Oil Oil 137 106-108
120 120 120 89,120 120
Oligo(amides)
C2H5CO-[NH(CH2)SCOL-NHC3H7
Refs. 120,128 120 120
Amides)
0
R
n
MoL wt.
m.p. ( C)
Refs.
M-C4H9
0 1 2 0 1 2
168.3 281.4 394.6 202.3 315.5 428.6
53 129 148-150 76-78 135 157
122 122 122 122 122 122
CH2C6H5
MoI. wt.
8.1.4.6. Cationic Oligo(amides)
8.1.4.2. Oligo(aminocapmic Amides) H+[NH(CH 2 ) 5 CO] n -NHR C L "
CH2C6H5
n
m.p. ( 0 C)
n
MoI. wt.
Refs.
1 2 3 4 5 6 7 8 9 10 11
228.3 341.5 454.7 567.8 681.0 794.2 907.3 1020.5 1133.6 1246.8 1360.0
106 149 172 181 187 191 197 200 201 201 204
31,112 31,112 31,112 31 31,112 31,112 31,112 31,112 31,112 31,112 31
12 13 14 15 16
1473.1 1586.3 1699.3 1812.6 1925.8
202 200 205 206 206
31,112 31 31 31 31
8.1.4.8. Cyclic Oligo(amides) RF
na 1 2 3 4 5 6 7 8 9
MoI. wt.
m.p. ( 0 C)
TCW*
EAWC
113.2 226.3 339.5 452.6 565.8 678.9 792.1 905.3 1018.4
69.5 348 244 256-257 254 260 243 254 245
0.56 0.48 0.34 0.25 0.16 0.10 0.08 0.04 0.02
0.88 0.81 0.77 0.69 0.59 0.49 0.40
Refs. 14,17,27,78 4,24,28,29,45,78,98,110,111,112,148 4,24,28,29,45,78,98,111,112,147 4,24,28,29,45,78,98,111,112 4,24,29,78,98,111,112 4,24,29,60,98,111,112 29,30,60,98,111 29,30,60,98,111 29,30,68,138
8.1.4.8. cont'd RF
na
MoL wt.
10 11 12 13 14 15 16 18 20 21 22 24 25 26 27 28 30 32 33 34 36 38 40 48 50 55 56 60 64 70 72 80 90 100
m.p. (°C)
1131.8 1244.8 1357.9 1471.1 1584.3 1697.4 1810.6 2036.9 2263.2 2376.4 2489.5 2715.9 2829.0 2942.2 3055.3 3168.5 3394.8 3621.2 3734.3 3847.5 4073.8 4300.1 4526.4 5431.7 5658.1 6223.9 6337.0 6789.7 7242.3 7921.3 8147.6 9052.9 10184.5 11316.1
TCW b
EAWc
Refs.
257 249 262 249 263 256 261 263 259 248 250 252 249 246 244 247 255 248 231 231 228 230 235 234 229 226 229 227 226 225 225 224 222 221
117,137 138 117,137 138 117,137 138 117,137 117,137 117,137 138 117,137 117,137 138 137 138 137 117,137 137 138 137 137 137 137 138 138 138 138 138 138 138 138 138 138 138
a
n = 2-40: HPLC (trifluoroethanol/water mixtures), Ref. 117; n = 2-18: FD-MS, Ref. 117; n = 2-100: HPLC (trifluoroethanol/water, gradient elution, Ref. 138. PC, TLC: solvent, tetrahydrofuran/cyclohexane/water (186:14:10). PC, TLC: solvent, ethyl acetate/acetone/water (10:10:2), Refs. 29,134.
b
C
8.1.5. OLIGO(AMIDES) OF HIGHER co-AMINO ACIDS
8.1.5.2. Cyclic Oligo(amides) [— [NH(CH2^CO]n-[
(NYLON 7-12)
x
8.1.5.1. Linear Oligo(amides) H[NH(CH2) ^CO]nOH x 6 7 8 10
11
n 1 2 1 2 1 2 1 2 3 4 5 10 1 2
MoL wt. 145.2 272.4 159.2 300.4 173.3 328.5 201.3 384.6 567.9 751.2 934.5 1850.8 215.3 412.6
0
m.p. ( C) 195 205-208 188 191-192 184 184-186 186-187 189-190 183-184 177-179 177-178 181-182 186-187 192-193
n 6
Refs. 34,35 36 4,37 4,38 4,34 4 34,38,39 4,40,140 5,40,115,140 40,63,115 63 63,67 41 31
6
7
8 9
1 2 3 4 5 6 8 10 1 2 3 4 5 6 1 2 1 2
MoL wt.
m.p. (0C)
Refs.
127.2 254.4 381.6 508.8 636.0 763.2 1017.5 1271.9 141.2 282.4 423.6 564.8 706.0 847.2 155.3 310.5 169.3 338.4
29-30 236-237 259-261 215-216 236 244-245 258-259 262-263 72-73 277 217 219 215 215 138-139 201 162 238
14,17,42 4,10 89 89 89 89 89 89 13,14,34,42 4,10,76,77 89 82,89 89 89 14,42 4,10 14,42 10,144
8.1.5.2. cont'd x
n 10 10
11
14
8.1.6.4. Linear Oligo(amides) of p-Aminobenzoic Acid
m.p. (0C)
MoI. wt.
1 2 4 5 6 7 8 9 3 1 2 3 2
183.3 366.6 741.2 926.6 1111.9 1297.2 1482.5 1667.8 549.9 197.3 394.6 531.9 478.8
155 188-189 203 204 217 205 221 201 184 155 212 175 182
Refs. 42,43,75 4,10,44,75,98 140 140 140 140 140 140 44,60,75,98 13,14,42,75 60,61,75,98,115 31,75 139
R
n
MoI. wt.
m.p. (0C)
H
2 3 2 3 4
256.1 375.4 284.1 403.2 522.2
276 >310 176 >266 >330
C2H5
Refs. 86 86 86 86 86
8.1.6.5. Cyclic Oligo(amides) of 4-Amino-2,3-dihydroquinoline3-Carboxylic Acid
8.1.6. OLIGO(AMIDES) OFAROMATIC AMINO ACIDS 8.1.6.1. Linear Oligo(amides) of o-Aminobenzoic Acid
n
MoI. wt.
m.p. (0C)
Refs.
1 2 3 4
137.1 256.3 375.4 494.5
146 203-204 256 d
46-48 46,123,124,131 46,131 46
R
n
MoI. wt.
m.p. (0C)
H-C3H7 CH 2 C 6 H 5
4 4
857.0 1049.2
198 206
Ref. 97 97
8.1.7. CYCLIC DIAMIDES OF ALIPHATIC DICARBOXYLIC ACIDS AND DIAMINES j — [NH(CH2^NH- CO(CH2)xCO]n-| n
MoI. wt.
m.p. (0C)
6 7 8
1 1 1 1 2 3 4 1 1 1
142.2 170.2 198.3 226.3 452.6 679.0 905.3 254.3 282.4 310.5
201 238 304 337 234 246 244 238 267 209
9 10 11 12
1 1 1 1
338.5 366.6 394.6 422.7
228 195 206 186
x
Refs.
8.1.6.2. Cyclic Oligo(amides) of o-Aminobenzoic Acids 2 3 4 5
Ri H CH 3
R2 H H
C 6 H 5 CH 2
H
CH 3
CH 3 CH 3
n
MoI. wt.
m.p. (0C)
Refs.
2 2 3 4 2 3 3 3
238.2 266.3 399.2 532.2 418.2 627.3 669.3 441.2
335-337 207 >320 >300 158-159 260-263 260-263 >300
47,125-128,131 47 131 130 131 131 129 129
142 49,50,74,139 49,51,139 49,139 143 143 143 49,51,139 49,139 8,49,139,146
49,139,147 8,49,139 139 139
8.1.8. OLIGO(AMIDES) OFADIPIC ACID AND HEXAMETHYLENE DIAMINE (NYLON 6.6) 8.1.8.1. Linear Oligo(amides) H[NH(CH 2 ) 6 NH-CO(CH 2 ) 4 CO] n OH 8.1.6.3. Cyclic Oligo(amides) of m-Aminobenzoic Acids n
R
n
MoI. wt.
CH 3
3
399.2
m.p. (0C) >320
Ref. 132
1 2 3 4 5 10
MoI. wt.
m.p. (0C)
Refs.
244.3 470.7 696.9 923.3 1149.5 2281.1
193 221-222 246-248 247-249 247-250 250-255
52,53 52,53,63 52,53,63 31,63,65 31,63,65 63
8.1.8.2. End-Group Protected
Oligo(amides)
8.1.8.3. Oligomeric Diamines H 2 f [NH(CH 2 )6NH-CO(CH 2 )4CO] w -NH(CH2)6NHj 2Cl"
8.1.8.2.1. OLIGOMERIC DICARBOXYLIC ACID DIPROPYLAMIDES
C3H 7 NH-CO(CH2)4CO-[NH(CH2)6NH-CO(CH2)4CO] n -NHC3H7 0
n
MoI. wt.
m.p. ( C)
Refs.
1 2 3 4 5
454.7 681.0 907.3 1133.6 1359.9
229-230 239-242 248-250 257-260 258-261
64 64 64 64 64
n
MoI. wt.
m.p. ( 0 C)
Refs.
1 2 3 4 5
415.4 641.7 868.0 1094.4 1320.7
248-250 249-251 252-254 251-254 252-255
65 65 65 65 65
8.1.8.4. Oligomeric Dicarboxylic Acids 8.1.8.2.2. OLIGOMERIC DIPROPIONYL DIAMINES
HOOC(CH 2 ) 4 C O - [NH(CH 2 ) 6 NH-CO(CH 2 ) 4 CO] »OH
C2H 5 CO-[NH(CH2)6NH-CO(CH2)4CO] n -NH(CH2)6NH-COC 2 H5 n
MoI. wt.
m.p. ( 0 C)
Refs.
n
MoI. wt.
m.p. ( 0 C)
Refs.
1 2 3
454.7 681.0 907.3
202-203 226-228 229-231
64 64 64
1 2 3 4
372.4 598.7 825.0 1051.3
188-189 200-205 210-211 214-219
56 56,57 56 31
8.1.8.5. Cyclic Oligo(amides) na
MoI. wt.
m.p. ( 0 C)
TCW*
EAW C
1 2 3 4 5 6 7 8 9 10 12 14 16 18 20
226.3 452.6 678.9 905.3 1131.6 1357.9 1584.3 1810.6 2036.9 2263.2 2715.9 3168.5 3621.2 4073.8 4526.4
254 243-244 235 273 279 279 291 282 280 280 280 292 284 275 270
0.47 0.28 0.13 0.06
0.51 0.38 0.23 0.16
a
Refs. 51,53-55,62,80,81,90,98,108 53-55,62,80,81,90,98,109 53,55,62,98 53,60,62,98 149 149 149 149 149 149 149 149 149 149 149
n = 1-20: HPLC (trifluoroethanol/water, gradient elution), Ref. 149. PC, TLC: solvent: tetrahydrofuran/cyclohexane/water (186:14:10). PC, TLC: solvent: ethyl acetate/acetone/water .(10:10:2).
fe C
8.1.9. OLIGO(AMIDES) OF SEBACIC ACID AND HEXAMETHYLENEDIAMINE (NYLON 6.10)
8.1.9.3. Oligomeric Diamines H[NH(CH 2 ) 6 NH-CO(CH 2 ) 8 CO] n -NH(CH 2 ) 6 NH 2
8.1.9.1. Linear Oligo(amides)
H[NH(CH 2 ) 6 NH-CO(CH 2 )8CO] M OH 0
n
MoI. wt.
m.p. ( C)
Refs.
1 2 3
300.4 582.8 865.3
187-188 196-199 208-210
58 63,67 63,67
n
MoI. wt.
m.p. ( 0 C)
Refs.
1 2 3
398.6 681.1 963.5
129-131 177-179 203-210
57,58 58 58
8.1.9.4. Oligomeric Dicarboxylic Acids 8.1.9.2. Cyclic Oligo(amides) f~ [NH(CH 2 ) 6 NH~CO(CH 2 ) 8 CO] n -| HOOC(CH 2 ) 8 CO-[NH(CH 2 ) 6 NH-CO(CH 2 ) 8 CO] WOH n 1 2 3
MoI. wt. 282.4 564.8 847.3
m.p. ( 0 C) 232 222 221
Refs. 51,98,145 58,60,98,145 145
n
MoI. wt.
m.p. ( 0 C)
Refs.
1 2 3
494.6 767.1 1049.5
156-159 182-184 181-185
57,58 57,58 58
8.1.10. OLIGO(AMIDES)OFDECANEDICARBOXYLICACIDAND p,p '-DIAMINO-DICYCLOHEXYLMETHANE (QIANA TYPE)
8.1.13. OLIGO(AMIDES) OF A^-DIALKYLETHYLENEDIAMINE AND DICARBOXYLIC ACIDS 8.1.13.1. Aliphatic Dicarboxylic Acids [-NRCH2CH2NR- CO(CH2)xCO]/n
n 1
Config.
m.p. (0C)
Refs.
trans-trans cis-trans cis-cis
310-314 269-272 254-257
83 83 83
MoI. wt. 404.6
8.1.11. OLIGO(AMIDES) OF OXALIC ACID AND HEXAMETHYLENEDIAMINE [— [NH(CH2)6NH~ COCO]n-^
n
MoI. wt.
1 2 3
170.2 340.4 510.6
m.p. (0C)
Refs.
232 303 345
66 66 66
8.1.12. OLIGO(AMIDES) OF TEREPHTHALIC ACID AND
R
x
C 6 H 5 CH 2
3 5 7
n 2 2 2
MoI. wt.
m.p. (0C)
672.8 729.0 785.1
231-234 199-201 199-204
Refs. 79 79 79
8.1.13.2. Terephthalic Acid
R
n
MoI. wt.
m.p. (0C)
CH 3 C 6 H 5 CH 2
3 3 4 6
654.8 1111.4 1481.8 2222.8
114-123 255-257 143-145 140-144
99 100 100 100
Refs.
Refs.
8.1.13.3. Pyridine-2.5-Dicarboxylic Acid
PENTAMETHYLENEDIAMINE n
MoI. wt.
m.p. (0C)
2
464.3
407
Refs. 59
R
n
MoI. wt.
m.p. (0C)
CH 3
3 4
663.8 885.0
123-129 132-136
99 99
REFERENCES
1. J. H. Ford, Org. Syn., Coll. Vol. Ill, 34; T. W. J. Taylor, J. Chem. Soc, 1897 (1928). 2. H. Th. Hanson, E. L. Smith, J. Biol. Chem., 175, 833 (1948). 3. E. Adams, N. C. Davis, E. L. Smith, J. Biol. Chem., 199, 845 (1952). 4. M. Rothe, Habilitationsschrift, Universitat Halle, DDR, 1960. 5. M. Rothe, Unpublished data. 6. R. W. Holley, A. D. Holley, J. Am. Chem. Soc, 71, 2129 (1949). 7. S. Murahashi, H. Sekiguchi, H. Yuki, Compt. Rend., 248, 1521 (1959). .8. M. Rothe, R. Timler, Chem. Ber., 95, 783 (1962). 9. H. K. Hall, Jr., J. Am. Chem. Soc, 80, 6404 (1958). 10. M. Rothe, Angew. Chem., 74, 725 (1962). 11. C C . DeWitt, Org. Syn., Coll. vol. II, 25 (1943). 12. R. L. Evans, F. Irreverre, J. Org. Chem., 24, 863 (1959). 13. K. Dachs, E. Schwarz, Angew. Chem., 74, 540 (1962). 14. R. Huisgen, H. Brade, H. WaIz, I. Glogger, Chem. Ber., 90, 1437 (1957). 15. S. J. Kanewskaja, Chem. Ber., 69, 266 (1936). 16. H. Sekiguchi, Bull. Sci. Chim. (France), 1835 (1960). 17. O. Wallach, Ann. Chem., 312, 171 (1900); 324, 281 (1902). 18. M. Rothe, R. HoBbach, Makromol. Chem., 70, 150 (1964). 19. N. Yoda, A. Miyake, J. Polym. Sci., 43, 117 (1960).
20. S. Gabriel, A. Maass, Chem. Ber., 32, 1266 (1899). 21. J. C. Eck, Org. Syn., Coll. vol. II, 28 (1943); C. Y. Meyers, L. E. Miller, Org. Syn., Coll. vol. IV, 39 (1963). 22. G. M. van der Want, A. Staverman, Rec. Trav. Chim., 71,379 (1952). 23. H. Zahn, D. Hildebrand, Chem. Ber., 90, 320 (1957). 24. M. Rothe, R-W. Kunitz, Ann. Chem., 609, 88 (1957); Angew. Chem., 68, 414 (1956). 25. G. M. van der Want, H. Peters, P. Inklaar, Rec. Trav. Chim., 71, 1221 (1952). 26. H. Zahn, D. Hildebrand, Chem. Ber., 92, 1963 (1959). 27. C. S. Marvel, J. C. Eck, Org. Syn., Coll. vol. II, 371 (1943). 28. P. H. Hermans, Rec. Trav. Chim., 72, 798 (1953); Nature, 177, 126 (1956). 29. M. Rothe, J. Polym. Sci., 30, 227 (1958). 30. H. Zahn, J. Kunde, Angew. Chem., 70, 189 (1958). 31. H. Zahn, G. B. Gleitsmann, Angew. Chem., 75, 772 (1963). 32. H. A. Offe, Z. Naturforsch, 2b, 182 (1947). 33. K. Gehrke, Faserforsch. Textiltechn., 13, 556 (1962). 34. D. D. Coffman, N. L. Cox, E. L. Martin, W. E. Mochel, F. J. van Natta, J. Polym. Sci., 3, 85 (1948). 35. C. F. Horn, B. T. Freure, H. Vineyard, H. J. Decker. Angew. Chem., 74, 531 (1962). 36. M. Rothe, R. HoBbach, unpublished data. 37. A. G. Goldsobel, Chem. Ber., 27, 3121 (1894).
38. T. Gaeumann, H. H. Guenthardt, HeIv. Chim. Acta, 35, 53 (1952). 39. M. Genas, Angew. Chem., 74, 535 (1962). 40. M. Zahn, H. Roedel, J. Kunde, J. Polym. ScL, 36, 539 (1959). 41. A. Neuberger, Proc. Roy. Soc. A, 158, 68, 84 (1937). 42. L. Ruzicka, M. Kobelt, O. Haefliger, V. Prelog, HeIv. Chim. Acta, 32, 544 (1949). 43. W. Ziegenbein, W. Lang, Angew. Chem., 74, 943 (1962), 44. H. Zahn, J. Kunde, Chem. Ber., 94, 2470 (1961). 45. I. Rothe, M. Rothe, Chem. Ber., 88, 284 (1955). 46. H. Meyer, Ann. Chem., 351, 267 (1907). 47. G. Schroeter, O. Eisleb, Ann. Chem., 367, 101 (1909); Chem. Ber., 52, 2224 (1919). 48. E. Mohr, F. Koehler, H. Ulrich, J. Prakt. Chem., 79, 281 (1909); 80, 1 (1909). 49. J. Dale, R. Coulon, J. Chem. Soc, 182 (1964). 50. G. I. Glover, H. Rapoport, J. Am.Chem. Soc, 86, 3397 (1964). 51. H. Stetter, J. Marx, Ann. Chem., 607, 59 (1957). 52. H. Zahn, R Schmidt, Makromol. Chem., 36, 1 (1959). 53. I. Rothe, M. Rothe, Makromol. Chem., 68, 206 (1963). 54. H. Zahn, F. Schmidt, Chem. Ber., 92, 1381 (1959); H. Zahn, P. Miro, F. Schmidt, Chem. Ber., 90, 1411 (1957). 55. M. Rothe, I. Rothe, H. Bruenig, K.-D. Schwenke, Angew. Chem., 71, 700 (1959). 56. H. Zahn, W. Lauer, Makromol. Chem., 23, 85 (1957). 57. C. D. Cowell, Chem. Ind., 577 (1954). 58. H. Zahn, G. B. Gleitsmann, Makromol. Chem., 60, 45 (1963). 59. H. K. Livingston, R. L. Gregory, Polymer, 13, 297 (1972). 60. P. Kusch, H. Zahn, Angew. Chem., 77, 720 (1965). 61. H. Zahn, H.-D. Stolper, G. Heidemann, Chem. Ber., 98,3251 (1965). 62. H. Zahn., P. Kusch. Chem. Ber., 98, 2588 (1965). 63. P. Kusch, Kolloid-Z., 208, 138 (1966); H. Klostermeyer, J. Halstr0m, P. Kusch, J. Foehles, W. Lunkenheimer, Peptides, 113 (1967), North-Holland Publ. Co., Amsterdam. 64. H. Zahn, O. R Garg, Kolloid-Z., 208, 132 (1966). 65. H. Zahn, P. Kusch, J. Shah, Kolloid-Z., 216/7, 298 (1967); H. Zahn, Z. Ges. Textil-Ind., 66, 928 (1964). 66. O. Vogl, A. C. Knight, Macromolecules, 1, 311, 315 (1968). 67. H. Zahn, P. Kusch, Z. Ges. Textil-Ind., 69, 880 (1967). 68. M. Rothe, U. Kress, unpublished data. 69. M. Rothe, W. Dunkel, J. Polym. ScL, Polym. Lett., 5, 589 (1967). 70. M. Rothe, I. Rothe, Makromol. Chem., 85, 307 (1965). 71. G. I. Glover, R. B. Smith, H. Rapoport, J. Am. Chem. Soc, 87, 2003 (1965). 72. D. N. White, J. D. Dunitz, Israel J. Chem., 10, 249 (1972). 73. T. Winkler, T. Leutert, HeIv. Chim. Acta, 65, 1760 (1982). 74. T. Srikrishnan, J. D. Dunitza, Acta Cryst. B, 31,1372 (1975). 75. R. Feldmann, R. Feinauer, Angew. Makromol. Chem., 34, 9 (1973). 76. J. Marik, J. Mitera, J. Kralicek, J. Stehlicek, Eur. Polym. J., 13, 961 (1977).
77. I. Falgova, J. Kondelikova, J. Kralicek, Angew. Makromol. Chem., 49, 75 (1976). 78. R. Okada, T. Fukumura, H. Tanzawa, J. Polym. ScL, Polym. Lett., 4, 971 (1960). 79. E. Schwartz, A. Shanzer, J. Chem. Soc, Chem. Commun. 634 (1981). 80. P. D. Frayer, J. L. Koenig, J. B. Lando, J. Macromol. ScLPhys. B, 3, 329 (1969). 81. C J . Brown, A. Hill, R. V. Youle, Nature, 177, 128 (1956). 82. Y. Okuno, K. Horita, O. Yonemitsu, Chem. Pharm. Bull., 31, 737 (1983). 83. G. E. Hahn, P. Kusch, V. Rossbach, H. Zahn, Makromol. Chem., 186, 297 (1985). 84. M. Rothe, B. Benz, unpublished data. 85. M. Guaita, L. F. Thomas, Makromol. Chem., 117, 171 (1968). 86. H. Bredereck, H. v. Schuh, Chem. Ber., 81, 715 (1948). 87. L. Trossarelli, M. Guaita, A. Priola, Makromol. Chem., 109, 253 (1967). 88. G. Camino, L. Costa, L. Trossarelli, J. Polym. ScL, Polym. Chem. Ed., 18, 377 (1980). 89. M. Rothe, Ch. Seltenreich, R. HoBbach, H. Emmert, unpublished data. 90. L. E. Alexander, J. Polym. ScL, Polym. Lett. Ed., 10, 759 (1972). 91. J. Lowbridge, E. Mtetwa, R. J. Ridge, C. N. C. Drey, J. Chem. Soc, Perkin Trans. I, 155, (1986). 92. C. N. C. Drey, E. Mtetwa, J. Chem. Soc, Perkin Trans. I, 1587 (1982). 93. D. N. White, C. Morrow, R J. Cox, C. N. C. Drey, J. Lowbridge, J. Chem. Soc, Perkin Trans. II, 239 (1982). 94. C. N. C. Drey, R. J. Ridge, J. Chem. Soc, Perkin Trans. I, 2468 (1981). 95. C. N. C. Drey, J. Lowbridge, R. J. Ridge, J. Chem. Soc, Perkin Trans. I, 2001 (1973). 96. W. Ried, K. Marquardt, Ann. Chem., 642, 141 (1961). 97. H. Berenbold, W-H. Gundel, Ann. Chem., 532 (1978). 98. G. Heidemann, Encycl. Polym. Sci. Technol., 9, 485 (1968). 99. F. Voegtle, W. M. Miiller, Angew. Chem., 96, 711 (1984). 100. F. Behm, W. Simon, W M. Miiller, F. Voegtle, HeIv. Chim. Acta, 68, 940 (1985); F. Voegtle, H. Puff, E. Friedrichs, W. M. Miiller, J. Chem. Soc, Chem. Commun., 1398 (1982). 101. J. L. Van Winkle, J. D. McClure, R H. Williams, J. Org. Chem., 31, 3300 (1966). 102. L. Birkofer, I. Storch, Chem. Ber., 86, 749 (1953). 103. M. D. Slimmer, Chem. Ber., 35, 400 (1902). 104. L. Birkofer, J. Schramm, Ann. Chem., 2195 (1975). 105. R. Graf, Ann. Chem., 661, 111 (1963). 106. D. H. Johnson, J. Chem. Soc. C, 126 (1968). 107. E. Testa, L. Fontanella, Ann. Chem., 625, 95 (1959). 108. M. G. Northolt, L. E. Alexander, J. Phys. Chem., 72, 2838 (1968). 109. M. G. Northolt, Acta Cryst. B, 26, 240 (1970). 110. M. G. Northolt, L. E. Alexander, Acta Cryst. B, 27, 523 (1971). 111. G. Heidemann, H.-J. Nettelbeck, Faserforsch. Textiltechn., 18, 183 (1967).
112. H. Halboth, J. Polym. Sci. C, 729 (1969); H. Halboth, G. Rehage, Faserforsch. Textiltechn., 18, 177 (1967). 113. M. Rothe, A. Haberle, unpublished data. 114. M. Rothe, F. Wehowsky, unpublished data. 115. M. Rothe, W. Fischer, unpublished data. 116. M. Rothe, D. Miihlhausen, unpublished data. 117. M. Rothe, M. Lohmiiller, G. Schmidtberg, unpublished data. 118. M. Rothe, W. Helmling, unpublished data. 119. H. Bredereck, K. Bredereck, Chem. Ber., 94, 2278 (1961). 120. M. Rothe, M. Schlipf, unpublished data. 121. M. Rothe, D. Jacob, unpublished data. 122. M. Rothe, W. Muller, unpublished data. 123. R. P. Staiger, E. B. Miller, J. Org. Chem., 24, 1214 (1959). 124. S. Petersen, E. Tietze, Ann. Chem., 623, 166 (1959). 125. N. S. Dokunikhin, L. A. Galva, J. D. Kraft, Dokl. Akad. Nauk SSSR, 81, 1073 (1951). 126. F. C. Cooper, M. W. Partridge, J. Chem. Soc, 3429 (1954). 127. H. N. Rydon, N. H. P. Smith, D. Williams, J. Chem. Soc, 1900 (1957). 128. D. J. Williams, J. Chem. Soc, Chem. Commun., 170 (1977). 129. S. J. Edge, W. D. Ollis, J. S. Stephanatou, J. F. Stoddart, J. Chem. Soc, Perkin Trans. I, 1701 (1982); S. J. Edge. W. D. Ollis, J. S. Stephanatou, J. F. Stoddart, D. J. Williams, K. A, Woode, Tetrahedron Lett., 2229 (1981). 130. A. Hoorfar, W. D. Ollis, J. F. Stoddart, D. J. Williams, Tetrahedron Lett., 4211 (1980); A. Hoorfar, W. D. Ollis, J. F. Stoddart, J. Chem. Soc, Perkin Trans. I, 1721 (1982). 131. A. Hoorfar, W. D. Oills, J. A. Price, J. S. Stephanatou, J. F. Stoddart, J. Chem. Soc, Perkin Trans. I, 1649 (1982); W. D. Ollis, J. S. Stephanatou, J. F. Stoddart, A. G. Ferrige,
132.
133. 134. 135. 136. 137.
138. 139. 140. 141. 142. 143. 144. 145. 146. 147. 148. 149.
Angew. Chem., 88, 223 (1976); W. D. Ollis, J. A. Price, J. S. Stephanatou, J. F. Stoddart, Angew. Chem., 87, 169 (1975). F. E. Elhadi, W. D. Ollis, J. F. Stoddart, D. J. Williams, K. A. Woode, Tetrahedron Lett., 4215 (1980); F. E. Elhadi, W. D. Ollis, J. F. Stoddart, J. Chem. Soc, Perkin Trans. I, 1727 (1982). M. Rothe, E. Bigdeli, unpublished data. M. Rothe, Makromol. Chem., 35, 183 (1960). M. Rothe, G. Ries, unpublished data. M. Rothe, M. Schilling, unpublished data. M. Rothe, M. Lohmiiller, U. Breuksch, G. Schmidtberg, Angew. Chem., 106, 2047 (1994); Angew. Chem., Int. Ed. Engl., 33, 1960 (1994). M. Rothe, T. Mohr, B. Trnka, R. Berginski, unpublished data. M. Rothe, E. W. Reinold, unpublished data. M. Rothe, H. Ritsche-Thoma, unpublished data. M. Rothe, E. Gatter, unpublished data. M. Rothe, K. Steiner, W. Knobloch, unpublished data. M. Rothe, K. Kitzelmann, unpublished data. M. Rothe, N. Grtiner, unpublished data. M. Rothe, M. Gehrmann, unpublished data. H. P. GroBmann, J. Schwede, B. Heise, V. Rauschenberger, E. W. Reinold, M. Rothe, Polymer Bull., 32, 653 (1994). J. Dybal, B. Schneider, D. Doskocilova, J. Baldrian, H. Pavlikova, J. Kvarda, I. Prokopova, Polymer, 38,2483 (1997). G. Di Silvestro, R Sozzani, S. Bruckner, L. Malpezzi, C. Guaita, Makromol. Chem., 188, 2745 (1987). M. Rothe, G. Dangel, G. Ries, unpublished data.
8.2. OLIGO(PEPTIDES)
8.2.2. OLIGO(PEPTIDES) OF SARCOSINE
8.2.1. OLIGO(PEPTIDES) OF GLYCINE
8.2.2.1. Linear Oligo(peptides) H[N(CH3)CH2CO]nOH
8.2.1.1. Linear Oligo(peptides) H[NHCH2CO]nOH
n
n
MoL wt.
m.p. (0C)
1 2 3 4 5 6
75.1 132.1 189.2 246.2 303.3 360.3
233-236 210-215 235 240 270 >256d
Refs. 1 2,7,75 3,4,75 4,5,75 4,5,75,78 6
1 2
m.p. (0C)
MoI. wt. 89.1 160.2
211-213 190-191
Refs. 1 13,17,21
8.2.2.2. Cyclic Oligo(peptides) |— [N(CH3)CH2CO]^-I 8.2.1.2. Cyclic Oligo(peptides) [-[NHCH2CO]n-] n n 2 4 5 6 7 8 9 10 11
0
MoI. wt.
m.p. ( C)
114.1 228.2 285.3 342.3 399.4 456.4 513.5 570.5 627.6
309 340 >330 >360 >280 >350 290 290 300
MoI. wt.
m.p. (0C)
142.2 213.3 284.4 355.5 426.5 497.7 568.7 639.8 711.0 853.0
147 221 >350 255 315 296 338 >320
Refs.
Refs. 2,7,79,131,174,177,184 8,9,77,79,80,191,205,206 9,77-80,136 4,8,10,11,77,79,80,131 77,79,131 77,79,131,205 77,79,131 77,79,131 77,79,131
2 3 4 5 6 7 8 9 10 12
>320
13,27,51,61,177,187,191,204 51,191,192,197 51,166,191-195,198 51,191-193,199 17,51,163,166,191,193,200 51,191,193,201 51,191,193,196,202 17,163 193,203 17,163
8.2.3. OLIGO(PEPTIDES) OF L - A L A N I N E 8.2.3.1. Linear Oligo(peptides) H[NHCH(CH 3 )CO] nOH Specific rotation n
MoI. wt.
m.p. ( 0 C)
1 2 3 4 5 6 7
89.1 160.2 231.3 302.3 373.4 444.5 515.6
298 257-263 269-272 >320 >320 >320
8.2.3.2. Endgroup Protected Oligo(peptides)
[ai\D +14.5 -38.5 -85.7 -131.0 -150.0 -167.0
( 0 C)
c (%)
25 27 27 27 27 27
10 0.9 0.6 0.6 0.5 0.3
Solvent 6.0 N HCl 0.2 N HCl 0.2 N HCl 0.2 N HCl 0.2 N HCl 0.2 N HCl
Refs. 1 6,12,15,73,85,138,139 14,15,73,85,138,139 15,16,73,85,138,139 15,16,85,138 15,16,85,138 15
R-[NHCH(CH 3 )CO] n -R'
Specific rotation R'
n
MoI. wt.
m.p. ( 0 C)
BOC
OMe
Zb
OEt
2 3 4 5 6 7 2 3 4 5 6 7 10 2 3 4 5 6 7 8 9 3 4 5 6 7 3 5 6 7 8 9
274.3 345.4 416.5 487.6 558.6 629.7 322.4 393.4 464.5 535.6 606.7 677.8 891.0 363.4 434.5 505.6 576.7 647.7 718.8 789.9 861.0 419.5 490.6 561.6 632.7 703.8 460.5 602.7 673.8 744.9 816.0 887.1
110-111 193-194 >240d >240d >240d >240d 116 192 251-253 250 >275d >275d >250d 135-136 198-200 270-271 >275d >275d >275d >275d >275d 138-140 240-241 >250d >250d >250d 110-111 25Od >275d >275d >275d >275d
R
Mo
MEEA
OEt
Mo
[
c (%)
0.5 0.5 0.5 0.5 0.25 0.25 0.2 0.47 0.48 0.46 0.45 0.45 0.45 0.44 0.20 0.55 0.49 0.20 0.45 0.50 0.44 0.40 0.21 0.23 0.25 0.22
Solvent HFIP HFIP HFIP HFIP HFIP HFIP TFE TFE TFE TFE TFE TFE TFE TFE TFE TFE TFE TFE TFE TFE TFE TFE TFE TFE TFE TFE TFE TFE TFE TFE TFE TFE
Refs. 86,95,102,103 86,87,95,102,103 86,87,95,102,103 86,87,95,102,103 86,87,102,103 86,87,102,103 81-83 14,81-83 81 81-83 81 81 82,83 81 81 81 81 81 81 81 81 81 81 81 81 81 81,84 81,84 81,84 81,84 81,84 81,84
a
t = 22°C. Z-, C 6 H 5 CH 2 -OCO-; BOC-, (CH 3 HC-OCO-; MEEA-, C H 3 O C H 2 C H 2 O C H 2 C H 2 O C H 2 C O - ; -OMe, -CH 3 ; -OEt, -OC 2 H 5 ;
b
- M o , O^
^ N - ; TFE, trifluorethanol; HFIP, Hexafluoroisopropanol.
8.2.3.3. Cyclic Oligo(peptides) P-[NHCH(CH 3 )CO]^ 1 Specific rotation n 2 4 6
MoI. wt.
m.p. ( 0 C)
[
142.2 284.3 426.5
297 250 >310
-29.6 -68 -210.4
( 0 C) 20 22 20
c (%)
Solvent
1.9 0.5 0.02
H2O DMF H2O
Refs. 6,79,174,183-185 134,135,195,206 136,137
8.2.3.3. cont'd Specific rotation n 7 8 9 10 11
MoI. wt.
m.p. ( 0 C)
[a]D
( 0 C)
497.6 568.6 639.7 710.8 781.8
302 331 321 368 289
-60.5 -62.1 -97.1 -102.7 -133.0
20 20 20 20 20
8.2.4. OLIGO(PEPTIDES) OF O C - A M I N O I S O B U T Y R I C C 6 H 5 CH 2 OCO-[NHC(CH 3 ) 2 COL-OX X
n
MoL wt.
C(CH 3 ) 3
1 2 3 4 5 6 7 8 9 10 11 12 1 2 3 4 5 6
293.4 378.5 463.6 558.7 633.8 718.9 804.0 889.1 974.2 1059.3 1144.4 1229.5 237.2 322.4 407.5 482.5 577.7 662.8
C(CH 3 ) 3
m.p. (0C) 60-1 134 166.5-167.5 178 236 215-218 229-230 247-248 262-263 257-258 271-272 >300 88-89 161-162.5 205-206 243-244 254-256 243-245
c (%)
Solvent
2.1 1.4 1 0.1 0.002
H2O H2O H2O H2O H2O
Refs. 79 79 79 79 79
ACID
Refs. 88,90,91,94 90,91,94 88,91-94 88,89,91-94 88,89,91-94 88,91 91 91 91 91 91 91 90,151,152 151 88,92 88,92 88,92 88
8.2.5. OLIGO(PEPTIDES) OF HYDROPHOBIC AMINO ACIDS (a-AMINOBUTYRIC ACIDS, NORVALINE, VALINE, NORELEUCINE, LEUCINE, ISOLEUCINE, CYCLOHEXYLALANINE, PHENYLALANINE, TRIYPTOPHAN) 8.2.5.1. Linear Oligo(peptides) H[NHCHRCO] n OH Specific rotation R L-VaI -CH(CH 3 ) 2 L-Leu -CH 2 CH(CH 3 ) 2
L-IIe -CH(CH 3 )CH 2 CH 3
n
MoL wt.
[a]D
( 0 C)
1 2 3 1 2 3 4 1 2
117.2 216.3 315.4 131.2 244.3 357.5 470.7 131.2 244.3
+28.8 +10.8 -41.8 +13.9 -13.7 -51.4 - 90.0 +40.6 +17.1
20 25 21 25 23 20 20 20 25
8.2.5.2. Endgroup Protected Oligo(peptides)
c (%)
Solvent
3.4 2.0 2.7 9.1 1.0 3.1 7.6 1 1 1 eq. HCl
6 N HCl H2O INCl 4.5 N HCl INNaOH INNaOH 1 N NaOH 6 N HCl H2O+
Refs. 1 18,19 19 1 18,22-24,74 26 26 1 20
(CH 3 ) 3 COCO-[NHCHRCO] n -OCH 3 Specific rotation
R
n
MoL wt.
L-Abu -CH 2 CH 3
2 3 4 5
302.3 387.5 472.6 557.7
m.p. ( 0 C) 108-109 126-127 228-229 >250
[a]r -5.95 -10.84 -16.72 -20.44
Solvent HFIP° HFIP a HFIP° HFIPfl
Refs. 95 95 95 95
8.2.5.2. cont'd Specific rotation m.p. ( 0 C)
R
n
MoL wt.
L-Nva
6 7 2
642.8 727.8 330.4
>250 >250 95-96
L-VaI
3 4 5 6 7 2
429.5 528.7 627.8 726.9 826.1 330.4
119-120 207-208 220 220 220 166-167
3
429.5
170-171
4
528.7
247-248
5
627.8
>260
6
726.9
>260
7
826.1
>260
2 3 4 5 6 7 2 3 4 5 6 7 2 3 4 5 6 7 8 2
358.5 471.6 584.8 698.0 811.1 924.3 358.5 471.6 584.8 698.0 811.1 924.3 358.5 471.6 584.8 698.0 811.1 924.3 1037.5 358.5
63-64 146-147 214-215 >240 >240 >240 141-142 158-159 208-209 >250 >250 >250 158-159 193-194 245 >250d >250d >240d >240d 133-134
3
471.6
175-176
4
584.8
245
5
698.0
>250d
6
811.1
>250d
7 2 3 4 5 6 7 2
924.3 438.6 591.8 745.1 898.3 1051.5 1204.7 426.5
>250d 117-118 171-172 203-204 >240 >240 >240 121-122
3
573.7
173-174
L-NIe
L-Leu
L-IIe
D-alle
L-Cha
L-Phe
[a]r -23.12 -27.21
Solvent
Refs.
HFIP a HFIP a
-48.3 -40.8 -76.7 -77.4 -91.0 -107.5 -103.6 -126.2 -94.3 193.0 +37.8 -144.5 -3.88 -6.51 -6.42 -7.74 -7.26 -7.51 -46.9 -75.1 -92.6 -101.0 -111.1 -120.0 -44.0 -67.6 -83.4 -87.8 -93.9 +13.9 +24.6 +30.1 + 39.9 +48.1 + 58.3 +58.3 + 73.5
TFE* HFA6 TFE* HFA* TFE* HFA* TFE* HFA* TFE* HFA* TFE* HFA* HFIPC HFIPC HFIPC HFIPC HFIPC HFIPC HFA <* HFA rf HFA^ HFA HFA^ HFA TFE' TFE* TFE* TFE* TFE* TFE* TFE* TFE' HFIP* TFE' HFIP* TFE' HFIP*
+55.0 + 94.8 +55.3 + 101.8 +109.4 -43.3 -54.1 -57.7 -61.2 -65.6 -66.9 0.00 -8.7 -15.3 -14.9
TFE' HFTP* TFE' HFIP* HHP* HFIP* HFIP* HFIP* HFIP* HFIP* HHP* TFE' DMF' TFE1 DMF'
95 95 98,102,103,105,113,153 95,97,98,102,103,105,113,153 95,97,98,102,103,105,113,153 95,97,98,102,103,153 97-99,102,103,153 97,98,102,103,153 96,102,103,112,113,115 96,102,103,112,113,115 153 96,102,103,112,113,115 153 96,102,103,112,115,153 96,102,103,153 96,102,103,112,153
rf
rf
95,106 95,106 95,106 95,106 106 106 100,102,104,111 100,102,104,111,153 100,102,104,111,153 100,102,104,111,153 100,102,104,111,153 100,102,104,111,153 56-58,101,102,112,115,116 56-58,101,102,112,115,116 56,57,101,102,112,115,116 56,57,101,102,112,115,116 56,57,101,102,112,115,116 56,101,102 56,101 115,116 115,116 115,116
115,116 115,116 115 110,111,115 110,111 110,111 110,111,114 110,111 110,111 102,107-109,111,112 102,107-109,111,112
8.2.5.2. cont'd Specific rotation R
n
MoI. wt.
m.p. ( 0 C)
4
720.8
196-197
5
868.0
213-214
6
1015.2
223-226
7 8 9
1162.3 1309.5 1456.7
>235 >235 >235
[a]r
Solvent
-22.2 -16.1 -28.3 - 19.2 -25.0 -21.1 -22.1
Refs.
TFE' DMF' TFE' DMF' TFE' DMF' DMF'
102,107-109,111,112 102,107-109,111,112 102,108,109,111 102,108,109,111 108,109 108,109
a
A = 546nm; T = 200C; c = 5x W-4M; a[(7r/18O) rad x cm 2 /gl; HFIP = hexafluoroisopropanol. ^A = 589 nm; T = 25°C; c = 3 x 10 " 3 M (n = 2-6), 3 x 10 ~4 M (n = 7); TFE = trifluoroethanol; HFA = hexafluoroacetone sesquihydrate. c A = 589 nm; T = 22°C; c = 10 ~3 M; HFIP = hexafluoroisopropanol. ^A = 589 nm; T = 25°C; c = 3 x 10 ~3 M; HFA = hexafluoroacetone sesquihydrate. e A = 589 nm; T = 25°C; c = 0.025-0.2%; TFE = trifluoroethanol. ^A = 589 nm; T = 250C; c = 0.6%; TFE = trifluoroethanol. 8 X = 589 nm; T = 210C; c = 0.1%; hexafluoroacetone sesquihydrate. h A = 589 nm; T = 200C; c = 0.1-0.2%; HFIP = hexafluoroisopropanol. 'A = 589nm; Tin TFE = 23°C, in DMF= 18°C; c = 0.2%; TFE = trifluoroethanol.
8.2.5.3. Endgroup Protected Oligo(peptides) ofTryptophan X-[NHCHRCO]n-OCH3 Specific rotation R
X
n
MoI. wt.
m.p. ( 0 C)
2 3 1 2 3 4 5
538.5 721.8 276.3 428.4 580.6 732.7 884.9
196 85-95 108-109 153-154
151-154
[a]f?
c (%)
Solvent
-13
1
MeOH
-2.4 -47.6 -66.8 -65.6 -65.0
1.0 0.5 0.5 0.5 0.5
MeOH MeOH MeOH MeOH MeOH
Refs. 208,225 208 140 140 140 140 140
a
Z- = Benzyloxycarbonyl-.
8.2.5.4. Cyclic Oligo(peptides) ^ [ N H C H R C O ] ^ Specific rotation R
n
MoI. wt.
m.p. ( 0 C)
L-VaI
2
198.3
269-271
L-Leu
2
226.3
5 2 5 2 5 10 2
565.8 226.3 565.8 294.4 735.9 1471.8 372.4
L-IIe L-Phe
L-Trp
( 0 C)
c (%)
Solvent
-77.5
18-22
1.0
CH 3 COOH
207
277
-46.0
20
0.8
CH3COOH
22,25,177,184,185, 188,207
>300 308 357 315-316 250-254 251.5
-71 -60.0
15 18-22
1.0 1.0
EtOH CH3COOH
-100 -124.3 -142 -14.7
25-28 25 20 20
0.2 1.0 0.4
CH3COOH DMF MeOH CH3COOH
132 131,207 131 177,184,185,188 78 131 230,232
[a] D
Refs.
8.2.5.5. Endgroup Protected Oligo(Dipeptides)
R'[NHCHRiCO-NHCHR 2 CO] n -R"* Specific rotation
R''
Ri
R2
n
MoI. wt.
m.p. ( 0 C)
[a]|?
c (%)
Bocfl
OMe
D-VaI L-CH(CH3)2
L-VaI D-CH(CH3)2
Nps"
OEt
L-Leu -CH 2 CH(CH 3 ) 2
L-AIa -CH3
1 2 3 4 6 8 2 3 4 5 6 8
300.4 528.7 727.0 925.2 1321.8 1718.3 567.6 751.8 936.0 1120.2 1304.4 1672.8
110.7 209.6 232.7 261.1 d d 110-111 203-205 257-26Od >270d >270d >270d
-23.7 -17.8 -21.0 -8.9 -6.2 -11.4 -66.5 -96.9 -101.3 -84.6 -50.0 -52.6
1.02 1.00 1.02 1.00 1.12 1.05 2.0 2.0 2.0 2.0 2.0 2.0
R'
a
Solvent
Refs.
CHCl 3 118 CHCl 3 118 CHCl 3 118 CHCl 3 117,118 CHCl 3 118 CHCl 3 118 HFIP/TFE a (1:2) 119 HFIP/TFE (1:2) 119 HFIP/TFE (1:2) 119 HFIP/TFE (1:2) 119 HFIP/TFE (1:2) 119 HFIP/TFE (1:2) 119
Boc- — ten. butyloxycarbonyl-; Nps. = 0-nitrophenylsulfenyl-; HFIP = hexafluoroisopropanol; TFE = trifluoroethanol.
8.2.6. OLIGO(PEPTIDES) OF L - A N D D - P R O L I N E
8.2.6.1. Linear Oligo(all-L-peptides) n 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 25 28 30 31 34 37 40
n H[N-CHCO] n OH
MoI. wt.
m.p. ( 0 C)
115.2 212.3 309.4 406.5 503.6 600.7 697.8 794.9 892.0 989.1 1086.2 1183.3 1280.4 1377.5 1474.6 1571.7 1668.8 1765.9 1863.0 1960.1 2057.3 2154.5 2445.7 2737.0 2931.3 3028.5 3320.1 3611.4 3902.7
220-222 144-145 122 170 189 209 228 >280 >280 >300 >300 >300 >300 >300 >300 >300 >300 >300 >300 >300 >300 >300 >300 >300 >300 >300 >300 >300 >300
£ F -Vahies fl 1.00 0.84 0.72 0.60 0.52
1.00 0.91 0.77 0.72 0.66 0.60
1.00 0.92 0.83 0.75 0.70 0.64
1.00 0.95 0.90 0.84 100 0.93
1.00 0.93
1.00 0.92
1.00 0.95 0.93
1.00 0.94 0.90 0.86 0.81
1.00 0.93-530
1.00 0.94
[a]£°*
Refs.
-87 -175 -220 -293 -338 -376 -394 -412 -435 -456 -466 -472 -480 -491 -496 -499 -505 -509 -513 -520 -521 -523 -526 -528 -530 -532 70 -528 -532
1 52,62,69,70,150,171-173 53,62,69,70,150,171-173 62,69,70,150,171-173 62,69,70,150,172,173 62,69,70,150,172,173 62,69,70,150 62,69,70,150 62,69,150 62,69,70,150 62,69,70,150 62,69,70,150 69,70 69 62,69,70 69,70 69 69,70 69 69,70 70 70 70 70 70 70 70 70
a
Paper electrophoresis; buffer; HCOOH/CH3COOH/H2O (1:1:3), 1000-5000V, 40-115mA, 40-240min. *c(%)=l,H2O. 8.2.6.2. Endgroup Protected
Oligo(peptides) n
8.2.6.2.1.tert-BuTYLOXYCARBONYLOLIGO(ALL-L-PROLINES) (CH 3 ) 3 COCO—[N-CHCO] n -OH n 1 2 3 4
MoI. wt. 215.3 312.4 409.5 506.6
m.p. ( 0 C)
R%
[*]$"
Refs.
137-138 191-193 219-220 178
0.84 0.68 0.60 0.53
-105 -153.5 -173 -194
62,72,169,179 62,150,167,179,181 62,150,167,179 62,150,167
8.2.6.2.1. cont'd n
MoI. wt.
m.p. ( 0 C)
R%
5 6 7 8 9 10 11 12 15
603.7 700.8 797.9 894.0 991.1 1088.2 1185.3 1282.4 1573.7
225 247 267 >280 >280 >280 >300 >300 >300
0.47 0.41 0.37 0.33 0.29 0.25 0.23 0.22 0.22
a
[a] Jj**
Refs.
-220 -239 -247 -256 -265 -272 -269 -277 -291
62,150,167 62,150,167 62,150 62,150 62,150 62,150 62,150 62,150 62,150
TLC: solvent, fl-butanol/acetone/acetic acid/ammonia, 1:4/water (9:3:2:2:4). c (%) = 1, CHCl3.
b
8.2.6.2.2. ten-AMYLOXYCARBONYL
OLIGO(ALL-L-PROLINES)
Specific rotation n
MoI. wt.
1 2 3 4 5 6 8
229.3 326.4 423.5 520.6 617.7 714.8 908.0
m.p. ( 0 C)
[
( 0 C)
c (%)
Solvent
94-95.5 157-159 200-201.5 207.5-208.5 224.5-226 240-242 280
-47.2 -113 -170 -227 -248 -291 -318
21 25 25 24 24 24 22
1.7 2.0 2.2 2.1 2.3 2.1 0.9
EtOH EtOH EtOH EtOH EtOH EtOH EtOH
Refs. 63-68,170,179 64-68,179 64-68,179,182 64-68 64-68 64-68 64-68
8.2.6.2.4.tert-BuTYLOXYCARBONYLOLIGO(D,L-DIPROLINE)
8.2.6.2.3. tert-B UT YLOX YC ARBON YL D,L-OLIGO(DIPROLINES)
BENZYL ESTERS
n 1 2 3 a
MoI. wt. 312.4 506.6 700.8
m.p. (0C) 204 188-189 220-221
[a]^
Refs.
-70.1 -38.8 -32.4
158,165 158 158,159
c ( % ) = l , DMF.
n
MoI. wt.
m.p. (0C)
[a]^
Refs.
2 3 4
612.7 806.9 1001.2
64-66 157-160 146-148
-24.0 -23.2 -20.4
164 164 164
a
c (%) = !, DMF.
8.2.6.3. Cyclic Oligo(peptides) 8.2.6.3.1. CYCLIC OLIGO(ALL-L-PROLINES)
n
MoI. wt.
m.p. (0C)
2 3
194.2 291.3
146 358
MD
(0C)
-151.6 +48.5
19 25
8.2.6.3.2. CYCLIC OLIGO(L,D-DIPROLINES)
n 1 2 3 4 6 9 12
MoI. wt. 194.2 388.4 582.6 776.8 1165.2 1747.8 2330.4
m.p. (0C)
Refs.
194-199 >300d >310d >250d >280d >250d >250d
158,180,185,186 158 158,159 158 158 158 158
C (%)
Solvent
Refs.
0.5 0.48
H2O CH 3 OH
54,55,180,185 53,154-157,162,163,168,176,189,190
8.2.6.3.3. CYCLIC OLIGO(D,L,L-TRIPROLINES)
Specific rotation n
MoI. wt.
m.p. ( 0 C)
1 2 3 4 5
291.2 582.3 873.5 1164.6 1455.8
181-184 304 23Od 25Od 25Od
[a]|?
c (%)
Solvent
1 1 1 1 0.5
H2O H2O H2O H2O H2O
+70.7 -60.9 -114.5 -72.0 -101.8
Refs. 159-163 159-163 159-163 159-163 159-163
8.2.7. OLIGO(PEPTIDES) OF L - A Z E T I D I N E - 2 - C A R B O X Y L I C ACID I 8.2.7.1. Cyclic Oligo(peptides)
I
r[N-CHCO]nH
n
MoI. wt.
m.p. ( 0 C)
2 3 6
166.2 249.3 498.5
207-212 334-340 339-350
[a]f,78fl
Refs.
+8.2 +20.8 -352.0
175 175 175
«c(%) = 0.5, H 2 O.
8.2.8. OLIGO(PEPTIDES) OF L - H Y D R O X Y AND L-MERCAPTO AMINO ACIDS 8.2.8.1. Linear Oligo(peptides) H[NHCHRCO] n OH Specific rotation
L-Ser -CH 2 OH L-Tyr -CH 2 C 6 H 4 OH L-Cys -CH 2 SH1.5HC1 L-Met -CH 2 CH 2 SCH 3
n
MoI. wt.
1 2 1 2 3 1 2 1 2 3
105.1 192.2 181.2 344.4 507.6 121.1 224.2 149.2 280.4 411.6
m.p. ( 0 C)
285-288 181-182
229-231 219-220
[a] D
( 0 C)
c (%)
Solvent 0
+14.5 +14.2 -7.3 +30.1
25 25 25 19
9.3 7 4 4
NHCl NHCl 6.1 N HCl H 2 O + l e q . HCl
+7.6 +35 +23.4 +27.0 -70.0
26 22 20 24 16
12 1 5 2 1
NHCl 0.2 N HCl 3 N HCl H2O H2O
Refs. 1 28,35,139 1 29-31 31 1 37 1 32-34 33
8.2.8.2. Endgroup Protected Oligo(peptides) (CH 3 )3COCO-[NHCHRCO] n -OCH 3 Specific rotation R
n
MoI. wt.
m.p. ( 0 C)
L-Cys(Me) -CH 2 SCH 3
2 3 4 5 6 7 2 3 4 5 6 7
366.5 483.7 600.8 718.0 835.2 952.3 394.5 525.8 656.9 788.1 919.3 1050.5
94-95 104-105 191-192 211-212 >220 >220 66-67 92-96 191-194 236 d 245 d >275
L-Met -CH 2 CH 2 SCH 3
a
HFIP = hexafluoroisopropanol.
[a] D
-29.6 -37.6 -41.4 -48.1 -50.3 -54.8
c (%)
0.003 M 0.003 M 0.03M 0.003M 0.03M 0.03 M
Solvent*
HFIP a HFIP HFIP HFIP HHP HFIP
Refs. 102,121,122,133 102,121,122,133 102,121,122,133 102,121,122,133 102,121,122,133 102,121,122,133 102,123,124,127-129 102,123,124,127-129 102,123,124,127-129 102,123,124,127-129 102,123,124,126-129 102,123-129
8.2.8J.
Formyl-Oligo(L-Methionines)
HCO-[NHCHRCO]n-OH Specific rotation
R
n
m.p. (0C)
MoI. w t .
[
c (%)
Solvent0
Refs.
L-Met
2
308.4
125-126
-44.8
0.5
HFIP
130
-CH2CH2SCH3
3 4 5 6
439.6 570.8 702.0 833.2
176-177 195-196 216-217 230-231 d
-56.7 -67.2 -63.3 -81.8
0.5 0.5 0.5 0.5
HFIP HFIP HFIP HHP
130 130 130 130
8.2.8.4.
Cyclic
Oligo(peptides)
[-[NHCHRCO] n -J Specific rotation
R
n
MoI. w t .
-CH2OH -CH2C6H4OH
2 2
174.2 326.4
m.p. (0C) 247 277-280
[
(0C)
c (%)
Solvent*
67.5 -223.8
25 20
2.2 2.4
H2O NaOH
Refs. 35,174,183 36,174
8.2.8.5. Oligo(peptides) of Cystine CyS= —NHCHCO— CH2SSpecific rotation n
m.p. (0C)
MD
(0C)
H-CyS-CyS-OH
222.3
-29
25
1
NHCl
38
H-CyS-CyS-OH I I H-CyS-CyS-OH
444.6
-58.7
26
1
NHCl
37,38
R
a
Solvent
Refs.
HFIP = hexafluoroisopropanol.
8.2.9. OLIGO(PEPTIDES) OF ACIDIC AMINO ACIDS 8.2.9.1. a- and to-Oligo(peptides) of h-Aspartic Acid and L-Glutamic Acid H[NH-X-CO] n OH Specific rotation X
n
MoI. wt.
[a]o
Asp
2
248.2
+18.5
-CHCH2 I
3
363 3
+6
C 0 0 H
GIu -CHCH2CH2COOH GIu -CHCHCH2 2 I C 0 0 H
2
' 478.3 593.4 708.5 147.1 276.3 4 <)5.4 276.3
3
405<4
4 5 6 7
534.5 663.6 792.7 921.8
4 5 6 1 2 3
'° +16.1 +6.1 +8.7 +31.2 +18.2 -7.2 +4.2 ~12 -16.0 -14.8 -17.2 -19.1
(0C)
c (%)
20 20
20 20 20 22.4 24 19 24 20
24 20 20 20
2 2
1 1 2 1 1-2 1.4 1-2 2
1-2 1-5 1-5 1-5
Solvent
Refs.
0.5 N HCl
76
0.5 N HCl 0.5 N HCl 0.5 N HCl 0.5 N HCl 6 N HCl 0.5 N HCl H2O 0.5 N HCl 0.5 N HCl 0.5 N HCl 0.5 N HCl 0.5 N HCl 0.5 N HCl
76 76 76 76 1 42-44 45 43,44,46,47,59,178 48,59,178 59,178 59 59 59,71
8.2.9.2. y-Oligo(peptides) of D-Glutamic Acid Esters H[NH-X-CO] n -OC(CH 3 ) 3 Specific rotation X
n
D-GIu -CHCH2CH2I COOC(CH3)3
MoL wt.
m.p. ( 0 C)
-[a]J?
629.8 ° 1000.2
81-84 125-127.5 126-131
+17.9 +22.3 +27.6
3 4
815
5 6
llg54
>58
8.2.9.3. ai-Oligo(peptides) of y-Unsubstituted L-Glutamic Acid Derivatives
c (%) 3 3 3
+ 2 9 4
3
Solvent
Refs.
MeOH MeOH MeOH
59 59 59
M e 0 H
59
CH 3 CO-[NHCH(CH 2 CH 2 COOH)CO] n -NHC 2 H 5
Specific rotation na
MoI. wt.
[a]|5
c (%)
Solvent
Ref.
1 2 3
216.2 345.4 474.3
-23 -36 -49.5
1 1 1
H2O H2O H2O
226 226 226
a
n = 2-12: ion-exchange chromatography, IR, CD, MS, pK values, Refs. 227,228.
8.2.9.4.
R'
Asp -CH 2 COOCH 3
-CH 2 COOC 2 H 5
GIu -CH 2 CH 2 COOCH 3
-CH 2 CH 2 COOC 2 H 5
GIu -CH 2 CH 2 COOC 2 H 5
-CH 2 CH 2 COOC 2 H 5
a
n
MoI. wt.
m.p. ( 0 C)
[a]|f
c (%)
Solvent 0
Refs.
2 3 4 5 6 8 11 14 2 3 4 5 6 7 9 11 2 3 4 5 7 8 9
452.5 581.6 710.7 839.8 968.9 1227.2 1614.5 2001.9 480.5 623.6 766.8 910.0 1053.1 1196.3 1482.5 1768.8 494.5 651.7 808.9 966.0 1280.4 1437.5 1594.7
80-81 127-128 143-144 161-163 175-178 207 d 224 d 233 d 86 124 139 200 250 259 d d 104-105 127-128 137-139 177-178.5 >235 >235 >235
+17.9 -1.01 -13.1 -19.1 -26.6 -35.1 -42.9 -46.0 -12.4 -18.0 -21.3 -22.7 -26.7 -28.7 -32.6 -35.6 -17.9 -27.1 -30.9 -26.5 -20.9 -16.5 -7.6
3.1 3.1 1.1 0.1 0.7 0.5 0.45 0.3 2 2 2 2 2 2 2 2
DCA DCA DCA DCA DCA DCA DCA DCA DCA DCA DCA DCA DCA DCA DCA DCA TFE TFE TFE TFE TFE TFE TFE
49,146 49,146 49,146 49,146 49 49,141,146 49,146 49,146 50,141,146 50,146 50,141,146 50,141,146 50,146 50,141,146 50,146 50,146 43,120,142-145 43,120,142-145 142-145 142-145 142-144 142,143,145 142,143,145
2
1 1
7
DCA, dichloroacetic acid; TI E, trifluoroethanol.
8.2.9.5. a-Oligo(peptides) of Benzyloxycarbonyl L-Aspartic Acid and L- and D-Glutamic Acid co-Alkyl Esters C 6 H 5 CH 2 OCO-[NH-X-CO] n -OR Specific rotation X L-Asp -CHCH2 I COOC(CH3)3
R C(CH 3 ) 3
w
MoI. wt. 2 3
4 5
6
550.7 721 9
893.1
10643
1235.4
m.p. (0C) 70-72 93
"95 97-99 121-123 157-162
[a] D -23.0 ~221 -19.3 -18.7 -20.0
( 0 C)
c (%)
25 25
25 25 25
1 l
Solvent 0 DMF D M F
1 1 1
DMF DMF DMF
Refs. 76 76
76 76 76
8.2.9.5.
cont'd Specific rotation
X
R n
L-GIu -CHCH2CH2I COOCH3
CH 3
MoL wt. 2
452.5 738.6
6 7 2
1319.6 1504.8 578.7
97-98 135-137 135-139 175-179 195-198 206-213 88.5-91 77.5-81.5 95-97 99-102 73-77 74-78 83-84
3
763 9
79
3
595 5
4
D-GIu -CHCH C H I COOC(CH3)3
C(CH 3 ) 3
5
8817
6 7 2 4
1024.8 1153.9 578.7 763 9 949.1
5
11343
3
L-GIu
C(CH 3 ) 3
-CHCH2CH2I COOC(CH3)3
m.p. ( 0 C)
949.1
4 5
11343
6 7
1319.6 1504.8
[
87-89 102-103.5 123-125 130-132
( 0 C)
c (%)
-25.2 -26.1 -28.2 -30.1 -31.5 -32.8 +27.4 +30.6 +34.5 +36.1 +42.4 +42.9 -25.4
20 20 20 20 20 20 25 25 25 25 25 25 22
5 5 5 5 5 5 3 3 3 3 3 3 1
-30-2 -33.2 -36.8 -39.9 -43.7
21
l
22 23 22.5 21
Solvent 0
Refs.
DMF DMF DMF DMF DMF DMF MeOH MeOH MeOH MeOH MeOH MeOH MeOH
59 59 59 59 59 59 59 59 59 59 59 59 71
M e 0 H
1 1 1 1
MeOH MeOH MeOH MeOH
71
71 71 71 71
8.2.9.6. OL-Oligo(peptides) of Acetyl L-Glutamic Acid Esters CH3CO-[NHCH(CH2CH2COOC2H5)CO]nOC2H5 Specific rotation n
MoI. wt.
2 3 4 5 8
402.4 559.6 716.8 873.9 1345.5
a
m.p. ( 0 C) 94-95 150-151 171 >230 >230
[a]f?
c (%)
Solvent 41
Ref.
-29.1 -31.2 -39.3 -34.9 -17.3
0.5-1.5 0.5-1.5 0.5-1.5 0.5-1.5 0.5-1.5
TFE TFE TFE TFE TFE
142 142 142 142 142
TFE, Trifluoroethanol
8.2.9.7. OL-Oligo(peptides) of o-Nitrophenylsulfenyl
L-Glutamic Acid Amides and Esters N p s f l - [ N H C H ( C H 2 C H 2 C O O C H 2 C 6 H 5 ) C O ] n - R Specific rotation
R
n
NHC 2 H 5
1 2 4 6 2 4 8 12
OCH 2 C 6 H 5
a
MoI. wt.
m.p. ( 0 C)
417.5 636.7 1075.2 1513.6 699.7 1138.1 2014.9 2891.7
92-93 147-148 180-182 233-234 65-67 114-115 198-205 236-238
[
-40.0 -26.2 -8.2 +7.1
( 0 C)
20 22 25 26
c(%)
1.0 1.0 0.9 0.5
Solvent
Ref.
CHCl 3 CHCl 3 CHCl 3 CHCl 3
147 147 147 148 149 149 149 149
Solvent
Ref.
Nps = o-Nitrophenylsulfenyl.
8.2.9.8. Cyclo-y-Oligo(peptides)
of Glutamic Acid r - [NHCHCH2CH2CO]^-]
I
COOR Specific rotation
R
n
MoI. wt.
m.p. ( 0 C)
[
( 0 C)
c (%)
H
2 3 4 2 3 4
258.2 387.3 516.5 370.4 555.7 740.9
189-192 235-238 232-236 220-222 203-206 230-232
+14.0 +90.0 +38.5 +23.0 -52.5 -38.0
22 22 22 23 23 23
0.5 0.5 0.45 1 1 0.5
C(CH 3 ) 3
0.1 N HCl 0.1 N HCl 0.1 N HCl DMF DMF DMF
60 60 60 60 60 60
8.2.10. OLIGO(PEPTIDES) OF BASIC L-AMINO ACIDS (LYSINE, ORNITHINE, ARGININE, HISTIDINE) 8.2.10.1. Linear Oligo(peptides) H[NHCHRCO]nOH Specific rotation R
n
Rva
MoI. wt.
( 0 C)
[a]D
c (%)
Solvent
Lys -(CH 2 ) 4 NH 2
1 146.2 0.24 +25.7 25 1.6 6 N HCl 2 274.4 0.17 +5.6 25 2 6 N HCl 3 402.6 0.12 -2.2 24 2 0.5 N HCl 4 530.7 0.09 5 658.9 0.06 n = 2-20: Ion-exchange chromatography, Refs. 209-212; n = 2-22; ORD, pK values, Ref. 209; n = 2 - 5 : CD, Ref. 217. Lys(Boc)* 1 246.3 237-255 +4.7 26 0.88 2 N NH 3 -(CH 2 ) 4 NH-Boc 2 474.6 188 +16.4 20 1 MeOH 3 702.9 185-187 +7.4 20 1 MeOH Arg 2 330.4 224-226° +1780^ 1.4 NHCl -(CH 2 ) 3 -NHCNH 2 3 486.6 227-232* + 1540crf 3.9 NHCl b Il 4 642.7 238-241 + 1030c'<* 1.8 NHCl NH
Refs. 1 39,40 40,41 40 40 219 213,214 214 216 126 216
a
TLC in n-butanol/acetic acid/water/pyridine (30:6:24:20). Boc = tert butyloxycarbonyl-. As flavianates. ^A = 224 nm b c
8.2.10.2. Endgroup Protected Oligo(peptides) X-[NHCHRCO] n -Y Specific rotation R
X
Lys(Boc)* -(CH 2 ) 4 NH-Boc
Y
n
Z
OCH 3
Z
OC(CH 3 ) 3
Z
NHCH 3
Z
OH
Boc Boc
OC(CH 3 ) 3 OH
H Boc
Suco a OCH 2 C 6 H 5
Lys(Z) -(CH 2 ) 4 NH-Z
Boc
OH
Om(Boc) -(CH 2 ) 3 NH-Boc
Z
OCH 3
Z
OCH 3
Lys(Z)* -(CH 2 ) 4 NH-Z
Orn(Boc) Arg(NO2) — (CH2)3— NHCNH2 N-NO2
MoI. wt.
m.p. ( 0 C)
1 394.5 Oil 2 622.8 97-98 4 1079.4 121 8 2192.6 >260 2 664.8 82-84 4 1121.4 143-145 2 721.8 129 4 1078.3 174 8 1991.5 >260 16 3817.7 >260 1 380.4 Oil 2 790.0 112 3 837.0 107 7 1773.2 268 3 802.0 114 4 1031.0 92-95 n = 1,5-8,10,20: TLC, IR, CD 2 732.8 80 3 995.1 140 4 1257.4 156-158 5 1519.7 170 7 2044.3 245-248 2 642.7 97-105 4 1167.3 124-127 8 2216.5 1235-140 1 380.4 71 2 594.7 125 3 809.0 147 4 1023.2 152 5 1237.5 165-171 1 367.4 153-153.5 3 769.7 133-136 4
970.9
139-140
k (nm)
( 0 C)
c (%)
Solvent
-10.6 -5.5 -15.3 -16.4 -10.4 -15.5 •-14.4 -16.6 -18.0 -14.6 -2.4 -3.1 -12.2 -19.0 -5.5 -15.4
589 589 589 589 578 578 589 589 589 589 589 578 589 578 578 589
26 20 22 22 22 20 22 22 22 22 26 22 20 22 22 20
1.9 2.1 2.1 2.1 1 1
2.0 1 1 1 1 1
Acetone Acetone CH3COOH CH3COOH DMF DMF CH3COOH CH3COOH CH3COOH CH3COOH Acetone CH3COOH MeOH DMF DMF MeOH
-14.0 -16.2 -15.7 -16.7 -13.9
578 578 578 578 578
1 1 1 1 1
DMF DMF DMF DMF DMF
-14.4 -15.1 -13.7 -17.8 -5.1
589 589 589 589 589
1.08 1.34 1.1 1 1.05
90% AcOH b 90% AcOH 90% AcOH MeOH DMF
[ah
27 20 20 20 25
Refs. 219 218-220 220 220 213 213 220 220 220 220 219 213 214 213 213 214 213 213 213 213 213 215 215 215 221 221,222 222 221,222 222 216 216 216
8.2.10.2.
cont'd Specific rotation
R
X
His(7t-Bom)fe
a b
BOc
Y OCH 3
w
MoL w t 3 4 5 6 7
904.1 1161.4 1418.7 1676.0 1933.3
m.p. ( 0 C)
[ah
I (nm)
( 0 C)
c (%)
67-69 78-81 93-97 117-122 155-163
-15.5 -21.2 -22.3 -23.3 -23.2
589 589 589 589 589
20 20 20 20 20
0.49 0.49 0.48 0.52 0.52
Solvent MeOH MeOH MeOH MeOH MeOH
Refs. 223 223 223 223 223
Suco=/?-oxymethylbenzylcholestan-3-p-yl succinate. Z- = Benzyloxycarbonyl-; Boc- = tert butyloxycarbonyl-; Ti-Bom-= 7V(7c)-benzyloxymethyl-; AcOH = acetic acid.
REFERENCES 1. J. P. Greenstein, M. Wintz, "Chemistry of the Amino Acids", vol. Ill, Wiley, New York, 1961. 2. E. Fischer, E. Fourneau, Chem. Ber., 34, 2868 (1901). 3. E. Fischer, Chem. Ber., 36, 2982 (1903). 4. M. Rothe, H. Bruenig, G. Eppert, J. Prakt. Chem., 8, 323 (1959). 5. E. Fischer, Chem. Ber., 37, 2486 (1904). 6. E. Fischer, Chem. Ber., 39, 453 (1906). 7. H. F. Schott, J. B. Larkin, L. B. Rockland, M. S. Dunn, J. Org. Chem., 12, 490 (1947). 8. R. Schwyzer, B. Iselin, W. Rittel, P. Sieber, HeIv. Chim. Acta, 39, 872 (1956). 9. M. Rothe, G. Luedke, unpublished data. 10. J. C. Sheehan, W. L. Richardson, J. Am. Chem. Soc, 76, 6239 (1954); J. C. Sheehan, M. Goodman, W. L. Richardson, J. Am. Chem. Soc, 77, 6391 (1955). 11. D. G. Ballard, C. H. Bamford, F. J. Weymouth, Proc. Roy. Soc. A, 227 155 (1955). 12. B. F. Erlanger, E. Brand, J. Am. Chem. Soc, 73, 3508 (1951). 13. F. Sigmund, E. Liedl, Hoppe-Seyler's Z. Physiol. Chem., 202, 268, 275 (1931). 14. E. Brand, B. F. Erlanger, H. Sachs, J. Polatnick, J. Am. Chem. Soc, 73, 3510 (1951). 15. H. Zahn, A. Meifiner, Ann. Chem., 636, 132 (1960). 16. E. Brand, B. F. Erlanger, H. Sachs, J. Am. Chem. Soc, 74, 1849 (1952). 17. M. Rothe, R. Theyson, W. Taiber, unpublished data. 18. M. A. Nyman, R. M. Herbst, J. Org. Chem., 15, 108 (1950). 19. S. Shankman, Y. Schvo, J. Am. Chem. Soc, 80,1164 (1958). 20. T. Sugimura, W. K. Paik, unpublished data. 21. S. P. Datta, R. Leberman, B. R. Rabin, Trans. Faraday Soc, 55, 1982 (1959). 22. E. Fischer, Chem. Ber., 39, 2893 (1906). 23. F. H. Carpenter, D. T. Gish, J. Am. Chem. Soc, 74, 3818 (1952). 24. F. C. McKay, N. F. Albertson, J. Am. Soc, 79, 4686 (1957). 25. M. M. Exner, R. J. Kostelnik, Biopolymers, 16,1387 (1977). 26. E. Abderhalden, R. Fleischmann, Fermentforsch., 9, 524 (1928). 27. Y. Shibata, T. Asahina, Bull. Chem. Soc, Japan, 1, 71 (1927).
28. J. S. Fruton, J. Biol. Chem., 146, 463 (1942). 29. M. Bergmann, L. Zervas, L. Salzmann, H. Schleich, HoppeSeyler's Z. Physiol. Chem., 224, 17 (1934). 30. J. L. Bailey, J. Chem. Soc, 3461 (1950). 31. A. E. Barkdoll, W. F. Ross, J. Am. Chem. Soc, 66, 951 (1944). 32. C. A. Dekker, S. R Taylor, Jr., J. S. Fruton, J. Biol. Chem., 180, 155 (1949). 33. M. Brenner, R. W. Pfister, HeIv. Chim. Acta, 34, 2085 (1951). 34. H. B. Milne, C-H. Peng, J. Am. Chem. Soc, 79, 645 (1957). 35. E. Fischer, Chem. Ber., 40, 1501 (1907); E. Fischer, W. A. Jacobs, Chem. Ber., 39, 2942 (1906). 36. E. Fischer, W. Schrauth, Ann. Chem., 354, 21 (1907). 37. J. R Greenstein, J. Biol. Chem., 121, 9 (1937). 38. N. Izumiya, J. P. Greenstein, Arch. Biochem. Biophys., 52, 203 (1954); R. Wade, M. Wintz, J. P. Greenstein, J. Am. Chem. Soc, 78, 373 (1956). 39. B. F. Erlanger, E. Brand, J. Am. Chem. Soc, 73, 4025 (1951); 72, 3314 (1950). 40. S. G. Waley, J. Watson, J. Chem. Soc, 475 (1953). 41. E. Brand, B. F. Erlanger, J. Polatnick, H. Sachs, D. Kirschenbaum, J. Am. Chem. Soc, 73, 4027 (1957). 42. M. Bergmann, L. Zervas, Chem. Ber., 65, 1192 (1932). 43. S. Goldschmidt, C. Jutz, Chem. Ber., 89, 518 (1956). 44. H. Sachs, E. Brand, J. Am. Chem. Soc, 75, 4608 (1953). 45. D. A. Rowlands, G. T. Young, Biochem. J., 65, 516 (1957). 46. V. Bruckner, M. Szekerke, J. Kovacs, Hoppe-Seyler's Z. Physiol. Chem., 309, 25 (1957). 47. W. L. Le Quesne, G. T. Young, J. Chem. Soc, 1959, (1950). 48. H. Sachs, E. Brand, J. Am. Chem. Soc, 76, 1811 (1954). 49. M. Goodman, F. Boardman, J. Listowsky, J. Am. Chem. Soc, 85, 2483 2491 (1963). 50. M. Goodman, E. E. Schmitt, D. A. Yphantis, J. Am. Chem. Soc, 84, 1283, 1288, 3770 (1962). 51. J. Dale, K. Titlestad, Chem. Commun., 656 (1969). 52. N. C. Davis, E. L. Smith, J. Biol. Chem., 200, 373 (1953). 53. M. Rothe, K.-D. Steffen, I. Rothe, Angew. Chem., 77, 347 (1965). 54. J. Kapfhammer, A. Mathes, Hoppe-Seyler's Z. Physiol. Chem., 223, 43 (1934).
55. E. Abderhalden, H. Nienburg, Fermentforsch., 13, 573 (1933). 56. C. Toniolo, Bipolymers, 10, 1707 (1971). 57. U. Widmer, G. P. Lorenzi, Chimia, 25, 236 (1971). 58. J. E. Shields, S. T. McDowell, J. Pavlos, G. R. Gray, J. Am. Chem. Soc, 90, 3549 (1968). 59. M. Kajtar, M. Hollosi, Acta Chim. Acad. Sci. Hung., 65,403 (1970); M. Kajtar, V. Bruckner, Tetrahedron Lett., 4813 (1966). 60. M. Hollosi, M. Kajtar, Acta Chim. Acad. Sci. Hung., 73,247 (1972); M. Kajtar, M. Hollosi, G. Snatzke, Tetrahedron, 27, 5659 (1971). 61. S. M. McElvain, P. M. Laughton, J. Am. Chem. Soc, 73,448 (1951). 62. M. Rothe, R. Theyson, K.-D. Steffen, Tetrahedron Lett., 4063 (1970). 63. S. Sakakibara, M. Shin, M. Fujino, Y. Shimonishi, S. Inoue, N. Inukai, Bull. Chem. Soc. Japan, 38, 1522 (1965). 64. M. Miyoshi, T. Kimura, S. Sakakibara, Bull. Chem. Soc. Japan, 43, 2941 (1970). 65. T. Isemura, H. Okabayashi, S. Sakakibara, Biopolymers, 6, 307 (1968). 66. H. Okabayashi, T. Isemura, S. Sakakibara, Biopolymers, 6, 323 (1968). 67. H. Okabayashi, T. Isemura, Bull. Chem. Soc. Japan, 43, 20 (1970). 68. H. Okabayashi, T. Isemura, Bull. Chem. Soc. Japan, 43, 359 (1970). 69. M. Rothe, J. Mazanek, Tetrahedron Lett., 3795 (1972). 70. M. Rothe, H. Rott, J. Mazanek, Peptides 1976, Proc. 14th Europ. Peptide Symp., A. Loffet (Ed.), Edition de l'Universite de Bruxelles, p. 309. 71. J. Meienhofer, P. M. Jacobs, H. A. Godwin, I. H. Rosenberg, J. Org. Chem., 35, 4137 (1970). 72. E. Schnabel, Ann. Chem., 702, 188 (1967). 73. A. K. Mitra, I. Ostashevsky, C. F. Brewer, Int. J. Peptide Protein Res., 22, 502 (1983). 74. F. C. Carpenter, D. T. Gish, J. Am. Chem. Soc, 74, 3818 (1952). 75. A. Nakamura, O. Jardetzky, Biochemistry, 7, 1226 (1968); Proc. Natl. Acad. Sci. USA, 58, 2212 (1967). 76. M. Kajtar, M. Hollosi, Zs. Riedl, Acta Chim. Acad. Sci. Hung., 88, 301 (1976). 77. M. Rothe, D. Muhlhausen, Angew. Chem., 88, 338 (1976); Angew. Chem. Int. Ed. Engl., 15, 307 (1976). 78. Y. A. Bara, A. Friedrich, W. Hehlein, H. Kessler, P. Kondor, M. Molter, H.-J. Veith, Chem. Ber., I l l , 1029 (1978); Y. A. Bara, A. Friedrich, H. Kessler, M. Molter, ibid., I l l , 1045 (1978). 79. M. Rothe, E. Frank, G. Schmidtberg, in: K. Brunfeldt (Ed.), "Peptides 1980", Proc. 16th Eur. Peptide Symp., Scriptor, Copenhagen 1981, p. 258. 80. M. Rothe, Hj. Schaeffer, unpublished data. 81. M. Goodman, R. Rupp, F. Naider, Bioorg. Chem., 1, 294, 310 (1971). 82. M. Goodman, M. Langsam, Biopolymers, 4, 275 (1966). 83. M. Goodman, M. Langsam, I. G. Rosen, Biopolymers, 4, 305 (1966).
84. M. Goodman, N. Ueyama, F. Naider, Biopolymers, 14, 901 (1975). 85. I. Schechter, A. Berger, Biochemistry, 5, 3362 (1966). 86. G. M. Bonora, D. Nisato, C. Toniolo, Makromol. Chem., 176,2535 (1975); C. Toniolo, G. M. Bonora, ibid., 176,2547 (1975); J. Polym. Sci., Polym. Chem. Ed., 14, 515 (1976). 87. U. Narayanan, T. A. Keiderling, G. M. Bonora, C. Toniolo, Biopolymers, 24, 1257 (1985). 88. D. S. Jones, G. W. Kenner, J. Preston, R. C. Sheppard, J. Chem. Soc, 6227 (1965). 89. M. Y. AIi, J. Dale, K. Titlestad, Acta Chem. Scand., 27,1509 (1973). 90. D. Leibfritz, E. Haupt, N. Dubischar, H. Lachmann, R. Oekonomopulos, G. Jung, Tetrahedron, 38, 2165 (1982). 91. C. Toniolo, G. M. Bonora, V. Barone, A. Bavoso, E. Benedetti, B. Di Blasio, P. Grimaldi, F. LeIj, V. Pavone, C. Pedone, Macromolecules, 18, 895 (1985). 92. E. Benedetti, A. Bavoso, B. Di Blasio, V. Pavone, C. Pedone, M. Crisma, G. M. Bonora, C. Toniolo, J. Am. Chem. Soc, 104, 2437 (1982). 93. G. M. Bonora, C. Mapelli, C. Toniolo, R. R. Wilkening, E. S. Stevens, Int. J. Biol. Macromol., 6, 179 (1984). 94. R. R. Wilkening, E. S. Stevens, G. M. Bonora, C. Toniolo, J. Am. Chem. Soc, 105, 2560 (1983). 95. C. Toniolo, G. M. Bonora, M. Crisma, F. Bertanzon, E. S. Stevens, Makromol. Chem., 182, 3149 (1981). 96. C. Toniolo, G. M. Bonora, A. Fontana, Int. J. Peptide Protein Res., 6, 371 (1974). 97. C. Toniolo, G. M. Bonora, A. Fontana, Bull. Soc. Chim. BeIg., 84, 305 (1975). 98. G. M. Bonora, A. Maglione, A. Fontana, C. Toniolo, Bull. Soc. Chim. BeIg., 84, 299 (1975). 99. P. Spadon, A. Del Pra, Int. J. Peptide Protein Res., 15, 54 (1980). 100. G. M. Bonora, A. Maglione, C. Toniolo, Polymer, 15, 767 (1974). 101. M. Goodman, F. Naider, C. Toniolo, Biopolymers, 10, 1719 (1971). 102. M. Palumbo, S. Da Rin, G. M. Bonora, C. Toniolo, Makromol. Chem., 177, 1477 (1976). 103. J. S. Balcerski, E. S. Pysh, G. M. Bonora, C. Toniolo, J. Am. Chem. Soc, 98, 3470 (1976). 104. M. M. Kelly, E. S. Pysh, G. M. Bonora, C. Toniolo, J. Am. Chem. Soc, 99, 3264 (1977). 105. E. S. Pysh, C. Toniolo, J. Am. Chem. Soc, 99, 6211 (1977). 106. G. M. Bonora, C. Toniolo, Makromol. Chem., 179, 1453 (1978). 107. C. Toniolo, G. M. Bonora, Gazz. Chim. Ital., 104, 843 (1974). 108. E. Peggion, M. Palumbo, G. M. Bonora, C. Toniolo, Bioorg. Chem., 3, 125 (1974). 109. C. Toniolo, G. M. Bonora, Bioorg. Chem., 3, 114 (1974). 110. G. M. Bonora, C. Toniolo, Gazz. Chim. Ital., 107, 195 (1977). 111. C. Toniolo, G. M. Bonora, M. Palumbo, E. Peggion, E. S. Stevens, Biopolymers, 17, 1713 (1978). 112. M. H. Baron, C. De Loze, C. Toniolo, G. D. Fasman, Biopolymers, 17, 2225 (1978); 18, 411 (1979).
113. C. Toniolo, G. M. Bonora, G. R. Sullivan, W. H. Bearden, J. D. Roberts, J. Org. Chem., 45, 288 (1980). 114. D. R. Rueda, R Spadon, G. Zanotti, Gazz. Chim. Ital., 109, 389 (1979). 115. C. Toniolo, G. M. Bonora, S. Salardi, Int. J. Biol. Macromol., 3, 377 (1981). 116. U. Widmer, G. P. Lorenzi, P. Pino, Biopolymers, 18, 239 (1979). 117. G. P. Lorenzi, L. Tomasic, H. Jaeckle, Makromol. Chem., Rapid Commun., 1, 729 (1980). 118. L. Tomasic, A. Stefani, G. R Lorenzi, HeIv. Chim. Acta, 63, 2000 (1980). 119. R. Katakai, J. Chem. Soc, Perkin Trans. I, 905 (1979). 120. J. Semb, J. H. Boothe, R. B. Angier, C. W. Waller, J. H. Mowat, B. L. Hutchings, Y. Subbarow, J. Am. Chem. Soc, 71, 2310 (1949). 121. G. M. Bonora, A. Maglione, C. Toniolo, Gazz. Chim. Ital., 105, 1055 (1975). 122. R. T. Coffey, E. S. Stevens, C. Toniolo, G. M. Bonora, Makromol. Chem., 182, 941 (1981). 123. F. Naider, J. M. Becker, Biopolymers, 13,1011,1747 (1974). 124. G. M. Bonora, C. Toniolo, Biopolymers, 13, 2179 (1974). 125. M. Goodman, A. A. Ribeiro, F. Naider, Proc. Natl. Acad. Sci. USA, 75, 4647 (1978). 126. F. Naider, J. M. Becker, A. Ribeiro, M. Goodman, Biopolymers, 17, 2213 (1978). 127. A. A. Ribeiro, M. Goodman, F. Naider, J. Am. Chem. Soc, 100, 3903 (1978); Int. J. Peptide Protein Res., 14, 414 (1979). 128. F. Naider, A. A. Ribeiro, M. Goodman, Biopolymers, 19, 1799 (1980). 129. D. J. Paskowski, E. S. Stevens, G. M. Bonora, C. Toniolo, Biochim. Biophys. Acta, 535, 188 (1978). 130. C. Bismara, G. M. Bonora, C. Toniolo, E. L. Becker, R. J. Freer, Int. J. Peptide Protein Res., 26, 482 (1985). 131. M. Rothe, F. Wehowsky, H. Ott, unpublished data. 132. A. Sakurai, Y. Okumura, Bull. Chem. Soc Japan, 52, 540 (1979). 133. C. Toniolo, G. M. Bonora, A. Scatturin, Gazz. Chim. Ital., 105, 1063 (1975). 134. M. Fridkin, A. Patchornik, E. Katchalski, J. Am. Chem. Soc, 87, 4646 (1965). 135. B. V. Rozynov, V. M. Burikov, V. V. Shilin, A. A. Kiryushkin, Zh. Obsh. Khim., 38,2690 (1968); J. Gen. Chem. USSR, 38, 2602 (1968). 136. V. T. Ivanov, V. V. Shilin, Y. Bernat, Y A. Ovchinnikov, Zh. Obsh. Khim., 41, 2318 (1971); J. Gen. Chem. USSR, 41, 2341 (1971). 137. S. L. Portnova, T. A. Balashova, V. F. Bystrov, V. V. Shilin, Y Bernat, V. T. Ivanov, Y. A. Ovchinnikov, Chem. Nat. Compd., 7, 307 (1971). 138. P. Sutton, J. L. Koenig, Biopolymers, 9, 615 (1970). 139. J. Beacham, V. T. Ivanov, P. M. Scopes, D. R. Sparrow, J. Chem. Soc. C, 1449 (1966); J. Beacham, V. T Ivanov, G. W. Kenner, R. C. Sheppard, J. Chem. Soc, Chem. Commun., 386 (1965). 140. M. Ueki, S. Ikeda, T. Handa, Bull. Chem. Soc. Japan, 54, 3865 (1981).
141. P. A. Temussi, M. Goodman, Proc. Natl. Acad. Sci. USA, 68, 1767 (1971). 142. M. Goodman, I. G. Rosen, M. Safdy, Biopolymers, 2, 503 (1964); M. Goodman, I. G. Rosen, Biopolymers, 2, 537 (1964). 143. M. Goodman, Y. Masuda, A. S. Verdini, Biopolymers, 10, 1031 (1971). 144. A. Ribeiro, R. P. Saltman, M. Goodman, Biopolymers, 19, 1771 (1980). 145. M. Goodman, A. S. Verdini, C. Toniolo, W. D. Phillips, F. A. Bovey, Proc Natl. Acad. Sci. USA, 64, 444 (1969). 146. M. Goodman, I. Listowsky, Y Masuda, F. Boardman, Biopolymers, 1, 33 (1963). 147. K. Okahashi, S. Ikeda, Int. J. Peptide Protein Res., 13, 462 (1979); K. Okahashi, S. Ikeda, Biopolymers, 18, 2105 (1979). 148. S. Ikeda, K. Okahashi, Biopolymers, 18, 2115 (1979); T. Imae, K. Okahashi, S. Ikeda, Biopolymers, 20, 2553 (1981). 149. T. Ozaki, A. Shoji, M. Furukawa, Makromol. Chem., 183, 771 (1982). 150. M. Rothe, P. Grauer, unpublished data. 151. M. T. Leplawy, D. S. Jones, G. W. Kenner, R. C. Sheppard, Tetrahedron, 11, 39 (1960). 152. W. J. McGahren, M. Goodman, Tetrahedron, 23, 2017 (1963). 153. U. Narayanan, T. A. Keiderling, G. M. Bonora, C. Toniolo, J. Am. Chem. Soc, 108, 2431 (1986). 154. M. Rothe, R. Theysohn, K.-D. Steffen, M. Kostrzewa, M. Zamani, in: E. Scoffone, (Ed.) "Peptides 1969", Proc 10th Europ. Peptides Symp., North-Holland, Amsterdam, 1971, p. 179. 155. R. Deslauriers, J. C. P. Smith, M. Rothe, Proc. 4th Amer. Peptide Symp., Ed. R. Walter, J. Meienhofer, Ann Arbor Sci. Publ., 1975, p. 91. 156. G. Kartha, G. Ambady, R V. Shankar, Nature, 247, 204 (1974); M. E. Druyan, C. L. Coulter in: R. Walter, J. Meienhofer (Eds.), Proc 4th Amer. Peptide Symp, Ann Arbor Sci. Publ., 1975, p. 85; M. E. Druyan, C. L. Coulter, R. Walter, G. Kartha, G. K. Ambady, J. Am. Chem. Soc, 98, 5496 (1976). 157. H. Kessler, A. Friedrich, W. E. Hull, J. Org. Chem., 46, 3892 (1981). 158. M. Rothe, W. Maestle, unpublished data. 159. M. Rothe, W. Maestle, Angew. Chem., 94, 223 (1982); Angew. Chem. Int. Ed. Engl., 21,220 (1982); Angew. Chem. Suppl., 533 (1982). 160. J. W. Bats, A. Friedrich, H. Fuess, H. Kessler, W. Maestle, M. Rothe, Angew. Chem., 91, 573 (1979); Angew. Chem. Int. Ed. Engl., 18, 538 (1979). 161. J. W Bats, H. Fuess, J. Am. Chem. Soc, 102, 2065 (1980). 162. H. Kessler, W. Bermel, A. Friedrich, G. Krack, W. E. Hull, J. Am. Chem. Soc, 104, 6297 (1982); H. Kessler, W. Bermel, H. Forster, Angew. Chem., 94, 703 (1982); Angew. Chem. Int. Ed. Engl., 21, 689 (1982). 163. W. Maestle, M. Rothe, in: J. Z. Siemion, G. Kupryszewski (Eds.), "Peptides 1978", Proc 15th Eur. Peptide Symp., Wroclaw Univ. Press, Wroclaw, p. 179. 164. M. Maestle, T. Weber, M. Rothe, unpublished data.
165. E. Benedetti, B. Di Blasio, V. Pavone, C. Pedone, C. Toniolo, G. M. Bonora, Macromolecules, 13, 1454 (1980). 166. T. Sugihara, Y. Imanishi, T. Higashimura, Biopolymers, 14, 723 (1975). 167. C. M. Deber, F. A. Bovey, J. P. Carver, E. R. Blout, J. Am. Chem. Soc, 92, 6191 (1970). 168. C. M. Deber, D. A. Torchia, E. R. Blout, J. Am. Chem. Soc, 93, 4893 (1971). 169. E. Benedetti, M. R. Ciajolo, A. Maisto, Acta Cryst. B, 30, 1783 (1974). 170. E. Benedetti, A. Ciajolo, B. Di Blasio, V. Pavone, C. Pedone, C. Toniolo, G. M. Bonora, Int. J. Peptide Protein Res., 14, 130 (1979). 171. M. Rothe, H. Rott, Angew. Chem., 88, 844 (1976); Angew. Chem. Int. Ed. Engl., 15, 770 (1976). 172. Y.-Y. H. Chao, R. Bersohn, Biopolymers, 17, 2761 (1978). 173. A. E. Tonelli, J. Am. Chem. Soc, 92, 6187 (1970). 174. A. Chemizard, S. David, Bull. Soc Chim. France, 184 (1966). 175. R. Boni, A. S. Verdini, C. M. Deber, E. R. Blout, Biopolymers, 17, 2385 (1978); J.-P. Meraldi, E. R. Blout, R. Boni, A. S. Verdini, ibid., 17, 2401 (1978). 176. J. Vicar, P. Malon, A. Trka, J. Smolikova, J. Fric, K. Blaha, Coll. Czech. Chem. Commun., 42, 2701 (1977). 177. K. Blaha, J. Fric, Coll. Czech. Chem. Commun., 35, 619 (1970); K. Blaha, J. Smolikova, A. Vitek, ibid., 31, 4296 (1966); K. Blaha, Z. Samek, ibid., 32, 3780 (1967). 178. H.-J. Burkhardt, H. K. Mitchell, Arch. Biochem. Biophys., 94, 32 (1961). 179. E. Benedetti, A. Bavoso, B. Di Blasio, V. Pavone, C. Pedone, C. Toniolo, G. M. Bonora, Biopolymers, 22, 305 (1983). 180. I. Vicar, J. Smolikova, K. Blaha, Coll. Czech. Chem. Commun., 37, 4060 (1972); J. Z. Siemion, Ann. Chem., 748, 88 (1971). 181. M. E. Kamwaya, O. Oster, H. Bradaczek, Acta Cryst. B, 37, 1564 (1981). 182. G. Kartha, T. Ashida, M. Kakudo, Acta Cryst. B, 30, 1861 (1974). 183. H. Brockmann, H. Musso, Chem. Ber., 89, 241 (1956). 184. W. Pickenhagen, P. Dietrich, B. Keil, J. Polonski, F. Nonaille, E. Lederer, HeIv. Chim. Acta, 58, 1078 (1975). 185. C. Eguchi, A. Kakuta, Bull. Chem. Soc. Japan, 47, 2277 (1974). 186. P. E. Young, V. Madison, E. R. Blout, J. Am. Chem. Soc, 48, 5365 (1976). 187. T. Sugihara, Y. Imanishi, T. Higashimura, Biopolymers, 12, 2823 (1973). 188. D. E. Nitecki, B. Halpern, J. W. Westley, J. Org. Chem., 33, 864 (1968). 189. M. Rothe, I. Rothe, T. Toth, K.-D. Steffen, in: H. C. Beyerman, A. van de Linde, W. Maassen van den Brink (Eds.), "Peptides 1966", Proc. 8th Eur. Peptide Symp., NorthHolland Publ. Co., Amsterdam, 1967, p. 8. 190. M. Rothe, R. They son, D. Muhlhausen, F. Eisenbeiss, W. Schindler, in: J. Meienhofer (Ed.), "Chemistry and Biology of Peptides", Proc 3rd Amer. Peptide Symp., Ann Arbor Sci. Publ., Ann Arbor, 1972, p. 51. 191. K. Titlestad, Acta Chem. Scand. B, 29, 153 (1975).
192. J. Dale, K. Titlestad, Acta Chem. Scand. B, 29, 353 (1975). 193. J. Dale, P. Groth, K. Titlestad, Acta Chem. Scand. B, 31, 523 (1977). 194. J. Dale, K. Titlestad, J. Chem. Soc, Chem. Commun., 1403 (1970). 195. J. Dale, K. Titlestad, J. Chem. Soc, Chem. Commun., 255 (1972). 196. K. Titlestad, P. Groth, J. Dale, M. Y. AIi, J. Chem. Soc, Chem. Commun., 346 (1973). 197. P. Groth, Acta. Scand. A, 30, 838 (1976). 198. P. Groth, Acta. Scand. 24, 780 (1970). 199. P. Groth, Acta. Scand. 27, 3419 (1973); K. Titlestad, P. Groth, J. Dale, J. Chem. Soc, Chem. Commun., 646 (1973). 200. P. Groth, Acta. Scand. A, 31, 232 (1977). 201. P. Groth, Acta. Scand. A, 29, 38 (1975). 202. P. Groth, Acta. Scand. 27, 3217 (1973). 203. P. Groth, Acta. Scand. A, 30, 840 (1976). 204. P. Groth, Acta. Scand. 23, 3155 (1969). 205. J. Dale, K. Titlestad, Tetrahedron Lett., 379 (1978). 206. K. Titlestad, Acta Chem. Scand. B, 31, 641 (1977). 207. K. Suzuki, Y. Sasaki, N. Endo, Y Mihara, Chem. Pharm. Bull, 29, 233 (1981). 208. H. Eckstein, Ann. Chem., 2145 (1976). 209. A. Yaron, M. C. Otey, H. A. Sober, E. Katchalski, S. EhrlichRogozinski, A. Berger, Biopolymers, 11, 607 (1972); A. Yaron, E. Katchalski, A. Berger, G. D. Fasman, H. A. Sober, Biopolymers, 10, 1107 (1971). 210. J. W. Stewart, M. A. Stahmann, J. Chromatogr., 9, 233 (1962); in: M. A. Stahmann (Ed.), "Polyamino Acids, Polypeptides, and Proteins", The University of Wisconsin Press, Madison, 1962, p. 95; H. A. Sober, in: M. A. Stahmann (Ed.), "Polyamino Acis, Polypeptides, and Proteins", The University of Wisconsin Press, Madison, 1962, p. 105. 211. O. Grahl-Nielsen, G. L. Trisch, Biochemistry, 8,187 (1969). 212. N. Yu. Kozhevnikova, G. R Vlasov, Zh. Obshch, Khim., 49, 924 (1979); J. Gen. Chem. USSR, 49, 800 (1979). 213. E. Schnabel, Hoppe-Seyler's Z. Physiol. Chem., 357, 1365 (1976). 214. G. P. Vlasov, V R. Glushenkova, T. N. Prokopyuk, Zh. Obshch. Khim., 41, 430 (1971); J. Gen. Chem. USSR, 41, 422 (1971). 215. L. B. Nadezhdina, T. A. Komogorova, G. P. Vlasov, Zh. Obshch, Khim., 51, 214 (1981); J. Gen. Chem. USSR, 51, 187 (1981). 216. H. Ito, I. Ichikizaki, T. Ando, Int. J. Protein Res., 1, 59 (1970). 217. W. L. Mattice, W. H. Harrison, III, Biopolymers, 14, 2025 (1975). 218. H. Yajima, K. Kawasaki, H. Minami, H. Kawatani, N. Mizokami, Y. Kiso, F. Tamura, Chem. Pharm. Bull., 18, 1394 (1970). 219. R. Schwyzer, W. Rittel, HeIv. Chim. Acta, 44, 159 (1961). 220. I. Geczy, Acta Chim. Acad. Sci. Hung., 115, 345 (1984); H. A. Van der Schee, G. I. Tesser, unpublished data. 221. G. I. Tesser, J. T. Buis, Rec Trav. Chim. Pays-Bas, 90, 444 (1971).
222. F. Marchiori, G. Bonn, B. Filippi, V. Moretto, G. M. Bonora, C. Toniolo, Int. J. Peptide Protein Res., 14, 143 (1979); F. Marchiori, G. Bonn, D. Stivanello, V. Moreto, G. Chessa, Hoppe-Seyler's Z. Physiol. Chem., 363, 1483 (1982). 223. G. M. Bonora, C. Toniolo, J. H. Jones, K. N. Rajasekharan, Int. J. Peptide Protein Res., 27, 1 (1986); K. N. Rajshekharan, J. H. Jones, G. M. Bonora, C. Toniolo, Int. J. Peptide Protein Res., 26, 605 (1985). 224. C. Toniolo, G. M. Bonora, I. F. Liischer, C. H. Schneider, Int. J. Peptide Protein Res., 23, 47 (1984). 225. M. Wilchek, A. Patchornik, J. Org. Chem., 28, 1874 (1963). 226. M. Rinaudo, A. Domard, G. Spach, Biopolymers, 12, 2199 (1973); M. Rinaudo, A. Domard, ibid., 12, 2211 (1973).
227. M. Rinaudo, A. Domard, Biopolymers, 14, 2035 (1975); J. Am. Chem. Soc, 98, 6360 (1976). 228. C. Bosso, A. Domard, F. M. Devienne, R. Combarieu, Spectros. Int. J., 3, 81 (1984). 229. R. Guarnaccia, G. R Lorenzi, V. Rizzo, P. L. Luisi, Biopolymers, 14,2329 (1975); R L. Luisi, V. Rizzo, G. P. Lorenzi, B. Straub, U. Suter, R. Guarnaccia, ibid., 14, 2347 (1975). 230. R. Deslauriers, Z. Gronka, K. Schaumburg, T. Shiba, R. Walter, J. Am. Chem. Soc, 97, 5093 (1975). 231. N. Go, H. A. Scheraga, Macromolecules, 6, 525 (1973). 232. H. Edelhoch, R. E. Lippoldt, M. Wilchek, J. Biol. Chem., 243,4799 (1968); H. Edelhoch, R. S. Bernstein, M. Wilchek, ibid., 243, 5985 (1968).
8.3. OLIGO(IMINES) 8.3.1. LINEAR OLIGO(IMINES) 8.3.1.1. Linear Oligo(ethylene imines) H[NHCH2CH2LNH2 n
MoI. wt.
1 2 3 4 7 9
60.1 103.1 146.2 189.2 318.5 404.7
m.p. (0C)
b.p. (°C/mbar)
11.0
116.5/1013 207.1/1013 277.9/1013 333/1013 109-110/11 199-200/1
12.0
d1^ (g/cm3)
jiff
0.8994 0.9586 0.9839 0.9994
1.4536 1.4810 1.4951 1.5015 1.5132 1.5161
Refs. 1,2 1-3 1-4 1-3 2,5 2,5
8.3.1.2. Linear Oligo(alkylene imines) R-[NH(CH ^ 6 NH(CH 2 )Io] n -R' R7
R H
OH
(CH2)ioOH
OH
H
NH(CH2)6NH2
n
MoI. wt.
m.p. (0C)
1 2 3 1 2 3 1 2 3
272.5 526.9 781.4 428.8 683.2 937.7 370.7 625.1 879.6
64-67 70-72 85-86 99-100 90-93 80-84 70-72 86-88 81-85
Ref. 6 6 6 6 6 6 6 6 6
8.3.2. CYCLIC OLIGO(IMINES) [-[NH(CH 2 )J n -I x 2
3 4 5 6
n
MoI. wt.
1 2 4 1 2 1 2 1 2 1 2 3 4 5 6
43.1 86.1 172.3 57.1 114.2 71.1 142.2 85.2 170.3 99.2 198.2 297.5 396.7 495.9 595.1
m.p. (0C)
104 35 14-15
-9
72 42 59-60 45 67-68
b.p. (°C/mbar)
d4 (g/cm3)/°C
55-56/1013 145-146/1013 110/10" 4 63/1013 186-188/1013 88/1013 95/16 106/1013 108-110/16 138/1013
0.8321/24
0.8436/20 0.8520/22.5 0.9020/18 0.8606/20 0.9195/13 0.8864/21
Refs. 2,7,8 8,9 10 11 8,11-13 14 8,13 14 8 8,15,16 13,17,18 17 17 17 17
8.3.2. cont'd x 7 8 9 13
n
MoI. wt.
m.p. (0C)
b.p. (°C/mbar)
d4 (g/cm3)/°C
Refs.
1 2 1 2 1 2 1 2
113.1 226.2 127.2 254.5 141.3 282.5 197.4 394.7
-33 26
162/1013
0.8895/20 0.9012/30 0.9021/21
16,19 19 16 20 16 19 16 21
90/32 55
0.8982/21 38 50-51 52
REFERENCES 1. A. L. Wilson, Ind. Eng. Chem., 27, 870 (1935). 2. G. D. Jones, A. Langsjoen, M. M. Ch. Neumann, J. Zomlefer, J. Org. Chem., 9, 125 (1944). 3. H. B. Jonassen, T. B. Crumpler, T. D. O'Brien, J. Am. Chem. Soc, 67, 1709 (1945). 4. F. G. Mann, J. Chem. Soc, 461 (1934). 5. G. S. Whitby, N. Wellman, V. W. Floutz, L. H. Stephens, Ind. Eng. Chem., 42, 445 (1950). 6. H. Zahn, G. B. Gleitsmann, Makromol. Chem., 63, 129 (1963). 7. C. F. H. Allen, F. W. Spangler, E. R. Webster, Org. Syn., 30,38 (1950). 8. J. v. Braun, G. Blessing, F. Zobel, Chem. Ber., 57, 185 (1924). 9. A. Ladenburg, J. Abel, Chem. Ber., 21, 758 (1888). 10. H. Stetter, K.-H. Mayer, Chem. Ber., 94, 1410 (1961). 11. C C . Howard, W. Marckwald, Chem. Ber., 32, 2031, 2038 (1899).
12. E. L. Buhle, A. M. Moore, F. Y. Wiselogle, J. Am. Chem. Soc, 65, 29 (1943). 13. H. Stetter, J. Marx, Ann. Chem., 607, 59 (1958); H. Stetter, H. Spangenberger, Chem. Ber., 91, 1982 (1958). 14. T. S. Stevens, In E. R. Rodd (Ed.), "Chemistry of Carbon Compounds", Vol. IV, Part A, 1st ed., Elsevier, Amsterdam, 1953, p. 61; N. Campbell, ibid., p. 570. 15. K. Ziegler, Ph. Orth, Chem. Ber., 66, 1867 (1933). 16. L. Ruzicka, M. Kobelt, O. Haefliger, V. Prelog, HeIv. Chim. Acta, 32, 544 (1944). 17. H. Zahn, H. Spoor, Chem. Ber., 89, 1296 (1956); 92, 1375 (1959). 18. M. A. Th. Rogers, Nature (London), 177, 128 (1956). 19. A. Mueller, E. Srepel, E. Funder-Fritzsche, F. Dicher, Monatsh. Chem., 83, 386 (1952). 20. A. Mueller, L. Kindlmann, Chem. Ber., 74, 416 (1941). 21. A. Mueller, Chem. Ber., 67, 295 (1934).
8.4.
8.4.4. CYCLIC OLIGO(UREAS)
OLIGO(UREAS)
8.4.1. OLIGO(METHYLENE UREAS) H[NHCONHCH2] ^NHCONH2 n
MoI. wt.
m.p. (0C)
Refs.
1 2 3 5
132.1 204.2 276.3 420.5
218 d 227 231-233 236 d
1,2 1 1,2 2
8.4.2. OLIGO(METHYLENE THIOUREAS) H[NHCSNHCH 2 ] nNHCSNH 2
zw
m.p. (0C)
MoI. wt.
1 2 3
164.3 252.4 340.5
n
MoI. wt.
m.p. (0C)
2
504.6
300-301
5
1 2
422.6 845.1
157-158 180-181
5 5
Refs.
Refs.
198 d 21Od 215 d
3,4 3 3
8.4.5. OLIGO(CARBONYLPIPERAZINES)
3.4.3. OLIGO(METHYLOLTHIOUREAS) R [ N H C S N H C H 2 L O H R
n
MoI. wt.
m.p. (0C)
H
1 2 1 2
106.2 194.3 136.2 224.3
104-105 190-192 d 92 132
CH 2 OH
Refs.
n
MoI. wt.
m.p. (0C)
3,4 3 3 3,4
0 1 2 3
196.3 308.4 420.5 532.7
42-43 177 267 337
Refs. 6,7 7,8 7 7
REFERENCES 1. A. A. Wanscheidt, S. K. Naumova, J. P. Melnikowa, Zh. Obshch. Khim., 10, 1968 (1940); through Chem. Zentralbl., II, 184 (1941). 2. H. Kadowaki, Bull. Chem. Soc. Japan, 11, 248 (1936). 3. H. J. Becher, R Griffel, Chem. Ber., 91, 691 (1958). 4. H. Staudinger, K. Wagner, Makromol. Chem., 12, 168 (1954).
D.
5. S. Foti, P. Maravigna, G. Montaudo, Macromolecules, 15, 883 (1982). 6. B. Ktihn, Chem. Ber., 33, 2900 (1900). 7. R. Schwalm, W. Heitz, Makromol. Chem., 187, 1415 (1986). 8. D. E. Rivett, J. F. K. Wilshire, Aust. J. Chem., 19, 869 (1966).
CARBON CHAIN OLIGOMERS CONTAINING MAIN CHAIN CYCLIC UNITS
TABLE 9. OLIGO(CYCLOPENTYLENES) n
MoI. wt.
m.p. (0C)
b.p. (°C/mbar)
df (g/cm3)
1 2 3 4 6
70.1 138.3 206.3 274.5 410.7
-93.9
42.3/1013 190/1013 293-294/1013 369-370/1013 235/0.13
0.7510 0.8646 0.9177 0.9564
TABLE 10.
OLIGO(SPIRANES)
143-146
R
n
MoI. wt.
CH2 (CH 2)2
5 3 5 7 3 5 7 9
216.3 244.4 324.5 406.6 272.5 352.6 432.7 512.8
(CH2)3
m.p. (0C)
Refs. 1,2 1,2 1,2 1
b.p. (°C/mbar)
Refs.
78/0.4 84/0.07 61 107-108 52.5 79.5 103-104 138-140
3 3 3 3 3 3 3 3
120-122/0.07
TABLE 11. OLIGO(XYLYLENES) 11.2. CYCLIC OLIGO(XYLYLENES)
11.1. LINEAR OLIGO(XYLYLENES)
n
MoL wt.
m.p. (0C)
b.p. (°C/mbar)
0-
106.2 210.3 106.2 210.3 106.2 210.3 314.5
-25 66.5 -47.4
144/1013 177-178/127 139/1013 296/1013 138/1013 178/24
1 2 m- 1 2 p1 2 3
13-14 82 141-142
Refs. 5-7 7,8 7,9-12,30 10,13
n
MoI. wt.
m.p. (0C)
0-
208.3 312.5 416.6 208.3 208.3 312.5 416.6
112-112.5 184.5 205 132-133 285-287 170-171 179-182
2 3 4 m- 2 p- 2 3 4
b.p. (°C/mbar)
290/1013
Refs. 5,6,14 5,6 15 10 8,11-13,19,30 10,,13,30 13
TABLE 16. OLIGO(p-PHENYLENE OXIDES)
TABLE 12. OLIGO(STILBENES) n
MoI. wt.
1 2 3 4 5 6 7
180.2 282.4 384.5 486.5 588.7 690.9 793.0
m.p. (0C) 124 265 350-352 360-374 395-400 415-420 425
Refs. 17 16-18 17 16,17 16,17 16,17 16,17
n
MoI. wt.
m.p. (0C)
Refs.
1 2 3 4
170.2 262.3 354.4 446.5
28 73 105 142
23,27 23,27 23,27
TABLE 17. OLIGO(p-PHENYLENE SULFIDES)
TABLE 13. OLIGO(BENZYLS) n
MoI. wt.
m.p. (0C)
1 2 3 4 5
168.2 258.3 348.4 438.6 528.7
25.1 82 90 120 153-156
Refs.
20,23 21,23 23 22,23
n
MoI. wt.
m.p. (0C)
Refs.
1 2 3 4
186.4 294.5 402.6 510.7
-21.5 80 110 150
23,28 23 23
TABLE 14. OLIGO-(2,5-DIMETHYL-BENZYLS) TABLE 18. OLIGO(p-PHENOXYPHENYLMETHANES)
n
MoI. wt.
1 2 4 6
224.3 342.5 578.8 815.1
m.p. (0C) 60-61 153-154 234-236 262-266
Refs. 22,24 22 22 22
n
MoI. wt.
m.p. (0C)
1 2
350.4 532.7
59 101
Refs. 23 23
TABLE 15. OLIGO(2,3,5,6-TETRAMETH YL-BENZYLS) TABLE 19. OLIGO(DIPHENYLMETHANES)
n
MoI. wt.
m.p. (0C)
Refs.
1 2 3 4
280.5 426.7 572.9 719.1
155-156 263-264 305-307 335-337
22,25 22,26 22 22
n
MoI. wt.
m.p. (0C)
Refs.
1 2 3 4
168.2 334.5 500.7 666.9
25.1 115 180 240
4,29 4 4
REFERENCES 1. 2. 3. 4. 5.
J. V. Braun, J. Reitz-Kopp, Chem. Ben, 74, 1105 (1941). G. E. Goheen, J. Am. Chem. Soc, 63, 744 (1941). E. Buchta, K. Geibel, Ann. Chem., 678, 53 (1964). M. Busch, W. Weber, J. Prakt. Chem., 146, 1 (1936). W. Baker, R. Banks, D. R. Lyon, F. G. Mann, J. Chem. Soc, 27 (1945). 6. A. C. Cope, S. W. Fenton, J. Am. Chem. Soc, 73, 1668 (1951).
7. G. H. Coleman, W. H. Hoist, R. D. Maxwell, J. Am. Chem. Soc, 58, 2310 (1936). 8. M. Swarcz, J. Chem. Phys., 16, 128 (1948). 9. T. Reichstein, R. Oppenauer, HeIv. Chim. Acta, 16, 1373 (1933). 10. W. Baker, J. F. W. McOmie, J. M. Norman, J. Chem. Soc, 1114(1951).
11. C. J. Brown, A. C. Farthing, Nature (London), 164, 915 (1949); J. Chem. Soc, 3261, 3265, 3270, (1953). 12. D. J. Cram, H. Steinberg, J. Am. Chem. Soc, 73, 5691 (1951). 13. L. A. Errede, R. S. Gregorian, J. M. Hoyt, J. Am. Chem. Soc, 82, 5218 (1960). 14. L. A. Errede, J. Am. Chem. Soc, 83, 949 (1961). 15. E. D. Bergmann, Z. P elchowicz, J. Am. Chem. Soc, 75,4281 (1953). 16. G. Drefahl, G. Ploetner, Chem. Ber., 94, 907 (1961); 91, 1274 (1958). 17. G. Drefahl, R. Kuehmstedt, H. Oswald, H.-H. Hoerhold, Makromol. Chem., 131, 89 (1970). 18. T. W. Campbell, R. N. McDonald, J. Org. Chem., 24, 1246 (1959). 19. H. E. Winberg, E S. Fawcett, W. E. Mochel, C. W. Theobald, J. Am. Chem. Soc, 82, 1428 (1960).
20. A. B. Galun, A. Kaluszymer, E. D. Bergmann, J. Org. Chem., 27, 1426 (1961). 21. E. Connerade, Bull. Soc Chim. Beiges, 44, 411 (1935). 22. G. Montaudo, F. Bottino, S. Caccamese, R Finocchiaro, G. Bruno, J. Polym. Sci. A-I, 8, 2453 (1970). 23. G. Montaudo, G. Bruno, P. Maravigna, P. Finocchiaro, G. Centineo, J. Polym. Sci., 11, 65 (1973). 24. R. C. Huston, D. T. Ewing, J. Am. Chem. Soc, 37, 2394 (1915). 25. C. M. Welch, H. A. Smith, J. Am. Chem. Soc, 73, 4391 (1951). 26. H. Kaemmerer, M. Harris, Makromol. Chem., 66, 215 (1963). 27. H. Staudinger, F. Staiger, Ann. Chem., 517, 67 (1935). 28. E. Bourgeois, A. Fonassin, Bull. Chim. France, 9, 941 (1911). 29. N. Wolf, Chem. Ber., 14, 2031 (1881). 30. J. R. Schaefgen, J. Polym. Sci., 15, 203 (1955).
TABLE 20. PHENOL-FORMALDEHYDE AND RELATED OLIGOMERS
20.1.2.2.
20.1. LINEAR PHENOL-FORMALDEHYDE OLIGOMERS 20.1.1. PHENOL-FORMALDEHYDE OLIGOMERS
0
n
MoI. wt.
m.p. ( C)
Refs.
1 2 3 4 5 6
200.2 306.4 412.5 518.6 624.7 730.8
119-120 158-159 161-162 148-150 203-204 213-214
1-4 2-6 3,4 4,7 4 4
n
MoI. wt.
m.p. (0C)
Refs.
1 2 3 4 5
136.1 256.3 376.5 496.7 616.9
70-72 148 183-184 204-205 152-154
61 11,13-16 11 11 61
20.1.2. /7-CRESOL-FORMALDEHYDE OLIGOMERS
20.1.3. p-tert BUTYLPHENOL-FORMALDEHYDE OLIGOMERS
20.1.2.1.
20.1.3.1.
n
MoI. wt.
m.p. (0C)
Refs.
2 3 4 5 6 7 8 9 11
228.3 348.4 468.6 588.7 708.9 829.1 949.2 1069.4 1189.5 1429.8
126 214-215 173 130 215-217 225-230 167-170 205-210 175-180 245
8-10,56-58 8-11,56-58 8,9,56,57 12,56,57 12 12 12 12 12 12
n 1 2 3 4 5 6 7 8 10
MoI. wt.
m.p. (0C)
Refs.
312.5 474.7 636.9 799.2 961.4 1123.6 1285.9 1448.1 1772.6
156 218-220 211 216-217 250 249-250 253-256 224-226 140
17,18,62 17,18,62 17,18,62 17,18,62 17,18,62 17,18 18 17 17
20.1.8. OLIGOMERS WITH CARBONYL AND SULFONYL BRIDGES
20.1.3.2.
20.1.8.1.
n
MoL wt.
m.p. (0C)
Refs.
0 1 2 4
220.4 340.5 460.7 701.0
70-71 125-130 82-84 188-190
61 61 61 61
/i
MoI. wt.
m.p. (0C)
Refs.
1 2
242.3 376.4
106-107 122-123
23,24,56-58 24,56,57
n
MoI. wt.
m.p. (0C)
Refs.
1 2 3
347.2 517.4 687.6
179 238-240 246-252
25 25 25
20.1.4. 2,4,6-MESITOL-FORMALDEHYDE OLIGOMERS 20.1.8.2.
n
MoL wt.
m.p. (0C)
1 2
284.4 432.6
188 257
Refs. 19 19
20.1.5. 4-CARBOXY-PHENOL-FORMALDEHYDE OLIGOMERS
20.2.
OLIGOMERIC PHENOL ALCOHOLS
20.2.1. OLIGOMERICPHENOLALCOHOLS n
MoL wt.
1 2
288.3 438.4
0
m.p. ( C) 305-307 310
Refs. 59 59
20.1.6. 4-BROMO-PHENOL-FORMALDEHYDE OLIGOMERS
n
MoL wt.
m.p. (0C)
1 2
124.1 230.3
86-87 121.5-123
Refs. 3,26 3,27,28
20.2.2. PHENOL DIALCOHOLS
/i
MoL wt.
m.p. (0C)
Refs.
1 2
358.1 543.1
183-184 237-238
1,60 60
20.1.7. /7-CRESOL-ACETALDEHYDE OLIGOMERS
n
MoL wt.
m.p. (0C)
Refs.
1 2
154.2 260.3
101 126-127
29-32 28
20.2.3. /7-CRESOL MONOALCOHOLS R
n
MoI. wt.
m.p. (0C)
Refs.
H H CH3 CH3 CH3
1 2 1 2 3
241.3 373.5 270.4 404.6 538.7
141 214-215 135-135.5 154-155 204-205
20,21 21 22 63 63
n
M o L wt.
1 2 4
138.2 258.3 498.6
m.p. (0C) 107 148
Refs. 8,33,34 8,9,35 36
20.2.4. /7-CRESOL DIALCOHOLS 20.3.2.
n
MoL wt.
1 2 3
168.2 288.3 408.5
m.p. (0C)
Refs.
133-134 151.5 203
13,37 9,35,38,39 9,39,40
n
MoL wt.
m.p. (0C)
Ref.
2
540.7
325-330
46
n
MoL wt.
Refs.
2
916.2
1
1201.5
20.3.3.
20.2.5. p-tert BUTYLPHENOL DIALCOHOLS
n
MoL wt.
m.p. (0C)
Refs.
1 2
210.3 372.5
74-75 117-118
41 18
R
20.2.6. o-HYDROXYDIBENZYL ETHERS
47 43,47
20.4. BRANCHED PHENOL-FORMALDEHYDE OLIGOMERS n
MoI. wt.
m.p. (0C)
Refs. 20.4.1.
2
318.4
85
42
20.3. CYCLIC PHENOL-FORMALDEHYDE OLIGOMERS
MoL wt.
m.p. (0C)
Ref.
158
48
20.3.1. 376.5 X -CH 2 -
R -CH 3 -C(CH3)3
/i MoL wt. m.p. (0C) 4 4
480.6 648.9
300 344-346
5 6 8 -C 6 H 5 4 6 8 -C 6 Hn 4 -CH 2 C 6 H 5 4 -C(CH3)2CH2CH3 4 -C(CH3)2CH2C(CH3)2 4 -CH 2 OCH 2 - -CH 3 4 -C(CH3) 3 3
811.1 973.5 1298.0 728.9 1093.4 1457.8 753.1 785.0 705.0 813.2 600.7 576-8
310 380-381 411-412 407-409 408-410 421-423 330 330 280 333 264-266 245
Refs. 36,43 18,44, 65,66 68 65,66,68 65,66,68 18,66,67 66,67 66,67 18 18 18 18 42 45
20.4.2.
Ri
R2
MoL wt.
m.p. (0C)
Refs.
H H CH3
H CH3 CH3
411.5 453.6 495.6
184-187 185-186
49 30,50 51
20.4.3.
20.5. HYDROQUINONE OLIGOMERS 20.5.1.
Ri
R2
n
MoL w.t
m.p. (0C)
H CH3 CH3
H CH3 CH3
1 1 2
624.7 737.0 1217.5
185-187 207-208 190-191
n
MoI. wt.
m.p. (0C)
Refs.
1 2
300.4 462.5
97-98 146-147
64 64
Refs. 52,53 6,53,54 54
20.5.2.
R
n
MoL wt.
m.p. (0C)
Refs.
H
0 1 0 1 2 3 4
300.4 462.5 328.4 490.6 652.8 815.0 977.2
97-98 192-193 162-163 242-243 283-284 306-307 326-328
64 64 64 64 64 64 64
CH3
REFERENCES
1. C A . Buehler, D. E. Cooper, E. O. Scrudder, J. Org. Chem., 81, 316 (1943). 2. S. R. Finn, J. W. James, C. J. S. Standen, J. Appl. Chem., 4, 497 (1954); S. R. Finn, G. Lewis, N. J. L. Megson, J. Soc. Chem. Ind., 69, 551 (1950); S. R. Finn, G. Lewis, J. Appl. Chem., 1, 524 (1954). 3. D. A. Fraser, R. W. Hall, P. A. Jenkins, A. L. J. Raum, J. Appl. Chem., 7, 689 (1957). 4. H. Kaemmerer, H. Lenz, Makromol. Chem., 27, 162 (1958). 5. H. L. Bender, A. G. Franham, J. W. Guyer, F. N. Apel, T. B. Gibb, Jr., Ind. Eng. Chem., 44, 1619 (1952). 6. A. C. Davis, B. T. Hayes, R. F. Hunter, J. Appl. Chem., 3, 312 (1923). 7. S. Seto, H. Horiuchi, A. Takahashi, J. Chem. Soc. Japan, Ind. Chem. Sect., 58, 378 (1955). 8. H. Kaemmerer, W. Rausch, Makromol. Chem., 24, 152 (1957). 9. M. Koebner, Z. Angew. Chem., 46, 251 (1953). 10. N. J. L. Megson, A. A. Drummond, J. Soc. Chem. Ind., 49,251 T (1930). 11. E. Ziegler, I. Hontschik, L. Milowiz, Montash. Chem., 78,334 (1948). 12. H. Kaemmerer, W. Rausch, H. Schweikert, Makromol. Chem., 56, 123 (1962). 13. K. Auwers, Chem. Ber., 40, 2524 (1907). 14. K. Fries, K. Kann, Ann. Chem., 353, 335 (1907). 15. K. Hultzsch, Chem. Ber., 74, 989 (1941).
16. A. Zinke, E. Ziegler, Chem. Ber., 74, 541 (1941). 17. H. Kaemmerer, K. Haberer, Monatsh. Chem., 95,1589 (1964). 18. A. Zinke, R. Kretz, E. Leggewie, K. Hoessinger, Monatsh. Chem., 83, 1213 (1952). 19. S. R. Finn, J. W. G. Musty, J. Soc. Chem. Ind., 69 (Suppl. No. 1), S 3 (1950). 20. E. Adler, H. V. Euler, G. J. Gie, Arkiv Kemi, 16A, No. 12 (1943). 21. L. M. Debing, Trans. Electrochem. Soc, 90, 277 (1946). 22. H. V. Euler, E. Adler, J. O. Cedwall, Arkiv Kemi, 15A, No. 19 (1942). 23. A. V. Bayer, V. Frewsen, Ann. Chem., 212, 344 (1882). 24. H. Kaemmerer, G. Buesing, H.-G. Haub, Makromol. Chem., 66, 82 (1963). 25. H. Kaemmerer, M. Harris, Makromol. Chem., 62, 18 (1963); J. Polym. Sci. A, 2, 4003 (1964). 26. L. Lederer, J. Prakt. Chem., 50, 223 (1894). 27. S. R. Finn, J. W. James, C. J. S. Standen, Chem. Ind., 188, (1954); J. Appl. Chem., 4, 296 (1954). 28. A. T. Carpenter, R. F. Hunter, J. Appl. Chem., 3, 486 (1953). 29. S. R. Finn, J. W. G. Musty, J. Appl. Chem., 2, 88 (1952). 30. J. H. Freeman, J. Am. Chem. Soc, 74, 6257 (1952). 31. H. Kaemmerer, M. Grossmann, Chem. Ber., 86, 1492 (1953). 32. J. Reese, Angew. Chem., 64, 399 (1952). 33. H. V. Euler, E. Adler, G. Eklund, O. Toerngren, Arkiv Kemi, 15B, No. 9 (1942).
34. 35. 36. 37. 38. 39. 40. 41. 42. 43. 44. 45. 46. 47. 48. 49. 50. 51. 52. 53. 54.
O. Manasse, Chem. Ber., 27, 2409 (1894). P. Maitland, D. C. Pepper, J. Soc. Chem. Ind., 61, 66 (1942). B. T. Hayes, R. F. Hunter, J. Appl. Chem., 8, 743 (1958). F. Ullmann, K. Brittner, Chem. Ber., 42, 2539 (1909). F. Adler, Arkiv Kemi, 14B, No. 23 (1941). S. R. Finn, G. J. Lewis, J. Soc. Chem. Ind., 69, 132 (1950). S. Kyrning, Arkiv Kemi, 15A, No. 2 (1941). F. Hanus, E. Fuchs, J. Prakt. Chem., 153, 327 (1939). H. Kaemmerer, M. Dahm, Kunstst. Plast., 6, 1 (1959). B. T. Hayes, R. F. Hunter, Chem. Ind., 193, (1956). A. Zinke, E. Ziegler, Chem. Ber., 77, 264 (1944). K. Hultzsch, Kunststoffe, 52, 19 (1962). H. V. Euler, E. Adler, B. Bergstroem, Arkiv Kemi, 14B, No. 30 (1941). R. F. Hunter, C. Turner, Chem. Ind., 72, (1957). E. Ziegler, Monatsh. Chem., 79, 142 (1948). E. Ziegler, Oester, Chem. Ztg., 49, 92 (1948). A. T. Carpenter, R. F. Hunter, J. Appl. Chem., 1, 217 (1951). A. T. Carpenter, R. F. Hunter, J. Chem. Soc, 2731, (1954). H. Kaemmerer, H. Lenz, Kunststoffe, 51, 26 (1961). A. C. Davis, B. T. Hayes, R. F. Hunter, J. Appl. Chem., 7, 521 (1957). R. F. Hunter, C. Turner, J. Appl. Chem., 7, 528 (1957).
55. H. v. Euler, E. Adler, S. V. Kispeczy, A. M. Fagerlund, Arkiv Kemi, 14A, No. 10 (1940). 56. H.-J. Eichhoff, H. Kaemmerer, D. Weller, Makromol. Chem., 129, 109 (1969). 57. H.-J. Eichhoff, H. Kaemmerer, D. Weller, Makromol. Chem., 132, 163 (1970). 58. H. Kaemmerer, G. Gros, H. Schweikert, Makromol. Chem., 143, 135 (1971). 59. H. Kaemmerer, W. Lotz, Makromol. Chem., 145, 1 (1971). 60. H. Kaemmerer, G. Gros, Makromol. Chem., 149, 85 (1971). 61. M. B. Huglin, G. J. Knight, W. W. Wright, Makromol. Chem., 152, 67, 83 (1972). 62. T. Carins, G. Eglinton, Nature (London), 196, 535 (1962). 63. H. Kaemmerer, A. Kiegel, unpublished results. 64. G. Manecke, D. Zeipner, Makromol. Chem., 129, 183 (1969). 65. C. D. Gutsche, B. Dhawan, K. H. No, R. Muthukrishnan, J. Am. Chem. Soc, 103, 3782 (1981). 66. C. D. Gutsche, Top. Curr. Chem., 123, (1984); Ace. Chem. Res., 16, 161 (1983). 67. C. D. Gutcshe, K. H. No, J. Org. Chem., 47,2708 (1982); C. D. Gutsche, P. F. Pagoria, ibid., 50, 5795 (1985). 68. A. Ninagawa, H. Matsuda, Makromol. Chem., Rapid Commun., 3, 65 (1982).
TABLE 21. OLIGO(PHENYLENES)
21.2. /w-OLIGO(PHENYLENES)
21.1.
21.2.1. LINEARm-OLIGO(PHENYLENES)
0-OLIGO(PHENYLENES)
21.1.1. LINEAR o-OLIGO(PHENYLENES)
n
MoI. wt.
m.p. (0C)
b.p. (0C)
Refs.
3 4 6 8
230.3 306.4 458.6 610.8
59 119 217 320
332 420
1,2 1,3-6 3,5 5
n
MoI. wt.
m.p. (0C)
b.p. (0C)
3 4 5 6 8 9
230.3 306.4 382.5 458.6 610.8 689.9
89 86.5-87.5 117-117.5 148 129-131 195-200
365 419
12-14 3,6,15-17 12,15,16 3,15,17,18 15,17 18
Refs.
Refs.
21.2.2. CYCLIC m-OLIGO(PHENYLENES) n
MoI. wt.
m.p. (0C)
6 8
456.6 608.8
509.5-511 449-451
19 19
21.1.2. CYCLIC o-OLIGO(PHENYLENES)
n
MoI. wt.
m.p. (0C)
2 3 4 6 8
152.2 228.3 304.4 456.6 608.8
111 196.5 233 432 425
Refs. 4,5,7-9 10,11 4,5 5 5
21.2.3. OLIGO(3-METHYL-m-PHENYLENES)
n
MoI. wt.
m.p. (0C)
b.p. (°C)
Refs.
2 3
182.3 272.4
9-9.5 65
280
20-23 12
21.3.
/7-OLIGO(PHENYLENES)
21.3.1. /7-OLIGO(PHENYLENES)
n
MoL wt.
m.p. (0C)
b.p. (°C/mm)
1 2 3 4 5 6
78.1 154.2 230.3 306.4 382.5 458.6
5.5 71 215 322 395 465
80.1 156 376 428/10
Solubility (g/L toluene) oo 430 7.4 0.12 <0.005
n
MoL wt.
m.p. (0C)
b.p. (0C)
1 2 3
92.1 182.3 272.4
-95
110.6 273-274
43
Refs. 22,23,32 33
m.p. (0C)
b.p. (°C)
1 2 3 4 5
106.2 210.3 314.5 418.6 522.8
13.3 53-54 182-183 264-266 307-309
138.4
n
MoL wt.
m.p. (0C)
Solubility (g/L toluene)
1 2
182.3 362.5
24 96
490
Refs. 20,23,36 37
21.3.6. OLIGO(3,3 '-DIMETHYL-BIPHENYLENES)
21.3.3. OLIGO(2,5-DIMETHYL-/?-PHENYLENES)
MoL wt.
24 3,12,14,25,26 3,12,16,21,25,26 12,16,21,25,21,2K 3,29-31
21.3.5. OLIGO(2,2 '-DIMETHYL-BIPHENYLENES)
21.3.2. OLIGO(3-METHYL-/?-PHENYLENES)
n
Refs.
Solubility (g/L toluene) oc 700 28 1.1 0.24
Refs. 20,34 34 34 34
n
MoL wt.
m.p. (0C)
1 2 3 4 5 6
182.3 362.5 542.8 723.0 903.3 1083.5
9-9.5 76.5 142 273 285 298
b.p. (0C)
Solubility (g/L toluene)
280
oo 512 87 <6.5 ~2 <0.8
Refs. 20-23,38 27,37 39 39,40 39,40 39,40
21.3.4. 0 0 0 0 ( 2 , 3 , 5 , 6 - T E T R A M E T H Y L - P - P H E N Y L E N E S )
21.3.7. OLIGO(3,3 "-DIMETHYL-p-TERPHENYLENES)
n
MoL wt.
m.p. (0C)
1 2 3 4
134.2 266.4 398.6 530.8
79.2 136-137 270-272 270-272
b.p. (0C) 196-198
Solubility (g/L toluene) oc 365 24 3.4
Refs. 34,35 34 34
n
MoL wt.
m.p. (0C)
Solubility (g/L toluene)
Refs.
1 2
258.4 514.7
140-141 258
4.9 0.4
27,37 37
21.3.10. OLIGO(2',3''-DIMETHOXY-p-QUATERPHENYLENES)
21.3.8. OLIGO(2,5-DIMETHOXY-p-PHENYLENES)
n
MoI. wt.
m.p. (0C)
1 2 3 4
138.2 274.3 410.5 546.6
56 105 189 246
b.p. (0C)
Refs.
212.6 20,41 41 41
n
MoI. wt.
m.p. (0C)
Solubility (g/L toluene)
1 2
366.5 730.9
183-184 276-277
13 0.2
Refs. 43 43
21.3.9. OLIGO(3,3 '-DIMETHOXY-BIPHENYLENES) 21.4. OLIGO(p-QUINONES)
n
MoI. wt.
1 2
214.3 426.5
m.p. (0C)
36 158
b.p. (0C)
Solubility (g/L toluene)
328 22
Refs.
42 38,43
n
MoI. wt.
m.p. (0C)
Refs.
1 2 3 4
108.1 214.2 320.3 426.3
116.5 194 >230 230-270
41 41 41
REFERENCES 1. W. Bachmann, H. T. Clarke, J. Am. Chem. Soc, 49, 2089 (1927). 2. C. F. H. Allen, F. P. Pingert, J. Am. Chem. Soc, 64, 1365 (1942). 3. J. A. Cade, A. Pilbeam, Tetrahedron, 20,519 (1964); J. Chem. Soc, 114(1964). 4. W. S. Rapson, R. G. Shuttleworth, J. N. van Niekerk, J. Chem. Soc, 326 (1943). 5. G. Wittig, G. Lehmann, Chem. Ber., 90,875 (1957); G. Wittig, G. Klar, Ann. Chem., 704, 91 (1967). 6. S. T. Bowden, J. Chem. Soc, 1111 (1931). 7. W. Baker, M. P. V. Boarland, J. F. W. McOmie, J. Chem. Soc, 1476 (1954). 8. W. C. Lothrop, J. Am. Chem. Soc, 63, 1187 (1941). 9. G. Wittig, W. Herwig, Chem. Ber., 87, 1511 (1954). 10. C. Mannich, Chem. Ber., 40, 159 (1907). 11. P G . Copeland, R. E. Dean, D. McNeil, J. Chem. Soc, 1689 (1960). 12. M. Busch, W. Weber, J. Prakt. Chem., 146, 1 (1936). 13. A. E. Gillam, D. H. Hey, J. Chem. Soc, 1170 (1939); H. France, I. M. Heilbron, D. H. Hey, J. Chem. Soc, 1288 (1939); 1364 (1938). 14. G. F. Woods, J. W. Tucker, J. Am. Chem. Soc, 70, 2174 (1948). 15. R. L. Alexander, Jr., J. Org. Chem., 21, 1464 (1956). 16. G. F. Woods, F. T. Reed, J. Am. Chem. Soc, 71, 1348 (1949). 17. M. Bennett, N. B. Sunshine, G. F. Woods, J. Org. Chem., 28, 2514 (1963); W. Davey, D. H. Maass, J. Chem. Soc, 4386 (1963).
18. L. Silverman, W. Houk, Anal. Chem., 27, 1956 (1955). 19. H. A. Staab, F. Binnig, Tetrahedron Lett., 319 (1964); Chem. Ber., 100, 293 (1967); H. Braunling, F. Binnig, H. A. Staab, ibid., 100, 880 (1967). 20. F. Ullmann, G. M. Meyer, O. Loewenthal, E. Gilli, Ann. Chem., 332, 38 (1904). 21. E. Mueller, T. Toepel, Chem. Ber., 72, 273 (1939). 22. G. F. Woods, A. L. Van Artsdale, F. T. Reed, J. Am. Chem. Soc, 72, 3221 (1950). 23. E. A. Johnson, J. Chem. Soc, 4155 (1957). 24. E. Clar, "Polycyclic Hydrocarbons", Academic, New York, Springer, Berlin, 1964. 25. O. Gerngross, M. Dunkel, Chem. Ber., 57, 739 (1924); O. Gerngross, C. Schachnow, R. Jonas, Chem. Ber., 57, 747 (1954). 26. H. O. Wirth, K. H. Goenner, W. Kern, Makromol. Chem., 63, 53 (1963). 27. H. O. Wirth, K. H. Goenner, R. Stueck, W. Kern, Makromol. Chem., 63, 30 (1963). 28. T. W. Campbell, R. N. McDonald, J. Org. Chem., 24, 730 (1959). 29. P. Kovacic, R. M. Lange, J. Org. Chem., 29, 2416 (1964). 30. T. Nozaki, M. Tamura, Y. Harada, K. Saito, Bull. Chem. Soc Japan, 33, 1329 (1960). 31. R. Pummerer, K. Bittner, Chem. Ber., 57, 84 (1924); R. Pummerer, L. Seligsberger, Chem. Ber., 64, 2477 (1931). 32. F. Mayer, K. Freitag, Chem. Ber., 54, 347 (1921). 33. H. O. Wirth, H. Hefner, W. Kern, unpublished results. 34. H. O. Wirth, F. U. Herrmann, W. Kern, Makromol. Chem., 80, 120 (1964).
35. E. Marcus, W. M. Lauer, R. T. Arnold, J. Am. Chem. Soc, 80, 3742 (1958). 36. D. M. Hall, M. S. Lesslie, E. E. Turner, J. Chem. Soc, 711 (1950). 37. W. Kern, M. Seibel, H. O. Wirth, Makromol. Chem., 29, 164 (1959). 38. W. Schlenk, M. Brauns, Chem. Ber., 48, 661 (1914). 39. W. Kern, W. Gruber, H. O. Wirth, Makromol. Chem., 37, 198 (1960).
40. W. Heitz, R. Ullrich, W. Kern, Makromol. Chem., 98, 29 (1966). 41. H. Erdtmann, M. Granath, G. Schultz, Acta Chem. Scand., 8, 1442 (1954). 42. N. Kornblum, Org. Syn. Coll. Vol. Ill, 295 (1962). 43. W. Kern, H. W. Ebersbach, I. Ziegler, Makromol. Chem., 31, 154 (1959).
E. OLrGOMERS CONTAINING HETEROCYCLIC RINGS IN THE MAIN CHAIN
TABLE 22. 22.1.
HETEROCYCLIC OLIGOMERS
OLIGO(FURAN)DERIVATIVES
22.1.1. OLIGO(FURFURYL) ALCOHOLS
n 1 2 3
m.p. (0C)
MoL wt. 98.1 178.2 258.3
-2.5 62-62.5
b.p. (°C/mbar)
nj?
171/1000 141-143/12 192.5-295/8
1.4868 1.5290
Refs. 10,11 10-12,14 10-12,14
22.1.2. OLIGO(FURFURYL) FURANS Ri
R2
n
MoI. wt.
H
H
1 2 3 4 1 2 3 1 2 3 4 5 1 2 3 1 2 3 1 2
148.2 228.2 308.3 388.4 162.2 256.3 350.4 176.2 284.3 392.5 500.6 608.7 190.2 312.4 434.6 204.3 340.4 476.6 216.3 364.5
H
CH3
CH3
CH3
CH3
C2H5
C2H5
C2H5
m.p. (0C)
b.p. (°C/mbar)
df (g/cm3)
nf
78/16 141-146/11
1.102
1.5048 1.5324
91/28 114-116/0.13 165-168/0.04 73-76/7-8 120-123/1.3 163-167/1.3
1.073
1.4993
1.043
1.4966
1.030
1.5172
1.033 1.045 1.046 1.023 1.028 1.034
1.4970 1.5094 1.5173 1.4978 1.5089 1.5199
1.018
1.5221
74-75 99-101
-12 47.0/47.5 Oil 83-85
-9 to-8 13-17 86.8-87.6
68-70/3 143-145/1.3 205-210/1.3 76-77/3 162-163/2 212-215/2 94-95/2 200-205/2
Refs. 10,12,14-15,39 10,12 10,12,14 10,14 16,17 17 16,17 17,18 17,18 17,18 17 17 18 19 19 20 20 20 21 21
22.1.4. FURANOPHANES R' H H CH 3 CH 3 CH 3 C2H5 H
R"
n
CH 3 4 r-2,c-7,c-12,c-17C2H5 4 r-2,c-7,c-12,c-17CH 3 4 CH 3 5 6 C2H5 4 C2H5 4 4
22.1.5. TETRAHYDROFURANOPHANES MoL wt.
m.p. (0C)
376.4
140-142 191.0-192.0 83-88 152.0-153.0 243 Oil 182 174 249-250 268-269
432.5 432.5 540.7 648.8 488.5 544.7 592.8
Refs.
n
16,17,22 22 22 22 18,23,24 17 17,18,24 18,19,22,24 18,20,24 21,24
4
m.p. (0C)
MoI. wt.
448.7 204-209 r-(lS, 3S, 6R, 8S, HR, 13R, 16S, 18R)- 218 r-(lS, 3R, 6S, 8R, HS, 13R, 16S, 18R)- 221 5 560.8 Oil 6 673.0 75-80
Refs. 17,18,20,21,23 25 25 17 17
22.2. OLIGO(THIOPHENE) DERIVATIVES 22.2.1. OLIGO(2.5-THIENYLENES) n
MoI. wt.
m.p. (0C)
b.p. (°C/mbar)
n™
1 2 3 4 5 6 7 8
84.1 166.3 248.4 330.5 412.5 494.8 576.9 659.0
-38.4 33-34 96-97 215-216 257-258 304-305 327-328 364
84.2/1013 125/16
1.5289
22.3.
Refs. 1,27,28,34,41,42,44,49 1,3,26,28,30-33,42,44,47,49 1,3,27-29,41,42,44,46,49 1,3,28,29,42,48 3,27,28,42,44,46 3,29,48 42,46
OLIGO(PYRROLE) DERIVATIVES
22.3.1. OLIGO(PYRROLE) DERIVATIVES
n
MoI. wt.
m.p. (0C)
1
2
214.3
105-106
2
2
174.2
59
3
4 4
428.6 588.8
291 272.0-272.5
No.
Oligomers
R
22.3.2. OLIGO[2,5-(N-METHYL)PYRROLENES]
b.p. (°C/mbar)
Refs. 21,43
125-126/4
35
36,37 21
22.4. OLIGO(PYRIDINE) DERIVATIVES 22.4.1. OLIGO(2,6-PYRIDYLENES)
n
MoI. wt.
1 2 4 5 6 8 16
81.1 160.2 318.4 397.5 476.6 634.8 1267.6
0
m.p. ( C) 14-15 134 145 160 178-182 240-256
b.p. (°C/mbar) 114-115/99.6 77-78/0.5
Refs. 13,42 42 42 42 42 42
n
MoI. wt. m.p. (0C)
1 2 3 4 5 6
79.1 156.2 233.3 310.4 387.5 464.5
-42 70.1 89-90 219-220 265 350
b.p. (°C/mbar)
n$
115.5/1013 273-275/1013 370/1013
1.5095
Refs. 4,5 2,4-6 5 5 5
22.4.2. OLIGO(3,5-PYRIDYLENES)
0
n
MoI. wt.
m.p. ( C)
b.p. (°C/mbar)
nf
1 2 3
79.1 156.2 233.3
-42 68 249-251
115.5 291-292/981
1.5095
3
264.2
233
42,45
4
328.5
255-256
42,45
5
492.7
420
42,45
6
328.5
300-301
42,45
7
528.7
410
45
8
312.3
355-360
45
Refs.
4,9 9
22.4.3. OLIGO(2,6-QUINOLYLENES)
n
MoI. wt.
m.p. (0C)
1 2 3 4
129.2 256.3 383.5 510.6
-15.6 144 267-269 348-350
b.p. (°C/mbar)
nj?
238.1/1013
Refs.
1.6268 7,8 8 8
22.5. CYCLIC OLIGO(HETEROCYCLICS) No.
MoI. wt.
m.p. (0C)
Refs.
1
188.2
189-190
38
2
220.3
194.5-196
38
REFERENCES
1. J. W. Sease, L. Zechmeister, J. Am. Chem. Soc, 69, 270 (1947). 2. Th. Kauffmann, J. Konig, A. Woltermann, Chem. Ber., 109, 3864 (1976). 3. W. Steinkopff, R. Leitsmann, K. H. Hoffmann, Ann. Chem., 546, 180 (1941). 4. G. T. Morgan, F. H. Burstall, J. Chem. Soc, 20 (1932). 5. F. H. Burstall, J. Chem. Soc, 1662 (1938). 6. F. H. Case, W. H. Butte, J. Org. Chem., 26, 4415 (1961). 7. H. Weidel, Monatsh. Chem., 8, 120, 141 (1887). 8. S. G. Waley, J. Chem. Soc, 2008 (1948). 9. M. Busch, W. Weber, J. Prakt. Chem., 146, 1 (1936). 10. J. T. Barr, S. B. Wallon, J. Appl. Polym. ScL, 15,1079 (1971). 11. A. R Dunlop, F. N. Peters, Ind. Eng. Chem., 34, 814 (1942). 12. A. H. Fawcett, W. Dadamba, Makromol. Chem., 183, 2799 (1982). 13. J. Gj0s, S. Gronowitz, Acta Chem. Scand., 25, 2596 (1971). 14. K. Takano, Nippon Kagaku Zasski, 79, 955 (1958); Chem. Abstr., 54,453Oe (1960); ibid., 80, 313 (1959); Chem. Abstr., 55, 5453g (1961).
15. H. Gilman, G. F. Wright, J. Am. Chem. Soc, 55, 3302 (1933). 16. W. H. Brown, H. Sanatzky, Can. J. Chem., 34, 1147 (1956). 17. Y. Kobuke, K. Hanji, K. Horiguchi, M. Asada, Y. Nakayama, J. Furukawa, J. Am. Chem. Soc, 98, 7414 (1976). 18. R. G. Ackman, W. H. Brown, G. F. Wright, J. Org. Chem., 20, 1147(1955). 19. W. H. Brown, W. N. French, Can. J. Chem., 36, 537 (1958). 20. R. E. Beals, W. H. Brown, J. Org. Chem., 21, 447 (1956). 21. W. H. Brown, B. J. Hutchinson, M. H. MacKinnon, Can. J. Chem., 49, 4017 (1971). 22. A. G. S. Hogberg, M. Weber, Acta Chem. Scand. B, 37, 55 (1983). 23. M. Chastrette, F. Chastrette, J. Sabadie, Org. Synth., 57, 74 (1977). 24. M. De Sousa Healy, A. J. Rest, J. Chem. Soc, Chem. Commun., 149 (1981); J. Chem. Soc, Perkin Trans. I, 973 (1985). 25. M. Van Beylen, B. Roland, G. S. D. King, J. Aerts, J. Chem. Res. (S), 388 (1985); (M), 4201 (1985). 26. J. Kagan, S. K. Arora, Heterocycles, 20, 1941 (1983). 27. J. Kagan, S. K. Arora, Heterocycles, 20, 1937 (1983). 28. J. Kagan, S. K. Arora, Tetrahedron Lett., 24, 4043 (1983).
29. J. Kagan, S. K. Arora, J. Org. Chem., 48, 4317 (1983). 30. K. E. Schulte, J. Reisch, L. Homer, Chem. Ber., 95, 1943 (1962). 31. H. J. Kooreman, H. Wynberg, Rec. Trav. Chim. Pays-Bas, 86, 37 (1967). 32. T. Asano, S. Ito, N. Saito, K. Hatakeda, Heterocycles, 6, 317 (1977). 33. J.-P. Beny, S. N. Dhawan, J. Kagan, S. Sundless, J. Org. Chem., 47, 2201 (1982). 34. J.-P. Morizur, Bull. Soc. Chim. France, 1331 (1964); J.-P. Morizur, C. R., Ser. C, 254, 1093 (1962). 35. W. H. Brown, W. N. French, Can. J. Chem., 36, 371 (1958). 36. A. V. Baeyer, Chem. Ber., 19, 2184 (1886). 37. V. V. Chelintzev, B. V. Tronov, S. G. Karmanov, J. Russ. Phys. Chem., 48, 1210 (1916); Chem. Abstr. 11, 1418 (1917). 38. H. E. Winberg, F. S. Fawcett, W. E. Mochel, C. W. Theobald, J. Am. Chem. Soc, 82, 1428 (1960). 39. T. Reichstein, A. Griissner, H. Zschokke, HeIv. Chim. Acta, 15, 1066 (1932). 40. R. Grigg, J. A. Knight, M. V. Sargent, J. Chem. Soc. C, 976 (1966).
41. R. E. Atkinson, R. F. Curtis, G. T. Phillips, J. Chem. Soc. C, 2011 (1967). 42. Th. Kauffmann, Angew. Chem., 91, 1 (1979). Angew. Chem., Int. Ed. Engl., 18, 1 (1979). 43. D. Dolphin, R. Grigg, M. V. Sargent, D. H. Williams, J. A. Knight, Tetrahedron, 21, 3441 (1965). 44. D. D. Cunningham, L. Laguren-Davidson, H. B. Mark Jr., Ch. V. Pham, H. Zimmer, J. Chem. Soc, Chem. Commun., 1021 (1987). 45. Th. Kauffmann, B. Greving, R. Kriegesmann, A. Mitschker, A. Woltermann, Chem. Ber., I l l , 1330 (1978). 46. J. Nakayama, T. Konishi, S. Murabayashi, M. Hoshino, Heterocycles, 26, 1793 (1987). 47. J. Nakayama, Y. Nakamura, T. Tajiri, M. Hoshino, Heterocycles, 24, 637 (1986). 48. J. Nakayama, Y. Nakamura, S. Murabayashi, M. Hoshino, Heterocycles, 26, 939 (1987). 49. K. Tamao, S. Kodama, I. Nakajima, M. Kumada, A. Minato, K. Suzuki, Tetrahedron, 38, 3347 (1982).
TABLE 23. OLIGCKSACCHARIDES) 23.2. OLIGOMERIC HEXOSES 23.1. OLIGOMERIC PENTOSES 23.1.1. OLIGO(p-XYLOPYRANOSES)fl 23.2.1. MALTO-OLIGOfl
0
/I
MoI. wt.
m.p. ( C)
[a]|?inH 2 O
1 2 3 4 5 6 7
150.1 282.2 414.4 546.5 678.6 810.7 942.8
153 186-187 215-216 224-226 240-242 237-242 240-242
19.2 -25.6 -48.1 -61.9 -72.9 -78.5 -74.0
n
MoI. wt.
m.p. (0C)
1 2 3 4 5 6 7
180.2 342.3 504.4 666.6 828.7 990.9 1153.0
146 160-165
a
[a]£f in H 2 O 52.6 136.0 160.0 177.0 180.3 184.7 186.4
Refs. 4-6.
"Refs. 1-3.
23.1.2. OLIGO(p-XYLOPYRANOSE ACETATES)0
23.2.2. CYCLODEXTRINSa n
MoI. wt.
m.p. (0C)
[a] Jf
2 3 4 5 6
534.5 750.7 966.9 1183.1 1399.3
155.5-156 109-110 201-202 249-250 260-261
-74.5 -84.3 -93.7 -97.5 -102.0
fl
Refs. 1-3.
c in CHCl 3 0.9 0.6 0.8 1.1 1.5
n
MoI. wt.
6 7 8
972.8 1135.0 1297.1
a
Refs. 4-6.
[a] D (c = l, H 2 O) 149.0 158.8 170.0
23.2.6. GENTIO-OLIGOSES0
23.2.3. CELLO-OLIGOSES0
n
MoL wt.
m.p. (0C)
[
1 2 3 4
180.2 342.3 504.4 666.6
150 190-195
52.5 9.6 -10.5 -19.5
Specific rotation n
MoL wt.
m.p. ( 0 C)
[
( 0 C)
1 2 3 4 5 6 7
180.2 342.3 504.4 666.6 828.7 990.9 1153.0
150 225 d 238 d 253 d 267 d 278 d 286 d
52.5 34.6 21.6 16.5 11.0 10.0 7.3
20 20 26 23 30 30 30
a
c in H 2 O 4 8 4 3.4 4.1 1.2 0.1
a
Ref. 15.
23.2.7. GALACTO-OLIGOSESa
Refs. 7-14.
23.2.4. CELLO-OLIGOSE ACETATES a
n
MoL wt.
m.p. (0C)
[a] D in H 2 O
1 2 3 4
180.2 342.3 504.4 666.6
167 210-211 115-120
-52.5 173 58 53
a
Ref. 15.
23.2.8. MANNO-OLIGOSESa
Specific rotation
r „120-25 n
MoL wt.
1 2 3 4 5 6 7
390.4 678.6 966.9 1255.1 1543.4 1831.6 2119.8
fl
m.p. (0C) 113 229.5 223-224 230-234 240-241 252-255 263-266
(c = 5, in CHCl3) 101.6 41.0 22.6 13.4 4.2 -0.2 -4.4
n
MoL wt.
m.p. (0C)
[a] D
(0C)
c, H 2 O
1 2 3 4
180.2 342.3 504.4 666.6
132 193-194 137-137.5 232-234
-7.7 -23.3 -31
25
0.9 1.3 1.6
"Refs. 16,17. 23.3.
Refs. 7-14.
OLIGOMERIC AMINO SUGARS
23.3.1. N-ACETYL CHITO-OLIGOSESa
23.2.5. ISOMALTO-OLIGOSESa
Specific rotation
n
MoL wt.
1 2 3 4 5 6
180.2 342.3 504.4 666.6 828.7 990.9
fl
Ref. 15.
0
m.p. ( C) 146 225 d
n
MoL wt.
m.p. (0C)
1 2 3 4 5 6 7
221.2 424.4 627.6 830.8 1034.0 1237.2 1440.4
260-262 d 290-311 d 290-30Od 285-295 d
MD
C
in H 2 O
[
153 160 163
"Refs. 18,19.
17.2 2.2 -4.1 -9.1 -11.4 -12.6
0.5 0.9 1.0 1.0 0.8 0.3
REFERENCES 1. R. L. Whistler, C-C. Tu, J. Am. Chem. Soc, 74, 4334 (1952). 2. R. H. Marchessault, T. E. Timell, J. Polym. Sci. C, 2, 49 (1963). 3. C. T. Bishop, Can. J. Chem., 33, 1073 (1955). 4. W. J. Whelan, J. M. Bailey, P. J. P. Roberts, J. Chem. Soc, 1293 (1953). 5. J. M. Bailey, W. J. Whelan, S. Peart, J. Chem. Soc, 3692 (1950). 6. K. Freudenberg, F. Cramer, Chem. Ber., 83, 296 (1950). 7. E. E. Dickey, M. L. Wolfrom, J. Am. Chem. Soc, 71, 825 (1949). 8. M. L. Wolfrom, J. C. Dacons, J. Am. Chem. Soc, 74, 5331 (1952). 9. L. Zechmeister, G. Toth, Chem. Ber., 64, 854 (1931). 10. K. Hess, K. Dziengel, Chem. Ber., 68, 1594 (1935).
11. C. S. Hudson, J. M. Johnson, J. Am. Chem. Soc, 37, 1276 (1915). 12. R. Willstaetter, L. Zechmeister, Chem. Ber., 46, 2401 (1913); 62, 722 (1929). 13. K. Freudenberg, G. Blomquist, Chem. Ber., 68, 2070 (1935). 14. H. Staudinger, E. V. Leopold, Chem. Ber., 67, 479 (1934). 15. W. Walter, in: H. M. Rauen (Ed.), "Biochemisches Taschenbuch", part 1, 2nd ed., Springer, Berlin, 1954, p. 98. 16. R. L. Whistler, C. G. Smith, J. Am. Chem. Soc, 74, 3795 (1952). 17. R. L. Whistler, J. Z. Stein, J. Am. Chem. Soc, 73, 4187 (1951). 18. S. A. Barker, A. B. Foster, M. Stacey, J. M. Webber, J. Chem. Soc, 2218 (1958). 19. H. P. Lenk, M. Wenzel, E. Schuette, Hoppe-Seyler's Z. Physiol. Chem., 326, 116 (1961).
S E C T I O N
P H Y S I C A L S
O
M
E
I
M
P
O
C R
O T
N A
V
S N
T T
A
N
T
S
P
O
L
O Y
M
F E
R
S
P h y s i c a l
C o n s t a n t s
o f
R u b b e r y
P o l y m e r s
lsao Furuta, S h i n - l c h i K i m u r a , M a s a m i c h i I w a m a Yokkaichi Research Laboratories, Japan Synthetic Rubber Co. Ltd., Yokkaichi Mie, Japan
A. Introduction B. Tables Table 1. 1,4-c/s(96-98%)Poly(butadiene) Table 2. Poly(butadiene-coacrylonitrile) Table 3. Poly(butadiene-co-styrene) Table 4. Poly(chloroprene)(CR Neoprene) Table 5. Poly(isobutene)-coisoprene)Butyl Rubber (MR) Table 6. Polyisoprene, Natural Rubber Table 7. Ethylene-Propylene-DieneTerpolymer (EPDM) C. References A.
V-1 V-1 V-1 V-2 V-3 V-3 V-4 V-5 V-6 V-6
INTRODUCTION
Where a range is given, there are available several observations which differ. In most cases the differences are thought to be real, arising from differences in the rubber rather than from errors of observation. Where a single value
is given, it is either because no other observations are available or because there seems to be no significant disagreement among values within the errors of observation. Where values are not given, data have not been found. Where dashes are shown, either the physical measurement is impossible or the constant in question is not adequately defined under the given conditions. The values shown refer to specific vulcanizates cited in the corresponding references. Other vulcanizates may yield a broader range of values. The values are expressed in the International System of Units (SI), the modern metric system, described in National Bureau of Standards Special Publication 330, 1981 edition, and in American Society for Testing and Materials Metric Practice Guide E380-85. Values are given for constants at a temperature of 25°C (273.15 K) and a pressure of 1 normal atmosphere = 101.325 kPa.
B. TABLES TABLE 1. 1,4-c#s(96-98%)POLY(BUTADIENE) Property Density Coefficient of expansion Glass transition temperature Specific heat Thermal conductivity Thermal diffusivity Solubility parameter Polymer-solvent interaction parameter (25-30 0 C)
Units kg/m 3 K-1CxIO6) 0 C J/kg/K (x 103) W/m/K (x 10 ~3) m 2 /s (x 10~9) MPa 1 / 2
Unvulcanized 669 1.96
Refs.
Refs.
1.01
1
- 1 1 0 to - 95 1.960-1.970 200
3 1 5
2 4
17.0
6
0.51 0.53 0.45 0.44 0.36
7 7 8 7 7
Solvent n-Heptane n-Hexane Cyclohexane Benzene Toluene
Pure-gum vulcanizate
TABLE 1.
cont'd
Property
Units
Equilibrium melting temperature
K (0C)
Temperature of most rapid crystallization Heat of fusion of crystal
K (0C) J/kg (x 103)
Refractive index Molar polarizability Dielectric constant (50Hz) Dielectric loss factor (50Hz) Compressibility Young's modulus Shear modulus Storage modulus (1 Hz) Loss modulus Loss tangent
ND cm 3 (x 10~25)
TABLE 2.
Pa^(XlO"12) Pa (x 106) Pa (x 106) log Pa log Pa
Unvulcanized
Refs.
1.0 • 0 - 52 to - 57 47 169 1.526 71.4 2.3 0.8 500
10 11 3 11 10 12 12 3 3 2
Pure-gum vulcanizate
1.3 0.96 5.98 4.79 0.065
Refs.
9 9 9 9 9
POLY(BUTADIENE-CO-ACRYLONITRILE)
Property
Units
Density
kg/m3
Glass transition temperature
0
Specific heat Thermal conductivity Thermal diffusivity Solubility parameter
J/kg/K(xlO 3 ) W/m/K (x 10 ~3) m 2 s (x 10~9) MPa 1 / 2
Unvulcanized
Refs.
C
18.5-21.0 (18-39%)
Pure-gum vuicanizate
Refs.
0.95a (20%) 1.02 (45%) - 85 + A(20-40%) (A =AN%) 1.970(40%) 250 (18-35%)
3 3 3
1.519(20%) 1.521 (45%) 5.5 (27%) 4.8 (40%) 35 (27%) 42 (40%)
3 3 3 3 3 3
3 3
6
Polymer-solvent interaction parameter (25-300C) AN% Solvent n-Heptane rc-Hexane Dichloromethane Cyclohexane Benzene Toluene Refractive index Dielectric constant (10 6 Hz) Dielectric loss factor (10 6 Hz) a
Bound acrylonitrile content ( = AN%)).
N0
18 0.96 0.99 0.39 0.70 0.39 0.43
30 1.88 0.31 1.42 0.31 0.8
39 3.6 2.8 0.32 2.6 0.32 0.6
9 9 9 9 9 8
TABLE 3. POLY(BUTADIENE-co-STYRENE) (23.5-25% BOUND STYRENE CONTENT) Property Density Coefficient of expansion Glass transition temperature Specific heat Thermal conductivity Thermal diffusivity Solubility parameter Polymer-solvent interaction parameter (25-300C)
Units kg/m3 K- 1 CxIO 6 ) C J/kg/K(xlO 3 ) W/m/K (x 10 " 3 ) m2/s (x 10 ~9) MPa1/2
0
Unvulcanized
Refs.
933 (932.5-933.5) 660 - 64 to - 59 1.89
43 43 43 43 45
17.0
Pure-gum vulcanizate
Refs.
980 940-1000 660 - 52 1.83 190-250 90
17 17 17,18,44 21 24 46,47 48
6
Solvent n-Heptane n-Hexane Dichloromethane Cyclohexane Benzene Toluene Heat of combustion Refractive index
J/kg (x 106) ND
Molar polarizability Dielectric constant (1 kHz) Dielectric loss factor Electric conductivity Compressibility Bulk modulus (isothermal) Young's modulus
cm3 (x 10~25) Sm" 1 (x 10~15) Pa- 1 CxIO" 1 2 ) Pa(xlO 6 ) Pa (x 106)
Shear modulus
Pa(xlO 6 )
Shear compliance
Pa^(XlO"6)
Storage modulus
log Pa
Loss modulus
log Pa
Loss tangent Tensile strength Ultimate elongation
0.59 0.66 0.47 0.48 0.40 0.31 56.5 1.5345 (1.534-1.535) 2.5 0.0009 530 1890
5.82 (5.82-5.85) 4.94 (4.56-4.94) 0.13 (0.05-0.13)
9 9 9 9 9 13 43 43 43 33 33
2.66 0.0009
49 49
510 1960 1.6 1.0-2.0 0.53 0.3-0.7 7 3-10 5.88 5.64-6.20 4.92 4.73-5.04 0.11
50 49 21,35 35 21 35 21,35 21,35 64 64 64 64 64
1.4-3.0 400-600
19,42 19,42
40 40 40 40 40 40
MPa %
33 33
TABLE 4. POLY(CHLOROPRENE) (CR NEOPRENE) Property Density Coefficient of expansion Glass transition temperature Specific heat Thermal conductivity Thermal diffusivity Solubility parameter
Units kg/m3 K" 1 (x 106) 0 C J/kg/K(xl0 3 ) W/m/K (x 10~3) m2/s MPa1/2
Unvulcanized 1230 600 -45 2.2-2.2 192 10 ~9 18.5
Refs.
Pure-gum vulcanizate
43,51,58 46,58 60 46 58
1320 610-720 -45 2.1-2.2 192
Refs. 17 17,58,59 21,59,60,61 46 58
6
References page V- 6
TABLE 4. cont'd Property
Units
Unvulcanized
Refs.
Pure-gum vulcanizate
Refs.
Polymer-solvent interaction parameter (25-300C) Solvent n-Heptane n-Hexane Dicyclomethane Cyclohexane Benzene Toluene Equilibrium melting temperature Temperature of most rapid crystallization Heat of fusion of crystal Refractive index Dielectric constant Dielectric loss factor Electric conductivity Compressibility Bulk modulus (isothermal) Young's modulus Shear modulus Shear compliance Poisson's ratio Storage modulus Loss modulus Loss tangent Tensile strength Ultimate elongation
K (0C) K (0C) J/kg (x 103) ND
0.85 0.89 0.53 0.69 0.26 0.70 328-351 (55-78) 268 ( - 5) 95 1.558
Sm" 1 (x 10~15) Pa^(XlO"12) Pa (x 106) Pa(XlO 6 ) Pa (x 106) Pa^(XlO"6)
9 9 9 9 9 13 62,63 65 63 20
480 2080
49,50 50
Unvulcanized
Refs.
log Pa log Pa MPa %
261 (-12) 6.5-8.1 0.03/0.86 3-1400 440 2270 1.6 0.52 2.0 0.49974 5.81 5.04 0.17 25-38 800-1000
65,66 33 33 33 49,50 50 21,35 21 19,21,35 38 57,59 57,59 57,59 19,42 19,42
TABLE 5. POLY(ISOBUTENE-co-ISOPRENE) BUTYL RUBBER (NR) Property Density Coefficient of expansion Glass transition temperature Specific heat Thermal conductivity Thermal diffusivity Solubility parameter Polymer- solvent interaction parameter
Units kg/m" 3 K^(XlO6) C J/kg/K(xlO 3 ) W/m/K (x 10~3) m 2 /s (x 10 ~9) MPa 1/2
0
917 750 -71 1.95 16.0
51 53 53 23,24,29
Pure-gum vulcanizate 933 930-970 560 -63 1.85 130 70
Refs. 52 17 52,54 21 24 47 55
6
Solvent rc-Heptane /z-Hexane Dicyclomethane Cyclohexane Benzene Toluene Equilibrium melting temperature Temperature of most rapid crystallization Refractive index Dielectric constant (IkHz) Dielectric loss factor
K (0C) K (0C) ND
0.48 0.52 0.58 0.44 0.66 0.56 275 (1.5) 239 ( - 34) 1.5081 2.38 0.003
14 14 14 14 14 14 53 53 43 33 33
2.42 0.0054
33 33
TABLE 5.
cont'd
Property
Units
Compressibility Bulk modulus (isothermal) Young's modulus Shear modulus
Pa" 1 (x 1012) Pa(xlO6) Pa(xlO6) Pa(xlO6)
Shear compliance Strage modulus Loss modulus Loss tangent Tensile strength Ultimate elongation
Pa" 1 (x 10~6) log Pa log Pa
TABLE 6.
Unvulcanized
6.50 5.98 0.3
Refs.
56 56 56
MPa %
Pure-gum vulcanizate 508 1970 1.0 0.33 0.2-0.5 3.1 5.64 5.48 0.7 18-21 750-950
Refs. 54 54 21,35 21,35 19,21,35 21 57 57 57 19,42 19,42
POLYISOPRENE, NATURAL RUBBER
Property
Units
Density
kg/m3
Coefficient of expansion Glass transition temperature
0
Specific heat Thermal conductivity Thermal diffusivity Solubility parameter Polymer-Solvent interaction parameter (25-30 0 C)
K" 1 (x 106) C
J/kg/K(xl0 3 ) W/m/K (x 10 ~3) m 2 /s (x 10) MPa1/2
Unvulcanized 913 906-916 670 -72 (-74 to-69) 1.905 134 1.7
Refs.
Pure-gum vulcanizate
16 970 16 (920-1000) 16 660 2 0 - 6 3 20 (-72 to-61) 22,23 1.828 16 153 70 6
Refs. 17,18 19 16 21 21 24 25,26 27
Solvent ^-Heptane /i-Hexane Dichloromethane Cyclohexane Benzene Toluene Equilibrium melting temperature Temperature of most rapid crystallization Heat of fusion of crystal Heat of combustion Refractive index Molar polarizability Dielectric constant (1 kHz) Dielectric loss factor (1 kHz) Electric conductivity Compressibility Bulk modulus (isothermal) Young's modulus
K( 0 C) K (0C) J/kg (x 103) J/kg (x 106) NDK-1 cm 3 (x 10~25)
Shear modulus
Pa (x 106)
Shear compliance
Pa^(XlO"6)
Poisson's ratio Storage modulus
log Pa
Loss modulus
log Pa
Sm" 1 (x IO"15) Pa^(XlO"12) Pa(xlO6) Pa (x 106)
0.43 0.47 0.40 0.53 0.44 0.39
9 9 9 9 9 9
308.6(35.5) 248 ( - 25) 67.3 45.2 1.5191(25°C)
28 30 31 16 32
2.37-2.45 0.001-0.003 2.57 515 1940
16,33 33 16,33 34 34
5.61 5.53-5.75 4.46 (4.43_4.65)
40 40
313(40)
29
44.4 1.5264 2.68 0.002-0.04 2-100 514 1950 1.3 (1.0-2.0) 0.43 0.3-0.7 2.3 (1.5-3.5) 0.49989 5.61 5.49-5.78 3.80 3.72-4.48
16 16 33 33 16,33 34 34 35,36 19,35 21,36 21,37 21,36 21,37 34,38,39 41 41
References page V-6
TABLE 6. cont'd Property
Units
Loss tangent Tensile strength Ultimate elongation
Unvulcanized 0.09 0.07-0.13
Refs. 40
MPa %
Pure-gum vulcanizate 0.016 0.01-0.05 17-25 750-850
Refs. 41 19,42 19,42
TABLE 7. ETHYLENE-PROPYLENE-DIENE-TERPOLYMER (EPDM) Property Density Glass transition temperature Specific heat Thermal conductivity Thermal diffusivity Solubility parameter Polymer-Solvent interaction parameter (25-30 0 C)
Units kg/m3 C J/kg/K (x 103) W/m/K (x 10 ~3) m 2 /s (x 10~9) MPa 1/2
Unvulcanized
Refs.
Pure-gum vulcanizate 0.85 — 60 to — 69 2340
0
16.0-16.5
Refs. 3 1 3
6
Solvent n-Heptane w-Hexane Dichloromethane Cyclohexane Benzene Toluene Refractive index Young's modulus Shear modulus Storage modulus (IHz) Loss modulus (1 Hz) Loss tangent (1 Hz)
ND Pa(xlO6) Pa(xlO6) MPa MPa
0.44 0.49 0.32 0.35 0.58 0.49
15 16 16 15 15 15 1.48 2.0 1.59 1.59 0.12 0.077
3 13 13 13 13 13
C. REFERENCES 1. J. Brandrup, E. H. Immergut, (eds.) "Polymer Handbook", 3rd Edition, 1989. 2. J. W. Barlow, Polym. Eng. ScL, 18 (3), 238 (1978). 3. W. J. Roff, J. R. Scott, Fibers, Films, Plastics and Rubbers (A Handbook of Common Polymer). 4. J. Grebowicz, W. Aycock, B. Wunderlich, Polymer, 27 (4), 575 (1986). 5. "Hikinzokuzairyou Data Book", Nihon Kensa Kikaku Kyoukai. 6. "Kobunshi Data Handbook, Ouyouhen", Kobunnsi Gakkai ed. Baihukan. 7. A. F. M. Barton, CRC Handbook of Polymer-Liquid Interaction Parameter and Solubility Parameters, CRC Press, Inc, Boca Raton, FL, 1983. 8. A. G. Shvart, Kolloid Zh., 18, 755 (1953). 9. C. Shibuya, K. Ogino, T. Nakagawa, Chemical composition dependence of a polymer-solvent interaction parameter. 10. G. Natta, G. Moraglio, Makromol. Chem., 66, 218 (1963).
11. W. S. Bahary, D. I. Sapper, J. H. Lane, Rubber Chem. Technol., 40, 1529 (1967). 12. J. Furukawa, S. Yamasita, T. Kotani, M. Kawasima, J. Appl. Polym. ScL, 13, 2527 (1969). 13. "Gomu Kougyou Binran", Nihon Gomu Kyoukai, (1993). 14. G. M. Bristow, W. F. Watson, Trans. Faraday Soc, 59, 1731 (1958). 15. A. G. Shvart, E. K. Chefranova, L. A. Itokovskaya, Solubility parameters of resins based on dimethylvinylethylp- hydroxyphenylmethane, Kolloidn Zh., 32, 603 (1970); Colloid J. USSR, 32, 506 (1970). 16. L. A. Wood, "Values of the Physical Constants of Rubber", Proceedings of the Rubber Technology Conf. (Institution of the Rubber Industry, London), 1938, p. 933; Rubber Chem. Technol., 12, 130 (1939). 17. N. Bekkedahl, F. L. Roth, National Bureau of Standards, unpublished observations of density and expansivity, 1948. 18. A. J. Wildschut, "Technological and Physical Investigations on Natural and Synthetic Rubbers", Elsevier, New York, 1946.
19. B. B. S. T. Boonstra,"Properties of Elastomers", Chapter 4 of Vol. Ill in R. Houwink (Ed.), "Elastomers. Their Chemistry, Physics, and Technology", Elsevier, New York, 1948. 20. L. A. Wood, "Synthetic Rubbers: A Review of Their Compositions, Properties, and Uses," Natl. Bur. Std. Circ, C427 (1940); Rubber Chem. Tech., 13, 861 (1940); India Rubber World, 102, No. 433 (1940). 21. L. A. Wood, F. L. Roth, Proc. 4th Rubber Technology Conference, London, 1962, p. 328, Institution of the Rubber Industry, London, 1963; Rubber Chem. Technol., 36, 611 (1963). 22. S. S. Chang, A. B. Bestul, J. Res. Nat. Bur. Std., 75A, 113 (1971). 23. L. A. Wood, N. Bekkedahl, J. Polym. ScL, Part B, Polym. Lett, 5, 169 (1967). 24. W. H. Hamill, B. Mrowca, R. L. Anthony, Ind. Eng. Chem., 38, 106 (1946); Rubber Chem. Technol., 19, 622 (1946). 25. L. C. Carwile, H. J. Hoge, "Thermal Conductivity of Soft Vulcanized Natural Rubber, Selected Values", in: "Advances in Thermophysical Properties at Extreme Temperatures and Pressures", American Society of Mechanical Engineers, New York, 1965; Rubber Chem. Technol., 39, 126 (1966). 26. M. N. Pilsworth, Jr., H. J. Hoge, H. E. Robinson; J. Mater., 7 (4), 550 (1972). 27. D. Hands, Rubber Chem. Technol. (Rubber Rev.), 50, 480 (1977). 28. E. N. Dalai, K. D. Taylor, P. J. Phillips, Polymer, 24, 1623 (1983). 29. G. T. Furukawa, M. L. Reilly, J. Res. Nat. Bur. Std. 56, 285 (1956); RP 2676. 30. L. A. Wood, N. Bekkedahl, J. Res. Natl. Bur. Std., 36, 489 (1946); RP 1718; J. Appl. Phys., 17, 362 (1946); Rubber Chem. Technol., 19, 1145 (1946). 31. H. G. Kim, L. Mandelkern, J. Polym. Sci. A-2, 10, 1125 (1972). 32. L. A. Wood, L. W. Tilton, Proc. 2nd Rubber Technology Conference, London; 1948, p. 142, Institution of the Rubber Industry, London; J. Res. Natl. Bur. Std., 43, 57 (1949), RP 2004. 33. A. T. McPherson, Rubber Chem. Technol. (Rubber Rev.), 36, 1230 (1963). 34. L. A. Wood, G. M. Martin, J. Res. Natl. Bur. Std., 68A, 259 (1964); Rubber Chem. Technol., 37, 850 (1964). 35. G. M. Martin, F. L. Roth, R. D. Stieler, Trans. Inst, Rubber Ind., 32, 189 (1956); Rubber Chem. Technol., 30, 876 (1957). 36. F. L. Roth, G. W. Bullman, L. A. Wood, J. Res. Natl. Bur. Std., 29A, 347 (1965); Rubber Chem. Technol., 39, 397 (1966). 37. W. Philipoff, J. Appl. Phys., 24, 685 (1953). 38. B. P. Holownia, J. Inst. Rubber Ind. 8, 157 (1974); Rubber Chem. Technol., 48, 246 (1975). 39. G. K. Rightmire, Am. Soc. Mech. End. Trans. Series F, J. Lubrication Technol., 381. July 1970.
40. L. J. Zapas, S. L. Shufler, T. W deWitt, J. Polym. Sci., 18, 245 (1955); Rubber Chem. Technol., 29, 725 (1956). 41. J. D. Ferry, R. G. Mancke, E. Maekawa, Y. Oyanagi, R. A. Dickie; J. Phy. Chem., 68, 3414 (1964). 42. J. M. Ball, G. C. Maassen, Symp. Applications of Synthetic Rubbers, American Society for Testing Materials, March 2, 1944, p. 27. 43. L. A. Wood, "Physical Chemistry of Synthetic Rubbers", Chapter 10 in: G. S. Whitby (Ed.), "Synthetic Rubbers", J Wiley, New York 1954. 44. I. B. Prettyman, "Physical Properties of Natural and Synthetic Rubber Stocks", Handbook of Chemistry and Physics, Chemical Rubber Pub. Co., Cleveland, in: 1962, p. 1564. 45. R. D. Rands, Jr., W. J. Ferguson, G. Allen, Polymer, 10, 495 (1964). 46. A. R. Payne, J. R. Scott, "Engineering Design with Rubber". Interscience, New York, 1960. 47. H. Shilling, Kautschuk Gummi, 16, 84 (1963). 48. J. Rehner, Jr., J. Polym. Sci., 2, 263 (1947); Rubber Chem. Technol., 21, 82 (1948). 49. W. H. S. Naunton et al., "Rubber in Engineering," Ministry of Supply, London, 1945, or Chemical Publishing Co., Brooklyn, NY, p. 30. 50. W. S. Cramer, I. Silver, NSVORD Report 1778, Feb. 1951, US Naval Ordnance Lab., White Oak, MD. 51. L. A. Wood, N. Bekkedahl, F. L. Roth, J. Res. Natl. Bur. Std., 29, 391 (1942) RP 1507; Ind. Eng. Chem., 34, 1291 (1942); Rubber Chem. Technol., 16, 244 (1943). 52. N. Bekkdahl, J. Res. Natl. Bur. Std., 43, 145 (1949). 53. R. M. KeIl, B. Bennett, P. B. Stickney; Rubber Chem. Technol., 31, 499 (1958). 54. C. Price, J. Padget, M. C. Kirkham, G. Allen; Polymer, 10, 495 (1969). 55. D. R. MacRae, R. L. Zapp, Rubber Age, 82, 831 (1958). 56. L. Schmieder, K. WoIk, Kolloid-Z., 134, 149 (1953). 57. J. H. Dillon, I. B. Prettyman, G. L. Hall, J. Appl. Phys., 15, 309 (1944); Rubber Chem. Technol., 17, 597 (1944). 58. N. L. Catton,"The Neoprenes", Rubber Chemicals Division, E. I. DuPont de Numours and Company, Wilmington, DE, 1953. 59. T. P. Yin, R. Pariser, J. Appl. Polym. Sci., 7, 667 (1963). 60. R. M. KeIl, B. Bennett, P B. Stickney, J. Appl. Polym. Sci., 2, 8 (1959). 61. A. N. Gent, J. Polym. ScL, A3, 3787 (1965). 62. W. R. Krigbaum, J. V. Dawkins, G. H. Via, Y. I. Balta; J. Polym. Sci. A-2, 4, 475 (1966). 63. J. T. Maynard, W. E. Mochel, J. Polym. Sci., 13, 235 (1954). 64. W. P Fletcher, A. N. Gent, Brit. J. Appl. Phys., 8, 194 (1957). 65. R. M. Murray, J. D. Detenber, Rubber Chem. Technol., 34, 668 (1961). 66. P. R. Johnson, Rubber Chem. Technol., (Rubber Rev.), 49, 650 (1976).
S E C T I O N
S
O
L
I
D
S T A T E
V l
P R O P E R T I E S
C r y s t a l l o g r a p h i c f o r
D a t a
V a r i o u s
a n d
M e l t i n g
P o i n t s
P o l y m e r s
R o b e r t L. M i l l e r Michigan Molecular Institute, 1910 West St. Andrew Rd., Midland, Ml 48640, USA
A. Introduction 1. Nomenclature 2. Examples of Polymer Names 2.1. Polymer Names Based on Source 2.2. Polymer Names Based on Structure References for Introduction B. Crystallographic Data for Various Polymers Table 1. Poly(olefins) Table 2. Poly(vinyls) and Poly(vinylidenes) Table 3. Poly(aromatics) and Poly(imides) Table 4. Poly(dienes) and Poly(diynes) Table 5. Poly(peptides) Table 6. Poly(amides) Table 7. Poly(esters) Table 8. Poly(urethanes) and Poly(ureas) Table 9. Poly(ethers) Table 10. Poly(oxides) Table 11. Poly(sulfides) and Poly(sulfones) Table 12. Poly(saccharides) Table 13. Other Polymers C. Melting Points of Polymers D. Appendix: Formula Index to the Tables E. References
A.
Vl-I Vl-I VI-2 VI-2 VI-3 VI-5 VI-5 VI-6 Vl-13 Vl-15 VI-22 VI-26 VI-33 VI-40 VI-49 VI-51 VI-52 VI-57 VI-59 VI-64 VI-71 Vl-113 VI-159
INTRODUCTION
These tables contain data for approximately 2700 polymers. In general, the format and organization of the tables follows that used in the 2nd edition of the "Polymer Handbook" (Section B: Crystallographic Data; Section C: Melting Points; Section D: Formula Index and Section E: References). The Formula Index is included as an aid to the searcher: it permits one to determine the polymer name used in these tables from the structural line formula for the polymer of interest. To avoid the duplication of data for polymers appearing in both the Crystallographic Data and Melting Point tables, the entry in the Melting Point table has been flagged with an asterisk (*).
1. Nomenclature
Contrary to the rest of the Polymer Handbook, the ACSIUPAC nomenclature proposals (1,2) for naming regular single-strand organic polymers have not been adopted for these tables. Basically, the nomenclature used in this portion of the Polymer Handbook is that of the 1st and 2nd editions and of the 1967 recommendations of the IUPAC Nomenclature Committee (3). The majority of polymers were named as the bivalent radical(s) comprising the constitutional repeating unit (CRU), with priority in naming given to (a) incorporation of important structural features (amide, ester, oxide, etc.) and (b) emphasis on symmetry of the CRU (when present). As in the past, many common polymers (poly(styrene), poly(vinyl chloride), etc.) were named according to source names. In the majority of cases, the polymer was named according to its structure, particularly when the CRU was composed of two or more subunits following each other in a regular fashion. An example is poly(ethylene terephthalate). With more complicated structures, the CRU was divided into its possible subunits, each of which was treated as a bivalent radical and so named. One of the subunits was treated as the parent compound, for example, the "terephthalic acid" of the above example. For poly(amides) and poly(esters), the acid was chosen as the parent compound; for poly(urethanes) it was the isocyanate. Whenever the CRU (or a portion thereof) exhibited a center of symmetry, naming began with the central subunit using Chemical Abstracts/IUPAC names for the constituent bivalent radicals (see under examples). Conjunctive names were used as needed in constructing names. For symmetrical units, this process of naming could be continued indefinitely. Unsymmetrical bivalent units were named with replacement nomenclature, or from end to end, depending upon the complexity of the bivalent radical and the ease of naming by the alternative choices. Replacement nomenclature was used, for example, to name poly(hexamethylene 6-oxaheptadecanediamide). The polymer from the symmetrical oxyacid would be named poly(hexamethylene oxydicaprylamide).
More complicated structures without symmetry were named end to end. This method was particularly appropriate for the poly(oxides) of the form -(R-O-R'-O^ (and for the analogous sulfides, sulfones, ureas, and anhydrides) and for the poly(co-amino acids) and for the poly (G)-hydroxy acids). The constitutional hydrocarbon subunits were ordered alphabetically in naming the polymer as, for example, in poly(methyleneoxy pentamethylene oxide). For silicon-containing polymers, bivalent radical names replaced the source-based silane/siloxane names. For
example, the source-named polymer, poly[(tetramethylsilphenylene) siloxane], appears in these tables as poly(/?phenylene tetramethyldisiloxanylene). For the regular polymers of multipeptides, a cyclic permutation of the individual peptide residues in the constitutional base unit was performed to permit alphabetical ordering without loss of directional or sequential sense. Thus, poly(alanylglycyl-proline) is the name given to polymers prepared form (ala-gly-pro), (gly-pro-ala), and (pro-ala-gly), but not from (ala-pro-gly) or from either of its cyclic permutations.
2. Examples of Polymer Names 2.1. Polymer Names Based on Source Olefin, Vinyl, and Acyclic Polymers [-CH 2 -CH 2 -J n
Poly(ethylene)
[-CH-CH2-Jn
PoIy(I-butene)
I
CH 2 -CH 3 [-CH-CH 2 -] n
Poly(acrylonitrile)
I
CN [-CH-CH 2 -J n
Poly(vinyl chloride)
I
Cl
[-CH-CH2-Jn
Poly(methyl acrylate)
I
COOCH3 Poly(amides)l [-NH-CH 2 -COO-J n
Poly(glycine)
[-NH-(CH 2 ) 2 -COO-] n
Poly(3-aminopropionic acid) (poly (|3-alanine))
[-NH-(CH 2 ) 3 -COO-] n
Poly(4-aminobuyric acid)
[-NH-(CH 2 ) 4 -COO-] n
Poly(5-aminovaleric acid)
[-NH-(CH 2 ) 5 -COO-] n
Poly(6-aminocaproic acid)
[-NH-(CH 2 ) 6 -COO-] n
Poly(7-aminoenanthic acid)
[-NH-(CH 2 ) 7 -COO-] n
Poly(8-aminocaprylic acid)
[-NH-(CH 2 ) 8 -COO-L
Poly(9-aminopelargonic acid)
[-NH-(CH 2 ) 9 -COO-] n
Poly(10-aminocapric acid)
[-NH-(CH 2 ) lo-COO-] „
PoIy(11-aminoundecanoic acid)
[-NH-(CH2)n-C00-]n
PoIy(12-aminolauric acid)
Poly(oxides) [-CH 2 -O-J n
Poly(oxymethylene)
[-CHO-Jn
Poly(acetaldehyde)
I
CH3 1
Poly(esters) are treated similarly.
Poly(ethylene oxide) Poly(propylene oxide)
Poly(trimethylene oxide)
2.2.
Polymer Names Based on Structure
(a) Linking Radicals Ethylene Trimethylene Oxydiethylene Ethylenedioxy-diethylene Sulfonyldiethylene
methylphosphinidene-ditrimethylene /?-Phenylenediethylene 4,4/-Biphenylenediethylene 4,4 '-Methylenediphenylene 4,4 '-Ethylidenediphenylene
4,4 '-Isopropylidenediphenylene
4,4 '-Butylidenediphenylene
4,4'-(2,2-Butylidene)diphenylene 4,4 '-Oxydiphenylene
4,4 '-Sulfonyldiphenylene
(b) Parent Compounds Oxalate (oxamide) Malonate (malonamide) Succinate (succinamide) Glutarate (glutaramide)
References page VI-159
Adipate (adipamide) Pimelate (pimelamide) Suberate (suberamide) Azelaate (azelaamide) Sebacate (sebacamide) Nonanedioate (nonanediamide) Oxydipropionate p-Phenylene diacetate /7-Phenylenedipropionate 4,4'-DIbCnZOaIe 4,4 '-Methylenedibenzoate 4,4 '-Oxydibenzoate
4,4' -Sulfonyldibenzoate
4,4' -Oxy dipheny lenediacetate 4,4 /-(Ethylenedioxy)dibenzoate /?-(Phenylenedioxy)diacetate (p-Carboxyphenoxy)acetate 1,4-Piperazinediacetate (c) Polymer Names
Poly(esters)2 Poly(ethylene terephthalate) Poly(ethylene 4,4'-dibenzoate) Poly(ethylenep-phenylenediacetate)
Poly(ethylene 4,4 '-isopropylidenedibenzoate)
Poly(ethylene 4,4 '-sulfonyldibenzoate)
Poly(urethanes) Poly(trimethylene ethylene-urethane) 2
Poly(amides) are treated similarly.
Poly(oxides), Poly(sulfides), Poly(amines) Poly(ethylene trimethylene oxide) Poly(ethylene trimethylene sulfide) Poly(ethylene trimethylene amine)
REFERENCES FOR INTRODUCTION 1. ACS Structure-based Nomenclature for Linear Polymers, Macromolecules, 1, 193 (1968). 2. IUPAC Appendices on Tentative Nomenclature, Symbols, Units, and Standards - Number 29, Nomenclature of Regular Single-strand Organic Polymers, November 1972 - Macromolecules, 6, 149 (1973). 3. 1967 IUPAC Report on Nomenclature, J. Polym. Sci. B, 6, 257 (1968). B. CRYSTALLOGRAPHIC DATA FOR VARIOUS POLYMERS
The following table presents crystallographic data for about 750 polymers (and for their many polymorphs) grouped, according to the generic structure of the constitutional base unit, into poly(olefins), poly(vinyls) and poly(vinylidenes), poly(aromatics) and poly(imides), poly(dienes) and poly(diynes), poly(peptides), poly(amides), poly(esters), poly(urethanes) and poly(ureas), poly(ethers), poly(oxides), poly(sulfides) and poly(sulfones), poly(saccharides), and other polymers. Where a polymer might be included in more than one group the following group definitions were used: 1. Poly(olefins): those olefin polymers not containing aromatic rings; all substituted derivatives of these, excluding the vinyl and vinylidene polymers. For example, poly(ethylene), poly(tetrafluoroethylene), and poly(cyclopentene), but not poly(styrene) or poly(vinyl chloride). 2. Poly(vinyls) and Poly(vinylidenes): those vinyl and vinylidene polymers containing atoms other than carbon and hydrogen, excepting the poly(ethers). Thus, poly(vinyl chloride) but not poly(methylvinyl ether). 3. Poly(aromatics) and Poly(imides): those hydrocarbon polymers containing aromatic rings, including heterocyclic ones. Thus, poly(styrene), poly(p-xylylene), and poly(p-phenylene pyromellitimide). 4. Poly(peptides): those polymers whose basic structure, ignoring substituents, is poly(2-aminoacetic acid), that is, poly(glycine). This group contains mainly the synthetic poly(oc-amino acids). 5. Poly(amides): all amide polymers except the poly(ocamino acids), which are separately grouped under poly(peptides). 6. The remaining categories contain polymers according to functional groups as, for example, the poly(esters). Poly(ethers) and poly(oxides) are differentiated accord-
ing to whether the ether linkage is in the side-group or in the chain backbone, respectively. For example, poly(l-butoxy-2-chloroethylene) is a poly (ether) and poly(oxymethylene) is a poly(oxide). 7. Those polymers not otherwise categorized, such as the poly(phosphazenes) and the poly(siloxanes), are grouped in the "other" category. Within each group, polymers are listed alphabetically according to the basic structure, ignoring substituents (excepting the polypeptides, all of which have the same base structure). Substituted polymers are listed alphabetically according to the substituent under the entry for the unsubstituted polymer. Thus, poly(tetrafluoroethylene) and poly(4-methyl-l-pentene) appear, respectively, under polyethylene) and poly(l-pentene). Included as part of the polymer name column is the molecular weight of the chemical repeat unit of the chain, that is, of the constitutional base unit. This is given in parentheses just below the polymer name. The values reported are in grams per mole. Unless otherwise indicated, the reference cited in the last column applies to all of the data in that line of the tables. Where an entry in a line has been taken from a source different from that listed in the reference column, a solidus (/) separates the value of the entry from the reference citation. For example, one value of the melting point of poly(l-butene) is given as "126/12" which is to be read as "126°C according to Ref. 12". The crystal system, where known, is given in column 2 of the table, using the abbreviations given later. The next column contains the space group symbol (the Schoenflies notation is used because of the limitations of common printers at mainframe installations) with the subscript portion of the symbol preceding the superscript portion. Thus, according to Ref. 14, the poly(ethylene) unit cell is orthorhombic (Ortho) with space group D ^ (D2h-16). For a fuller discussion of space group symbols, see "International Tables for X-Ray Crystallography", Vol. I, Kynoch Press, Birmingham, England, 1952. The dimensions of the unit cell (a, b, c) are given next, in Angstroms (1 A = 0.1nm). c is the fiber axis. Unless otherwise indicated, the unit cell angles are all 90°. Where only one angle differs from 90°, its value is given. When all three angles differ from 90°, their values are listed in the order a, /3, 7. The next column contains the number of constitutional base units in the unit cell described. Columns 9 and 10 contain the densities of the completely crystalline and of the completely amorphous polymer, respectively. The values given, normally approReferences page VI-159
priate to room temperature, are in grams per cubic centimeter (lg/cm 3 = 103kg/m3). For uniformity crystallographic densities (column 9) have been recalculated on the basis of the 1969 IUPAC atomic weight values. Melting points in degrees Celsius and heats of fusion in kilojoules per mole are listed in the next two columns. The heats of fusion correspond to the amount of substance represented by the molecular weight associated with each polymer name. Column 13 of the tables indicate briefly the conformation of the polymer chain in the crystal (in a helical notation) either as reported in the reference cited or as inferred from the value of the fiber axis. The designation n *p/q specifies the number (n) of skeletal atoms in the asymmetric unit of the chain and the number of such asymmetric units (p) per q turns of the helix in the crystallographic repeat. Thus, poly(ethylene), as listed, has two carbon atoms in the backbone with one such unit per turn in the repeat - it is designated as a 2*1/1 helix. Alternatively, poly(ethylene) considered a poly(methylene) would be designated as a 1*2/1 helix - an entirely equivalent description of the conformation. Note that n may differ from the number of chain atoms in the constitutional base unit. On the one hand, isotactic poly(propene) has two skeletal atoms in the asymmetric unit and three units per turn (2*3/1). On the other hand, syndiotactic poly(propene) with the same constitutional base unit as isotactic
poly(propene) has four skeletal atoms in the asymmetric unit and two units per turn (4 * 2/1). In this case, n signifies the number of skeletal atoms in the stereobase unit. A fuller discussion of this helical notation is given in Hughes and Lauer, J. Chem. Phys., 30, 1165 (1959) and in Nagai and Kobayashi, J. Chem. Phys., 36, 1268 (1961). This list of polymers and data is not considered to be exhaustive. The compiler expands it as new information is unearthed and he is quite receptive to notification of omissions and/or corrections and to submission of unpublished data. AU of the data in this table cannot be considered to have the same validity - the number of polymers for which detailed, accurate, and reliable crystal structure analyses have been conducted is still quite limited. The reader may find it desirable to refer to the original literature cited so as to gain a fuller appreciation of the reasons for apparent discrepancies within the tables. The following abbrevaitions have been used in the tables. Tri Mono Ortho Tet Rho Hex P Phex
Triclinic Monoclinic Orthorhombic Tetragonal Rhombohedral (trigonal) Hexagonal Pseudo Pseudohexagonal
TABLE 1. POLY(OLEFINS) (-HCH-CHR-) Density (g/cm3)
Unit cell parameters Polymer Poly(acetylene) transI. (26.04)
II. c/s-transoid
Cryst syst.
Phex Mono Ortho Ortho Ortho Mono Port Ortho Ortho Ortho Ortho
Space group
D2h-16
C2h-5 C2h-5
Ortho Mono
D2h-16
Ortho Ortho Ortho Ortho Ortho
D2h-16
Orhto
D2h-16
D2h-16
a
b
c
4.2 4.26 7.32 7.37 5.62 4.24 7.41 3.99 7.20 7.31 7.26 7.46 7.38 7.330 3.73
4.2 7.33 4.24 4.065 4.92 7.32 4.08 7.29 4.15 4.06 4.24 4.08 4.09 4.090 3.73
2.43 2.46 2.46 2.45 2.592 2.46 2.48 2.51 2.44 2.45 2.47 2.46 2.457 2.457 2.44
7.61 7.74 7.68 7.45 7.62 7.61 7.66 7.62
4.39 4.32 4.46 4.30 4.46 4.39 4.42 4.44
5.12
5.12
Angles
Heat of fusion kj/mola
Chain conform. (n*p/q) Refs.
z
Crystal.
1 2 2 2 2 2 2 2 2 2 2 2 2 2 1
1.16 1.126 1.33 1.178 1.207 1.133 1.153 1.184 1.186 1.189 1.137 1.155 1.166 1.174 1.286
2*1/1 2*1/1 2*1/1 2*1/1 2*1/1 2*1/1 2*1/1 2*1/1 2*1/1 2*1/1 2*1/1 2*1/1 2*1/1 2*1/1 2*1/1
69 982 981 979 980 1213 1228 1229 1281 1282 1283 1323 1324 1369 980
4.47* 4.47 4.38 4.40* 4.38 4.36* 4.384 4.384
4 4 4 4 4 4 4 4
1.158 1.157 1.153 1.227 1.162 1.187 1.165 1.166
2*2/1 2*2/1 2*2/1 2*2/1 2*2/1 2*2/1 2*2/1 2*2/1
945 976 978 1229 1282 1323 1324 1369
4.84
3
1.180
2*3/1
977
/3 = 91.4
(3 = 91.5
7 = 98
Amorph."
Melting point (0C)*
czs-cisoid Hex
TABLE 1. cont'd Density (g/cm3)
Unit cell parameters Polymer -, difluorotrans(62.02) cis-, complex with: alkali metals Cs I. K I. II. Na I. Rb I. II. SbF6 and Poly(allene) 1.(40.06) II.
Cryst syst.
Space group
c
Ortho
7.58
4.29
Ortho
8.03
4.47
Tet
9.09
9.09
1230
Tet Ortho
8.46 5.94
8.46 16.37
1230 1231
Tet
8.5
8.5
1230
Tet Ortho
8.75 6.16
8.75 16.68
1230 1231
Mono Hex
8.66 9.8
7.36 9.8
2.4 5.4
8.20 6.37
7.81 5.12
3.88 3.88*
D2h-6 C2-2 or C2h-2
z
Crystal.
2.48
2
2.554
2*1/1
1385
4.64
4
2.473
2*2/1
1385
7 = 101
7 = 96.6
1261 1261 4 2
1.071 1.058
122/536
3.88
C4-2 or D4-3 Poly(allylbenzene), see Poly(propene) 3-phenylPoIy(I-butene) isotactic I. Rho D3d-6 (56.11) Hex Rho
II.
Chain conform. (n*p/q) Refs.
b
III. -, tetrafluoro(112.03)
Amorph.a
Heat of fusion kj/mola
a
Ortho Mono
Angles
Melting point (°C)a
Tet
Tet Tet Tet Tet Tet
S4-1 S4-1
D2d-7
6.88
6.88
17.7 17.3 17.70
17.7 17.3 17.70
15.4
8
6.50 6.7 6.51
18 18 18
2.042
0.951 0.96 0.950 0.950 0.95 0.95/12
126
0.87 0.868 0.860
0.819 0.886 0.902 0.888
126/12 132/250 133 136/277 139 135/320
15.42 14.89 14.85 14.91 14.5
15.42 14.89 18.85 14.91 14.5
21.05 20.87 20.6 20.76 21.1
44 44 44 44 44
130/380 124/277 126/313 120 122/320
8.96 8.88 8.92
(7.6) 7.56 7.45 7.6
8 8 8
(0.876) 0.897 0.906
106/277 110/984
8 8 22
0.937 0.946 0.964?
45
4 8 16 16 64 16
0.933 0.933 0.890 0.918 0.925 0.948
300/48 306/632 310/90 300/282
13.9/82 6.07/277 7.57 8.0/1285 7.01 6.92/320 138/380 142/984 142/313 4.06/320 6.28/277 6.9/1285 8.16
2*2/1 2*2/1
497 497
2*2/1
497
2*8/1
38
2*3/1 2*3/1 2*3/1
35 45 1284 252 983 391
2*11/3 2*11/3 2*11/3 2*11/3 *40//ll
866 207 350 1284 914 1195 207 876 531 461
0.868 III.
syndiotactic I. II. - , 3-methyl(70.14)
Ortho Ortho
D2-4
12.49 12.38 12.38
Ortho Ortho Mono
D2-5 D2-5 C2-2
16.9 16.81 9.94
6.05 6.06 13.9
7.78 7.73 20.4 20.0
9.55 9.55 19.1 19.25 34.3 19.25
8.54 17.08 17.8 17.20 34.3 17.20
6.84 6.84 6.85 6.85 6.85 6.63
Mono Mono Mono Port Tet Mono
C2h-5
C4v-12
7 =116.5 7-116.5 7=116 7=116.5 7 = 116.5
6.49/277 2*4/1 2*4/1 2*4/1
17.3/82
4*2/1 4*2/1 4*5/3
1435 1449 1435 1449
2*4/1 2*4/1 2*4/1 2*4/1 2*4/1 2*4/1
9 549 231 355 431 280
References page VI-159
TABLE 1. cont'd Density (g/cm3)
Unit cell parameters Polymer
Cryst syst.
Space group
- , 3-methyl- [1,3-via hydride shift] (70.14) - , 4-phenyl(132.21)
Port
CS-2
a
b
5.4
10.4
c
Angles
z
Crystal.
Amorph.a
7.8
18.0
6.61 6.55
Poly( 1,3-cyclobutylene) - , 1-cyano(79.10) Poly (1,2-cycloheptylene-a/f-ethylene) (124.23) Poly (1,2-cyclopentylene-afr-ethylene) (96.17) Ortho Ortho D2h-17 or D2h-14 Poly( 1,3-cyclopentylene-a/Mnethylene) (82.15) Ortho Ortho Poly(decenamer) transIll. Tri Ci-I (138.25) IV. Mono C2h-5 PoIy(I-decene) 1.(140.27) PoIy(I-docosene) 1.(308.59) II. III. Poly(dodecenamer) transIll. (166.31) IV.
10.97
20.02
6.46
10.92
7.73
9.10
9.86
9.86
5.02 5
6
1.064
0.962
single crystal II.
a = 130
6
0.901
4
0.950
3
1.703
0.87
206
2*3/1
772
135
4*2/1
324
4*1/1
635 637
4.36
18.8 13.30
847
9.0
74
9*1/1
259
7.83 8.05
9.02 9.00
4 4
1.032 1.006
185
4*2/1 4*2/1
247 412
7.69 13.30
6.21 15.52
4.80 4.80
2 8
1.190 1.101
146 128
4*1/1 4*1/1
267 340
4.40
5.39
12.30
66,104,118
1
0.985
10*1/1
477
7.42
5.00
12.40
/9 = 94.2
2
1.001
32.9/562 10*1/1
530
80/562
13.2
6.7
Mono
5.3
108
7.7
8
0.93
/3 = 94
8
0.93
Tri
Ci-I
4.40
5.39
14.78
66,104,118
1
0.986
Mono
C2h-5
7.43
5.00
14.85
/3 = 93.5
2
1.003
7.40 7.428 7.36 7.418 7.406 7.407
7.84 4.05
4.93 4.934 4.94 4.946 4.939 4.949
5.56 4.85
2*
150
90 91/872 83 75/949
2*4/1
949
2*4/1 2*
949
12*1/1
477
41.2/562 12*1/1
530
45/48 49/872 49/250
2.534 2.532 2.534 2.546 2.547 2.551
120 2.54
34/250 40/537
80/439 84/562
13.2
Tri Pmono
483 67 1195
3*8/
88
D2h-16
2*3/1 2*3/1
262 264
4.6
370
7.5
D2h-16
158 160/90 159/282 168/187
332
25.3
Ortho
Ortho Ortho Ortho Ortho Ortho Ortho
Chain conform. (n*p/q) Refs.
8.76 8.76
PoIy(I-dodecene) 1.(168.32)
Poly(ethylene) 1.(28.05)
Heat of fusion kj/mola
55 68/319
1.041 - , 4-trimethylsilyl(128.29) Ortho Poly(2-butene-fl/f-ethylene) (84.16) Mono C2h-5 Poly(chlorotrifluoroethylene-tf/f-ethylene) (144.52) Hex
Melting point ( 0 C) a
63,71,82 7 = 105
2 2 2 2 2 2
1.008 1.004 1.011 0.997 1.000 0.9961
96 1
0.999 0.991 1.003 1.004 0.966
0.855 0.887 0.811 0.852
2*
137/85 142/315 141/206 145/351 141/286
8.03/85 8.12/262 7.70/86 8.67/700 7.79/156
146/362
7.62/343 8.37/260
141
8.2
2*1/1 2*1/1 2*1/1 2*1/1 2*1/1 2*1/1
2*1/1 2*1/1
150
14 892 15 535 311 1421 138 363 406 939 72 58
TABLE 1. cont'd Density (g/cm3)
Unit cell parameters Polymer
III. (hi press.) -, chlorotrifluoro(116.47)
-, ethylsilylisotactic (86.21) -, tetrafluoro11.(50.01)
I and IV. (>20°C)
III. (hi press.)
Cryst syst. Pmono Mono Tri Ortho Tet
Space group
C2h-3
Hex Hex Hex Hex Hex
Hex
Phex Tri Tri Mono
C3I-2
a
b
c
7.11 8.09 4.285 8.46 4.26
5.46 4.79 4.820 4.88 4.26
2.534 2.53* 2.54 2.45 8.52
6.34 6.5 6.438 6.385 6.4
6.34 6.5 6.438 6.385 6.4
21.60
21.60
35 35 41.5 42 42.5 43
5.54 4.875 5.59 9.76 5.648 5.61 5.59 5.61 5.66 5.65 5.67
16.8 5.105 16.88 16.88 1.3**
9.50 8.73 8.53
5.05 5.69 5.72
2.62 2.62 2.62
5.59 5.63 5.61
5.59 5.63 5.61
14.34
Hex Ortho Ortho
C2-2
Phex Tri Hex Hex Hex Hex Mono Ortho Ortho
C2h-3 D2h-16 D2h-16
-, trifluoro(82.02)
Hex Hex Hex Poly(ethylene), complexes with: -, perhydrotriphenylene Hex
C6-6 or C6h-2
z
Crystal.
- 96.5 7 = 107.9 90,110,108
2 2 1 2 4
0.953 0.998 1.002 0.920 1.20
14 14 17 17 17 16
2.222 2.11 2.18 2.217 2.18
2.08/49
2.19/49 2.192
1.925 2.032
7
Approx.
6.50
5.54 4.882 5.59 5.59 9.649 5.61 9.52 5.61 5.66 5.65 5.67
17.06 16.8 19.50 19.54
Amorph.a
Angles
18
0.981
7 = 119.5 13 90,87,87 4 7' = 119.3 13 /3 = 90 26 7 2 7=119.3 88,90,92 26 13 15 15
2.406 2.744 2.347 2.344 2.344 2.381 2.358 2.302 2.306
Melting point (°C)a
220/49 210/46 222/341
5.02/88
Chain conform. (n*p/q) Refs. 2*1/1 2*1/1 2*1/1 2*1/1 2*4/1
557 253 254 792 946
2*14/1 2*14/1
208 21 777 296 629 205 139 116
2*17/ 2*17/1 2*16/1 215 2*3/1
2.0/1195
327/46
2.060
330 330/101 346 332/89 334/1357
4 4 4
2.304 2.742 2.552 2.598
2.50 6.75
1 3
2.013 2.205
222/726 213/985
14.34
4.78
2
1.071
181
8.22 8.30
8.22 13.81
11.02 11.00
12.38
6.28
2.5
7 = 105.5
Heat of fusion kj/mola
3.4/1195 1*13/1 1*4/ 1*13/6 1*13/ Irreg 1*13/6 1*13/1 2.87/91 1*13/1 4.10/989 1*15/7 4.64 1*15/ 1*15/7 1*2/1 1*2/1 1*2/1
489
11 266 209 602 987 1286 1321 11 209 988 1286 66 681 857 986
5.4/726 2*1/1 5.44/985 2*3/1
389 854 1192
4*1/1
1124
-, urea (at 83 K) Poly(ethylidene) (28.05)
992 993 4
0.958
100/617
1*2/1
178
51/439
7*2/1
97
17/250
2*3/1 2*3/1
150 359
52/129
2*3/1 2*3/1 2*19/6
67 685 685
195/619 200/618
Poly(heptenamer) transI. (96.17) PoIy(I-heptene) 1.(98.19)
Ortho
D2h-16 orC2v-9
7.40
-, 5-methyl(112.22) (S) Mono C2-2 18.40 (S), (R) Tet S4-1 20.00 PoIy(I-hexadecene) 11.(224.43) Ortho 7.5 Poly(hexafluoroisobutylene-a/f-vinylidene fluoride) (228.08) Ortho C2v-21 10.64
5.00
17.10
4
1.010
6.45
10.62 20.00
6.40 6.36 38.76
63.2 18.37
/? = 90
6 76
0.900 0.913
6.6
8
0.95
68/250
2*4/1
150
7.83
8
1.980
327
4*2/1
947
References page VI-159
TABLE 1. cont'd Density (g/cm3)
Unit cell parameters Polymer PoIy(I-hexene) (84.16) -, 4-methyl(98.19) -, 5-methyl(98.19) Poly(isobutene) (56.11)
Cryst syst.
Space group
Mono Ortho
a
b
c
22.2 11.7
8.89 26.9
13.7 13.7
7 = 94.5
z
Crystal.
-55/48
2*7/2 2*7/2
150 150
28 28
0.845 0.858
200/9 190/632
2*7/2 2*7/1
67 569
3 6
0.835 0.862
130 110/282
2*3/1 2*3/1
9 685
2*8/5 2*8/3
34 801 139
2*4/1
150
2*
493
8*
639
19.64 19.85
19.64 19.85
14.00 13.50
Hex Mono
C2-2
10.2 17.62
10.2 10.17
6.50 6.33
Ortho Ortho
D2-4 D2-4
6.94 6.88
11.96 11.91
18.63 18.60
16 16
0.964 0.978
70.4
6.6
8
0.96
Hex
4.24
0.915 0.912/53 0.842
cis-
44/66
4.24
Tri
Ci-I
4.34
5.41
9.78 9.78
64,105,119
1
1.008
Mono
C2h-5
7.43
5.00
9.90
/3 = 95.2
2
0.999
Mono
C2h-6
4.58
9.50
17.11
(3 = 98
4
0.993
-5
10.9
67/439 73/284 76 77/562 62/439
20.1/284
38 PoIy(I-octene) (at 90K) (112.22) Poly(pentenamer) transI. (68.12) PoIy(I-pentene) isotactic Ia. (70.13)
Mono
Ortho
5.6
C2v-9 orD2h-16
Mono Mono
38
7.28
4.97
11.35 21.15 22.4
20.85 11.20 21.2
Ib. Mono
24.3
19.3
Mono Port
35.65 19.30
20.2 16.90
19.60 21.20
16.75 11.48
Ha.
lib. III. syndiotactic
Port Ortho
D2-4
7.6
0 = 97
11.90
6.49 6.49 6.49* 6.5 6.50* 6.60 7.13* 7.08 7.08 14.39
/3 = 99.6 /3 = 99.6 7 = 91
S4-1
20.3 20.35
20.3 20.35
8*1/1 25.3 23.8/562 8*1/1
126 476 1377 530
8*2/1
905 1376
2*4/1
1209
21.0
8
0.93
5 10-38/48 10/872
4
1.051
23 34/682
12.0/682 5*2/1
147
12 12 24
0.923 0.922 0.907 0.96
130/276 130/380 111/501
6.28/501 2*3/1 2*3/1 2*3/1
2*4/1 2*4/1
355 355 931 408 355 931 152 818 355
2*4/1 2*7/2
355 834
7 = 96
24
0.922
7 = 91 7 = 116
40 16
0.907 0.898
7=115.3
16 28
0.887 0.931
0.85 2*3/1 2*3/1 75/48 78/282 80/9 79/501
42 -, 5-amino-, -, Af,iV-diisobutyl(197.37) -, -, Af,Af-diisopropyl(169.31) - , 4,4-dimethyl(98.19) Tet Tet
12.0/82
80/6 100/90
0.867 IV.
Chain conform. (n*p/q) Refs.
0.726 0.908
Cl-I
(3 = 90
Amorph.a
Heat of fusion kj/mola
14 28
Tet Tet
Poly(norbornene), see PoIy(I -vinylene-3-methylene) Poly (1 -octadecene) 11.(252.49) Ortho 7.5 III. Poly(octamethylene) -, 1-methyl(126.24) Poly(octenamer) transIll. (110.20)
Angles
Melting point (°C)a
4.00/501
2.94
1452
6.85
112
2*
191
7.32
130
2*
191
231/282 350/90 380/441
2*7/2 2*4/1
431 442
13.8 7.01
28 16
0.803 0.899
TABLE 1. cont'd Density (g/cm3)
Unit cell parameters Polymer - , 5-hydroxy(86.13) - , 3-methyl(84.16)
- , 4-methylisotactic I. (84.16)
Cryst syst.
Space group
III.
quenched syndiotactic I.
II. III.
Angles
z
Crystal.
C4-6
13.35
13.35
6.80
8
0.922
Tet Tet Tet Tet Tet Tet Tet Tet Tet
S4-1
18.66 18.70 18.53 18.54 18.50 18.60 18.63 18.70 18.66
18.66 18.70 18.53 18.54 18.50 18.60 18.63 18.70 18.66
13.80 13.54 13.76 13.84 13.76 13.85 13.85 13.68 13.65
28 28 28 28 28 28 28 28 28
19.16 19.36 19.38 19.46
19.16 19.36 19.38 19.46
16 16 16 16
0.814 0.826 0.828 0.822 0.831 0.817 0.814 0.818 0.823 0.828 0.855 0.846 0.853 0.8408
16.88 22.17
16.88 22.17
18 18
0.808 0.883?
18.03
18.03
48
0.880
S4-1 D2d-7
C4-6
Hex Hex Tet
II.
c
Tet
Tet Tet
- , 5-trimethylsilyl(142.32) Poly(propene) isotactic I. (42.08)
b
Amorph.a
Heat of fusion kj/mol a
6.5
II. III.
IV. (hi press) V. syndiotactic
a
Melting point (°C)a
S4-1
7.12 7.05 6.98 7.022 6.5 6.31 6.69 46.91
362/632 273/129 200/441
>0.835
Hex Rho Rho Ortho Hex Rho Ortho Rho Tri Tri Ortho Tet Ortho Ortho Ortho Phex Ortho
C2h-6 Ci-I C2h-5
C2h-5 C2h-3 C2h-5
D3-4
C3-2
D2h-24
D2-2 D2-5 D2h-27
C2v-9
6.65 6.66 13.36 6.65 6.63 6.64 6.69
20.96 20.78 11.00 20.73 20.78 20.88 20.98
6.50 6.495 6.502* 6.50 6.504 6.51 6.504
/3 = 99.3 /3 = 99.62 93,81,108 /3-99.7 (3 = 99.5 /3 = 98.7 /3 = 99.5
12 12 12 12 12 12 12
0.938 0.946 0.935 0.947 0.949 0.940 0.931
6.65
20.80
6.50
/3 = 99.33
12
0.945
12.74 19.08 6.38 19.08 22.03 19.08 11.03 11 6.47 6.54 8.54 5.97
12.74 19.08 6.38 11.01 22.03 19.08 19.08 11 10.71 21.40 9.93 5.97
6.35 6.49 6.33 6.490 6.490 (6.49) 6.49 6.5
0.939 0.922 0.939 0.922 0.922 0.922 0.921 0.92
6.50 42.41 6
12 27 3 18 36 27 18 9 6 12 48
14.5 14.50 14.50
5.8 5.60 11.20
7.4 7.40 7.40
8 8 16
0.898 0.930 0.930 0.898
11.17
5.05 5.06 11.8
5.22
7 ; = 99.07 89,100,99
4
0.85/45
0.854
0.907/112
0.946 0.935 0.88/167
0.947
19.7/82 11.9/370 9.9/1195 5.2/1288 5.5/1331
2*
191
2*4/1
622
2*7/2 2*7/2 2*7/2 2*7/2 Irreg. 2*7/2 2*7/2 2*7/2 2*7/2
125 75
2*4/1 2*4/1 2*4/1 2*4/1 2* 2*3/1 2*3/1?
55 936 894 452 333 67 689 1177 1198 94 8 8 1197 1453 845 1454 990
210
4*12/7
1455
133/71
2*3/1
67
176/10 9.92/82 2*3/1 189/392 7.96/478 2*3/1 186/394 8.8/394 2*3/1 208/676 5.80/676 2*3/1 165/282 10.5/474 2*3/1 178/349 10.0/358 2*3/1 183/380 6.16/182 2*3/1 180/250 7.91/251 2*3/1 220/974 10.9/83 2*3/1 220/975 6.9/1195 186/1003 9.3/1212 147/789 4.22/789 2*3/1 200/975 8.2/1212 2*3/1 170/974 4.0/1404 2*3/1 192/1212 2*3/1 183/1404 2*3/1 2*3/1 2*3/1 3*3/1 2*3/1 2*3/1 cf ref 2*3/1
127 308 170 519 626 131 136 330 991
0.838
6.55
Mono Mono Tri Mono Mono Mono Mono Mono Mono
235/48 228/282 238/632 250/94
Chain conform. (n*p/q) Refs.
0.858/393
161/415 138/545
0.858
160/1459
1.88/545 4*2/1 2.1/1195 4*2/1 8.3/1458 4*2/1 8.0/1459 4*1/1 4*/l 4*
166 485 196 308 308 1456 1457 1642 308 592 1408 943 169 430 1330 409 306 1430 845
References page VI-159
TABLE 1. cont'd Density (g/cm3)
Unit cell parameters Polymer (hi press.) IV. (252.48) -, 3-cyclohexyl1.(124.23)
II. -, 3-cyclopentyl(110.20)
Cryst syst.
Space group
a
b
Tri
Cl-I
5.72
7.64
11.60
Tet
C4-5 or S4-2
21.06
21.06
Rho
C4-3 or C3i-2
19.12
Tet
C4-5 or S4-2
Tet - , hexafluoro(150.02) -, 3-phenyl- [allylbenzene] (118.18)
-, 3-silyl(72.18) -, trimethylsilyl(114.26) Poly(propene-alt-ethylene) syndiotactic (70.14) Mono Poly (1 -tetradecene) 11.(196.38) Ortho
II.
Tet
Poly(vinylcyclopentane) 1.(96.17) Tet II.
Tet
III.
Tet
Poly(vinylcyclopropane) I. (68.12) Rho
b
z
Crystal.
73,89,112
1
0.942
20.09
40
0.926
19.12
6.33
9
0.926
20.34
20.34
47.49
96
0.894
20.30
20.30
47.40
96
0.899
Amorph."
Heat of fusion kj/mola
Chain conform. (n*p/q) Refs.
12*1/1
1460
2*10/3
431
2*3/1
431
2*24/7
431
2*24/7
625
160
2*4/1
268
6.40
230/90 208/187 185/282
2*3/1
67
6.45
128/71
2*3/1
67
6.50
360/71
2*3/1
67
11.62
9.00
7.5
56.0
6.6
9.6 8.57 9.46
9.25 11.20 5.81
5.0 5.04
34.12
34.12
C4h-6
23.4
C4h-6
230/90 215/282 214/328
210/328 225/90
7 = 67.03
55 8
0.94
4 4
1.93 1.758
6.6
64
23.4
6.5
21.99 21.76
21.99 21.76
C4-5 or S4-2
20.48
C4h-6 C4-5 or S4-2 D4h-1 or D4h-7
C3-2 or C3-3 II. Tet S4-2 PoIy(I-vinylene-3-cyclopentylene) [norbornene] trans(94.16) Mono CWMono a
Angles
11.19
Poly(tetrafluoroethylene-aZf-ethylene) (128.07) Mono Ortho Poly(vinylcyclobutane) (82.15) Tet Poly(vinylcycloheptane) (124.23) Tet Poly(vinylcyclohexane) 1.(110.20) Tet Tet
c
Melting point (0C)"
2*4/1
150
267
4*1/1 4*1/1
722 1287 1321
1.14
228/437
2*4/1
431
16
0.927
>300/437
2*4/1
431
6.43 6.50
16 16
0.942 0.951
305/90 300/282 372/441 383/328
2*4/1 2*4/1
431 67
20.48
44.58
96
0.940
2*24/7
431
20.14
20.14
6.50
16
0.969
2*4/7
431
20.14
20.14
19.5
48
0.969
2*12/3
431
37.3
37.3
19.8
0.927
2*10/3
431
13.6
13.6
6.5 6.48
9
0.981
2*3/1
175 526
15.21
15.21
20.85
40
0.938
2*10/3
526
5.13 4.64
4.78 4.22
11.8 11.56 9.84
2 2
1.150 1.749
5*2/ 5*2/1 5*2/1
620 1451 1451
7 = 96
57/250 57/872
1450
1.684
270/441 292/328
230
202 7 = 73.5 7 = 68.1
The numbers after the solidus (/) are reference citations. The unit cell parameter assignment has been changed from that published so as to make c the fiber axis.
TABLE 2. POLY(VINYLS) AND POLY(VINYLIDENES) (-HCH-CHR- and -HCH-RCR-) Density (g/cm3)
Unit cell parameters Polymer
Cryst syst.
Poly(acrylamide) - , WV-dibutyl(183.30)
Hex
Space group
-, N-isopropyl(113.16) Poly(acrylic acid) -, allyl ester (112.13) -, biphenyloxyhexamethylene ester (324.42) Phex -, sec-butyl ester (128.17) Ortho -, tert-butyl ester (128.17) Ortho -, p-carboxyphenyl ester (192.17) Mono -, isobutyl ester (128.17) Ortho -, isopropyl ester isotactic (114.14)
a
b
c
26.3
26.3
6.3
Angles
z
12
Crystal.
Amorph.a
Melting point (°C)a
Heat of fusion kj/mola
0.97 (1.06) 1.118
Chain conform. (n*p/q) Refs.
2*3/1
1.070
6.5
93
200
2*
102
90
2*3/1
278
2*3/1
1122
23.5
23.5
6.48
6
1.043
17.92
10.34
6.49
6
1.062
130
2*3/1
401
17.92
10.50
6.45 6.48
6
1.047
193/16 200
2*3/1 2*3/1
67 401
21.50
7.42
6.68fc
4
1.445
2*
865
17.92
17.92
6.42
12
1.239
81
2*3/1
401
6.5 6.32
162/120 162 178/541
2*3/1
1.08
67 149
5.18
1.18
115
4*1/1
113
4.86/775.23/77 4*1/1 4*1/1 4*1/1 4*1/1 4*1/1 4*1/1 4*1/1 4*1/1
76 486 575 133 162 210 322 1001 1332 1631 804 1631
/3=124
5.9/541
syndiotactic Poly(acrylonitrile) syndiotactic (53.06)
II?
Hex Ortho Ortho Ortho Ortho Ortho Phex Ortho Ortho
C2v-16
C2v-9
Ortho
5.99 21.18 10.6 10.20 18.1 10.55 6.1 21.0 10.7 9.03 21.48 21.18
5.99 11.60 11.6 6.10 6.12 5.80 6.11 11.9 12.1 5.24 11.55 11.71
4.74 11.4 15.08
(5.1) 5.04 5.10 5.00 5.08 (5.1) 5.04 (5.1)
317/77 341/499
16 8 4 8 4 2 16 8
1.125 1.137 1.111 1.273 1.134 1.07 1.119 1.07
7.096
24
1.201
2*4/
4.74 11.4
2.55 8.2
1 16
1.538 1.32
2*1/1 2*4/1
133 1461
15.08
8.54
16
1.151
2*4/1
347
5.02/871 2*5/2 2*5/1 vi ref * 10/1 * 10/1 4*5/2
30 520 868 1002 1462 30
*9/l *30/4
1397 1005
4*37/4
1004
7=120
isotactic Tet (gel) Tet Poly(isopropenylmethyl ketone) (84.12) Tet
240
240/255 200/379 Poly(methacrylic acid) -, methyl ester isotactic (100.12) Port Ortho Ortho Tri Ortho syndiotactic it-st stereocomplex (1:2) Mono -, - , chloroacetone complex syndiotactic Mono
D2h-24
21.08 21.08 20.98 20.57 41.96
21.5
43.5
12.17 12.17 12.06 12.49 24.34
16.5
43.5
10.55 10.50 10.40 10.56 10.50
93,88,91
18.4 73.6
7=112
35.4
7=107
20 20 20 20 80
1.228 1.234 1.264 1.228 1.240
1.22/31
160/31 220/855
1.19/31
200/31
260/1006
References page VI-159
TABLE 2. cont'd Density (g/cm3)
Unit cell parameters Polymer
Cryst syst.
Space group
-, octadecyl ester syndiotactic (338.58) Hex Poly(methacrylontirile) 1.(67.09) Phex II. Mono Poly(thiolacrylic acid) -, sec-b\xty\ ester (144.23) Rho -, isobutyl ester (144.23) Mono -, isopropyl ester (130.20) Rho -, propyl ester (130.20) Mono Poly(vinyl acetate) -, trifluoro(140.06) Ortho Poly(vinyl alcohol) (44.05) Mono Mono Mono
quenched single crystal 12 complex Poly(vinyl bromide) (106.95) Poly(vinyl chloride) (62.50)
single crystal Poly(vinyl fluoride) (46.04)
Poly(vinyl formate) isotactic (72.06)
a
b
4.73
4.73
9.03 7.87 13.5
9.03 8.97 7.71
c
Angles
30.2 6.87 6.87 7.62
(3 = 91.1
z
Crystal.
1
0.961
36
4 4 8
0.918 0.918 1.134
250/436
Chain conform. (n*p/q) Refs.
500 2* 2*4/1
427 729 427
6.35
2*3/1
401
Cs-2
6.42
2*
401
C3-2
6.42
2*
401
Cs-2
6.4
2*3/1
401
2*
638
9.54
12.44
4.8
4
1.633 1.350 1.34/410 1.350 1.345 1.352 1.343 1.490 1.133
7.81 7.81 7.805
5.51 5.43 5.485
2.52*
7-91.7 7 = 91.5 2.533* 7 - 92.2
2 2 2
Mono Mono Ortho Hex Mono
C2h-2
7.81 7.84 7.42 5.45 7.87
5.50 5.52 5.25 5.45 5.53
2.52* 7 = 92 2.52* 7 = 93 2.52* 2.51 2.525* 7 = 93.3
2 2 2 1 2
Ortho
D2h-ll
11.0
5.6
5.1
4
2.26
Ortho Ortho Ortho Mono Ortho
D2h-ll D2h-ll
10.6 10.40 10.11 10.65 10.24
5.4 5.30 5.27 5.20 5.24
5.1 5.10 5.12 5.15* 5.08
4 4 4 4 4
1.42 1.477 1.522 1.456 1.523
4.93 4.95 4.938
2.53 2.52 2.518
1 2 1
1.436 1.430 1.4377
18
1.502
Rho
Heat of fusion kj/mola
C3-2
C2h-2
Hex Ortho Mono
Amorph.a
Melting point (°C)a
C2v-20
D2h-ll
C2v-14
C3v-6D3d-6
4.93 8.57 4.938
15.9
15.9
7 = 90
y = 120
6.55
175/821 1.291/1 1.27/410 1.26/53 1.269
232/310 243/480 265/323 228/433 267/450
6.87/433 2*1/1 6.99/480 2*1/1 7.1/1195 2*1/1
117 1.41/413
2*1/1 2*1/1 2*1/1 2*1/1 2*1/1
29 316 132 184 261 1441 261 151 1424
4*1/1
772
273/372 310/423 212/143
11/372 4.9/835 2.8/145 3.3/423
4*1/1 4*1/1 4*1/1 4*1/1 4*1/1
7 235 64 140 718
200/79 230/434
7.54/79
2*1/1 2*1/1 2*1/1
62 236 1463
2*3/1
232
4*1/1
232
syndiotactic 5.0 Poly(vinylidene bromide) (185.85) Mono Poly(vinylidene chloride) (96.94) Mono Mono Mono Mono
C2h-2
C2-2
25.88
13.87
4.77*
7=109.8
16
3.065
6.71 13.69 22.54 6.73
12.51 6.296 12.53 12.54
4.68* 4.67* 4.68* 4.68*
7=123 7=124.8 7 = 95.8 7=123.6
4 4 16 4
1.954 1.948 1.958 1.957
33 1.66/43
200/721 190/46 195
4*1/1 4*1/1 5.68 2*2/1
1.7754 Poly(vinylidene fluoride) a (II) Mono (64.04) Ortho Mono Ortho Mono Mono
C2v-4 C2-2 C2v-9 C2h-5 C2-2,l
5.02 4.96 17.72 9.66 4.96 9.64
25.4 9.64 11.68 4.96 9.64 5.02
4.62 4.62 4.57* 4.64 4.62 4.64*
/3=107 7 = 92.7 /3 = 90 7 = 91.1
10 4 16 4 4 4
1.888 1.925 1.801 1.913 1.925 1.895
1.68/776 1.67/770
185/434 170/995 220/443 171/373 178 178/726
6.7/823 6.2/886 4*1/1 5.96/726 4*1/1 2*2/1 4*1/1 4*1/1
915 32 33 245 231 462 171 994 417 418 604 168
TABLE 2. cont'd Density (g/cm3)
Unit cell parameters Polymer
P(I)
Y (HI)
Cryst syst.
Space group
Port Ortho
C2-2
Ortho Ortho Ortho Ortho Mono Mono Ortho Mono
C2v-14 C2v-14 C2v-14
8(IV) (polar alpha) Ortho Poly(vinylmethyl ketone) (70.09) Tet Tet
Cs-4 C2-3 C2v-16
C2v-9 S4-1
a
b
c
5.02 9.60 9.80 8.45 8.58 8.47 8.60 4.96 8.66 4.97 4.96 4.96 4.96
9.63 5.00 5.05 4.88 4.91 4.90 4.97 9.58 4.93 9.66 9.67 9.64 9.64
4.62 4.655
14.52 14.56
14.52 14.56
Chain conform. (n*p/q) Refs.
Crystal.
4 4 4 2 2 2 2 8 2 8 8
1.904 1.904
188/846 213/1464
2*2/1
2.022 1.972 2.002 1.936 1.942 1.945 1.930 1.930
212/443 191 207/942
2*1/1 2*1/1 2*1/1
218/846 197 184/995 231/1464
4.62
4
1.925
8*1/1 2*1/1 8*1/1 8*1/1 4*1/1 4*1/1
563 597 750 417 604 418 597 996 604 997 998 999 1000
14.40 14.10
28 28
1.073 1.090
2*7/2 2*7/2
164 379
/3 = 92.9 /3 = 91 /3 = 93
Amorph.*
Heat of fusion kj/mola
z
2.55 2.56 2.56 2.57 9.23 2.58 9.18 9.20
Angles
Melting point (°C)a
170
a The numbers after the solidus (/) are reference citations. * The unit cell parameter assignment has been changed from that published so as to make c the fiber axis.
TABLE 3.
POLY(AROMATICS) AND POLY(IMIDES) Density (g/cm3)
Unit cell parameters Polymer
Cryst syst.
Space group
a
b
Poly(4,4 '-benzobisthiazole-diphenylene pyromellitimide) (556.57) Ortho D2-3 5.70 8.11 Poly(2,6-benzothiazole) (133.17) Port 6.044 3.417 Poly(2,5(6)-benzoxazole) (117.11) Port 6.061 3.384 Poly(4,4 '-biphenylene 3,3' ,4,4 '-biphenylenetetracarboximide) (442.43) - , 2,2'-bis(trifluoromethyl)(578.43) Mono 15.40 9.90 Mono 15.40 9.918 -, 2,2'-dimethyl(470.48) Tri 20.49 15.30 - , 3,3'-dimethyl(470.48) Ortho 16.7 13.0 Poly(4,4 '-biphenylene 4,4 '-carbonyl(3,3 ;-dicarboxy)-dibenzamide) (506.47) Poly(4,4 '-biphenylene 3,3 ',4,4'-carbonyldiphenylenetetracarboximide) (470.44) Poly(4,4'-biphenylenedioxy-3,3 '-biphenylene pyromellitimide) (550.53) Ortho 7.89 6.29 Ortho 7.85 6.37 Poly[2,2 '-(4,4 '-biphenylene) 6,6 '-diquinoline] -, di-/?-phenyl(558.63) Ortho 16.2 5.31 Poly(4,4'-biphenylene 4,4'-oxy(3,3 '-dicarboxy)-dibenzamide) (494.46) Poly(4,4 '-biphenylene 3,3 ',4,4 '-oxydiphenylenetetracarboximide) (458.43) Poly(4,4 '-biphenylene 1,4-pyromellitamide) (402.36) Poly(4,4 '-biphenylene pyromellitimide) (366.33) 8.58 5.48 Ortho D2h-9 8.57 5.51
c
Angles
Amorph.a
Melting point (0C)a
Heat of fusion kj/mola
Chain conform. (n*p/q) Refs.
z
Crystal.
24.8
2
1.612
22*1/1
1433
12.19
2
1.756
5*2/1
1235
11.58
2
1.638
5*2/1
1235
1.480 20.25 20.21
7 = 56 7 = 56.2
4 4
1.501 1.4977
40.0
62,52,80
16
1.443
8
1.404
1335 18*1/1 18*1/1
1494 1495
18*2/1
1584
18*1/1
1289
21.2
21*1/1
1178
21.6
19*1/1
1178
23*1/1 34*1/1
1475 1498
20*1/1
1500
21*1/1
1178
19*1/1
1178
16*1/1
1178
15*1/1 15*1/1
908 928 1476
20.5
25.11 25.31
2 2
1.467 1.444
21.4
2
1.008
1.341
388
21.0 21.3
900/1018
16.1 16.6 16.6 16.78
2 2
1.559 1.535
827/1018
References page VI-159
TABLE 3. cont'd Density (g/cm3)
Unit cell parameters Polymer
Cryst syst.
Space group
a
b
Poly(2,2 '-bithiophene) -, 3,3'didecyl(444.78) Ortho 17.6 4.5 -, 3,3'-dihexyl(332.56) Ortho 11.8 4.5 -, 3,3'-dioctyl(388.67) Mono C2h-4 14.6 4.42 Ortho 14.5 4.5 Ortho 14.6 4.42 Poly(4,4 '-carbonyldiphenylene pyromellitimide) (394.34) Ortho 7.9 6.65 Poly(decamethylene 3,3 ',4,4'-oxydiphenylenetetracarboximide) (446.50) Poly(decamethylene pyromellitimide) (354.40) Mono 19.8 4.61
c
Amorph.a
Heat of fusion kj/mola
Chain conform. (n*p/q) Refs.
z
Crystal.
15.6
2
1.20
6*2/1
1485
15.6*
2
1.33
6*2/1
1485
2 2 2
1.36 1.27 1.27
6*2/1 6*2/1 6*2/1
1484 1485 1486
4
1.520
16*2/1
908 1013
21*1/1
896
14.73 15.6* 15.70
Angles
Melting point (°C)a
/3 = 90
31.0fe 32.8 23.5 19.2
7 = 96
4
1.350
318 323/1267
17*1/1
1395
19.1
90,111,100
1
1.409
308
20*1/1
1015
18.9 7=108.4 1 18.96 Mono 18.95 4.54 21.5 7=101.3 4 21.43 Y 22.05 5 20.95 Poly(3,4 '-ethylenedioxydiethylenedioxydiphenylene 3,3 ',4,4 '-oxydiphenylenetetracarboximide) (606.59) Poly(3,4'-ethylenedioxydiphenylene 3,3 ',4,4'-oxydiphenylenetetracarboximide) (518.48) Poly(2,7-fluorenylene 1,4-pyromellitamide) (414.37) 15.9 Poly(2,7-fluoenylene pyromellitimide) (378.34) 16.3 Poly(hexamethylene 3,3 ',4,4'-oxydiphenylenetetracarboximide) (390.40) 19.5 Tri 8.34 9.18 19.6 90,134,117 2 Poly(hexamethylene pyromellitimide) (298.30) 24.88 Poly[4,4 '-(isophthaloyldiamino)-diphenylene 3,3 ',4,4 '-oxydiphenylenetetracarboximide] (620.58) Ortho 9.84 4.95 28.5 2 Poly [4,4' -(isophthaloyldiamino)-diphenylene /7-phenyleneditrimellitatediimide] (768.69) Ortho 6.03 7.58 73.6 4 Poly[4,4 '-(isophthaloyldiamino)-diphenylene pyromellitimide] (528.48) 24.2
1.289
19*1/1
1395 1371 1015 1371 1371 1371
Poly(dodecamethylene (432.52) Poly(dodecamethylene a (382.46) P
1,4,5,8-naphthalenetetracarboximide) Tri 6.23 pyromellitimide) Mono 5.58
4.68 4.89
1.401
(1.462)
297 305/1267
19*1/1
268
88.0
1493
340
72.5
1493
238
15*1/1
1178
14*1/1
1178
17*1/1
896 1015
430 1.485
320
1.518
1395 26*1/1
1190
33*2/1
1191
22*1/1
1191 1335
34*1/1
1498
16*2/1
908 1013 1014
1.382 Poly[isophthaloy 1-4,4 '-diphenylenedioxy-4,4 '-diphenylene 3,3 ',4,4'-carbonyldiphenylenetetracarboximide] (786.75) Ortho 8.07 6.135 37.50 2 1.07 Poly(4,4 '-methylenediphenylene pyromellitimide) (380.36) 29.1 Ortho 8.20 6.55 32.4 4 1.452 14.1 Poly(methylene-/?-phenylene) (90.12) Ortho 8.16 6.32 9.90 4 1.172 - , oc-methyl(104.15) Ortho 10.42 Poly (methy lene-3,5 -toluene) - , 2,6-diamino(134.18) Ortho 12.82 Poly(2,6-naphthalene 2,4-cyclobutylenedicarboxylic acid) - , bis(2,4-dichlorophenyl) ester (558.24) Tri Ci-I 6.00
350
170 142/744
5*2/1
745
219/1007
5*2/1
848
5.97
9.62
4
1.156
13.83
9.69
8
1.037
4*2/1
1351
8.93
13.48
1
1.396
9*1/1
950
70,94,101
TABLE 3. cont'd Density (g/cm3)
Unit cell parameters Polymer
Cryst syst.
Space group
a
be
Angles
Poly(4,4 '-neopentylenedioxydiphenylene 3,3 ',4,4 '-carbonyldiphenylenetetracarboximide) (572.57) Mono 9.60 5.82 24.6 7 = 81.1 Poly(nonamethylene 3,3 ',4,4'-oxydiphenylenetetracarboximide) (432.48) 21.3 Poly(nonamethylene pyromellitimide) (340.38) 32.0 Poly(octamethylene 3,3 ',4,4 '-oxydiphenylenetetracarboximide) (418.45) Tri 8.37 4.95 Tri 8.37 4.95 Poly(octamethylene pyromellitimide) (326.35) Mono 20.8 4.76
z
Crystal.
2
1.400
Amorph."
Melting point (°C)a
Heat of fusion kj/mola
Chain conform. (n*p/q) Refs.
24*1/1
1499
20*1/1
1015
303 >350
1395 1267 19*1/1
21.5 21.5
90,38,104 90,38,104
1 1
1.372 1.396
16.9
7 = 95.5
4
1.301
Poly(3,4'-oxydiethylenedioxdiphenylene 3,3 ',4,4'-oxydiphenylenetetracarboximide) (562.34) Poly(3,4 '-oxydiphenylene 3,3',4,4'-biphenylenetetracarboximide) (458.43) Mono 14.8 8.20 20.6 7 = 56 Poly [4,4 '"-((4 ',4 "-oxydiphenylene)-dioxy)-diphenylene /?-phenyleneditrimellitatediimide] (806.74) 5.68 8.09 78.6 Poly[4,4 '"-((4 ',4 "-oxydiphenylene)-dioxy)-diphenylene pyromellitimide] (566.53) 8.44 5.66 53.4 53.4 Poly(4,4 '-oxydiphenylene 3,3 ',4,4'-oxydiphenylenetetracarboximide) (474.43) Mono 5.17 10.85 38.2 7=103.7 Poly[4,4'-oxydiphenylene 3,3 '-(/?-phenylene)-ditrimellitatediamide] (658.58) 26.3 Poly(4,4 '-oxydiphenylene p-phenyleneditrimellitatediimide) A. (622.54) Mono 5.56 7.94 58.0 7 = 86 5.56 7.94 59.0 /3 = 86 28.7
1.30 202
19*1/1
896 1015
362 383/1267
15*1/1
1395
304
80.2
1493
4
1.469
18*1/1
1289
4
1.484
37*2/1
963
4
1.475
547/1018
26*2/1
963 908
4
1.514
427/1018
20*2/1
684
26*2/1
1178
27*2/1 27*2/1
658 963 1178 1335 963
4 4
1.619 1.591
8
1.410
1.366 B. Poly (4,4' -oxydiphenylene 1,4-pyromellitamide) (418.36)
13.12
7.84
57.0
27*2/1
15.2
17*1/1
1178 1335
15*2/1 15*2/1
1477 1478
16*2/1 16*2/1
642 684 877 1477 1478 1178 1477
1.410 Poly(3,4 '-oxydiphenylene pyromellitimide) (382.33) Ortho Ortho D2-9 Poly(4,4 '-oxydiphenylene pyromellitimide) 1.(382.33) Ortho Ortho Ortho C2-2 Ortho Mono C2-2 II. Poly(m-phenylene) (76.10) Poly(/7-phenylene) (76.10)
- , complex with: K (l/2K/unit) SbCl5 (l/2Sb/unit) SbF5 (l/3Sb/unit)
Ortho
8.48 5.75
5.62 8.48
33.65 33.2
4 4
1.583 1.569
6.35 6.31 4.66 8.36 6.45
4.05 3.97 5.96 5.63 4.01
2 2 2 4 2
1.514 1.58 1.411 1.633 1.507
5.93
4.70
32.6 32 32.9* 33.03 32.58 15.9 33.00
2
1.380
7 = 100 7 = 90
597/1018
16*2/1 16*2/1 16*2/1 790/964
Ortho Ortho Mono Ortho Ortho
pgg
7.81 7.80 8.06 7.82 7.79
Ortho
D2h-9
6.04
5.53 5.56 5.55 5.60 5.51
4.20 4.20 4.30 4.20 (4.20)
/3=100
2 2 2 2 2
1.393 1.388 1.334 1.374 1.402
6.90/964 3*
<550/735 15.0/964 4*1/1 1400/964 4*1/1 4*1/1 4*1/1 4*1/1 4*2/1
475 1290 1334 1448 1466 508
15.6
4.35
4
4*1/1
1231
Ortho
15.6
6.2
4.2
2
4*1/1
1393
Hex
12.0
12.0
4.2
3
4*1/1
1393
References page VI-159
TABLE 3. cont'd Density (g/cm3)
Unit cell parameters Polymer
Cryst syst.
Space group
a
b
c
Angles
z
Crystal.
Amorph.a
Poly(p-phenylene benzobisoxazole) [PBO] (234.21) Mono 5.64 3.58 12.07 7=100.4 1 1.622 Mono 11.20 3.540 12.050 7=101.3 2 1.660 Mono Cs-2 11.20 3.54 12.05 7=101.3 2 1.660 Port 11.8 3.54 12.1 2 1.55 - , complex with poly (phosphoric acid) I. Mono 12.6 11.6 12.2 7 = 98 II. Mono 7.0 5.8 12.0 7 = 99 Poly(p-phenylene benzobisthiazole) [PBT] (266.34) Mono 5.83 3.54 12.35 7 = 96 1 1.745 Mono 11.96 3.555 12.35 7=100.9 2 1.716 Mono 11.79 3.539 12.514 7 = 94.0 2 1.698 - , complex with poly (phosphoric acid) Ortho 15.9 20.6 36.9 Mono 8.15 24.49 37.2 7 = 94.5 2.15 Poly(p-phenylenecyclobutylene) - , 2,4-dipyridyl(284.36) Ortho D2h-15 19.16 10.69 7.45 4 1.238 Ortho D2h-15 18.9 10.5 7.53 4 1.26 Poly(p-phenylene 2,4-cyclobutylenedicarboxylic acid) - , diethyl ester (274.32) Mono C2h-5 8.62 9.98 8.16* /9=102 2 1.327 - , dimethyl ester (246.26) Tri Ci-I 6.04 7.42 7.82* 101,106,72 1 1.284 -, diphenyl ester (370.40) Mono C2h-5 7.50 17.3 7.50* (3 = 102 2 1.292 -, dipropyl ester -, - , 2,4-dicyano(352.39) Mono C2h-2 6.19 20.1 7.58 /9 = 96 2 1.248 Poly [4,4 '"-((4 ',4 "-(p-phenylenedioxy)-diphenylene)-dioxy)-diphenylene p-phenyleneditrimellitatediimide] (898.84) 5.66 8.14 43.5 2 1.489 Poly[4,4 '"-((4',4"-(p-phenylenedioxy)-diphenylene)-dioxy)-diphenylene pyromellitimide] (658.62) 8.44 5.66 31.3 2 1.463 31.3 Poly[4,4'-(/?-phenylenedioxy)-diphenylene 4,4'-oxy(3,3 '-dicarboxy)-dibenzamide] (602.56) 24.6 Poly[4,4'-(>-phenylenedioxy)-diphenylene 3,3 ',4,4 '-oxydiphenylenetetracarboximide] (566.52) Tri 10.52 9.45 26.1 90,95,98 4 1.472 26.0
Melting point (°C)fl
Heat of fusion kj/mola
Chain conform. (n*p/q) Refs.
11*1/1 11*1/1 11*1/1 11*1/1
1492 1492 11*1/1 11*1/1 11*1/1
1016 1017 1488
250
11*3/1
1316 1491
340
7*1/1 7*1/1
202 723
347/723
7*1/1
893
415/723
7*1/1
893
420/723
7*1/1
893
335/723
7*1/1
893
42*1/1
963
31*1/1
963 908
27*1/1
1178
25*1/1
684 1178 1335
32*1/1
658
21*1/1
1178
22*1/1
1178
1.341 Poly[4,4/-(p-phenylenedioxy)-diphenylenep-phenyleneditrimellitatediimide] (714.64) Ortho 5.64 8.05 34.5 Poly [4,4 '-(m-phenylenedioxy)-diphenylene 1,4-pyromellitamide] (510.46) 19.8 Poly [4,4 '-(p-phenylenedioxy)-diphenylene 1,4-pyromellitamide] (510.46) 19.6 Poly [4,4'-(m-phenylenedioxy)-diphenylene pyromellitimide] (474.43) 8.76 5.47 43.4 43.4 21.7 Poly [4,4 '-(p-phenylenedioxy)-diphenylene pyromellitimide] (474.43) Mono 5.64 8.30 21.8 Ortho 8.23 5.58 22.09 21.0 Poly(/?-phenylene-1,3,4-oxadizaole) a Ortho D2-4 12.35 6.55 14.0 (144.13) Poly[p-phenylene 4,4'-oxy(3,3 /-dicarboxy)-dibenzamide] (418.36) 16.6 Poly(p-phenylene 3,3', 4,4'-oxydiphenylenetetracarboximide) (382.33) 16.9 Poly(p-phenylene 1,4-pyromellitamide) (326.26) 12.2
2
/3 = 98.7
1.515
1263 1488 1489 1490
4
1.515
20*2/1
963 908 1178
2 2
1.562 1.553
21*1/1 21*1/1
684 1477 1178
8
1.69
7*2/1
1496
17*1/1
1178
15*1/1
1178
12*1/1
1178
TABLE 3. cont'd Density (g/cm3)
Unit cell parameters Polymer
Cryst syst.
Space group
Poly(ra-phenylene pyromellitimide) (290.23) Ortho Poly(p-phenylene pyromellitimide) (290.23)
b
c
Angles
z
Crystal.
21.5
4
1.618
10*2/1
1013
8.58
5.48
12.3 12.3
2
1.667
11*1/1
908 928
7.90 8.1
6.05 6.1
6.58 6.6
2 2
1.286 1.24
6*1/1 6*1/1
1236 1465
10.10 9.40 10.80 10.45 10.32
6.60 6.60 6.70 6.60 6.60
6.58 6.58 6.6 6.58 6.58
2 2 2 2 2
6*1/1 6*1/1 6*1/1 6*1/1 6*1/1
1399 1399 1465 1399 1399
D2h-15 C2v-5
10.8 18.36 18.36 18.40
18.4 10.88 10.88 10.89
7.4 7.52 7.52 73.45
4 4 4 4
1.28 1.257 1.257 1.265
7*2/1 7*2/1 7*2/1 7*2/1
558 564 950 1238
D3d-6 D3d-6 D3d-6
22.08 21.9 22.08
22.08 21.9 22.08
18 18 18
1.113 1.127 1.118
240/10 9.00/89 2*3/1 250/90 8.37/174 2*3/1 242/1415 8.5/1415 2*3/1
4*6/1 4*6/1
6 128 1388 139 411 1008 1009
8.6/1407 4*1/1 4*1/1 4*1/1 4*1/1 4*1/1 4*1/1 4*2/1 4*2/1
1418 1388 1470 1291 1370 1418 1401 1419
4*2/1 4*2/1 4*2/1 4*2/1 4*2/1
1370 1419 1436 1474 1473
gel Ortho
P y - , complex with: CH 2 Cl 2 C7H8 I2 - , p-tert-butyl- , - , isotactic (160.26) - , 0-fluoro- , - , isotactic (122.14) - , p-fluoro- , - , isotactic (122.14) - , a-methyl- , - , isotactic (118.18) - , - , (p-methyl- , - , - , isotactic (132.21)
Mono Hex Hex
C2h-5 D3h-4
21.0
16.4
19.84 26.26 26.3
12.90 26.26 26.3
Ortho
D2h-16
Ortho
D2h-10
21.4
17.1
Mono Mono Mono
C2h-5 C2h-5 C2h-5
17.48 17.58 17.29
13.27 13.26 12.85
a = 123 a =123
6.626 6.65 6.594
8.81
28.82
30.6 30.6 5.06 5.045 5.1 5.06 5.08 5.06 7.5 7.7 7.5 7.7 7.71 7.71 7.79
321 343/723
1.041.065/17 1.024 1.052
235/282
10/1121
48 7 - 95
8 18 18
1.072 1.033 1.02
266/1372 269/1407 270 286/1417
7 = 122 7 =121.2 7 = 120.3
8
1.077
16
1.01
8 8 8
1.114 1.100 2.054
0.950
Rho
C3v-6
22.15
22.15
6.63
18
1.296
Port
D2-4
17.6
12.1
8.30 8.25
8
0.924
Rho
Chain conform. (n*p/q) Refs.
7.18
1.114
syndiotactic a
Amorph.a
Heat of fusion kj/mola
7.72
Poly(p-phenylenevinylene) (102.14) Mono - , complex with: AsF5 Ortho CIO4 Ortho FeCl3 Ortho H 2 SO 4 Ortho SbF5 Ortho Poly (2,5 -pyrazinecyclobutylene) - , 2,4-diphenyl(284.36) Ortho Ortho Ortho Ortho Poly(styrene) isotactic (104.15) Rho Rho Rho
a
Melting point (°C)a
300 308/1372
198
270/75
2*3/1
123
265/75
2*4/1 2*4/1
67 791
2*3/1
357
6.6
224/888
10.0/888
References page VI-159
TABLE 3. cont'd Density (g/cm3)
Unit cell parameters Polymer
Cryst syst.
Space group
- , m-methyl- , -, isotactic (118.18)
Tet
-, o-methyl- , - , isotactic (118.18) - , - , /7-fluoro- , - , - , isotactic (136.17) -, p-methyl-, -, isotactic (118.18) - , - , syndiotactic I.
a
b
c
Angles
z
S4-1
19.81
19.81
44
Tet
C4-5 orS4-2
19.9
19.9
21.74 57.1 78.9 57.0
Tet
C4v-12
19.01
19.01
8.10
16
Crystal.
Amorph."
1.012
1.073
12.9
1.04/67
~7.8
Heat of fusion kj/mol*
Chain conform. (n*p/q) Refs.
215 215/74
2*11/3 2*29/8 2*40/ 11
80 163 431 103
360/74
2*4/1
125
360/75
2*4/1
67
205/1402
2*
1.005
8.05
II. ~7.8 III. Ortho D2h-16 13.36 23.21 5.12 IV. ~5.1 (mesomorphic) V. ~5.1 -, trimethylsilyl-, - , isotactic (176.34) 60.4 Poly[4,4 '-(terephthaloyldiamino)-diphenylene pyromellitimide] (528.48) Mono C2h-5 8.64 5.18 25.38 Poly [4,4' -(terephthaloy ldiamino)-dipheny lene p-pheny leneditrimellitatediimide] (768.69) 37.63 Poly(p-terphenylene pyromellitimide) (442.43) 20.9 8.58 5.48 20.9 Poly(2,2 ':5 ',2 "-terthiophene) - , 3,3"-dioctyl(470.79) Ortho 14.7 4.33 23.55 Poly (4,4' -thiodiphenylene p-pheny leneditrimellitatediimide) (638.61) Ortho 6.61 8.02 53.6 Poly(4,4 '-thiodiphenylene pyromellitimide) (398.39) 29.4 Ortho 8.57 6.37 61.5 Poly(2,5-thiophene) (82.12) Ortho 7.80 5.55 8.03 Mono 7.83 5.55 8.20 7.79 5.53 7.7 Ortho 7.80 5.55 8.03 -, 3-decyla Mono 22.32 16.76 7.77 (222.39) (at 12O0C) Mono 22.08 16.72 7.76 p Mono C2-2 22.36 17.40 7.77 Ortho 23.9 3.8 15.6 Mono 51.9 7.74 7.8* (at 173K) Mono C2-2 22.54 17.17 7.749 (at 12O0C) Mono 21.54 17.17 7.750 -, 3-dodecyl1.(250.44) Ortho 25.83 7.75 7.77 Ortho 51.9 7.74 8.0 Ortho 21.71 3.97 7.8 II. Mono 19.8 9.37 8.07 - , 3-hexadecyl(306.55) Ortho 24.74 4.21 7.8
Melting point (°C)fl
180/1472 173/1372 200/1472 8
0.977
103 1471
4*1/1
1471 1471 1471 1471
284 (3 = 90
2
1.545
103 23*2/1
1191
34*2/1
1191 908 928
2
1.495
19*1/1
2
1.04
9*2/1
1486
4
1.493
27*2/1
808
8
1.576
16*4/1
908 1013
4 4 4 4
1.569 1.539 1.64 1.569
3*2/1 3*2/1 3*2/1 3*2/1
1276 1276 1336 1448
7 = 95.5
8
1.021
3*2/1
1630
7 = 95.6 7 = 90.5 7 = 86 = 90.3 7 = 90.3
8 8 4 9 8 8
1.036 0.977 1.042 0.94 0.985 1.0310
3*2/1 3*2/1 3*4/1 3*2/1 3*2/1 3*2/1
1630 1447 1482 1487 1447 1630
7 = 77
4 8 2 4
1.069 1.04 1.24 1/140
3*2/1 3*2/1 3*2/1 3*2/1
1479 1481 1483 1623
2
1.25
3*2/1
1483
/3 = 96
7
TABLE 3. cont'6 Density (g/cm3)
Unit cell parameters Polymer -, 3-hexyl(166.28)
Cryst syst.
Space group
Ortho Ortho
a
b
c
16.63 33.6
7.75 7.66
37.25
23.15
19
19
Angles
Amorph."
Melting point (°C)fl
Heat of fusion kj/molfl
Chain conform. (n*p/q) Refs.
z
Crystal.
7.77 7.7
4 8
1.069 1.11
3*2/1 3*2/1
1479 1481
7.77
24
1.932
3*2/1
1480
22
1.63
6*11/1
1259
8 2 2 8 4
1.06 1.32 1.063 1.03 1.166
3*2/1 3*2/1 3*2/1 3*2/1 3*2/1
1481 1483 1486 1487 1623
-, - , iodine doped Ortho -, 3-methyl- (with 50% CF3SO3-) (96.15) Hex -, 3-octyl1.(194.34) Ortho Ortho Ortho Mono II. Mono - , 3-phenyl-, -, 4'-octyl(270.43) Ortho -, 3-tetradecyl(278.50) Ortho Poly(tridecamethylene pyromellitimide) (396.49) Poly(undecamethylene pyromellitimide) (368.43) Poly(N-vinyl carbazole) (193.25) Hex Hex Ortho Phex Rho PoIy(I-vinyl naphthalene) (154.21) Tet C4v-12 Poly(2-vinylpyridine) (105.14) Rho C3-2 Poly(/?-xylylene) a Mono (104.15) Ortho Mono Mono
12.2
41.3 17.40 20.3 42.0 15.3
7.63 3.61 3.81 7.67 9.43
7.7 7.8 7.85 7.8 8.07
28.4
5.06
7.44
2
0.840
3*2/1
1637
24.73
3.82
7.8
2
1.26
3*2/1
1483
7 = 87 7 = 72
39.2
263
1395
32.0
292
1395
12.30 12.00 21.6 12.3 12.00
12.30 12.00 12.5 12.3 12.00
7.44 6.47 7.44
0.988 1.193 0.958
6.39
3 3 6 3 3
21.20
21.20
8.10
16
1.125
15.49
15.49
6.7 6.56
9
1.153
11.68 21.3 5.92 5.9
6.10 33.6 10.64 10.64
9.16 6.58 6.55 6.55
4 31 2 2
1.086 1.138 1.179 1.19
> 320/228
2*3/1 2*3/1 2*3/1 2*3/1 2*3/1
126 825 1010 607 813
360/75
2*4/1
122
2*3/1
185 861
425/142 30.2/82 6*2/1 420/219 6*1/1 375/82 6*1/1 435/1187 6*1/1
223 426 595 1181
1.208
212
/3=102.5 /3=134.7 /3=135
1.05
400/395 440/546 P
- , chloro(138.60) -, ethyl(132.21) - , isopropyl(146.23) a b
Mono Rho Hex
8.10 20.52 20.52
5.25 20.52 20.52
6.53 6.55 6.58 6.55
/3 = 95
Tri Mono
5.92 5.9
12.8 12.8
6.55 6.55
Mono
5.9
13.4
Mono
5.9
14.1
C3-1
2 16 16
1.250 1.158 1.153
90,90,135 /3=135
2 2
1.312 1.32
6.55
/3=135
2
1.20
6.55
/3=135
2
1.26
6*1/1 6*1/1 6*1/1
223 1011 426 224
290/395
6*1/1 6*1/1
1012 1181
170/395
6*1/1
1181
6*1/1
1181
420 412
The number after the solidus (/) are reference citations. The unit cell parameter assignment has been changed from that published so as to make c the fiber axis.
References page VI-159
TABLE 4. POLY(DIENES) AND POLY(DIYNES) Density (g/cm3)
Unit cell parameters Polymer
Cryst syst.
1,4-Poly(2,3-azabutadiene) - , 1,4-diethyltrans(112.18) 1,2-Poly( 1,3-butadiene) syndiotactic (54.09) Ortho isotactic Rho 1,4-Poly( 1,3-butadiene) transI. Phex (54.09) Mono
Space group
a
b
c
Angles
z
Crystal.
Amorph.fl
Heat of fusion kj/molfl
4.72
D2h-ll
10.98
D3d-6
17.3
C2h-5
6.60 17.3
Phex Hex
Chain conform. (n*p/q) Refs.
4*1/1
1504
5.14
4
0.964
154
4*1/1
7
6.5
18
0.96
120
2*3/1
12
1 4
1.03 1.036
1 1
0.930 0.908
100/352 96/451 55/624 141/352 148/44 145/451 142/624
10.0/352 4*1/1 13.8/4514*1/1 6.31/624 4.61/352 4*1/1 5.99/342 4*1/1 4.61/451 3.62/624
37 496 1195 154 550
8 4
0.821 1.011
6.3/335 1 12/1121
9.2/353 8*1/1
60 124 1195
4*11/3
367
4.54 8.63
4.54 9.11
4.9 4.83
4.88 4.95
4.88 4.95
4.68 4.66
8.53 4.60
8.16 9.50
12.66 8.60
/3=114
0.891 II. (>65°C)
Melting point (0C)"
cisMono Mono or - , 2-tert-butylcis(110.20) Tri - , chlorinated c/s-threo-disyndiotactic (125.00) Mono ?ra«s-erythro-diisotactic Mono - , 2-chloro- [chloroprene] trans(88.54) Ortho Ortho cis-
C2h-5 Cs-4 C2h-6
/2 = 83.33 /3=109
0.902
13.95
20.78
15.3
C2h-4
7.37
5.30
10.10
C2h-5
7.05
8.05
5.10
D2-4
8.84 9.0
10.24 8.23
4.79 4.79
22
0.908
106
/3=134
2
1.463
4*2/1
768
/3=100
2
1.456
4*1/1
768
4 4
1.356 1.658
4*1/1 4*1/1
40 109
4*1/1
275
4*1/1 4*1/1
221 565 699
115/229 80/81
8.37/81
70/1157 - , 1-cyano trans(79.10) - , 2,3-dichlorotransI. (122.98) Mono II. Ortho - , - , thiourea complex Mono Mono - , 2,3-dimethyltrans(82.15) Ortho cis-
4.8
C2h-5 C2v-9
5.34 8.81
9.95 12.34
4.86 4.80 4.80
/3 = 93.5
C2Hh5 C2h-5
9.87 9.91
15.83 15.85
12.53 12.5
/3=114.1 /3=114.1
C2v-9
9.13
13.00
4.35 4.70
2 4
1.604 1.565 1.44 1.44
4
565 803
260 272/221
0.978
7.0 - , - , thiourea complex Mono - , 2-methyl- [isoprene] transot (68.12) Mono
C2h-5
10.40
15.47
12.5
C2h-5
7.98
6.29
8.70 8.76 8.77
D2-4
7.78 7.85
11.78 11.9
4.72 4.8*
4*1/1
198 /3=114.4
(3 = 102
220
1.22
4
1.051
4 4
1.046 1.009
803
80/1121
13/1121 4*2/1 10/1128
65/46 64/81
8.0/1128 4*1/1 10.6/287 4*1/1
0.905 P(LM)
Ortho Ortho
104 699
288 502 715 1127 40 288
TABLE 4.
cont'd Density (g/cm3)
Unit cell parameters Polymer
Cryst syst.
Space group
Ortho
a
b
7.83
11.87
c
Angles
4.75
z
Crystal.
4
1.025
Amorph.a
0.906
8(HM)
Mono
e cisMono
C2h-5
Ortho Mono Ortho
D2h-15
-, -, 3-chlorotrans(102.56) -, - , hydrochlorinated (104.58) Port C2h-5 Ortho -, 2-methylacetoxytrans(126.15) Ortho -, perhydrotriphenylene complex trans2 phtp/monomer Hex C6h-2 cis-, 2-propyltrans(96.17)
5.9 7.84
7.9 5.99
9.2
7 = 94
4 4
1.06
7.80
6.29
12.46 25.2
8.89 8.97
8.10 8.20*
/3 = 92
8 16
1.009 0.976
26.3 12.4
8.9 8.9
8.15* 8.15*
7=109.5
16 8
1.01 1.101
Melting point (°C)a
Heat of fusion kj/mola
82/287 78/630 78/568 80/1170 74/81 80/287 87/568 89/1170
12.7/81
Chain conform. (n*p/q) Refs. 4*1/1
502 1195
4*2/1
502 492
492 0.906/53 0.910/47
28/81 36/50 14/287 36/1169
4.9 5.83 11.9
10.38 10.4
8.95 9.1*
16.2
9.3
14.26
/3 = 90
4.40/81 8*1/1 4.6/1195 8*1/1 8*1/1
40 288 124 1019 1019
4*1/1
165
4 8
1.282 1.23
115 110
4*2/1 4*2/1
229 70
4.75
4
1.17
135
4*1/1
165
14.26
4.78
1
1.079
183/1124
10.95
6.65
9.2
4
0.95
42 42/368
8.22
8.22
11.01
23.12 20.8
7.87 8.0
9.69 9.7
13.25
7.63
9.17
9.92
5.33 53.86
54.36 10.98
4.88 4.880
18.30 18.13 19.93 18.9
10.78 10.81 9.58 10.89
4.89* 4.89* 4.83* 4.83*
7= 7= 7= 7=
39.03 39.16 6.11 6.02
798
8*1/1
368
- , urea complex Hex D6-2 1,4-Poly( 1,3-butadiyne) - , 1,4-(4,4 '-diphenyleneglutarate)(330.34) Mono C2h-6 Mono C2h-6 Poly(chloroprene), see Poly(butadiene), 2-chloro1,12-PoIy(U 1-dodecadiyne) macromonomer Mono C2h-5 (160.26) cross-polymer Mono C2h-5 5,8-Poly(5,7-dodecadiynediol) - , l,12-bisOV-butoxycarbonyl)methylurethane(508.61) Ortho D2-3 -,1,12-bis(ethylurethane)(336.43) Mono C2h-5 Mono (hi temp) Mono C2h-5 Mono -,1,12-bis(phenylurethane)(432.52) Mono C2h-5 Mono C2h-5 -, l,12-bis(p-toluylsulfonyl)(502.64) Tri Ci-I (HOK) Tri Ci-I 10,13-Poly(10,12-heptacosadiynoic acid) (as Li salt) (400.65)
6.229 6.205 20.13 20.01 65
827
/3 = 111.29 /3=106
4 4
1.336 1.41
4*2/1 4*2/1
948 913
14.15*
7=118.5
4
0.847
12*1/1
12.2
7=123.5
4
1.146
2 4
1.195 1.170
4*1/1 4*1/1
1319 1329
95 94 91 91
2 2 2 2
1.163 1.169 1.212 1.124
4*1/1 4*1/1 4*1/1 4*1/1
1318 1320 1318 1320
4.909 4.90*
/3=106.85 /3=106.42
2 2
1.258 1.259
4*1/1 4*1/1
95 1353
4.91 4.91
95,94,89 95,94,89
1 1
1.391 1.420
4*1/1 4*1/1
381 381
1022 1022
1268
References page VI-159
TABLE 4. cont'd Density (g/cm3)
Unit cell parameters Polymer
Cryst syst.
1,4-PoIy(1,3-heptadiene) transisotactic (96.17) Mono - , 6-methyltransisotactic (110.20) 1,4-PoIy (1,3-hexadiene) transisotactic (82.15) Ortho --, 5-methyltransisotactic (96.17) 2,5-Poly(2,4-hexadiene) frajw-erythro-diisotactic (82.15) - , 2,5-dimethyltrans(110.20)
Space group
a
b
c
Angles
z
Crystal.
C2-2
8.62
7.95
4.85
/9 = 99
2
0.973
2,5-Poly(2,4-hexadienedioic acid) tazns-erythro-diisotactic - , diisopropyl ester (226.27) Ortho 2,5-Poly(2,4-hexadienoic acid) /rans-erythro-diisotactic - , 6-amino0.5 CdCl4/unit Tri Ci-I (254.25) Tri Ci-I - , - , hydrochloride (163.60) - , butyl ester (168.24) Ortho - , ethyl ester (140.18) - , isoamyl ester (182.26) - , isobutyl ester (168.24) - , isopropyl ester (154.21) - , methyl ester (126.16) frans-threo-diisotactic -methyl ester (126.16) 2,5-Poly(2,4-hexadiyne) - , l,6-di(AT-carbazoyl)(408.50) Mono Mono Mono - , - , hexabromoMono 2,5-Poly(2,4-hexadiynediol) (50mrad) Mono (" annld) Mono (110.11) Mono - , l,6-bis(ethylurethane)(252.27) Mono
C2h-5 C2h-5 C2h-5
C2h-5 C2h-5
C2h-5
14.02
14.16
9.67* 7.214
8.02
Heat of fusion kj/molfl
Chain conform. (n*p/q) Refs.
85/371
4*1/1
375
119
4*1/1
371
82/371
4*1/1
274
4.85
88
4*1/1
371
2.3
84
2*1/1
525
4.8
265 265/376
4*1/1
183
4.85
D2-4
Amorph."
Melting point (°C)a
4.85
10.28
9.70
10.70 7.245
17.79 18.59
4
93,90,90 104,97,96
1.000
4
1.064
230/420
8*1/1
420
8 4
1.838 1.823
347
4*2/1 8*1/1
1123 1188
334 11.36
9.70
4.80
2
4*1/1
384
4.80
4*1/1
384
4.80
4*1/1
384
4.80
4*1/1
384
4.80
4*1/1
384
4.80 4.8
4*1/1 4*1/1
384 1208
9.4
4*2/1
1208
4*1/1 4*1/1 4*1/1
951 611 830
4*1/1
1503
13.03 12.82 12.87
17.55 17.33 17.40
4.92* 4.886* 4.907*
7=108.7 7=108.3 7 = 108.3
14.21
20.67
4.75*
7=106.8
15.78 16.05 16.09
4.703 4.819 4.793
/3=110.34 /3=106.08 /3=106.4
2 2 2
1.258 1.196 1.203
4*1/1 4*1/1 4*1/1
903 903 904
17.96
4.88
7 = 98.42
4
1.277
4*1/1
1240
4.176 4.115 4.109 15.14
2 2 2
1.056
1123
1.273 1.316 1.300
TABLE 4. cont'd Density (g/cm3)
Unit cell parameters Polymer
Cryst syst.
Space group
- , l,6-bis(phenylsulfonyl)- , - , di-/?-fluoro(426.41) Mono C2h-5 Mono C2h-5 Mono C2h-5 - , - , di-/?-methoxy(450.48) Tri Ci-I - , l,6-bis(phenylurethane)1.(348.36) Tri Ci-I (5 dioxane/unit) II. III. - , 1,6-bis-(/?-toluylsulfonyl)1.(418.48) Mono C2h-5 Mono C2h-5 Mono C2h-5 II. (120K) Mono C2h-5 - , 1 -(p-toluylsulfonyl)-6-(/7-fluorophenylsulfonyl)1.(422.44) Mono II. (143K) Mono Poly(isoprene), see Poly(butadiene), 2-methyl10, 13-Poly(10,12-nonacosadiynoic acid) (as Li salt) Ortho (428.70) 1,9-Poly( 1,8-nonadiyne) macromonomer Mono C2-2 (118.18) cross-polymer Mono C2h-5 1,4-PoIy (1,3-octadiene) transisotactic (110.20) 2,5-Poly(2,4,6-octatriynediol) (134.14) Mono C2h-5 - , l,8-bis(phenylurethane)(372.38) Mono C2h-5 10,13-Poly(10,12-pentacosadiynoic acid) (as Li salt) (372.59) 1,2-PoIy (1,3-pentadiene) transsyndiotactic (68.12) - , 4-methylisotactic II. Tet D2d-10 (82.15) syndiotactic I. II. 1,4-Poly( 1,3-pentadiene) transisotactic (68.12) Ortho Ortho D2-4 cisisotactic Ortho D2-4
a
b
13.93 13.89 13.96
14.06 14.10 14.10
12.72 16.78
8.543 12.53
Melting point (°C)a
Heat of fusion kj/mola
Chain conform. (n*p/q) Refs.
— Angles
z
Crystal.
4.90* 4.91* 4.914*
7=113.3 7=113.2 7 = 113.56
2 2 2
1.606 1.602 1.597
4*1/1 4*1/1 4*1/1
1378 1379 1380
4.902*
110,103,79
1
1.542
4*1/1
1021
4.89* 4.9 4.9 4.9
84,83,69
2
1.340
4*1/1 4*1/1 4*1/1
716 749 749 749
35/1020 4*1/1 4*1/1 4*1/1 4*1/1
898 1277 1381 899
c
Amorph."
14.49 14.53 14.91 14.93
14.94 14.96 14.48 25.56
4.910* 4.912* 4.93 4.910*
7 =118.14 7=118.21 7=118.0 7 = 92
2 2 2 4
1.482 1.477 1.479 1.484
14.22 14.10
14.52 14.43
4.909* 4.906*
7=116.1 7=116.3
2 2
1.541 1.566
4*1/1 4*1/1
1337 1337
4
1.04
4*1/1
1268
7 = 90.8
4
0.837
9*2/1
1023
/9=101.71
4
1.016
9*2/1
1023
4*1/1
371
70
7.88 9.30
8.11
4.89
5.67
21.00*
17.5
4.85
4.85
102/1020
87
4.11
19.59
4.80
(3 = 109
2
1.219
4*1/1
780
24.65
30.74
4.89
(3 = 92.2
8
1.336
4*1/1
780
60
1268
5.1
17.80
17.80
36.50
72
0.849
10
4*1/1
230
167/707
2*18/5
488
12*1/1 4*1/1
1502 1502
11.73 5.05
19.73 19.80
4.85 4.86
4.8 4.85
4 4
0.98 0.969
9.47
5.97
8.15 8.15
4
0.982
95 104/1126
4*1/1 4*1/1
189 200
44
4*2/1 4*2/1
844 263
53
8*1/1 8*1/1
1431 234
syndiotactic Mono
C2h-5
6.34
9.12
8.50 8.50
/3=
105.9
4
0.957
References page VI-159
TABLE 4. cont'd Density (g/cm3)
Unit cell parameters Polymer - , 2-methyltransisotactic (RT) (82.15) (153K) cisisotactic a (-130) P(RT)
Cryst syst.
Space group
a
Mono
C2h-5
Mono
Ortho Ortho
b
c
12.89
9.186
C2h-5
12.78
9.084
D2h-15 D2-4
10.74 9.30
- , 3-methylcisisotactic (82.15)1. II. syndiotactic II. 1,4-PoIy (1,3-pentadiynol) - , 1-N-carbazoly(245.28) Mono C2h-5 2,5-Poly(5-phenyl-2,4-pentadienoic acid) frans-erythro-diisotactic - , butyl ester (230.31) -methyl ester (188.23) 1,24-Poly( 1,11,13,23-tetracostetrayne) cross-polymer Mono C2h-4 (322.54)
16.49
26.8*
13.04 7.73
19.51
8.254
Angles
z
Crystal.
4.820* /3 = 93.5
4
0.958
4.824* /3 = 93.6
4
0.977
7.87 7.90
8 4
0.990 0.961
Amorph."
Melting point (°C)a
Heat of fusion kj/mola
4*1/1
1317
4*1/1
1317
4*2/1 4*2/1
1364 1364
8.02 6.97
*2/l *3/l
1497 1497
8.6
8*1/1
1501
4*1/1
1354
4.80
4*1/1
384
4.80
4*1/1
384
4.873* 7=124.27
4.91*
7=119.6
4
2
195/1365
Chain conform. (n*p/q) Refs.
175 165 165/1365
1.257
1.136
1264
a
The number after the solidus (/) are reference citations. * The unit cell parameter assignment has been changed from that published so as to make c the fiber axis.
TABLE 5.
POLY(PEPTIDES) -(NH-CHR-COK Density (g/cm3)
Unit cell parameters Polymer Poly(L-alanine) a helix (71.08) P - , phenyla helix (147.18) co helix
Cryst syst.
Space group
a
b
hex
8.55
8.55
Ortho Ortho
4.79 4.734
10.7 10.54
Hex
11.55
11.55
Tet 11.28 Tet 12.86 Poly(p-alanine), see Poly(3-aminopropionic acid) Poly(L-alanyl-D-alanyl-L-alanyl-D-valine) (312.37) Ortho 9.5 Poly(L-alanyl-L-alanylglycine) (200.22) Ortho 9.44 -phenyl- [2nd alanyl] (275.31) Poly(L-alanyl-L-alanylglycyl-L-prolyl-L-prolylglycine) (450.49) Ortho 10.5 Poly(L-alanyl-D-alanyl-L-valyl-D-valine) (340.42) Ortho 9.5
11.28 12.86
31.0 9.96
34.1
c
70.3 6.88 6.89
5.91 5.59
Angles
z
Crystal.
Amorph.a
Melting point (°C)a
Heat of fusion kj/mola
Chain conform. (n*p/q) Refs.
47
1.246
3*47/13
507
4 4
1.339 1.373
3*2/1 3*2/1
507 509
3*18/5
1025
4 4
1.300 1.057
3*4/1 3*4/1
1024 1025
11.0
8
1.281
12*1/1
1046
20.94*
8
1.351
9*2/1
753
15
9*
774
29.5
18*
755
11.0
8
1.269
12*1/1
1046
TABLE 5. cont'd Density (g/cm3)
Unit cell parameters Polymer
Cryst syst.
Space group
a
b
c
Angles
z
Crystal.
Poly(L-alanyl-4-aminobutyric acid) (156.18) Ortho 9.4 9.9 9.2 4 1.21 Poly(L-alanyl-6-aminocaproic acid) (184.24) Ortho 9.4 9.8 11.5* 4 1.16 Poly(L-alanyl-3-aminopropionic acid) (142.16) Ortho 9.4 9.8 16.1* 8 1.27 Poly(L-alanyl-l 1-aminoundecanoic acid) (254.37) Ortho D2-5 4.79 10.35 29.8 4 1.144 Poly(L-alanyl-5-aminovaleric acid) (170.21) Ortho 9.4 10.7 20.7* 8 1.09 Poly(L-alanyl-L-glutamylglycine) - , y-ethyl(285.30) Mono 9.54 8.54 21.36* 7 = 106 4 1.133 Poly(L-alanylglycine) 1.(128.13) Ortho 9.42 8.87 6.95* 4 1.466 Ortho 9.44 8.96 6.94* 4 1.450 II. Ortho 4.72 14.4 9.6 4 1.30 Poly(L-alanylglycyl-L-alanylglycyl-L-alanylglycyl-L-alanylglycyl-L-alanylglycyl-L-alanylglycyl-L-glutamylglycine) (990.98) Ortho 9.64 9.62 48.65 4 1.459 Poly(L-alanylglycyl-L-alanylglyclyl-L-alanylglycyl-L-alanylglycyl-L-alanylglycyl-L-glutamylglycine) (850.84) Ortho 9.57 9.70 41.70 4 1.460 Poly(L-alanylglycyl-L-alanylglycyl-L-alanylglycyl-L-alanylglycyl-L-glutamylglycine) (710.70) Ortho 9.48 10.28 34.75 4 1.394 Poly(L-alanylglycyl-L-alanylglycyl-L-alanylglycyl-L-glutamylglycine) 1.(570.56) Ortho 9.48 17.34 18.8 4 1.226 II. Ortho 9.48 10.60 27.80 4 1.356 Poly(L-alanylglycyl-L-alanylglycyl-L-serylglycine) (400.39) Ortho 9.39 9.05 20.55* 4 1.522 Poly(L-alanylglycyl-L-alanyl-L-prolyglycyl-L-proline) (450.49) Ortho 10.5 29.5 Poly(L-alanylglycylglycine) 11.(185.18) Mono 8.86 22.0 9.42 (3 = 90 9 1.507 (monohydrate) Mono C2-2 11.0 4.8 9.45 /9 = 90 2 1.35 Poly(L-alanylglycylglycylglycine) 11.(242.24) Hex 4.89 4.89 36.60 3 1.592 Poly(L-alanylglycyl-L-proline) dry Hex 11.9 11.9 28.8 10 1.06 wet Hex 11.4 11.4 9.3 3 1.07 (225.25) Poly(L-alanylglycyl-L-prolyl-L-prolyglycyl-L-proline) (476.53) Ortho 10.6 28.7 Poly(L-alanyl-L-prolyglycine) with H 2 O Mono C2-2 8.6 7.2 9.4 (3 = 90 2 1.4 (225.25) Poly(L-alanyl-L-prolylglycyl-L-prolyl-L-prolylglycine) (476.53) Hex 11.9 11.9 29.5 5 1.093 Poly(L-alanyl-D-valine) (170.21) Port 9.7 14.7 6.2 4 1.28 Ortho 9.5 29.4 11.1 16 1.459? Poly(2-aminoisobutyric acid) (85.11) Hex 8.7 8.7 5.96 3 1.08 - , dichloroacetic acid complex (106.60) Hex C3v-6 21.8 21.8 5.95 18 1.301 (1 DCA/6 residues) Poly(L-arginine) - , hydrochloride a helix Hex 14.7 14.7 27.0 18 1.406 (2.5 H2O/residue) (192.65) J3 Mono 9.26 22.05 6.76 7-108.9 4 1.438 (>5 H2O/residue)
Amorph.a
Melting point (°C)a
Heat of fusion kj/mola
Chain conform. (n*p/q) Refs.
8*1/1
969
10*1/1
969
7*2/1
969
15*2/1
1619
9*2/1
969
9*2/1
756
6*1/1 6*1/1 6*2/1
591 754 741
42*1/1
1648
36*1/1
1648
30*1/1
1648
24*1/1 24*1/1
1633 1648
18*
754
18*
755
9*1/1 9*1/1
596 740
12*3/1
740
9*10/3 9*3/1
614 614
18*
755
9*1/1
18*
616
755
6*1/1 6*2/1
1176 1046
3*3/1
967
3*3/1
1053
3*18/
641
3*2/1
641
References page VI-159
TABLE 5. cont'd Density (g/cm3)
Unit cell parameters Polymer
Cryst syst.
Poly(L-aspartic acid) -, P-benzyl© helix Tet (205.21) Tet Tet racemic Ortho -, - , /?-chloroa helix Hex (239.66) Hex ©helix Tet Mono - , - , /7-methyla helix Hex (219.24) ©helix Mono - , a-n-butyl1.(171.20) Hex Phex II. Tet - , a-ethyl- , - , 2-methoxy(173.17) Phex - , P-ethyl-, -, 2-phenyla helix Tet (219.24) P Ortho 71 helix Ortho >200°C Hex ? Hex -, a-isobutyl1.(171.20) Ortho Hex II. Tet Tet - , P-n-propyl P Mono (157.17) - , - , 3-phenyl(232.26) Hex (at 1400C) Ortho Poly(L-cysteine) - , s-benzyloxycarbonylP I. Ortho (237.27) II. Ortho - , 5-benzylthio© helix Tet (225.32) Poly(2,4-diaminobutyric acid) - , Af-benzyloxycarbonyl(234.26) Rho Poly(D-glutamic acid) -, y-benzyl- , -, chlorometa Phex (253.68) ortho Phex para Ortho Hex
Space group
5.30 5.42 5.3 5.68
4 4 4 2
1.341 1.320 1.34 1.310
3*4/1 3*4/1 3*4/1 3*2/1
582 703 837 1026
14.9 14.8 23.3 13.4
27.0 27 5.20 5.2
18 4 8 18
1.380 1.40 1.128 1.41
3*18/5 3*18/5 3*4/1 3*4/1
606 1505 606 1505
14.9
14.9
27
4
1.26
3*18/5
1505
16.6
13.4
5.28
7 = 108
4
1.304
3*4/1
1505
C2-2 C4-2
13.5 13.45 14.15
13.5 13.45 14.15
19.9 20.6 4.90
7=120
13 13 4
1.177 1.145 1.338
4*13/4 4*13/4 4*4/1
1507 1508 1508
C2-2
12.40
12.40
20.74
7 = 120
13
1.354
4*13/4
1508
13.2
13.2
27.0
18
1.393
3*18/5
1027
17.7 20.3 17.1 23.4
4.76 11.7 17.1 23.4
6.83 19.89 19.89
2 17 17
1.265 1.310 1.229
3*2/1 3*17/4 3*17/4
1027 1028 1028 1027
13.5 13.5 14.0 13.98
23.4 13.5 14.0 13.98
19.9 19.9 4.95 4.94
26 13 4 4
1.176 1.177 1.172 1.178
4*13/4 4*13/4 4*4/1 4*4/1
1312 1506 1312 1506
9.57
25.08
8
1.288
3*2/1
579
7 14
1.220 1.141
3*7/2 3*7/2
1628 1628
C2-2
13.85 13.80 13.88 21.4
13.85 13.80 13.88 4.28
14.9 14.8 23.3 16.4
15.6 28.0
C4-2
15.6 16.1
c
6.79b
Angles
7 = 99
7 = 96
10.5 10.5
Amorph."
Chain conform. (n*p/q) Refs.
Crystal.
D4-4
b
Heat of fusion kj/mola
z
D6-3
a
Melting point (0C)a
286/1310
4.76
32.4
6.95*
4
1.470
3*2/1
578
4.89
32.8
6.89*
4
1.426
3*2/1
578
14.28
14.28
5.55
4
1.322
3*4/1
1029
27.5
27.5
27.0
56
1.232
3*18/5
720
15.30
15.30
26.99
7 = 60.23
18
1.382
3*18/5
932
15.07 15.24 15.24
15.07 26.40 15.24
27.15 10.68 10.67
7 = 60.03
18 14 7
1.420 1.372 1.374
3*18/5 3*7/2 3*7/2
932 932 1033
TABLE 5. cont'd Density (g/cm3)
Unit cell parameters Polymer -, y-rt-hexyla helix (213.27) - , y-methyla helix (143.14) P
Cryst syst.
a
b
Hex
15.89
15.89
Hex
12.0
12.0
Ortho
Poly(L-glutamic acid) P I. Mono (129.12) Mono II. Mono Ortho -, y-w-amyl(199.25) Hex Hex -, y-benzyla helix A. Mono (219.24) Hex B. Tri Mono Mono (dry) Ortho Mono C. Hex (racemic) Hex Mono Hex D. Hex E. Hex single crystal Mono racemic mixture I. Ortho II. Mono -, -, chlorometa Hex (racemic) Hex (253.68) ortho Ortho (racemic) Hex para Ortho (racemic) Ortho - , y-w-butyl(185.22) Phex (at 1000C) Ortho -, y-calcium P (wet) Mono -, y-w-dodecyl(297.44) Hex -, y-ethyla helix I. Phex (157.17) Phex T. III. H. -, -, 2-chloro(191.61) -, -, 2-phenyl(233.27)
Space group
C2-2
c
Angles
27
9.49 9.44
19.09 23.37
7.07 6.81
9.66 9.79 9.75 4.95
9.10 9.35 8.06 15.6
6.98* 6.82* 6.84* 6.90
7 = 90
7=105 7=105 7 =104
Crystal.
18
1.08
Amorph."
Heat of fusion kj/mola
Chain conform. (n*p/q) Refs. 3*18/5
859
3*18/5
1162
8 8
1.484 1.266
3*2/1
954 812
4 4 4 4
1.447 1.422 1.644 1.610
3*2/1 3*2/1 3*2/1 3*2/1
585 966 966 836
18 18
1.12 1.13
3*18/5 3*18/5
1040 1279
3*18/5 3*18/5 3*18/5 3*18/5 3*18/5 *43/12 3*18/5 3*18/5 * 71/20 3*18/5 3*7/2 3*7/ 3*7/2
1030 952 587 702 952 757 1030 584 584 1030 1030 953 1030 926
15.1 15
15.1 15
15.3 30 15.25 25.2 15.88 14.76 29.06 14.95 14.95 15.05 14.8 39.05 64.36 5.52
14.6 30 15.25 15.0 13.00 25.40 13.20 14.95 14.95 14.78 14.8 39.05 64.36 5.11
24.4 25.6
15.4 15.6
15.50 15.49
15.50 15.49
27.10 26.84
18 18
1.345 1.360
3*18/5 3*18/5
1032 1035
26.50 15.24 15.24 15.12
30.60 15.24 26.40 26.09
27.02 27.23 10.67 10.72
72 18 14 14
1.384 1.384 1.374 1.394
3*18/5 3*18/5 3*7/2 3*7/2
1032 1034 1032 932
14.1 25.4
14.1 14.66
(27) 27
18 36
1.13 1.101
3*18/5 3*18/5
1040 1040
9.40
12.82
27.6
27.6
12.5 12.16
12.5 12.16
Tet Phex Ortho
11.72 12.9 22.95
11.72 12.9 13.25
Phex
11.7
11.7
Hex Ortho
15.60 15.38
15.60 26.65
(27) 27
z
Melting point (0C)*
7=121.7 27.0 26.8 27.1 64.11 27.27 27.1 106 27 10.50 10.58 10.5 22.25
84,84,122 7=122.5 7=113.7 (3 = 96 = 56
7
7 = 119.4
/3 = 97.8
72 18 30 18 86 36 18 71 18 7 49 2
1.257 1.278 1.279 1.303 1.260 1.305 1.260 1.252 1.279 1.277 1.285 1.171
1031 1031
7=107.7
6.83*
7 = 114
7=100.3
585 1292
27.0 108.9 16.4 108.9 108.9 108.9 16.56 (27) 54.4
7=110 7=109.5
18 73
1.18 1.255 1.274 1.25 1.151
3*18/5 *73/20 3*11/3 3*73/20 3*73/20 3*73/20
826 955 1036 955 955 955
7=123
73 73
7=118.7
11
1.760
3*11/3
1036
72
1.225 1.251
3*18/5 3*18/5
1038 1039
References page VI-159
TABLE 5. cont'd Density (g/cm3)
Unit cell parameters Polymer
Cryst syst.
Space group
a
b
c
Angles
z
Crystal.
Amorph.a
Melting point (°C)a
Heat of fusion kj/mola
Chain conform. (n*p/q) Refs.
- , y-n-hexyl-
(213.28)
Hex Hex
15.8 15.5
15.8 15.5
27 27
18 18
1.09 1.14
3*18/5 1040 3*18/5 1279
11.96 11.95 11.79
11.96 27.0 11.79
27.5
11.95 11.82 11.58
20.70 11.82 11.58
18 18 18 65 58 69 18
1.256 1.281 1.321 (1.284) 1.290 1.316 1.399
3*18/5 3*18/5 3*18/5 * 65/18 3*29/8 * 69/19 3*18/5
588 576 858 583 589 1204 1650
12.75 12.75 21.27 4.725 4.70
12.75 12.75 21.27
18 18
1.282 1.287 1.210
21
4
1.410
3*18/5 3*18/5 117/32 3*2/1 3*2/1
1293 1338 1204 702 1037
27.6 23.9
27.6 24.9
27
72 72
1.248
3*18/5 3*18/5
1041 1041
17.1
17.1
27
18
1.06
3*18/5
1279
14.4 24.6 24.3
14.4 14.2 24.3
(27) 60.0 60.0
18 80 120
1.19 1.085 1.112
3*18/5 * 40/11 *40/ll
1040 1040 1533
16.30
16.30
(27)
18
1.190
3*18/5
1038
15.9
15.9
-, y-methyla helix (143.14)
Hex Hex Hex
11.95
Ortho Hex Hex precursor to a (3 chloroform/18 mers) Hex Hex (at 17O0C) Rho P Ortho - , - , dimethyl phthalate complex 25% Hex extracted Phex - , y-n-octyl(241.33) Hex - , y-ft-propyl(171.20) Phex (at 1500C) Ortho Rho - , - , 3-phenyl(247.29) Hex - , y-sodium a helix Hex (hydrated) P (wet) Port Poly(L-glutamine) - , Af5-(4-hydroxybutyl)(200.24) Ortho - , //5-(2-hydroxyethyl)(172.18) Ptet - , N5-(3-hydroxypropyl)(186.21) Ortho Poly(D-glutamyl-L-glutamic acid) - , y-benzyla helix Hex (219.24) Hex Hex P Hex Ortho co helix Ortho Ortho Tc helix Hex Hex Ti-Ti 5.6 Hex Tt-Tt 7.2 Hex Tt-Tt 9.0 Mono Tt-Tt 10.8 Mono - , y-ethyl- , - , 2-phenyla helix Hex (233.27) Hex P Hex Tt helix Hex Poly(glycine) 1.(57.05) Mono C2h-5
14.4
7.0*
26.9 97.26 43.2 103.0 26.33 27.0 26.9 176.0 6.83 6.83
7 = 121.4
7 = 130
794 4.7
794
14.8
12.4
60.4
40
1.200
3*40/11
935
12.1
12.1
27
18
1.30
3*18/5
968
14.6
12.3
43.2
29
1.156
3*29/8
924
15.2 14.9 26.0 22.9 9.52 27 26.92 27.1 17.0 17.0 18.2 22.6 25.3 26.4
15.2 14.9 26.0 22.9 22.5 15.8 15.54 15.5 17.0 17.0 18.2 22.6 24.4 25.6
28 26.6 32.4 9.46
19 18 66 16
1.235 1.281 1.267 1.356
3*19/5 6*9/5 6*11/6 6*1/1
5.40 5.40 25.6 25.6 56.3 53.1 20.2 50.0
8 8 22 22 56 72 36
1.289 1.284 1.250 1.250 1.262 1.116 1.180 1.318
6*2/1 6*2/1 6*11/5 6*11/5 6*14/5 6*18/5 6*9/2 6*27/5
885 1042 1272 1042 1215 885 1042 1272 885 1272 1214 1214 1214 1214
15.9 27.5 24.2 17.6
15.9 27.5 24.2 17.6
26.5 32.4 4.75 25.7
18 66 8 22
1.204 1.205 1.286 1.236
6*9/5 6*11/6 6*1/1 6*11/5
1042 1272 1042 1272
2 4
1.30 1.669
3*2/1 3*2/1
581 1239
4.77 9.54
4.77 3.67
7.0 7.044*
7=117 7=118
7-66 7 = 113
365/795
TABLE 5.
cont'd Density (g/cm3)
Unit cell parameters Polymer
Cryst syst.
Space group
a
II. Hex C3-2 4.8 Poly(glycyl-6-aminocaproic acid) 1.(170.21) Hex 4.79 II. Mono 4.76 Poly(glycyl-12-aminododecanoic acid) 11.(254.37) Hex 4.79 Poly(glycyl-3-aminopropionic acid) 1.(128.13) Ortho 9.51 II. Hex 4.79 Poly(glycyl-3-aminopropionic acid-3-aminopropionic acid) (199.21) Hex 4.79 Poly(glycyl-11-aminoundecanoic acid) 1.(240.35) Ortho 9.60 II. Hex 4.79 Poly(glycylglycyl-L-proline) with H 2 O Mono C2-2 12.2 w/formicacid Mono C2-2 13.5 (211.22) Poly(glycylprolylhydroxyproline) (267.28) Hex 13.7 Poly(glycyl-L-prolyl-L-proline) dry Hex 12.5 (251.29) - , a-phenyl-(glycyl) (327.38) Ortho D2-4 14.3 Poly(L-histidine) -, 1-benzyl(227.27) Phex 17.4 - , hydrochloride (1 H2O/residue) Mono 14.95 (190.61) Poly(L-isoleucine) P Ortho 4.80 (113.16) Ortho 4.8 Poly(L-leucine) a helix Hex 13.22 (113.16) p Ortho 4.80 Poly(L-lysine) a helix Hex 19.55 (128.18) P Ortho 9.44 - , Zs-benzyloxycarbonyla helix Hex 16.69 (262.31) - , hydrobromide (1.4 H2O/residue) Ortho D2-3 9.52 (234.31) -, hydrochloride a helix Hex 16.80 >84%RH (164.64) P dry Ortho 4.62 65% RH Ortho 4.71 Poly(L-lysyl-L-lysyl-L-valine) a helix Hex 15.87 (355.48) P Ortho 9.35 (with 2HC1) - , di-benzyloxycarbonylP Ortho 9.38 (623.75)
b
c
4.8
9.3
4.79
35.1 3.96
4.79 15.20 4.79 4.79
Angles
16.95* 22.2 35.2
z
Crystal.
3
1.53
3
1.216
276/1524
10*3/1
1311 1311
6
1.131
230/1524
6*16/1
1512
16 3
1.389 1.447
7*2/1 7*3/1
1294 1294
3
1.419
11*3/4
1313
15*2/1 15*
1391 1391
37.5* 4.79 9.3 9.3
13.7
Heat of Chain fusion conform. kj/mol" (n*p/q) Refs. 3*3/1
/?=113
112.8
4.9 4.9
Amorph.a
Melting point (0C)"
2 2
1.4
9*1/1 9*1/1
615 615
28.2
10
0.97
9*10/
612
12.5
28.7
10
1.07
9*10/
613
13.5
9.4
4
1.198
9*1/1
965
17.4
27.0
7=130
18
1.085
3*18/5
719
14.95
45.0
7=116.5
45
1.582
3*15/4
1295
4 4
1.018 1.032
3*2/1 3*2/1
806 1025
22.36 23
6.88 6.6
/? = 90 /? = 94
273
13.22 23.56
6.88
4
0.966
19.55
3*
806
3*2/1
806
3*
586
17.16
6.8b
6
1.16
3*2/1
586
16.69
26.90
18
1.208
3*18/5
577
16.44
6.80
4
1.46
3*2/1
923
16.80
15.20 16.67
666
6.66 6.66
4 4
2.338
15.87
666 666 9*
1047
15.04
20.88
4
0.969
9*2/1
1047
28.24
20.22
8
1.547
9*2/1
1048
References page VI-159
TABLE 5. cont'd Density (g/cm3)
Unit cell parameters Polymer
Cryst syst.
Poly(L-methionine) a helix Hex (131.19) Poly(D-methionyl-L-methionine) P Mono (131.19) Poly(L-ornithine) -, iV-benzoyla helix Hex (218.26) -, -, /7-bromoco helix Ortho 8297.15* -, -, /7-chloroo) helix Ortho (252.70) -, -, />-fluoroco helix Ortho (236.25) - , iV-benzyloxycarbonyl1.(248.28) Mono Phex Hex II. Ortho Tet III. Ortho -, hydrobromide a helix Hex (>86% RH) P (wet) Ortho (to 85% RH) Poly(L-proline) 1.(97.12) Hex II. Rho Rho Rho -, acid complexes -,acetic Tet -,formic Tet • - , propionic Tet highly solvated Ortho - , hydroxyA. (113.12) Hex B. >66%RH Phex - , - , O-acetyl11.(155.15) Hex Poly(L-serine) -, O-acetylP Ortho (129.12) Poly(L-tyrosine) -, (9-benzyloxycarbonyl(297.31) Mono Poly(L-valine) a helix Hex (99.13) P Ortho Ortho a b
Space group
a
b
c
11.49
11.49
70.5
18.05
4.71
15.0
D2-4
14.66*
15.0
26.5
24.6
18.4
Angles
/3=110.4
5.68
z
Crystal.
Amorph.*
Melting point (°C)a
Heat of fusion kj/mola
Chain conform. (n*p/q) Refs.
47
1.270
3*47/13
867
8
1.492
6*2/1
850
18
1.263
3*18/5
1373
8
1.535
3*4/1
1373
D2-4
24.1
18.5
5.68
8
1.326
3*4/1
1373
D2-4
23.8
18.7
5.68
8
1.241
3*4/1
1373
23.3 23.0 22.8 29.40 20.8 22.09
22.7 22.6 22.8 14.70 20.8 19.95
22 22 22 36 80 80
1.213 1.238 1.228 1.272 1.270 1.247
3*11/3 3*11/3 3*11/3 3*18/5 3*40/1 3*40/1
720 1043 1296 1043 1296 1296
16.2 (16) 16.4 27.0 60.00 60.00
7=119.2 7 = 119.5
15.0 4.60
C2-2 C3-3 C3-3 C3-3
C3-3
30.2
6.64
8
9.05 6.62 6.62 6.68
9.05 6.62 6.62 6.68
19.0 9.36 9.31 9.36
10 3 3 3
9.13 8.92 9.13 9.00
9.13 8.92 9.13 25.1
19.0 19.0 19.0 19.0
10 10 10
12.3 15.75
12.3 15.75
9.15 22.88
11.4
11.4
9.71
D2-4
784
6.48
18.0
18.0
11.43
11.43
4.79 4.80
19.00 19.14
1.197 1.362 1.369 1.338
3*2/1
784
3*10/3 3*3/1 3*3/1 3*3/1
590 510 512 511
3*10/3 3*10/3 3*10/3
701 701 701 701
9
1.410
3* 3*8/3
580 1044
9.3
6
1.48
3*3/1
737
9.6*
3
1.065
3*3/1
706
11
1.20
3*11/3
849
18
0.970
3*18/5
1025
4 4
1.052 1.088
3*2/1 3*2/1
806 1045
16.5 (27) 6.88 6.59
7 =120.47
7=122
The number after the solidus (/) are reference citations. The unit cell parameter assignment has been changed from that published so as to make c the fiber axis.
TABLE 6. POLY(AMIDES) (-NH-X-NH-CO-Y-CO- or -NH-X-CO-) see also POLY(PEPTIDES) Density (g/cm3)
Unit cell parameters Polymer
Cryst syst.
Space group
Poly(2-aminoacetic acid), see Polyglycine Poly(/?-aminobenzoic acid) (119.12) Ortho D2-4 Ortho D2-4 Ortho D2-4 Poly(3-amino-2-butenoic acid) irrad. in vacuum (83.09) Mono irrad. in air Mono Poly(3-aminobutyric acid) (85.11) Ortho Poly(4-aminobutyric acid) a Mono (85.11) Mono C2-2 Mono P Mono 5 Hex -, 4-benzyloxycarbonyl-(L) 1.(219.24) Mono II. Hex - , 4-methyloxycarbonyl-(L) (143.14) Hex PoIy(10-aminocapric acid) a Tri (169.27) y Phex C2h-5 Hex Poly(6-aminocaproic acid) [caprolactam] a Mono C2-2 (113.16) Mono C2-2 Mono Mono C2-2 Mono Mono Mono C2-2
P Y
>150°C
Hex Hex Mono Mono Hex Ortho Mono Ortho Rho Mono
C2h-5 C2h-5
a
b
c
7.71 7.71 7.75
5.14 5.14 5.30
12.9 12.8 12.87
19.11
8.54
10.665
21.90
10.13
12.461
10.9
9.6
4.6
9.44 9.29 9.79
8.22 7.97 8.31
4.65
4.65
9.62 13.14
Angles
z
Crystal.
4 4 4
1.548 1.560 1.497
Amorph."
Melting point (°C)a
Heat of fusion kj/mol*
550/735
Chain conform. (n*p/q) Refs.
6*2/1 6*2/1 6*2/1
811 902 1434
/3 = 91.6
4*
1530
/3 = 96.8
4*
1530
4
1.17
330
4*1/1
503
260/337 260/244
5*2/1 5*2/1 5*2/1 5*2/1
272 457 1509 458 458
12.1* 12.24* 12.25 12.24*
7=116 7=114.5 7=117
8 8 8
1.340 1.375 1.273
19.30 13.14
12.30 10.0
(3 = 11.1
8 5
1.35 1.22
5*2/1 5*5/2
1359 1359
10.90
10.90
10.0
5
1.16
5*5/2
1359
9.80
5.12
27.54
54,90,110
4
1.110
11*2/1
1237
4.78 4.9
9.56 4.9
26.9 26.5
7=120
4 2
1.056 1.02
11*2/1 11*2/1
971 61
9.56 4.81 9.65 9.45 9.66 4.77 9.71
8.01 7.61 8.11 8.02 8.32 4.06 8.19
17.24* 17.10* 17.2* 17.08 17.0 17.25 17.40
7 = 67.5 7 = 79.5 7 = 66.3 7 = 68 7 = 65 7 = 66.5 7=115
8 4 8 8 8 2 8
1.232 1.221 1.220 1.252 1.214 1.224 1.199
1 1 4 4 2 4 4 4 4 2
1.250 1.23 1.10 1.10 1.162 1.165 1.132 1.194 1.188 1.191 1.146 1.138
4.8 4.85 9.35 9.33 4.79 4.82 9.14 4.83 4.90 4.86
4.8 4.85 4.81 4.78 4.79 7.82 4.84 7.83 16.28 4.65
8.6 8.4 16.60* 16.88* 16.7 16.70 16.68 16.68 8.22 16.87
17.9
16.2*
7 = 59.7
16.96*
7 = 90
7=120 7=121
7=121
7 = 60
188/337 177/146 1.09/839
0.917 1.114 1.10
1.09/839
215 223/153 223/244 226/293 214/304 272/839 260/1051 228/346 250/532
272/839
20.8/155 18.1/216 23.0/405 21.6/343 26/1121 19.4/839 27/1050 27.3 24.1/697 18.5/534
7*2/1 7*2/1 7*2/1 7*2/1 7*2/1 7*2/1 7*2/1
7*1/1 7*1/1 15.6/839 7*2/1 27/1050 7*2/1 7*2/1 7*2/1 7*2/1 7*2/1 7*1/1 7*2/1
3 26 135 212 334 891 1049 1050 449 213 222 1052 336 246 272 279 697 697 26 891
-, complex with 12
-, D-(-)-3-methyl(127.19)
Mono or
C2h-5 C2-2
9.13
Mono
C2-2
9.15
4.84
Poly(6-aminocaproic acid-a/f-11-aminoundecanoic acid) (296.46) Poly(6-aminocaproyl-5-aminovaleryl-3-aminopropionic acid) (297.40) Tri 4.9 10.7 Poly(8-aminocaprylic acid) a Mono C2-2 9.8 8.3 (141.21)
1510
4
1.125
22.5 21.6
51,77,62
2
1.28
22.4*
7=115
8
1.14 1.18
225/19 226/36
7*2/1
440
184
19*1/1
714
18*1/1
1437
185/146 202
30/1195 9*2/1
272 153
200/244 218/838
References page VI-159
TABLE 6.
cont'd Density (g/cm3)
Unit cell parameters Polymer
Cryst syst.
Space group
P y
Mono Hex Hex Phex C2h-5 Poly(2-aminocyclopentylenecarboxy acid) (111.14) Poly(7-aminoenanthic acid) (127.19) Tri Cl-I Tri Ci-I
a
b
c
4.79 4.9 4.77
4.79 4.9 9.54
21.7 21.7 21.9
8.25
4.54
7.8
9.8 4.9
10.0 5.4
9.8 9.85
Angles
z
Crystal.
Amorph."
1.088 1.04 1.087
1.04/495
7 = 120
2 2 4 2
1.26
4 1
1.18 1.21
56,90,69 49,77,63
Melting point (°C)a
13.3 Poly(peptide) Section
C2h-5
Ci-I Cl-I
Poly(2-aminopropionic acid), see Poly(alanine) Poly(3-aminopropionic acid) [P alanine] a Mono C2-2 (71.08) Mono P Ortho - , 2-butyl-2-methyl(141.21) - , 2,2-dimethyl1.(99.13) II. Ortho
13.3
Chain conform. (n*p/q) Refs.
18/1121 9*2/1 9*2/1 9*2/1
121 272 61 971
4*2/1
1059
8*1/1 8*1/1
918 61 153
233/215 225/146 217
1.20 -, (R)-3-methyl(141.21) - , (S)-4-methyl(141.21) -, (R)-5-methyl(141.21) - , (R)-6-methyl(141.21) Poly(aminoformic acid) - , N-butyl(99.13) Phex Poly(2-aminoisobutyric acid), see PoIy(12-aminolauric acid) Y Hex (197.32) Hex Phex Mono Mono Mono formed during planar extrusion Tri Poly(9-aminopelargonic acid) (155.24) Tri Tri
Heat of fusion kj/mola
223/291
9.24
179
479
9.43
176
479
9.11
182
479
9.57
188
479
15.4
16
1.12
1.023 1.10 1.034 1.045 1.048 1.126
2*8/3
522
208/1172 179/177
13*2/1 13*2/1 13*2/1 13*2/1 13*2/1 13*2/1
895 660 680 759 1054 1511
13*2/1
1511
4.80 4.70 4.79 4.87 4.90 9.28
4.80 4.70 9.58 9.38 4.67 4.85
32.1 31 31.9* 32.2* 32.1 31.35
7 = 120 7 = 121.5 7=121.7 7=124.4
2 2 4 4 2 4
9.28
5.29
31.35
59,90,60
4
1.223
4.9 9.7
5.4 9.7
12.5 12.6
49,77,64 64,90,67
1 4
1.15 1.07
210 194/146 198/292 209/177
10*1/1 10*1/1
421 918
9.33 9.60
8.73 8.96
4.78* 4.78*
7=120 7=122.5
4 4
1.400 1.361
340 330/337 357/1403
4*1/1 4*1/1
491 1265
9.56
7.56
4.78 a
4
1.366
4*1/1
1265
4*2/1
1093
11.57
-, 2-ethyl-2-methyl(113.16) -, 3-methyl-, see Poly(3-aminobutyric acid) -, 2-methyl-2-propyl(127.19) Poly(3-aminopropyl-5-aminovaleryl-6-aminocaproic acid) (297.40) Tri 4.9 PoIy(18-aminostearic acid) y Mono 4.76 (281.48) Poly(2-aminotetrahydropyran-6-carboxcylic acid) (127.14) Mono C2-1 11.79
10.95
10.7
0.972
175/528
0.99
8.3
72
8.4 8.39
189/73 273 268 270/402
8
1.239
4* 13 4*2/1
73 1093
8.5
76
4*2/1
1093
8.4
74
4*2/1
1093
21.6
51,77,62
2
1.28
18*1/1
1437
9.52
46.9
7 = 120
4
1.016
19*2/1
1055
14.40
19.43
7 = 98
20
1.292
5*10/3
1333
Double
305
TABLE 6. cont'd Density (g/cm3)
Unit cell parameters Polymer
Cryst syst.
PoIy(11-aminoundecanoic acid) a Tri (183.30) Tri Tri Tri Tri
II. y
Space group
Cl-I Ci-I
Mono Mono
a
b
c
9.5 4.78 4.9 9.6 4.78 4.78
10.0 4.13 5.4 4.2 4.13
9.75 9.48
Poly(5-aminovaleric acid) a Tri Cl-I 9.5 (99.13) Poly(4,4 '-benzanilidylene terephthalamide) (357.37) Poly(1,3-cyclohexylenedimethylene adipamide) cis(252.36) Tri 4.8 Poly( 1,3-cyclohexylenedimethylene dodecanediamide) cis(336.52) Tri 4.8 Poly(1,3-cyclohexylenedimethylene suberamide) cis(280.41) Tri 4.8 Poly(decamethylene adipamide) [10.6] (282.43)
Angles
z
Crystal.
15.0 13.1 14.9 15.0 14.9 14.1
60,90,67 90,75,66 49,77,63 72,90,64 82,75,66 a = 63.5
4 1 1 2 1
1.10 1.343 1.15 1.19 1.174
8.02 4.5 7.68
15.0& 29.4^ 14.78
7=115 7 = 118.5
4 4
1.145 1.10
5.6
7.5
48,90,67
2
1.30
Chain conform. (n*p/q) Refs.
183/292 220 182/146 194/101 186 188/444 226/1161
27/1161 41/343
12*1/1 12*1/1 12*1/1 12*1/1 12*1/1 12*1/1
918 365 61 59 263 1057
12*1/1 12*1/1
529 529 1056
258/402
6*1/1
18*1/1
1425
13*2/1
1058
29.6
26,85,75
2
1.19
19.0
44.6
16,90,83
2
1.12
19*2/1
1058
14.5
34.8
22,85,76
2
1.15
15*2/1
1058
18*1/1
110
20.0
253/1201
918
12.6
230 236/244 240/544 214/137
y Phex Poly(4,4 '-decamethy lenedipiperazine sebacamide) (476.75)
Poly (decamethy lene succinamide) [10.4] (254.37) Tri 4.9 Poly(dodecamethylene oxamide) [12.2] (254.37) Poly(dodecamethylene phosphinylidenedipropionamide) - , methyl-(diacid) (372.49) Poly(dodecamethylene malonamide) [12.3] (268.40) Mono 8.48 Poly(dodecamethylene sebacamide) [12.10] a Tri 5.0 (366.59) P Tri 5.0 Poly(dodecamethylene succinamide) [12.4] (282.43) Tri 4.9
1.01
Heat of fusion kj/mol a
18.63
Poly(decamethylene azelamide) [10.9] (324.51)
Poly(decamethylene 4-octenediamide) trans(308.47) Poly(decamethylene phosphinylidenedipropionamide) - , methyl-(diacid) (344.44) Poly(decamethylene sebacamide) [10.10] (338.54) Tri 4.9
Amorph.a
Melting point (°C)a
68.2/405 2 1 * 36.7/159
2
65 130/159 129/402
69.1/159 28*
24.1
243
20*1/1
657
20
173
19*1/1
831
51.1/118 22*1/1 34.7/159 * 1/1 72.0/405 32.7/160
1412 110
5.4
27.8 25.6
49,76,63
1
1.14
203/244 197 198/454 216/137
5.5
19.8
49,77,63
1
1.18
242
16*1/1
1626
19.5
230
16*1/1
743
21.55
180
4.71
41.30
/5=101
4
1.101
5.25
29.2
51,75,63
1
1.15
8.16
29.2
90,75,68
1
1.15
5.5
22.3
49,77,63
1
1.17
173/339
237
831 17*2/1
1523
24*1/1
1513
24*1/1
1513
18*1/1
1626
References page VI-159
TABLE 6.
cont'd Density (g/cm3)
Unit cell parameters Polymer
Cryst syst.
Space group
a
b
Poly[4,4 '-(ethylenedioxydiphenylene)-ditrimethylene adipamide] (438.57) Poly(ethylene-L-tartaramide) - , di-O-methyl(202.21) Tri 4.95 6.87 Poly(heptamethylene adipamide) [7.6] Y Phex C2-2 (240.35) Poly(heptamethylene y (282.43) Poly(heptamethylene (254.37)
c
Angles
4.82
Crystal.
Amorph."
Heat of fusion kj/mola
26.3
9.10
59,90,106
azelamide) [7.9] Phex pimelamide) [7.7] Phex Cs-I
z
Melting point (°C)a
18.95*
7=120
1
1.337
312
Chain conform. (n*p/q) Refs.
25*1/1
516
8*1/1
1629
2
209/291 226/339 250/244
65
1
201/244
65
1
1.105
214/244
16*1/1
63
16*1/1
65
205/2 196/339 228/1625
Y Phex Poly(heptamethylene sebacamide) [7.10] Y Phex C2-2 (296.46) Poly(heptamethylene suberamide) [7.8] Y Phex C2-2 (268.40) Poly(hexamethylene adipamide) [6.6] a I. Tri Ci-I (226.32) Mono Tri Tri Tri Tri
II.
Tri
P
4.9 15.7 5.00 4.87 4.97 4.96
glutaramide) [6.5] Mono C2h-6 Mono malonamide) [6.3] Mono 4-octenediamide)
5.4 10.5 4.17 5.26 5.47 5.52
187/339 208/244
65
2
230/244
65
8.0 5.9 5.87
17.2 16.23 16.50
90,77,67 57,80,60 56,81,60
2 1 1
7.8
5.3
40.15*
7 = 87
4
1.08
4.60 5.23
8.62 8.50
30.95* 30.55
/3=114 /3=110
4 4
8.60
4.62
25.70
/3=100.4
4
17.12
48,77,63 0 = 73 81,76,63 50,76,64 48,77,62 48,76,62
2
4.9 5 4.91
5.45
17.2 17.3 17.3 17.15 17.29 17.41
1
1.24 1.240 1.204 1.241 1.214 1.208 1.225 1.220 1.152 1.165 1.25 1.10 1.119
4.95
P Tri Ci-I high temp. Tri (17O0C) Tri Poly(hexamethylene azelamide) [6.9] (268.40) Mono Poly(hexamethylene (212.29) (at 19O0C) Poly(hexamethylene (184.24) Poly(hexamethylene trans(252.36) Poly[hexamethylene (170.21) Poly(hexamethylene (318.41) Poly(hexamethylene a (282.43)
18.95
52,80,63
1 9 1 1 1 1
1
1.09/52 1.12/495
14*1/1 14*1/1 14*1/1
25 402 407 891 1180 1409 1179 54 1180 1179 25 1060 1409
Tri
Ci-I
46.5/82 40/155 36.8/216 68/1121 58/1166 46.9/405 53.2
14*1/1 14*1/1 14*1/1 14*1/1 14*1/1 14*1/1
269.5
43.4 41.9
14*1/1
226/244 185/339
17*2/1
402
1.258 1.105
241/402
13*2/1 13*2/1
1514 1514
1.218
241/1524
11*2/1
1523
259
16*1/1
657
1.095 1.069 1.095 1.09/495
19.1 oxamide) [6.2] Tri Ci-I /n-phenylenedisulfonamide) Mono C2h-3 sebacamide) [6.10] Tri Ci-I Tri
265/2 270/289 301/1166 280/1121
5.15
7.54
12.39
32,74,62
1
1.280
320/402
10*1/1
956
7.70
7.76
14.1
/3=117
2
1.409
170
13*1/1
1384
4.95 4.86
5.4 5.05
22.4 22.35
49,76,63 55,76,62
1 1
1.16 1.189 1.152 1.189 1.17 1.20
228/51 215/291 233/244 225/454 216
30.6/160 18*1/1 56.5/137 18*1/1 58.6/405
25 891 54 52 153 25
4.9
8.0
22.4
90,77,67
2
1.041
18*1/1
TABLE 6. cont'd Density (g/cm3)
Unit cell parameters Polymer
Cryst syst.
Space group
Poly(hexamethylene suberamide) [6.8] (254.37) Tri Mono quenched Phex Poly(hexamethylene succinamide) [6.4] (198.26) Tri
a
b
9.60
8.26
9.7
9.7
4.9
5.3
c
Angles
z
Crystal.
19.7
7 = 115
1 4
1.193
Amorph.a
Melting point (°C)a
Heat of fusion kj/mola
232/244 235/291 241/1202
Chain conform. (n*p/q) Refs.
16*1/1
7=120 14.8
51,77,62
65 1515 1515
1
1.25
275
12*1/1
1626
230
12*1/1
1629
371 371/829 D350/291
14*1/1
828
285/1524 306/402
9*2/1
1522
212/402 Poly(hexamethylene-L-tartaramide) - , di-O-methyl(252.32) Tri Poly(hexamethylene terephthalamide) [6.T] (246.31)
Poly(methylene adipamide) [1.6] (156.18) Mono
C2h-6
5.00
13.20
62,90,112
1
1.191
15.6
8.04
4
1.333
39.5
4
1.06
20*2/1
1315
6.06 6.1 5.22
45.0 45.5 52.6
4 4 4
1.060 1.03 1.037
23*2/1 23*2/1 23*2/1
1315 1315 1315
6.1
35.8
4
1.08
18*2/1
1315
5.32
40.5
4
1.093
18*2/1
1315
6.1
41.4
4
1.05
21*2/1
1315
6.1
37.6
4
1.07
19*2/1
1315
6.1
49.4
4
1.02
25*2/1
1315
6.1
47.4
4
1.02
24*2/1
1315
6.1
43.5
4
1.04
22*2/1
1315
4.96
44.7
4
1.059
23*2/1
1440
10.52 9.64
4.96 4.96
44.7 44.7
4 4
1.118 1.220
23*2/1 23*2/1
1440 1440
8.12
4.79
35.2*
3
1.166
15*2/1
1522
4.79
4.79
26.1
3
1.366
8*3/1
1522
4.79
4.79
18.0
3
1.589
6*3/2
1313
4.79
4.79
34.5
3
1.237
10*3/1
1522
8.10
4.79
30.0*
4
1.211
13*2/1
1522
Poly (4,4'-methylenedicyclohexylene azelamide) trans-, trans (362.56) Ortho 9.4 Poly(4,4 '-methylenedicyclohexylene dodecanediamide) trans-, transI. Ortho C2v-5 9.30 (404.64) Ortho 9.4 II. Mono 9.50 Poly(4,4 '-methylenedicyclohexylene pimelamide) trans-, transit Ortho 9.4 (334.50) II. Mono 9.57 Poly(4,4 '-methylenedicyclohexylene sebacamide) trans-, trans(376.58) Ortho 9.4 Poly(4,4 '-methylenedicyclohexylene suberamide) trans-, trans(348.53) Ortho 9.4 Poly(4,4'-methylenedicyclohexylene tetradecanediamide) trans-, trans(432.60) Ortho 9.4 Poly(4,4 '-methylenedicyclohexylene tridecanediamide) trans-, trans(418.66) Ortho 9.4 Poly(4,4 '-methylenedicyclohexylene undecandediamide) trans-, trans(390.61) Ortho 9.4 Poly(4,4 '-methylenediphenylene dodecanediamide) 1.(392.54) Ortho 11.10 II. Ortho III. Ortho Poly(methylene dodecanediamide) [1.12] (240.35) Mono C2h-6 Poly(methylene glutaramide) [1.5] (142.16) Rho D3-5 Poly(methylene malonamide) [1.3] (114.10) Hex Poly(methylene pimelamide) [1.7] (170.21) Rho D3-5 Poly(methylene sebacamide) [1.10] (212.29) Mono C2h-6
6.84
4.79
20.2*
6.1
7 = 90
7 = 96.6
7 = 99.6
7
= 90
7 = 90
290 256/1443
259/1524
260/4024
266/1524 268/1537
References page VI-159
TABLE 6. cont'd Density (g/cm3)
Unit cell parameters Polymer
Cryst syst.
Space group
Poly(methylene suberamide) [1.8] (184.24) Mono C2h-6 Poly(nonamethylene azelamide) [9.9] (310.48)
y Phex Poly(nonamethylene malonamide) [9.3] (226.32) Ortho Poly(octamethylene azelamide) [8.9] Y Phex (296.46) Poly(octamethylene malonamide) [8.3] (212.29) Mono Poly(octamethylene suberamide) [8.8] (282.43) Tri Poly(octamethylene succinamide) [8.4] (226.32) Tri Poly(octamethylene-L-tartaramide) - , di-O-methyl(286.37) Tri Poly(octamethylene terephthalamide) [8.T] (274.36) Poly(pentamethylene azelamide) [5.9] (254.37) Poly(pentamethylene glutaramide) [5.5] (198.26) Mono C2-3 Poly(pentamethylene malonamide) [5.3] (170.21) Ortho Poly(pentamethylene pimelamide) [5.7] y Mono Cs-2 (226.32) Poly(pentamethylene terephthalamide) [5.T] (232.28) - , 2-methyl-(diamine) (246.31) Ortho Poly(3,8-phenanthridinonediyl terephthalamide) (355.35) Mono Poly(m-phenylene adipamide) (218.26) Poly(p-phenylene dodecanediamide) (302.42) Poly(m-phenylene isophthalamide) (238.25) Ortho Tri Cl-I Tri Cl-I Ortho - , hexamethylphosphorictriamide complex (596.66) Mono (2 HMPT/monomer) Poly(/?-phenylene phthalamide) (238.25) Ortho D2h-14 Poly(p-phenylene pimelamide) (232.28) Poly(m-phenylene sebacamide) (274.36) Poly(/7-phenylene sebacamide) (274.36)
a
8.08
b
4.79
c
25.2^
Angles
z
Crystal.
= 90
4
1.255
7
24.0
Amorph.a
Melting point (°C)a
Heat of fusion kj/mola
Chain conform. (n*p/q) Refs.
276/1524
11*2/1
1522
177 189/2 165/339
20*1/1
110
1 8.32
4.71
32.70
4
65 1.173
2
8.50
4.71
30.70
/5=101.7
4
14*2/1 206/244
1.172
1
233/1524
1523 65
13*2/1
216/291 225/244
1523 65
4.9
5.4
17.3
51,77,62
1
1.20
254
14*1/1
1626
5.00
6.82
15.7
57,90,111
1
1.175
208
14*1/1
1629
17.9
335
16*1/1
828
19.5
179/291
16*1/1
2
8.30
4.79
13.8
8.47
4.62
22.40
4.83
9.35
16.62
7
7
= 90
= 58.9
2
1.200
198/291 247/1625
12*1/1
1624
4
1.290
195/402 248/1524
10*2/1
1523
2
1.169
228 183/291
14*1/1
1210
354 353/829
13*1/1
828
1.460
13*2/1
1529
1.50
16*1/1
1063
11*1/1
828
19*1/1
828
10*1/1 10*1/1 10*1/1 10*2/1
735 856 878 1062
14.1
4.61
36.7
26.5
8.1
6.5
17.2
16 7
= 60
2
11.8
344 296/402
21.2 6.7 5.27 5.36 5.1
4.71 5.25 5.36 5
11.0 11.3 11.3 23.2
112,111,88 113,113,88
1 1 1 2
1.14 1.470 1.443 1.34
9.43
16.94
11.3
/3-123.4
2
1.315
5.5
8.1
4
1.56
22.8
375/735 390/748 1.33
957
10*1/1
396
14.7
372
14*1/1
828
14.9
258
17*1/1
828
18.5
334
18*1/1
828
TABLE 6. cont'd Density (g/cm3)
Unit cell parameters Polymer
Cryst syst.
Space group
Poly(m-phenylene suberamide) (246.31) Poly(p-phenylene suberamide) (246.31) Poly(m-phenylene terephthalamide) (238.25) - , 4-methyl-(diamine) (252.27) Mono Poly(/?-phenylene terephthalamide) 1.(238.25) Port Cs-I Mono Mono C2h-5 Ortho Mono Port Cs-2 Ortho II.
a
b
c
Angles
z
Crystal.
Amorph.a
Melting point (°C)a
Heat of fusion kj/mola
Chain conform. (n*p/q) Refs.
13.0
302
15*1/1
828
16.3
374
16*1/1
828
11*2/1
1398
12*1/1 12*1/1 12*1/1 12*1/1 12*1/1 12*1/1 12*1/1
761 1061 902 1525 1527 1620 1638 1526 958 1526
500/748 8.57
7.54
22.11
/3=116.3
4
1.308
7.87 7.728 7.80 7.78 7.79 7.88 7.60
5.18 5.184 5.19 5.28 5.18 5.22 5.04 4.8 5.1 4.8
12.9 12.81 12.9 12.9 12.89 12.9 12.78 12.7 12.9 12.7
7 = 90 7 = 90.04 7 = 90
2 2 2 2 2 2 2
1.504 1.542 1.515 1.493 1.522 1.491 1.616
2
1.50
8.0
7 = 92.2
500/748 600/735
a = 88 12*1/1
a = 88
single crystals & spherulites 11.5 - , 2,2'-difluoro(274.23) Port 8.6 5.0 Poly(/?-phenylene 2,5-thiophenediamide) (272.46) Mono 4.29 5.09 Poly(piperazine adipamide) (196.25) Poly( 1,4-piperazine 1,3-cyclobutylenedicarboximide) - , 2,4-diphenyl-(diacid) trans(346.43) Ortho 8.74 5.93 Poly( 1,4-piperazine 4-octenediamide) trans(222.29) Mono C2h-5 4.54 10.00 Poly(piperazine sebacamide) (252.36) Poly(2,5-pyrimidine terephthalamide) (240.22) Ortho 7.3 5.1 Poly(4,4 '-sulfonyldiphenylene terephthalamide) (378.40) Poly(terephthaloyldihydrazo-di(p-aminobenzoyl) terephthalamide) (562.54) Port 8.5 4.9 Poly(tetramethylene adipamide) [4.6] (198.26) Tri Cl-I 4.95 5.47 Mono 9.6 8.26 Tri 4.9 5.5 Poly(tetramethylene Y (240.35) Poly(tetramethylene 156.18* Poly(tetramethylene trans(224.30) Poly(tetramethylene (170.21)
1297
13.0 25.2
7 = 98
1.63
12*1/1
1528
2
1.489
11*2/1
1532
10*1/1
386
9*1/1
934
12*1/1
873
9.2
355
9.22
13.50
/?=110.2
1
1.204
2
1.283
12.8
2
4.62
Poly(tetramethylene-L-tartaramide) - , di-O-methyl(230.26) Tri
16* 12*1/1
15.45 29.69 14.66 14.7 14.8
20.40
1531 1203
48,78,64 7=115 46,78,64
2
1.51
1 4 1
1.245 1.246 1.29
/?= 102.5
4
295/291 308/51 350 41.6 319/1518
28*1/1
760
12*1/1 12*1/1 12*1/1
1516 1517 1655
223/339 253/402 1.303
17.0 succinamide) [4.4] Tri
26.0/81
1.67
2
8.65
252/657 180/81
azelamide) [4.9] Phex malonamide) [4.3] Mono 4-octenediamide)
2
65
277/1524
9*2/1
1523
294
14*1/1
657
4.9
5.5
12.3
49,77,62
1
1.29
d 287/402
10*1/1
1626
5.00
7.06
10.80
59,90,110
1
1.270
266
10*1/1
1629
References page VI-159
Next Page
TABLE 6. cont'd Density (g/cm3)
Unit cell parameters Polymer
Cryst syst.
Space group
Poly(tridecamethylene tridecanediamide) [13.13] y Mono (422.70) Mono Poly(m-xylylene adipamide) (246.31) Mono Tri Ci-I Poly(/7-xylylene sebacamide) (302.42) Tri
a b
a
b
c
9.22 4.88
4.94 4.73
34.47 34.0
5.10 12.01
4.70 4.83
15.2 29.8
5.74
4.87
20.6
Angles
z
Crystal.
Amorph."
/3=121.1 7=121
2 1
1.044 1.043
1.01
' = 69.6 75,26,65
1 2
76,55,65
1
7
Melting point ( 0 C) a
Heat of fusion kj/mola
Chain conform. (n*p/q) Refs.
> 183 97.2 172/1521
28*1/1 28*1/1
1519 1520
1.198 1.250
246/326 244/544
13*1/1 13*2/1
84 459
1.168
300/290 281/385 291/454 268/291
18*1/1
204
The number after the solidus (/) are reference citations. The unit cell parameter assignment has been changed from that published so as to make c the fiber axis.
TABLE 7.
POLY(ESTERS) ( - O - X - O - C O - Y - C O - or - O - X - C O - ) Density (g/cm3)
Unit cell parameters Polymer
Cryst syst.
Space group
a
Poly(4,4 '-bicyclohexylene sebacate) - , trans-, trans(364.53) Mono 11.16 smectic Mono 11.98 Poly(4,4'-bicyclohexylene undecanedioate) - , trans-, trans(378.55) Mono 12.4 smectic Mono 12.3 Poly(4,4 '-biphenylene 4,4'-biphenylenedicarboxylate) (392.11) Ortho 7.83 Poly(4,4 '-biphenylene terephthalate) (316.31) Ortho 7.20 Poly(3,4 '-carbonyldiphenylene terephthalate) (344.32) Ortho C2v-17 12.51 Poly(l,3-cyclobutylene carbonate) - , 2,2,4,4-tetramethyltrans(170.21) Tri 9.25 cisOrtho 9.16 Poly(l,4-cyclohexylene adipate) trans(226.27) PoIy(1,4-cyclohexylenedimethylene adipate) transI. Mono C2h-5 6.938 (254.33) cis-
b
Amorph.a
Melting point ( 0 C) 0
Heat of fusion kj/mola
Chain conform. (n*p/q) Refs.
c
Angles
z
Crystal.
5.27 5.48
19.48 19.76
/3 = 49.0 /3 = 52.5
2 2
1.400 1.176
20*1/1 20*1/1
1636 1636
5.21 5.55
23.0 20.6
/3 = 43.5 /3 = 51.4
2 2
1.229 1.144
21*1/1 21*1/1
1636 1636
5.50
20.66
2
1.464
20*1/1
1622
16*
1622
16*4/1
1562
5.23 7.561
67.66
8.28
(6.9)
8.22
12.9
16
7
= 96.5 4
1.4292
1.08
360
6*1/1
364
1.164
253
6*2/1
364
225/762
12*1/1
763
124/547
14*1/1
1262
12*1/1
1193
13.5
9.761
15.97
/3 = 41.4
2
1.181
55/547 PoIy(1,4-cyclohexylenedimethylene succinate) trans(226.27) Mono C2h-5 cis-
6.486
9.482
13.51
/3 = 45.9
2
1.259
147/547 62/547
Poly(1,4-cyclohexylenedimethylene terephthalate) trans(274.32) Tri Tri Ci-I cisTri
6.37 6.46
6.63 6.65
14.2 14.2
89,47,114 89,47,115
1 1
1.266 1.260
318/547
14*1/1 14*1/1
199 1077
6.02
6.01
13.7
89,53,112
1
1.319
256/547
14*1/1
199
S E C T I O N
S
O
L
U
T
I
O
N
V I I
P R O P E R T I E S
V i s c o s i t y
-
a n d o f
M o l e c u l a r
W e i g h t
U n p e r t u r b e d L i n e a r
C h a i n
R e l a t i o n s h i p s
D i m e n s i o n s M o l e c u l e s
M . Kurata, Y. T s u n a s h i m a Institute for Chemical Research, Kyoto University, Uji, Kyoto, Japan
A. Introduction 1. The Viscosity - Molecular Weight Relationship 2. Unperturbed Dimensions of Linear Chain Molecules B. Effect of Molecular Weight Distribution on the Viscosity Constant K C. Tables of Viscosity - Molecular Weight Relationships, [77] - KM3 Table 1. Main-Chain Acyclic Carbon Polymers 1.1. Poly(dienes) 1.2. Poly(alkenes), Poly(acetylenes) 1.3. Poly(acrylic acid) and Derivatives 1.4. Poly(oc-substituted acrylic acid) and Derivatives 1.5. Poly(vinyl ethers) 1.6. Poly(vinyl alcohol), Poly(vinyl halides) 1.7. Poly(vinyI esters) 1.8. Poly(styrene) and Derivatives 1.9. Other Compounds 1.10. Copolymers Table 2. Main-Chain Carbocyclic Polymers Table 3. Main-Chain Heteroatom Polymers 3.1. Poly(oxides), Poly(ethers) 3.2. Poly(esters), Poly(carbonates) 3.3. Poly(amides) 3.4. Poly(amino acids) 3.5. Poly(ureas), Poly(urethanes), Poly(imines) 3.6. Poly(sulfides) 3.7. Poly(phosphates) 3.8. Poly(siloxanes), Poly(silsesquioxanes) 3.9. Poly(heterocyclics)
VII-2 VII-2 VII-4 VII-5 VII-5 VII-5 VII-5 VII-7 VII-10 VU-13 VII-17 VII-17 VII-18 VII-19 VII-24 VII-27 VII-31 VII-32 VII-32 VII-34 VII-36 VII-38 VII-39 VII-39 VII-39 VII-40 VII-41
3.10. Copolymers (Maleic Anhydride, Sulfones) 3.11. Other Compounds Table 4. Cellulose and Derivatives, Poly(saccharides) Table 5. Miscellaneous D. Calculated Unperturbed Dimensions of Freely Rotating Chains E. Unperturbed Dimensions of Linear Polymer Molecules Table 6. Main-Chain Acyclic Carbon Polymers 6.1. Poly(dienes) 6.2. Poly(alkenes), Poly(acetylenes) 6.3. Poly(acrylic acid) and Derivatives 6.4. Poly(a-substituted acrylic acid) and Derivatives 6.5. Poly(vinyl ethers), Poly(vinyl alcohol), Poly(vinyl esters), Poly(vinyl halides) 6.6. Poly(styrene) and Derivatives 6.7. Other Compounds 6.8. Copolymers Table 7. Main-Chain Carbocyclic Polymers Table 8. Main-Chain Heteroatom Polymers 8.1. Poly(oxides), Poly(ethers) 8.2. Poly(esters), Poly(carbonates) 8.3. Poly(amides) 8.4. Poly(amino acids) 8.5. Poly(urethanes) 8.6. Poly(sulfides) 8.7. Poly(phosphates) 8.8. Poly(si loxanes), Poly(silsesquioxanes), Poly(silmethylenes) 8.9. Poly(heterocyclics)
VII-42 VII-42 VII-43 VII-46 VII-46 VII-47 VII-47 VII-47 VII-48 VII-49 VH-50 VII-53 VII-54 VII-56 VII-58 VII-60 VII-60 VII-60 VII-61 VII-63 VII-63 VII-63 VII-63 VII-64 VII-64 VII-64
8.10. Copolymers (Maleic Anhydride, Sulfones, Siloxanes) 8.11. Other Compounds Table 9. Cellulose and Derivatives, Poly(saccharides) F. References
VII-65 VII-66 VII-66 VII-68
A.
INTRODUCTION
1.
The Viscosity - Molecular Weight Relationship
The limiting viscosity number [77] of a solution - which has long been called the intrinsic viscosity - is defined as (Al) in terms of the solvent viscosity, 770, the solution viscosity, 77, and the solute concentration, c. The concentration, c, is expressed in grams of solute per milliliter of solution or, more frequently, in grams of solute per 100 milliliters of solution, the limiting viscosity number being given in the reciprocal of these units, i.e., in milliliters per gram or in deciliters per gram. Here, following the IUPAC 1952recommendations (1), we adopt the former unit. The quantity [77] of a polymer solution is a measure of the capacity of a polymer molecule to enhance the viscosity, which depends on the size and the shape of the polymer molecule. Within a given series of polymer homologs, [77] increases with the molecular weight M; hence it is a measure of M. Section C gives the limiting viscosity number molecular weight relationships for polymers, in various solvents and at various temperatures. The table contains the constants of the equation (A2) which is known as the Mark-Houwink-Sakurada equation. It is now well established that for linear, flexible polymers, under special conditions of temperature or solvent, (usually known as the Flory "theta" temperature or solvent, (2)), the above equation becomes (A3) In the tables, the 6 sign in parenthesis (next to the temperature data) indicates that the viscosity constants were obtained under the theta condition. Since Eq. (A3) is approximately valid over the whole molecular weight range, Kg and a — 0.50 may be used without modification, outside of the molecular weight range in which they were determined. However, it must be noted that [77] is rather sensitive to temperature in the vicinity of 9, especially when M is higher than 5 x 105. In ordinary good solvents, the constants K and a obtained are valid only within a rather limited range of M
(3,4). It is therefore, quite probable that the tabulated relationships are in error outside the indicated range of M (see eighth column in the table). As for the effect of temperature, however, both K and a mostly become insensitive to the temperature when a exceeds about 0.70, and they may be used in a 10-degree range on either side of temperature at which the constants were determined. The method of determination of the molecular weight and the number of fractionated samples (Fr.) or whole polymer samples (WP) used to determine the [77]-M relationship are also given in the ninth and the sixth or seventh columns, respectively. The abbreviations used are as follows: (A) Methods Yielding the Number-Average Molecular Weight (Mn) CR cryoscopy EG end-group titration VOS vapor pressure osmometry EB ebullioscopy OS osmotic pressure (B) Methods Yielding the Weight-Average Molecular Weight (Af w ) LS light scattering LLS low-angle laser light scattering SE sedimentation equilibrium SEC, GPC size exclusion chromatography gel permeation chromatography SA approach to the sedimentation equilibrium (Archibald's method) (C) Empirical or Semi-Empirical Methods EM electron microscopy GPC gel permeation chromatography LV limiting viscosity number - molecular weight relationship PR analysis of polymerization rate (yielding M n ) DV diffusion and viscosity MV melt viscosity - molecular weight relationship SD sedimentation and diffusion SV sedimentation and viscosity Thus, for example, the constants tabulated are for the [77]M relationships, expressed in terms of Mn or Mw, if the method is specified as OS or LS, respectively; Le., (A4) or (A5) The values OfATn and Kw, especially the former, are greatly influenced by the molecular weight distribution (MWD) of the polymer samples, and caution must be taken in using these relationships.
To illustrate this effect, let us assume that (i) Equation (A2) is applicable to the molecule i with molecular weight M, over the whole range of M; Le., (A6) (ii) The weight fraction w,- of the molecules i in a given sample can be represented by a continuous exponential function, (A7) (A8) or by the log-normal function, (A9) where h, A, p, and Mo are constants, and T represents the gamma function. Then, since [77] = ^ 1 - Wify]^ we obtain (AlO) (AU) for the exponential MWD, and
Based on the above consideration, we classify the heterogeneity of polymers into four classes, A-D, as shown in the last column of the table in Section B, and indicate it in the tenth column of the tables in Section C, as a measure of the heterogeneity of the reference samples used. It is desirable that readers select their own relationship by inspecting these data on heterogeneity as well as those on the number of samples and the molecular weight range. Generally speaking, a "good" [?7]-M relationship is one that has been obtained on the basis of Mw for at least four samples of classes A and B (exceptionally C) or on the basis of Mn for those of class A (exceptionally B), whose molecular weights range over at least one half orders of magnitude. In the "Remarks" column of Section C, we have occasionally indicated by the letter R, a "recommended" relationship for the convenience of readers. In the range of low molecular weight (mostly less than 104), the constant a becomes 0.50 irrespective of the solvent. This type of relationship cannot be used, even approximately, at higher molecular weights. This case is noted by the letter L. High conversion polymers are also marked by the letter H, where the [rj]-M relationships are less reproducible due to chain branching than are ordinary ones. The abbreviations used are as follows: A
(A12) (A13) for the log-normal MWD (5). The values of Kn/K and Kw IK calculated by these equations are shown in Section B. This table may be used for estimating an error due to MWD in the determination of M. As an example, let us assume that a given polymer sample has the exponential MWD with Mw/Mn = 2.0, while an available [77]-Mn equation has been obtained for samples with a narrow MWD, e.g., M^fMn = 1.1. Further, let a be 0.70. Then, to find the correct value of Mn of the given sample from [77], we must use Eq. (A4) with Kn = 1.54K9 instead of the available equation with ^ n = 1.06AT. Use of the latter would lead to an overestimate Mn which is related to the correct Mn by (A14) The error amounts to about 70%, i.e., Mn = 1.7Mn. Thus, application of the viscosity equation written in Mn is to be restricted to within a narrow class of samples, unless an appropriate correction is made. On the other hand, if an [77]-Mw equation is available for the same pair of working and reference samples as above, we have (A15) instead of Eq. (A14). Hence, the error Mw amounts to only 6% (M^ = 0.94Mw), which will be negligible for more practical purposes.
B C D H L R
Narrow MWD polymers, or well-fractionated polymers, Mw/Mn < 1.25 Ordinary fractionated polymers, 1.30 2.5 High conversion polymers, including branches Limited to low-molecular-weight polymers Recommended relationship
In Section C, polymers are arranged according to their structure in subgroups. Within each subgroup, the polymers are, in principle, given in alphabetical order. Within each polymer, the solvents are also arranged in alphabetical order, followed by the mixed solvents. Chain configurational data are occasionally given in the first column. The data given in parentheses refer to only one set of viscosity constants listed in the same row, while the data given without parentheses refer to a series of sets listed in the same and succeeding rows. Thus, for example, the data "N content, 13.9 wt.%" are effective only for the sixth row of cellulose trinitrate, and the data "95%-cw, 1%-trans, 4%-l,2" are effective for the fourth to eighth rows of polybutadiene. The tables in Section C are essentially based on the table published by Kurata and Stockmeyer (3). Data were also taken from tables published by Peterlin (7), Meyerhoff (8), Elias (9), and Krause (10), the last one including a number of unpublished data on acrylic and methacrylic polymers. We are also grateful to these authors. Thanks are also due to J. Brandrup and K. Kamide for their help with this compilation. References page VII - 68
2.
Unperturbed Dimensions of Linear Chain Molecules
The mean-square end-to-end distance (r2) of a linear chain molecule in solution is usually expressed in terms of two basic quantities, the unperturbed mean-square end-to-end distance {r2)0 and the expansion factor a; i.e., (A16) The latter quantity a represents the effect of "long-range interactions" which can be described as an osmotic swelling of the chain by the solvent-polymer interactions, while the unperturbed dimension (r 2 ) 0 represents the effect of "short-range interactions" such as bond angle restrictions and steric hindrances to internal rotation. The steric hindrances are also influenced by the torques exerted on the chain by solvent molecules, but the effect is rather small in many cases (11). For sufficiently long chain, (r 2 } 0 becomes proportional to ]T\ mlJ where Yi1 is the number of the jth-kind bond of length //. The quantity C00, defined by (A17) is often called the characteristic ratio and it serves as a measure of the effect of short-range interactions. The freely rotating state is a hypothetical state of the chain in which the bond angle restrictions are retained, but the steric hindrances to internal rotation are released. The mean-square end-to-end distance of the freely rotating chain (r 2 ) 0f can be readily calculated from the given basic structure of the chain. For instance, if the chain consists of only one kind of bond of length /, we obtain (A18) where n is the number of bonds and 6 is the supplement of the valence bond angle. For vinyl polymer chains, / = 0.154 [nm], cos (9 = 1/3, and n = M/m = 2M/MU; and hence
and temperature. The values of ro/M1/'2, rof/M1/2, a and C00 are given, together with the experimental values of Soz/M^2, ap, or Ko from which ro was computed. S0Z which is the abbreviation of (S2) ^ 2 is the z-average value of the unperturbed radius of gyration, ap is the persistence length, and Ko is the viscosity constant corresponding to KQ in Eq. (A3). The methods used to determine these quantities are also indicated in the tenth column of the tables by using the following abbreviations: (A) Light scattering LT Zimm's plot in a theta solvent yielding Soz/Mlj2. After a heterogeneity correction is made, the tabulated value of ro/M'/2^61/25Ow/My2) is obtained. LD dissymmetry method in a theta solvent. Less reliable for heterogeneous samples than the former method. LG Zimm's plot in good solvents yielding Sz/MI/2. After corrections for the excluded volume effect and heterogeneity are made, the tabulated value of ro/M 1 / 2 is obtained (3,12). (B) X-ray small-angle scattering XS the persistence length ap is obtained irrespective of the solvent nature. The tabulated values of ro/M1^2 are the asymptotic values for infinitely high molecular weight (13,14). (C) Limiting viscosity number VT viscosity - molecular weight relationship in a theta solvent. Equation (A3) ro/M 1 / 2 is calculated by the Flory and Fox relation, K0 ^ ^o{ro/M^2)\ The following values of
(A19) where Mu is the molecular weight of the repeating unit and m is the average molecular weight per skeletal link. Similar expressions for r^ (~ (r2)of ) c a n ^ e a * so obtained for more complicated chains. The results are summarized in Section D. The ratio of (r2)0 to (r 2 ) 0f , then, represents the effect of steric hindrance on the average chain dimensions: (A20) The quantity a is independent of n. Section E gives a list of the unperturbed dimensions of linear chain molecules which were obtained under various conditions of solvent
2.1 x 1023 for poorly fractionated or unfractionated polymers (class C or D) VG
viscosity - molecular weight relationship in good solvents. Ko was estimated by using the Kurata-Stockmeyer-Fixman plot (3,4) or other analogous plots (12). VWC viscosity analyzed by the wormlike cylinder model. VA viscosity in good solvents. The correction of excluded volume effect is made by using the Flory -Krigbaum-Orofino theory of the second virial coefficient A 2 or other analogous theories (12).
LT or XS. The listed values of ro/M1/2 sometimes scatter appreciably, reflecting the difficulty involved, both experimental and theoretical, in the determination of this quantity. Especially in the case of cellulose chains, the right magnitude of ro is yet in controversy (542, 549,3,691,696,688,678,686,12). In recent papers, emphasis has often been put on the effect of temperature or solvent on the unperturbed dimensions. These data are put together at the end of the tabulation for each polymer. Section E is also based on the tables published by Kurata and Stockmeyer (3).
(D) Method yielding the temperature dependence of roST stress - temperature coefficient of undiluted or swollen samples. VTe viscosity - temperature coefficient of the intrinsic viscosity The polymers are arranged in Section E in the same order as in Section C. For each polymer, smoothed values of ro/M 1 / 2 , a, and C00, which were mostly obtained by VT or VG, are given in the first line, followed by some typical values obtained by more direct methods such as
B. EFFECT OF MOLECULAR WEIGHT DISTRIBUTION ON THE VISCOSITY CONSTANT K a = 0.5 My1JMn
KjK
a=0.6
Ky1IK
KJK
a^0.7
Ky,/K
KJK
a = 0.8
Ky1IK
KjK
a = 0.9
K^/K
KjK
a = 1.0
Ky1)K KJK
K^/K
Class
MOLECULAR WEIGHT 30 4.87 15 3.46 10 2.83 5 2.03 3 1.60 2 1.33 1.75 1.25 1.50 1.18 1.25 1.09 1.10 1.04
DISTRIBUTION: EXPONENTIAL TYPE (Eq. 0.890 6.91 0.897 9.85 0.893 4.57 0.900 6.08 0.896 3.59 0.903 4.59 0.907 2.40 0.913 2.85 0.921 1.79 0.926 2.02 0.940 1.43 0.943 1.54 0.948 1.33 0.951 1.42 0.959 1.23 0.961 1.28 0.975 1.12 0.977 1.15 0.989 1.05 0.989 1.06
(A7)) 0.911 0.914 0.917 0.925 0.936 0.951 0.958 0.967 0.980 0.991
14.18 8.16 5.91 3.42 2.29 1.68 1.51 1.35 1.18 1.07
0.933 0.935 0.937 0.943 0.952 0.963 0.968 0.975 0.985 0.993
20.56 11.02 7.67 4.12 2.62 1.83 1.63 1.42 1.21 1.09
0.963 0.964 0.965 0.968 0.973 0.979 0.982 0.986 0.991 0.996
30 15 10 5 3 2 1.75 1.50 1.25 1.10
1 1 1 1 1 1 1 1 1 1
D D D D D C B B A A
MOLECULAR WEIGHT 30 3.58 15 2.76 10 2.37 5 1.83 3 1.51 2 1.30 1.75 1.23 1.50 1.16 1.25 1.09 1.10 1.04
DISTRIBUTION: NORMAL TYPE (Eq. (A9)) 0.654 5.12 0.665 7.57 0.713 3.67 0.723 5.01 0.750 3.02 0.759 3.94 0.818 2.17 0.824 2.61 0.872 1.69 0.877 1.92 0.917 1.39 0.920 1.51 0.932 1.31 0.935 1.40 0.951 1.21 0.953 1.27 0.973 1.11 0.974 1.14 0.988 1.05 0.989 1.06
0.700 0.753 0.785 0.845 0.891 0.930 0.943 0.958 0.977 0.990
11.58 7.03 5.25 3.19 2.21 1.65 1.50 1.34 1.17 1.07
0.762 0.805 0.832 0.879 0.916 0.946 0.956 0.968 0.982 0.992
18.32 10.13 7.16 3.96 2.56 1.81 1.61 1.41 1.21 1.08
0.858 0.885 0.902 0.930 0.952 0.969 0.975 0.982 0.990 0.996
30 15 10 5 3 2 1.75 1.50 1.25 1.10
1 1 1 1 1 1 1 1 1 1
D D D D D C B B A A
C.
TABLES O F VISCOSITY - M O L E C U L A R W E I G H T RELATIONSHIPS, [if] = KM*
TABLE 1. MAIN-CHAIN ACYCLIC CARBON POLYMERS No. of samples Polymer
Solvent
Temp. ( 0 C)
K(xlO3) (ml/g)
a
Fr.
W.P.
MoL wt. range (xlO~4)
Method(s)
Remarks
Refs.
-
2.1-23.2 2.1-23.2 3.8-6.1 5-50 5-50 5-50 15-50 15-50 15-35
LG LG LG OS OS OS LS LS LS
B-C B-C B-C A,R A A A A B
889 889 889 15 15 15 16 16 17
1.1. POLY(DIENES) Poly(butadiene) linear ring 98%-cij, 2%-l,2
95%-cis, \%-trcms, 4%-l,2
Dioxane Toluene Toluene Benzene Isobutyl acetate Toluene Benzene Cyclohexane 5-Methyl-2-hexanone
12.1 35 35 30(0) 20.5 30 30 30 12.6(6»)
139 16.9 11.8-10.6 33.7 185 30.5 8.5 11.2 150
0.52 0.765 0.765 0.715 0.50 0.725 0.78 0.75 0.50
4 6 3 9 6 9 4 4 4
References page VII - 68
TABLE 1. cont'd No. of samples Polymer
Solvent
3-Pentanone Toluene 94%-cw, 4%-trans, 2%-l,2 Benzene Dioxane 92%-cis, 3%-trans, 5%-l,2 Benzene 51%-trans, 43%-cis, 6%-l,2 Toluene 51%-trans, 36%-cis, 7%-l,2 Tetrahydrofiiran 11%-trans, 4%-cis, 25%-l,2 Cyclohexane 19%-trans, 21%-cis Cyclohexane 97%-frans, 3%-1,2 Cyclohexane Toluene ca. 100%-cw Benzene Heptane/hexane (1/1, v/v) 65%-l,2, 25%-trans, 10%-cw Toluene 5°C-emulsion, randomly 3-Pentanone branched 50°C-emulsion, randomly Benzene branched Poly(butadiene-c0-acrylonitrile), Buna-N rubber Acetone Benzene Chloroform Toluene Poly(butadiene-co-styrene), Buna-S, GR-S, or SBR rubber Benzene Cyclohexane 2-Pentanone Toluene
linear fraction Toluene branched fraction Toluene Poly( 1 -butenylene-co- vinylethylene) 43%-l,2 1,4-Dioxane Tetrahydrofuran Poly(2-terf-butylbutadiene) Benzene Octane Poly(chloroprene) NeopreneCG Benzene NeopreneGN Benzene NeopreneW Benzene
type, unspecified Poly(isoprene) natural rubber
synthetic cis 85-91%-cw
Butanone Butyl acetate Carbon tetrachloride Cyclohexane Toluene Benzene Cyclohexane 4-Methyl-2-pentanone 2-Pentanone Toluene Hexane Toluene Toluene 2,2,4-Trimethylpentane Heptane/propanol (78/22, v/v)
X(xlO3) (ml/g)
Temp. (0C) 10.3(0) 30 25 20.2(0) 32 30 30 25 20 40 30 32 20
152 33.9 41.4 205 10 39 25.6 12 36 28.2 29.4 14.5 138
25 24(9) 5(0)
a 0.50 0.688 0.70 0.50 0.77 0.713 0.74 0.77 0.70 0.70 0.753 0.76 0.53
110 0.62 M2^[rj\ = 7.15 + 3.47M
Fr.
W.R
MoI. wt. range (xlO4)
4 8 8 8 13 6 2 8 12 7 6 8 5
-
10-25 10-65 9-120 9-120 10-160 11-25 1-57 230-880 23-130 4-17 5-16 18-50 ?
LS OS OS OS LS OS LS LS LS LS OS LS SD
B A A A B,R A A C B,R B A A A
17 18 19 19 20 21 733 22 23 24 25 26 27
8 10
-
7-70 10-100
OS OS
B C
28 29
5-124
OS
C
29
B B B B
28 28 28 28
M2I*[rj]4/3 = 4.61 +0.3287M 16
25 25 25 25
Method(s)
Remarks
Refs.
50 13 54 49
0.64 0.55 0.68 0.64
5 5 5 7
-
2.5-10 2.5-10 2.5-10 2.5-40
OS OS OS OS
25 25 30 21 (0) 25 30 30 30 30
52.5 54 31.6 185 52.5 16.5 37.9 21.4 535
0.66 0.66 0.70 0.50 0.667 0.78 0.71 0.74 0.48
24 8 6 6 25 6 15 20
9 -
1-160 1-165 5-25 5-25 2.5-50 3-35 5-25 3-20 20-100
OS OS OS OS OS OS OS OS OS
A AJR B
45 46 47 47 28 48 47 41 41
15.7 (0) 30 21 21
173 32.3 4.2 4.2
0.50 0.72 0.80 0.80
6 6 -
8 7
0.88-22 0.88-22 6-90 6-35
LLS, SEC, OS LLS, SEC, OS SD SD
A A A A
890 890 30 30
25 25 25 25 25(0) 25 25 45.5 (0) 25
2.02 14.6 15.5 15.5 113 37.8 22.1 107 50
0.89 0.73 0.71 0.72 0.50 0.62 0.69 0.50 0.615
10 16 8 9 7 7 7 7 13
-
6-150 2-96 5-100 5-80 15-300 15-300 15-300 15-70 4-120
OS OS OS LS LS LS LS LS OS
B B B B,R A A A B B
31 32 33 34 35 35 35 34 28
30 27 35 14.5(0) 25 35 20 30 30 30 30 30
18.5 30 60.7 119 50.2 17.4 68.4 8.51 20.0 15 22.2 37
0.74 0.70 0.57 0.50 0.667 0.74 0.58 0.77 0.728 0.74 0.683 0.63
-
4 1
20
4 -
5 5 -
12 16 8 6
8-28 ca. 185 5-100 8-28 7-100 5-100 5-80 20-100 14-580 2-15 23-580 43-580
OS LS, SD LS OS OS LS SD LS LS PR LS LS
C C B C B,R B A A A,R A A A
37 38 698 37 39 698 40 41 42 43 42 42
B A A B
TABLE 1. cont'd No. of samples Polymer 84%-m, 14%-trans, 2%~1,2
71%-m, 22%-trans, 7%-3,4
guttapercha
synthetic trans synthetic trans (98%)
98% \A-trans
70% CW-1,4, 23% trans-1,4 7% 3,4 76% cis-1,4, 19% trans-1,4 5% 3,4 star type 70% cis-1,4, 23% trans-1,4 7% 3,4 (mol. wt. of arm = various) 3 arm 4 arm 8 arm
Solvent Benzene
Temp. (0C)
Dioxane Cyclohexane Dioxane 4-Methyl-2-pentanone Toluene Benzene Dioxane Propyl acetate Benzene Benzene Cyclohexane Hexane Toluene Benzene Cyclohexane »7. Hexane Toluene Cyclohexane
25 25 34(9) 35 35 35 35 25 47.7 (0) 60 (0) 32 30 30 30 30 30 30 30 30 25
Cyclohexane
25
/ST(XlO3) (ml/g)
a
Fr.
W.P.
MoI. wt. range (xlO~4)
Method(s)
Remarks
OS OS OS OS OS OS OS OS OS OS LS LS LS LS LS LS LS LS LS LS
B B B A A A A A,R A C C B B B B B B B B A
44 44 44 786 786 786 786 19 19 37 26 699 699 699 699 887 887 887 887 891
Refs.
13.3 11.2 145 20.2 94 76 17.5 35.5 191 232 43.7 18.1 16.2 13.8 17.6 18.1 16.2 13.8 17.6 20.5
0.78 0.78 0.50 0.73 0.53 0.56 0.74 0.71 0.50 0.50 0.65 0.722 0.736 0.711 0.729 0.722 0.736 0.711 0.729 0.730
20 25 30 5 5 5 5 9 9 24
~ 3 -
8 7
-
6 8 7 5 11
-
2-80 2-60 2-50 2-32 2-32 2-32 2-32 0.2-5 0.2-5 10-20 8-140 14-77 14-77 14-77 14-77 14-69 16-130 16-105 14-77 1.5-342
18.0
0.74
5
-
33-724
LS
A
892
0.757 0.753 0.493 0.726 0.501 0.741 0.502 0.764 0.722 0.736 0.711 0.729
~ 6 6 6 4
-
-
14-70 14-70 14-70 14-70
LS LS L LS LS LS LS LS LS LS LS LS
B B B B
893 893 893 893 893 893 893 893 894 894 894 894
0.68 0.63 0.57 0.73 0.60 0.65 0.55 0.72
5 5 5 5 6 6 6 6
-
3-54 3-54 3-54 3-54 3-48 3-48 3-48 3-48
OS OS OS OS OS OS OS OS
A A A A A A A A
786 786 786 786 786 786 786 786
0.50 0.77
7 7
-
1.3-27 1.3-27
LLS, SEC, OS LLS, SEC, OS
A A
890 890
0.52 0.75 0.66
8 8 11
-
1.1-14 1.1-14 25-130
LLS, SEC, OS LLS, SEC, OS LS
A A
890 890 36
1.04 0.61 0.52 0.76 0.50 0.72
12 10 6 6 3 U
-
2-18 4-700 2.7-55 2.7-55 10-130 0.03-0.5
LS LS LLS9SEC LLS5SEC LS EG
B B A A C B,L
86 87 896 896 81 82
Cyclohexane 25 12.5 Cyclohexane 25 11.6 1,4-Dioxane 34 75.5 Toluene 34 9.47 12 arm 1,4-Dioxane 34 53.9 Toluene 34 5.70 16 arm 1,4-Dioxane 34 37.4 Toluene 34 3.04 trans 1,4 Benzene 30 18.1 Cyclohexane 30 16.2 Hexane 30 13.8 Toluene 30 17.6 Poly(isoprene)-/?/0c£-poly(styrene), A*-B „ k/n, (50/50, w/w) Cyclohexane 35 21.8 Dioxane 35 32.6 4-Methyl-2-pentanone 35 53.1 Toluene 35 14.6 k/n, (25/75, w/w) Cyclohexane 35 39.3 Dioxane 35 24.8 4-Methyl-2-pentanone 35 62.8 Toluene 35 14.3 Poly(isopropenylethylene-co-l-methyl-l-vinylethylene)20-25%-l,2,70-75%-3,4 2-Octanol 30.5(0) 102 Tetrahydrofuran 30 11.6 Poly( 1 -methyl-1 -butylene-a?-isopropenylethylene) 51 %-1,4,49%-3,4 2-Octanol 41.3 78 Tetrahydrofuran 30 14.6 Poly(l,l,2-trichlorobutadiene) Benzene 25 31.6
S
-
1.2. POLY(ALKENES), POLY(ACETYLENES) Poly(alkene)C l0 -C l8 Poly(alkene) C 1 2 -C 1 8 Poly(l-butene) atactic
Toluene Cetane 2-Octanol Tetrahydrofuran Anisole Benzene
25 38 23.6 25 86.2(0) 30
12.7 21 60.5 8.24 123 22.4
References page VII - 68
TABLE 1. cont'd No. of samples Polymer
isotactic
Solvent Ethylcyclohexane Phenyl ether Anisole Decalin Ethylcyclohexane Heptane Nonane Phenetole Phenyl ether 1,2,4,-Trichlorobenzene Cyclohexane/propanol (80/20, v/v) (70/30, v/v) (65/35, v/v)
Poly(ethylene) low pressure
Biphenyl 1-Chloronaphthalene
Decalin
Decanol Diphenyl ether Diphenylmethane Dodecanol
Octanol Tetralin
1,2,4-Trichlorobenzene
3,5,5-Trimethylhexyl acetate p-Xylene
Temp. (0C) 70 141 (0) 89(0) 115 70 35 60 80 64.5(0) 148(0) 135 35 35 35 127.5 (0) 130(0) 125 125 125 129 135 135 135 135 135 153.3(0) 161.4(0) 142.2(0) 137.3(0) 138(0) 144.5 180.1 (0) 105 120 120 130 130 130 135 135 135 121
AT(XlO3) (ml/g)
a
Fr.
W.P.
MoI. wt. range (xlO" 4 )
Method(s)
Remarks
Refs.
C A B
81 700 700 83 81 83 83 81 700 700 701
7.34 104 111 9.49 7.34 4.73 15.0 5.85 113 103 H.8
0.80 0.50 0.50 0.73 0.80 0.80 0.69 0.80 0.50 0.50 0.729
5 5 5 6 4 6 6 4 5 5
-
4-130 2-66 4-57 4.5-90 8-94 4.5-90 4.5-90 11-94 4-57 4-57
LS OS OS LS LS LS LS LS OS OS GPC
102 253 497
0.59 0.51 0.44
6 6 6
-
3-73 3-73 3-73
LS LS LS
B-C B-C B-C
702 702 702
323 302 138 18.4 43 27.1 67.7 46 62 58.5 62 302 295 315 307 316
0.50 0.50 0.58 0.78 0.67 0.71 0.67 0.73 0.70 0.725 0.70 0.50 0.50 0.50 0.50 0.50 0.61 0.50 0.83 0.78 0.77 0.76 0.725 0.72 0.64 0.706 0.691 0.55
4 5 ? 10 10 26 ~ 23 7 9 7 ? 6 ? 5 6 ? 4 36 20 6 9 4 19 4 6
2-30 5.7-27 ? 5-100 5-100 5-100 3-100 3-64 2-105 0.4-50 3-120 2-105 2-105 2-105 2-105 8-32 0.8-59 2-105 13-57 5-100 0.3-50 2-30 0.4-50 8-17 3-45 0.8-123
B
1-59
LV LS, GPC LS LS LS LS LS LS LS OS GPC7LS LV LS LV LV LS LS LV LS LS LS OS OS LS LS GPC, LS GPC LS
58 703 59 60 61 62 63 64 65,66 67,68 704 58 65 58 58 69 705 58 70 60 71 71 72 73 706 704 701 705
0.83 0.83 0.725
4 8 ?
-
13-50 1-18 0.4-50
LS OS LV
C C B,R
70 74 75
(0.65) 0.738 0.63 0.63
9 8 7 -
22 7
LS OS OS OS CR
D B D D A
76 77 78 79 80
0.71
-
3
54-116
LS
B
898
0.51 0.64 0.502 0.543 0.523 0.522
6 6 6 6 6 6
-
0.92-23 0.92-23 2.8-39 2.8-39 2.8-39 2.8-39
LLS, SEC, OS LLS, SEC5 OS LS LS LS LS
A A A A A A
890 890 897 897 897 897
286 16.2 23.6 32.6 43.5 51 37.8 95.4 51 51.6
105 16.5 105 17.6 105 51 Paraffin wax (Afn = 390 ± 10) 150 (42) high pressure Decalin 70 38.73 p-Xylene 75 135 81 105 (normal paraffin) Carbon tetrachloride 20 [77] = - 1 . 1 4 + 0.104 M Poly(ethylene-a/Metrafluoroethylene) Diisobutyl adipate 240 2.3 Poly(ethylene-co-isopropylethylene) n-Hexyl acetate 65 171 Tetrahydrofuran 30 71.3 Poly(ethylene-ctf-propylene) Benzene 19.0 201 214 136 n-Decyl acetate 5.0 162 n-Heptyl acetate 38.0 156
~ ? > 10 8 10 -
0.04-11 0.2-3.5 0.2-7.6 1-10 0.024-0.048
A
A B B
? C,D D D B,R B B B B B B F B C B B B,R D A B
TABLE 1. cont'd
Polymer
Solvent
Poiy(ethylene-co-propylene-c-diene), EPDM rubber Cyclohexane Poly(isobutene) Anisole Benzene
Benzene
40 105(0) 24(0) 25 30 40 60 25 30 25 10 20 30 40 50 25 30 30 25 25 20 25 25 10 20 30 40 50 86(0) 0 15 25 30 50 60 90 25(0)
lsoamyl isovalerate
25(0)
Benzene Carbon tetrachloride 5-Methyl-3-heptanone Toluene
22.8(0) 25 55.5(0) 25 30 60.9 30
Benzene Carbon tetrachloride Chloroform Cyclohexane
Cyclohexane
Cyclohexane Decalin Diisobutylene n-Heptane Isooctane
Phenetole Toluene
oligomer-polymer
Poly(isobutene-co-isoprene), butyl rubber
Poly(methylbutylene)
Temp. (0C)
«-Hexyl acetate Tetrahydrofuran Poly (isopropy lethy lene-co-1 -methyl-1 -ethylethylene) 2-Octanol Tetrahydrofuran Poly(3-methyl-l-butene) Diisobutylene Poly( 1 -methy lbutylene-c-isopropylethy lene) 2-Octanol Tetrahydrofuran Poly(4-methyl-l-pentene) Biphenyl Decalin Diphenyl ether Diphenylmethane Poly(l-octene) Bromobenzene Cyclohexane Phenetole
26.2 30 20 53.3 30 194.6(0) 130 210.0(0) 176.6(0) 25 30 50.4(0)
(ml/g)
53.1 91 107 83 61 43 26 100 29 71 25.6 24.2 23.3 22.9 22.4 40 27.6 26.5 13.5 22 36 130 15.8 38.1 36.8 36.2 34.6 33.6 91 40 24 87 20 20 13.5 12.6 (M w >10 5 ) (M w <10 5 ) (Af w >10 5 ) (M w <10 5 ) 115 10.7 109 66 21.4 169 42.2
No. of samples tf(xlO3) a Fr. W.P.
0.75 0.50 0.50 0.53 0.56 0.60 0.66 0.504 0.68 0.55 0.639 0.697 0.699 0.701 0.702 0.72 0.69 0.69 0.740 0.70 0.64 0.50 0.697 0.624 0.626 0.627 0.631 0.633 0.50 0.60 0.65 0.56 0.67 0.68 0.71 0.72 0.50 Not const, 0.50 Not const. 0.50 0.78 0.50 0.60 0.678 0.51 0.68
MoI. wt. range (xl(T4)
Method(s)
20 15 9 9 9 9 12 12 6 7 12 6 23 5 4 8 6 6 5 6 4 3 19
3-30 18-188 18-188 ~ 0.05-126 0.05-126 0.05-126 0.05-126 9 1.35-148 0.05-126 5.7-490 6 2.6-110 6 2.6-110 6 2.6-110 6 2.6-110 6 2.6-110 14-34 4-71 0.05-126 18 6.4-161 530-1680 1-130 0.4-2.5 7 0.84-148 6 2.6-110 6 2.6-110 6 2.6-110 6 2.6-110 6 2.6-110 5-188 1-146 - 1 - 1 4 6 14-34 1-146 - 1 - 1 4 6 11-146 46-146 0.011-179
OS LV LV OS, CR OS1CR OS, CR OS, CR SEC1LLS OS, CR LS LV LV LV LV LV OS OS OS, CR SEC5LLS LS OS OS SEC, LLS LV LV LV LV LV LV LV LV OS LV LV LV LV LS
A B B B,R B B B A-B B A(?) A-B A-B A-B A-B A-B B A,R B A-B A-B A,R A,L A-B A-B A-B A-B A-B A-B B B B B B,R B B B A
41 49 49 50 50 50 50 1010 50 899 901 901 901 901 901 51 52 50 1010 53,54 55,52 56 1010 901 901 901 901 901 49 50 50 51 50 50 50 50 904
19
-
0.011-179
LS
A
904
5 6 5 5 8 8 8
-
15-72 10-30 15-72 15-30 10-30 0.84-60 0.84-60
LS OS LS OS OS LLS, SEC, OS LLS, SEC, OS
A A A A A A A
787 57 787 57 57 890 890
Remarks
Refs.
92 10.3 42
0.49 0.75 0.63
7 7 6
-
1.5-28 1.5-28 1-20
LLS, SEC, OS LLS, SEC, OS LS
A A A
890 890 85
74 29.8 152 19.5 158 160 2.90 5.75 65.5
0.52 0.68 0.50 0.75 0.50 0.50 0.78 0.78 0.50
8 8 7 5 6 6 5 6 4
-
1.1-43 1.1-43 6-30 6-30 6-30 6-30 25-400 25-400 60-400
LLS, SEC, OS LLS, SEC, OS OS OS OS OS LS LS LS
A A B B B B A A A
890 890 707 707 707 707 84 84 84
References page VII - 68
TABLE 1. cont'd No. of samples Polymer Poly(pentenamer) 80-85%-/ra«j, 19-12%-cis PoIy(I-phenyl-1-propyne)
Solvent
Cyclohexane Isopentyi acetate Toluene Cyclohexane Toluene
Temp. (0C)
K(XlO 3 ) (ml/g)
30 56.9 38(0) 234 30 52.1 36(6) (wormlike behavior) 25 (wormlike behavior)
Fr.
W.P.
MoI. wt. range (xlO~ 4 )
0.68 0.50 0.69 0.5--0.8
5 8 10 12
-
3.6-63 3.6-63 3.6-63 1.6-145
LS LS LS LS, SE
B B B A
788 788 788 902
Not const.
12
-
1.6-145
LS, SE
A
902
-
2.8-39 2.3-42 2.3-42 6-31 2-34 4-71 4-33 6-31 2-34 1.5-33 2-39 2-62 2-72 4-71 2-34 3.7-21 3.7-21 ? 2-34 5-42 5-50 10-170 5-63 2-62 10-100 5-42 5-42 3-48 3-48 2-11 4-54 5-50 ? 9-45
LS LS, SEC LS, SEC OS OS LV OS OS OS OS OS LS LS LV OS OS OS ? OS LV OS LS LS LS LS LV LV OS OS OS OS OS OS LS
A A A A A B A A A A A A,R D B A A A
897 897 897 88 89 708 90 88 89 90 91 88 92 708 89 90 90 93 89 94 708 95 96 88 97 94 94 90 90 98 96 708 99 100
a
Method(s)
Remarks
Refs.
Poly(propylene)
atactic
n-Octyl acetate 3-Nonanol 1-Octanol Benzene Biphenyl 1-Chloronaphthalene Cyclohexane Cyclohexanone Decalin
Isobutyl acetate Isopentyi acetate Phenyl ether
isotactic
Tetralin Toluene Biphenyl 1-Chloronaphthalene Decalin Dibenzyl ether Diphenyl ether
Tetralin
syndiotactic head-to-head 94%-trans> 6%-l,2 S9%-trans,U%-\>2
p-Xylene Heptane Cyclohexane Cyclohexane
27.0 5.0 77.0 25 30 129(0) 74(0) 25 30 92(0) 135 135 135 58(0) 34 (0) 145 153(0) 130 30 125.1 (0) 125(0) 139 145 135 135 183.2 (0) 142.8 (0) 145(0) 153 135 135 135 85 30
175 113 110 27.0 33.8 128.3 182 16.0 20.9 172 15.8 11.0 54.3 158,5 168.5 192 120 1.24 21.8 152 141.0 21.5 4.9 11.0 10.0 106 137 132 112 2.5 9.17 19.3 96 31.2
0.512 0.536 0.504 0.71 0.67 0.50 0.50 0.80 0.76 0.50 0.77 0.80 0.65 0.50 0.50 0.47 0.50 0.96 0.725 0.50 0.50 0.67 0.80 0.80 0.80 0.50 0.50 0.50 0.54 1.0 0.80 0.74 0.63 0.71
6 7 7 6 6 3 3 6 6 4 6 6 3 6 3 3
10 -
7 4 5 Il 9 6 4 4 4 4 4 5 9 5 12 5
-
30 30 30 30
493 4.16 295 3.82
0.39 0.86 0.43 0.90
5 5 3
-
0.2-1.1 2.1-4.2 0.3-0.8 1 7-3.2
VOS, OS VOS, OS VOS, OS VOS, OS
30 30 30 25 30
6.31 68 6.5 19.1 5.31
0.80 0.66 0.82 0.71 0.79
7 7 7
21 5 -
2-50 1-20 4-127 49-320 15-153
SD PR OS LS LS
B C B D B
101 102 710 905 972
30 30 30
9.1 8.9 10.6
0.84 0.83 0.80
8 8 8
-
1.3-5.5 1.3-5.5 1.3-5.5
VOS1GPC VOS, GPC VOS5GPC
A-B A-B A-B
908 908 908
0.93 0.92 0.89
7 7 7
-
0.7-2.9 0.7-2.9 0.7-2.9
VOS, GPC COS 5 GPC COS 5 GPC
A-B A-B A-B
909 909 909
5
-
A A B A,R A,R A,R A A A A A,R B A L L
709 709 709 709
1.3. P O L Y ( A C R Y L I C ACID) AND DERIVATIVES Poly(acrylamide)
Water
Aq. NaCl(IN) Aq. NaCl (0.12M) Poly(/V-acryloyl-m-aminobenzoic acid) W,tf-Dimethylacetamide /V,/V-Dimethylformamide Dimethyl sulfoxide Poly(/V-acryloyl-0-aminobenzoic acid) /V,Af-Dimethylformamide Dimethyl sulfoxide Tetrahydrofuran
25 25 25
3.74 3.83 3.39
TABLE 1. cont'd
Polymer
Solvent
Temp. (0C)
Poly(acrylamide-co-yV,yV,M-trimethyl aminoethyl chloride acrylate) 70% acrylamide Aq. NaCl(IN) 25 Poly(acrylic acid) 1,4-Dioxane 30(0) -,sodium salt Aq. NaOH (2M) 25 Aq. NaCl (0.012 M) 20 (IM) 25 Poly(acrylic acid) -, sodium salt Aq. NaCl (0.05M) 25 (0.1 M) 25 (0.3M) 25 (0.5M) (1.0M) Aq. NaBr (1.5M) (1.5M) (0.5M) (0.1 M) (0.05M) (0.025 M) (0.01 M)
Poly(acrylonitnle) (polymerized at - 300C) (polymerized at 600C)
(0.005 M) (0.0025 M) Aq. NaSCN (1.12M) 7-Butyrolactone
Dimethylformarnide
(Deionized DMF)
(polymerized at - 300C) (polymerized at 6O0C)
Dimethylacetamide
Dimethyl sulfoxide
Ethylene carbonate Ethylene carbonate/water (85/15, w/w)
25 25 15 15(0) 15(0) 15 25 15 25 15 15 25 15 25 15 15 30(0) 30(0) 20 30 30 30 50 20 25 25 25 25 25 25 25 25 25 30 30 30 35 35 50 20 35 50 20 50 140 50 25
(ml/g)
tf(xlO3) a
No. of samples — Fr. W.P.
MoI. wt. range (xlO~ 4 )
Method(s)
Remarks
Refs.
10.5 76 42.2
0.73 0.50 0.64
12
6 4 -
45-270 13-82 4-50
LS OS OS
D B C
905 104 105
15.47
0.93 0.90
7 12
-. -
7-180 4-50
LV OS
B C
106 105
7.35 14.6 16.9
0.88 0.80 0.75
4 4 4
-
9.4-60 9.4-60 9.4-60
LLS 5 GPC LLS, GPC LLS, GPC
B-C B-C B-C
906 906 906
18.6 41.5
0.72 0.63
4 4
-
9.4-60 9.4-60
LLS, GPC LLS, GPC
B-C B-C
906 906
145 165 124 52.7 50.6 25.4 31.2 28.1 16.3 17.6 13.6 13.2 (44.2) (24.9) 154 121 34.3 57.2 34.2 40.0 28.7 17.7 16.6 24.3 39.2 52.0 15.5 57.4 39.6 44.3 69.8 29.6 20.9 33.5 27.8 31.7 30.0 30.7 27.5 27.4 32.1 28.3 20.9 29.5
0.50 0.50 0.50 0.628 0.656 0.755 0.755 0.77 0.84 0.85 0.89 0.91 0.83 0.89 0.50 0.50 0.730 0.67 0.70 0.69 0.740 0.78 0.81 0.75 0.75 0.690 0.80 0.73 0.75 0.70 0.65 0.74 0.75 0.72 0.76 0.746 0.752 0.761 0.767 0.764 0750 0.758 0.75 0.718
4 5 4 7 7 7 7 7 7 7 7 7 7 7 5 4 5 6 5 5 5 5 7 3 7 7 9 12 22 6 6 6 9 9 13
-
5 4 16 5 8 7 7 21 6 6 -
9.4-60 6-64 12-83 1-50 2-80 1-50 2-80 1-50 1-50 2-80 1-50 2-80 1-50 1-50 6-64 12-83 4-40 4-30 6-30 15-53 4-40 7-30 5-27 3-25 3-100 5-52 3-10 0.3-1.5 4-30 2-20 8-140 4-30 6-30 16-48 3-58 9-76 4-102 2-40 2-40 2-40 9-40 9-40 4-40 7-40
LLS, GPC LV LS LV LV LV LV LV LV LV LV LV LV LV LV LS LV (LS) SA SA LS LS LS SD LS OS LS LS 5 SD EG OS LS LS SA SA LS DV LS LV LV LV LV LV LV LS LV
B-C C C C C,R C C C C C C C C C C C A,R B B D A B B C C B,R B-C L C C C B B D B A,R A A A A A A A
906 107 108 109 110 109 110 109 109 110 109 HO 109 109 107 111 134 135 135 136 134 137 138 139 140 711 141 142 143 143 144 135 135 136 145 134 134 134 134 134 134 134 146 134
263
0.49
7
-
5.2-52
LS, OS
A-B
951
-
References page VII - 68
TABLE 1. cont'd No. of samples Polymer
Solvent Hydroxyacetonitrile Aq. HNO 3 (60%)
Poly(benzyl acrylate) Poly(butyl acrylate) Poly(ter?-butyl acrylate)
Butanone Acetone Acetone Butanone Hexane Methanol Pentane Poly (1,1 -dihydroperfluorobuty 1 acrylate) Benzofluoride Methyl perfluorobutyrate Poly(MW-dimethylacrylamide) Methanol Water Poly(ethyl acrylate)
Poly(2-ferrocenylethyl acrylate) Poly(ferrocenylmethyl acrylate) Poly(hexadecyl acrylate) Poly(N-isopropylacrylamide) Poly(isopropyl acrylate)
Acetone Benzene Butanone Chloroform Ethyl acetate Benzene Benzene Methanol Heptane Tetrahydrofuran Water Acetone Benzene
Bromobenzene
isotactic
Chloroform 2,2,3,3-tetrafluoropropanol
atacti
c syndiotactic isotactic atactic and syndiotactic Poly(methyl acrylate)
Acetone
Benzene
Butanone
Dimethyl malonate Ethyl acetate Isopentyl acetate 2-methylcyclohexanol Toluene
Temp. (0C) 20 50 0 20 35 25 25 25 24.2 (0) 25 25
X(xlO3) (ml/g) 40.9 35.4 33.9 30.7 0.587 6.85 4.7 3.2 49.0 16.0 22.0
a
MoI. wt. range (xlO~ 4 )
Method(s)
Remarks
LV LV LV LV OS LS LS LS LS LS LS
A A A A C B B B B B
134 134 134 134 337 112 712 712 712 712 712
Fr.
W.P.
0.697 0.707 0.740 0.747 0.883 0.75 0.75 0.80 0.50 0.61 0.57
8 8 6 5 ? 5 5 5 5 5
6 -
4-34 4-34 2-40 4-40 ? 5-27 7-31 7-31 7-31 7-31 7-31
Refs.
26.6 26.6 25 25 40 25 30 30 30 30 30 25 25 30 20 27 20(9) 30 25 25 30 25 60 30 25
13 12 17.5 23.2 20.0 51 20.0 27.7 2.68 31.4 26.0 4.68 6.84 48.7 1.74 9.59 145 13.0 14.9 12.4 11.8 11.3 11.6 14.1 19.7
0.56 0.60 0.68 0.81 0.65 0.59 0.66 0.67 0.80 0.68 0.66 0.70 0.75 0.55 0.82 0.65 0.50 0.69 0.70 0.701 0.71 0.704 0.698 0.72 0.697
7 7 7 5 5 6 8 8 6 9 20 4 20 20 5 7
3 3 8 6 4 7 5 5 3 8 6 -
20-200 20-200 5-122 5-122 11-122 35-450 16-50 5-67 48-700 9-54 9-54 1.4-2.7 0.7-2 6-70 I-10 10-100 10-100 6-30 7-70 4-100 7-20 4-100 4-100 7-30 10-65
LS LS LS LS LS LS OS OS LS OS OS VOS, GPC VOS, GPC OS LS OS OS LS OS LS LS LS LS LS LS
B B C C C B,R B,R C B-C C C D C-D C B A A B B B,R B B B B B
113 113 103 103 103 114 115 116 117 116 116 713 714 116 118 975 975 119 120 121 119 121 121 122 121
25 25 60 60 20 25 25 25 30 25 30 30 30 35 20 25 30 35 30 35 62.5(6») 56.0(0) 30 35
17.3 15.9 17.9 14.7 (7.40) 5.5 19.8 5.20 28.2 2.58 4.5 3.56 4.59 12.8 3.5 14.1 3.97 (34) 3.51 11 68 68 7.79 21
0.703 0.708 0.693 0.704 (0.76) 0.77 0.66 0.77 0.52 0.85 0.78 0.798 0.795 0.71 0.81 0.67 0.772 (0.61) 0.793 0.69 0.50 0.50 0.697 0.60
6 6 4 6 8 9 11 7 4 7 6 6 13 4 6 4 6 4 6 -
4 7 5 3 8 7
8-110 20-110 10-65 20-110 7-32 28-160 30-250 4-183 4-45 20-130 7-160 25-190 15-140 5-30 6-240 17-68 25-190 5-47 50-190 24-148 20-160 40-105 25-190 12-69
LS LS LS LS OS LS LS LS OS OS LS LS OS OS LS LS LS LV LS LS LS LS LS LS
B B B B
121 121 121 121 123 124 125 715 126 127 128 129 129 130 128 131 129 132 129 133 129 129 129 133
B,R B B B
B.R B C A-B.R B B C B A B B B A
TABLE 1. cont'd No. of samples Polymer
Solvent Butanone-2-propanol (42/58, v/v) (1/1, v/v)
branched (42/58 v/v) PolyU-methylphenyl acrylate) Butyl acetate Poly(morpholinocarbonylethylene) Dimethylformamide Aqueous NaCl (0.1 M) Poly(piperidinocarbonylethylene) Dimethylformamide Poly(propyl acrylate) Butanone
W.P.
MoI. wt. range (xlO4)
Method(s)
Remarks
-
29-140 14-83 50-190 37-250 2-110
LS LS LS LS SD
B C B B A
124 108 129 125 346
? ? ? 4
-
? ? ? 71-181
LS LS LS LS
C C C A
338 338 338 117
0.82 0.62 (0.77) 0.774 0.81 0.68 (0.89) 0.78 0.80 0.648 0.630 0.726 0.50 0.50 0.50 0.63 0.675 0.499 0.66 0.73 0.505 0.476 0.76
5 6 10 5 3 8 6 6 6 10 8 9 5 6 6 6 6 4 5 7 6
9 3 -
17-120 100-600 8-300 1270-2070 25-260 11-670 67-132 4-800 8-80 1230-2450 1330-2070 959-2160 30-260 4-800 40-170 46-870 2.8-107 2.8-107 2.8-107 14-155 6.8-155 3.4-155 3.4-155
LS LS LS LS LS OS LS OS LS LS LS LS LLS, SEC LLS, SEC LLS, SEC LLS, SEC LLS1SEC LLS, SEC LLS5SEC
B B,R B A A A A A A A A
339 150 151 912 152 150 153 154 155 912 912 912 152 154 156 157 917 917 917 917 917 917 917
7.8 9.0 35.5
0.68 0.64 0.50
8 8 8
-
4-113 4-113 4-113
LS LS LS
B B B
771 771 771
5.75 16 4.1 4.1 2.4 47 9.4
0.68 0.60 0.71 0.71 0.78 0.49 0.68
15 6 7 7 15 6 6
-
6-350 11-204 15-2500 20-2500 6-300 11-204 7-88
LS LS LS LS LS LS L
1.35
4 5
-
26-74 48-140
LS LS
1.25 0.50 0.72
5 6 6
-
26-11 3.2-54 3.2-54
LS LLS, SEC LLS5SEC
0.66 0.58 0.70 0.494 0.651 0.494 0.687
8 8 8 6 7 6 7
-
10-610 10-610 10-610 4.8-31 5.1-475 5.1-475 5.1-475
LS LS LS
K(xlO3) (ml/g)
a
81 54.4 72 290 14.7
0.50 0.50 0.50 0.40 0.63
5 4 4 6 8
18 64 32 15.0
0.65 0.68 0.56 0.687
30 25 30 25 23 25 30 20 25 25 25 25 21.5(0) 21.5 (0) 23.7(0) 25 25 10.0 30 25 10.0 64.0 30
1.03 18.4 (4.0) 3.82 1.56 9.7 (1.15) 2.9 4.37 21.0 23.7 6.13 29.5 38 36.6 22.0 12.0 62.0 15.2 5.91 46.0 62.1 5.84
25 25 18.4(0) 20 25 20 20 20 25 25
Temp. ( 0 C)
20(9) 27.5 (0) 30(0) 20(6) 25 25 20 25 30
Fr.
Refs.
1.4. POLY(a SUBSTITUTED ACRYLIC ACID) AND DERIVATIVES Poly(benzyl methacrylate) Poly(butyl methacrylate)
Benzene Acetone Benzene Benzene Butanone
Chloroform Cyclohexane Dioxane Methyl ethyl ketone 2-Propanol
Poly(fer?-butyl methacrylate) anionic
Butyl acetate Butanone Cyclohexane Tetrahydrofuran free radical Butanone Cyclohexane ^-Heptane Tetrahydrofuran Poiy(2-ter?-butylphenyl methacrylate) Benzene Butanone Cyclohexane Poly(4-f
Unc. Unc. Unc. 35.7 (0) 30
37.5 30 35 30
0.00115 This relation not followed 0.00446 47.4 6.83 9.2 20.0 6.1 49.2 8.84 35.4 6.03
A B A C B,R
B
A-B B B
340 716 341 341 342 716 716 369 369
A-B A-B
369 914 914
A A A A-B B-C B-C B-C
343 343 343 915 915 915 915
References page VII - 68
TABLE 1. cont'd
Polymer Poly(cyclohexyl methacrylate)
Solvent Benzene Butanol
Butanone Cyclohexane
(ml/g)
No. of samples tf(xlO3) a Fr. W.P.
MoI. wt. range (xlO4)
Method(s)
30 25 23(6) 22.5(6) 25 25 30 25
8.4 3.54 33.7 45.2 31.8 5.79 7.0 8.8
0.69 0.77 0.50 0.50 0.533 0.68 0.66 0.67
5 9 5
-
6 5 9
-
80-200 10-419 57-445 10-125 10-125 57-560 80-200 10-419
LS LS LS LS LS LS LS LS
25 35 45 30 30 36 30 30 30 30
8.65 4.07 43.2 26.0 8.70 54.8 10.9 19.4 13.6 8.38
0.63 0.74 0.488 0.549 0.677 0.487 0.659 0.588 0.631 0.696
8 8 7 8 8 8 8 9 9 9
-
4-60 4-60 6.6-418 3.1-418 3.1-418 4.6-358 2.9-358 2.9-358 2.9-358 2.9-358
25 25 25 (6) 25 (6)
18.4 33.1 75.0 78.0
0.65 0.59 0.50 0.50
4 8 4 9
-
45 25 U (6) 30 31 30 23 13(0) 29.5 (0) 25 27.4 (6) 23 35 36.9(0)
38.6 3.61 34.7 4.56 36.6 1.05 8.64 32.2 34.8 2.21 33.7 2.83 8.6 47.5
0.485 0.712 0.50 0.73 0.53 0.64 0.64 0.50 0.50 0.77 0.50 0.79 0.71 0.50
9 7 10 10 10 10 8 7 7 8 8 10 4
23(0)
47.3
0.50
35 35(0)
47.6 56.4
Temp. (0C)
Remarks
Refs.
A
344 717 345 718 718 345 344 717
LS LS
B B A-C A-C A-C A-B A-B A-B A-B A-B
719 719 915 915 915 915 915 915 915 915
3.4-33 3.4-82 5.7-33 3.4-82
OS, SEC OS, SEC OS, SEC OS, SEC
A A A A
923 923 923 923
11 -
8.7-575 42-575 2.9-92 2.9-92 10-135 10-135 26-360 26-360 27-240 48-332 48-332 20-263 65-1200 22-130
LLS1SEC LLS, SEC LS, OS, SEC LS, OS, SEC LS, OS, SEC LS, OS, SEC LS LS LS LS LS LS LS LS
A-B A-B B B B B A A A A A A C B
911 911 913 913 913 913 158 158 159 160 160 161 162 156
10
-
20-263
LS
A
161
0.53 0.50
6 6
-
78-500 60-420
LS LS
A A
162 162
3.12
0.76
-
6
2-9
VOS, GPC
C,D
713
27.8 5.9 2.37 3.92 35.1
0.58 0.71 0.78 0.75 0.56
3 5 5 9
6 -
0.6-3.6 130-440 130-440 130-440 20-110
SD SD SD LS
C,D B B B
714 163 163 163 164
33.1 2.12 43.0
0.5 0.78 0.50
20 8 8
-
10-2000 6-41 6-41
SD LS LS
A A
730 165 165
10.6 12.9 52.4
0.70 0.69 0.51
6 5 7
-
4-52 4-52 4-52
LS LS LS
A,B A,B A,B
720 720 720
0.71
-
14
19-950
LS
A B A A B
Poly(cyclohexylthiolmethacrylate) Cyclohexane Tetrahydrofuran Poly(cyclooctyl methacrylate) 2-Butanol 1,4-Dioxane Toluene Poly(cyclopentyl methacrylate) Cyclohexane 1,4-Dioxane Ethyl acetate Methyl ethyl ketone Toluene Poly(2,6-dimethylphenyl methacrylate) Chlorobenzene Tetrahydrofuran Tetrahydrofuran/water Toluene Poly(diphenylmethyl methacrylate) 3-Heptanone Toluene Poly(decyl methacrylate) Ethyl acetate Tetrahydrofuran Poly(dodecyl methacrylate) Amy 1 acetate Tetrahydrofuran Poly(dodecyl methacrylate) Butyl acetate Isopropyl acetate Pentanol Poly(2-ethylbutyl methacrylate) Butanone 2-Propanol Poly(ethyl methacrylate) Butanone Ethyl acetate 2-Propanol Butanone-2-propanol (1/7, v/v) Ethyl acetate/ethanol (2/9, v/v) (1/6, v/v) Poly(2-ferrocenylethyl methacrylate) Benzene Poly(ferrocenylmethyl methacrylate) Benzene Polytfiexadecyl methacrylate) Benzene Carbon tetrachloride Heptane
25 21 21 21 25
Poly[4-(4-hexadecyloxybenzoyloxy)-phenyl methacrylate] Carbon tetrachloride Poly(hexyl methacrylate) Butanone 23 2-Propanol 32.6 (0) Poly(2-hydroxyethyl methacrylate) Dimethylformamide 30 Dimethyl sulfoxide 30 Methanol 30 PoIy[I -(2-hydroxyethyl) pyridiniumbenzene sulfonate methacrylate] Aq. KCL (0.5M) 25
2.62
721
TABLE 1. cont'd No. of samples Polymer
Solvent
PoIy[I(2-hydroxyethyl) trimethylammoniumbenzene sulfonate Aq. KCl (0.5M) Poly[AK2-hydroxypropyi) methacrylamide] Aqueous KCl (0.1 M) PolyfD.L-isobornyl methacrylate) 1-Octanol Tetrahydrofuran Poly(isobutyl methacrylate) Acetone
Acetone Benzene Benzene Butanone
Carbon tetrachloride 1,4-Dioxane 2-Hydroxymethyltetrahydrofuran Poly(5-p-methyl methacrylate) Benzene Cyclohexane 2-Pentanone Tetrahydrofuran Poly(methacrolein) Dimethylformamide Poly(methacrylie acid) M/V-Dimethylformamide/ l,4-dioxane(5/7, v/v) Methanol Aq. HCl (0.002 M) Aq. NaNO 3 (2M) Poly(methacrylonitrile) Acetone Dimethylformamide Poly(2-methoxyethyl methacrylate) Butanone Tetrahydrofuran Poly(methyl butacrylate) Butanol Butanone Poty(methyl ot-chloroacrylate) Chloroform Poly(methyl ethacrylate) Benzene Butanone 2,6-Dimethyl-4-heptanone Poly(methyl methacrylate) atactic Acetone
Acetonitrile
Benzene
Temp. ( 0 C)
AT(XlO 3 ) (ml/g)
Method(s)
a
Fr.
4.04
0.70
-
8
15-400
LS
721
25 39.6(0) 30 25 25 60 25 25 25 20 25 30 44 25 25 25
11.0 31.7 3.68 0.199 23.4 18.2 8.41 3.88 7.03 5.56 8.61 7.47 2.18 4.88 6.89 85.8
0.67 0.50 0.73 0.94 0.66 0.68 0.66 0.74 0.77 0.73 0.70 0.71 0.79 0.72 0.68 0.56
12 6 6 6 6 6 6 5 6 6 7 6 6 6 6 6
-
2-500 9-120 9-120 300-1100 50-116 50-116 1020-3460 1020-3460 50-116 300-1100 300-1100 300-1100 300-1100 1020-3460 1020-3460 50-116
LS GPC GPC LS OS OS OS LS LS LS LS OS
722 723 723 166 724 724 919 919 724 166 166 166 166 919 919 724
25 25 25(9) 25 20
9.6 11.5 43.6 11.5 2.8
0.67 0.65 0.50 0.65 0.97
6 6 6 6 -
?
12-230 12-230 12-230 12-230 0.5-2
LS LS LS LS OS, CR
B B B B ?
771 771 771 771 204
103 242 66 44.9 95.5 306
0.50 0.51 0.50 0.65 0.56 0.503
7 6 7 6 -
4 15
27.5-101 4-20 10-90 8-70 35-100 0.6-8
LS OS LV OS OS LV
B C B C C,H
907 147 148 149 202 203
methacrylate] 25
26.9(6) 26 30 25 20 29.2
W.P.
MoL wt. range (xlO4)
Remarks
C
C C C C -
Refs.
25 25 13 (6) 30 30 30 30 11.4(0)
7.34 7.57 57.0 5.43 3.08 2.35 4.29 67.6
0.71 0.71 0.50 0.73 0.78 0.82 0.75 0.50
12 12 4 10 8 6 10 10
-
4-220 4-220 6-60 7-430 20-780 16-110 4-200 4-200
LS LS LS LS LS LS LS LS
A-B A-B A A D A A A
725 725 168 168 726 168 168 168
20 20 25 25 25 25 25 25 25 25 30 39 46 30 45(6) 50 65 20 20 25 25
5.5 3.90 7.5 6.76 7.5 5.3 9.6 7.5 2.45 6.59 7.7 6.40 6.18 39.3 48 29 9.8 8.35 15.1 7.24 5.5
0.73 0.76 0.70 0.71 0.70 0.73 0.69 0.70 0.80 0.71 0.70 0.72 0.72 0.50 0.50 0.54 0.64 0.73 0.70 0.76 0.76
7 7 9 10 14 7 4 4 9 6 6 6 6 6 6 6 5 7 7 10 Il
6 -
7-700 7-700 8-137 3-700 2-740 2-780 180-350 3-98 6-210 5-41 6-263 5-41 5-41 10-86 10-260 10-260 10-260 7-700 8-90 6-100 2-740
SD SD LS SD LS, SD LS LS LS OS OS LS OS OS LV LV LV LV SD SD OS LS
A-B.R A-B B A-B A-B A-B,R A-B B-C B-C B A-B B B A-B A-BJR A-B A-B A-B
169 169 170 171 172 173 174 175 176 177 178 177 177 178 179 180 180 169 181 182 173
B A-BjR
References page VII - 68
TABLE 1. cont'd No. of samples Polymer
Solvent
Butanone
plasma initiated Butyl chloride Chloroform
living type
/?-Cymene 1,2-Dichloroethane Ethyl acetate 3-Heptanone 4-Heptanone Methyl isobutyrate Methyl methacrylate
Methyl methacrylate Nitroethane 3-Octane Propanol Tetrachloroethane 2,2,3,3-Tetrafluoropropanol Tetrahydrofuran Toluene
B utanone/2-propanol (55/45, v/v) (50/50, v/v) Methanol/toluene (9/5, v/v) oligomer-polymer atactic,/racem =0.79
isotacdc
Acetonitrile Benzene n-Butyl chloride Acetone Acetonitrile
MoL wt. range (xlO~4)
Method(s)
8 6 7 34 6 -
24-450 0.03-1 6-250 4-73 0.02-2 0.3-2 5-41 5-41 8-137 41-330 3-98 16-910 1610-3000 13-68 1.4-60 6-100 8-200 3-780 8-137 40-330 5-41 13-263 5-41 5-41 7-400 6.6-171 3-98 6-263 6-110 6.6-171 1-172 19-260 1.8-160 1.8-160 1.8-160 13-170 10-200 13-260 6.6-171 5-41 5-41 7-95
LS EB LS OS OS LS OS OS LS LS LS LS LS SA OS OS SD LS LS LS OS LS OS OS LS LV LS LS SD LV LS LV LS LS LS LV LS LV LV OS OS LV
7 6 10 6 6 6
-
4-330 5-41 0.2-7 19-263 5-41 5-41
LS LS OS OS LV OS OS
A A-B B A,L A-B B B
732 174 177 195 178 177 177
6 7 5 3
-
40-300 30-280 77-490 60-300
LS LS LS LS
A-B A-B A-B A-B
174 196 186 156
22 15 21 7 5 5
-
0.032-283 0.032-75.8 0.032-283 5-128 3-19 3-19
LS LS LS LS LV LV
A A A A-B A A
916 916 916 199 198 198
AT(XlO3) (ml/g)
a
Fr.
3.80 83 5.2 6.27 104 195 6.74 6.52 6.8 7.1 6.8 9.39 11 ±2 50.5 9.6 4.88 4.85 6.0 4.8 3.4 5.81 4.3 5.02 3.90 5.1 57.5 17.0 5.3 21.1 63.1 48 9.9 16.2 11.3 21.2 6.75 5.70 50 67.9 12.8 12.2 7.2
0.79 0.52 0.76 0.76 0.50 0.41 0.75 0.76 0.72 0.72 0.72 0.68 0.69 0.50 0.78 0.82 0.80 0.79 0.80 0.83 0.79 0.80 0.80 0.79 0.79 0.50 0.68 0.77 0.64 0.50 0.50 0.67 0.65 0.68 0.64 0.72 0.74 0.50 0.50 0.73 0.73 0.79
5 7 9 5 9 5 6 6 9 7 4 15
6 -
4 18 8 9 12 9 6 6 6 6 13 4 4 8 4 5 6 9 9 9 3 2 3 4 6 6 7
25 25 25 25 30 39 53
7.5 7.1 8.12 78 7.0 7.24 6.63
0.72 0.73 0.71 0.50 0.71 0.72 0.73
23 25 (0) 25(0) 26.2(0)
47.0 59.2 42.8 55.9
0.55 0.50 0.50 0.50
44.0 30.0 40.8 30 20 27.6(0)
23.0 130 75.5
Temp. ( 0 C) 25 25 30 30 30 30 39 53 25 25 25 25 25 35.4(0) 20 20 20 20 25 25 25 30 39 53 Unc. 159.7 (0) 25 30 20 33.7 (0) 33.8(0) 30 20 40 60 30 25 72(0) 84.4(0) 25 53 25
Not const. Not const. Not const. 0.63 0.448 0.500
W.P.
Remarks
A,L A~B,R A A,L A-B,L B B B,R A-B B-C A-B A-B B A-BJR A-B B A-B B A-B B B B A-B B-C A-B 1 R A-B A-B 1 R A-B A A A A-B C A-B A-B B B A
Refs. 183 184 178 185 185 178 177 177 170 174 175 186 727 187 188 182 169 173,189 170 174 177 178 177 177 190 191 175 178 192 191 179 178 918 918 918 178 193 179 191 177 177 194
TABLE 1. cont'd No. of samples Polymer
Solvent
Benzene p-Cymene 3-Heptanone Propanol 2,2,3,3-Tetrafluoropropanol Butanone/2-propanol (1/1. v/v)
Temp. ( 0 C)
ZiC(XlO3) (ml/g)
a
Fr.
W.P. -
MoI. wt. range (xMT4)
Method(s)
Remarks
Refs.
LV LV LS LS LV LV LV LV
A A B A-B A-B A-B A-B B
198 198 728 199 191 191 191 194
35 50 27.5 (0) 30 152.1 (0) 40.0(0) 75.9(0) 25
46 26.2 76.2 5.2 56.6 87.0 76.1 7.05
0.546 0.602 0.50 0.76 0.50 0.50 0.50 0.78
5 5 6 5 4 4 4 11
-
3-19 3-19 13-68 5-128 7-131 7-131 7-131 2-100
30.3 (0)
90.0
0.50
4
-
7-131
LV
A-B
191
4 4
8
73-232 73-232
LS LS LS
A A H
785 785 731
6 4
-
17-262 57-262
LS LS
B B
729 729
20 10 10 4 4 4 8 11 11
4 -
20-220 20-170 33-1250 33-1250 62-320 62-320 62-320 10-320 1.5-93 1.5-93
SD LS LS LS LS LS LS LS LS, OS, SEC LS, OS, SEC
5 5 12
-
3.6-21 3.6-21 1.5-94
VOS, SEC VOS, SEC LS
A-B A-B B
7
-
16-62
OS
B
6
-
4-85
GPC
6 6 6
-
48-59 48-59 48-59
SEC SEC SEC
A-B A-B A-B
921 921 921
10 10 6
4 -
85-510 8.2-138 8.2-138 4-85
LS LS, OS, SEC LS, OS, SEC GPC
D B B
905 913 913 735
5%-iso, 51%-hetero, 43%-syndiotactic
Acetonitrile/chlorobenzene (4.4/95.6, v/v) 25 (0) 68.3 0.50 (91.2/8.8, v/v) 25(0) 63.5 0.50 Poly(a-methyleneglutaronitrile) Dimethylformamide 25 31.6 0.65 Poly(methyl phenylacrylate), see 1.9 Other Compounds poly(l-methoxycarbonyl-l-phenylethylene) Poly(p-naphthyl methacrylate) Benzene 20 27.2 0.55 Tetralin 20(0) 47.5 0.50 Poly[4-(4-nonyloxy-phenyl methacrylate], Poly(phenylmethacrylic ester of nonyloxybenzoic acid) Carbon tetrachloride 24.3 0.5 Poly(octadecyl methacrylate) Tetrahydrofuran 30 2.5 0.75 Poly(octyl methacrylate) Butanol 16.8(0) 26.8 0.50 Butanone 23 4.47 0.69 Butyl acetone 10.5 (0) 0.45 20 0.53 30 0.54 Poly(tf-phenyl methacrylamide) Acetone 20 28.2 0.75 n-Propyl acetate 36(0) 37.1 0.50 Tetrahydrofuran 30 8.95 0.67 Poly(2-selenolylmethyl methacrylate) Chlorobenzene 25 36.3 056 Tetrahydrofuran 25 18.1 0.65 Poly(stearyl methacrylate) Tetrahydrofuran 30 9.0 0.67 Poly(tetrahydrofurfuryl methacrylate) Acetone 30 24.0 0.66 Poly(tetrahydro-4H-pyranyl 2-methacrylate) Isobutanol 30.4(0) 31.9 0.50 Poly(2-thiophenmethyl methacrylate) Chlorobenzene 25(0) 4.35 0.50 Tetrahydrofuran 25 6.95 0.72 Thiophen 25 9.00 0.66 Poly(ivyV,N-trimethyl aminoethyl chloride acrylate) Aq. NaCl(IN) 25 2.3 0.82 Poly(tridecyl methacrylate) Ethyl acetate 27(0) 32.2 0.50 Tetrahydrofuran 30 4.74 0.71 Tetrahydrofuran 30 2.93 0.76 Poly[2-(triphenylmethoxy)ethyl methacrylate] Mesitylene 47(0) 30 0.50 1.5.
C,H B B C C C B B
730 200 201 201 920 920 920 370 913 913 922 922 733,751 734 735
LV
736
POLY(VINYLETHERS)
Poly[(hexadecyloxy)ethylene] Poly(methoxyethylene)
Heptane Benzene Butanone Poly[(octadecyloxy)ethylene] Benzene Tetrahydrofuran Poly(vinyl methyl ether), see Poly(methoxyethylene)
21 30 30 25 30
70.8 76 137 170 224
0.50 0.60 0.56 0.47 0.35
6 13 13 -
7 7
0.5-3 1-45 1-45 0.1-1.5 9.4-11
SD LS LS LS LS
B,L B B D,H D,H
205 206 206 200 200
0.74
7
-
7-51
OS
B
234
1.6. POLY(VINYL ALCOHOL), POLY(VINYL HALIDES) Poly(chlorotrifluoroethylene)
2,5-Dichlorobenzotrifluoride
130
6.15
References page VII-68
TABLE 1. cont'd
Polymer
Solvent
Temp. (0C)
(ml/g)
tf(xlO3) a
Poly(tetrafluoroethylene-fl/f-ethylene), see also Poly(ethylene-a//-tetra-fluoroethylene) in group 1.2 Poly(vinyl alcohol) Water 25 20 0.76 25 300 0.50 25 140 0.60 30 66.6 0.64 30 42.8 0.64 30 45.3 0.64 30 73.4 0.63 80 94 0.56 Phenol/water (85/15, v/v) 30 24.6 0.80 Water/dimethylsulfoxide (100/0, v/v) 30 74.3 0.63 (90/10, v/v) 30 Not clear Poly(vinyl bromide) Cyclohexanone 25 32.8 0.55 Tetrahydrofuran 25 15.9 0.64 Methanol/tetrahydrofuran (17/83, v/v) 20 38.8 0.50 Poly(vinyl chloride) Benzyl alcohol 155.4(0) 156 0.50 Chlorobenzene 30 71.2 0.59 Cyclohexanone 20 11.6 0.85 20 13.7 1.0 20 112.5 0.63 25 12.3 0.83 25 24 0.77 25 204 0.56 25 174 0.55 25 8.5 0.75 25 13.8 0.78 30 16.3 0.77 Tetrahydrofuran 20 3.63 0.92 25 15.0 0.77 25 16.3 0.766 25 49.8 0.69 30 63.8 0.65 30 83.3 0.83 30 219 0.54 Poly(vinyl fluoride) Dimethylformamide 90 6.42 0.80 Poly(vinylidene chloride) Hexamethylphos25 25.8 0.65 phoramide l-Methyl-2-pyrrolidone 25 13.1 0.69 Tetramethylene sulfoxide 25 13.9 0.69 Poly(vinylidene fluoride) N,N-Dimethylacetamide, A^N^dimethylformamide, Af-methylpyrrolidone, M^-dimethyl-MA^-trimethylene urea 25 45 0.70
1.7.
No. of samples — Fr. W.P.
MoI. wt. range (xl(T4)
Method(s)
Remarks
B
Refs.
6 4 3 8 7 -
14 5 21
0.6-2.1 0.9-17 1-7 0.6-16 1-80 1-80 3-12 10-46 3-12
OS SD SD OS LS LS LV LS LV
B B C A,R B B B
208 209 210 212 213 213 737 214 215
7 5 7 7
-
DP = 815-2830 DP = 815-3400 2-10 2-10
VG VG LS LS
C C B B
924 924 217 217
7 9 7 7 5 11 13 ? 6 5 28 6 20 22 23 5 9 7 16 -
6 5 3 9 7
2-10 4-35 3-19 2-10 7-13 9-15 2-14 3-14 2-15 6-22 4-20 1-12 3-19 2-17 1-12 2-30 4-40 3-32 3-19 5-30 14-66 0.8-12
LS LS SA OS OS OS OS OS OS LS LS LS SA OS LS LS LS LS SA LS SV LS
B B B C C,D D,H
D C
218 219 220 221 222 222 223 224 225 226 227 228 220 229 228 230 231 232 220 233 235 738
-
7 7
0.8-12 0.8-12
LS LS
C C
738 738
LS
-
925
7
C C B A,B,R B B A,B A,B,R A-B B
POLY(VINYLESTERS)
Poly(allyl acetate) Poly(vinyl acetate)
Benzene Acetone
27 66 0.53 6 [77] = 0.104M 050 + 0.00725M 090 18 24.5 0.67 20 15.8 0.69 25 21.4 0.68 25 18.8 0.69 25 14.6 0.72 25 10.8 0.72 30 17.6 0.68 30 8.6 0.74 30 17.4 0.70 30 10.2 0.72 30 10.1 0.73
8 21 6 6 6 ? 10 16 8 ? 11
? 6 8 -
0.1-0.3 0.3-150 4-34 19-72 4-34 ? 0.7-1.3 0.9-2.5 2-163 8-66 7-68 3-126 6-150
CR LS OS LS OS LS EG EG OS LS OS LS LS
A B B C,L B,L A-B A-B C A
216 236 237 238 237 239 240 240 241 242 243 244 236
TABLE 1. cont'd No. of samples Polymer
Poly(vinyl Poly(vinyl Poiy(vinyl Poly(vinyl
Solvent
benzoate) butyrate) caproate) 4-chlorobenzoate)
Poly(vinyl formate)
Poly(vinyl isobutyrate) Poly(vinyl isocaproate) Poly(vinyl pivalate)
Poly(vinyl sulfate)
Temp. (0C)
K (xlO3) (ml/g)
a
30 [77] =0.097 M 0 5 0 +0.00723 M 0 ^ 46 13.8 0.71 Acetonitrile 25 16.2 0.71 30 41.5 0.62 Benzene 30 22 0.65 30 56.3 0.62 30 56.3 0.62 35 21.6 0.675 Butanone 25 13.4 0.71 25 42 0.62 30 10.7 0.71 Chlorobenzene 25 110 0.50 25 94.4 0.56 53 53.7 0.60 67 28.9 0.65 Chloroform 20 15.8 0.74 25 20.3 0.72 53 14.7 0.74 Dioxane 25 11.4 0.74 53, 60 10.2 0.75 Ethanol 56.9(0) 90 0.50 Ethyl formate 30 32 0.65 3-Heptanone 26.8(0) 82.0 0.50 29(0) 92.9 0.50 Methanol 6(0) 101 0.50 25 38.0 0.59 30 31.4 0.60 53 36.6 0.59 6-Methyl-3-heptanone 66(0) 82.0 0.50 66(0) 78.0 0.50 4-Methyl-2-pentanone 30 44.9 0.60 Tetrahydrofuran 25 16 0.70 35 15.6 0.708 Toluene 25 108 0.53 67 156 0.49 1,2,4-Trichlorobenzene 35 33.0 0.623 Heptane/3-methyl-2-butanone (27.3/72.7, v/v) 25 92 0.50 Xylene 32.5 (0) 62.0 0.50 Benzene 30 11.15 0.735 Benzene 30 15.47 0.689 Water 30 64.0 0.64 Butanol/butanone 60(0) 73 0.50 (47/53, v/v) Acetone 30 29.3 0.63 Acetonitrile 30 14.1 0.717 Dioxane 30 20.7 0.68 Methyl acetate 30 37.6 0.61 Methyl formate 30 14.1 0.722 Benzene 30 11.05 0.711 Benzene 30 51.0 0.575 Acetone 25 2.88 0.77 Butanone-methanol 20 53 0.50 (0.897 g/ml) Aq. NaCl (0.5 M) 20 0.55 1.06
MoI. wt. range (xlO~4)
Method(s)
Remarks A A B A-B A-B B B A-B A AJB C A A A A
Fr.
W.P.
22 6 4 5 24 12 14 6 15 9 6 6 6 ? 5 5 5 5 5 4 5 18
13 ? 13 -
0.3-150 4-34 24-215 97-153 34-102 3-86 7-54 5-40 25-346 2-120 3-120 0.15-7 4-34 4-34 4-34 7-68 4-34 4-34 4-34 4-34 4-150 16-154 4-150 5-83 0.3-150 4-22 3-120 4-22 14-83 9-150 12-69 5-50 1.7-117 4-15 4-15 5-40
LS OS LS LS LS OS LS LS LS SD,LS LS OS OS OS OS OS OS OS OS OS OS, LS LS OS, LS LS OS, LS, VOS OS LS OS LS OS, LS LS GPC GPC OS OS LS
6 5 7 7
4 4 -
25-287 10-24 3-15 3-126 6-35 6-35
LS OS OS OS LV LV
C B C C B B
244 334 256 256 336 336
4 2
9 9 8 7 7 4 4 -
3-41 3-41 3-41 3-24 3-24 5-20 3-17 40-217 222-344
LV LV LV LV LV OS OS LS LS
C C C C C C C C C
257 257 257 257 257 256 256 258 258
6
-
1-6
LV
C
261
13 22 13 20
-
15-219 0.91-352 15-219 0.91-352
LS LS LS LS
A-B A-B A-B A-B
937 937 937 937
5 5 9 3 5 11 9 4 4
A A B B A A-B A A-B B C B A-B A B,C B B B
Refs. 236 236 246 247 248 249 250 251 252 253 244 195 236 236 236 243 236 236 237 237 236 247 236 255 236,245 237 244 237 255 236 247 739 740 237 237 251
1.8. POLY(STYRENE) AND DERIVATIVES Poly(4-acetoxystyrene)
Butyl acetate Dioxane Isopropyl acetate Tetrahydrofuran
26.8(0) 25 19.7(0) 25
52.0 16.7 52.0 17.5
0.50 0.65 0.50 0.64
References page VII - 68
TABLE 1. cont'd
Polymer Poly(4-bromostyrene)
Poly(p-terf-butylstyrene)
Poly(2-chlorostyrene)
Solvent Benzene Chlorobenzene Toluene Benzene Benzene Cyclohexane Cyclohexane 1-Hexanol Cyclohexane 1,4-Dioxane 1-Nitropropane 1-Nitropropane 3-Nonanol 2-Octanol 2-Octanol Tetrahydrofuran Butanone Toluene
Poly(4-chlorostyrene)
Benzene Benzene-methanol (4.5/1, v/v) Butanone Chlorobenzene Chloroform Dioxane Ethylbenzene Toluene
Poly(4-cyclohexylstyrene) Poly(2,5-dichlorostyrene)
Poly(3,4-dichlorostyrene)
Poly(2,4-dimethylstyrene)
PoIy(1,4-divinylbenzene) Poly(3-fluorostyrene)
Poly(4-fluorostyrene)
Poly(4-hydroxystyrene)
Heptane Toluene Toluene Ethanol/ethyl acetate (1/15, w/w) Chlorobenzene 0-Dichlorobenzene Butanol/butyl acetate (1/13, w/w) Benzene Butyl acetate Cyclohexane Toluene frans-Decalin Benzene Butanone Carbon tetrachloride Chloroform Benzene Butanone Carbon tetrachloride Chloroform Dioxane Ethyl propionate Isobutyl acetate Tetrahydrofuran 1-Chloro-n-hexane
(ml/g)
No. of samples tf(xlO3) a Fr. W.P.
MoI. wt. range (xlO 4 )
Method(s)
Remarks
20(6) 26.3 (0) 30 30 35 35 25 35 65.0 35.0 25.0 38.0 31.0 31 (0) 10.9 32.7 32.7 30.0 24.5 (0) 25 (0) 25 30 30 26.7 41.6(0)
95.5 50.0 7.43 18.2 7.1 6.58 8.52 9.9 64.7 11.1 21.4 14.3 60.0 61 66.5 60.8 61.0 10.4 46.8 46.0 11.5 14.3 30.6 29.3 56.8
0.53 0.50 0.69 0.57 0.74 0.739 0.717 0.71 0.480 0.694 0.604 0.644 0.489 0.49 0.490 0.492 0.489 0.70 0.50 0.50 0.66 0.65 0.56 0.56 0.50
10 5 5 5 4 7 10 4 6 7 4 4 7 4 6 6 7 7 7 5 6 10 5 5
8 -
3-30 84-250 59-400 63-400 1.8-640 1.3-174 1.3-240 1.8-640 16-240 2.7-45.5 9.3-45.5 9.3-45.5 2.7-45.5 1.8-640 16-240 16-240 2.7-45.5 2.7-45.5 20-80 20-100 14-101 23-143 10-200 34-180 34-180
OS LS LS LS LS LLS, SEC, OS LLS, SEC, OS LS LLS, SEC, OS OS, LLS OS, LLS OS, LLS OS, LLS LS LLS, SEC, OS LLS, SEC, OS OS, LLS OS, LLS LS LS LS LS LS LV LV
B A,R A A A A A A A A A A A A A A A A A,R A,B A,B A C B B
347 348 348 349 741 934 934 741 934 938 938 938 938 741 934 934 938 938 742 743 743 350 351 744 744
25 30 30 30 30 30 20 25 30 30 30 30 30 21 30.5(0)
29 3.52 2.19 14.8 17.6 21.8 24.1 13.2 13.0 11.8 5.37 32.3 10.6 12.6 35.5
0.59 0.75 0.80 0.65 0.62 0.60 0.605 0.645 0.64 0.65 0.71 0.54 0.69 0.69 0.50
7 6 6 6 6 7 7 6 7 9 8
8 8 7 7 ~ -
3-140 17-270 17-270 10-200 10-200 10-180 2-40 1-244 3-140 21-140 17-270 4-30 2-30 7-66 50-130
LS OS OS LS LS LS LS LS LS LS OS OS OS LS LS
BJR B B C C B B B B,R A B A-B A-B
352 353 353 351 351 745 354 355 352 349 353 266 266 356 357
30 30 32.9 (0)
4.39 4.11
0.72 0.73 0.50
7 7 8
-
8-51 8-51 40-540
OS OS LS
A A
358 358 359
20 20 20 30 25.0(0) 25 25 25 25 25 25 25 25 25 25 25 25 5.7
3.8 10.2 14.8 9.52 286 15.3 13.8 65.6 12.8 40.8 11.1 82.8 16.1 20.3 63.7 59.4 37.2 91.6
0.79 0.68 0.65 0.70 0.32 0.69 0.70 0.53 0.70 0.58 0.73 0.50 0.69 0.66 0.52 0.53 0.60 0.468
6 8 7 7
9 -
3-22 3-22 3-22 5-120 0.7-180
LS LS LS LS LS, SE
B,C B,C B,C C Branching
-
8
0.5-8 1-15
LS LS
C C
11 11 11 10 9
8 -
0.2-13 3.8-583 3.8-583 3.8-583 3.8-583 5.9-90.3
LS LS LS LS LS LS, SEC, OS
C A
746 746 746 333 895 747 747 747 747 747 747 747 747 940 940 940 940 888
Temp. (0C)
Refs.
TABLE 1. cont'd
Polymer
Solvent
Poly(4-iodostyrene) Dioxane Poly((p-isopropyl-a-methylstyrene) Tetrahydrofuran Poly(/?-isopropylstyrene) Toluene Poly(o-methoxystyrene) Butanone Toluene Methanol/toluene (25/75, v/v) Poly(/?-methoxystyrene) Butanone Chlorocyclohexane Pentyl acetate Toluene
(ml/g)
No. of samples tf(xlO3) a Fr. W.P.
20
33
0.51
10
6
10-118
LV
B-C
360
25 25 30 30 30(0)
45 12.3 18.6 6.40 57.5
0.55 0.69 0.59 0.71 0.50
8 5 5 4
5 ~ -
1-63 14-75 13-35 13-35 15-30
LS LS LS LS LS
A-D B1C A-B A-B A-B
748 265 362 362 362
30 35 25 25 25 30 30 30(0)
3.75 8.6 17.7 55 10.5 5.28 18.0 62.1
0.73 0.68 0.63 0.52 0.70 0.73 0.62 0.50
5 6 16 16 16 5 6 5
-
13-75 1-100 22-220 22-220 22-220 13-75 1-100 7-180
LS LS LS LS LS LS LS LS
A-B B A A A B B B
362 352 363 363 363 362 352 362
10.3 9.15 73 78 76 76.0 71.3 67 7.06 7.81 10.8 24.9 66.0 72.7 2.2 76.8
0.72 0.726 0.50 0.50 0.50 0.50 0.51 0.50 0.744 0.73 0.71 0.647 0.50 0.50 0.80 0.50
4 5 8 6 4
9 6 10 9 6 9 9 9 9 6 13 -
4-170 37.5-685 4-750 9-400 2-66 4-170 3-140 8-750 8-750 3-60 2-66 14-91 2-370 2-18 1-100 14-91
LS LS LS, OS LS LS LS LS LS, OS LS, OS SD LS OS LS LS LS OS
A A A A A A A A A A A B B B B B
319 873 320 321 322 323 324 320 320 325 322,326 327 328 328 329 327
71.8 94.9 79.6 94.8 65.1 74.6 86.4 74.0 83.0 40.0 19.4 13.3 11.1 10.1 33.6 27.0 26.5 7.36 11.76 17.42 70 8.86
0.491 0.459 0.477 0.461 0.497 0.484 0.474 0.493 0.480 0.56 0.67 0.70 0.69 0.71 0.570 0.590 0.594 0.76 0.70 0.64 0.50 0.74
9 9 9 9 9 9 9 11 11 16 16 16 16 16 8 15 8 9 7 7 6 9
-
5.9-90.3 5.9-90.3 5.9-90.3 5.9-90.3 5.9-90.3 5.9-90.3 5.9-90.3 2.01-90.3 2.01-90.3 0.2-130 0.2-130 0.2-130 0.2-130 0.2-130 6.0-107 5.4-354 6.0-107 8-115 15-83 15-83 16-200 19-180
LLS, SEC, OS LLS, SEC, OS LLS, SEC, OS LLS, SEC, OS LLS, SEC, OS LLS, SEC, OS LLS, SEC, OS LLS, SEC, OS LLS, SEC, OS OS5GPC OS, GPC OS, GPC OS, GPC OS, GPC LLS, LS LLS5LS LLS, LS OS OS OS LS LS
A A A A A A A A A B B B B B A A A A A A A A
888 888 888 888 888 888 888 888 888 927 927 927 927 927 935 935 935 330 330 330 331 331
22
0.68
6
-
11-133
SV
A
332
4.37 6.3 12.3
0.736 0.78 0.72
18 7
21 -
10-260 1-300 0.6-520
OS SD SD
C A AJR
364 270 271
Temp. (0C)
Methanol/toluene (28.1/71.9, v/v) Poly(a-methylstyrene) anionic, (ca. 50%-hetero, ca. 40%-syndio) Benzene 30 30 Cyclohexane 34.5 (0) 37 (0) 38 (0) 38.6(0) 39 rrans-Decalin 9.5 (9) Toluene 25 25 30 cationic Benzene 30 (10%-hetero, 90%-syndio) Cyclohexane 32.5 (9) (19%-hetero, 80%-syndio) 33.3(0) Toluene 30(0) Benzene/methanol 30 (79.4/20.6, v/v) 10.0 1-Chloro-n-heptane 20.0 27.0 1-Chloro-n-octane 43.0 53.0 80.0 n-Hexyl acetate 85.0 Cyclohexane 34.5 trans-Deca\in 10.0 n-Butyl chloride 35.5 Carbon tetrachloride 45 Chloroform 25 Tetrahydrofuran 25 Toluene 25 M-Butyl chloride 5 25 50 Poly(m-methylstyrene) Benzene 30 Cyclohexane 30 Ethyl acetate 30 Poly(p-methylstyrene) Diethyl succinate 16.4 (0) Toluene 30 Poly(methylstyrene), position of substituent, unspecified Cyclohexane 20 Poly[(2,3,4,5,6-pentafluorostyrene)] 4-Methyl-2-pentanone 20 Poly(styrene) Benzene 20 atactic 20
MoI. wt. range (xl
Method(s)
Remarks
Refs.
References page VII - 68
TABLE 1. cont'd No. of samples Polymer
Solvent
Butanone
Butyl chloride n-Butyl chloride
Temp. (0C)
#(xlO3) (nuVg)
25 25 25 25 25 25 34 25 25 25 30 34 35 40.8 25
22.7 41.7 34.0 9.52 9.18 11.3 9.8 39 30.5 19.5 23 28.9 17.1 15.1 17.4
50 Carbon tetrachloride
Chlorobenzene Chloroform
Cyclohexane
cw-Decalin Decalin (100%-trans)
Decalin (13%~trans)
Dichloroethane 1,2-Dichloroethane Diethyl malonate Diethyl oxalate Dimethylformamide Dioxane Ethyl acetate/cyclohexane (100/0-10/90)
10 20 30 40 50 25.7 25 25 30 28 34(0) 34(6) 34.5 (0) 35(6) 35(0) 35(0) 40 45 50 50 25 20 23 23.8(0) 25 30 60 18(0) 30 40 60 100 25 35 35 34.2 (0) 55.8 (0) 35 34
10 25 40 55 65
a
Fr.
0.72 0.60 0.65 0.744 0.743 0.73 0.737 0.58 0.60 0.635 0.62 0.60 0.64 0.659 0.662 (Af w >3.7x 104) 16.2 0.665 (M w >3.7x 104) 12.6 0.717 12.0 0.720 11.4 0.724 11.2 0.725 11.0 0.726 7.4 0.749 7.16 0.76 11.2 0.73 4.9 0.794 108.0 0.479 82 0.50 90.2 0.503 84.6 0.50 80 0.50 70 0.50 76 0.50 41.6 0.554 34.7 0.575 26.9 0.599 36.4 0.584 40 0.574 149 0.44 98 0.48 0.50 67 0.52 61 0.53 22 0.63 77 0.50 36 0.58 37 0.58 22 0.64 15.7 0.67 21.0 0.66 14.3 0.69 14.3 0.69 71.8 0.50 73.0 0.50 31.8 0.603 15.0 0.694 18.2-43.8 11.0 9.32 9.07 8.79 8.90
0.54-0.67 0.733 0.738 0.739 0.742 0.740
W.P.
MoI. wt. range (xlO~4)
Method(s)
Remarks
Refs.
9 U 6 6 10 10 16 5 7 7 10 13 5 8
7 -
0.2-0.8 0.1-1 0.04-0.8 3-61 3-70 7-180 8-80 1-180 7-150 12-280 40-370 8-80 4-640 29-106 0.97-67.5
CR CR EG OS LS OS DV LS OS LS LS DV LS LS LLS, SEC
C,L B,L A,L A A A A A,R A A B A A B A
272 272 273 274 275 276 277 278 276 279 280 281,282 752 283 933
8
-
0.97-67.5
LLS, SEC
A
933
4 8 5 4 7 15 9 8 3 8 10 10 10 10 7 8 7 7 7 6 4 4 4 4 4 6 7 11 11 3 3 5 10
6 6 6 6 6 -
1.8-180 1.8-180 1.8-180 1.8-180 1.8-180 62-424 12-280 7-150 19-373 0.6-69 1-70 0.6-69 14-200 8-42 3-200 4-137 4-137 4-137 4-137 4-52 4.8-2360 14-200 14-200 14-200 14-200 14-200 14-140 14-140 14-140 14-140 14-200 1-180 10-500 9-540 39-400 39-400 0.4-87 8-80
LV LV LV LV LV LS LS OS OS OS LV OS LS LS SD LS LS LS LS LS LS LS LS LS LS LS LS LS LS LS LS LS LS LS LS LV LV LS DV
A-B A-B A-B A-B A-B B A A B A A A A1R A B B B B B A A A A A A A A A A A A A A A A B B A A
901 901 901 901 901 283 279 276 284 285 274 285 286 287 288 283 283 283 283 289 936 290 290 290 290 290 290 290 290 290 290 290 278 689 752 291 291 754 282
5 -
6 6 6 6 6
11-96 1.8-180 1.8-180 1.8-180 1.8-180 1.8-180
LV LV LV LV LV
A A-B A-B A-B A-B A-B
939 901 901 901 901 901
TABLE 1. cont'd No. of samples Polymer
Solvent Ethylbenzene Ethylcyclohexane Methylcyclohexane 4-Methyl-2-pentanone Tetrahydrofuran Toluene
atactic, anionic
Tnchloro benzene Benzene/methanol (74/26, v/v) B utanone/methanol (97.5/2.5, v/v) (95.9/5.0, v/v) (92.5/7.5, v/v) (89/11, v/v) Butanone/2-propanol (6/1, v/v) (82.6/17.4, v/v) Chloroform/methanol (90/10, v/v) (80/20, v/v) (75/25, v/v) (74.7/24.3, v/v) Dioxane/methanol (65.1/34.9, v/v) Toluene/methanol (90/10, v/v) (80/20, v/v) (76.9/24.8, v/v) (75.2/24.8, v/v) Benzene
Cyclohexane
Cyclohexene Decalin (66%-ds) Decalin (99%-trans) Dichloroethane Dioctyl phthalate Tetrahydrofuran
Temp. (0C)
K(xlO3) (ml/g)
a
25 17.6 0.68 70(0) 75 0.50 70(0) 76 0.50 70.5(0) 69.6 0.50 35 61.9 0.53 25 11.0 0.725 25 14 0.70 20 4.16 0.788 25 7.5 0.75 25 8.48 0.748 25 10.5 0.73 25 17 0.69 25 7.54 0.783 25 13.4 0.71 25 44 0.65 25 {a increases with M) 25 100 0.50 30 9.2 0.72 30 12.0 0.71 30 11.0 0.725 34 9.7 0.733 35 12.6 0.71 35 12.9 0.71 135 1.75 0.67 34(0) 89 0.50
Fr.
W.P.
MoK wt. range (xlO~ 4 ) 7-150 36-127 ? 39-400 5-100 1-100
Method(s)
Remarks A B
L A,R,L A B A-B A A B
Refs.
5 2 ? 3
? -
-
7
10 8 7 6 9 ? 5 10 8 9 8 7 W 16
? ~ 9 -
4-137 12-280 4-52 16-100 1-160 5-80 7-150 0.5-4.5 0.08-3.7 0.05-0.5 4-146 40-370 8-85 S-SO 3-650 5-100
OS LV ? LV LS GPC LS LS LS LS LS LS OS OS OS CR CR LS LS OS DV LS LS
10
-
8-80
DV
A
276 292 293 291 698 749 756 283 279 289 294 278 295 276 296 297 298 299 280 300 282 752 698 697 277
B B A C B A A A,R A A
25 25 25 25(0)
22.4 26.3 35.7 73
0.62 0.60 0.57 0.50
8 8 8 8
-
12-280 12-280 12-280 12-280
LS LS . LS LS
A A A A
279 279 279 279
23(0) 34(0)
73 71.8
0.50 0.50
9 10
-
4-146 8-80
LS DV
A A
299 282
25 25 25 25 (0)
7.7 12 46 73
0.75 0.68 0.54 0.50
8 8 8 8
-
12-280 12-280 12-280 12-280
LS LS LS LS
A A A A
279,278 279,278 279,278 279,278
34(0)
72.6
0.50
10
-
8-80
DV
A
282
10.4 26 92 88 100 7.8 8.5 11.5 9.50 74.5 85 88 88 91 86 16.3 80 81 8.38 80 13.63
0 715 0.612 0.50 0.50 0.50 0.75 0.75 0.73 0.74 0.50 0.50 0.50 0.50 0.50 0.50 0.68 0.50 0.50 0.74 0.50 0.714
8 8 12 10 17 -
7 12 5 6 ? 12 9 4 7 3 6 8 5 4 -
12-280 12-280 0.07-3.5 8-80 0.04-1 40-6000 2.5-150 25-300 31-500 ? 0.04-150 31-970 1-6000 25-300 2-50 20-107 2-50 31-760 25-300 40-160 2-4000
LS LS DV DV VOS, EB LS VOS LS LS LS LS LS LS LS LS LS LS LS LS LS LS, OS, SD
A A A,L A A,L A,R A A A B A,R A A A A A A A A A A,R
25 25 25 34(0) 25 25 30 30 30 34(0) 34.5 (0) 34.5(0) 34.5(0) 34.6 (0) 35(0) 25 12.2 (0) 20.4(0) 30 22.0(0) 25
17 13
279 279 298,297 282 301 750 301 302 649 304 301,303 649 750 302 305 306 303 649 302 303 753
References page VII - 68
TABLE 1. cont'd No. of samples Polymer
Solvent
Fr.
W.P.
MoI. wt. range (xlO4)
14.6 0.70 10.69 0.724 ll.2 0.72 9.77 0.73 34.5 0.62 8.81 0.75 10.4 0.73 9.5 0.77 10.6 0.735 25.9 0.734 17.9 0.677 11.0 0.725 9.3 0.72 (a decreases with M) (a decreases with M) (a decreases with M) 53 0.61 0.465 0.5 0.67 53 0.50 0.52 12.0 0.68 6.38 0.734 55.6 0.50 12.4 0.67
6 20 6 7 3 5 7 5 5 9 9 8 12 3 12 8 10 8 8 10 10
6 12 25 5 15 -
42-842 3-4000 3-24 1-104 0.4-230 25-300 2.6-50 4-75 4-37 9-32 2-100 3-37 15-71 30-200 8-300 8-300
-
25 5.7 0.76 35 36 0.55 35(6) 63.1 0.50 50 26.5 0.58 35 7.4 0.73 35 (0) 66.5 0.50 35 74.7 0.73 16.6-30.1 (0) (depend on M w ) 35 Not const. 34.5 (not 0) 30 0.5 34.5 (not 0) 24 0.5 34(0) g' =0.94 (3 branches)* g' =0.82 (4 branches)* 15 g' = 0.48 (9 branches)* 25 g ' = 0.90 (3 branches) * 34 g'=0.84 (4 branches)* 25 (0.344) (1.0) 25 (0.312) (1.0)
5 5 9 9 9 6 6 -
-
Temp. (0C)
Thiophenol Toluene
isotactic
25 20 20 25 25 30 30.3 30 30 30 25 30 30 25 35 (0) 30 25 35 (not 0) 40 35 34.5 35 30 25 25 40.0 35.0
Benzene Chloroform o-Dichlorobenzene Toluene
branched, random type
head-to-head
Butanone Cyclohexane Toluene Tetrahydrofuran
Cyclohexane Tetrahydrofuran
ring star type three branches four branches
Toluene Cyclohexane Toluene Benzene Cyclohexane Cyclohexane
star type 3 arm
Toluene Cyclohexane Toluene Cyclohexane
star type 15 arm 20 arm star type, anionic
Toluene Cyclohexane Cyclohexane Cyclohexane
regular H-shaped
Decalin Toluene Poly(styrenesulfonic acid)
£(xlO3) (ml/g)
Aq. HCl (0.52M) Aq. NaCl (0.52M) -, sodium salt Aq. NaCl (4.17M) (0.5M) (0.1 M) (0.05M) (0.02M) (0.01 M) (0.05M) Aq. KCl (3.1M) a g' = 0?] of branched molecules/fr] of linear molecules with
25(6») 25 25 25 25 25 25 25 same mol. wt.
a
Method(s)
Remarks
Refs.
A A,R
0.69-43.6 16.1-43.6 0.69-43.6 3-27 4.4-27.6 3-27 ?-18 3^27 0.7-44 0.7-44
LS LS1 OS, SD SD SD SD LS OS, LS OS OS OS LV OS LS LS LS LS LS GPC GPC GPC LLS, GPC LS LLS, GPC LS LLS, GPC LS LS
778 753 307 308 309 302 310 311 312 284 313 312 314 315 316 316 756 926 926 926 928 930 928 930 928 755 755
3-96 3-96 5-140 5-140 5-140 11-170 11-170 -
OS, GPC OS, GPC OS, LS OS, LS OS, LS LS LS LS
A A A A A A A
757 757 758 758 758 759 759 931
A-B A-B
931 941 941 304 304 318 304 304 365 365
4 3
-
86-302 26-148
LS LS, OS, GPC LS, OS, GPC
3 3
-
18-46 18-46
LV LV
A,R B A A A-B,R C-D C A-B A-B7R B-C A A C B B B A-B A-B A-B A-B A-B
20.4 18.6 17.8 13.9 10.1 2.8 2.3 20.4
0.50 0.64 0.68 0.72 0.78 0.89 0.93 0.50
4 6 6 6 6 5 5 4
-
49-228 39-234 39-234 39-234 39-234 39-234 49-234 49-234
LS LS LS LS LS LS LS LS
B B,R B B B B B B
366 366 366 366 366 366 366 366
12.3 172
0.757 0.50
10 10
-
85-122 85-122
OS, LS OS, LS
B B
1011 1011
1.9. OTHERCOMPOUNDS Poly(2-acrylamino-2-methylpropanesulfonarnide) Water Water/1,4-dioxane (81.5/18.5, v/v)
25 25(0)
TABLE 1. cont'd No. of samples Polymer PoIy(allylammonium chloride)
Poly[(bipheny!-4-yl)-ethylene]
Poly(terf-butyl crotonate)
Solvent Aqueous NaCl (0.05 M) (0.2M) (0.5M) (1.0M) Benzene
Butyl chloride Toluene
Poly(carbanilinoxyethylene), (Poly(vinyl carbanilate))
Dioxane Dioxane/methanol (28/72, v/v) Poly(dibutyl itaconate) Toluene Poly(dicyclohexyl itaconate) Tetrahydrofuran Toluene Poly(didecyl itaconate) Toluene Poly(diethyl fumarate) Benzene Poly(didodecyl itaconate) Toluene Poly(diethyl itaconate) Toluene Poly[di(ethylcyclohexyl) itaconate] Toluene Poly(dihexadecyl itaconate) Toluene Poly(dihexy] itaconate) Toluene Poly(diicosayl itaconate) Toluene Poly(diisopropyl fumarate) Benzene Poly(dimethyl itaconate) Benzene Poly[di(methylcyclohexyl) itaconate] Toluene Poly(dioctyl itaconate) Toluene Poly(diphenylmethylene) Benzene Poly(diphenyl itaconate) Toluene Poly(dioctadecyl itaconate) Toluene Poly(dipropyl itaconate) Toluene Poly[di(propylcyclohexyl itaconate] Pentyl acetate Toluene Poly(ditetradecyl itaconate) Toluene Poly(diundecyl itaconate) Toluene Poly( 1 -methoxycarbonyl-1 -phenylethylene) Benzene Chloroform Ethylbenzene Poly(monodecyl itaconate) Tetrahydrofuran Poly(monododecyl itaconate)
Tetrahydrofuran
Fr.
W.P.
MoI. wt. range (xMT4)
0.975 0.815 0.794 0.714 0.619 0.59 0.589 0.82 0.82
9 7 6 9 5 6 5 10
11 -
4.1-18 2.8-18 2.8-18 4.1-18 7-170 1-110 7-170 0.2-32 0.6-35
LS LS LS LS LS LV LS OS, GPC OS, GPC
B B B A A
900 900 900 900 264 264 264 760 760
13.7
0.68
11
-
6-200
LS
A
335
64.5 5.70 23.3 13.1 8.01 1.62 11.7 1.48
0.51 0.70 0.58 0.623 0.64 0.87 0.59 0.80
5 8 5 10 11 10 -
~ -
6-200 20-105 5-56 5-56 13-82 ?-20
8
5-61
LS LS OS OS LS OS, GPC LS LS
A B B B B A-B B
335 762 761 761 762 1009 945 762
0.73 0.60 0.72 0.56 0.98
_ 11
8 _ -
12-122 _ 4.7-30
LS LS LS L S OS, GPC
B B A-B
763 945 762 945 1009
0.68
-
8
4-120
LS
B
762
0.76 0.71 0.328 0.69 0.59 0.78
-
13-102 11-163 1-90 5.7-57
6
13-109
LS LS ? LS LS LS
B
? 9 -
8
25 25 25
2.02 3.67 218 4.47 13.1 1.62
763 762 267 943 945 762
25 25 25 25
14.0 2.23 9.91 10.01
0.56 0.73 0.61 0.61
B B -
763 763 945 762
Temp. (0C)
AT(XlO 3 ) (ml/g)
25 25 25 25 20 30 75 25 25
2.40 7.18 7.19 13.9 21.4 29.5 27.7 7.7 7.7
20 20(0) 25 25 25 25 30 25 25
25 2.62 25 H.4 25 3.71 25 14.3 30 0.753 (Wormlike behavior) 25 5.15 25 25
16-170
Remarks
-
-
Refs.
-
4
9-250
8 8 8 11
-
6-40 6-40 6-40 3.3-72.4
LS LS LS LS, SEC
A A A A
361 361 361 1006
0.65
9
-
1.7-233
LS, SEC
A
949
0.66
8
-
9.0-45
LS
-
943
0.65
12
-
6.5-52
LS
-
943
0.35 0.53
3 3
-
9-51 9-51
OS OS
5.89 13.4
0.74 0.63
4 5
-
18-130 18-160
LS LS
19.6 18.6 7.87 5.77
0.67 0.70 0.85 0.88
4 4 4 4
-
1-21 1-21 1-21 1-21
OS, GPC OS, GPC OS, GPC OS, GPC
5.97 241 29.2
0.566 0.661 0.507 Not const.
16-91 16-91
Method(s)
LS LS LS LS
30 35.6 30 12.7 15(6») 51.4 25 (Wormlike behavior) 25 11.2 (Wormlike behavior) 25 5.26
Poly[bis(phenylethyl) itaconate] Toluene Poly[bis(phenyl-n-propyl) itaconate] Toluene 25 Poly(9-vinyladenine) Aq. NaCl (0.1 M)/ NaAs(CH3)2(0.1M); pH7 26 40 PoIy(I -vinyl-3-benzylimidazolium chloride) Aq. NaCl (0.2M) 25 Methanol/N(CH3)4 25 Br(0.01 M) Poly(4-vinylbenzyl trimethylamrnonium chloride) Aq. NaCl (0.5 M) 25 (0.1 M) 25 (0.01 M) 25 (0.002 M) 25
a
830 830 B B
813 813
764 764 764 764
References page VII - 68
TABLE 1. cont'd No. of samples Polymer Poly(vinylcarbazole)
Solvent Benzene Bromobenzene Chlorobenzene Chloroform Cyclohexanone 1,2-Dichlorobenzene 1,3-Dichlorobenzene Nitrobenzene
Tetrachloroethane Tetrahydrofuran Toluene Poly(N-vinyl-3,6-dibromo carbazole) p-Chloro-m-cresol o-Chlorophenol PoIy(I-vinylimidazole) Aq. NaCl (0.1 M) (5.0M) Aq. NaSCN (0.1 M) Methanol/N(CH3)4 Br(0.01 M) protonated Aq. HCl (0.1 M)/ NaCl(IM) Poly(5-vinyl-2-methylpyridine) Butanone Dimethylformamide Methanol
PoIy(I-vinylnaphthalene)
Benzene
Poly(2-vinylnaphthalene)
Benzene
Poly(3-vinylpyrene)
Poly(2-vinylpyridine)
Decalin/toluene (13/10, w/w) Chloroform 1,2-Dichlorobenzene Tetrahydrofuran Benzene Ben e
z ne Benzene
Poly(2-vinylpyridine 1-oxide)
Butanone Dimethylformamide Dioxane Methanol Methyl ethyl ketone Pyridine 2-Propanol Pyridine Pyridine Ethanol/water (92/8, w/w) Benzyl alcohol 1-Butanol Chloroform Methanol
Temp. (0C) 25 25 30 45 25 25 25 25 25 25 30 45 25 25 37 (0) 112.9(0) 60.0(0) 25 25(0) 25(0) 25 25(0)
Fr.
W.P.
MoI. wt. range (xlO4)
0.58 0.76 0.755 0.776 0.74 0.67 0.61 0.68 0.75 0.69 0.716 0.739 0.68 0.65 0.50
11 7 6 6 7 8 9 7 6 6 6 6 9 10 7
-
0.7-45 7-49 7-57 7-57 7-49 3-45 2-45 4-44 7-49 7-49 7-57 7-57 2-45 1-45 4-107
LS GPC GPC GPC GPC LS LS GPC GPC GPC GPC GPC LS LS OS
A A-B A-B A-B A-B A A A-B A-B A-B A-B A-B A A A
367 765 766 766 765 367 367 767 767 765 766 766 367 367 368
30.2 27.5 122 121 105 48.5
0.50 0.50 0.51 0.50 0.50 0.63
7 8 5 8 5 6
-
4.8-125 4.8-125 9-90 5-90 9-90 9-130
LS LS LS LS
B B B B
942 942 813 813 813 813
169
0.50
5
-
9-90
LS
B
813 375 376 377 377 376 375 264 264 268 264 264 269
IC(XlO 3 ) (ml/g) 30.5 5.14 5.23 4.44 5.93 13.6 20.0 11.0 5.6 9.25 7.19 6.03 12.9 14.4 76.2
a
Method(s)
Remarks
Refs.
25 25 25 25 25 25 20 75 17 20 75 30.2(0)
13.9 19 13.0 18.0 18.6 8.0 2.20 1.03 1.7 6.90 8.69
0.65 0.64 0.76 0.83 0.70 0.76 0.82 0.88 0.80 0.719 0.695 0.50
5 15 6 8 9 9 4 4 11 6 6 8
-
13-88 6-100 4-40 4-40 7-80 13-88 4-17 4-17 10-100 6-68 6-69 10-100
LS LS OS OS LS LS LS LS LS LS LS LS
A A A-B A-B A A B B
25(0) 25 25 25 25 10 10 11-4(0) 12 15 25 25 25 25 25 25 25 25 25 25
51.0 11.7 31.8 6.6 17.0 151 149 81 56.0 31.8 97.2 14.7 30.9 11.3 93.3 9.84 18.4 9.9 13.8 12.2
0.500 0.655 0.547 0.72 0.64 0.445 0.43 0.50 0.53 0.59 0.47 0.67 0.58 0.73 0.480 0.727 0.67 0.73 0.69 0.73
9 9 9 3 14 5 5 5 5 5 14 14 14 14 5 5 5 4 14 14
-
3-50 3-50 3-50 3-11 3-93 9.4-196 9.4-196 9.4-196 9.4-196 9.4-196 3-93 3-93 3-93 3-93 9.4-196 9.4-196 9.4-196 9.4-196 3-93 3-93
LS LS LS LS LS LS, OS LS, OS LS, OS LS, OS LS, OS LS LS LS LS LS, OS LS, OS LS, OS LS, OS LS LS
A A A B,C A A A A A B,C B,C B,C B,C A A A A B,C B,C
768 768 768 769 371 944 952 952 952 952 207 371 371 371 944 944 952 952 207 371
9.35 7.78 15.8 7.55
0.73 0.72 0.64 0.72
14 14 14 14
-
1.3-34 1.3-34 1.3-34 13-34
LS LS LS LS
A-B A-B A-B A-B
946 946 946 946
25 25 25 25
B B
TABLE 1. cont'd No. of samples Polymer
Poly(4-vinylpyridine)
Poly(vinylpyrrolidone)
Solvent 1-Propanol 2-Propanol Ethanol Water Butanone/2-propanol Ethanol/water (92/8, w/w) Chloroform Methanol Water
Acetone/water (66.8/33.2, v/v) Aq. Na 2 SO 4 (0.55M) Poly( 1 - vinyl-2-pyrrolidone) high M low M Poly(vinylsulfonic acid)
Aq. sodium acetate (0.1 M) Aq. sodium acetate (0.1 M) Aq. KBr (0.347 M)
Aq. KCl (0.349 M) (0.650 M) (1.001 M) Aq. NaBr (0346 M)
Poly(vinyltrimcthylsilane) 1.10.
(1.008 M) Aq. NaCi (1.003 M) (0.5M) Cyclohexane
MoK wt. range (xlO4)
Method(s)
Remarks
3 -
1.3-34 13-34 1-4 10-185 10-185 7-224 7-224
LS LS SD LS LS LS LS
A-B A-B C A-B A-B B B
946 946 372 373 373 374 374
4 3 15 9 6 -
2 6 5 3
2-23 2-23 1-9 0.7-10 1-4 1-20 8-110 1.2-108
LS LS SD LS SD SD OS LS
B B B B,R C,D B A,R B
378 378 379 378 211 381 383 384
5
-
9-46
OS
B
770
4-220
-
-
948
0.2-4
-
-
948
Temp. (0C)
/C(XlO 3 ) (ml/g)
a
Fr.
W.R
25 25 25 25 25 25 25
10.3 12.0 (1.51) 25.0 22.0 38.0 12.0
0.70 0.68 (0.52) 0.68 0.687 0.57 0.73
14 14 8 8 7 7
25 30 20 25 25 30 30 25 {0)
19.4 23 64 67.6 4.1 14 39.3 75.0
0.64 0.65 0.58 0.55 0.85 0.70 0.59 0.50
25 (0)
58.0
0.500
25
5.7(0) 15 30 50 5.5 (0) 25 26.0(0) 44.5(0) -0.6(0) 10 20 30 40.1(0)
68.8 30.8 24.5 26.6 68.2 16.7 79.5 80.3 95.5 26.8 25.1 22.0 94.5
0.74 (Mixed) 0.53 (Mixed) 0.50 0.61 0.75 0.76 0.50 079 0.50 0.50 0.50 0.73 0.76 0.79 0.50
32.4(0) 20 25
96.1 21.5 8.2
0.50 0.65 0.71
5 5
6 -
4-39 0.3-3 59-213
LS SD LS
B C B
259 260 610
0.50 0.50
7 5
-
0.06-1.26 0.15-0.40
OS OS
A A
590 590
0.65
?
?
?
?
0.79
6
-
2-21
LS
0.743 0.502
11 8
-
2-53
LS
0.62 0.68
16 4
-
15-120 10-78
LS LS
B B
593 594
0.61 0.77
11 Il
-
19-56 19-56
LS LS
B B
595 595
0.74
6
-
14-58
LS
B
773
25
8.86
Refs.
64
5 5 5 5 5 5 5 5 5 5 5 5 5
-
4-39 8-39 8-39 8-39 4-39 4-39 4-39 4-39 4-39 8-39 8-39 8-39 4-39
LS LS LS LS LS LS LS LS LS LS LS LS LS
B B B B B B B B B B B B B
259 259 259 259 259 259 259 259 259 259 259 259 259
COPOLYMERS
Poly(acrylonitrile-co-butadiene), see also Poly(butadiene-a?-acrylonitrile) in group 1.1 (18/82, w/w, random) Toluene 25 251 (26/74, w/w, random) Toluene 25 260 Poly(acrylonitrile-«?-glycidyl methacrylate) Dimethyiformamide 30 175 Poly(acrylonitrile-ctf-methyl acrylate) Dimethyiformamide 20 17.9 Poly (acrylonitri Ie-j/fl/-methyl acrylate), (91.5/8.5, w/w) Dimethyiformamide 25 21.3 Ethylene carbonate/water 25(0) 152 (82.5/17.5, w/w) Poly(acrylonitrile-c-styrene) (38.3/61.7, mol/mol,) Butanone 30 36 Tetrahydrofuran 25 21.5 azeotropic (62.6/37.4, mol/mol, random) Butanone 30 53 Dimethyiformamide 30 12 Poly(acrylonitrile-67ar-styrene) (27.4/72.6, mol/mol) Dimethyiformamide 30 12.0
591 B
592 772 772
References page VII - 68
TABLE 1. cont'd No. of samples Polymer
Solvent
Temp. (0C)
K(XlO3) (ml/g)
a
Fr.
(38.5/61.5, mol/mol) Dimethylformamide 30 16.2 0.73 6 (47.5/52.5, mol/mol) Dimethylformamide 30 17.2 0.73 6 Poly (aery lonitriie-a/f-styrene) (1/1, mol/mol) Butanone 30 24.3 0.67 10 Dimethylformamide 30 7.63 0.76 9 Butanone/methanol 30(6) 140 0.50 10 (63.6/36.4, v/v) Poly (aery lonitrile-co-vinylidene chloride) 58 wt.% AN 7-Butyrolactone 25 112 0.576 8 Dimethylacetamide 25 99.9 0.603 8 Dimethylformamide 25 102 0.591 8 Af-methyl-2-pyrrolidone 25 114 0.595 8 70 wt.% HNO 3 25 142 0.521 8 Poly(jP-aminobenzoic acid-jtaf-6-aminohexanoic acid) (1/1, mol/mol) Dichloroacetic acid 30 23.7 1.13 4 Trifluoroacetic acid 30 132.5 0.99 4 Poly(butadiene-co-methacrylamide) (90/10, w/w, random) Toluene 25 437 0.50 5 PoIy(butadiene-c-2-methyl-5-vinylpyridine) Toluene 25 309 0.50 5 Poly(butadiene-co-styrene), see also Poly(butadiene-co-styrene) in group 1.1 (84/16 mol/mol, random) Benzene 25 39.4 0.70 4 Dibutyl phthalate 56 472 0.40 6 2-Pentanone 23.8 (B) 167 0.50 5 Poiy(butyl itaconate-c-dibutyl itaconate), (40/60, mol/mol, random) Acetone 25 575 0.32 6 Methanol 25 354 0.32 7 w-Xylene 25 1040 0.21 7 Poly(butyl methacrylate-a/f-styrene) Butanone 25 5.3 0.76 10 Poly(butyl methacrylate-.yta/-styrene) (1/1, mol/mol) Butanone 25 4.9 0.77 10 35 5.98 0.75 8 Cyclohexane 35 7.88 0.70 6 Poly(ferf-butylphenyl methacrylate)-.sf<2f-vinylpyrrolidone) (33.7/66.3, mol/mol) Benzene 25 118 0.53 5 Chloroform 25 105 0.57 5 (60.4/39.6, mol/mol) Benzene 25 130 0.55 4 Chloroform 25 247 0.51 4 Poly(^-^r/-butylstyrene)-^/oc/c-poly(dimethyl-siloxane)-^/oc/:-poly(p-f«rr-butylstyrene) 28 wt.% PBS Methyl ethyl ketone 10 252 0.39 4 15 58.9 0.50 4 20 40.5 0.54 4 31 19.3 0.61 4 38 10.7 0.66 4 Benzene 35 15.4 0.66 4 Methyl ethyl ketone 15(9) 58.9 0.50 4 20 40.5 0.54 4 31 19.3 0.61 4 Poly(/?-chlorostyrene-jfaf-methylmethacrylate), (52/48, mol/mol) Benzene 27 7.94 0.72 9 Benzene/hexane 22.3(0) 64 050 8 (60/40, v/v) Poly(4-chlorostyrene)-£>/ocA:-poly(styrene)-^/oc/:-poly(4-chlorostyrene), A * - B „ - A * 2k/n, (33/67, mol/mol) Carbon tetrachloride 40 6.24 0.76 Cumene 40 5.88 0.76 2k/n, (50/50, mol/mol) Carbon tetrachloride 40 6.63 0.74 Cumene 40 5.76 0.75 Poly(diethyl fumarate-a?-isobutene) 50/50, mol/mol Benzene/petrol ether 20 340 0.44 4 Poly(diethyl fumarate-co-vinylcarbazole) Benzene 25 14.6 0.67 6
W.P.
MoI. wt. range (xlO4)
Method(s)
Remarks
-
22-106 14-78
LS LS
B B
773 773
-
5-100 8-100 5-100
LS LS LS
B B B
774 774 774
-
4.2-50 4.2-50 4.2-50 4.2-50 4.2-50
LS LS LS LS LS
-
961 961 961 961 961
-
12-60 12-60
LS LS
-
0.09-0.11
OS
A
590
-
0.08-1.04
OS
A
590
-
2-51 2-51 7-51
OS OS OS
A A A
596 596 596
-
9-70 11-110 11-110
LS LS LS
B B B
597 597 597
-
32-320
LS
B
776
-
15-208 22-56 34-50
LS LS LS
B B B
776 777 777
-
33-96 33-96
OS OS OS OS
C C C C
779 779 779 779
-
12-129 12-129 12-129 12-129 12-129 9 3-128 9.3-128 9.3-128 9.3-128
OS5GPC OS, GPC OS, GPC OS, GPC OS, GPC OS, LS OS, LS OS, LS OS, LS
C-D C-D C-D C-D C-D B B B B
957 957 957 957 957 960 960 960 960
-
15-120 15-120
LS LS
C C
598 598
5 5 10 10
14-61 14-61 19-74 19-74
OS OS OS OS
A A A A
780 780 780 780
-
1-14
SD
C
599
-
2-13
LS
B
789
Refs.
775 775
TABLE 1. cont'd No. of samples Polymer
Solvent
Temp. (0C)
K(XlO 3 ) (ml/g)
a
Poly(p-diethylphosphonomethylstyrene-c-styrene), (1/4, mol/tnol, random) Benzene 20 1.95 0.90 Tetrachloroethane 20 0.0836 1.18 Poly(dimethyl itaconate-co-styrene) (75/25, w/w) Toluene 25 6.6 0.68 (67/33, w/w) 25 9.0 0.67 (59/41, w/w) 25 9.7 0.67 (49/51, w/w) 25 11.7 0.67 (29.5/70.5, w/w) 25 12.8 0.67 (27/73, w/w) 25 10.9 0.69 (0/100, w/w) 25 11.45 0.712 Poly(dimethyl siloxane-codiphenylsiloxane) (54/45, mol/mol) Benzene 25 40.7 0.60 Dimethyl phthalate 82.5 512 0.31 Ethanol/toluene 29.5 (6) 78 0.50 (37/63, w/w) (66/34, mol/mol) Benzene 25 15.6 0.68 Hexane 36(6) 141 0.44 Benzene/2-propanol 42(0) 74 0.50 (44/56, w/w) Poly(divinylstyrene-a?-styrene), see also Poly(styrene), branched, random type, in group 1.8. Benzene 25 37.2 0.70 Octane 21 162 0.50 Poly(ethyl acrylate-j/aMnethyl methacrylate), (80/20, mol/mol) Acetone 25 62 0.57 Poly(ethyl methacrylate a/r-styrene) Butanone 25 9.3 0.72 Poly(ethyl methacrylate-jfaf-styrene) (1/1, mol/mol) Butanone 25 12.0 0.70 Poly(ethylene-co-a-methyl-styrene), [(ET)w (MS) ,Jp m/n = 3/4 Cyclohexane 30 92 0.56 Dioxane 30 76 0.58 Toluene 30 32 0.68 Butanone/cyclohexane 30(6) 135 0.50 (60/40, v/v) m/n = 5/4 Cyclohexane 30 65 0.60 Dioxane 30 89 0.56 Toluene 30 37 0.66 Butanone/cyclohexane 30(0) 140 0.50 (75/25, v/v) m/n = 5/7 Cyclohexane 30(0) 112 0.50 Dioxane 30 123 0.49 Toluene 30 56 0.58 Poly(hexadecyl methacrylate-co-methyl methacrylate) (25/75, mol/mol, random) Heptane 25 85.0 0.38 Propyl acetate 25 17.1 0.62 (38/62, mol/mol, random) Chloroform 25 36.3 0.57 Heptane 25 6.9 0.65 Propyl acetate 25 53.6 0.50 (50/50, mol/mol, random) Chloroform 25 53 0.54 Heptane 25 32.0 0.52 Propyl acetate 25 91.3 0.43 PoIy(I-hexene-co-sulfur dioxide), see Poly[sulfonyl(butylethylene) in group 3.10. Poly(isobutene-co-isoprene), see group 1.2. Poly(isoprene)-&/
Fr.
W.P.
MoI. wt. range (xlO" 4 )
5 11
-
15-50 9-51
SV SV
B B
6 6 8 7 8 8 12
-
6-22 4-19 5-38 6-24 7-36 6-40 3-58
LS LS LS LS LS LS LS
A A A A A A A
683 683 683 683 683 683 683
5 5 5
-
7-57 11-57 7-35
OS OS OS
A A A
596 596 596
4 4 4
-
3.7-100 3.7-100 3.7-100
LS LS LS
A A A
596 596 596
5 6
-
5-80 5-80
SD SD
10
-
65-800
LS
B
114
9
-
19-470
LS
B
776
10
-
3-185
LS
B
776
5 5 5 5
-
0.7-6 0.7-6 0.7-6 0.7-6
SA SA SA SA
B B B B
604 604 604 604
5 5 5 5
-
0.8-7 0.8-7 0.8-7 0.8-7
SA SA SA SA
B B B B
604 604 604 604
4 4 4
-
1.5-7 1.5-7 1.5-7
SA SA SA
B B B
604 604 604
8 8 8 8 8 8 8 8
-
4-47 4-47 16-195 4-47 4-47 10-154 4-47 4-47
LS LS LS LS LS LS LS LS
A A A A A A A A
605 605 605 605 605 605 605 605
7 7 7 7
-
29-130 29-130 29-130 29-130
LV LV LV LV
B B B B
842 842 842 842
9
-
26-105
LS
Method(s)
Remarks
Refs.
602 602
607
DN-Degree of neutralization
References page VII - 68
TABLE 1.
Polymer
cont'd
Solvent
Temp. (0C)
K (xlO3) (ml/g)
a
No. of samples — —— Fr. W.P.
Poly(4-methoxystyrene-jfaf-styrene) (24.4/75.6, mol/mol) Toluene 25 7.0 0.75 9 (26.4/73.6, mol/mol) Butanone 25,50 40 0.585 8 Toluene 25 18.6 0.68 8 (46.2/53.8, moVmol) Toluene 25 7.3 0.755 13 (53.0/47.0, mol/mol) Butanone 25(0) 100 0.49 7 Toluene 25 37 0.615 7 (74.0/26.0, mol/mol) Toluene 25 8.2 0.755 9 (75.6/34.4, mol/mol) tert-Butylbenzene 25 (0) 83 0.49 6 Toluene 25 16.9 0.673 7 Poly(methyl acrylate-Jta/'-methylmethacrylate) (17/83, w/w) Butanone 25 11.7 0.70 4 (29/71, w/w) 25 11.1 0.63 4 (67/33, w/w) 25 36.6 0.60 4 Poly(methyl acrylate-co-styrene) (22/78, mol/mol, random) Benzene 30 8.93 0.744 16 Butanone 30 21.1 0.640 12 2-Methylcyclohexanol 43.5 (0) 77 0.50 8 (33/67, mol/mol, random) Benzene 30 7.18 0.759 9 Butanone 30 11.4 0.696 4 2-Methylcyclohexanol 35.0(0) 76 0.50 7 (47/53, mol/mol, random) Butanone 30 10.7 0.724 9 (50/50, mol/mol, random) Ethyl acetate 35 41.6 0.57 9 (59/41, mol/mol, random) Benzene 30 6.15 0.780 6 Butanone 30 11.3 0.703 4 2-Methylcyclohexanol 36.6 (0) 76 0.50 6 (76/24, mol/mol, random) Benzene 30 7.42 0.766 6 Butanone 30 9.16 0.728 5 2-Methylcyclohexanol 29.4 (0) 75 0.50 5 Poly(methyl methacrylate-co-p-isopropylstyrene), 2/3, mol/mol, graft Butanone 25 0.021 1.11 Poly(methyl methacrylate-co-2-methyl-5-vinylpyridine) (85/15, mol/mol, random) Acetic acid 25 170 0.51 3 Poly(methyl methacrylate-co-styrene) (10/90, mol/mol, random) 1-Chlorobutane 40.8 16.6 0.609 5 (30/70, mol/mol, random) 1-Chlorobutane 30 17.6 0.67 9 Cyclohexanol 64.0(0) 71.6 0.51 4 Toluene 30 8.32 0.75 10 (44/56, mol/mol, random) 1-Chlorobutane 30 24.9 0.63 10 Cyclohexanol 64.0(0) 70.0 0.51 4 Toluene 30 13.2 0.71 11 (50/50, mol/mol, random) Butanone 25 15.4 0.675 11 (52/48, mol/mol, random) 1-Chlorobutane 40.8 49.0 0.575 5 (71/29, mol/mol, random) 1-Chlorobutane 30 24.9 0.63 10 Cyclohexanol 68.0(0) 97.3 0.47 5 Toluene 30 11.4 0.70 8 (94/6, mol/mol, random) 1-Chlorobutane 40.8 27.6 0.617 5 nearly equimolar, three blocks (MSM) Cyclohexanol 81.0(0) lim M v v ^oM e /M l / 2 = 63 PS% 86.1-90.4, graft (S on M; Mps= 0.7-1.0 x 104) Benzene 25 [77] = 0.00918 M J 5 7 4 V 7 7 Butanone 25 \rj\ = 0.0390 M j ^ V ' 5 9 graft Bromoform 56 0.6 6 Poly(methyl methacrylate)-6/od:-poly(styrene), A*-B,,, k/n, (54/46, w/w) Butanone 30 9.4 0.69 6 1-Chlorobutane 30 22.4 0.60 6 Toluene 30 7.3 0.73 6 Poly(2-methyl-l-pentene-c0~sulfur dioxide), see Poly[sulfonyl(l-methyl- 1-propylethylene)], group 3.10. Poly(a-methylstyrene-co-styrene) Benzene 20 14.4 0.69 5 PoIy(I -octadecane-a/r-maleic acid) Ethyl acetate 25 55 0.48 6
MoL wt. range (xlO~ 4 )
Method(s)
Remarks
-
4-42 7-80 7-80 3.5-70 7-80 7-80 5-35 7-80 7-80
OS LV LV OS LV LV OS LV LV
B B B B B B B B B
781 782 782 781 782 782 781 782 782
-
56-208 37-137 71-187
LS LS LS
B B B
131 131 131
-
2.6-80 2.6-80 2.6-80 6.6-36 6.6-36 6.6-36 6.7-24.4 18-116 7-40 12-40 7-40 7.2-28 8.9-28 6.5-24
LS LS LS LS LS LS OS LS LS LS LS LS LS LS
A A A A A A A A A A A A A A
129 129 129 129 129 129 129 133 129 129 129 129 129 129
6
31-65
LS
-
37-150
LV
B
612
-
20-82 5-55 5-55 5-55 5-81 10-81 4.8-81 5-227 18-115 4.8-81 15-106 7-106 20-100
LS LS LS LS LS LS LS LS LS LS LS LS LS
B B B B B B B B B B B B B
613 614 614 614 614 614 614 615 613 614 614 614 613
7
3.4-147
LS
B
616
-
83-121 53-285 180-320
LV LV LV
-
5.8-93 5.8-93 5.8-93
LS LS LS
A A A
783 783 783
-
18-80
SV
A
332
-
2.4-9.9
LS
-
956
Refs.
611
617 617 618
Next Page
TABLE 1. cont'd
Polymer
Solvent
Temp.
K(xlO3)
( 0 C)
(ml/g)
No. of samples
range a
Fr.
Poly(octyl methacrylate-a//-styrene) Butanone 25 7.4 0.72 11 Poly(octyl methacrylate-staf-styrene), (1/1, mol/mol) Butanone 25 7.8 0.71 10 Poly(styrene)-6/oc/c-poly(butadiene)-^/oc/c-poly(styrene) 50 wt.%-PS Toluene 30 71.3 0.62 7 Poly(styrene)-/7/ocA:-poly(4-chloro-styrene)-^/oc^-poly(styrene), B,,-A*-B„ k/2n, (33/67, mol/mol) Carbon tetrachloride 40 6.10 0.77 Cumene 40 3.99 0.79 fc/2n, (50/50, mol/mol) Butanone 30 8.14 0.72 Carbon tetrachloride 40 5.58 0.76 Cumene 40 6.84 0.74 Toluene 30 4.62 0.79 k/ln, (66/34, mol/mol) Carbon tetrachloride 40 5.94 0.74 Cumene 40 5.21 0.75 Poly(styrene-cc-sulfur dioxide), see Poly[sulfonyl(phenylethylene)], group 3.10. Poly(styrene)-gra/?-poly(methyl methacrylate), MMA content, 13 wt.% Bromoform (16.5) (0.58) 5 Poly(styrene)-frfoc£-poly(dimethylsiloxane) 12-62% PS Methyl ethyl ketone 25 Various Various Various Poly(styrene-c0-monoethyl rnaleate) Acetone 26.4(0) 51.1 0.50 9 Dioxane 25 11.2 0.702 9 Tetrahydrofuran 25 7.50 0.695 9 -, sodium salt Aq. NaCl (0.005 M) 25 5.8 0.87 4 (0.01 M) 25 5.5 0.85 5 (0.03M) 25 6.3 0.80 5 (0.05M) 25 Il 0.73 5 (0.075M) 25 10 0.71 5 (0.15M) 25 15 0.65 5 (0.3M) 25 21 0.60 5 (0.6M) 25 55 0.50 5 Poly(styrene)-Z?/
TABLE 2.
MoI. wt.
W.P.
(xlO4)
Method(s)
Remarks
-
12-450
LS
B
776
-
10-198
LS
B
776
-
5.7-140
OS, LS
A-B
958
4 4 8 8 8 8 4 4
20-82 20-82 31-89 31-89 31-89 31-89 15-54 15-54
OS OS OS OS OS OS OS OS
A A A A A A A A
780 780 780 780 780 780 780 780
-
17-196
SD
A
784
-
Various
OS, GPC
B-C
955
-
20-180 20-180 20-180
LS LS LS
A A A
317 317 317
-
40-130 40-180 40-180 40-180 40-180 40-180 40-180 40-180
LS LS LS LS LS LS LS LS
A A A A A A A A
317 317 317 317 317 317 317 317
-
6.5-153 6.5-153 6.5-153
LS 5 OS LS, OS LS, OS
A A A
944 944 944
MoI. wt. range M(xlO4)
Method
Remarks
Refs.
MAIN-CHAIN CARBOCYCLIC POLYMERS
Polymer Poly(acenaphthenylene)
Solvent Benzene
Temp. (0C)
(ml/g)
25
30.04
25
Poly(4,7-dimethylindene) Poly(6-methylindene)
Ethylene chloride Dioxane Methylene chloride Toluene Benzene Benzene
25 25 25 25 25 25
2.82 20.0 11.5 6.92 6.76 3.5 34
No. of samples tf(xlO3) a Fr. WP 0.594
Il
Refs.
-
2-100
OS
B
262
0.74
4
-
4-100
LS
A,B
263
0.54 0.61 0.66 0.66 0.77 0.60
6 7 5 17 9 13
-
6-125 6-145 6-145 3-175 5.8-140 30-1320
LS LS LS LS LS LS
A,B A,B A,B AJB C,D CD
263 263 263 263 811 811
References page VII - 68
P o l y m e r - S o l v e n t
I n t e r a c t i o n
P a r a m e t e r s
N . Schuld, B.A. W o l f lnstitut fur Physikalische Chemie Universitat Mainz Mainz, FR Germany A. B. C. D. E. F. G. H. I. J. A.
Introduction Concentration Variables Conversion of Concentration Variables Basic Equations Methods of Determination Temperature Dependence Concentration Dependence Molecular Weight Dependence Polymer-Solvent Interaction Parameters, x References
VII-247 VII-247 VII-247 VII-247 VII-248 Vl 1-249 VII-249 VII-250 VII-250 VII-262
2. Weight fractions w,:
(B2) m{
3. Segment fractions S1- (hard core volume fractions): (B3) V* molar hard core volume (characteristic volumes) of components related to reduced volumes V,- by Vi = ViJVt* (11).
INTRODUCTION
The classical thermodynamics of binary polymer-solvent systems was developed independently by P. J. Flory (1-3) and M. L. Huggins (4-6). It is based on the well-known lattice model qualitatively formulated by K. H. Meyer (7), who pointed out the effect of the differences in molecular size of polymer and solvent molecules on the entropy of mixing. The quantitative calculation of the entropy of mixing led to the introduction of a dimensionless quantity, the so-called Flory-Huggins interaction parameter x> f ° r the thermodynamic description of polymer solutions. It was evident from the beginning that \ iS a function of T\ however, at first \ was considered to be independent of the concentration of the polymer. Subsequent experiments have shown the necessity of treating x a s a function of composition (8,9). Furthermore, x also depends on M 2 (the molecular weight of the polymer), not only at high dilution, but - according to recent experiments (10) - even at high concentrations of polymers.
C. CONVERSION OF CONCENTRATION VARIABLES
py pi are the densities of the solution and of the pure component i, Xjp — w\/p\ + W2/P2', p*, p* are the hard core (characteristic) densities of the solution and of the component 1, p* = Mi/V* where Af,- is the molar mass, l/p* = w\/p\ + W2/V2; V, V1 are the reduced volumes of the solution and of the component i.
B. CONCENTRATION VARIABLES Since the numerical value of the interaction parameter depends on the concentration variable chosen, one has to specify it in each case. The following three quantities are most frequently used, where the subscript 1 stands for the solvent and the subscript 2 for the polymer: D.
1. Volume fractions ?,•:
(Bl) n j moles of component i Vi molar volume of component i
weight of component i
BASIC EQUATIONS
The reduced molar Gibbs energy of mixing, &Gy[/RT, is given by the following equation:
(Dl)
where X1 is the mole fraction of component i, R is the gas constant, T is the absolute temperature and g stands for the integral polymer-solvent interaction parameter; g refers to the interaction (mixing of the pure liquid compounds) of a solvent molecule with a polymer segment, the size of which is defined by the molar volume of the solvent. This definition implies some difficulties as soon as mixed solvents or solvents with more than one segment are considered. Alternatively, the Gibbs energy of mixing can be normalized to the volume, so that it reads :
torial behavior: (D8) (D9) (DlO) From phenomenological thermodynamics, one obtains the interrelations between these parameters, given in Eqs. (D11-D13):
(D2) (DIl)
where B is an interaction energy-density parameter that no longer depends on the definition of a segment, and relates to g and molar volume of the segment Vseg by
(D12) (D13)
(D3) The sum (D4) of Eq. (Dl) is the combinatorial part of AGM- The remaining term (D5) is the so-called reduced residual Gibbs energy of mixing. Partial differentiation of AG/RT with respect to ni, the number of moles of solvent, or t%2, the number of moles of polymer, respectively, yields the reduced partial molar Gibbs energy of mixing of the solvent AG i/RT = AjJi1ZRT, or the reduced partial molar Gibbs energy of mixing of the polymer, AG2/RT = A[A2/RT: (D6)
Since it is the chemical potential of the solvent that is normally measured, x *s practically the only interaction parameter that can be directly obtained. In the following text, the term polymer-solvent interaction parameter (Flory-Huggins parameter) is, therefore, exclusively applied to xE. METHODS OF DETERMINATION Rearrangement of Eq. (D6) yields
(El) METHODS FOR THE DETERMINATION OF POLYMER-SOLVENT INTERACTION PARAMETERS Typical range of concentration
Methods
V? 2 ~»0
Scattering methods
LS SAXS SANS
0 <
Osmosis Light scattering Critical miscibility (only applicable with poor solvents) Differential vaporpressure methods
OS LS CM
0.3 <(pi < 0.8
Vapor-pressure methods
VP
(p2 -» 1
Inverse gas chromatography (gas liquid chromatography)
IGC
(D7) N = V2/V\ (where V1 = Vseg), the ratio of the molar volumes of the components is, in general, different from the degree of polymerization but proportional to it; x anc* £ are the Flory-Huggins interaction parameters in the differential equation for the solvent and for the polymer, respectively. Separating AGi and AG 2 like AG M (Eqs. D1-D5) into a combinatorial and a residual contribution yields the following expressions for the different interaction parameters, which demonstrates that they measure the deviation of a real polymer solution from purely combina-
Abbreviation in text
AVP
Refs. 20 129 21-25
26 3 27-30
Since AGi — RT In a \, the interaction parameter x ls accessible from the measured activity of the solvent. In order to get the information for the entire range of concentrations, a combination of several methods is necessary. The table given on the previous page shows the concentration ranges for the applicability of the most commonly used methods, the abbreviations used in the text to specify the method, and some pertinent references. Information stemming from the following sources is not incorporated in the tables: melting point depression of polymer (3,12,13), freezing point depression of solvents (8), swelling equilibria (3,14-17), and intrinsic viscosities (18,19).
According to experimental information, three characteristic behaviors can be distinguished: 1. Very often, x increases greatly with polymer concentration, particularly in the case of poor solvents. The systems benzene/polyisobutylene (PIB) (21,31,32), n-pentane/polyisobutylene (33,34), and cyclohexane/ polystyrene (22) (Figs. 1 and 2) constitute examples.
Benzene/PIB 7=0 = 250C n-pentane/PIB T = 25°C
F. TEMPERATURE DEPENDENCE X
The temperature dependence of \ can be described for most systems exhibiting UCSTs by means of the following equation: (Fl)
Cyclohexane/PfB T = 25°C
Knowing the temperature dependence of x, it is possible to split this quantity in its enthalpic and entropic part (^H
and xs)(F2) where
(F3)
Figure
1.
Examples for t h e v a r i a t i o n
of the
Flory-Huggins
i n t e r a c t i o n p a r a m e t e r , x (Eq. D 1 4 ) , w i t h t h e v o l u m e f r a c t i o n (p2
(F4)
of p o l y m e r for t h e systems b e n z e n e / p o l y O s o b u t y l e n e ) (PIB), np e n t a n e / P I B a n d c y c l o h e x a n e / P I B at t h e i n d i c a t e d t e m p e r a t u r e s .
G. CONCENTRATION DEPENDENCE The following expression for the Flory-Huggins parameter was deduced on the basis of the lattice theory (25):
Cyclohexane/PS T = e = 34°c
(Gl) where a and 7 are constants within a certain temperature range and {3 varies with T (/? = PQ + Px /T). For the integral interaction parameter, g, the equation reads:
x n-octane/PDMS T s 200C
(G2) Toluene/PS T = 25°C
For an analytical representation of the experimentally found concentration dependence, the following power series with n = 2 is normally adequate:
V2
(G3)
Figure 2 .
Examples for
the variation
of t h e
Flory-Huggins
i n t e r a c t i o n p a r a m e t e r , x (Eq- D 1 4 ) , w i t h t h e v o l u m e f r a c t i o n ^ of p o l y m e r for t h e systems c y c l o h e x a n e / p o l y s t y r e n e
(G4)
octane/poly(dimethyl
(PS),
2
n-
siloxane) (PDMS) a n d t o l u e n e / P S at t h e
indicated temperatures.
References page VII - 262
COEFFICIENTS X0/ Zi/ X2 O F SYSTEMS SELECTED FOR GRAPHICAL REPRESENTATION (Figs. 1 AND 2) System
T/(0C)
Xo
25 25 25 34 20 25
0.506 0.484 0.440 0.507 0.501 0.431
Benzene/PIB n-Pentane/PIB Cyclohexane/PIB Cyclohexane/PS /z-Octane/PDMS Toluene/PS
Xi 0.229 0.184 -0.083 0.149 -0.035 -0.311
Xi
Refs.
0.317 0.080 0.068 0.464 0.042 -0.036
2131,32 33,34 30,31,35 22 36 37
2. In some cases, x seems to be independent of composition, as proposed by the original Flory-Huggins theory. These findings mainly concern good solvents; examples are the systems cyclohexane/polyisobutylene (30,31,35) and n-octane/poly(dimethyl siloxane) (PDMS) (36) (Figs. 1 and 2). 3. In a few cases, mostly with highly exothermal systems, x decreases with concentration, as with toluene/polystyrene (37) (Fig. 2). The lines drawn in Figs. 1 and 2 have been calculated by means of Eq. (G3) and the coefficients Xi> collected in the table given above. H.
MOLECULAR WEIGHT DEPENDENCE
dilute polymer solutions, depend markedly on Mi_\ since this quantity is closely related (cf. Eq. II) to x» i t s dependence on chain length in this concentration regime is obvious. Recent experiments (10) have shown that x may depend on the molar mass of the polymer even for concentrated solutions. Furthermore, there is some evidence (given in Ref. 60, resulting from a common valuation of the data given in Refs. 83,58,33,30 and 90, and from a comparison of the results reported in Refs. 99 and 110) that even Xoo> the x parameter for an infinitely large excess of polymer, may depend on chain length. According to the few presently available experimental data, a reduction of x upon an increase of Mi according to some scaling law seems to be the normal case. I.
POLYMER-SOLVENT INTERACTION PARAMETERS, X
Values of the polymer-solvent interaction parameters, defined by Eq. (El) in terms of volume fractions, have been collected. They are tabulated as a function of polymer concentration for various temperatures. Data given on the basis of segment fractions, £2, or weight fractions, w>2, were converted into volume fractions ?2. If needed, Xo can be calculated from the second osmotic virial coefficient A 2 (see corresponding chapter in this Handbook by means of the following equation:
Second osmotic virial coefficients, as obtained from osmotic pressure or light scattering measurements with
Solvent
T (0C)
M1 (kg/mol)
x (0.0)
x (0.2)
(H)
x (0.4)
Cellulose acetate 2.5 Acetone Dioxane Methyl acetate Pyridine
30 30 30 30
104 104 104 104
0.30 0.31 0.43 0.07
0.51 0.51 0.59 0.09
Cellulose acetate 3.0 Dichloromethane Trichloromethane
25 30
157 157
0.38 0.36
0.45 0.45
Cellulose acetate x Dimethylformamide Dimethylformamide
50 70
36 36
Cellulose nitrate 2.6 Acetone Acetonitrile Cyclopentanone Dioxane Ethyl acetate Ethyl formate Isopentyl acetate Isopropyl ketone Methyl isopropyl ketone Methyl tert-butyl ketone Nitromethane rc-Propyl acetate
20 20 20 20 20 20 20 20 20 20 20 20
100 100 100 100 130 130 130 100 100 100 100 130
0.14 0.42 0.04 -0.08 -0.89 0.62 -0.5 0.16 0.66 -0.38
0.06 0.59 0.07 1.2 -0.43 -0.14 -1.8 -0.08 -0.52 -1.5 0.64 -0.83
x (0.6)
x (0.8)
x (LO)
0.49 0.51 0.67 0.39
0.55 0.31
-0.37 0.42 -0.71 -0.25 -1.35 -0.42 -3.3 -1.7 -1.6 -2.8 0.6 -2.0
-1.24 0.12 -2.4 -1.7 -3.2
-3.7 0.45 -4.1
-0.1
Method
Refs.
VP VP VP VP
38 38 38 38
VP VP
39 39
VP VP
40 40
VP VP VP VP VP VP VP VP VP VP VP VP
41 41 41 41 42 42 42 41 41 41 41 42
Solvent
T (0C)
M2 (kg/mol)
* (0.0)
x (0.2)
* (0.4)
x (0.6)
z (0.8)
x (1.0)
Method
Refs.
0.52 0.35 0.55 0.74
0.67 0.44 0.51 1.02
VP VP VP VP
43 43 43 44
1.28
VP
40
0.6 0.47
VP VP VP
45 45 46 47
Cellulose, hydroxypropyl Acetone Ethanol Tetrahydrofuran Water
25 25 25 25
Poly (aery lonitrile) Dimethylformamide
70
30.6
65 65 25 25
17 17
0.49
53
0.41
140-200 140-200 140-200
7 7 7
0.54-0.30 0.59-0.27 0.08-0.56
IGC IGC IGC
48 48 48
140-200 140-200 140-200 140-200
7 7 7 7
1.34-1.24 0.82-0.48 0.75-0.57 0.84-0.39
IGC IGC IGC IGC
48 48 48 48
13.1 13.1 65.2 13.1 13.1 13.1 13.1 13.1 13.1 13.1 65.2 13.1 12.2 65.2 13.1 13.1 13.1 13.1 13.1 200 13.1 13.1 13.1 13.1 13.1 13.1 13.1 13.1 13.1 13.1 13.1 13.1 13.1 13.1 13.1 13.1 13.1 65.2 13.1 13.1
1.64-1.32 2.86-2.36
IGC IGC VP IGC IGC IGC IGC IGC IGC IGC VP IGC IGC VP IGC IGC IGC IGC IGC VP IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC VP IGC IGC
49 49 50 49 49 49 49 49 49 49 50 49 49 50 49 49 49 49 49 51 49 49 49 49 49 49 49 49 49 49 49 49 49 49 49 49 49 50 49 49
Poly(oc-methyl styrene) Cumene a-Methylstyrene Toluene Poly(arylate) Chlorobenzene o-Dichlorobenzene Diethylene glycol diethyl ether rc-Dodecane Ethylbenzene Tetralin p-Xy lene Poly(butadiene) Acetone Acetonitrile Benzene
40-100 40-100 23.5 40-100 1-Butanol 40-100 Butyl acetate 40-100 Butyronitrile 40-100 l-Chlorobutane 40-100 1-Chloropentane 40-100 1-Chloropropane 40-100 Cyclohexane 23.5 40-100 Dibutylether 40-100 Dichloromethane 23.5 Diethylether 40-100 Diethylketone 40-100 Dipropylether 40-100 Ethanol 40-100 Ethyl acetate 40-100 Ethylbenzene 80 Ethylcyclohexane 40-100 n-Heptane 40-100 1-Heptene 40-100 w-Hexane 40-100 1-Hexene 40-100 Methanol 40-100 Methyl acetate 40-100 Methyl cyclohexane 40-100 Methyl ethyl ketone 40-100 Methyl isobutyl ketone 40-100 n-Octane 40-100 1-Octene 40-100 «-Pentane 40-100 1-Propanol 40-100 2-Propanol 40-100 Propionitrile 40-100 Propyl acetate 40-100 Tetrachloromethane 23.5 Tetrachloromethane 40-100 Tetrahydrofuran 40-100
100 100 100 100
0.47 0.46 0.51
0.51 0.47 0.6
0.06
0.02 0.26-0.19 2.76-1.64 0.52-0.45 1.90-1.57 0.33-0.25 0.37-0.32 0.36-0.30 0.26 0.22-0.15 0.37-0.34
0.27
0.12 0.43-0.40 0.82-0.67 0.51-2.26 3.41-2.30 0.86-0.69
0.31
0.37 0.09-0.04 0.36-0.31 0.25-0.23 0.37-0.38 0.32-0.28 3.85-2.70 1.14-0.92 0.17-0.13 1.19-0.97 0.95-0.72 0.34-0.28 0.23-0.20 0.44-0.36 2.97-1.97 2.94-1.86 2.25-1.82 0.67-0.55
-0.04
-0.12 0.10-0.15 0.35-0.29
References page VII - 262
Solvent
Toluene Trichloromethane Trichloromethane Poly(butene-l) n-Decane n-Heptane n-Nonane n-Octane Poly(decene) Toluene Poly(dimethyl siloxane) Acetone Benzene
Cycloheptane Cyclohexane
Cyclooctane Cyclopentane n-Decane Diisobutyl ketone 1,4-Dioxane Ethyl n-butyl ketone Ethylbenzene n-Heptane
Hexamethyl disiloxane
n-Hexane
T ( 0 C)
M2 (kg/mol)
40-100 23.5 40-100
13.1 65.2 13.1
115-135 115-135 115-135 115-135
10 10 10 10
30
213.9
100 20 25 25 25 25 25 25 25-70 25-70 30 30 30 30 30 40 40 25-70 20 25 25 25-70 30 30 25-70 25-70 20 35 25-70 100 35 23.5 25-70 25-70 20 20 25-70 25-70 30 23.2 25 25 25 25-70 20 20 25 25-70 25-70 30 30 30
50 1.54 4.17 10 15.7 50 50 50 50 6.65 15.65 26 89 89 1.54 4.17 50 50 10 50 50
x (0.0)
% (0.4)
% (0.6)
x (08)
X
fl-0)
0.14-0.12 -0.2
0.49
0.56
0.41
89 50 50 30 80 50
0.44 0.46
0.44
0.39
0.35
0.64 0.56
0.71 0.65 0.66 0.66 0.76 0.66
0.77 0.72 0.8 0.73 0.82 0.73
0.85 0.75
0.71 0.71 0.72 0.45 0.74 0.81 0.73
0.63
0.48
0.50 0.50
0.43
0.43
0.42 0.46
0.05-0.07 0.30 0.38 0.32 0.36
IGC IGC IGC IGC
52 52 52 52
0.32
VP
53
1.33 0.85 (0.76)
IGC VP VP VP OS1VP VP VP, IGC IGC VP, IGC IGC VP VP VP VP VP VP VP VP, IGC OS OS, VP VP, IGC VP, IGC VP VP VP, IGC VP, IGC
54 36 55 55 56 57 58 59 58 59 60 60 60 61 60 55 55 58 62 56 58 58 63 64 58 58 65 66 58 54 66 36 58 59 65 36 58 59 64 36 55 55 58 58 40 65 61 58 59 67 67 67
0.79 0.79 0.81 0.79-0.74 0.81-0.75 0.74 0.75 0.74 0.77 (0.72) (0.83) 0.56-0.53 0.47 0.47 0.47-0.48 0.42 0.45 0.66-0.61 0.42-0.46 0.64
0.52
0.40
0.63
0.7
0.45
0.45
0.46
0.3 0.27 0.21
0.28 0.25 0.22
0.43 0.26 0.24 0.25
0.40 0.41 0.37 0.38 0.38
Refs.
49 50 49
1.32-1.18 1.06 0.54
Method
IGC VP IGC
-0.34
0.49
80 50 50 50 30 50 50 50 89 50 1.54 4.17 50 50 30 89 50 50 6.65 15.65 26
% (0.2)
0.77-0.73 0.83-0.78 0.50 0.48 0.48-0.50 0.50-0.49 0.45 0.25 0.28 0.28-0.34 0.45 0.50 0.43 0.46-0.47 0.45 0.39 0.40 0.41
OS VP, IGC IGC OS VP VP, IGC IGC VP VP,IGC IGC VP VP VP VP VP, IGC VP, IGC VP VP VP, IGC IGC VP VP VP
Solvent
T (0C)
M 2 (kg/mol)
30 30 30 35 25-70 20 25 30 35 50 20 25 100 25-70 25-70 25-70 25-70 25-70 25-70 140
89 89 89 89 50 80 280 50 80 80 80 50
50 30 50 50 4.17 50 50 50 144 4.17 50 50 30 50 50
m-Xylene -Xylene
23.2 20 20 20 25 25 25-70 35 35 40 25-70 25-70 20 20 25 100 100 20 25 25 25 25-70 25-70 40 100 30 100 20 25 25-70 25 25 25-70 25-70 25-70
Poly(dodecene) Toluene
30
94.9
Poly(e-caprolactam) Tetrachloromethane
65
10.7
Poly(epichlorohydrin) Acetone Benzene
100 100
Mesitylene Methyl ethyl ketone
Methyl isobutyl ketone 2-Methylbutane 2-MethyIheptane 2-Methylhexane 3-Methylhexane 2-Methylpentane Octamethylcyclotetra siloxane Octamethyltrisiloxane n-Octane
n-Pentane
Tetrachloromethane Toluene
Trichloromethane 2,2,4-Trimethylpentane /7-Xylene
x (0.0)
x (0.2)
x (0.6)
X (1.0)
0.41 0.38 0.40 0.41
0.43 0.40 0.41 0.42 0.95-0.86
0.57 0.51
0.64
0.79
0.57 0.56 0.54 0.39 1.10 0.49-0.47 0.52-0.50 0.45-0.46 0.46 0.45-0.43 0.45-0.43
0.42
0.51
0.38
0.25
0.22
0.19
0.17
0.50 0.50 0.36
0.51 0.49 0.40
0.52 0.50 0.44
0.14 0.53 0.55 0.51 0.52 0.56-0.52 0.54
0.42
0.45
0.50
0.40
0.40
0.43
0.41
0.40
0.59 0.53
0.64 0.58 0.59
0.72 0.65 0.65
0.63
89 30 4.17 50 50 50 50 50 50
* (0.8)
0.50
50 50 50 50 50 50 10.1
50 1.54 4.17 50 50 50 4.17
x (04)
0.68 0.64
0.35
0.35
(0.44) 0.45-0.49 0.41-0.43 0.48 0.40 0.45 0.31 0.36 0.82 (0.74) 0.75 0.75-0.71 0.80-0.75 (0.69) 0.59 0.65 0.60 0.43
0.38
0.58
0.67
0.34
0.47
0.61
0.54
0.46
0.39
0.45-0.43 0.78 0.75 0.80-0.77 0.82-0.76 0.86-0.80 0.74
0.28 0.25
Method
Refs.
VP VP VP VP VP, IGC OS OS VP OS OS OS IGC IGC VP, IGC IGC VP, IGC IGC VP, IGC IGC VP
61 64 67 61 58 66 68 69 66 66 66 59 54 58 59 58 59 58 59 70
VP
VP VP, IGC VP VP, IGC IGC VP, IGC VP, IGC
36 65 36 62 55 58 59 59 71 55 58 59 65 36 58 54 54 36 55 55 58 58 59 55 54 72 54 65 55 58 36 58 59 58 58
VP
53
VP
73
IGC IGC
54 54
VP OS VP VP, IGC IGC IGC OS VP VP, IGC IGC VP VP1IGC IGC IGC VP VP VP VP, IGC VP, IGC IGC VP IGC VP IGC
References page VII - 262
Solvent n-Butane 1-Butanol Butyl acetate Chlorobenzene 1-Chlorobutane Chloromethane 1-Chloropentane Cycloheptane Cyclohexane Cyclohexene Cyclooctane Cyclopentane /z-Decane 1,1-Dichloroethane 1,2-Dichloroethane Dichloromethane 1,4-Dioxane Ethanol Ethyl acetate Ethyl benzene n-Heptane n-Hexane Methyl acetate Methyl ethyl ketone n-Nonane n-Octane n-Pentane 1-PentanoI Propane 1-Propanol Propyl acetate Tetrachloromethane Tetrahydrofuran Toluene 1,1,1-Trichloroethane Trichloroethylene Trichloromethane n-Undecane Poly(ethyl methacrylate) Dichloromethane Tetrachloromethane Toluene Trichloromethane Poly(ethylene glycol) Ethylbenzene
Poly(ethylene oxide) Benzene
Cyclohexane rc-Decane Ethanol n-Octane Toluene Trichloromethane Poly(ethylene)HD ds-Decalin
T( 0 C)
M 2 (kg/mol)
x (0.0)
x (0.2)
x (0.4)
* (0.6)
x (0.8)
100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 23.5 23.5 23.5 23.5 70 70 70 70
144 144.4 144 144
-0.94
2 3.272 4 6
50.3 70 70 100 100 100 100 100 99.8 100 100
6.1 100 6.1
149
105
0.38
0.18 0.19
0.14 0.14
x (1.0)
Method
1.65 1.12 0.36 0.24 0.62 0.36 0.65 1.19 1.25 0.84 1.20 1.16 2.12 0.33 0.20 0.18 0.04 1.58 0.35 0.44 1.79 1.72 0.39 0.20 1.99 1.89 1.64 1.03 1.71 1.22 0.33 0.69 0.01 0.31 0.46 0.53 0.25 2.24
IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC
54 54 54 54 54 54 54 54 54 54 54 54 54 54 54 54 54 54 54 54 54 54 54 54 54 54 54 54 54 54 54 54 54 54 54 54 54 54
-0.52 -0.01 0.19 -1.05
-0.66 -0.12 0.15
VP VP VP VP
74 74 74 74
0.87 0.42 0.85 0.71
0.83 0.45 0.82 0.69
VP VP VP VP
75 40 75 75
0.1 0.23 0.12
0.22 0.09
0.26 -0.55
VP VP VP IGC IGC IGC IGC IGC VP IGC IGC
76 73 76 54 54 54 54 54 40 54 54
0.07
IGC
77
0.13 1.23 2.10 0.70 1.85 5.2
0.41
Refs.
0.3
Solvent
T (0C)
f«mj-Decalin rt-Decane
149 145-190 149 185 2,4-Dimethyl hexane 149 3,4-Dimethyl hexane 149 n-Dodecane 149 Ethylbenzene 149 Mesitylene 149 2-Methylheptane 149 3-Methylhexane 149 rc-Nonane 149 rc-Octane 149 Tetralin 149 Toluene 149 2,2,4-Trimethyl hexane 149 2,2,4-Trimethyl pentane 149 m-Xylene 149 p-Xylene 149 Poly(ethylene)LD Benzene 1-Butanol Chlorobenzene Cyclohexane Cyclohexanol cw-Decalin rra/w-Decalin n-Decane 2,4-Dimethyl hexane 2,5-Dimethyl hexane 3,4-Dimethyl hexane rc-Dodecane
125-135 135 135 125-135 135 120-145 120-145 120-145 120-145 120-145 120-145 110-145 120-145 Ethylbenzene 120-145 n-Heptane 108.9 Mesitylene 120-145 3-Methyl heptane 120-145 3-Methylhexane 120-145 H-Nonane 120-145 H-Octane 120-145 Phenol 135 Tetrachloromethane 135 Tetralin 120-145 Toluene 120-145 Trichloromethane 135 2,2,4-Trimethyl hexane 120-145 2,2,4-Trimethyl pentane 120-145 m-Xylene 120-145 />-Xylene 120-145
Poly(heptene) Toluene Poly(isobutylene) Benzene
M2 (kg/mol)
x (0.0)
% (0.2)
* (0.4)
x (0.6)
* (0.8)
105 105 105 105 105 105 105 105 105 105 105 105 105 105 105 105 105
82 82 82 82 82 82 82 82 0.45 82 82 82 82 82
0.29
0.31
0.34
30
224.1
0.48
0.45
0.43
10 25 25 25 25 25 25 25-50 25-65 26.9 39.6
40
0.67
0.78
0.92
0.57
0.50
0.66
0.75
0.88
0.76
0.82
0.82 0.80
Refs.
IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC
77 28 77 78 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77
0.43-0.36 1.38 0.34 0.18 1.22 0.03 0.02-0.00 0.25-0.26 0.34-0.32 0.35 0.25 0.18 0.23-0.24 0.33
IGC IGC IGC IGC IGC
79 79 79 79 79 77 77 77 77 77 77 28 77 77 80 77 77 77 77 77 79 79 77 77 79 77 77 77 77
VP
0.91 1.06 0.87 0.86
0.57 0.73 0.70
Method
0.05 0.18 0.31 0.12 0.38 0.31 0.28 0.37 0.28 0.39 0.40 0.34 0.36 0.32 0.39 0.35 0.40 0.34 0.32
0.24-0.25 0.31-0.30 0.33-0.34 0.28 0.31-0.30 1.5 0.24 0.29-0.28 0.34 0.41 0.29-0.28 0.34 0.29 0.27-0.28
82 82 82 82
40
(10)
0.2
82 82
40 40 40 50 90 66 40
Z
0.91-0.79 0.86-0.61 1.07
IGC IGC IGC
VP
53
VP IGC VP IGC IGC VP OS IGC IGC VP VP
32 30 32 81 83 82 21 30 83 84 32
References page VII - 262
Solvent
n-Butane Chlorobenzene Cyclohexane
2,2-Dimethylpropane Ethylbenzene n-Heptane ^-Hexane Methyl ethyl ketone 2-Methylbutane n-Nonane n-Octane n-Pentane
Tetrachloromethane Toluene Trichloromethane Poly(isoprene) Acetone Benzene
T (0C) 40 40 40-65 60 65 65 80 100 100 25 25 25 25 25 25 25 25-65 25-50 40-65 40 40 60 65 100 25-46 35 25 40 25 25-65 25 25 25-65 100 25-35 35-46 25 25 25 25-65 25 25 25 25 25 25 25 25-50 25-65 35 35 40 45 55 100 100 100 25 10 25 25 25 25
M2 (kg/mol)
% (0.0)
x (0.2)
x (0.4)
50 50 53 50 50 100 50 26.1 40 40 40 50 50 66 40 66 53 50 50 50 50
* (0.8)
0.69 0.65
0.75 0.74
0.52 0.73 0.73 0.4
0.60 0.74 0.74 0.49
0.42
0.41
0.33
0.37
* (1.0) 0.83 0.87-0.77 0.69 0.75 0.74 0.58 0.65 0.70
0.403 0.42
0.43 0.56 0.54
0.44 0.43 0.54-0.42 0.43-0.40 0.47-0.42 0.30 0.33
0.38 0.45 0.41 0.38
0.52 0.48 0.39 0.82-0.87
1000 1000 50 50
0.34 0.4
40 40 40 50 40 1000 1000 40 40 40 40 40 40 40 50 62 66 1000 66 40 62 1000 62 62 62
x (0.6)
0.82 0.55 0.5 0.57 0.57-0.47 0.65
0.4
0.4 0.63-0.50 1.55 0.65 0.65-0.68 0.49 0.52
0.44
0.48 0.57
0.62
0.68
0.48
0.53
0.57
0.62
0.63
0.48
0.53
0.57
0.62
0.63
0.58 0.62 0.57 0.56
0.63 0.62
0.63 0.62
0.62 0.63
0.63 0.63
0.53
0.52-0.43 0.75 0.73 0.72 0.28 0.68 0.70 0.68 0.70-0.60 0.72-0.57 0.62
0.48 0.60 0.78
100
100
0.40
0.41
0.41
0.42 0.41
0.39
0.40
0.41
0.43 0.41
1.27 0.43 0.41 0.43 0.42
1.8 0.41 0.46 0.43
Method VP VP
Refs.
VP VP VP VP IGC VP VP VP VP
82 85 86 82 82 82 85 87 87 88 35 81 83 82 89 30 83 30 86 82 82 85 82 87 90 90 82 82
IGC IGC IGC VP IGC IGC VP VP IGC IGC OS IGC VP IGC IGC VP, IGC VP IGC VP IGC IGC VP VP VP VP VP IGC IGC IGC
81 83 81 82 83 87 90 90 81 81 91 83 34 81 83 58 33 30 90 30 83 33 90 33 33 33 87 87 87
VP VP OS, VP IGC VP VP
92 93 94 96 95 93
VP VP VP VP IGC IGC OS VP IGC IGC VP OS IGC IGC IGC
Solvent
T (0C)
25-55 40 40 Ethyl acetate 25 25 50 50 Ethylbenzene 25-55 «-Heptane 25-55 /i-Hexane 25-55 Methyl ethyl ketone 25 45 2-Methylheptane 25-55 2-Methylhexane 25-55 2-Methylpentane 25-55 n-Octane 25-55 n-Pentane 25-55 Tetrachloromethane 23.5 Toluene 25-55 30 Trichloromethane 23.5 2,2,4-Trimethylpentane 25-55 p-Xylene 25-55 Poly(methyl acryiate) Acetone Benzene n-Butane 1-Butanol n-Butylbenzene tert-Butylbenzene n-Butylcyclohexane Cyclohexane ris-Decalin trans-D&cahn n-Decane Dichloromethane 1,4-Dioxane n-Dodecane Ethanol Ethyl acetate Ethylbenzene n-Heptane n-Hexane Methyl ethyl ketone Naphthalene n-Nonane n-Octane n-Pentane Propane n-Tetradecane Tetrahydrofuran Tetralin 3,3,4,4-Tetramethylhexane Toluene Trichloromethane 3,4,5-Trimethylheptane 2,2,5-Trimethylhexane 2,2,4-Trimethylpentane Poly(methyl methacrylate) 1,2-Dichloroethane
100 90-110 100 100 90-110 90-110 90-110 90-110 90-110 90-110 88-110 23.5 100 90-110 100 100 90-110 100 100 100 100-110 100 90-110 100 100 90-110 100 90-110 90-110 90-110 23.5 90-110 90-110 90-110
23.5 50 50
M2 (kg/mol)
x (0.0)
x (0.2)
% (0.4)
x (0.6)
* (0.8)
0.82 0.81 0.77 0.79
0.41 0.41 0.96 0.96 0.91 0.92
100 0.69 0.68 0.68
100
0.86 0.83
1.05 0.99
0.20
0.10
0.42 0.25
0.38 0.16
x U-O) 0.46-0.43 0.44 0.44 1.24 1.23 0.34-0.30 0.51-0.49 0.54-0.50 1.43 1.20 0.50-0.47 0.52-0.50 0.56-0.52 0.49-0.46 0.61-0.53 0.36-0.32
270 100
0.46
0.49-0.46 0.28-0.26
0.4 0.51-0.46 1.86 0.79 1.15-1.05 1.03-0.95 2.34-2.13 1.72-1.51 2.07-1.84 2.13-1.90 2.68-2.43
200 200 200 200 200 200 200 200 63.2
-0.22
-0.43 0.20 3.00-2.75 1.01 0.43 0.83-0.75 2.10 2.08 0.40 0.49-0.47 2.4 2.38-2.19 1.92 2.5 3.36-3.06 0.34 1.04-0.95 2.17-1.95
200 200
200 200 200 200 200 200 63.2 200 200 200
33.2 5.5 8.43
0.67-0.62 -0.53
-0.58 2.44-2.20 2.48-2.21 2.35-2.07
-0.63 0.25 0.14
-0.7 0.17 0.21
-0.74 0.32 0.33
Method
Refs.
IGC IGC VP VP VP VP VP IGC IGC IGC VP VP IGC IGC IGC IGC IGC VP IGC VP VP IGC IGC
96 96 93 97 92 97 92 96 96 96 92 92 96 96 96 96 96 50 96 98 50 96 96
IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC VP IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC IGC
54 99 54 54 99 99 99 99 99 99 99 74 54 99 54 54 99 54 54 54 99 54 99 54 54 99 54 99 99
IGC VP IGC IGC IGC
99 74 99 99 99
VP VP VP
74 40 40
References page VII - 262
Solvent
3,3-Dimethyl-2butanone
Mesitylene Tetrachloromethane
Toluene
/7-Xylene
Poly(n-butyl acrylate) Benzene Toluene Trichloromethane Poly(n-butyl methacrylate) Acetone Acetonitrile Benzene 1,2-Dichloroethane Ethanol Ethyl acetate rc-Hexane Mesitylene Methyl ethyl ketone 1-Propanol 2-Propanol Toluene Trichloromethane m-Xylene o-Xylene Poly(c-chlorostyrene) Benzene
T(0C) 70 70 50 50.2 69.3 70.3 130 50 50.2 69.7 70.7 23.5 48.5 49.8 50 50 50.1 69.6 70 70 70.4 160 50 70 100 136.2 23.5 23.5 23.5
120 120 50.5 50.8 40 60 80 120 120 100 50.5 120 120 27 56 86 50.2 50.5 120 70.8 71.3
M2 (kg/mol)
(0.4)
x (0.6)
x (0.8)
5.5 8.43 3.15
0.06
0.21 0.31 0.45
0.33 0.28 0.34
VP VP VP
40 40 100
8.56 3.15 8.56 8.43 3.16 8.56 3.15 8.56 33.2 19.77 3.16 36.41 72 8.56 3.16 36.41 72 8.56 110 8.43 8.43 8.46 8.46
0.55
0.55 0.63 0.57 0.85 0.56 0.6 0.57 0.53
0.6 0.46 0.74 0.99
VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP
100 100 100 40 100 100 100 100 74 101 100 40 40 100 100 40 100 100 102 100 100 100 100
VP VP VP
74 74 74
IGC IGC VP VP VP VP VP IGC IGC VP VP IGC IGC VP VP VP VP VP IGC VP VP
103 103 40 40 104 104 104 103 103 40 40 103 103 104 104 104 40 40 103 40 40
VP VP VP
105 105 105
(0.0)
x (0.2)
35 35 36.8 36.8 8.9 8.9 8.9 35 35 36.8 36.8 35 35 8.9 8.9 8.9 36.8 36.8 35 36.8 36.8 607 607 607
Poly(octadecene) Toluene
30
193.5
Poly(/?-bromostyrene) Toluene
20
10
z
0.59
0.56
0.62
0.53
0.53 0.60 0.50 0.51 0.58 0.53 0.45 0.44 0.51
0.65 0.62 0.66 0.45 0.45 0.69 0.51 0.53 0.73 0.63 0.51 0.50 0.71
0.67 0.89 0.77 0.46
0.89 0.84 0.73 0.63
0.17 0.05 -0.39
0.02
z (1.0)
0.89 0.71
33 33 33
25 40 40
Methyl ethyl ketone
Z
0.12 -0.32
0.93 1.40 0.509 0.484 0.477
0.492 0.432 0.399
0.57 0.55 0.53
0.54 0.49 0.46
0.21 0.41 0.68 0.66 0.63
0.65 0.59 0.54 0.24 0.01
0.14 0.37 0.86 0.8 0.76
1.09 0.99 0.89
0.41 0.3
0.44
1.38 1.19 1.01 0.67 0.78 0.62 1.01 1.29 1.11 0.95
Refs.
0.82 0.72 0.64 0.17
1.03 0.88 0.77
0.48 0.26
0.4 0.27
0.56
0.58 0.56
0.60 0.62 0.83
0.51
0.74
VP
53
0.64
0.65
VP
106
0.10
0.50
Method
0.62 0.67 1.02
Solvent
T (0C)
M 2 (kg/mol)
% (0.0)
% (0.2)
x (0.4)
x (0.6)
z (08)
x (10)
Method
Refs.
Poly(p-chlorostyrene) Toluene
22
10
0.53
0.58
0.55
VP
106
Poly(p-methyl styrene) Toluene
20
10
0.41
0.4
0.35
VP
106
500 500 3.35
0.16 0.15 0.45
0.03 0.08 0.48
VP VP VP
107 107 108
1.72 0.51 0.22 1.11
IGC IGC IGC VP
87 87 87 109
1.01 0.18 0.22 1.66 1.55 0.29 0.55 0.43 0.61
VP IGC VP VP IGC IGC IGC IGC
109 29 87 109 109 87 87 87 87
IGC VP VP IGC IGC IGC IGC IGC VP VP VP VP VP VP VP VP VP VP VP VP VP IGC IGC IGC IGC IGC VP IGC IGC IGC IGC IGC CM, LS LS, CM CM, LS CM IGC IGC
110 111 111 112 110 110 110 110 113 113 114 37 115 115 116 115 115 116 115 115 116 78 117 110 118 30 102 99 110 110 110 110 120 119 120 120 99 99
Polypropylene glycol) Benzene Methanol Poly(propylene) Acetone Benzene Cyclohexane 2,4-Dimethyl3-pentanone n-Hexane w-Octane 3-Pentanone Tetrachloromethane Tetrahydrofuran Toluene Trichloromethane Poly(styrene) Acetic acid Acetone
Acetonitrile Aniline Benzaldehyde Benzene
Benzyl alcohol 1-Butanol 2-Butanol n-Butyl acetate tert-Butyl acetate
n-Butylbenzene *-Butylcyclohexane
47.2 74.7 25 100 100 100 25 45 80 100 25 45 100 100 100 100 162-229 25 50 150 162-229 162-229 162-229 162-229 20 20 23.5 25 30 30 40 50 50 60 70 70 80 120 133-210 162-229 140-200 150-200 130-155 160-180 162-229 162-229 162-229 162-229 10 30 50 143-183 183-203 160-180
-0.03 0.02
-0.07 -0.02
20
0.55
0.61
0.7
0.86
20
0.57
0.57
0.64
0.79
0.70 0.70
0.82 0.71
1.08 0.97
0.81 0.80
0.94 0.92
20 20
20 15.7 15.7 17.5 20 20 20 20 20 500 600 90 19.2 103.8 218 19.2 103.8 218 19.2 103.8 218 200 20 76 97 275 120 20 20 20 20 11 11 11 11 120 120
3.00-2.15 1.1 0.65 1.30-0.56 2.02-0.93 1.11-0.68 1.22-0.80
0.57 0.49 0.42
0.37
0.39 0.46 0.30 0.32 0.41 0.54 0.26 0.45 0.53 0.25 0.32 0.40 0.14
0.21 0.44 0.19 0.26 0.3 0.35 0.28 0.26 0.21 0.31 0.27 0.35 0.23 0.33 0.32-0.20 0.66-0.13 0.59-0.60 0.38 0.31-0.28 0.29-0.24 1.42-0.65 1.47-0.82 1.71-0.81 1.01-0.45
0.50 0.50 0.49
0.54 0.54 0.53
0.64 0.64 0.63 0.73-0.52 0.38-0.35 0.77-0.71
References page VII - 262
Solvent
Chlorobenzene Cyclohexane
Cyclohexanone ds-Decalin trans-Decalin n-Decane Di(«-propyl)ether -Dichlorobenzene 1,2-Dichloroethane Dichloromethane Diethyl ether Diisopropyl ether Dimethylformamide 1,4-Dioxane
n-Dodecane Ethanol Ethyl acetate Ethylbenzene
Ethylene glycol
T ( 0 C)
162-229 20 30 30 30 30 30 30 34 35 35 40 40 44 45 45 50 50 50 55 60 60 65 65 70 70 80 150 140-200 162-229 160-180 162-229 183-203 183-203 140-200 183-203 20 133-210 162-229 23.5 162-229 162-229 162-229 140-200 20 20 50 133-171 162-229 183-203 162-229 150 162-229 30 50 50 70 70 130 140 150 120-185 133-210 140-200 160-180 162-229
M2 (kg/mo!)
i (0.0)
% (0.2)
% (0.4)
20 500
% (0.6)
* (0.8)
% (1.0)
0.68
0.92
0.78 0.79 0.87 0.71 0.69 0.75
0.77 0.98 0.89 0.92 0.93
1.14
0.75 0.75 0.76 0.72
0.91 0.92 0.92 0.93
(1.15)
0.73 0.66 0.52 0.72 0.66 0.62 0.72
0.85 0.82 0.73
(1.02)
0.73 0.78 0.89
(0.82)
0.60 0.65 0.57 0.68
0.65 0.65 0.71 0.8
(0.70)
0.81
0.91
0.68-0.28 0.57
19.2 100 103.8 150 218 25.1 51 233 100 218 25.1 51 233 100 103.8 150 233 100 218 51 233 19.2 103.8 218 17.5 76 20 120 20 120 120 76 120 500 200 20 600 20 20 20 76 200 500 10.3 200 20 120 20 17.5 20 230 19.2 103.8 19.2 103.8 275 275 17.5 200 76 275 20
0.47
0.65
0.57 0.56 0.56
0.64
0.63
0.49
0.57 0.55 0.55
0.48
0.34 0.53
0.55 0.59
0.48
0.53 0.51
0.55
0.50 0.50 0.49
0.64
0.63
0.71
0.92 0.47 1.05-0.85 1.11-0.46 0.62-0.53 1.08-0.49 0.47-0.42 0.52-0.46 1.51-1.13 1.01-0.94 0.59-0.30 0.85-0.22
0.24
0.10 0.62-0.21 0.78-0.71 1.42-0.41 1.29-1.16
0.67
0.40 0.88
0.23
0.28
0.35 0.44 0.61
0.35 0.44 0.78
0.40 0.66 0.75 0.74 0.71 0.33
0.43 0.91 0.65 0.83 0.39
1.10 0.52-0.39 0.95-0.42 1.09-1.00 1.80-0.43 0.46 1.14-0.35
0.43 0.46 0.27 0.22-0.14 0.40-0.23 0.57-0.58 0.32-0.25 3.77-2.23
Method
IGC VP CM VP VP VP VP VP OS, VP LS HSGC VP VP OS, VP LS HSGC VP VP VP HSGC VP VP LS HSGC VP VP VP IGC IGC IGC IGC IGC IGC IGC IGC IGC VP IGC IGC VP IGC IGC IGC IGC VP VP VP IGC IGC IGC IGC IGC IGC VP VP VP VP VP VP VP IGC IGC IGC IGC VP IGC
Refs.
110 113 25 115 121 115 122 123 22 23 124 121 116 22 23 124 121 115 122 124 121 116 23 124 115 115 116 112 118 110 99 110 99 99 118 99 113 117 110 114 110 110 110 118 113 113 101 117 110 99 110 112 110 123 125 125 125 125 102 102 112 29 117 118 102 110
Solvent Formamide n-Heptane n-Hexadecane n-Hexane Methanol Methyl cyclohexane Methyl ethyl ketone
Naphthalene Nitrobenzene n-Nonane n-Octane n-Octane /-Octane 1-Octanol n-Pentane 1-Pentanol 3-Pentanone 1-Propanol 2-Propanol Propyl acetate Pyridine Styrene Tetrachloromethane
n-Tetradecane Tetrahydrofuran Tetralin 3,3,4,4-Tetramethylhexane Toluene
Trichloroethane Trichloroethylene
T(0C)
M1 (kg/mo!)
162-229 140-200 162-229 183-203 162-229 162-229 72 25 48.5 70 120-200 133-171 162-229 183-203 162-229 130-175 150 162-229 162-229 162-229 162-229 162-229 20 20 120-200 162-229 162-229 25 70 162-229 133-210 20 23.5 133-171 162-229 183-203 162-229 183-203 160-180
20 76 20 120 20 20 110 290 10.3 290 35 200 20 120 20 53.7 17.5 20 20 20 20 20 200 500 9 20 20 290 290 20 200 500 600 200 20 120 20 120 120
20 20 22 23.5 25 25 25 25 25 40 45 48.5 49.8 60 65 69.5 80 100 110 130 133-210 162-229 140-200 23.5 162-229
200 500 10 600 51 90 100 170 290 218 51 10.3 45 218 51 45 290 103.8 275 275 200 20 76 600 20
x (0.0)
0.49
x (0.2)
0.58
* (0.4)
0.67 0.63 0.63
* (0.6)
0.69 0.67 0.63
Z
(0.8)
x (1.0)
Method
4.11-3.16 1.49-1.14 1.33-0.25 1.22-1.14 1.35-0.03 2.19-0.44
IGC IGC IGC IGC IGC IGC OS VP VP VP IGC IGC IGC IGC IGC VP IGC IGC IGC IGC IGC IGC VP VP IGC IGC IGC VP VP IGC IGC VP VP IGC IGC IGC IGC IGC IGC
110 118 110 99 110 110 126 127 101 127 128 117 110 99 110 51 112 110 110 110 110 110 113 113 128 110 110 111 111 110 117 113 114 117 110 99 110 99 99
VP VP VP VP LS VP SAXS OS VP VP LS VP VP VP LS VP VP VP VP VP IGC IGC IGC VP IGC
113 113 106 114 23 37 129 130 127 116 23 101 40 116 23 40 127 131 102 102 117 110 118 114 110
0.77 0.73 0.72 1.13-0.9 0.80-0.67 L16-0.36 0.13-0.11 1.18-0.72 1.00-0.97 1.24 2.19-0.80 1.72-0.35 1.14-0.55 1.12-0.83 1.75-0.86
0.63
0.65 0.65
0.95 0.87 1.54/1.38/1.4 1.71-0.27 1.74-0.15'
0.66 0.61
0.66 0.6
0.66 0.59 1.02-0.23 0.23/0.28/0.23
0.37
0.37 0.31 0.49-0.19 0.90-0.26 1.14-1.08 0.70-0.16 0.20-0.11 0.90-0.76
0.40
0.44 0.43
0.37 0.37 0.41
0.37 0.35
0.52 0.41 0.39 0.39
0.34 0.33
0.30 0.40
0.23
0.16
0.42
0.37 0.36
0.31 0.37
0.34
0.33 0.45 0.35
0.32 0.53 0.37
0.57 0.35 0.48 0.37
0.57
0.42
0.25
0.37 0.40 0.52
0.40
0.07
0.3 0.35 0.21
0.18 0.32-0.21 0.67-0.04 0.57-0.56
-0.1 0.69-0.12
Refs.
References page VII - 262
Solvent Trichloromethane
Water m-Xylene o-Xylene
m-Xylene
T( 0 C)
Vinyl acetate Poly (vinyl methyl ether) Acetone Cyclohexane Ethyl acetate Ethylbenzene rc-Octane
% (0.2)
* (0.4)
0.52 0.45
0.32 0.34
8.6 109.1 170 1041 170 110
150 150 150 150 150
68.5 68.5 68.5 68.5 68.5
t
(0.6)
0.23 0.23
t
(0.8)
z(1.0)
0.17 0.14 1.4-1.48 0.43-0.01 4.40-3.10
0.61 0.48 0.53 0.52
0.52 0.43 0.43 0.39 0.38-0.25 0.72-0.26 0.39-0.35
12 12 12 12 12 12 12 12 12 12 12 12 12 12 12
25 30 30 30 30 40 30
Poly (vinyl methyl ketone) n-Decane 83-163 rc-Dodecane 113-173 n-Heptane 73-163 n-Nonane 73-163 n-Octane 73-163 n-Undecane 83-163
).
% (0.0)
25 290 50 290 120-200 9 162-229 20 162-229 20 100 19.2 100 19.2 100 103.8 100 1538 133-210 200 162-229 20 130-175 53.7
Poly(tert-butyl methacrylate) Benzene 50 69.5 Ethylbenzene 69.5 Mesitylene 100 Methyl ethyl ketone 50 69.5 3-Pentanone 50 Tetrachloromethane 50 Toluene 100 50 69.6 Trichloromethane 50 m-Xylene 69.5 -Xylene 69.5 p-Xylene 69.5 Poly(vinyl acetate) Acetone
M1 (kg/mol)
0.25
500 500 500 500 500 500
VP VP IGC IGC IGC VP VP VP VP IGC IGC VP
111 111 128 110 110 40 40 40 40 117 110 51 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40
0.36 0.36 0.69 0.71 0.52 0.62 0.58 0.42 0.44 0.44 0.44 0.62 0.63 0.57
VP VP VP VP VP VP VP VP VP VP VP VP VP VP VP
0.38 0.38
0.48 0.55 0.33 0.55 0.34 0.22
SAXS VP VP VP VP VP VP
132 133 133 134 133 134 135
0.54 0.47 0.21 0.10 0.97
IGC IGC IGC IGC IGC
112 112 112 112 112
3.91-3.54 3.89-3.16 3.56-3.05 3.48-3.20 3.55-3.11 3.86-3.68
IGC IGC IGC IGC IGC IGC
136 136 136 136 136 136
0.41 0.41
Refs.
0.39 0.31 0.62 0.70 0.33 0.43 0.63 0.42 0.47 0.44 0.37 0.03 0.67 0.55 0.42
0.454 0.31
Method
0.29
0.31 0.35
REFERENCES 1. R J . Flory, J. Chem. Phys., 10, 51 (1942). 2. P. J. Flory, J. Chem. Phys., 12, 425 (1944). 3. P. J. Flory, "Principles of Polymer Chemistry", Cornell University Press, Ithaca, 1953. 4. M. L. Huggins, J. Chem. Phys., 46, 151 (1942). 5. M. L. Huggins, J. Am. Chem. Soc, 64, 1712 (1942).
6. M. L. Huggins, "Physical Chemistry of High Polymers", Wiley, New York, 1958. 7. K. H. Meyer, Z. Phys. Chem., 44, 383 (1939). 8. R. A. Orwoll, Rubber Chem. Technol., 50, 451 (1977). 9. A. F. M. Barton, "Handbook of Solubility Parameters and Dher Cohesion Parameters", CRC Press, Boca Raton, 1983.
10. H. M. Petri, N. Schuld, B. A. Wolf, Macromolecules, 28, 4975 (1995). 11. P. J. Flory, Disc. Faraday Soc, 49, 7 (1970). 12. P. J. Flory, J. Chem. Phys., 17, 223 (1949). 13. C E . Anagnostopoulos, A. Y.Coran,H. R.Gamrath, J. Appl. Polym. ScL, 4, 181 (1960). 14. P. J. Flory, Rehner, Jr., J. Chem. Phys., 11, 521 (1943). 15. P. J. Flory, J. Chem. Phys., 18, 108 (1950). 16. P. Doty, H. S. Zable, J. Polym. Sci., 1, 90 (1946). 17. A. F. Blanchard, P. M. Wootton, J. Polym. Sci., 34, 627 (1959). 18. G. M. Bristow, W. F. Watson, Trans. Faraday Soc, 54, 1742 (1958). 19. C. M. Kok, A. Rudin, J. Appl. Polym. Sci., 27, 353 (1982). 20. M. B. Huglin (Ed.), "Light Scattering from Polymer Solutions", Academic Press, London (1972). 21. R J. Flory, H. Daoust, J. Polym. Sci., 25, 429 (1957). 22. W. R. Krigbaum, D. O. Geymer, J. Am. Chem. Soc, 81, 1859 (1959). 23. T. G. Scholte, Eur. Polym. J., 6, 1063 (1970). 24. R. Koningsveld, L. A. Kleintjens, A. R. Shultz, J. Polym. Sci. Part A-2, 8, 1261 (1970). 25. R. Koningsveld, L. A. Kleintjens, Macromolecules, 4, 637 (1971). 26. C. A. Haynes, R. A. Beyon, R. S. King, H. W. Blanch, J. M. Prausnitz, J. Chem., Phys., 93, 5612 (1989). 27. O. Smidsrod, J. E. Guillet, Macromolecules, 2, 272 (1969). 28. D. Patterson, Y. B. Tewari, H. R Schreiber, J. E. Guillet, Macromolecules, 4, 356 (1971). 29. N. F. Brockmeier, R. W. McCoy, J. A. Meyer, Macromolecules, 5, 464 (1972). 30. R. D. Newman, J. M. Prausnitz, J. Chem. Phys., 76, 1492 (1972). 31. P. J. Flory, J. Am. Chem. Soc, 65, 372 (1943). 32. B. E. Eichinger, P. J. Flory, Trans. Faraday Soc, 64, 2053 (1968). 33. C. H. Baker, W. B. Brown, G. Gee, J. S. Rowlinson, D. Stubley, Y. E. Yeadon, Polymer, 3, 215 (1962). 34. B. E. Eichinger, P. J. Flory, Trans. Faraday Soc, 64, 2066 (1968). 35. B. E. Eichinger, P. J. Flory, Trans. Faraday Soc, 64, 2061 (1968). 36. R. S. Chahal, W-P. Kao, D. Patterson, J. Chem. Soc, Faraday Trans. 1, 69, 1834 (1973). 37. I. Noda, Y. Higo, N. Ueno, T. Fujimoto, Macromolecules, 17, 1055 (1984). 38. W. R. Moore, R. Shuttleworth, J. Polym. Sci., Part A, 1, 733 (1963). 39. W. R. Moore, R. Shuttleworth, J. Polym. Sci., Part A, 1,1985 (1963). 40. C. Wohlfarth, Physical Sciences Data Vol. 44, Elsevier (1990). 41. E. C. Baughan, A. L. Jones, K. Stewart, Proc Roy. Soc, London, Ser. A, 225, 478 (1954). 42. A. L. Jones, Trans. Faraday Soc, 52, 1408 (1956). 43. J. S. Aspler, D. G. Gray, Polymer, 23, 43 (1982). 44. J. S. Aspler, D. G. Gray, Macromolecules, 12, 562 (1979).
45. S. G. Canagrata, D. Margerison, J. R Newport, Trans. Faraday Soc, 63, 3058 (1966). 46. I. Noda, N. Kato, T. Kitano, et al., Macromolecules, 14, 668 (1981). 47. A. Hamdouni, J. Leonard, V. T. Bui, Polymer Commun., 31, 258 (1990). 48. J. I. Eguiazabal, M. J. Fernandez-Berridi, J. J. Iruin, J. M. Elorza, Polym. Bull, 13, 463 (1985). 49. P. Alessi, A. Cortessi, P. Sacomani, E. Valles, Macromolecules, 26, 6175 (1993). 50. S. Saeki, J. C. Holste, D. C. Bonner, J. Polym. Sci., Polym. Phys. Ed., 20, 793 (1982). 51. Y. Iwai, Y. Arai, J. Chem. Eng., Japan, 22, 155 (1989). 52. G. Charlet, R. Ducasse, G. Delmas, Polymer, 22, 1190 (1981). 53. P. J. T. Tait, P. J. Livesey, Polymer, 11, 359 (1970). 54. P. Munk, P. Hattam, Q. Du, et. al., J. Appl. Polym. Sci.: Appl. Polym. Symp., 45, 289 (1990). 55. E. Dolch, M. Glaser, A. Heintz, H. Wagner, R. N. Lichtenthaler, Ber. Bunsenges. Phys. Chem., 88, 479 (1984). 56. P. J. Flory, H. Shih, Macromolecules, 5, 761 (1972). 57. M. J. Newing, Trans. Faraday Soc, 46, 613 (1950). 58. R. N. Lichtenthaler, D. D. Liu, J. M. Prausnitz, Ber. Bunsengesell, 78, 470 (1974). 59. W. R. Summers, Y. B. Tewari, H. P. Schreiber, Macromolecules, 5, 12 (1972). 60. A. J. Ashworth, G. J. Price, Macromolecules, 19,358 (1986). 61. A. J. Ashworth, G. J. Price, Thermochim. Acta, 82, 161 (1984). 62. N. Kuwahara, T. Okazawa, M. Keneko, J. Polym. Sci., Part C, 23, 543 (1968). 63. R. W. Brotzman, B. E. Eichinger, Macromolecules, 15, 531 (1982). 64. A. J. Ashworth, et. al., Macromolecules, 17, 1090 (1984). 65. W. E. Hammers, C. L. Ligny, J. Polym. Sci., Polym. Phys. Ed., 12, 2065 (1974). 66. T. Shiomi, Z. Izumi, F. Hamada, A. Nakajima, Macromolecules, 13, 1149 (1980). 67. A. J. Ashworth, G. J. Price, J. Chem. Soc, Faraday Trans. I, 81, 473 (1985). 68. D. W. Scott, J. Am. Chem. Soc, 68, 1877 (1946). 69. A. Muramoto, Polymer, 23, 1311 (1982). 70. R. C. Osthoff,W. T. Grubb,J. Am. Chem. Soc,76,399(1954). 71. K. Sugamiya, N. Kuwahara, M. Kaneko, Macromolecules, 7, 66 (1974). 72. A. J. Ashworth, G. J. Price, Macromolecules, 19, 362 (1986). 73. C. Panayiotou, J. H. Vera, Polym. J., 16, 89 (1984). 74. S. Saeki, J. Holste, D. C. Bonner, J. Polym. Sci. Polym. Phys, Ed., 21, 2049 (1983). 75. C. Wohlfarth, W. Zschoch, M. T. Ratzsch, Acta Polymerica, 32,616(1981). 76. C. Booth, C. J. Devoy, Polymer, 12, 309 (1971). 77. H. P. Schreiber, Y. B. Tewari, D. Patterson. J. Polym. Sci., Polym. Phys. Ed., 11, 15 (1973). 78. N. F. Brockmeier, R. W. McCoy, J. A. Meyer, Macromolecules, 5, 130 (1972).
79. G. DiPaola-Baranyi, J. E. Guillet, H.-E. Jeberien, J. Klein, Makromol. Chem., 181, 215 (1980). 80. J. H. van der Waails, J. J. Hermans, Rec. Trav. Chim. Pays Bas., 69, 971 (1950). 81. Y.-K. Leung, B. E. Eichinger, J. Phys. Chem., 78,60 (1974). 82. H. Masuoka, N. Murashige, M. Yorizane, Fluid Phase Equil., 18, 155 (1984). 83. Y-K. Leung, B. E. Eichinger, Macromolecules, 7, 685 (1974). 84. R. S. Jessup, J. Res. Nat. Bur. Stand., 60, 47 (1958). 85. N.-H. Wang, S. Takashima, H. Masuoka, Kagaku Kogaku Ronbunshu, 15, 313 (1989). 86. R. N. Lichtenthaler, D. D. Liu, J. M. Prausnitz, Macromolecules, 7, 565 (1974). 87. Q. Du, P. Hattam, R Munk, J. Chem. Eng. Data, 35, 367 (1990). 88. Y Nakamura, K. Akasaka, K. Katayama, T. Norisuye, A. Teramoto, Macromolecules, 25, 1134 (1992). 89. P. J. Flory, J. Am. Chem. Soc, 65, 372 (1943). 90. S. Prager, E. Bagley, R A. Long, J. Am. Chem. Soc, 75, 2742 (1953). 91. P. J. Flory, J. L. Ellenson, B. E. Eichinger, Macromolecules, 1, 279 (1968). 92. C. Booth, G. Gee. G. Holden, G. R. Williamson, Polymer, 5, 343 (1964). 93. B. E. Eichinger, P. J. Flory, Trans. Faraday Soc, 64, 2035 (1968). 94. G. Gee. J. Chem. Soc, 5, 280 (1947). 95. G. Gee, J. B. M. Herbert, R. C. Roberts, Polymer, 6, 541 (1965). 96. Y B. Tewari, H. R Schreiber, Macromolecules, 5, 329 (1972). 97. C. Booth, G. Gee, G. R. Williamson, J. Polym. ScL, 23, 3 (1957). 98. K. H. Meyer, E. Wolff, C. G. Boissonnas, HeIv. Chim. Acta, 23, 430 (1940). 99. G. DiPaola-Baranyi, J. Guillet, Macromolecules, 11, 228 (1978). 100. E. Regener, C. Wohlfarth, M. T. Ratzsch, S. Horing, Acta Polymerica, 39, 618 (1988). 101. P. J. T. Tait, A. M. Abushihada, Polymer, 18, 810 (1977). 102. J. S. Vrentas, J. L. Duda, S. T. Hsieh, Ind. Eng. Chem., Process Des. Dev., 22, 326 (1983). 103. D. J. Walsh, J. G. McKeown, Polymer, 21, 1330 (1980). 104. S. P. Nunes, B. A. Wolf, Macromolecules, 20, 1948 (1987). 105. K. Gekko, K. Matsumura, Bull. Chem. Soc Japan, 46, 1554 (1973). 106. R. Corneliussen, S. A. Rice, H. Yamakawa, J. Chem. Phys., 38, 1768 (1963). 107. C. Booth, C. J. Devoy, Polymer, 12, 320 (1971).
108. M. L. Lakhanpal, B. E. Conway. J. Polym. SdL, 46, 75 (1960). 109. W. B. Brown, G. Gee, W. D: Taylor, Polymer, 5, 362 (1964). 110. S. Gundiiz, S. Dincer, Polymer, 21, 1041 (1980). 111. C. E. H. Bawn, M. A. Wajid, Trans. Faraday Soc, 52, 1658 (1956). 112. S. Klotz, R. H. Schuster, H.-J. Cantow, Makromol. Chem., 187, 1491 (1986). 113. E. C. Baughan, Trans. Faraday Soc, 44, 495 (1948). 114. S. Saeki, J. C. Holste, D. C. Bonner, J. Polym. ScL, Poly. Phys. Ed., 19, 307 (1981). 115. M. T. Ratzsch, M. Opel, C. Wohlfarth, Acta Polymerica, 31, 218 (1980). 116. N.-H. Wang, S. Takashima, H. Matsuoka, Kagaku Kogaku Ronbunshu, 15, 795 (1989). 117. F. H. Covitz, J. King, J. Polym. Sci. A, 10, 689 (1972). 118. M. Galin, M. C. Rupprecht, Polymer, 19, 506 (1978). 119. B. A. Wolf, H. J. Adam, J. Chem. Phys., 75, 4121 (1981). 120. K. Schotsch, B. A. Wolf, H.-E. Jeberien, J. Klein, Makromol. Chem., 185, 2169 (1984). 121. Y C. Bae, J. J. Shim, D. S. Soane, J. M. Prausnitz, J. Polym. ScL, 47, 1193 (1993). 122. K. Schmoll, E. Jeckel, Z. Elektrochemie, 60, 756 (1956). 123. T. Katayama, K. Matsumura, Y Urahama, Kagaju Kogaku, 35, 1012 (1971). 124. H. M. Petri, B. A. Wolf. Macromolecules, 27, 2714 (1994). 125. M. T. Ratzsch, G. Illig, C. Wohlfarth, Acta Polymerica, 33, 89 (1982). 126. K. Kamide, K. Sugamiya, T. Kawai, Y Miyazaki, Polym. J., 12, 67 (1980). 127. C. E. H. Bawn, R. F. J . Freeman, A. R. Kamaliddin, Trans. Faraday Soc, 46, 677 (1950). 128. C. Uriate, M. J. Fdez.-Berride, J. M. Elorza, J. J. Iruin, L. Kleintjens, Polymer, 30, 1493 (1989). 129. S. Kinugasa, H. Hayashi, F. Hamada, A. Nakajima, Macromolecules, 18, 582 (1985). 130. C. E. Bawn, E. S. Hill and M. A. Wajid, Trans. Faraday Soc, 52, 1651 (1958). 131. G. Illig, Dissertation, TH Leuna-Merseburg, 1981. 132. A. M. Hecht, F. Horkay, E.Geissler, J. P. Benoit, Macromolecules, 24, 4183 (1991). 133. K. Mathsumara, T. Katayama, Kagaku Kogaku, 38, 388 (1974). 134. R. J. Kokes, A. R. DiPietro, F. A. Long, J. Am. Chem. Soc, 75, 6319 (1953). 135. A. Nakajima, H. Yamakawa, I. Sakurada, J. Polym. Sci., 35, 489 (1959). 136. Zeki Y Al-Saigh, Poly. Int., 40, 25 (1996).
Concentration Dependence of the Viscosity of Dilute Polymer Solutions: Huggins and Schulz-Blaschke Constants Cl i f o rd K . S c h o f PPG Industre is, Inc. Asilon Park, PA, USA A. Introduction VII-265 B. Tables VII-266 Table 1. Huggins Constants VII-266 1.1. Poly(dienes) and Poly(alkenes) VII-266 1.2. Poly(acrylic acid) and Poly(methacrylic acid) Derivatives VII-268 1.3. Vinyl Polymers VII-272 1.4. Poly(oxides) VII-277 1.5. Poly(esters) VII-278 1.6. Polyamides VII-279 1.7. Other Compounds VII-280 1.8. Cellulose, Cellulose Derivatives, and Polysaccharides VII-282 Table 2. Schulz-Blaschke Constants VII-284 C. References VII-285 A.
INTRODUCTION
The dependence of the viscosity of dilute polymer solutions on concentration can be described by a power series: (Al) where 77 is the viscosity of the solution and 770 is the viscosity of the solvent. This equation is usually presented in another form:
(specific viscosity), can be put in the form (A4) which becomes the Huggins equation (1) (A5) where k^ is the Huggins viscosity constant that is the most commonly used dilute solution viscosity number or index. It is easily determined from the slope of a plot of 77sp/c versus c. The Huggins constant can be thought of as a measure of the "goodness" of the solvent for the polymer with values around 0.3 in good solvents and 0.5-1 in theta solvents. It should be noted that these generalizations break down with extremely dilute solutions (2) and with chain aggregation (3). In both cases, values tend to be higher. The Huggins constant is independent of molecular weight for many polymers, but is dependent on molecular weight for polymers that associate easily in solution (3). The Huggins equation and Huggins constants can be used to determine values for the limiting viscosity number, [77]. For extrapolation procedures related to [77] and k^, see (Ref. 4). Applications of the Huggins equation to measure [77] are given in Refs. (5,6). The latter gives an equation for [T?]: (A6)
(A2) where [77] is the limiting viscosity number and ki(k\,k2) • • •) is a dimensionless constant. If terms with the third and higher powers of concentration are neglected, then Eq. (A2) becomes (A3) which, since 77/770 = rjTG\ (viscosity ratio) and 77rei — 1 == Vsp
which can be used for single point determinations, i.e., calculating [77] from a single viscosity measurement at a known concentration. Computer programs relating solution viscosity and molecular parameters are found in Refs. (7,8). Other semiempirical equations, such as those of Kraemer and Schulz and Blaschke, also are used for processing viscosity data. The Kraemer equation (Ref. 9) is (A7)
where kk is the Kraemer constant. Sometimes, the term k^ [rj] c is written as positive and the constants are listed as negative numbers. The result is the same. The SchulzBlaschke equation (10) is (A8) Although few Schulz-Blaschke constants have been published, some investigators contend that the SchulzBlaschke equation is superior because it works with a wider range of concentrations and is not bound to a constant specific viscosity region (11). On the other hand, it is not recommended for single point determinations because of large errors (6). Huggins' and Kraemer's equations, used singly or in combined form, are better (6). In addition to the polymer-solvent system, Jc^ and ksb depend on concentration (whether semidilute, dilute, or extremely dilute), molecular weight, degree of branching, shear rate of measurement, and whether there can be preferential solvation (copolymers and mixed solvents). With polymers in good solvents, measured values for the Huggins constant are between 0.3 and 0.4. In some cases, they are even lower (2). With decreasing goodness of the solvent, the Huggins constant increases steadily, reaching 0.55 or more for theta conditions. Regarding concentration, deGennes (12) has defined a critical concentration, c*, above which solutions are semidilute and below which they are dilute. Most k^ and A:sb values have been measured in the dilute region. Dondos (2) has defined another critical concentration, c**, below which the solution is called extremely dilute. Values for &h measured below c** tend to be higher than those measured between c* and c**. It is interesting that Peterson and Fixman (13) predicted higher values for Huggins constants except for those below c**. It may be that the low values in the dilute region are due to polymer coil compression because of lack of sufficient volume (2). The Huggins constant is not supposed to be dependent on the molecular weight of the polymer. In many cases, it is not (14-18), or the dependence is small (14,19,20), but other results show definite molecular weight dependence
(3,21). It appears that the Huggins constant is related to molecular weight in polymers that associate in solution, either by the effect of strong ionic or polar interactions, or by the effect of hydrogen bonds (3). There is a relationship between fch and the coil expansion factor or coefficient of expansion, a, which is a measure of the extent of the expansion of the polymer coil in a particular solvent. In good solvents, the coil is more extended than in poor solvents and a is correspondingly larger. The Huggins constant seems to vary with a3 (3,14,22,23). One expression for this is (Ref. 23) (A9) Although there is no agreement in the literature as regards the influence of branching on viscosity constants, most results indicate that k^ and /csb increase with higher degrees of branching (24-26). There is no agreement on the effect of shearing on viscosity constants either, the literature indicating both increases (27) and decreases (28) with increasing shear rate. Shearing that produced chain scission lowered the limiting viscosity number [77] and raised >th, and did so more at higher shear rates, although there was a tendency toward stabilization at the highest shear rates (29). The influence of shear rate is usually neglected below 1500 sec ~J (H). Huggins constants also can be determined for dilute suspensions. The £h value for such a suspension is sensitive to the degree and nature of the polydispersity of the specimen (30). The following tables contain Huggins and SchulzBlaschke constants taken from the literature, along with the relevant references. The values are listed by limiting viscosity number [77], the units of which are ml/g. Values marked with an asterisk (*) are interpolated values from the literature (mostly mean values calculated by Stickler and Sutterlin (H)). For information on molecular weight and other factors, as well as conditions of measurement not given in the tables, the reader may refer to the original publications.
B. TABLES TABLE 1. HUGGINS CONSTANTS Polymer
Solvent
T( 0 C)
Remarks
[tj]
kh
Refs.
1.1. POLY(DIENES) AND POLY(ALKENES) Poly(l,3-butadiene), cis
Toluene Phenyloctane Dioctyl phthalate
Poly(isoprene) cis Poly(isoprene) stars
Toluene Cyclohexane
25 25 50 16.5 21.5 25 25
Three-armed stars Four-armed stars Three-armed stars Four-armed stars
451 447 147 162
0.46 0.46 0.95 0.77
35.4 37.6 185 195
0.33 0.35 0.4 0.46
31 32
31 33
TABLE 1. cont'd Solvent
T( 0 C)
Toluene 1,4-Dioxane Toluene 1,4-Dioxane Benzene n-Hexane Tetrahydrofuran
34 34 34 34 30 30 25?
Gutta percha Poly(chloroprene)
Toluene Benzene
25 25
Poly(ethylene)
Tetralin /7-Xylene
80 100
Low pressure
Tetralin p-Xylene
80 81
Low pressure Low pressure
p-Xylene Benzene
81 105 20
High pressure High pressure
Polymer
Natural rubber Natural rubber (epoxidized)
Poly(isobutene)
Remarks Chlorosilane-linked stars Divinylbenzene-linked stars
1% Epoxy 9.5% Epoxy 18% Epoxy
24 25 30
Poly(isobutene)
Carbon tetrachloride Chlorobenzene Cyclohexane
40 30 25 25
Cyclohexane
30
Cyclohexane
30
Dibutyl ether Diisobutylene Heptane Isooctane
25 25 25 30
30
Poly(propylene)
Ref. also includes data for 10 20, 40, 50C
Mv - (16-926) x 103 Ref. also includes data for 10, 20, 40, 50C; only small variation in k across range Ref. also includes data for 20, 40 C; only small variation in k across range
Tetrachioroethane Tetradecane Toluene Benzene
25 25 25 30
Atactic
Carbon tetrachloride Chlorobenzene Chloroform
50 30 30
Atactic Atactic Atactic
fa]
kh
Refs.
14-780 14-164 82-195 30-70.5 354 170 415 218 30
0.35-0.88 0.63-9.2 0.50-1.02 0.71-1.19 0.32 0.35 0.84 0.43 4.27
10 30-120 150 200
0.58* 0.34 ±0.06* 0.43 0.52*
38 97 327
0.71 0.45 0.69
35 71 141 153 159
0.38 0.27 0.39 0.65 0.89
24 107 128 27 100 183 30 100 240 30-320 14-42 155 19 54 384 309 484 29 84 261 389 165
0.54 0.87 0.49* 0.49 0.59 0.7 0.49* 0.57* 0.70* 0.42 * db 0.02 0.36 0.36 0.38 ± 0.02 0.35 ±0.04 0.30 ±0.01 0.32 0.19 0.41 0.34 0.33 0.31 0.33 0.40 ±0.05 0.3 0.57 0.43 0.37 0.42 0.94 0.58 0.47 0.27 0.33 0.36 0.43 0.42 0.42 0.25 0.33 0.31
185 22 56 157 219 8.4 16.7 35.7 276 189 171 30 95 150 253 165 196
33 33 34 34 35 31 36
37 38,39 40 38,39
38,39 39,41 14 42 14 14 14 43 14 44 45 46
14 47 14 46
48 14 14 14 49 50 49 50 50 50
References page VII - 285
TABLE 1. cont'd Polymer
Solvent a-Chloronaphthalene Cyclohexane
T (0C)
Remarks
139 30
Atactic Atactic
60-70 30 135 30 30 34
Isotactic Atactic Isotactic Atactic Atactic Atactic
Toluene
30 30 30 130 30
Atactic Atactic Atactic Atactic Atactic
p-Xylene
125
Atactic
Decalin 2-Ethyl hexyl acetate n-Heptane Isoamyl acetate Isopropyl ether Tetrahydrofuran Tetralin
[i/]
kh
Refs.
45-330 276 277
0.27 db 0.02 0.24 0.36 0.25
120 205 26 65 98 156 176 155
0.38 0.34 0.45 0.65 0.83 0.36 0.32 0.36
30-120 190-220 180
0.36* ±0.02 0.40* ±0.03 0.35
20 150 240
0.35 0.25 0.25
70-190 157 106 134-296 170-245 309-342 239-711 117
0.3 0.4 0.28 0.31 0.31* 0.34 ±0.1 0.33 0.35
46-177
0.35
34 36 38 40 145 148 145 47 55 64 72 160 149 159 166 142 144 147 16-50
0.55 0.45 0.35 0.25 0.29 0.29 0.36 0.7 0.54 0.45 0.4 0.24 0.4 0.3 0.25 0.32 0.3 0.26 ~0.5to~~0.3
133 120-970 134
0.31 0.25-0.27 0.28
51 49 50 52 50 51 50 50 49 50 50 50 51 49 51 51
1.2. POLY(ACRYLIC ACID) AND POLY(METHACRYLIC ACID) DERIVATIVES Poly(acrylic acid)
Poly(acrylonitrile)
Poly(ethyl acrylate)
Water (0.1M NaCl) Water (0.25 M NaCl)
25 25
Dimethyl formamide
25 30
Acetone
Poly(decyl methacrylate)
Isooctane
Poly(ethyl methacrylate)
Benzene /i-Butanol
n-Butyl bromide
n-Butyl chloride Methyl acetate Ethyl acetate
40, 50, 60, 70 60 30 30 25
35 52 60 45 52 60 70 42 50 58 65 40 47 61 20-53 35 45 55 65
Degree of Degree of Degree of also for
neutr. = 0 neutr. = 0.3 neutr. = 0.76; data 5, 15, 35, 45 C
Telomers Ref. also includes data for 50, 75, 100 C
Conformational changes occurred in this range
53 54
55 56,57 55,58 59 60 59 56 61 60 62 63,64 65 66
67 67
67
67 68 67 69 67
TABLE 1. cont'd Polymer
Solvent
T(0C) 20-65
Isobutyl acetate
20-65
Isoamyl acetate
50 70 80 37 44 51 60 23-45 40 50-70 47
Isopropanol
Methyl ethyl ketone Methyl n-propyl ketone m-Xylene
Remarks Conformational changes occurred in this range Conformational changes occurred in this range
Water (0.1 M NaCl) Water (0.25 M NaCl)
25 25
Poly(methacrylonitrile)
Dimethyl formamide
29
Poly(methyl acrylate)
Acetone
30
Benzene
Carbon tetrachloride/ methanol Chlorobenzene Chloroform Ethyl acetate Methyl ethyl ketone
40 25 30 35 40 45, 55 35 25 30 35 40 30,35,40 25 30
Toluene
Poly (methyl methacrylate)
Acetone Benzene
35, 40 25 30 35 40 45 55 25 25? 20 25
Degree of neutr. = 0 Degree of neutr. = 0.1 Degree of neutr. = 0.3 Degree of neutr. = 0.81; also data for 5, 15, 35, 45 C Anionic
Vol. fraction of methanol: 0.33 ([77] maximum, k minimum)
kh
Refs.
12-48 ~ 0 . 4 5 t o ~ - 0 . 1 13-45 ~ 0.5 to ^ — 0.15 145 152 156 88 129 151 183 157-158 196 183-189 131
54 61 70 Poly(methacrylic acid)
[tj]
0.39 0.37 0.32 1.06 0.27 0.39 0.43 0.34-0.35 0.2 0.33 ±0.01 0.39
134 137 139
0.33 0.33 0.29
30 35 240 575
2.33 0.65 0.33 0.3
26 60-143 95-298 333 314 52-343 383 50-335 382 48-330 25-214
0.4 0.34* ±0.03 0.38 0.37 0.38 0.37 0.31 0.38 0.38 0.38 2.94 ±0.06
53-305 220 215 222 115-120 45 85 116 108 302 104 34-147 61 201 34-160 69 35-169 35-175
0.4 0.41 0.39 0.36 0.50 ±0.01 0.65 0.56 0.39 0.45 0.43 0.44 0.59 0.59 0.33 0.52
85 4 9.5 14 22 26-40 68-331 667
0.35 0.25 1.65* 0.69* 0.5 0.35 0.30* 0.25 ±0.01 0.18
68 68 67 67
67 67 67
53 54
70 71 72 72 71 72 71 72 71 73 71 74 74 75 73 72 73 71 73 72 71 73 71 71 7 ^ 82 77 78
References page VII - 285
TABLE 1. cont'd Polymer
Solvent
T( 0 C)
Remarks 90% Isotactic
Butyl acetate
25
90% Isotactic n-Butyl bromide Chloroform
Cyclohexanone Dimethyl formamide Ethyl acetate Isoamyl acetate Methyl ethyl ketone
Di-n-propyl ketone Tetrachloroethane Tetrahydrofuran Toluene
35 50 58 25
30,60 40, 60 50 70 25 25 50 65 80 25
30, 60 33.8 35-50 25 30 25
30 0-Xylene
m-Xylene
p-Xylene
Poly(hexyl methacrylate) Poly(heptyl methacrylate) Poly(octyl methacrylate) Poly(tetradecyl methacrylate)
w-Heptane rc-Heptane n-Heptane n-Heptane
60 40 50 60 70 40 50 60 70 40 50 60 70 30 30 30 30
Star-branched polymer
Star-branched polymer
[iy]
kh
Refs.
41 49-61 73-125 7 29 64 110 22 39 52 47 63 70 19 146 223-275 390 870 138, 152 146 136 56 53 36 44 47 7 27 56 137 151 172
0.39 0.33 0.3* ±0.03 0.9 0.67 0.58 0.47 0.67 0.61 0.57 0.5 0.41 0.35 0.32 0.25 0.38 0.22* 0.18 0.44 0.45 0.4 0.48 0.38 0.41 0.71 0.63 0.5 0.9 0.49 0.4 0.33 0.4 0.49
11.4 17
1.66* 1.48
101 24 40 9 24 55 83 229 414 37 80
0.29 0.161* 0.49* 0.63 0.46 0.41 0.33 0.25 0.23 0.43 ±0.04 0.41 ±0.03
68 72 76 81 55 62 71 80 42 48 59 64 31 45 64 58
0.34 0.21 0.32 0.27 0.48 0.67 0.55 0.35 1.31 1.26 0.93 0.47 0.5 0.44 0.45 0.32
14 78
14 67
79 80 67 14 82 14 67 78 14 78 75 80 81 78 14 81 78 14 78 44,80 80 67
67
67
83 83 83 83
TABLE 1. cont'd Polymer Poly(cyclobutyl methyl methacrylate)
Poly(cyclohexyl methyl methacrylate)
Poly(cyclooctyl methacrylate)
Solvent 1-Butanol
T( 0 C)
Remarks
40
Tetrahydrofuran
30
1-Butanol
45
Cyclohexane
30
Tetrahydrofuran
30
1-Hexanol
38
Cyclohexane
30
Tetrahydrofuran
30
Cyclohexane
30
Tetrahydrofuran
30
Toluene
25
M
kh
Refs.
13
1.49
20 36 22 57 142 10
1.16 1.33 0.36 0.31 0.3 0.74
17 41 17 54 91 16 35 105 10 16 23 17 38 25 76
0.81 0.62 0.18 0.43 0.31 0.52 0.35 0.36 0.94 1.46 1.77 0.26 0.39 0.4 0.37
9 18 36 9 17 36 19
0.69 0.49 0.38 0.7 0.55 0.37 0.4
95 230 13 39 73 22.6-98.0 34.0-88.4 33.9-54.1
0.34 0.35 0.76 0.73 0.61 0.42 0.41 0.61
11.6 24.7 28.2 13.5 16.5 18.5 23 62.7 13-42 22-87 14-23 29-155 29-148 33-178 11-111 11.0-99 11.0-98 10.0-91 11-133 11-111 9.0-64 10.0-87
0.79 0.47 0.52 0.32 0.55 0.45 0.41 0.37 1.25 0.48 1.17 0.42 0.43 0.36 0.34 0.33 0.35 0.35 0.29 0.3 0.4 0.33
84
84 84
84 84 84 84 84
Poly(cycloundecyl methacrylate)
Poly(diphenyl methyl methacrylate)
Poly(2,6-diisopropyl phenyl methacrylate) Poly(2,3-epoxypropyl methacrylate)
Poly(pentachlorophenyl methacrylate)
Poly(2-biphenyl methacrylate) Poly(4-biphenyl methacrylate)
3-Heptanone
45
Tetrahydrofuran Toluene Tetrahydrofuran/water (90.9/9.1, v/v) Tetrahydrofuran
25 25 25
1,4-Dioxane
25
Benzene Toluene Ethyl benzene oXylene Chlorobenzene 0-Dichlorobenzene Chloroform Tetrahydrofuran Benzene 1,4-Dioxane Chloroform Tetrahydrofuran Benzene 1,4-Dioxane
40 25 25 25 25 25 25 25 25 25 25 25 25 25
25
Theta solvent
84 84 85
85 224
86 86
87
88
89
References page VII - 285
TABLE 1. cont'd Solvent
T(0C)
Poly(di-isobornyl methacrylate)
Tetrahydrofuran 1-Octanol
30 39.6
Poly(acrylamide)
Water
25
Water (1M NaCl) Water (pH 7)
25 30
Poly(4-isopropyl styrene) Poly(4-isopropyl a-methyl styrene)
Toluene Toluene
25 21.5
Poly(styrene)
Benzene
25 25 25
Polymer
Remarks
[tj]
kh
25.3-104 13.1 23 1300-1700 274 1353 1200-1900 21
0.23 ±0.01 1.29 1.13 0.35 av. 0.16 0.5 0.33 av. 0.46
44-139 16.5 25.5 44 60 105 73.5 1.7 5.5 10.2 40.4 43 126 150 7, 13.7 82.9, 132 187,432
0.34 ±0.04 0.52 0.3 0.42 0.33 0.37 0.36 0.79 0.71 0.54 0.54 0.38 0.35 0.33 0.57 0.38 0.36
14.5 43 180 386
0.55 0.41 0.33 0.29
10.7-60.7 10.8-114 42 16 48 178
0.84 ±0.03 0.77±0.06 0.6 0.5 0.52 0.48 0.78 0.61
1.5 2.5 3.7 5.4 6.6 9 29-31 43,44 97
1.3 0.91 0.96 0.93 0.81 0.67 0.86* ±0.02 0.59 0.59
152 174 47
0.51 0.49 0.53 1.28 0.50 ±0.005 0.41* ±0.02 0.43* ±0.02 0.45* ±0.02 0.6 0.71
Refs. 90
6 91 6 92
1.3. VINYL POLYMERS
Atactic Atactic
Benzene/isopropanol Butyl acetate
25 25
Theta temperature, atactic
4-terf-Butyltoluene
50
Atactic
Carbon tetrachloride
25 30
Chloroform Cyclohexane
30, 60 30 34.5 = 6> 31, 95 34 34.5 34.5 34.5
Ref. also includes data for 10,20,40, 50C
Ref. also includes data for 15, 20, 25, 32, 40, 50C Trifunctional star molecule Oc** c 2.1x10*; k > 0.5 for MW < 2.1 x 105
34.5
cw-Decaline franj-Decaline
34 34.3, 34.8 34.5 35 36 40 40, 22 45 50 20 20
Branched Trifunctional star molecule Atactic
Trifunctional star c
55 20 60 120 38 80
93 94
95 96 109
14 97 98 46
81 46 95 99 2 100 101 109
102 95 97 103 14 14 95 2 99 14 14
TABLE 1.
cont'd
Polymer
Solvent
T( 0 C)
Remarks
25 30 Diethyl malonate
34
Theta temperature
40 Dimethyl formamide
25 30 35
Dioctyl phthalate
95 25 35 45
1,4-Dioxane
25
Ethyl benzene
25
Methyl ethyl ketone
25 30 40 40.3 60 25 15 21
1-Methyl naphthalene Toluene
25 25 25
c < c** c > c** Ref. also includes data for 10, 40, 55,65 C
0.49* ±0.01 0.51* ±0.02 0.4 0.42 0.47 0.5 0.5 0.47 0.5 0.44 0.39
12.2 77.2 188 20-700 49 89 51 86 45 54-87
0.48 0.4 0.41 0.48 0.59 0.58 0.57 0.5 0.56 0.5 0.81 0.35 0.503 0.423 0.365 0.291
13.4 26.1 41.7 384
Atactic
292 40-125 360 460
0.34 0.35 ±0.03 0.30 ±0.05 0.25 ±0.08
Anionic
8 14 36-272 41-123 56 71 63-84 14 73-234 28 98 203 12.6 28.1 64 362
0.51 0.44 0.34 ±0.03 0.34 ±0.02 0.41 0.38 0.31 0.46 ±0.02 0.38 ±0.015 0.41 ±0.02 0.39 0.34 ±0.01 0.56 0.43 0.38 0.32
28-80 68 30 42-66 91 134 3.7 6.6 8.4
0.51-0.52 0.33 0.46 0.35* 0.37 0.41 1.54 1.13 0.79
Thermal Branched
30
25
50 130 47 117 45 82 45 83 19 36 76-172
0.54 ±0.09
Linear
Poly(vinyl acetate)
kh
44-151
30
60 Toluene/methanol (77/23) 25 Acetone 18 25
[tj]
Theta temperature
Refs.
14 14 14 14 14 57 104 105 14 14 14 2 46
98 57,81 64 106 81 107 97 99 98,107 39,108 39,108 102 102 39,81,83 106 83 95 83 104
81 23 110 39,64,110
111,112
References page VII - 285
TABLE 1. cont'd Polymer
T( 0 C)
Solvent
Remarks
30
Benzene
32, 39,46 30
30
Zero shear plot Emulsion polymer
35
Branched
35
Linear
40
Zero shear plot Chlorobenzene
2-Chloroethylene Chloroform
Dioxane Methanol
Toluene
Water
Poly (vinyl alcohol)
18 25 32, 39, 46 25 18 25 32, 39,46 18 25 32,39,46 18 25 30 32,39,46 18 25 30 32, 39,46 25
Dimethyl sulfoxide DMSO/water (4/1, w/w)
30 30
Partially alcoholized 72.5% Hydrolyzed, unfract. Middle fractions 77.9% Hydrolyzed, unfract. Middle fractions 73.3% Hydrolyzed, unfract. Middle fractions No cooling Precooled to form clusters
[*/]
kh
Refs.
11.6, 12.9 20.8 27.1 70 250 450 65, 64, 63 126 50-450 147 197 262 281 124-381 77 133 229 45 72-200 300 500 700 137-177 196-250 281-570 204 243 268 354 197-413 71 37-45 66-69 99-121 68, 67, 65
0.53 0.38 0.34 0.35* ±0.02 0.37* ±0.02 0.39 ±0.02 0.41, 0.42, 0.44 0.17 0.37 ±0.03 0.25 0.3 0.45 0.65 0.34 1.42 1.21 1.05 0.28 0.35* ±0.02 0.37* ±0.02 0.39* ±0.02 0.42* ±0.02 0.33* ±0.01 0.34* ±0.01 0.35* ±0.01 0.25 0.28 0.36 0.44 0.42 0.44 0.35* ±0.03 0.44* ±0.01 0.35* ±0.04 0.43, 0.44, 0.4
101 45 62-92 146 99, 95, 92 77 75 74,73,72 41 30 40 50
0.34 0.31 0.37* ±0.02 0.28 0.37, 0.39, 0.41 0.27 0.29 0.31,0.32,0.34 0.61 0.41* ±0.04 0.49* ±0.03 0.57* ±0.03
44,45,47 46 46
0.52,0.41,0.39 0.57 0.55
47, 47, 48
0.56, 0.56, 0.54
21 20 9.5 10 20.2 20.6
0.67 0.98 2.27 3.87 1.03 1.2
122 77-99
0.43 0.75 ± 0.03
113 110 28 113 28
113 115
115 28
110 39,110 110 64 110 39,110 110 110 39,110 110 110 39,110 116 110 110 39,110 116 110 117 118
H9 225
TABLE 1. cont'd Polymer
Solvent
T (0C)
Remarks
M
Precooled to form clusters Precooled to form clusters Water Water
25 30 30(?)
100 132
Poly(vinyl chloride)
30
Water (boric acid/ 0.167MNaOH)
30
Water
60
Acetone Anisole Bromobenzene Butyl acetate 7-Butyrolactone Chlorobenzene Chloroform Cyclohexanone
20 25 25 25 25 25 20 20 25 30 20-60 80
Cyclopentanone 1,2-Dichloroethane Dimethyl formamide Dioxane
20 25 25 25
Ethyl acetate Ethyl acetyl acetate Methyl ethyl ketone
25 25 25
Morpholine
30 50 69
Nitrobenzene Tetrachloroethane
25 25
Refs.
30 42.1 71, 77, 86.5 96 165
1.1 1.8 0.5 0.57* 0.59 0.69 0.71 0.81
40 40 50 60 70-80 100 170
0.59* 0.9 0.60* 0.66* 0.68* 0.74* 0.83*
119,121 123 121
88, 85 78 22 28 42 84 32 59 36 34 40 43 34 39 38
0.65, 0.7 1.6 25 16 5.5 1.8 1.26 0.93 0.42 0.46 0.4 0.38 0.43 0.42 0.49
114
30 30 30
Water (dil. NaOH)
kh
0.042 M, 0.084 M NaOH 0.167MNaOH 0.005 M Boric acid 0.01 M 0.02 M 0.06 M
Samples with different tacticity
90-130 100-121 23-132 94 108 287 338 438 46 41 40 33 40 50 60 70 39 34 26 32 47-83 71 89 108 64 79 98 58 70 87 41 29 36-76 93
120,139 119,121 122
114
123
14 14 14 14 14 14 14 64,124 0.34 125,126 0.35 127,128,129 130 0.36 131 0.43 0.57 0.64 0.48 0.33 14 0.4 14 0.3 14 0.5 14 0.48* 0.44* 0.41 * 0.38* 0.43 14 0.43 14 0.34 14 0.35 0.38 ±0.01 0.64 132 0.57 0.49 0.81 132 0.67 0.53 0.85 132 0.7 0.55 0.33 14 0.42 14 0.37* ±0.01 0.35
References page VII - 285
TABLE 1. cont'd Polymer
Solvent Tetrahydrofuran
T( 0 C) 20
Remarks
[if]
kh
Refs.
100% Conversion
20-143 49 171 201-220 76-91 107 44 46
0.28* ±0.02 0.35 0.31 0.36* ±0.02 0.44* ±0.01 0.47 0.35 0.46
133 14 133
7 22-38 93-134 7 21-37 92-133 21-37 91-129 7 21-36 91-126 21-36 90-122 30 63.2 75.6 53.9 85.2 57.2 75.1 50 113 48 162 44 134 62 74 48 107 106 131 206 16 27 37 15 27 37 15 26 36 14 25 36 14 25 35 18 46 67-107 18 45 86 106
0.55 0.51* ±0.04 0.34* ±0.01 0.56 0.51* ±0.03 0.35* ±0.01 0.54* ±0.02 0.36* ±0.01 0.51 0.51* ±0.12 0.36* ±0.01 0.43* ±0.01 0.36* ±0.01 2.69 0.49 0.58 1.01 0.201 2.29 0.43 0.34 0.54 0.3 0.51 0.3 0.55 0.42 0.46 0.3 0.46 0.63 0.5 0.36 0.46 0.45 0.41* ±0.03 0.47 0.48 0.43* ±0.02 0.61 0.57 0.43* ±0.02 0.75 0.46 0.44* ±0.01 0.78 0.6 0.49* ±0.01 0.5 0.41 0.35* ±0.01 0.5 0.43 0.38 0.36
30
Poly(vinyl cyanoethyl ether) Poly(vinyl biphenyl)
Tetrahydrofurftiryl alcohol Tetramethylene sulfoxide Water Acetone Benzene
25 25 30 30 20 30 45 65 75
Poly(vinyl butyral)
Methanol Ethanol «-Propanol Isopropanol n-Butanol Isobutanol Cyclohexanone Acetone
25 25 25 25 25 25 25 30
Acetonitrile
30
Dioxane
30
Methyl acetate
30
Methyl formate
30
Poly(W-vinyl imidazole)
Water (0.2 M NaBr)
25
PoIy(I-vinyl naphthalene)
Benzene
20
Poly(vinyl formate)
30 45 65 75 Poly(2-vinyl naphthalene)
Benzene
20 30
Degree of neutr. = 0 Degree of neutr. = 0.3 Degree of neutr. = 0.8
132 14 14 121 121 134 134 134 134 134 135 135 135 135 135 135 135 136 136 136 136 136 137
134
134 134 134 134 134 134
TABLE 1. cont'd Polymer
Solvent
T(0C)
Remarks
45 65 75 Poly (vinyl phenylketone) Poly(4~vinylpyridine) Poly(vinyl pyrollidone)
Benzene Ethanol Dimethyl formamide Methanol Methanol -I- 0.33 N GC Ethanol
25 25 25 25 25 25
Propanol
25
Water
15 25 35 45 55 65 25 35 25 36 25 39
Water (salt soln.)
Poly(vinyltrimethylsilane) Poly(vinyl 4-trimethylsilyl benzoate) Poly(vinyl 3-trimethylsilyl benzoate) Poly(vinylidene fluoride)
1.4.
kh
Refs.
17 43 63-103 17 20 43-101 17 43-100
0.58 0.45 0.39* ±0.01 0.51 0.43 0.38* ±0.06 0.48 0.38* ±0.06
134
0.45 GC; guanidine hydrochloride
1.2MNaH 2 PO 4 Theta temperature 0.5MNa 2 SO 4 Theta temperature 0.5MNa 2 CO 3 Theta temperature; Ref. contains data for seven other salts
33 30.7 34 28 34 29 17.2 15 13.3 11.5 10.6 1.25 15.5 14.7 16.9 12.9 16.2 15.5
0.45 0.62 0.77 0.81 0.95 1.3 0.97 1.99 0.85 2.16 1.07 2.6
134 134 112 138 139 140
141
226
Cyclohexane Toluene
25 25
96-154 136
0.35 ±0.03 0.19
142 143
Toluene
25
214
0.54
143
Dimethylacetamide
25
76 116 143 189 325 108 124 132 174 74 128 175 -75 ? —65
0.35 0.37 0.32 0.27
144
0.33 0.37 0.42 0.47 0.31 0.36 0.39 0.54 0.47 0.4
2 48 3 82 3 45 3 39 1.1 1.9 2.4 5.5
-3.7 0.4 -0.9 0.4 -0.6 0.4 -2.5 0.4 8.16 3.41 2.06 2.3
25
Polyethylene glycol monovinyl ether)
[rj]
Dimethyl formamide
25
Water Ethanol Dimethyl formamide
25 25 25
Benzene
20
Chloroform
20
Dimethyl formamide
20
Toluene
30
[77] corr. for aggregation
0.42 145
144
146
POLY(OXIDES)
Poly(oxyethylene)
35
147 147 147 147 148
References page VII - 285
TABLE 1. cont'd Polymer
Solvent Water
Water
J( 0 C) 10.2 18.1 24 32 20
Remarks
fa]
MW=LOxIO 5
25 30 35
Water (2.40M NaCl)
25 54 Water (1.5 M Na acetate) 25 55 Water (1.5MNa formate) 25 52 Water (0.80M KF) 25 49 Water (2.40M KNO3) 25 53 Water (urea)
Theta temperature Theta temperature Theta temperature Theta temperature Theta temperature; Refs. 149-151 include data on a number of other salts
kh
Refs.
98.3 91.4 84.9 77.5 3 5 37.7 28.1 36.5 41.1 1.7 3 5 10.8 26.1 17 28.9 20.8 29.5 21.2 29.5 22.7 26 20
0.63 0.71 0.87 0.97 1.1 0.4 0.39 0.39 0.46 0.22 4.95 2.42 0.93 0.44 0.82 1.64 0.56 0.9 0.57 0.98 0.56 0.76 0.55 0.87
227
97 89 80 116 109-96 135-270 69 102
0.53 0.57 0.72 0.43 0.47 ±0.03 0.3 0.23 0.21
227
147 149 150 149 150 148
150 149 149 151 149
Poly(oxymethylene)
p-Chlorophenol Dimethyl formamide
10.2 20.1 32 10.2 16-32 60 140
Poly(oxypropylene)
Benzene
150 35
152 153
25 25 25
154 154 155 155
1.5.
152 152
POLY(ESTERS)
Poly(oxyethyleneoxy adipoyl) Poly(bis(oxyethylene) oxyadipoyl)
Poly(oxyethyleneoxy sebacoyl) Poly(oxyethyleneoxy terephthaloyl) Poly(mono-ethyl itaconate)
Cyclohexanone Dimethyl formamide Methyl ethyl ketone
Oligomers with different functionality Nonfunctional 3.1 3.6 4.3 Monofunctional 3.3 4.2 4.5 5.2 Bifunctional 3.5 4.1 4.8 5.3 5.7 8.7
0.39, 0.42 0.46 0.42 0.3 0.34 0.42 0.32 0.25 0.32 0.26 0.22 0.3 0.25
155
155
Cyclohexanone
25
154
w-Cresol/phenol (1/1)
25
156
Methanol (0.1M KI)
25
2-Ethoxyethanol
25
40.2 67.1 86 41.3 55 71
0.25 0.34 0.47 0.2 0.22 0.3
157 157
TABLE 1. cont'd Polymer 1.6.
T( 0 C)
Solvent
Remarks
[if]
kh
Kefs.
POLYAMIDES
Poly(iminoadipoylimino hexamethylene) (Nylon 66)
ra-Cresol Formic acid (90%)
20 25
Poly(iminoisophthaloyl imino-l,2-phenylene)
Dimethyl formamide (1.18N LiCl)
25
Poly[imino(l-oxohexa methylene)] (Nylon 6)
Tricresol
25
m-Cresol
?
Tricresol
20-60 25
Formic acid (85%)
(68.8%)
Hexafluoroisopropanol Sulfuric acid (96%) (93%)
Poly[imino(l-oxo-undecamethylene)] Poly(iminoterephthaloyl imino-l,2-phenylene) Poly(amidobenzimidazole) Aramid
(0.019 vol.% water)
25
25 25 25
25
(62%)
25
(60%)
25
(52.5%)
25
Sulfuric acid Dimethyl formamide (1.18NLiCl) Sulfuric acid fibers
1,3- and 1,4-phenylene polymers also in this Ref. (in DMF/LiCl and sulfuric acid/LiCl) Polymers with different end groups Branched polymers with 27-220 different end groups
25
(80%)
(33%) Phenol: CCl 4 (1 :1) Nylon 12
83 100 120 140 200
(0.05MCF 3 COONa)
50 109 335 70 80 85 48 86 460 32 200 240 558 965 1340 73 101 155 305 200-500 94-104 63 125 490 502 48 90 325 34 60 195 52 54 57 30 50 135 152
25 25 45 75 25 25
1,3- and 1,4-phenylene polymers also in this Ref. (in sulfuric acid)
25 25 25 25 25
Virgin fibers Heated to 1400C Heated to 1600C Heated to 2000C Heated to 2500C
0.2 0.22* ±0.01 0.24* ± 0.02 0.27* ±0.02 0.29* ±0.01
158 159
160 161 2.75-0.26 1.1 0.49 0.29 0.32* ±0.08 0.22* ±0.06 0.18* ±0.02 0.24 0.12 0.13 0.38 0.32 0.34 0.56 0.89 1.31 0.24 0.66 1.36 3.36 0.23 0.30* ±0.07 0.42 0.26 0.23 0.19 0.5 0.34 0.3 1.06 0.74 0.36 0.52* ±0.1 0.44* ±0.1 0.34* ±0.06 1.37 0.96 0.44 0.39
162 163 161,164
165
164
164 166
166
167 165 164
164 164 165 164
165 168 160 160 440 460 440 500 520
0.5 0.54 0.65 0.6 0.6
169
References page VII - 285
TABLE 1.
cont'd
Polymer Poly(/?-benzanalide terephthalamide) Poly(caprolactam) 1.7.
Solvent Sulfuric acid
T( 0 C) 25
Sulfuric acid (80%)
Remarks Rod-like polymer, high MW Low MW Fibers
Iq]
kh
Refs.
>100 <10 121-143
~0.5 >L0 0.29* ±0.02
170
32.4 46.7 51.9 52.7 58.6 45.1 51.4 68 218 178 480 44-555 51-755 32 37 39 40 50 55 54 386 243 224 170 280 253 243 247 49 55 62 74 80 93 57 68 74 80 98 106 77 43 37 25 23
1.87 0.95 0.87 0.41 0.54 0.95 0.91 0.53 0.27 0.31 0.25 0.36* ±0.03 0.36* ±0.01 0.9 0.29 0.16 0.15 0.45 0.48 0.53 0.21 0.23 0.25 0.28 0.11 0.21 0.23 0.5 0.7 0.55 0.41 0.41 0.34 0.29 0.56 0.5
171
OTHERCOMPOUNDS
Al-isopropoxypoly( vinyl butyral)
Methanol Ethanol /2-Propanol Isopropanol n-Butanol Isobutanol Cyclohexanone Water Water Water Water Tetrahydrofuran Cyclohexanone Water (0.5 M salt)
25 25 25 25 25 25 25 25
Poly(dimethylaminoethyl methacrylate dimethyl sulfate)
Water (0.1M salt)
30
Poly[3-dimethyl(methacryl oyloxyethyl)ammonium propane sulfonate]
Water (KCl)
30
Water (0.5 M)
30
Poly(2-acrylamido-2-methyl propanesulfonic acid) Poly(2-acrylamido-2-methyl propane sulfonamide Poly(epichlorohydrin) Poly(/Vyv'-dimethyl(acryl amidopropyl) ammomium propane sulfonate
25 25 25 30
NH4Cl LiCl NaCl KCl MgCl2 CaCl2 SrCl2 KF KCl KBr KI LiCl NaCl KCl CsCl 0.25 M 0.30M 0.40M 0.50M 0.8 M 1.50M LiCl NaCl KCl KBr 10
KClO4 CaCl2 Poly(ether imide)
Dichloromethane
10 25
Pyridine
10 ^ 10
2
N-Methyl pyrollidone
51
25
NMP/water (96/9)
Polyethylene imine) Polyethylene oxide)urethanes
Water (1M NaCl) Tetrahydrofuran
10 25 50 25 50 35 25
Na-polyphosphate
Water (NaBr)
25
NMP/water (95/5)
Different hydrophobic end caps
135
228 228 229 172 173
174
175
175
041
0.39 0.38 0.37 0.37 043
1?6
0.66 2.13 2.44
176
0 48
45 33 34 29 25 23 10.4-64.4 19, 18.5,24
0.59 \ 0.8 1.16 1.93 2.23 0.76 * ± 0.02 0.4
50-276
0.29* ±0.04
176
vi*> 176 230 177 178
TABLE 1. cont'd Polymer
Solvent
T( 0 C)
Poly(di-n-hexylsilane)
Tetrahydrofuran
25
Poly(oxydimethylsilylene)
Benzene Carbon tetrachloride Chlorobenzene Cyclohexane n-Heptane Methyl ethyl ketone Tetrahydrofuran Toluene
25 25 25 25 25 25 25 25
Poly(methylene Af, Af-dimethy lpiperidinium chloride) Poly[bis(2-phenylethoxy) phosphazene]
Water (NaCl) Tetrahydrofuran
25
Phenolphthalein poly(aryl ether sulfone)
Dimethyl formamide
25
Chloroform
25
Poly(phenyl quinoxaline)
Poly(sodium acrylate)
Poly(styrene sulfonic acid), potassium salt
Sodium polystyrenesulfonate)-diallyldimethyl ammonium chloride
20-60
Chloroform 25? Chloroform/toluene (98/2) Chloroform/toluene (95/5) Chloroform/ethanol (95/5) Water (NaCl) 25
Water (0.4% NaCl) 10% NaCl 0.40% NaCl 1.30% NaCl 5.00% NaCl 10.00% NaCl Water (KCl)
25
Remarks
kh
Refs.
58 87 133 143 192 515 831 251 312 219 324 305 151 319 62-241 146 577-727 10-210
0.33 0.36 0.34 0.4 0.44 0.38 0.66 0.44 0.51 0.61 0.37 0.45 0.8 0.39 0.55* ±0.02 0.51 0.46* ±0.01 0.35-0.50
179
0.42 0.62 0.32 0.49 0.62 0.51 0.74 0.89 0.78 0.53 0.33 0.31 0.06 0.38 0.42 0.51 0.65 0.34 0.48 0.37 0.6 2.2 6.3 0.75 1.14 3.73 12.4 20 0.76 0.49 2.93 6.62 18.7 4.92 0.37 0.26 0.73 1.28 7.91 22.9 2.51 0.39 0.29
231
Ionic strengths ranging 0.1-0.5M
MW = O.8xlO 5 MW = 2.20 x 105 MW = 4.90 xlO 5 Reference includes data from additional solvents, molecular weights
0.4% NaCl 1.30% 5.00% 10.00% 3% C8 substitution 3% C12 substitution
25
[if]
Ionic str., Z= LOOM / = 4.0 x 10"1 M, MW 41.5 /=1.0 x 10" 2 M ^3.OxIO-1M Z=LOxIO- 1 M / = LOOM, MW 109.5 Z=LOxIO- 1 M Z = 7.0 XlO- 1 M Z = 3.0 XlO- 1 M Z=LOxIO- 1 M Z = 3.1 M, MW 1170 Z=LOM Z=LOxIO- 1 M Z=LOxIO- 3 M Z = 3.0 x 10" 4 M Z = 3.0 x 10' 5 M Z= 10" 4 M Z=IO - 3 M Z= 10" 2 M Z = 0.5 M
8.4 11.7 12.9 29 53.6 89.3 28.5 50.5 82.7 65 75 62 78 256 153 77 59 276 78 278 165 64 34 8.2 15.7 27.5 39 65.7 15.7 39.9 83.5 105 148 16.6 115 361 3353 5786 9661 4480 2750 1150 202
180 180 180 180 180 180 180 180 181 182 182 183
Bo Bo 184
185
186,187
233
References page VII - 285
TABLE 1. cont'd Polymer
Solvent
T( 0 C)
Remarks
M
kh
Refs.
Ref. also gives data for copolymers with acrylamide Poly(thiopropylene) 1.8.
Benzene
20
188
CELLULOSE, CELLULOSE DERIVATIVES, AND POLYSACCHARIDES
Alginate(sodium) Amylose
Arabinoglucuronoxylan Cellulose
Cellulose acetate
Water Water Water Water Water
(NaCl/CuCl2) (KOH) (NaOH) (KOH-NaCl) (IN KOH)
Water Cd-ethylenediamine (Cadoxen) Cu-ethylenediamine (Cuoxen) Zn-ethylenediamine (Zincoxen) LiCl/dimethylacetamide Acetone Formic acid Pyridine
Cellulose diacetate
Dimethyl formamide
30 25 25 25 25 30 35 40 25 20 25 25
Near gelation point
25 30 30 30 30 25
30 25?
MW = 4.2 to 4.5 x 105
Subst. = 2.34 as-is reprecipitated Subst. = 2.34 as-is reprecipitated Subst. = 2.55 as-is reprecipitated
Cellulose triacetate
Acetic acid
25
Chloroform
25
Methylene chloride Tetrachloroethane
15-30 25
Cellulose acetate phthalate
Water (NaCl solns.)
35
Cellulose nitrate
Acetone Diethyl adipate Isoamyl acetate Water Ethyl acetate Water
20 25 25 20 20 20
Methyl cellulose Ethyl cellulose Ethyl hydroxyethyl cellulose
Water
0
15
0.27
139 129 121 107 41.6 ±2.2 339-1395 426-510 440 466 510 248-383
0.19 0.2 0.48 0.88 3.6 ±0.6 0.50 ±0.01 0.46* ±0.01 0.54* ±0.02 0.59 0.65 0.47* ±0.09
641-682
0.43-0.59
295 196 185 155
0.56 0.8 1.3 1
158 145 230 200 199 195 72 117 43 72
0.48 0.87 0.32 0.72 0.29 0.35 0.42 0.57 0.45 0.43
50 82 90 71 68 695-1195
0.34 0.38 8.64 3.36 1.69 0.53* ±0.08
400 41-188 440 175 135 125 140 423 845 1052 1218 402 794 977 1130
1.2 0.65 ±0.15 1 11.3 18 13 7.5 0.57 0.74 0.8 0.87 0.43 0.59 0.68 0.75
Q temp. = 27°C Salt cone. = 0.002 M Salt cone. = 0.006 M Salt cone. =0.0. IM
0.5mM/gSDS l.OmM/g 2.0mM/g 5.0mM/g Hydroxyethyl cellulose
180
234 189 189 189 190 190 190 190 235 191 192 192 192 236 193 193 193 194
195
196 196 197 196 198 191 199 200 237 191 238
201
201
TABLE 1. cont'd Polymer
Solvent
T( 0 C)
Remarks
20 25 25
35
40 60 25
Water
Degraded hydroxyethyl cellulose Hydrophobically modified hydroxyethyl cellulose
Water Water Water Water Water
(LiCl) (KCl (CuCl2) (MnCl2)
Water
Hydroxypropyl cellulose Water Hydroxy propylrnethyl cellulose Water Na-carboxymethyl cellulose Water (NaCl)
Lyzozyme
Water (1M NaCl) Water (1N NaOH) Water (NaCl) 0.5 M NaCl/10% cadox. 0.5 M K, NaH phosphates Water 10% Cadoxen Water 10% Cadoxen 88% Formic acid Water
Microbial polysaccharide
Water (NaCl)
Acidic hetero polysaccharides p-D-Glucan
25 25 25 25 25 25 40 60 20 20 25 25 25 25 30 30
5 15 25 40 55 25?
pH 2.2 pH 3.0 pH 5.0 pH7.0 pH 9.0 pHll.O pH 12.0 1 x 10 "* to 1 x 10 ~3 M
Water (NaCl)
25?
Water (0.1 M NaCl)
25
Refs.
273 128 381 754 895 1062 370 725 875 1010 100 86 622 624 610 600 674 740 792 900* ±42 928 * ± 14 951 * ± 1 930* ±15
1.22 0.31 0.3 0.47 0.62 0.67 0.22 0.4 0.49 0.57 0.75 0.85 4.04 3.09 2.94 3.1 2.39 1.48 1.23 0.98* ±0.16 0.90 * ± 0.03 0.86* ±0.01 0.98* ±0.08
237 239 201
110 91 69 134 740
1.45 2.22 3.75 0.83 0.54
239
Subst. 0.75; 0.01, 0.1, and 0.2MNaCl Subst. 0.5-2.5 Subst. 0.5-2.5 from Auricularia auricula judae from Auricularia auricula judae
Enzyme from egg-whites (glycoside hydrolase)
Kelco S-657; 0.001 M NaCl
Kelco S-130; 0.001 M NaCl
0.1 M NaCl
Xanthan gum
kh
Thermal degradation in water or salt soln. at 60, 80, 1000C
0.1 M NaCl
Welan gum
[tj]
Native Renatured
201
239 202
202 202 202 202 202
237 198
72 101 4900 4050 265 353 750 3.05 2.83 2.66 2.49 2.41 752 838 1452 2194 680 750 1380 2097 738 1078 1537 2471 641 984 1510 2370 10300 13200
0.2 0.36 0.49 0.41 0.21 0.23 0.49 1.35 1.42 1.48 1.54 1.58 0.99 0.62 0.73 0.81 0.7 0.43 0.59 0.6 0.94 0.99 1 0.86 0.46 0.55 0.51 0.62 0.45 0.46
203 203 204 205 205 205 205 205 205 240
206
206
206
206
207
References page VII - 285
TABLE 2. SCHULZ-BLASCHKE CONSTANTS Polymer Poly(isoprene) Guttapercha Poly(chloroprene) Poly(methylene) Poly(ethylene) PoIy(I -butene) Poly(isobutene) Poly(acrylonitrile) Poly(methyl methacrylate)
Solvent
Toluene0 Benzene m-Xylene° Decalin Decalin Diisobutylene Dimethyl formamide Acetone
PoIy(I-ethylbutyl methacrylate Poly(n-hexyl methacrylate) Poly(n-octyl methacrylate) Poly(n-lauryl methacrylate) Poly(acrylamide) Poly(vinyl alcohol) Poly(vinyl chloride)
Methyl ethyl ketone Toluene0 Methyl ethyl ketone Isopropanol Methyl ethyl ketone Isopropanol Methyl ethyl ketone Isopropanol Methyl ethyl ketone n-Butanol Methyl ethyl ketone n-Butyl acetate Isopropyl acetate Water Water (IM NaCl) Water Cyclohexanone
25 32.6 23 16.8 23 23 13 25 25 30 25
Cyclohexanone0 Poly(vinyl acetate) Poly(styrene)
Benzene Toluene Benzene Butanone0 Chloroform Cyclohexane Ethyl acetate Methyl ethyl ketone Toluene0
Poly(a-methyl styrene)
Poly(2-methyl-5-vinyl tetrazole)
25 25 120 135 115 20 25 25 32 25 25 20 25 27.3 32 25 25 23 21.5 23 27.4
Benzene0 Butyl acetate Chloroform Chloroform0
Poly(ethyl methacrylate) Poly(n-butyl methacrylate)
T( 0 C)
m-Xylenefl Cyclohexane
25 20-60 30 25 25 30 25 25 34 25 30 25 30 25 30
Cyclohexane/ ethylacetate (50/50)
30
Chloroform
20
Remarks
[17]
ksh
Refs.
19-208
0.32
121-1535 ??sP
0.29 0.48
77sp
0.5
25-480
0.3
l/* sb = 5.411og(T7sp + 5)-1.15 7?sp < 1
0.5
VsP
0.33 1 0.36 0.89
rjsp < 1 ^sp
0.3 0.7 0.36 0.8 0.46 0.38 0.59 0.20* ±0.06 0.20* ±0.07 0.46* ±0.02 0.28 ±0.01 0.32 ± 0.03
Low pressure Stereoregular
Theta temperature Theta temperature Theta temperature Theta temperature Theta temperature
MW 69000-106000 reprecipitated 21-139 1/Jfc8b = 5.224 log(77sp 4- 4 ) - 0.65 1 l/* 8b = 10.534 log(7?sp + 3 ) - 2.65
28 34 52 68 78 37 56 88 119 164 26 37 56 86
0.82 0.99 1.05 1.02 0.77 0.4 0.29 0.37 0.38 0.39 0.4 0.26 0.41 0.26
208 209 208 210 211 208 208 208 211,212 213 208,212 212 10 208 214 213 211 208 211 211 211 211 211 211 211 211 211 211 211 6 6 122 215 208 130 213 208 208 213 208 208 208 208 214 208 214 208 216
216
217
TABLE 2.
cont'd
Polymer
Poly(oxyethylene)
Poly(oxydimethylsilylene) Poly(iminoadipoylimino hexamethylene) (Nylon 66)
Poly(amide imide) Cellulose Cellulose acetate Cellulose nitrate
Ethyl cellulose
Solvent
T( 0 C)
Dimethyl formamide
20
Methylene chloride
20
Acetonitrile Benzene Benzyl alcohol Carbon tetrachloride Dimethylformamide Dioxane Methanol Methyl acetate Water Butanone0 Chloroform* Formic acid (90%)
25 10 37 25 25 25 25 25 25 25 25 25 25
/V-Methyl pyrollidone Cadoxen Cuoxam Cuoxen Acetone Acetone
30 20 20 20 25 20
Ethyl acetate
27 20
Acetone Benzene Isobutanol /i-Butyl chloride Ethyl acetate
20, 30,40 20,30 40 20,30,40 20, 30,40 20, 30, 40 20
Remarks
[tj] 186 270 20 39 64 128 236 27 34 55 89 168 244 M v >10 4 M v >10 4 M v >10 4 M v >10 4 M v >10 4 M v >10 4 M v >10 4 M v >10 4 M v >10 4 M v >10 4
(13.7% N)
(13.7% N)
Subst. = 2.73 Subst. = 2.73 Subst. = 2.73 Subst. = 2.73 Subst. = 2.73 Subst. = 2.73
ksb 0.19 0.19 0.59 0.38 0.33 0.23 0.22 0.26 0.19 0.29 0.25 0.3 0.35 0.22 0.21 0.23 0.19 0.3 0.27 0.27 0.26 0.27 0.17
83 100 120 140 200 19-87 339-1395 946-1125 190-2800
0.2 0.22 * ± 0.02 0.24* ±0.02 0.26* ±0.02 0.28* ±0.01 0.3 0.29 ±0.08 0.29 0.29
180-500 500-1000 1000-1400 1400-2000 695-1995
0.29 0.34 0.37 0.4 0.30 ±0.03
200-600 600-1200 1200-1800 1800-2400 24-180 26-450 362-418 25-420 25-470 25-450 41-1888
0.26 0.3 0.33 0.37 0.35,0.33,0.32 0.36,0.35 0.34 0.34,0.33,0.32 0.33, 0.33, 0.32 0.29,0.28,0.27 0.31 ±0.05
Refs.
217
217
218 218 218 218 218 218 218 218 218 208 208 159
219 191 220 221 64 222
191 64 222
223 223 223 223 223 191
"&Sb is roughly calculable from the Arrhenius constant. C
REFERENCES 1. 2. 3. 4. 5.
M. L. Huggins, J. Am. Chem. Soc, 64, 2716 (1942). A. Dondos, C. Tsitsilianis, Polym. Int., 28, 151 (1992). I. Doit, Polymer (London), 29, 490 (1988). T. Sakai, J. Polym. Sci. A-2, 6, 1659 (1968). P. M. Reilly, B. M. E. van der Hoff, M. Ziogas, J. Appl. Polym. Sci., 24, 2087 (1979).
6. M. M. Rafi'ee Fanood, M. H. George, Polymer, 28, 2244 (1987). 7. A. Penati et al., J. Appl. Polym. Sci., 19, 2583 (1975). 8. A. Varada Rajulu, A. Padma, J. Polym. Mater., 6,15 (1989). 9. E. O. Kraemer, Ind. Eng. Chem., 30, 1200 (1938). 10. G. V. Schulz, F. Blaschke, J. Prakt. Chem., 158, 130 (1941), 159, 146 (1941).
11. M. Stickler, N. Siitterlin, in: J. Brandrup, E. H. Immergut (Eds.) "Polymer Handbook", 3rd Ed., Wiley-Interscience, Wiley, New York, 1989, p. VIM 83. 12. P. G. de Gennes, "Scaling Concepts in Polymer Physics", Cornell Univ. Press, Ithaca, NY, 1979. 13. J. M. Peterson, M. Fixman, J. Chem. Phys., 39,2516 (1963). 14. M. Bohdanecky, Collect. Czech. Chem. Commun., 35, 1972 (1970). 15. K. K. Chee, J. Appl. Polymer. ScL5 23, 1639 (1979). 16. M. Bohdanecky, Z. Tuzar, Collect, Czech. Chem. Commun., 34, 3318 (1969). 17. C. G. Seefried et al., J. Polym. Sci., Polym. Phys. Edn., 18, 817 (1980). 18. J. Moacanin, J. Appl. Polym. Sci., 1, 272 (1959). 19. N. Howard, M. B. Huglin, R. W. Richards, J. Appl. Polymer Sci., 16, 1525 (1972). 20. P. Munk, M. T. Abijaoude, M. E. Halbrook, J. Polym. Sci., Polym. Physics Edn., 16, 105 (1978). 21. B. Lanska et al., Eur. Polym. J., 14, 807 (1978). 22. R. Berger, Makromol. Chem., 102, 24 (1967). 23. A. A. Abdel-Azim, Macromol. Rapid Commun., 15, 183 (1994). 24. C. E. H. Bawn, M. B. Huglin, Polymer (London), 3, 615 (1962). 25. J. Blackford, R. F. Robertson, J. Polym. Sci. A, 3,1289,1303 (1965). 26. J. A. Manson, L. H. Cragg, Can. J. Chem., 30, 482 (1952); 36, 858 (1958). 27. L. M. Hobbs, V. C. Long, Polymer (London), 4, 479 (1963). 28. S. L. Kapur, S. Gundiah, J. Polym. Sci., 26, 89 (1957). 29. M. Moan, A. Omari, Polym. Degrad. and Stab., 35, 277 (1992). 30. R. B. Jones, Physica A (Amsterdam), 212, 43 (1994). 31. G. M. Bristow, J. Polym. Sci., 62, 168 (1962). 32. R. H. Colby et al., Macromolec, 24, 3873 (1991). 33. B. J. Bauer et al., Macromolec, 22, 2337 (1989). 34. S. L. Kapur, S. Gundiah, Makromol. Chem., 26, 119 (1958). 35. N. V. Bac, L. Terlemezyan, M. Mihailov, J. Appl. Polym. Sci., 50, 845 (1993). 36. J. Polacek, Collect. Czech. Chem. Commun., 25, 2103 (1960). 37. L. Nicolas, J. Polym. Sci., 29, 191 (1958). 38. Q. A. Trementozzi, J. Polym. Sci., 23, 887 (1957). 39. O. F. Solomon, I. Z. Ciuta, BuI. Inst. Politeh. "Gheorghe Gheorgie-Dej". Bucuresti, 30, 87 (1968). 40. E. Willert, R. Berger, G. Langhammer, Plaste Kautschuk, 14, 303 (1967). 41. H. J. Schuurmans, J. Polym. Sci., 57, 557 (1962). 42. V. P. Budtov, Vysokomol. Soedin., Ser. A, 9, 765, (1967). 43. W. F. Hadden, Jr., R. S. Porter, J. F. Johnson, J. Appl. Polym. Sci., 8, 1371 (1964). 44. L.-Y Chou, J. L. Zakin, J. Colloid Interface Sci., 25, 547 (1967). 45. A. Penati, G. Pagani, E. Beacco, Ann. Chim. (Rome), 64, 99 (1974).
46. F. Gundert, B. A. Wolf, Makromol. Chem., 187, 2969 (1986). 47. P. H. Plesch, P. P. Rutherford, Polymer, 1, 271 (1960). 48. H. Geerissen, P. Schiitzeichel, B. A. Wolf, Macromolec, 24, 304 (1991). 49. F. Danuso, G. Moraglio, Atti Accad. Nazi. Lincei, Rend., Classe Sci. Fis. Mat. Nat., 25, 509 (1958). 50. G. Moraglio, F. Danusso, Ann. Chim. (Rome), 49, 902 (1959). 51. K. Kamido, Kobunshi Kagaku, 21, 152 (1964). 52. P. Xie, Q. Ying, L. Shi, Gaofenzi Xuebao, 257 (1990); Chem. Abstr., 114, 123693h (1991). 53. G. Barone et al., Ric Sci., 36, 477 (1966). 54. M. Sakurai et al., Polym. J. (Tokyo), 25, 1247 (1993). 55. N. M. Beder, A. B. Pakshver, Khim, Volokna, 3, 21 (1961). 56. T. Shibukawa, K. Nakaguchi, Kobunshi Kagaku, 14, 353 (1957). 57. Y. Shimura, J. Polym. Sci. A-2, 4, 423 (1966). 58. S. Uchiyama, Sen-i Gakaishi, 22, 373 (1966). 59. T. Shibukawa, K. Nakaguchi, Kobunshi Kagaku, 14, 203 (1957). 60. M. Katayama, T. Ogoshi, Kobunshi Kagaku, 13, 114, 148 (1958). 61. N. S. Batty, J. T. Guthrie, Polymer, 19, 1145 (1978). 62. T. Shibukawa, K. Nakaguchi, Kobunshi Kagaku, 14, 291, 294 (1957). 63. H. Somitomo, Y. Yatsukama, Kobunshi Kagaku, 11, 65 (1954). 64. M. L. Huggins, "Physical Chemistry of High Polymers", Wiley, New York, 1958, p. 82. 65. Y. Pietrasantra, G. Rigal, P. Schaeffner, Makromol. Chem., 182, 1371 (1981). 66. N. Schott, B. Will, B. A. Wolf, Makromol. Chem., 189,2067 (1988). 67. P. Vasudevan, M. Santappa, Makromol. Chem., 137, 262 (1970). 68. J. Y. Olayemi, Makromol. Chem., 183, 2547 (1982). 69. K. Karunakaran, M. Santappa, Current Sci. (India), 33, 551 (1964). 70. J. Herz et al., Compt. Rend., 261, 1319 (1965). 71. N. Yokomichi, K. Ogino, T. Nakagawa, Nippon Kagaku Zasshi, 87, 233 (1996). 72. S. Gundiah, N. V. Viswanathan, S. L. Kapur, J. Sci. Ind. Res., 19B, 191 (1960). 73. B. Maitra, A. K. Nandi, Polymer, 34, 1260 (1993). 74. N. T. Srinivasan, M. Santappa, Makromol. Chem., 27, 61 (1958). 75. A. Kotera et al., Makromol. Chem., 87, 195 (1965). 76. A. Blumstein, F. W. Billmeyer, Jr., J. Polym. Sci. A-2, 4,465 (1966). 77. G. S. Kolesnikov, Tsing Han-Ming, Vysokomol. Soedin., 3, 1210(1961). 78. M. Bohdanecky, Coll. Czech. Chem. Commun., 31, 4095 (1966). 79. A. S. Badran et al., J. Appl. Polym. Sci., 45, 333 (1992). 80. S. Morimoto, A. Machi, Kogyo Gijutsuin Sen I Kogyo Shikensho Kenkyn Hokoku, 67, 1 (1964).
81. V. Efstratiadis et al., Polym. Int., 33, 171 (1994). 82. G. N. Tsidvintseva, Deposited Doc, 1978, VINITI 170478; Chem. Abstr., 91, 193784u (1979). 83. Z. Li, W. Zhang, K. Feng, Zhongshan Daxue Xuebao, Ziran Kexueban, 3, 27, (1986). 84. D. Pateropoulou, E. Siakali-Kioulafa, N. Hadjichristidis, Macromol. Chem. Phys., 195, 173 (1994). 85. J. W. Mays, N. Hadjichristidis, J. S. Linder, J. Polym. Sci. B: Polym. Phys., 28, 1181 (1990). 86. B. Bednar et al., Sb. Vys. Sk. Chem. Technol. Praze, 53, 241 (1980). 87. M. Becerra, D. Radic, L. Gargallo, Makromol. Chem., 179, 2241 (1978). 88. J. B. Alexopoulos, N. Hadjichristidis, Makromol. Chem., 180, 455 (1979). 89. J. B. Alexopoulos, N. Hajichristidis, A. Vassiliadis, Polymer, 16, 386 (1975). 90. N. Hadjichristidis et al., J. Polym. ScL, Polym. Phys. Ed., 22, 1745 (1984). 91. Rafi'ee Fanood, M. H. George, Polymer, 28, 2241 (1987). 92. H. Kamogawa, T. Sekiya, Kogyo Kagaku Zasshi, 63, 1631 (1960). 93. F. S. Holahan, S. S. Stivala, D. W. Levi, J. Polym. Sci. A, 3, 3987 (1965). 94. D. Landheer, S.-L. Malhotra, J. Macromol. Sci.-Chem. A, 16, 1349 (1981). 95. T. A. Orofino, F. Wenger, J. Phys. Chem., 67, 566 (1963). 96. M. Pulat, N. Uyysal, Cemil Senvar, Marmara Univ. Fen Blimleri Derg., 5, 125 (1988). 97. T. Arai et al., Macromolec, 28, 3609 (1995). 98. J. R. Urwin, J. M. Stearne, Makromol. Chem., 78, 204 (1964). 99. V. P. Budtov, Vysokomol. Soedin., Ser. A, 9, 765 (1967). 100. J. Schurz, H. Pippan, Monatsch. Chem., 94, 859 (1963). 101. K. K. Chee, J. Appl. Polym. Sci., 27, 1675 (1982). 102. M. Morton et al., J. Polym. Sci., 57, 471 (1962). 103. H.-G. Elias, O. Etter, Makromol. Chem., 66, 56 (1963). 104. J. L. Zakin, R. Wu, H. Luh, K. G. Mayan, J. Polym. Sci., Polym. Phys. Ed., 14, 299 (1976). 105. V. A. Myagchenkov, E. V. Kuzentsov, V. Ya. Kitkevich, Vysokomol. Soedin., 6, 1366 (1964). 106. A. I. Goldberg, W. P. Hohenstein, H. Mark, J. Polym. Sci., 2, 503 (1947). 107. U. Lohmander, R. Stroemberg, Makromol. Chem., 72, 143 (1964). 108. H. W. McCormick, J. Colloid Sci., 16, 635 (1961). 109. Y. Einaga et al., Macromolec, 22, 3419 (1989). 110. W. E. Moore, M. Muiphy, J. Polym. Sci., 56, 519 (1962). 111. A.M. Meffroy-Biget, A. Unanue, P. Stevenot, C. R. Hebd. Seances Acad. Sci., Ser. C, 281, 179 (1975). 112. A.-M. Meffroy-Biget et al., C. R. Hebd. Seances Acad. Sci., Serv. C, 281, 429 (1975). 113. K. Imai, U. Maeda, M. Matsumoto, Kobunshi Kagaku, 14, 419(1957). 114. M. Shibayama et al., Macromolec, 29, 885 (1986). 115. L. M. Hobbs, V. C. Long, Polymer, 4, 479 (1963).
116. M. Matsumoto, U. Maeda, K. Imai, Kobunshi Kagaku, 14, 425 (1957). 117. A. Beresniewicz, J. Polym. Sci., 39, 63 (1959). 118. F. Lerner, M. Alon, J. Polym. Sci. A: Polym. Chem., 25, 181 (1987). 119. M. Negishi et al., Kobunshi Kagaku, 14, 239 (1957). 120. L. Z. Vilenchik et al., Chromatographia, 24, 633 (1987). 121. M. Matsumota, K. Imai, Kobunshi Kagaku, 12, 402 (1955). 122. T. Ikaya, K. Imai, Kobunshi Ronbunshu, 36, 329 (1979). 123. Y. Sakaguchi, N. Yasuhira, Kobunshi Kagaku, 13, 437 (1956). 124. J. W. Breitenbach, E. L. Forster, A. J. Renner, Kolloid-A., 127, 1 (1952). 125. F. Dunusso, G. Moraglio, S. Gazzeva, Chim. Ind. (Milan), 36, 883 (1964). 126. L. C. Grotz, J. Polym. Sci. B, 2, 883 (1964). 127. G. M. Guzman, J. M. G. Faton, Anales Real Soc. Espan. Frs. Quim. (Madrid), 54-B, 263 (1958). 128. K. Goto, Y. Ono, S. Furusawa, Kobunshi Kagaku, 11, 437 (1954). 129. H. Sobue, Y. Tabata, Y. Tajima, Kogyo Kagaku Zasshi, 61, 1328 (1958). 130. L. Lapcik, V. Roubal, Zb. Pr. Chemikotechnol. Fak. SVST, 1972, 15 (1974). 131. E. L. Madruga, J. Millan, J. Polym. Sci., Polym. Chem. Ed., 12, 2111 (1974). 132. Y Nakamura, M. Saito, Kobunshi Kagaku, 17, 718 (1960). 133. F. Krasovec, J. Stefan, Inst. Reports (Ljubljana), 3, 203 (1956). 134. L. A. Utracki, R. Simha, Makromol. Chem., 177, 94 (1968). 135. R. Hippe, Bull. Acad. Pol. Sci., Ser. Sci. Chim., 23, 363 (1975). 136. K. Fujii et al., Kobunshi Kagaku, 19, 581 (1962). 137. M. Sakurai et al., Polymer J. (Tokyo), 26, 658 (1994). 138. D. O. Jordan, A. R. Mathieson, M. R. Porter, J. Polym. Sci., 21, 473 (1956). 139. L. Z. Vilenchik et al., Vysokomol. Soedin, Ser. B, 31 (2), 114 (1989). 140. G. Liang, X. Liang, R. Feng, Zhongshan Daxue Xuebao, Ziran Kexueban, 3, 126, (1980). 141. N. Ahmad, B. Ahmad, J. Chem. Soc. Pak., 12, 246 (1990). 142. A. B. Duchkova et al., Vysokomol. Soedin., 8, 1814 (1966). 143. H. Hopff, M. A. Osman, Makromol. Chem., 135,175 (1970). 144. G. Lutringer, G. WeM, Polymer, 32, 877 (1991). 145. G. Lutringer, B. Meurer, G. WeM, Polymer, 32, 884 (1991). 146. G. S. Nurkeeva et al., Vysokomol. Soedin., Ser. B, 28, 649 (1986). 147. G. Mueh, Kolloid-Z., 196, 64,c 140 (1964). 148. D. K. Thomas, A. Charlesby, J. Polym. Sci., 42, 195 (1960). 149. M. Ataman, J. Macromol. Sci.-Chem. A, 24, 967 (1987). 150. E. A. Boucher, P. M. Hines, J. Polym. Sci., Polym. Phys. Ed., 16, 501 (1978). 151. M. Ataman and E. A. Boucher, J. Polym. Sci.: Polym. Phys. Ed., 20, 1585 (1982). 152. W. Tummler, Plaste Kautschuk, 12, 582 (1965). 153. K. Okazaki, Kogyo Kagaku Zasshi, 64, 342 (1961).
154. A. Orszagh, F. Fejgin, Polimery, 8, 233 (1963). 155. N. N. Filatova et al, Polym. Sci. USSR, 24, 1144 (1982). 156. H. Sobue, A. Kajiura, Kogyo Kagaku Zasshi, 62, 1908 (1959). 157. L. Gargallo et al, Eur. Polym. J., 29, 609 (1993). 158. G. Prati, Ann. Chim. (Rome), 47, 51 (1957). 159. E. Heim, Faserforsch. u. Textiltech., 11, 513 (1960). 160. V. Z. Nikonov, L. B. Sokolov, Vysokomol. Soedin., 8, 1529 (1966). 161. J. Sebanda, J. Kralicek, Coll. Czech. Chem. Commun., 31, 2534 (1966). 162. J. Kralicek, J. Kondelikova, V. Kubanek, Sb. Vys. Sk. Chem.-Technol. Praze, Org. Chem. Technol. C, 18, 61 (1973). 163. L. Huppenthal, R. Szczepanska, Polimery (Warsaw), 21, 16 (1976). 164. R. Rybnikar, Faserforsch. U. Textiltech., 9, 500 (1958). 165. W. Sbrolli, T. Capaccioli, Chim. Ind. (Milan), 42, 243 (1960). 166. O. Quadrat, M. Bohdanecky, Coll. Czech. Chem. Commun., 29, 2469 (1964). 167. A. V. Pavlov, S. E. Bresler, S. R. Rafikov, Vysokomol. Soedin., 6, 2068 (1964). 168. M. K. Baloch, Polym. Bull. (Berlin), 34, 469 (1995). 169. L. V. Avrorova et al., Khim. Volokna, 20, (1988). 170. S. M. Aharoni, Macromolec, 20, 2010 (1987). 171. D. Pishev, N. Angelova, Przegl. Wlok. Tech. Wlok., 46, 5 (1992). 172. H. Li et al., Chemical Journal of Chinese Universities, 10, 1065 (1989). 173. W.-F. Lee, C-C. Tsai, Polymer, 36, 357 (1992). 174. D.-J. Liaw, S. J. Shian, K. R. Lee, J. Appl. Polym. Sci., 45,61 (1992). 175. D.-J. Liaw et al., J. Appl. Polym. Sci., 34, 999 (1987). 176. A. Viallat, R. Pedro Bom, J. P Cohen Addad, Polymer, 33, 4379 (1992). 177. C. Maechling-Strasser et al., Polymer, 33, 627 (1992). 178. U.-P. Strauss, J. Polym. Sci., 33, 291 (1958). 179. P. M. Cotts et al., Macromolec, 24, 6730 (1991). 180. M. Takeda, A. Yamada, T. Saito, Kobunshi Kagaku, 14, 265 (1957). 181. M. Takeda, A. Yamada, Kobunshi Kagaku, 14, 247 (1957). 182. J. Brzezinski, Polimery (Warsaw), 18, 67 (1973). 183. S. Maxim et al., Eur. Polym. J., 13, 105 (1977). 184. M. S. Matevosyan, A. A. Askadskii, G. L. Slonimskii, Vysokomol. Soedin., Ser. A, 29, 761 (1987). 185. B. Magny, I. Ilioponlos, R. Audebert, Polym. Comm., 32, 456 (1991). 186. R. M. Davis, W. B. Russel, Proc. IUPAC Macromol. Symp., 28, 902 (1982). 187. R. M. Davis, W. B. Russel, Macromolec, 20, 518 (1987). 188. V E. Eskin, A. E. Nesterrov, Vysokomol. Soedin., 8, 141 (1966). 189. S. R. Erilander, R. M. Purvinas, Starke, 20, 37 (1968). 190. M. K. S. Morsi, C. Sterling, J. Appl. Polym. Sci., 10, 925 (1966).
191. L. S. Bolotnikova, T. I. Samsonova, Zh. Prikl. Khim., 38, 2299 (1965). 192. M. W. Pandit, R. S. Singh, Indian J. Technol., 6, 172 (1968). 193. V. R Kharitonova, A. B. Pakshver, Kolloid. Zhur., 20, 110 (1958). 194. G. Khamrakulov et al., Vysokomol. Soedin, Ser. A, 35, 705 (1993). 195. L. A. Knypikova, T. A. Savitskaya, D. D. Grinshpan, Khim. Drev., 8, (1993). 196. P. Haward, R. S. Parikh, J. Polym. Sci. A-I, 6, 537 (1968). 197. I. I. Ryskina et al., Polym. Sci. USSR, 18, 2854 (1976). 198. C. Patel et al., J. Polym. Mater., 4, 35 (1987). 199. U. Lohmander, R. Stroemberg, Makromol. Chem., 72, 143 (1964). 200. F. Higashide, J. Nakajima, Kogyo Kagaku Zasshi, 69, 1329 (1966). 201. W. Brown, Arkiv Kemi, 18, 227 (1961). 202. A. Blazkova, J. Hrivikova, L. Lapcik, Chem. Pap., 44, 289 (1990). 203. K. Watanabe, M. Nakamura, Kogyo Kaguku Zassshi, 69, 1329 (1966). 204. D. A. I. Goring, S. Sitaramaiah, Polymer, 4, 7 (1963). 205. L. Zhang et al., Carbohydr. Res., 270, 1 (1995). 206. R. Urbani, D. A. Brant, Carbohydr. Polym., 11, 169 (1989). 207. M. Milas et al., Macromolec, 23, 2506 (1990). 208. M. Hoffman, Makromol. Chem., 24, 222, 245 (1957). 209. J. Polacek, J. Polym. Sci., 39, 469 (1959). 210. H. Wesslau, Makromol. Chem., 20, 111 (1956). 211. R. J. Valles, M. C. Otzinger, D. W. Levi, J. Appl. Polym. Sci., 4, 92 (1960). 212. H. Craubner, Makromol. Chem., 93, 24 (1966). 213. V V. Varadaiah, R. Rao, Polym. Sci., 19, 379 (1956). 214. V. E. Hart, J. Polym. Sci., 17, 215 (1955). 215. H. Anders, H. Zimmerman, H. Behnisch, Acta Polym., 37, 63 (1986). 216. L. D. Choo, L. M. Goo, Nonmunjip - Sanop Kwahak Kisul Yonguso (Inha Taehakkyo), 17, 247 (1989). 217. T. I. Bychkova et al., Vysokomol. Soedin., Ser. B, 28, 456 (1986). 218. H.-G. Elias, Makromol. Chem., 99, 219 (1966). 219. N. Tsubokawa, Y. Sone, Kobunshi Ronbunshu, 43, 71 (1986). 220. E. Husemann, G. V. Schulz, J. Makromol. Chem., I1 197 (1943). 221. M. Marx, Makromol. Chem., 16, 157 (1955); Papier, 10,135 (1956). 222. M. Marx, G. V. Schulz, Makromol. Chem., 31, 140 (1959); see also M. Marx-Figini, Makromol. Chem., 36, 220 (I960). 223. G. Meyerhoff, N. Sutterlin in Ref., 11, p. VII-200. 224. L. Gargallo, N. Hamidi, D. Radic, Polym. Int., 24, 1 (1991). 225. T. Takigawa, K. Urayama, T. Masuda, J. Chem. Phys., 93, 7310 (1990). 226. A. Guner, J. Appl. Polym. Sci., 62, 78 (1996). 227. S. I. Jeon, G. D. Chang, J. Korean Chem. Soc, 40, 748 (1996). 228. D. Dragan, Angew. Makromol. Chem., 236, 85 (1996).
229. S. R. Gooda, M. B. Huglin, Macromolec, 25, 4215 (1992). 230. I. H. Park, E.-J. Choi, Polymer, 37, 313 (1996). 231. J. A. Perdigon, M. P. Tarazona, E. Saiz, An. Quim. Int. Ed., 92, 385 (1996). 232. S.-Q. Bo et al., Chem. J. Chinese Univ. (Gaodeng Xuexiao Huaxue Xuebao), 17, 820 (1996). 233. F. Brand, H. Dautzenberg, Langmuir, 13, 2905 (1997). 234. H. Zheng et al., J. Chem. Phys., 105, 7746 (1996).
235. R. Dhami et al., Carbohydr. Polym., 28, 113 (1995). 236. T. Wang et al., Xianweisu Kexue Yu Jishu, 4, 7 (1996). 237. S. Nilsson, L.-O. Sundelof, B. Porsch, Carbohydr. Polym., 28, 265 (1995). 238. C. Holmberg, Colloid Polym. ScL, 274, 836 (1996). 239. L. Picton, G. Muller, Progr. Colloid Polym. ScL, 102, 26 (1996). 240. K. Monkos, Biochim. Biophys. Acta, 1339, 304 (1997).
Theta Solvents H a n s G . E l i a s Mcihg ian Moelcualr n I stiute, 1910 West St. Ande rws Rd,. Md ialnd, Ml 48640, A. Introduction 1. Fundamentals 1.1. Thermodynamics 1.2. Unperturbed Dimensions 2. Methods to Determine Theta Solvents 2.1. Phase Equilibrium (PE) 2.2. Second Virial Coefficient (A) 2.3. Cloud Point Titration (CP) 2.4. Cloud Temperature Titration (CT) 2.5. Unperturbed Dimensions (RGM, VM, DM, SM) 2.6. Other Methods B. Tables of Theta Solvents for Polymers Table 1. Homochain Polymers 1.1. Poly(alkanes) 1.2. Poly(alkenes) 1.3. Poly(styrenes) 1.4. Poly(vinyls) 1.5. Poly(acrylics) and Related Compounds 1.6. Poly(methacrylics) and Related Compounds 1.7. Other Carbon Chains Table 2. Heterochain Polymers 2.1. Poly(acetals) and Poly(ethers) 2.2. Poly(esters) 2.3. Poly(amides) 2.4. Polyureas and Polyurethanes 2.5. Polysaccharides 2.6. Carbon-Sulfur Chains 2.7. Silicon-Oxygen Chains 2.8. Phosphorus-Oxygen Chains C. References A.
INTRODUCTION
1.
Fundamentals
VII-291 VII-291 VII-291 VII-292 VII-293 VII-293 VII-293 VII-294 VII-294 VII-294 VII-294 VII-295 VII-295 VII-295 VII-299 VII-300 VII-305 VII-307 Vll-308 VII-312 VII-313 VII-313 VII-315 VII-316 VII-316 VII-316 VII-317 VII-317 VII-318 VII-318
/ . / Thermodynamics The theta state is defined as that state of a polymer solution at which the excess chemical potential, and correspondingly, the excess Gibbs energy of
dilution is zero. For a given polymer-solvent system, this state is obtained at a certain characteristic temperature, the theta temperature 0. A solvent at this temperature is called a theta solvent. Since Flory (110) was the first to show the importance of the theta state for a better understanding of physical structures and properties of polymers, the theta temperature is sometimes also called "Flory temperature". The name "van't Hoff temperature" has also been suggested (127). However, neither "Flory temperature" nor "van't Hoff temperature" has gained acceptance. The exact definition of the theta state is given by chemical thermodynamics. The chemical potential of a solvent 1, A/i i, can be split into an ideal term and an excess term: (Al) where the excess chemical potential at the thermodynamic temperature T is given by the enthalpy of dilution, Ai/1, and the excess entropy of dilution, AS|XC: (A2) A zero excess chemical potential does not imply that both the enthalpy of solution and the excess entropy of solution are zero as in the case of true ideal solutions where AH\ = 0 and A5f c = 0. Rather, a theta state means only that the terms on the right side of Eq. (A2) compensate each other at the theta temperature <9, i.e., Ai/1 = 0AS\*c for Afj,\KC at T — 0. Solutions in the theta state are thus not thermodynamically ideal but thermodynamically pseudoideal (306). The chemical potential cannot be measured directly. It may be expressed, however, by the product of the osmotic pressure IJ of the solution and the partial specific volume *vj of the solvent: (A3) The concentration dependence of the osmotic pressure of non-electrolyte solutions can be written as a power series (A4)
where C2 = m 2 /V is the mass concentration of the polymer (mass m2 of the polymer 2 per total volume V of the solution after mixing polymer and solvent) and Ai, A2, A3,... are first, second, third,... virial coefficients, respectively. The second virial coefficient is a measure of the interaction between two bodies, the third virial coefficient a measure of interactions between three bodies, etc. Second and third virial coefficients depend on the chemical structure and the molar mass of the polymer, the chemical structure of the solvent (and thus its interaction with the polymer), and the temperature. The first virial coefficient is given by (A5) where R is the general gas constant (R = 8.314510 J/K/mol) and Mn is the number-average molar mass of the polymer. Eq. (A4) is thus often written as (A6) where (Mn) is the apparent number-average molar mass, B = A2/RT, and C ^A3/RT. The third term of the right-hand side of Eq. (A4) is often negligible at low polymer concentrations. Combinations of Eqs. (Al), (A3) and (A4) then yields, (A7) Since by definition the excess chemical potential is zero at the theta temperature, the second virial coefficient (but not necessarily the third virial coefficient) is also zero (A 2 = 0 at T — 0). The concentration dependence of the reduced osmotic pressure, IJ/C2, is thus zero at the theta temperature, albeit at low concentrations only. The same reasoning applies to other colligative methods (cryoscopy, ebullioscopy, vapor phase osmometry) and also to those physical methods that measure concentration dependencies of apparent molar masses (static light scattering, sedimentation equilibrium, combination of sedimentation and diffusion coefficient, etc.). An example is static light scattering which yields at the scattering angle 7? —>0°: (A8) where (M w ) app = apparent mass-average molar mass, Ko- optical constant at zero angle, and /?o = Rayleigh ratio at zero scattering angle. The virial coefficients B and C of light scattering average differently over interactions than those of colligative measurements; B and C of poly molecular ("polydisperse") polymers are numerically different for osmotic pressure and light scattering measurements. The theta temperature may also be phenomenologically defined as the critical miscibility temperature at the limit of infinite molar mass (110). Since a solution may exhibit two
critical miscibility temperatures, a polymer solution may display two theta temperatures. In the case of endothermic solutions, a lowering of temperature leads to less positive second virial coefficients and the theta temperature corresponds to an upper critical solution temperature (UCST) in the limit of infinite molar mass. The theta temperature corresponds to a lower critical solution temperature (LCST) in the case of exothermic solutions (see, e.g., (92)). 1.2. Unperturbed Dimensions The thermodynamic behavior described above results from the fact that longrange interactions between polymer segments are absent in the theta state. Long-range interactions are intramolecular interactions between segments or groups of one and the same polymer molecule that are separated by many chemical bonds along the chain; they are remote in sequence but adjacent in space. Short-range interactions are interactions between chain groups that are near to each other in sequence. They are determined by the length of chain bonds, the valence angles between chain atoms, and the hindrance to rotation around chain bonds (usually due to a pair (4 chain bonds) or two pairs (5 chain bonds) of conformers in the chain). In a thermodynamically good solvent (A2 > 0), polymer-solvent interactions are much larger than polymer-polymer and solvent-solvent interactions. The polymer chain expands in order to minimize polymer-polymer contacts; the dimensions of these chains are said to be perturbed. In such perturbed chains, the space occupied by one polymer segment is excluded for all other segments of the same polymer chain, i.e., even at infinite dilution. In a theta solvent (A2 = 0), polymer-solvent interactions are just balanced by polymer-polymer and solventsolvent interactions. Long-range interactions disappear and the polymer chain assumes its so-called unperturbed dimensions which manifest themselves for linear chains by a dependence of the root-mean square radii of gyration s, on the square root of molar masses: (A9) Intrinsic viscosities [rj] are also controlled by the space requirements of polymer molecules. For unperturbed coils of linear chains, one can write (see textbooks of polymer science) (AlO) where ^o is usually assumed to be a universal constant (but see Ref. 498). The dependence of the radius of gyration, (s2) ' ,or the intrinsic viscosity, [77], on the square-root of the molar mass is generally taken as a manifestation of unperturbed dimensions and thus also of the presence of the theta state of the polymer. The assumption that theta conditions lead to unperturbed dimensions is often fulfilled within limits of error for most of the investigated polymers but it is not true in the general
sense. The thermodynamic definition of the theta state refers to the global properties of polymer solutions whereas the definition of unperturbed dimensions relates to the local properties of the chain. Both definitions agree exactly only if infinitely thin chains are surrounded by a locally and globally homogeneous continuum of solvent molecules. The ability of a theta solvent to generate unperturbed dimensions thus depends on the constitution and configuration of the polymer, the solvent, and the temperature [83] since all these factors influence long-range interactions (excluded volume effects and interactions with the solvent). Small molar mass dependencies of theta temperatures are sometimes detectable for single solvents (230), especially at low molar masses when the effects of end groups or small helical segments (525) become noticeable. However, if the macromolecules have long side chains and if the main chain and the side chains are constitutionally different, then the theta state of a polymer solution may not be identical with the unperturbed state of polymer coils, even for single solvents. An example is the solution of poly(octadecyl methacrylate) in butyl acetate which is in the theta state at 10.50C (A2 = 0). At this temperature, the exponent ay of the intrinsic viscosity/molar mass relationship of Eq. (AlO) was found as av = 0.44 instead of 0.50, due to a contraction of the long side chains (406). A similar discrepancy between the theta state of the polymer-solvent system and the unperturbed dimensions of the polymer coils has been found for cyclic poly(styrene) in cyclohexane where 0 = 28.5°C according to thermodynamics but ay — 0.40 at the same temperature; aw = 1/2 was observed for the considerably higher temperature of T = 400C (366). In both cases, intrinsic viscosities were assumed to reflect unperturbed dimensions. This is not necessarily true, however, since atactic poly(methyl methacrylate) exhibited the same reduced mean-square radius of gyration, (s2)Q/Mw, in the two theta solvents acetonitrile (<9 = 44°C) and w-butyl chloride (0 = 40.50C) whereas the corresponding viscosity quantities, [rj\e/Mj , definitely differed from each other despite the almost identical theta temperatures (512). In mixed solvents, these effects may be enhanced by a possible distribution of solvent components, depending on the polarities of the polymer 2 and liquids 1 and 3; 1 is a solvent and liquid 3 usually a non-solvent (precipitant). It seems that in the absence of large variations of theta temperatures, the unperturbed dimension of a given apolar polymer is approximately the same in various apolar solvents. However, unperturbed dimensions (as determined from intrinsic viscosities) may vary widely for polar polymers in various polar theta mixtures (31,95,154). For a review of various methods for the determination of unperturbed dimensions in mixed solvents see (526). 2. Methods to Determine Theta Solvents Methods for the determination of theta temperatures are discussed in greater detail in two reviews (527,528). As mentioned above, theta conditions do not neces-
sarily lead to unperturbed dimensions of coils (and vice versa). 2.1. Phase Equilibrium (PE) Binary mixtures of a polymer in a single solvent phase-separate at various temperatures, r sep , depending on the volume fraction 02 of the polymer. The maximum of the Tsep = /(02)-function is called the critical solution temperature Tcst. The experiment is repeated for a series of dilute solutions of polymers of the same constitution and configuration but of different molar mass. The relation between the critical solution temperature and the molar mass of the polymer is based on the FloryHuggins lattice theory which predicts that (All) where ip \ is the Flory residual-entropy parameter and r is the ratio of the molecular volume of the polymer to that of the solvent. Since r is proportional to the (number-average) molar mass of the polymer, Eq. (All) can be written as (A12) for polymers of sufficiently high r (or M n ) (Shultz-Flory method) (110,529). Extrapolation of the inverse critical solution temperatures to infinite molar mass delivers the inverse theta temperature 0. The data must be extrapolated not only to infinite molar mass but also to infinite dilution if used with mixed solvents (191). Furthermore, the method can be used only for phase separations into two liquid phases. Care must therefore be taken with crystalline polymers. 2.2. Second Virial Coefficient (A) All absolute methods for the determination of molar masses may be used; most commonly applied are membrane osmometry and static light scattering. Less frequently used are vapor phase osmometry and sedimentation equilibrium. Absolute methods that depend on specific solvent behaviour cannot be applied; examples are cryoscopy and ebullioscopy. Measurements must be performed at sufficiently low polymer concentrations in order to avoid effects of third virial coefficients. The concentration dependence of reciprocal apparent molar masses is determined for a given polymer-solvent pair at different temperatures. Second virial coefficients are calculated from the slopes of these curves (see Eqs. (A6) and (A8)) and plotted against temperature (110). The dependence of the second virial coefficients on temperature is linear only in the proximity of the theta temperature. Care must be taken, therefore, to work close to the theta temperature. Alternatively, the second virial coefficient may be measured at a constant temperature, using different solvent-nonsolvent ratios. However, appropriate precautions and corrections have to be used if mixed solvents are References page VII-318
used (Donnan equilibria in membrane osmometry, effects of differences in refractive indices in static light scattering, etc). 2.3. Cloud-Point Titration (CP) Dilute polymer solutions of different concentrations are titrated at constant temperature with a nonsolvent until the first sign of cloudiness. The volume fraction 03>cp of the nonsolvent 3 at the cloud point is then plotted against the logarithm of the volume fraction 02,cP of the polymer at the cloud point (89,90,531) and extrapolated to pure polymer: (A13) where Bcv is the slope of the 03)Cp =/(ln02,cP)-curve and 03@ is the volume fraction of the nonsolvent in the theta mixture solvent-nonsolvent. At high molar masses (small # cp ) and polymer densities p2 « 1 g/ml, mass-concentrations ^2xp ~ P202,cp (in g/ml) can be used instead of volume fractions 02,cp (93); neglect of these conditions may lead to errors (58). This "Elias method" has been shown to have theoretical justification from the Flory-Huggins lattice model (532,533); a comprehensive review of this method is available (93).
where r is the ratio of molecular volumes of polymer and solvent. 2.5. Unperturbed Dimensions (RGM, VISA, DM, SM) Root-mean-square radii of gyration, (s2)1^2, depend on the as power of the molar mass M (110): (A16) The exponent becomes a s — 1/2 for the unperturbed state where (s2) = (s2}0. The temperature dependence of the function (s2) =f(M) can thus be used to determine the temperature T0 at which as = 1/2 (RGM method). This method is cumbersome; more often used is the temperature dependence of the intrinsic viscosity/molar mass relationship (A17)
because av = 1/2 at the unperturbed state (at TQ) (VM method). Less often used are the corresponding relationships between molar masses and other hydrodynamic properties such as sedimentation coefficients (SM method) or diffusion coefficients (DM method). Unperturbed radii of gyration (from scattering experi2.4. Cloud Temperature Titration (CT) In a variation ments) always seem to indicate theta conditions (cf. Ref. of the cloud point titration method, cloud temperatures may 512) but the database is too small to allow definite proof. be determined by cooling or heating of dilute polymer Unperturbed dimensions from hydrodynamic measuresolutions of various concentrations until cloudiness appears ments in single solvents sometimes do not coincide with (58). The inverse cloud point temperature Tct is then plotted the theta state (cf. Refs. 366,466,512); see also Section 1.2. against the logarithm of the volume fraction 2,ct of the Hydrodynamic measurements in mixed solvents very often polymer 2 at the cloud point and extrapolated to pure deliver different unperturbed dimensions for theta condipolymer: tions (cf. Refs. 31,83,95,154). (A14) This method is also based on the Flory-Huggins lattice model (522,533). In a modification of the method, inverse cloud temperatures are plotted against 1/r06 (530), again based on the Flory-Huggins theory: (A15)
Method Abbreviation A CP CT PE VM
Name Second virial coefficient Cloud point titration Cloud point temperature Phase equilibria (critical solution temperature) Intrinsic viscosity/molar mass
2.6. Other Methods (IG, PL, R) The theta state and/or unperturbed dimensions have occasionally been determined by various other methods: refractometry (R) (7,24), dielectric measurements (E) (5), polarized luminescence (PL) (399), inverse gas chromatography (IG) (412), and dynamic light scattering (LS) (376). Common methods for the determination of theta temperatures 0, theta compositions ^1-, © of mixed solvents, and/or unperturbed dimensions are compared in the following table:
Required for the application Minimum number Knowledge of l>pe of of polymers molar mass solvent 3 1 1 3 3
Yes No No Yes Yes
Preferably single Mixed Preferably single Preferably single Single or mixed
Determined parameter O <£3.e O O £>03,e
B. TABLES OF THETA SOLVENTS FOR POLYMERS In the following tables, theta solvents and theta temperatures have been compiled for various polymers from the literature. The polymers are subdivided into groups of chemically similar compounds (see beginning of chapter for Contents). Within each group, polymers are arranged alphabetically, mostly according to the polymer names used in the original reference; no attempt has been made to use either IUPAC names (systematic names) or poly(monomer) names exclusively. Monomer units in alternating and random copolymers are listed alphabetically, regardless of their proportions; their relative amounts are given in parentheses on a mole/mole basis. Segments of block and graft copolymers are usually noted in the sequence reported by authors. The following abbreviations are used: alt (alternating), block (self-explanatory), co (statistical or random (or unspecified)), graft (self-explanatory). Polymers are further characterized by their tacticity (if any), provided it has been reported in the literature. Polymers by free radical polymerizations are usually assumed by authors to be "atactic". Tacticities are usually given as mole fractions of isotactic diads (JCJ), syndiotactic diads (jt5), isotactic triads (xa), syndiotactic triads (x ss ), heterotactic triads (^i8), ds-configurations (jtCis)» trans-
configurations (x trans)- If no quantitative characterization was reported, tacticities are described as it (predominantly isotactic), st (predominantly syndiotactic), at (neither predominantly iso- nor syndiotactic), cis (predominantly cis-tactic), or trans (predominantly trans-tactic). For each polymer, theta solvents are given in alphabetical order; no attempt was made to convert commonly used solvent names into systematic names (e.g. dioxane = 1,4dioxane). In mixed solvents, the liquid listed first may thus be a solvent or a nonsolvent. Compositions of mixed solvents are given in vol./vol. unless otherwise noted (ex: w/w indicates weight per weight). A recent (smaller) list (496) of "Theta Temperatures" is mainly concerned with unperturbed dimensions. Since these dimensions are often evaluated from measurements at nontheta temperatures using various theories of intrinsic viscosity/molar mass, or (far less frequent) radius of gyration/molar mass relationships, reported "theta temperatures" are often not theta temperatures per se but the temperatures at which measurements in thermodynamically good solvents have been performed. A comprehensive list of unperturbed dimensions of various polymers can be found in Section VII/1 of this Handbook and a list of characteristic ratios of polymethacrylates in (497).
TABLE 1. HOMOCHAIN POLYMERS Polymer (mol/mol)
Theta solvent (v/v)
Theta temp. (0C)
Method
Refs.
35 30 20 23 83 83 86.2 141 61 61 - 46 89.1 89 35.0 148 64.5
A, VM A, VM PE, VM PE, VM VM PE, VM PE PE, VM VM PE, VM PE, VM PE PE, VM VM PE 5 VM PE, VM
238 237 16 245,246 245 246 190 246 245 246 246 190 246 304 246 246
1.1. POLY(ALKANES) Poly(acenaphthylene)
Ethylene dichloride (1,2-dichloro ethane)
PoIy(I-butene), atactic
i-Amyl acetate Anisole Diphenyl ether Phenetole
-,isotactic
Toluene Anisole Cyclohexane/n-propanol (69/31) Diphenyl ether Phenetole
Poly(butene-c0-ethylene), 40 branches per 100 backbone carbon atoms Poly(ethylene)
3-Octanol 2-Octanol 1-Octanol f-Amyl alcohol Anisole Benzyl phenyl ether Bis(2-ethylhexyl) adipate Bis(2-ethylhexyl sebacate) Carbon disulfide n-Decanol Dibutyl phthalate Dioctyl adipate Diphenyl
5.0 29.0 59.0 199.2 153.5 191.5 170 145 145 150 -73 153.3 >200 145 128
VM VM VM PE PE PE PE VM PE PE PE PE PE VM PE
514 514 514 251 251 251 324 351 240 324 510 251 324 508 353
References page VII - 318
TABLE 1. cont'd Polymer (mol/mol)
Theta solvent (v/v)
Diphenyl ether Diphenyl methane Diphenylene oxide n-Dodecanol n-Heptane n-Hexane *-Hexanol//?-xylene (70/30) «-Hexanol/xylene (70/30) Nitrobenzene /?-Nonyl phenol «-Octane /i-Octanol p-Octyl phenol rc-Pentane 3,5,5-Trimethylhexyl acetate Poly(ethylene-a/f-propylene)
Poly(ethylene-co-propylene) Poly(ethyl ethylene) Poly(l-hexene)
Benzene n-Decyl acetate n-Heptyl acetate n-Hexyl acetate n-Octyl acetate Methanol/toluene (50/50) 2-Octanol Phenetole Butanone/n-hexane (29.8/70.2) Butanone//-propanol (37/63) (41.5/58.5) Dioxane/n-hexane (40/60) n-Hexyl chloride
Poly(isobutene)
/-Amyl benzyl ether i-Amyl butyrate i-Amyl /-valerate
i-Amyl n-valerate n-Amyl butyrate Anisole Benzene
n-Butanol/n-hexane (23.6/76.4) n-ButanoI/methyicyclohexane (29.2/70.8) (42.1/57.9) Butanone/carbon tetrachloride (33.7/66.3) Butanone/cyclohexane (36.8/63.2) Butanone/n-hexane (36.6/63.4) n-Butyl n-butyrate
Theta temp. (0C)
Method
Refs.
127.5 127.5 125 118 118 165 163.9 161.4 142.2 118 143.4 138 137.3 173.9 133.3 133 155 170 >200 162.4 210 180.1 174.5 85 80.0 126 121 19-21.4 5.0 38.0 60.9 27.0
PE, VM VM PE CT PE A PE, VM PE PE, VM PE PE PE, VM PE PE PE PE PE CT PE PE PE PE PE PE PE A PE CP CP CP CP CP
485 492 324 355 462 177 251,485 46 251,485 324 353 324 251 132 132 252 8 136 324 251 132 251 251 252 132 353 353 453 453 453 453 453 346 458 514 210 18 18 154 154 19 154 18 339 339 183 427 517 499 221 339 339 113 517 44 113 320 339 100 100 100 100 100 100 339
23.5 23.5 61.3 8 24 23.5 4 20.5 13 13 23.7 28 22.1 25.0 25.0 27 22.1 21.0 22.0 105.5 25.0 25 24.0 24 22.8 25.0 25.0 49.0 25.0 25.0 25.0 46.2
A, VM VM VM PE PE A, PE A, PE VM A, PE A A, VM A, VM A DM, VM A A SM, VM A A PE 5 VM A PE, VM VM A, VM CP CP CP CP CP CP A
TABLE 1. cont'd Polymer (mol/mol)
Theta solvent (v/v) Carbon tetrachloride/dioxane (63.8/36.2) Chlorobenzene/n-propanol (67.5/37.5) (76.0./24.0) (79.7/20.3) Chloroform/n-propanol (57.9/42.1) (77.1/22.9) (79.5/20.5) Cyclohexane/dioxane (45.1/54.9) Cyclohexane/n-propanol Cyclohexanol/toluene (29.3/70.7) Cyclopentane n-Decanol/n-hexane (41.1/58.9) n-Decanol/methylcyclohexane (47.5/52.5) Dibuty ether Dioxane/n-hexane (48.2/51.8) Dioxane/methylcyclohexane (51.0/49.0) Diphenyl ether Diphenyl ether/ethylbenzene (50/50) (25/75) Ethylbenzene Ethyl caproate Ethyl caprylate Ethyl heptanoate
Poly [ 1 -(4-methylpentyl)-1 -buty lene-a?1 -(1,5-dimethylhexy l)ethylene ( = hydrogenated poly(myrcene) Poly(2-methylpentene-l-sulfone) PoIy(I-octene)
CP CP CP CP CP CP CP CP VM CP
Refs.
PE, VM PE, VM
100 100 100 100 100 100 100 100 305 100 536 100 100 76 100 100 113 113 113 113 113 263 44 113 44 44 536 100 100 100 100 100 100 100 536 536 183 183 100 100 100 536 183 339 183 536 76 44 113 113
n-Hexyl acetate 2-Octanol 0-Chloronaphthalene o-Dichlorobenzene Diphenyl Diphenyl ether Diphenylmethane
60.9 37.6 165 133 194.6 210.0 176.6
A VM VM VM PE, VM PE 1 VM PE, VM
363 454 262 262 334 334 334
2-Octanol Butanone/fl-hexane (35.4/64.6) Butanone//-propanol n-Pentane Phenetole
51.0 11.5 22.5 162.5 50.4
VM PE PE PE PE
514 18 18 169 170
Toluene
Poly(4-methyl-l-pentene, 0.90 < Xx < 0.94
Method
25.0 49.0 25.0 14.0 49.0 25.0 14.0 25.0 35 25.0 188 25.0 25.0 204 25.0 25.0 148 76.0 26.8 -24.0 57 22 33 33 57 22 185 25.0 25.0 25.0 25.0 25.0 25.0 25.0 52 ± 2 45 72.7 24.0 25.0 25.0 25.0 153 47.7 55.5 5.9 103 76.0 87 86.0 -13.0
Ethyl hexanoate Ethyl octanoate 3-Ethylpentane n-Heptanol/n-hexane (37.4/62.6) H-Heptanol/methylcyclohexane (39.5/60.5) rt-Hexane//i-hexanol (68.3/31.7) n-Hexane/3-methylbutanone (57.6/43.4) n-Hexane/n-octanol (63.7/36.3) n-Hexane/n-pentanol (71.7/28.3) n-Hexane/n-propanol (80.3/19.7) 2-Methylbutane (M = 23000, 150000) - , (M = 760000) Methyl capronate Methyl caprylate Methylcycohexane/n-octanol (56.0/44.0) Methylcyclohexane/n-pentanol (65.2/34.8) Methylcyciohexane/w-propanol (74.2/25.8) 2-Methylhexane Methyl heptanoate 3-Methylheptanone-5 Methyl pelargonate 2-Methylpentane Pentane Phenetole Poly(2-methyl-2-butylene) ( = hydrogenated l,4-poly(isoprene)) Poly(methylethylene) Poly([S]-4-methyl-l-hexene), X1 > 0.95
Theta temp. (0C)
CP CP A, RGM, VM CP CP PE PE PE PE PE PE PE
CP CP CP CP CP CP CP A A CP CP CP A A 1 VM A A, RGM, VM
References page VII - 318
TABLE 1. cont'd Polymer (mol/mol)
Theta solvent (v/v)
Poly(l-pentene), atactic
Anisole i-Butyl acetate Diphenylmethane Phenetole Phenetole Phenyl ether i-Amyl acetate Anisole i-Butyl acetate Diphenylmethane 2-Pentanol Phenetole
-, isotactic
Poly(propylene), atactic
Phenyl ether i-Amyl acetate n-Amyl acetate n-Butanol/carbon tetrachloride (33/67) n-Butanol/n-hexane (32/68) n-Butanol/methylcyclohexane (34/66) /-Butyl acetate n-Butyl acetate Carbon tetrachloride/n-propanol (74/26) 1-Chloronaphthalene Cyclohexanone Diphenyl Diphenyl ether
-, isotactic
n-Hexane/fl-propanol Methylcyclohexane/n-propanol (69/31) 1-Octanol 2-OctanoI 3-Octanol n-Propyl acetate *-Amyl acetate i-Amyl benzylether p-t-Amyl phenol Benzyl phenyl ether Benzyl propionate rc-Butyl alcohol r-Butyl alcohol p-r-Butyl phenol 1-Chloronaphthalene /7-Cresol Dibenzyl ether Diphenyl Diphenyl ether
-, syndiotactic Poly(propylene), head-to-head
Diphenylmethane p-Ethyl phenol i-Octyl phenol /7-Octyl phenol i-Amyl acetate i-Amylacetate
Poly(vinyl ethylene), at
2-Octanol
Theta temp. (0C)
Method
Refs.
85 32.5 121.0 64.0 48.3 149 31.5 85 32.5 121.0 62.4 55.8 64.0 149 34 34 36.6 25.0 25.0 25.0 65.5 58.0 58.5 25.0 74 68 92 129 153.3 146 25 25 77 37 6 5.0 85.5 70 34 111 140.8 181.8 132 147.2 122 166.0 74 206 183.2 183.2 125.1 125.1 125.0 146.2 145 143 142.8 142.8 116.5 184 115 106 45 43 56.8 32.8
PE, VM PE, VM PE, VM PE, VM A PE, VM VM PE, VM PE, VM PE, VM PE A PE, VM PE, VM VM VM A CP CP CP A VM A CP PE A PE VM PE VM CP CP CP CP CP A A
472 472 472 472 192 472 243 472 472 472 219 192 472 472 69 244 333 78 78 78 333 244 332 78 171,521 314 171,521 244 172 244 78 78 453 453 453 333 152 69 448 448 448 448 448 448 448 521 448 255 448 255 448 244 172 171,521 244 255 448 448 448 448 448 152 471 514 458
PE PE PE PE PE PE PE A PE PE PE PE PE VM PE PE, VM VM PE PE PE PE PE PE A PE VM A, VM
TABLEI. cont'd Polymer (mol/mol) 1.2.
Theta solvent (v/v)
Theta temp. (0C)
Method
Refs.
POLY(ALKENES)
1,4-Poly(butadiene), 97.0% cis 95.0% cis 94.6% cis
94.0% cis 93.0% cis
^-Heptane /7-Propyl acetate Diethyl ketone 5-Methyl-2-hexanone/2-pentanone (1/3) (1/1) (3/1) 3-Pentanone 3-Pentanone/2-pentanone (3/2) Diethyl ketone Ethyl propyl ketone Propylene oxide Diethyl ketone Ethyl propyl ketone Propylene oxide
90.0% cis
-, 70% cis-1,4; 23% trans-1,4; 7% 3,4 -, 43% 1,2 units; trans/cis = 2.3/1 -, 36% cis; 57% trans; 7% 1,2-vinyl -, -, hydrogenated rc-Hexyl 1,4-Poly(butadiene), 9% cyclization 31% cyclization 46% cyclization 63% cyclization 81% cyclization Poly(butadiene-o>-styrene) (76.1/23.9) (75/25) (70/30) 1,4-Poly(chloroprene), cis
/-Butyl acetate n-Heptane/w-hexane (25/75) (50/50) 5-Methyl-2-hexanone 2-Pentanone 3-Pentanone Dioxane Dioxane Dioxane acetate Cyclohexanone/dioxane (12/88) Cyclohexanone/dioxane (17/83) Cyclohexanone/dioxane (21/79) Cyclohexanone/dioxane (30/70) Cyclohexanone/dioxane (39/61) Methyl /-butyl ketone 2-Pentanone /?-Octane /?-Octane Butanone Cyclohexane Cyclopentane Decalin, trans
1 ,4-Poly(2,3-dimethylbutadiene) >85% trans-1,4; 3% 1,2-vinyl 1,4-Poly(isoprene). Natural rubber 96% cis 94% cis trans (gutta percha) trans (other)
-, 51% 1,4-units (mainly trans; 49% 3,4units, 1-2% 1,2-units -, - . hydrogenated -, <5% 1,4-units, 20-25% 1,2-units, 70-75% 3,4-units
-1 35.5 10.3 46.2 32.7 22.3 10.3 30.0 213 240 146 208 14 237 - 22 141 35 20.5 20 5 12.6 59.7 10.6 22.3 15.7 26.5 65.0 30 30 30 30 30 46 21 21 21 25 25 45.5 56.3 2
PE 242 A, VM 242 VM 362 PE 2 PE 2 PE 2 PE 2 PE 2 PE 66 PE 66 PE 66 PE 66 PE 66 PE 66 PE 66 PE 66 PE 66 A, VM 70 PE 282 PE 282 PE 1 PE 1 PE 1 VM 447 A 363 A, VM 480 A 363 A, VM 358 A, VM 358 A, VM 358 A, VM 358 A, VM 358 PE 145 PE 145 VM 284 PE, DM, SM, VM 283 A 133 VM 455,495 PE 133 PE 133 A 455
Cyclohexane//i-propanol (81.3/18.7)
25
CP
483
Butanone H-Hexane/i-Propanol (1/1) 2-Pentanone Dioxane n-Heptane/n-Propanol (69.5/30.5; w/w) Methyl isobutyl ketone Methyl propyl ketone ^-Propyl acetate Dioxane /-Propanol/toluene (36.2/63.8) (35.5/64.5) (34.2/65.8) (33.5/66.5) (32.4/67.6)
25 21 14.5 31.2 25 16.5 33 60 47.7 50 45 40 35 30
VM VM PE PE A, CP, VM A A PE PE A, CP A, CP A, CP A, CP A, CP
88 284 352 11 74 42 42 352 352 11 11 11 11 11
2-Octanol 2-Octanol
41.3 55.3
A A
363 363
2-Octanol
30.5
A
363
References page VII-318
TABLE 1. cont'd Theta temp. (0C)
Polymer (mol/moi)
Theta solvent (v/v)
-, -, hydrogenated 1,4-Poly(isoprene), star 4-arm star 6-arm star 8-arm star 12-arm star 1,4-Poly(isoprene), 94% cis, linear 3 branches 11 branches 22 branches 22 branches l,2-co-3,4-Poly(isoprene) (35/65) 1,4-Poly(isoprene), brominated (30% of double bonds) Poly(isoprene-£/oc/:-styrene) Poly (1 -methyl-1 -butenylene-coisopropenylethylene) Poly(2-methyl-1,3-pentadiene) ( = PoIy(1,3-dimethyl-l-butenylene))
2-Octanol Dioxane Dioxane Dioxane Dioxane Dioxane Methyl propyl ketone Methyl propyl ketone Methyl propyl ketone Methyl propyl ketone Methyl isobutyl ketone Benzene/i-propanol (55/45)
26.2 34.1 33.4 33.5 32.8 32.9 33 33 27.8 23.5 15 20
A A A A A A A A A A A CP
363 130 130 130 20 20 42 42 42 42 42 98
Cyclohexane Butanone
20 44
A VM
310 347
2-Octanol
41.3
A
363
Dioxane 2-Octanol
61.2 28.9
VM VM
454 454
2-Octanol 2-Octanol /-Amyl acetate /-Amyl acetate Cyclohexane
51.0 35.9 38 38 36.0
A VM VM VM A
363 514 347,125 361 491
Butyl acetate /-Propyl acetate Benzene 1-Hexanol 1-Nitropropane
26.8 19.7 20 65.0 31.0 31.0 31 10.9 32.7 32.7
VM VM VM A, PE A, VM A, PE VM A, PE A, PE VM
367 367 168 515 197,465 515 370 515 515 370,473
Poly [ 1 -(4-methylpentyl)-1 -butylene-co l-(l,5-dimethylhexyl)ethylene] Poly(myrcene), 90% 1,4, 10% 3,4Poly(pentenamer), 80-85% trans 85% trans PoIy(I-phenyl-1-propyne) 1.3. POLY(STYRENES) Poly(4-acetoxystyrene) Poly(p-bromostyrene) Poly(p-f-butylstyrene)
3-Nonanol 2-Octanol 2-Octanol Poly(p-f-butylstyrene)-b/0c£-poly(dimethylsiloxane)-b/ocfc-poly(p-f-butylstyrene); 28wt.% butylstyrene units Poly(ochlorostyrene) Poly(p-chlorostyrene)
1-Nitropropane Butanone Butanone Benzene Benzene/methanol (5.5/1) (5.0/1) (4.5/1) n-Butyl acetate f-Butyl acetate n-Butyl carbitol Carbon tetrachloride Carbon tetrachloride/toluene (1/1) (5/2) Cumene Ethyl acetate Ethylbenzene Ethyl chloroacetate Methyl chloroacetate /-Propyl acetate
157 31 25 8 26.7 32.4 41.6 33.7 65.4 50.1 58.9 52.3 50.7 13.4 32.0 60.9 59.0 11.7 -7.5 -14.7 -1.3 -1.8 65.0 64.6 75.7 65.0
Method
PE PE PE, VM PE, VM PE PE PE VM PE PE PE PE PE PE PE PE PE VM PE PE PE PE PE PE PE PE
Refs.
365 365 224 224 139 139 139 195 156 156 196 158 156 196 196 158 157 195 158 156 158 156 158 156 156 158
TABLE 1. cont'd Polymer (mol/mol)
Theta solvent (v/v) /-Propyl benzene /-Propyl chloroacetate Tetrachloroethylene
Poly(p-chlorostyrene-a?-methyl methacrylate) (51.6/48.4) Poly(/?-decylstyrene) Poly(2,5-dichlorostyrene) Poly(3,4-dichlorostyrene) Poly(/?-hexylstyrene)
franj-Decalin/trichloroethylene (78/22) Butanone/ethylbutyl ketone (1/1.24)
Ethanol/ethyl acetate (6.3/93.7; w/w) rc-Butanol/n-butyl acetate (7.1/92.9; w/w) Butanone
Poly(/?-methoxystyrene)
/-Amyl acetate Benzene/cyclohexanol (61.2/38.8) Benzene/n-heptane (72.5/27.5) Benzene/methanol (73.7/26.3) Butanone/n-heptane (80.0/20.0) Butanone/rt-propanol (80.6/19.4) f-Butylbenzene Chloroform/cyclohexane (63.9/36.1) Chloroform/methanol (66.5/33.5) Cyclohexanol/toluene (37.2/62.8) Dichlorodecane Methyl isobutyl ketone
Poly(/?-methoxystyrene-costyrene) 26.4/73.6 53.0/47.0 75.6/24.4
Poly(a-methylstyrene) x% = 0.95; x ss = 0.90 Jt s = 0.91; * ss = 0.81 xs = 0.83; xss = 0.68 Jts = 0.65; xss = 0.44 xss = 0.44 * s = 0.64 atactic
/-Amyl formate /-Amyl formate /-Amyl propionate Hexyl methyl ketone /-Amyl formate /-Amyl propionate f-Butylbenzene Hexyl methyl ketone Cyclohexane Cyclohexane Cyclohexane Cyclohexane Cyclohexane Cyclohexane Benzene/methanol (79.4/20.6) Butanone n-Butyl chloride 1-Chlorodecane 1-Chloroheptane 1-Chlorohexane 1-Chlorooctane Cyclohexane toms-Decalin
isotactic Poly(p,/-propylstyrene) Poly(p,/-propylstyrene-co-styrene) (88/12) (56/44) (33/67) Poly(styrene)
Diethyl succinate w-Hexyl acetate Butanone Dioxane//-propanol (35/65) Dioxane/i-propanol (37/63) Dioxane/i-propanol (44/56) Dioxane/i-propanol (48/52) /-Amyl acetate Benzene Benzene/i-Propanol (58/42) Benzene/cyclohexanol (38.4/61.6) Benzene/n-heptane (44/56)
Theta temp. (0C) 59.0 - 8.2 -8.2 44.4
Method
Refs.
PE PE PE PE
156 156 158 156
VM A PE A A A PE PE A, CP CP A, CP A, CP A, CP PE A, CP A, CP A, CP PE CP
239 464 464 103 102 464 464 281 226 295 226 226 226 281 226 226 226 281 281
30.5 22.8 18.1 27.0 37.0 > 50.0 12.5 > 30 32.3 33.1 34.3 36.8 37.0 39 30 31 -10 139 80.0 20, 27 5.7, 10 43, 53 34.5 38 9.5 10.0 16.4 85.0 45 20
CT CT CT CT CT CT CT CT A A A A VM A, VM
CP
280 280 280 280 280 280 280 280 63 63 63 63 64 3 272 217 536 536 470 479 479 479 479 59 266 479 494 479 217 98
20 20 20 220 -49 249.8 35 25 35
CP CP CP PE PE PE A A, CP A
98 98 98 296 296 460 62 95 62
22.3 21.0 18.1 30.5 32.9 30.0 29.3 75.0 25 25 25 25 25 52.2 25 25 25 92.6 23.4
VM VM VM VM VM VM VM VM A, VM VM
References page VII - 318
TABLE 1. cont'd Polymer (mol/mol)
Theta solvent (v/v) Benzene/n-hexane (38/61) (34.7/65.3) Benzene/methanol (74.7/25.3) (74/26) (77.8/22.2) (78/22) (78/22) Benzene//-propanol (66/34) (64.2/35.8) (69/31) Bicyclohexyl Butanone Butanone/methanol (89/11) (89.7/11.3) (88.9/11.1) Butanone//-propanol (85.7/14.3) (82.6/17.4) (87/13) (87/13) /-Butyl acetate f-Butyl acetate Butylchioride n-Butyl formate Carbon tetrachloride/n-butanol (65/35) Carbon tetrachloride/heptane (53/47) Carbon tetrachloride/methanol (81.7/28.3) Chlorobenzene/di-z-propyl ether (32/68) 1-Chlorodecane l-Chlorodecane/3-methylcyclohexane (21.8/78.2) (25.0/75.0) (50.5/49.5) (90.0/10.0) 1-Chlorododecane Chloroform/methanol (74.7/25.3) (75.2/24.8) 1-Chloroundecane Cyclodecane Cycloheptane Cyclohexane
Theta temp. (0C)
Method
Refs.
20 25 35 34 25 23.5 21.5 20 25 35 61 148.8 25 25 30 23 34 67 67 - 46 - 34.7 109.3 35.6 - 9 -7.5 35 35 25 25 6 6.6 8.5
CP A, CP A VM A, CP A PE CP A, CP A PE PE A, VM A, CP PE A VM A A PE PE PE SM A CP A A A, CP A1 CP CT A VM
128 95 62 31 95 42 42 98 95 62 522 460 273 95 315 53 31 115 274 296 374 374 233 307 375 62 62 95 95 22 269 456
22.8 35.0 59.6 87.8 58.6 58.6 25 25 32.8 32.8 32.8 16 17 19.0 213 34.0 34.0 34.0 34.0 34.4 34.5 34.5 34.5 34.5 34.5 34.5 34.8 35.0 35.0 35.0 35.0 35.0
CT CT CT CT A VM A, VM A, CP A A VM PE PE VM PE VM PE A PE A, VM VM VM A VM DM, VM VM A A DM, SM DM A SM
22 22 22 22 269 456 273 95 269 270 456 445 445 456 371 31 189 307 439 188 2, 476 488 42 290 427 456 270 274 43,308 232 229 144
TABLE 1. cont'd Polymer (mol/mol)
Theta solvent (v/v)
Cyclohexane, deuterated Cyclohexane/methylcyclohexane (2/1) (1/1) (1/2) Cyclohexane/toluene (86.9/13.1) Cyclohexanol
Cyclopentane
Cyclooctane Decalin (wcis = 0) (wcis = 0) (Wc1S=O) (wcis=0) (wcis=0) (w c l s =0.20) (w c i s =0.23) (wcls = 0.50) (wcis = 0.54) (wcis =0.60) (w c i s =0.66) (w cis = 0.80) (wcis = 1.00) (Wcis = 1.00) (Wcis = 1.00) cis/trans cis/trans unknown unknown unknown Diethyl ether/dimethoxy ethane (0.7/0.3) Di(2-ethylhexyl) phthalate Diethyl malonate
Diethyl malonate/diethyl oxalate (4/1) (1/1) (1/4) Diethyl oxalate
Dimethyl succinate Dioctylphthalate
Theta temp. (0C) 35.0 35.0 40.2 40.0 38 43 48 54 15 79 83.5 83.5 83.5 86 87 87.8 19.6 19.6 19.8 20 20.5 20.6 154 154.5 154.2 12 20.5 23.8 22.8 21.2 21.0 20.4 21.2 19.3 15.5 16.0 15.0 15.2 14.0 12.5 12.2 10.8 19.3 14.5 31 29.5 18.2 - 5 - 27 22 31 34.2 34.5 35.6 35.9 36.0 40 47 52.6 51.5 55.8 58.2 59.6 67.6 22
Method
A A PE VM VM VM PE CT A VM A PE PE CT PE A, VM PE VM PE A, VM PE PE VM A CT A DM 1 VM PE 5 VM A PE A A A A A A CP PE A A A DM A A A VM VM PE A VM VM VM VM A VM VM CT VM
Refs. 328 439 328 439 438 2 2 2 315 135 118 290 307 461 8 22 203 368 460 536 456 204 536 368 203 445 456 153 22 26 427 119 26 268 26 160 26 451 26 26 451 523 271 42 289 153 182 356 356 160 307 2 456 42 270 503 2 2 2 307 2 456 22 456 26
References page VII - 318
TABLE 1.
cont'd
Polymer (mol/mol)
Theta solvent (v/v) Dioxane/n-heptane (41.5/58.5) DioxaneM-hexane (38/62) Dioxane/methanol (71.4/28.6) (65.1/34.9) (66.5/33.5) (66.5/33.5) Dioxane/i-propanol (55/45) (51.5/48.5) Ethyl acetate
Ethyl acetoacetate Ethylcyclohexane Heptane/nitropropane (58/42) Heptane/toluene (52.4/47.6) Hexane/3-methylbutanone (48/52) Hexyl m-xylene Methanol/tetrahydrofuran (28.7/71.3) Methanol/toluene (20/80) (23/77) (23.1/76.6) (24.8/75.2) (27.2/72.8) Methyl acetate Methyl cyclohexane
3-Methyl cyclohexanol Methyl cyclopentane D,L-Menthol 1-Phenyldecane i-Propyl acetate n-Propyl acetate
Poly(styrene), deuterated
D,L-Terpineol Tetrahydrofuran/water (92.3/7.7) Toluene (estimated theta temperature) Cyclohexane Cyclohexane, deuterated
Poly(styrene), H-shaped Poly(styrene), head-to-head
Carbondisulfide Cyclohexane Cyclohexane
Poly(styrene), combs (theta temperatures depend strongly on number and length of branches)
Benzene/methanol (78/22) Cyclohexane
Theta temp. (0C)
Method
Refs.
35 20 25 34 35 35 20 35 - 44.3 -44 - 43.5 139 108.5 70 75.0 35 30 20 12.5 25 25 25.0 25.0 34 45.0 43 114 60 67.2 68 68.0 69.3 70.5 70.5 98.0 98.0 75 144 115 28.0 30.6 - 27 107 - 80 178 78.5 25 -154 30 30 36 36 35 36 34.8 19 16
A CP A, CP VM A A 1 VM CP A LS PE CP PE CP PE VM A PE CP A A, CP A, VM CP VM VM VM PE PE VM A A VM A VM VM CT VM PE PE VM A PE PE PE PE PE VM CP
62 128 95 31 62 82 98 62 376 296 375 296 147 114 456 62 315 99 307 95 273 505 490 31,490 490 296 296 290 184 307 456 438 2 85 22 296 440 440 290 124 124 296 296 296 296 290 322 375 328 439 328 439 439 60 372 329 369
16-24 16-24 18-33 18-33 20-36 28-33
A, PE A PE RGM VM A
PE A, VM PE A, VM A, CT A
42 502 42 502 75 294
TABLE 1. cont'd Polymer (mol/mol)
I beta solvent (v/v) Decalin (cis-trans) Diethyl malonate
Poly(styrene), Poly(styrene), Poly(styrene), Poly(styrene),
3-star 9.4-star (6-15.5) stars cyclic
Poly (1,4-divinylbenzene) (soluble; by anionic polymerization) 1.4. POLY(VINYLS) Poly(2,5-dimethyl-4-vinylethynylpiperidol-4) Poly(divinyl ether-c-maleic anhydride methyl ester) (1/2) Poly(isobutyl vinyl ether-a/f-maleic anhydride) Poly(maleic acid-a/f-vinyl pyrrolidone) Poly(2-methyl-5-vinylpyridine)
Cyclohexane Cyclohexane Cyclohexane Cyclohexane
- , grafted by styrene Poly(vinyl alcohol)
PE A, VM PE A, VM A VM A VM A
42 502 42 502 493 486 524 366 373
A
364
Dimethylformamide
25
VM
444
VM VM VM VM VM PE VM PE PE VM PE VM PE PE PE PE PE, VM PE PE A A PE A,PE VM PE CP A PE PE PE PE A,PE A,PE A,PE A PE PE A,PE CP CP A A CP CP CP CP CP CP CP CP
302 235 235 434 434 123 120 123 123 120 123 120 123 123 123 123 123 123 123 167 167 338 316 223 28 147 42 250 250 338 250 316 222 223 42 250 345 223 380 380 42 42 147 147 357 357 357 357 357 258 536
Tetrahydrofuran Acetone NaCl/water (1 mol/1) Acetone/dimethylsulfoxide (65.4/34.6) Na2SO4/water (0.986 mol/1) /-Amyl acetate n-Amyl acetate
Ethyl n-butyrate Ethyl propionate Propionitrile n-Propyl acetate n-Propyl propionate Tetrahydronaphthalene Sodium cacodylate/water (0.1 mol/1) Sodium chloride/water (0.1 mol/1) Acetone/i-propanol (23/77) Butanone/i-propanol (73.2/26.8) rt-Butyl ethyl ketone Cetyl alcohol Di-i-butyl ketone Ethanol Ethanoymethanol (80/20) (60/40) (50/50) (40/60) n-Heptane/3-methylbutanone (26.8/73.2) (27.3/72.7) 3-Heptanone Methanol
-,branched
Refs.
25
/-Butyl methyl ketone
Poly(vinyl acetate)
4.5 4.5 22 22 34.8 22 18-33 40 28.5
Method
Decalin (trans)
/-Butyl acetate n-Butyl acetate
Poly(9-vinyl adenine)
Theta temp. (0C)
6-Methyl-3-heptanone z-Propanol Z-Propanol, deuterated Ethanol 3-Heptanone Di(i-butyl) ketone Ethyl acetoacetate r-Butanol/water (32.0/68.0; w/w) Ethanol/water (41.5/58.5; w/w) Methanol/water (41.7/58.3; w/w) /-Propanol/water (39.4/60.6; w/w) n-Propanol/water (35.1/64.9; w/w) NaCI/water(2mol/l)
30 29.8 25 25 25 53.2 48.2 48.4 49.0 21.8 21.8 37.4 38.7 50.0 25.4 -3.6 19.3 58.0 49.5 26 40 30 25 29.0 123 136.5 19 17 26.5 34 36 25 30 29 29 6 6 66 52.6 51.8 12-15 26 136.5 108.5 25 25 25 25 25 25 27 ± 3
References page VII - 318
TABLE 1. cont'd Polymer (mol/mol)
-, urethanized
4.9% 8.1% 11.5%
Poly(vinyl benzoate) Poly(4-vinyl biphenyl) Poly(vinyl bromide) Poly(vinyl carbanilate)
PoIy(TV-vinyl carbazole)
Poly(vinyl chloride)
Theta solvent (v/v) Water /?-Propanol/water (30/40) (40/50) K-Propanol/water (30/40) (40/50) n-Propanol/water (30/40) (40/50) Xylene 2-Methoxyethanol/dimethoxyethane (70.6/29.4) Methanol/tetrahydrofuran (17/83) Acetone/water (92.2/7.8) Butanone/water (44/56) Diethyl ketone Dioxane/methanol (28/72) Methanol/tetrahydrofuran (71.5/28.5) Chlorobenzene Chlorobenzene/methanol (85.9/14.1) 1,3-Dichlorobenzene/methanol (85.0/15.0) Nitrobenzene Toluene Benzyl alcohol rc-Butanol/cyclohexanone (15.8/100) (43.5/100) Cyclohexane/dimethylformamide (100/12.8) Cyclohexanone Dimethylformamide Methanol/tetrahydrofuran (42/58) Phenetol Tetrahydrofuran/water (100/5) (91.5/8.5) (100/11.9) (100/11.9) (100/9.5) 0-Xylene
-, isotactic and syndiotactic Poly(vinyl /?-chlorobenzoate) rc-Butanol/butanone (47/53) Poly(vinyl cyclohexane) Tetrahydrofuran Poly(vinylethylene) (98% 1,2-, 2% 1,4-) 1-Hexanol Poly (N- vinylimidazole) rc-Butanol Poly(vinyl methyl ether) Cyclohexane Poly(P-vinyl naphthalene) Decalin/toluene (56.5/43.5) Poly(vinyl pivalate) Acetone/methanol (38.2/61.8) Benzene/methanol (33.3/66.7) Butanone/methanol (24.6/75.4) Poly(3-vinylpyrene) Chloroform Methanol/tetrahydrofuran (8/92) Poly(2-vinylpyridine) Benzene
Poly(N-vinyrpyrrolidone)
Poly(vinyl stearate) PoIy(N-vinyl succinamic acid) Poly(vinyl sulfonic acid)
n-Heptane/n-propanol (59.6/40.4; w/w) Acetone/water (66.8/33.2) Dioxane NaCl/water (O.55mol/1) Water n-Octane NaCl/water (0.2mol/l) KBr/water (0.347 molA) KCl/water (0.349 mol/1) (0.65mol/l) (1.001 mol/1) NaBr/water (0.346 mol/1) (1.008 mol/1) NaCl/water (1.003 mol/1)
Theta temp. (0C)
Method
Refs.
97 30 60 30 60 30 60 32.5 30 20 20 20 35 20 20 - 37.4 25 25 -21.4 37 39 155.4 59 72 40.5 22 51 36.5 22 88 17 25 30 30 30 84
PE CT CT CT CT CT CT A A,VM A A A A A A VM CP,VM CP,VM VM A,VM A PE E E E A E E A,CP VM E A CT E CT VM E PE,VM A VM
79 299 299 299 299 299 299 301 237 56 41 41 41 41 41 207 126 126 207 200 249 303 4 4 4 321 4 4 137 377 4 186 253 4 253 377 6 298 97 514 337 520 104 80 80 80 319 319 413 81 378 149 90 39 234 381 313 265 87 87 87 87 87 87 87
60 25 66 25 51 30.2 20 20 20 25 25 11.4 15 16.2 25.0 25.0 -10 25 130.5 17 25 5.7 5.5 26.0 44.5 -0.6 40.1 32.4
A A,VM CP CP CP VM CP,VM VM VM PE CP,VM A PE CT VM VM PE PE PE PE PE PE PE
TABLE 1. cont'd Polymer (mol/mol)
Theta solvent (v/v)
Poly(l-vinyl-l,2,4-triazole)
Dimethylformamide Dimethylformamide/dioxane (76.6/23.4)
Theta temp. (0C)
Method
Refs.
25 25
VM CP
430 9i
25
CP
211
20 25 21
VM A, VM A, RGM
33 463 442
CP A, PE A, VM VM VM VM VM SM, VM DM, SM DM, SM DM, SM DM, SM DM, SM
391 263 536 387 163 384 468 384 306 285 285 285 285 285
1.5. POLY(ACRYLICS) AND RELATED COMPOUNDS Poly(acrylamide)
Methanol/water (2/3) (41/59) NaCl in water (0.1 mol/l)/methanol (59/41)
Poly(2-acrylamido-2-methylpropanesulfone amide) Poly(acrylic acid) Poly (aery lonitrile)
Poly(acrylonitrile-ctf-butadiene) (35/65) (40/60)
Poly(acrylonitrile-c0-methyl acrylate) (95/5) Poly(acrylonitrile-c0-methyl methacryiate) JC AN =0.236 JTAN=0.5 * AN =0.74 Poly(acrylonitrile-costyrene) (1/2) (51/49) Poly(/-butyl acrylate) Poly(f-butyl acrylate-co-vinylidene chloride) (16.7/83.3) Poly(cetyl acrylate) Poly(cyclohexyl methacryiate) Poly(decyl acrylate)
Dioxane/water (18.5/81.5) Dioxane Water/0.2 mol/1 HCl Dimethylformamide/methanol (81/19) Ethylene carbonate Ethylene carbonate/water (85/15; w/w) (85/15; v/v) Nitric acid/water (55/45; w/w) Butanone/cyclohexane (47.5/52.5) Acetonitrile/butanone (79/21) Benzene/cyclohexane (85.5/14.5) Butanone/cyclohexane (47.4/52.5) Butanone/Z-propanol (60/40) Cyclohexane/ethyl acetate (32.7/67.3) Ethylene carbonate/water (82.5/17.5; w/w) Nitric acid/water (51/49; w/w)
24.8 24.8
VM VM
385 385
Benzene Benzene/dimethylformamide (6.5/1) Benzene/dimethylformamide (5/3) Benzene/methanol (66.7/33.3) Dimethylformamide/methanol (44.7/55.3) Ethyl acetate Benzene/methanol (52/48) rc-Hexane
19.8 30 30 25 25 40-43 25 24.2
VM
VM
379 379 379 91 91 216 213 159
PE VM VM A, PE A, PE A, PE A PE A PE PE PE PE PE VM PE
12 341 450 340 340 340 388 388 388 388 212 212 212 212 323 12
Benzyl alcohol Butyl acetate w-Butanol /-Amyl alcohol n-Butyl alcohol Ethyl acetate n-Hexanol n-Pentanol
Poly(ethyl acrylate)
n-Butanol Ethanol Methanol w-Propanol
Poly(ethyl acrylate-co-vinylidene chloride) (14.9/85.1) Poly(hexyl acrylate-co-vinylidene chloride) (14.5/85.5) Poly(hexadecyl acrylate)
Ethyl acetoacetate Benzyl alcohol rc-Heptanol fl-Hexanol
Poly(phenyl aerylamide) Poly(Af-/-propyl acrylamide)
25 30 14 db 5 20 60 29.3 44 25 25 19-22 19-22 22 20 19-22
Water Dioxane Water
44 15.2 23.0 - 8.5 - 24.5 9-11 34 43.2 70 75.6 44.9 37.4 20.5 39.5 39.5 49.6
CP CP PE
56.8
PE
12
20.5 30.1 52.2 60.2 -8 20 31 30.6 30.6 20
A PE A PE A
388 388 388 388 441 389 142 390 534 382
PE VM LS VM
References page VII - 318
TABLE 1. cont'd Polymer (mol/mol)
Theta solvent (v/v)
Poly(i-propyl acrylate), atactic
l,2-Butanediol/l,3-butanediol (68.4/31.6) n-Decane l,2-Butanediol/l,3-butanediol (68.4/31.6) n-Decane n-Decane
isotactic syndiotactic Poly(n-octyl acrylate-co-vinylidene chloride) (15.5/84.4) Poly(phenyl acrylate) Sodium poly(acrylate)
Benzyl alcohol Ethyl lactate NaBr/water (1.504 mol/1)
Theta temp. (0C) 121.0 166.6 123.5 178.0 168.3 77.9 11.7 13.8 15.0
Method
Refs.
PE PE PE PE PE
218 218 354 354 218
PE A, CP VT A
12 146 383 452
1.6. POLY(METHACRYLICS) AND RELATED COMPOUNDS Poly(benzyl methacrylate) PolyO?-biphenyl methacrylate) Poly(DL-*'-bornyl methacrylate) Poly(4~f-butylcyclohexyl methacrylate) Poly(n~butyl methacrylate)
Poly(z-butyl methacrylate), isotactic
Cyclohexanone Cyclopentanol Benzene 1-Octanol Cyclohexane n-Butanoi i-Butanol n-Decane Dimethylformamide n-Dodecane Ethanol n-Hexadecane Methyl carbitol Methyl cellosolve n-Octane *-Propanol
Poly (/-butyl methacrylate)
Dimethylformamide Methyl carbitol Methyl cellosolve Cyclohexane
Poly(2-*-butylphenyl methacrylate) PoIyO?-r-butylphenyl methacrylate) Poly(2-chloroethyl methacrylate) Poly(cyclobutyl methacrylate) Poly(cyclobutylmethyl methacrylate) Poly(cyclododecyl methacrylate) Poly(cyclohexyl methacrylate)
n-Heptane Cyclohexane Cyclohexane o-Dichlorobenzene /i-Butanol n-Butanol Hexyl acetate n-Butanol
Poly(cyclooctyl methacrylate) Poly(cyclopentyl methacrylate) Poly(decyl methacrylate) Poly(2,6-dimethylphenyl methacrylate) Poly(2,6-diisopropylphenyl methacrylate)
n-Decane n-Decanol n-Dodecane n-Hexanol n-Nonanol n-Octane n-Octanol n-Propanol 2-Butanol Cyclohexane Ethyl acetate n-Pentanol Toluene Tetrahydrofuran/water (90.6/9.4) Tetrahydrofuran/water (90.1/9.1)
73.2 83.5 10 39.6 -133 40 10.7 84.8 23.6 101 «45 119.8 87.9 59.6 68.9 20.9 21.5 23 23.7 25 48.1 115.6 74.9 10 10 64 18.5 25 35.7 37.5 40.0 35 22.5 22.5 22.5 93.6 23.0 97.5 9.2 20.2 83.4 17.9 39.5 45 36 11 9.6 25.0 25.0 25
PE,VM A VM A VM VM PE VM IG VM PE PE VM VM A,VM IG A, PE A PE PE PE VM PE PE PE,VM VM A PE VM PE A,VM VM VM VM VM VM VM VM VM VM VM PE A A PE A A VM
291 292 129 396 288 288 205 205 254 205 412 205 254 254 205 205 50 412 54 348 254 254 254 466 518 518 336 121 397 404 504 404 166 131 312 312 312 312 312 312 312 312 312 404 404 401,457 140 411 411 467
TABLE 1. cont'd Polymer (mol/mol)
Theta solvent (v/v)
Poly(diphenylmethyl methacrylate) Poly(docosyl methacrylate) Poly(dodecyl methacrylate) Poly(ethylbutyl methacrylate) Poly(ethyl methacrylate)
3-Heptanone Amyl acetate /z-Amyl alcohol i-Propanol Butanone/*-propanol (12.5/87.5) /i-Butyl bromide Methyl «-propyl ketone /-Propanol m-Xylene
Poly(glycidyl methacrylate-co-lauryl methacrylate) (3/97)
Poly(«-hexyl methacrylate)
Ethanol/rc-heptane (69/31) (62/38) (56/44) (49/51) n-Heptane/Az-propanol (56/44) (70/30) j'-Propanol rt-Propanol
Poly(2-hydroxyethyl methacrylate), it
Poly(isobutyl methacrylate) Poly(rc-lauryl methacrylate)
Urea/water (4 mol/1) (6mol/l) (8 mol/1) 2-Butanol Ethanol 1-Propanol 2-Propanol Water 2-Hydroxymethyltetrahydrofuran /-Propyl acetate n-Pentanoi
Poly(5-p-menthyl methacrylate) Poly(methacrylic acid)
Poly(rnethacrylonitrile) Poiy(hexyleneoxyphenylenecarboxyphenyleneoxymethylene methacrylate) Poly(methyl w-butacrylate) Poly(methyl ethacrylate) Poly(methyl methacrylate)
2-Pentanone Dioxane/dimethylformamide (7/5) HCl/water (0.002 mol/1) Methanol NaCl/water (0.5 mol/1) (0.05 mol/1) Dimethylformamide Toluene Toluene-d8 n-Butanol DiO'-butyl) ketone Acetone Acetone/ethanol (47.7/52.3) Acetone/methanol (78.1/21.9) Acetonitrile
Acetonitrile/butanol (93/7) Acetonitrile/methanol (90/10) Acetonitrile/pentyl acetate (93/7) Acetonitriie/n-propanol
Theta temp. (0C)
Method
45 31 29.5 27.4 23 0 -1 36.9 36.9 -3
PE,VM A A,VM A, PE A, PE VM VM A, PE VM VM
405,478 401,457 247 77 52 349 349 54 474 349
-24 1 24 40 1 24 32.6 37 20.0 21.3 10 27.2 52.5 3.7 15.8 32.1 14.0 15.3 19.5 13 13 29.5 29.5 25 26.9 30 151 26 43 68 29.2
CP CP CP CP CP CP A, PE VM A PE VM VM VM VM VM VM VM VM PE A, PE PE, VM A, PE VM VM VM VM PE VM A A VM
257 257 257 257 257 257 47 34 388 388 86 86 86 484 484 484 484 484 507 48 489 206 208 336 392 165 393 394 164 164 275
15.5 6.5 13 11.4 -126 - ( 5 5 ±10) 25 25 28 30 30.5 32.3 38 44 44 44.0 45 ±10 60 25 25 25 25
A A A A VM A, CP VM VM A,VM RGM A, VM VM A DM,VM RGM VM PE, VM A A A A
Refs.
402 402 155 155 288 112 96 278 278 57 414 409 162 407,410,519 427 512,513 112 112 220 220 220 220
References page VII - 318
TABLE 1. cont'd Polymer (mol/mol)
Theta temp. (0C)
Theta solvent (v/v) /-Amyl acetate n-Amyl acetate n-Amyl methyl ketone Benzene Benzene/Vhexane (70/30) 2-Butanol/l-chlorobutane (80/20) Butanone Butanone/cyclohexane (59.5/40.5) Butanone/n-hexane (70.7/29.3) Butanone/i-propanol (58.2/41.8) (55/45) (55/45) (38/62) (50/50) (50/50) (50/50) (50/50) (58.2/41.8) (46.8/53.2) 2^Butoxyethanol «-Butyl acetate n-Butyl chloride
Carbon tetrachloride Carbon tetrachloride/rc-hexane (99.4/0.6) Carbon tetrachloride/methanol (53.3/46.7) Chloroform Cyclohexane/dioxane (53/47) (53.4/46.6) Cyclohexanol Cyclohexanone/j-propanol (51.6/48.4) Decalin (trans) Dichloroethane 2,2-Dimethyl-4-pentanone 2,4-Dimethyl-3-pentanone DioxaneM-hexane (59/41) Dioxane/water (85/15) 2-Ethoxyethanol Ethyl acetate Ethyl 2-Heptanone
tt-butyraldehyde
3-Heptanone 4-Heptanone n-Hexane/3-methyl-2-butanone (17/83) rc-Hexane/toluene (18.8/81.2) Methanol/toluene (64.3/35.7)
57.5 41 15 -223 20 39.2 -98 25 25 4 7.0 12.8 20 22.8 25 25 25 25 28.5 75.0 75.0 -20 32.6 34.0 35.0 35.0 35.0 35.4 35.4 40.6 40.8 40.8 40.8 27 25 25 -273 20 25 77.6 21-22 23.5 -233 35 41 46 20 25 27.1 30.1 37.8 -98 22 11 11.5 25 33.7 33.8 34 ± 1 0 40.4 20 25 26.2
Method A VM VM VM CP A VM A, CP A, CP A A A CP A PE VM A A A VM VM A A VM A RGM A VM A DM,VM RGM A VM CP CP VM A,VM A,CP VM VM VM PE VM PE CP A VM VM A,VM VM PE VM RGM VM PE PE VM A CP CP A, PE
Refs. 174 112 293 112 128 403 112 96 96 174 311 174 128 174 300 32 49 96 174 278 443 174 173 278 311 414 509 174 400 407 427 512,513 519 112 96 96 112 82 96 117 279 277 112 112 32 112 98 343 443 278 409 112 112 112 414 112 300 112,516 112 174 99 96 54
TABLE 1. cont'd Polymer (mol/mol)
Theta solvent (v/v) 2-Methoxyethanol Methyl *-butyrate Methyl methacrylate 2-Methyl-4-pentanone Methyl i-valerate Nitrobenzene//-propanol (51.6/48.4; w/w) Nitromethane 2-Octanone 3-Octanone Tetralin Toluene
A-, =0.07 x, =0.08 A, =0.09
x, =0.94
x,: = 1.00
Poly(methyl methacrylate-co-9,10-anthrylenedimethyl dimethacrylate (99.86/0.14) Poly(methyl methacrylate-/?/
Poly(methyl methacrylate-a/f-styrene) (50/50) Poly (methyl methacrylate-fr/c>cA: styrene) (14.9/85.1) (15.4/84.6) (26.8/73.2) (27.6/72.4) (various) (50/50) (50/50) (50.4/49.6) (50.4/49.6) (51.4/48.6) (51.4/48.6) (64.1/35.9) (64.1/35.9) Poly(methyl methacrylate-cc-styrene) (23.7/76.3)
(29.8/70.2) (30.6/69.4) (41.9/58.1)
(43.8/56.2) (44.8/55.2)
m-Xylene /7-Cymene n-Propanol Acetonitrile Butanone//-propanol (50/50) p-Cumene 3-Heptanone n-Propanol Acetonitrile Butanone//-propanol (55/45) «-Butyl chloride ButanoneA'-propanol (55/45) /1-Butyl chloride tt-Propanol
Theta temp. ( 0 C) -2 - 2 - (53 ±10) -163 -42 - 37 18 32.0 60 72 74 - ( 6 5 ±10) - 178 24 159.7 84.4 43.0 30.3 152.1 40.0 75.9 27.6 25.0 26.5 8.0 26.5 85.2
Method VM VM VM VM A A VM RGM PE PE CT VM PE VM PE PE A PE PE PE PE PE A A A A PE
Refs. 278 443 112 112 174 174 227 414 112 112,516 147 112 408 277 300 300 511 300 300 300 300 187 311 311 311 311 300
Toluene/octane (78/22)
25
PL
399
1-Chlorohexane 3-Heptanone 2-Methyl cyclohexanol 2-Octanone
93 84 62 94
PE PE PE PE
179 179 179 179
Cyclohexanol
60.8
A,VM
181
Cyclohexanol
2-Ethoxyethanol
84 84 84 84 82 81.6 81.1 81.3 81.0 81.0 81.3 80.5 69.5
A,VM A A, VM A PE A A, VM A,VM A,VM A A A A
181 267 180 267 179 118 181 180 180 267 267 267 267
BenzeneM-hexane (44/56) Benzene/?-propanol (57/43) /7-Hexane/3-methylbutane (40/60) Cyclohexanol 2-Ethoxyethanol Cyclohexanol 2-Ethoxyethanol BenzeneM-hexane (51/49) Benzene//-propanol (51/49) /?-Hexane/3-methylbutanone (34/66) Cyclohexanol 2-Ethoxyethanol Cyclohexanol 2-Ethoxyethanol
20 20 20 63.0 72.8 63.0 72.8 20.0 20.0 20.0 61.3 58.4 61.3 58.4
CP CP CP A5VM A,VM A A CP CP CP A,VM A,VM A A
99 99 99 180 180 267 267 99 99 99 180 180 267 267
2-Ethoxyethanol Cyclohexanol
References page VII - 318
TABLE 1. cont'd Polymer (mol/mol)
Theta solvent (v/v) (48.0/52.0) (50.0/50.0) (51.4/48.6) (57.7/42.3) (64.1/35.9) (70.7/29.3) (71.5/28.5) (73.9/26.1)
Poly(P-naphthyl methacrylate) Poly(octadecyl methacrylate) Poly(n-octyl methacrylate) PolyO-octyl methacrylate) PolyO'-octyl methacrylate-o?-styrene) (20/80) Poly(pentachlorophenyl methacrylate)
Cyclohexanol Cyclohexanol Cyclohexanol 2-Ethoxyethanol Benzene/n-hexane (59/41) Benzene/i-propanol (48/52) n-Hexane/3-methylbutanone (29/71) Cyclohexanol 2-Ethoxyethanol Cyclohexanol 2-Ethoxyethanol Cyclohexanol 2-Ethoxyethanol Benzene/«-hexane (62/38) Benzene/n-propanol (41/59) H-Hexane/3-methylbutanone (24/76) Tetralin Toluene Butyl acetate n-Butanol Acetone/n-heptane (64.1/35.9) Butanone/methanol (99.4/0.6) Benzene Benzene/ethylbenzene (5/5) Benzene/toluene (1/9) (5/5) Chloroform o-Dichlorobenzene Ethylbenzene
Poly(4-phenylbutyl-l-methacrylate) Poly(2-phenylethyl-l -methacrylate) Poly(phenyl thiolmethacrylate) Poly(stearyl methacrylate) Poly(tetrahydrofurfuryl methacrylate)
Theta temp. (0C) 61.6 68.6 81.3 81.0 20 20 20 80.5 69.5 68.0 40 68.2 40 20 20 20 20 52 10.5 16.8 25 25 37 40 30 10 14 35 -126 25 25 25 23.0 27.5 25 36 31.2
Poly(tetrahydro-4#-pyranyl-2-methacrylate) Poly(2,4,5-trichlorophenyl methacrylate)
1-Chloroundecane 1-Chloroheptane Butanone Propyl acetate 2-Hydroxymethyltetrahydrofuran/methanol (80/20) i-Butanol Benzene
Poly(tridecyl methacrylate)
Ethyl acetate
30.5 21.8 25.0 27
Acetone/methanol (99/1) Acetone/water (98/2) Benzene/methanol (60/40) Butanone/methanol (63/37) Chloroform/methanol (52/48) Ethyl acetate/methanol (65/31) Methanol/toluene (43/57) Tetrahydrofuran/water (87.4/12.6) Acetone/methanol (99/1) Acetone/water (97/3) Benzene/methanol (42/58) Butanone/methanol (38/62) Chloroform/methanol (40/60) Ethyl acetate/methanol (40/60) Methanol/toluene (54/46) Benzene/methanol (82/18) Chloroform/methanol (75/25) Methanol/toluene (21/79) Acetone/water (91/9) Benzene/n-heptane (53/47)
30 30 30 30 30 30 30 25.0 30 30 30 30 30 30 30 30 30 30 30 30
Method A, VM A A
Refs.
R, VM VM VM VM A PE,VM
181 118 178 178 99 99 99 178 178 180 180 267 267 99 99 99 264 264 406 51 161 161 287 24 287 287 287 287 288 287 288 24 477 477 176 401,457 359
A VM VM A
481 395 398 401,457
CP CP CP CP CP CP CP VM CP CP CP CP CP CP CP CP CP CP CP CP
350 350 350 350 350 350 350 470 350 350 350 350 350 350 350 350 350 350 350 350
CP CP CP A A A, VM A, VM A A CP CP CP VM VM A A, PE A, CP A, CP PE R5VM PE PE PE PE PE
1.7. OTHER CARBON CHAINS Poly[di(rt-amyl) itaconate]
Poly(dibenzyl itaconate) Poly[di(n-butyi) itaconate]
Poly[di(n-decyl) itaconate] Poly(diethyl itaconate)
TABLE 1. cont'd Polymer (mol/mol)
Poly[di(rc-heptyl) itaconate] Poly[di(n-hexyl) itaconate]
Poly(dimethyl itaconate)
Poly(N-2,4-dimethyl phenylmaleimide) Poly[di(rc-nonyl) itaconate] Poly[di(rc-octyl) itaconate]
Poly[di(n-propyl itaconate] Poly[di(«-undecyl) itaconate] Poly[/V-(rt-octadecyl) maleimide]
Poly(mono(n-octyl) itaconate) Poly(tetrafluoroetnylene-c0trifluoronitrosomethane (1/1)
Theta solvent (v/v) Butanone/mineral spirits (34/66) Ethanol/water (91/9) Benzene/methanol (42/58) Butanone/methanol (88/12) Benzene/methanol (64/36) Butanone/methanol (68/32) Chloroform/methanol (64/36) Ethyl acetate/methanol (78/22) Methanol/toluene (28/72) Acetone/methanol (71/29) Acetone/water (80/20) Benzene/n-hexane (93/7) Benzene/methanol (41/59) Butanone/cyclohexane (86/14) Butanone/n-hexane (90/10) Butanone/methanol (62/38) Chloroform/methanol (32/68) Ethanol/water (95/5) Butyl acetate Ethanol/water (5/95) Benzene/methanol (80/20) Butanone/methanol (99/1) Chloroform/methanol (71/29) Ethyl acetate/methanol (99/1) Methanol/toluene (22/78) Acetone/water (94/6) Ethanol/water (8/2) Benzene/methanol (83/17) Chloroform/methanol (77/23) w-Butanol n-Decanol «-Hexanol H-Octanol 2-Propanol Trichlorotrifluoroethane
Theta temp. (0C)
Method
Refs.
30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 21 30 30 30 30 30 30 30 30 30 30 120.5 39.3 78.9 53.6 30
CP CP CP CP CP CP CP CP CP CP CP CP CP CP CP CP CP CP DM,VM CP CP CP CP CP CP CP CP CP CP CP,VM CP1VM CP,VM CP,VM VM
350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 342 350 350 350 350 350 350 350 350 350 350 17 17 17 17 386
VM
248
35
TABLE 2. HETEROCHAIN POLYMERS Polymer (mol/mol) 2.1.
Theta solvent (v/v)
Theta temp. (0C)
Method
Refs.
POLY(ACETALS) AND POLY(ETHERS)
Poly(oxy-2,6-dimethyl-l,4-phenylene) Poly(oxyethylene); polyethylene oxide)
Methylene chloride Acetonitrile//-propyl ether (45/55) Benzene/i-octane (100/48) CaCl 2 /water(2mol/l) ChloroformM-hexane (54/46) (47.4/52.6) CsCl/water(2mol/l) Diethylene glyeol diethylether KCl/water(2mol/l) KF/water(0.30mol/l)
(0.50mol/l) (0.80mol/l) (1.00mol/l) KNO3/water (2mol/l) KOH/water(1.24mol/l) K 3 PO 4 /water(0.20mol/l)
89.2 20 70.8 71 82 86 20 20 60 50 54 57 78.0
VM CP CT PE CT CT CP CT,VM CT VM CT CT PE
66.0 49.0 38.0
PE PE PE
65 25 63.0
CT PE, VM PE
317 98 134 8 260 36 98 90 260 25 36 260 482
482 482 482 36 416 482
References page VII - 318
Table 2.
cont'd
Polymer (mol/mo!)
Theta solvent (v/v) (0.30mol/l) (0.35 mol/1) (0.40mol/l) K 2 SO 4 /water(0.45mol/l)
LiCl/water (2mol/l) Methyl /-butyl ketone MgCl 2 /water(2mol/l) MgSO4/water (0.39 mol/1)
NaCl/water (2mol/l) Na acetate/water (0.75 mol/1) (1.50mol/l) (2.00 mol/1) (3.00 mol/1) Na 2 S 2 O 3 (0.20mol/l) (0.30 mol/1) (0.40 mol/1) (0.50 mol/1) NH 4 Cl/water(2mol/l) Nitroethane//-propyl ether (45/55) RbCl/water(2mol/l) SrCl 2water (2 mol/1) ZnSO4/water (0.30mol/1) (0.35 mol/1) (0.45 mol/1) 21 salts in water (various concentrations) Water
Poly(oxyethylethylene), poly(butylene oxide) Poly(oxy(2-hydroxytrimethylene)oxy1,4-phenylene-isopropylidene1,4-phenylene) Poly(oxypropylene); poly(propylene oxide) Poly(oxytetrafluoroethylene)-co poly(oxydifluoromethylene) (40/60) Poly (oxytetramethylene); poly(tetrahydrofuran)
Theta temp. (0C) 45.0 38.0 26.0 34 34 35 35 90 90 50 80 90 42 42 42 45 60 61 75.0 55.0 45.0 31.0 74.0 63.0 52.0 41.0 76 77 20 56 73 82 54.0 48.0 35.0 97 5.1 96 102 103 108.3 117 92-109
Method
Refs.
PE PE PE CT CT PE VM CT CT VM CT CT CT CP
DM,VM CT A VM VM CT VT
482 482 482 259 36 13 25 36 260 25 260 36 259 36 536 13 260 260 482 482 482 482 482 482 482 482 260 36 98 260 260 36 482 482 482 417 45 36 418 416 419 260 383
PE CT CT PE PE PE PE PE PE PE PE CT CT CP CT CT CT PE PE PE
/-Propanol
29.8 30
VM VM
225 35
Cyclohexanone/toluene (32.5/67.5) Tetrahydrofuran/toluene (2/1) /-Octane
22 30 50
VM SM A
194 37 10
Freon TF
25
VM
415
Acetonitrile/benzene (61.5/38.5) Acetonitrile/butanone (38.3/61.7) Acetonitrile/carbon tetrachloride (50.2/49.8) Acetonitrile/chlorobenzene (60.1/39.9) Acetonitrile/tetrahydrofuran (58.7/41.3) Acetonitrile/toluene (61/39) rc-Butanol Butanone Chlorobenzene ChlorobenzeneM-octane (25.0/75.0) (21.5/78.5)
25 25 25 25 25 25 5 25 25 10 25.8
CP CP CP CP CP CP PE VM VM A, CP A, CP
94 94 94 94 94 94 107 214 214 106 106
Table 2. cont'd Polymer (mol/mol)
Theta solvent (v/v) (14.5/85.5) (13.0/87.0) (10.9/89.1)
Method
Refs.
i-Propanol Toluene Cyclohexane
46.0 63.0 80.0 26 33.5 30.4 33 44.6 28.3 27
A, CP A, CP A, CP VM PE PE A PE A PE
Cyclohexane/dioxane (32/68) s-Tetrachloroethane
25 25
CP VM
437 446
Dichloroethane Chloroform/heptane (50.2/49.8) 2,2,2-Trifluoroethanol/water (52.6/47.4)
25 25 25
A CP CP
420 421 421
Toluene
17.0
A, VM
506
Cyclohexanol
64
PE
360
Chloroform/n-hexane (65/35) (63/37) (62/38) (60/40) (59/41) (57/43) (56/44)
20 20 20 20 20 20 20
CP CP CP CP CP CP CP
98 99 98 98 98 98 98
BenzeneM-hexane (83.3/16.7) Cyclohexanol Chiorobenzene/K-hexane (75.9/24.1) rc-Hexane/nitrobenzene (43.3/56.7) Benzene/n-hexane (85.1/14.9) Chiorobenzene/rc-hexane (70.2/29.8) Nitrobenzene/rc-hexane (67.0/33.0)
25 77 25 25 25 25 25
CP PE CP CP CP CP CP
175 360 175 175 175 175 175
n-Butyl benzyl ether Chloroform Chloroform/ethanol (74.5/25.5) Cyclohexane/dioxane (36.1/63.9; w/w) Cyclohexanol Cyclohexanol
170 20 18 25 114.5 88
A A CP VM PE PE
27 73 193 241 360 360
Cyclohexane/dichloroacetic acid (6/4) Benzene/n-hexane (48.3/51.7) BromobenzeneM-hexane (45.0/55.0) ChlorobenzeneM-hexane (37.5/62.5)
25 25 25 25
A,VM CP CP CP
344 175 175 175
Butyl chloride
13
A,VM
143
Acetonitrile//-propyl ether (35.8/64.2) Chloroform/rt-hexane (56/44)
20 20
CP CP
98 98
^-ButanolM-heptane (81/19) Ethanol/n-heptane (39/61) (51/49) (59/41) /i-Heptane//i-propanol (35/65) (16/84)
1 1 24 40 1 24
CP CP CP CP CP CP
257 257 257 257 257 257
Cyclohexane/rc-heptane Diethyl malonate Ethyl acetate/n-hexane (22.7/77.3)
Poly(oxytrimethylene)
Theta temp. (0C)
106 106 106 214,228 105 105 199 105 9 55
2.2. POLY(ESTERS) Poly(bisphenol A-co-(isophthalic acid 4terephthalic acid; 1:1) Poly(decamethylene perfluorosebacate) Poly(diphenylphthalide dicarboxylic acida/f-/?,p'-dihydroxydiphenyl) Poly(P-hydroxybutyrate) Poly( 1 -(6-[4-(4-methoxyphenoxycarbonyl)phenoxyjhexyloxycarbonyl)-1 -methylethylene) Poly(oxyadipoyloxyhexamethylene); poly(hexamethylene adipate) Poly(oxyadipoly-poly(oxyethylene) mol. wt. of PEOX = 150 200 300 387 600 2580 7000 Poly(oxyadipoyloxytetramethylene); poly(tetramethylene adipate)
Poly(oxycaproyl); poly(£-caprolactone) Poly(oxycarbony loxy-1,4-pheny leneisopropylidene-1,4-phenylene); bisphenol A polycarbonate
Poly(oxyethyleneoxyadipoyl) Poiy(oxyethyleneoxysuberoyl) Poly(oxyethyleneoxyterephthaioyl); polyethylene terephthalate) Poly(oxyoctamethyleneoctasebacoyl) DL-Poly(oxy( 1 -oxo-3-methyltrimethylene)) poly(DL-^-methyl-propiolactone) Poly(oxy sebacoy loxy-poly (oxyethylene)); mol. wt. of PEOX = 387 Poly (12-oxy stearoy 1); poly(12-hydroxystearic acid)
References page VII-318
Table 2. cont'd Polymer (mol/mol) Poly(oxysuberoyl-poly(oxyethylene)) mol. wt. of PEOX = 387 Poly(oxysebacoyloxy-poly(oxyethylene)); mol. wt. of PEOX = 387 Poly(phenolphthalein-a/f-terephthalic acid) Poly[2,2-propane-bis(4-phenylthiocarbonate)] 2.3.
Theta solvent (v/v)
Theta temp. (0C)
Method
Refs.
Acetonitrile/i-propyl ether (38.6/61.4) Chloroform/n-hexane (58/42)
20 20
CP CP
98 98
Acetonitrile/i-propyl ether (35.8/64.2) ChloroformM-hexane (61/39) Tetrahydrofuran Chloroform/cyclohexane (76.5/23.5)
20 20 19 25
CP CP A VM
98 98 420 469
Dioxane/water (18.5/81.5) Dichloroethane/diethylene glycol (80/20)
25 25
A,VM A
475 209
Carbon tetrachloride/methanol (81.5/18.5) Methanol/toluene (19.5/80.5)
25 25
CP CP
Carbon tetrachloride/m-cresol/cyclohexane Formic acid/KCl/water
20 25
SM A,VM
335 101
CaCl2/methanol (15g/dl) Chloroform/perfluoro alcohol (7/3) m-Cresol/decalin (25/75) KCl in formic acid (2.3 mol/l)/water (90/10)
35 25 30 25
VM PE CT VM
256 198 148 422
POLY(AMIDES)
Poly(2-acrylamido-2-methylpropane sulfonamide) Poly(y-benzyl-L-glutamate) Poly ([n-hexylimino)carbony 1]; poly(n-hexyl isocyanate) Poly(iminoadipoyliminohexamethylene); poly(hexamethylene adipamide) Poly (imino( 1 -oxohexamethy lene)); poly(e-caprolactam)
Poly(iminoterephthaloylimino2,2,4/2,4,4-trimethylhexamethylene) Poly |7V-methylimino( 1 -oxodecamethylene)]; poly(N-methyldodecane lactam) Poly(L-proline) Poly(pyromellitic acid-c-4-amino-1,4phenyleneoxy-l,4-phenyleneamine) Poly(pyromellitic acid-co-4-amino-1,4phenyleneoxy-1,4-phenyleneoxy1,4-phenyleneamine)
29 29
Aniline Pyrroline
142 62
CT, PE PE
141 141
Dioxane Trifluoroethanol Water
30.5 130 100
A,VM A A
286 227 227
Dimethylacetamide/dioxane (1/2.5)
21
A,VM
449
Dimethylacetamide/dioxane (1/7.5)
21
A,VM
449
Dimethylformamide
82
VM
318
Acetone/dimethylformamide (21/79)
25
VM
23
Butanol/l,2-dichloroethane (38/62)
30
VM
435
Dichloroacetic acid Sulfuric acid (90%) 2,4,4-Trimethyl pentane
46 46 39.5
VM VM VM
109 109 236
Water Acetone/dimethyl sulfoxide (43.5/56.5) Dimethyl sulfoxide/methanol (49/51) Dimethyl sulfoxide/0.5 mol/1 KCl in water (25/75) Guanidinium chloride in water (4.2 mol/1) 0.33 mol/1 KCl in water
25 20 25.0
A VM VM
325 40 61
25 25 22.5 25 25 25 155 159.8 37 49
VM VM VM VM VM A PE PE PE PE
61 424 14 108 61 15 330 426 331 426
2.4. POLYUREAS, POLYURETHANES AND OTHER NITROGEN CHAINS Poly( 1,4-butylene glycol-c-4,4 '-diphenylmethanediisocyanate-co-poly(oxycaprolyl)) Poly(ethylene glycol-co-4,4; -dipheny 1methane diisocyanate) Poly[2-methoxy-4,6-di(p,p/-isopropylidene diphenyloxy) j-triazine] Poly(ureylene heptamethylene); Poly(heptamethylene urea) Polyurethane from polypropylene glycol and 2,4,4-tolylene diisocyanate 2.5.
POLYSACCHARIDES
Amylopectin Amylose
Amylose tricarbanilate Cellulose diacetate
Sodium acetate buffer Pyridine/water (86.7/13.3) Acetone Butanone
Table 2. cont'd Polymer (moi/mol)
Theta solvent (v/v)
Cellulose triacetate
Acetone
Cellulose tributyrate Cellulose tricaproate Cellulose tricaprylate
Tetrachloroethane Dimethylformarnide Dimethylformarnide 3-Phenylpropanol Anisole Cyclohexanol Water Water
Cellulose tricarbanilate Dextran Hydroxyethyl cellulose
Theta temp. (0C)
Method
Refs.
A PE PE PE PE A A PE PE A A A A
332 426 331 65 65 150 191 215 215 425 425 535 423
23.5 23.5 25
CP
501 501 261
105.5 26.8 25.0
VM PE VM
428 436 500
29.5 -7 -5.2 - 3 25 25 25 25 25 25 78.3 78.7 28 36.8 39.0 36.3 19.8 19.8 20.0 20.0 20.0 -38.2 -19.2 68 56.3 -81 -68.2 25 87 63 65 67 ± 2 4.8 18 2.1 -173.2 -173.2 -113.2
A A VM A CP CP CP CP CP CP VM A VM VM A A PE VM A PE A VM VM A A A VM CP PE CT PE
68 202 201 202 94 94 94 94 94 94 201 309 433,459 201 209 309 432 201 67 111 202 201 201 202 309 202 201 94 71 72 72 536 201 202 309 201 201 201
50 158.8 170 27 181 56.6 41 140 48 94 73 101.8 - 73
2.6. CARBON-SULFUR CHAINS Poly(arylate-arylenesulfonoxide) Poly(arylate-&/c>c&-arylenesulfonoxide) Poly(propylene sulfide) Poly(sulfonyl-1,4-phenyleneoxy1,4-phenylene-dimethylmethylene1,4-phenylene-oxy) Poly(arylene sulfonate) Poly(diphenylether sulfone)
Dioxane Dioxane n-Heptane/toluene (31.5/68.5) Dimethylsulfoxide Dioxane Dimethylformamide/methanol (83/17)
2.7. SILICON-OXYGEN CHAINS Poly(oxydimethylsilyiene) poly(dimethyl siloxane)
Acetone/toluene (6/5) Benzene Benzyl alcohol/carbon tetrachloride (21.2/78.8) Benzyl alcohol/chloroform (12.8/87.2) Benzyl alcohol/ethyl benzene (14.6/85.4) Benzyl alcohol/methylene chloride (22.7/77.3) Benzyl alcohol/trichloroethylene (21.7/78.3) Benzyl alcohol/toluene (16.2/83.8) Bromobenzene Bromocyclohexane Bromocyclohexane/phenetole (85.7/14.3) Butanone
n-Butyl acetate Chlorobenzene Chlorobenzene/dimethyl phthalate (88.2/11.8) Cyclohexane Cyclohexanol/toluene (34/66) Dichlorobenzene Ethanol/n-heptane (49/51) Ethyl acetate Ethyl iodide ^-Heptane rc-Hexane Methylcyclohexane
VM A A VM VM VM
References page VII-318
Table 2. cont'd Polymer (mol/mol)
Theta temp. (0C)
Theta solvent (v/v) Methylcyclopentane Nitroethane/toluene (25.9/74.1) Nitromethane/toluene (18.9/81.1) Nitropropane/toluene (36/64) n-Nonane rc-Octane Perfluorooctane/tetrachlorodifluoroethane (33.2/66.8; w/w) Phenetole
K-Propyl acetate Styrene Toluene Xylene Poly(methylphenylsiloxane) Poly(phenylsilasesquioxane)
Di-/-butylamine 1,2-Dichloroethane
Poly(Y-trifluoropropyl methyl siloxamer)
Mesitylene/toluene (30/70) Cyclohexyl acetate Methyl hexanoate
-98.2 25 25 25 -113.2 -143.2 22.5 83.0 83.0 89.3 89.5 -28.2 35 -30 -33.2 -47 -48.2 30.4 50.5 56 25 25 72.8
Method VM CP CP CP VM VM A, PE PE A VM A VM A A VM A VM VM VM A VM VM
Refs. 201 94 94 94 201 201 67 111 202 201 309 201 429 202 201 202 201 487 138,431 276 185 38 38
2.8. PHOSPHORUS-OXYGEN CHAINS Poly(phosphate)
LiBr/water (1.80mol/l) LiCl/water (0.40mol/l) NaBr/water (0.415 mol/1)
25 20 25
A A A
326 297 327
C. REFERENCES 1. M. Abe, H. Fujita, Rep. Progr. Polym. Phys. Japan, 7, 42 (1964). 2. M. Abe, H. Fujita, J. Phys. Chem., 69, 3263 (1965). 3. M. Abe, K. Sakato, T. Kageyama, M. Fukatsu, M. Kurata, Bull. Chem. Soc. Japan, 41, 2330 (1968). 4. P. Adamski, Vysokomol. Soedin. A, 13, 709 (1971); Polym. Sci. USSR, 13, 803 (1973). 5. P. Adamski, Vysokomol. Soedin. B, 13, 666 (1971). 6. P. Adamski, Zesz. Nauk Politech. Lodz, 23, 5 (1971). 7. P. Adamski, M. Kryshevski, IUPAC Symp. Macromolecules, Toronto, 1968. 8. A. M. Afifi-Effat, J. N. Hay, M. Wiles, J. Polym. Sci. B, 11, 87 (1973). 9. S. M. AIi, M. B. Huglin, Makromol. Chem., 84, 117 (1965). 10. G. Allen, C. Booth, C. Price, Polymer, 7, 167 (1966). 11. F. J. Ansorene, L. M. Revuelta, G. M. Guzman, J. J. Iruin, Europ. Polym. J., 18, 19 (1982). 12. M. Asahina, M. Sato, Bull. Chem. Soc. Japan, 35, 630 (1962). 13. F. E. Bailey, Jr., R. W. Callard, J. Appl. Polym. Sci., 1, 56 (1959). 14. W. Banks, C. T. Greenwood, Makromol. Chem., 67, 49 (1963); Carbohydrate Res., 7, 349 (1968). 15. W. Banks, C. T. Greenwood, J. Sloss, Makromol. Chem., 140, 109 (1970). 16. J. M. Barrales-Rienda, D. C. Pepper, Polymer, 8,337 (1967).
17. J. M. Barrales-Rienda, C. Romero Galicia, J. F. Freire, A. Horta, Macromolecules, 16, 337 (1983). 18. T. W. Bates, J. Biggins, K. J. Ivin, Makromol. Chem., 87,180 (1965). 19. T. W. Bates, K. J. Ivin, Polymer, 8, 263 (1967). 20. B. J. Bauer, N. Hadjichristidis, L. J. Fetters, J. E. L. Roovers, J. Am. Chem. Soc, 102, 2410 (1980). 21. U. Baumann, H. Schreiber, K. Tessmar, Makromol. Chem., 36, 81 (1960). 22. A. Bazuaye, M. B. Huglin, Polymer, 20, 44 (1979). 23. H. C. Beachell, J. C. Peterson, J. Polym. Sci. A-I, 7, 2021 (1969). 24. M. Becerra, D. Radic, L. Gargallo, Makromol. Chem. 179, 2241 (1978). 25. D. R. Beach, C. Booth, J. Polym. Sci. A-2, 7, 575 (1969). 26. G. C. Berry, J. Chem. Phys., 44, 4550 (1966). 27. G. C. Berry, H. Nomura, K. G. Mayhan, J. Polym. Sci. A-2, 5, 1 (1967). 28. G. C. Berry, H. Nakayasu, T. G. Fox, J. Polym. Sci., Polym. Phys. Ed., 17, 1825 (1979). 29. M. N. Berger, B. M. Tidswell, J. Polym. Sci.-Symp., 42, 1063 (1973). 30. U. Bianchi, V. Magnasco, C. Rossi, Ric. Sci., 28, 1412 (1958). 31. U. Bianchi, V. Magnasco, C. Rossi, Chim. Ind. (Milan), 40, 263 (1958).
32. M. Bohdanecky, Coll. Czech. Chem. Commun., 29, 876 (1964). 33. M. Bohdaneckv, V. Petrus, B. Sedlacek, Makromol. Chem., 184, 2061 (1983). 34. M. Bohdaneck>>, Z. Tuzar, Coll. Czech. Chem. Commun., 34, 3318 (1969). 35. C. Booth, R. Orme, Polymer, 11, 626 (1970). 36. E. A. Boucher, P. M. Hines, J. Polym. ScL, Polym. Phys. Ed., 16, 501 (1978). 37. J. Brezinski, B. Czamecka, Polimery Tworzywa, 14, 117 (1969). 38. R. R. Buch, H. M. Klimisch, O. K. Johannson, J. Polym. Sci. A-2, 7, 563 (1969). 39. W. Burchard, Habilitation Thesis, University of Freiburg, Germany. 40. W. Burchard, Makromol. Chem., 64, 110 (1963). 41. W. Burchard, Z. Physik. Chem. (Frankfurt/M.), 43, 265 (1964). 42. F. Candau, C. Strazielle, H. Benoit, Makromol. Chem., 170, 165 (1973). 43. H. -J. Cantow, Makromol. Chem., 30, 169 (1959). 44. D. K. Carpenter, J. H. Hsieh, ACS Polymer Preprints, 13, 981 (1972). 45. B. Chew, A. Couper, J. Chem. Soc. Faraday Soc, [1], 72,382 (1976). 46. R. Chiang, J. Phys. Chem., 69, 1645 (1965). 47. S. N. Chinai, J. Polym. Sci., 25, 413 (1957). 48. S. N. Chinai, J. Polym. Sci., 44, 475 (1959). 49. S. N. Chinai, C. W. Bondurant, J. Polym. Sci., 22, 555 (1956). 50. S. N. Chinai, R. A. Guzzi, J. Polym. Sci., 21, 417 (1956). 51. S. N. Chinai, A. L. Resnick, H. T. Lee, J. Polym. Sci., 33,471 (1958). 52. S. N. Chinai, R. J. Samuels, J. Polym. Sci., 19, 463 (1956). 53. S. N. Chinai, P C. Scherer, C. W. Bondurant, D. W. Levi, J. Polym. Sci., 22, 527, (1956). 54. S. N. Chinai, R. J. Valles, J. Polym. 39, 363 (1959). 55. D. S. Chiu, Y. Takahashi, J. E. Mark, Polymer, 17, 670 (1976). 56. A. Ciferri, M. Lauretti, Ann. Chim. (Rome), 48, 198 (1958). 57. E. Conn-Ginsberg, T. G. Fox, H. F. Mason, Polymer, 3, 97 (1962). 58. C. F. Cornet, H. van Ballegooijen, Polymer, 7, 293 (1966). 59. B. J. Cottam, J. M. G. Cowie, S. Bywater, Makromol. Chem., 86, 116(1965). 60. J. P. Cotton, D. Decker, H. Benoit, B. Farnoux, J. Higgins, G. Jannink, R. Ober, J. des Cloizeaux, Macromolecules, 7, 863 (1974). 61. J. M. G. Cowie, Makromol. Chem., 59, 189 (1963). 62. J. M. G. Cowie, J. Polymer. Sci. C, 23, 267 (1968). 63. J. M. G. Cowie, S. Bywater, J. Polym. Sci. A-2, 6, 499 (1968). 64. J. M. G. Cowie, S. Bywater, D. J. Worsfold, Polymer, 8, 105 (1967). 65. J. M. G. Cowie, A. Maconnachie, R. J. Ranson, Macromolecules, 4, 57 (1971). 66. J. M. G. Cowie, I. J. McEwen, Polymer, 16, 933 (1975).
67. V. Crescenci, P. J. Flory, J. Am. Chem. Soc, 86, 141 (1964). 68. A. Czuppon, IUPAC Symp. Macromolecules, Prague 1965, Preprint 459. 69. F. Danusso, G. Moraglio, Atti Accad. Nazi. Lincei Rend. Classe Sci. Fis. Mat. Nat., [8], 25, 509 (1958). 70. F. Danusso, G. Moraglio, G. Gianotti, J. Polym. Sci., 51,475 (1961). 71. J. V. Dawkins, M. Hemming, Makromol. Chem., 155, 75 (1972). 72. J. V. Dawkins, G. Taylor, Colloid Polym. Sci., 258, 79 (1980). 73. A. de Chirico, Chim. Ind. (Milan), 42, 248 (1960). 74. A. de Chirico, Chim. Ind. (Milan), 46, 53 (1964). 75. D. Decker, Makromol. Chem., 125, 136 (1969). 76. G. Delmas, D. Patterson, Polymer, 7, 513 (1966). 77. F. E. Didot, S. N. Chinai, D. W. Levi, J. Polym. Sci., 43, 557 (1960). 78. H. Dietschy, Ph.D. Thesis, ETH Zurich 1966. 79. H. A. Dieu, J. Polym. Sci., 12, 417 (1954). 80. J. Dohany, Ph.D. Thesis, ETH Zurich 1963. 81. A. Dondos, Makromol. Chem., 135. 181 (1970). 82. A. Dondos, H. Benoit, J. Polym. Sci. B, 7, 279 (1969). 83. A. Dondos, H. Benoit, Macromolecules, 4, 279 (1971). 84. P. Dreyfus, M. P. Dreyfus, Adv. Polym. Sci., 4, 528 (1967). 85. E. T. Dumitru, L. H. Cragg, Cited in ref. [110], p. 615. 86. K. Dusek, M. Bohdanecky, E. Prokopova, Eur. Polym. J., 10, 239 (1974). 87. H. Eisenberg, D. Woodside, J. Polym. Phys. 36,1844 (1962). 88. K. H. Elgert, PhD Thesis, Techn. Univ. of Munich, 1963. 89. H.-G. Elias, Makromol. Chem., 33, 140 (1959). 90. H.-G. Elias, Makromol. Chem., 50, 1 (1961). 91. H.-G. Elias, Makromol. Chem., 54, 78 (1962). 92. H.-G. Elias, "Makromolekiile", Hiithig and Wepf, Basle, Fourth Ed. 1981, p. 200; "Macromolecules", Plenum, New York, Second Ed. 1984, Vol. I., p. 232. 93. H.-G. Elias, in: L. H. Tung, (Ed.), 'Tractionation of Synthetic Polymers", Dekker, New York, 1977. 94. H.-G. Elias, G. Adank, Makromol. Chem., 69, 241 (1963). 95. H.-G. Elias, O. Etter, Makromol. Chem., 66, 56 (1963). 96. H.-G. Elias, O. Etter, Makromol. Chem., 89, 228 (1965). 97. H.-G. Elias, O. Etter, J. Makromol. Chem., 1, 431 (1966). 98. H.-G. Elias, U. Gruber, Makromol. Chem., 78, 72 (1964). 99. U. Gruber, H. -G. Elias, Makromol. Chem., 86, 168 (1965). 100. H. -G. Elias, F. W. Ibrahim, Makromol. Chem., 89, 12 (1965). 101. H. -G. Elias, R. Schumacher, Makromol. Chem., 76, 23 (1964). 102. V. E. Eskin, L. N. Andreeva, Vysokomol. Soedin., 3, 435 (1961); cited in J. Polym. Sci., 56, S 39 (1962). 103. V. E. Eskin, K. Z. Gumargalieva, Vysokomol. Soedin., 2, 265 (1960). 104. V. E. Eskin, O. Z. Korothina, Vysokomol. Soedin,, 2, 272 (1960); J. Polym. Sci. USSR, 2, 247 (1961). 105. J. M. Evans, M. B. Huglin, Makromol. Chem., 127, 141 (1969). 106. J. M. Evans, M. B. Huglin, Europ. Polym. J., 6, 1161 (1970).
107. J. M. Evans, M. B. Huglin, cited in [84]. 108. W. W. Everett, J. F. Foster, J. Am. Chem. Soc, 81, 3459, 3464 (1959). 109. J. Feisst, H.-G. Elias, Makromol. Chem., 82, 78 (1965). 110. P. J. Flory, "Principles of Polymer Chemistry", Cornell Univ. Press, Ithaca, NY, 1953. 111. P. J. Flory, L. Mandelkern, J. B. Kinsinger, W. B. Shultz, J. Am. Chem. Soc, 74, 3364 (1952). 112. T. G. Fox, Polymer, 3, 111 (1962). 113. T. G. Fox, P. J. Flory, J. Am. Chem. Soc, 73, 1909 (1959). 114. T. G. Fox, P. J. Flory, J. Am. Chem. Soc, 73, 1915 (1959). 115. T. G. Fox, J. B. Kinsinger, H. F. Mason, E. M. Schuele, Polymer, 3, 71 (1962). 116. D. M. French, A. W. Casey, C. I. Collins, P. Kirchner, ACS Polymer Preprints, 7, 447 (1966). 117. D. Froelich, Ph.D. Thesis, Univ. of Strasbourg, 1966; cited in [83]. 118. D. Froelich, H. Benoit, Makromol. Chem., 92, 224 (1966). 119. M. Fukuda, M. Fukutomi, Y. Kato, T. Hashimoto, J. Polym. Sci.-Polym. Chem. Ed., 12, 871 (1974). 120. C. Garbuglio, L. Crescentini, A. MuIa, G. B. Gechele, Makromol. Chem., 97, 97 (1966). 121. L. Gargallo, J. Niezzette, V. Desreux, Bull. Soc Roy. Sci. Liege, 1-2, 82 (1977); cited in [122]. 122. L. Gargallo, D. Radic, I. Katime, Europ. Polym. J., 16, 383 (1980). 123. G. B. Gechele, L. Crescentini, J. Polym. Sci. A, 3, 3599 (1965). 124. H. Geerissen, B. A. Wolf, Makromol. Chem., Rapid Commun., 3, 17 (1982). 125. G. Gianotti, U. Bonicelli, D. Borghi, Makromol. Chem., 166, 235 (1973). 126. C. Gonzalez, F Zamora, G. M. Guzman, L. M. Leon, Makromol. Chem., 185, 339 (1984). 127. T. B. Grimley, Proc Roy. Soc. [London] A, 212, 339 (1952). 128. U. Gruber, Ph.D. Thesis, ETH Zurich, 1964. 129. N. Hadjichristidis, Polymer, 16, 848 (1975). 130. N. Hadjichristidis, J. E. L. Roovers, J. Polym. Sci., Polym. Phys. Ed., 12, 2521 (1974). 131. J. Hakozaki, J. Chem. Soc Japan, Pure Chem. Sect. (Nippon Kagaku Zasshi), 82, 158 (1961). 132. F. Hamada, K. Fujisawa, A. Nakajima, Polym. J., 4, 316 (1973). 133. K. Hanafusa, A. Teramoto, H. Fujita, J. Chem. Phys., 70, 4004 (1966). 134. J. N. Hay, A. M. Afifi-Effat, Brit. Polym. J., 9, 1 (1977). 135. J. N. Hay, P A. Fitzgerald, J. Polym. Sci., Polym. Chem. Ed., 18, 1079 (1980). 136. J. N. Hay, M. Wiles, Brit. Polym. J., 10, 181 (1978). 137. W. Hayduk, H. A. Bromfield, J. Appl. Polym. Sci., 22, 149 (1978). 138. T. E. Helminiak, C. L. Benner, W. E. Gibbs, ACS Polymer Preprints, 8, 284 (1967). 139. I. Hernandez-Fuentes, M. G. Prolongo, Europ. Polym. J., 15, 571 (1979). 140. F. K. Herold, B. A. Wolf, Makromol. Chem., 184, 2539 (1981).
141. J. Herold, G. Meyerhoff, Europ. Polym. J., 15, 525 (1979). 142. M. Heskins, J. E. Guillet, J. Macromol. Sci. A, 2, 1441 (1968). 143. T. Hirosye, Y. Einaga, H. Fujita, Polym. J., 11, 819 (1979). 144. T. Homma, K. Kawahara, H. Fujita, M. Ueda, Makromol. Chem., 67, 132 (1963). 145. T. Homma, K. Kawahara, H. Fujita, J. Appl. Polym. Sci., 8, 2853 (1964). 146. F. Hooshmand-Mozaffar, M. K. Hoseinalizadeh-Khorasani, M. B. Huglin, Polymer, 21, 413 (1980). 147. F. Horii, Y Ikada, I. Sakurada, J. Polym. Sci., Polym. Chem. Ed., 12, 323 (1974). 148. N. Howard, M. B. Huglin, R. W. Richards, J. Appl. Polym. Sci., 16, 1525 (1972). 149. A. J. Hyde, R. B. Taylor, Polymer, 4, 1 (1963). 150. T. Ikeda, H. Kawaguchi, Rep. Progr. Polym. Phys. Japan, 9, 23 (1966). 151. H. Inagaki, A. Nakazawa, T. Kotaka, Bull. Inst. Chem. Res. Kyoto Univ., 43, 135 (1965). 152. H. Inagaki, T. Miyamoto, S. Ohta, J. Phys. Chem., 70, 3420 (1966). 153. H. Inagaki, H. Suzuki, M. Fujii, T Matsuo, J. Phys. Chem., 70, 1718 (1966). 154. K. J. Mn, H. A. Ende, G. Meyerhoff, Polymer, 3,129 (1962). 155. M. Iwama, H. Utiyama, M. Kurata, J. Macromol. Chem., 1, 701 (1966). 156. Y. Izumi, Y Miyake, Polym. J., 3, 647 (1972). 157. Y Izumi, Y. Miyake, Polym. J., 4, 205 (1973). 158. Y. Izumi, S. Otsuka, Y Miyake, Rep. Progr. Polym. Phys. Japan, 12, 13 (1969). 159. R. Jerome, V. Desreux, Europ. Polym. J., 6, 411 (1970). 160. R. M. Johnson, J. L. Schrag, J. D. Ferry, Polym. J., 1, 742 (1970). 161. M. Kalfus, J. Mitus, J. Polym. Sci. A-I, 4, 953 (1966). 162. K. Kamada, H. Sato, Polym. J., 2, 593 (1971). 163. K. Kamide, T. Terekawa, Makromol. Chem., 155,25 (1972). 164. Ye. A. Kanevskaya, P. I. Zubov, L. V. Ivanova, Yu. S. Lipatov, Vysokomol. Soedin., 6, 981 (1964); Polym. Sci. USSR, 6, 1080 (1964). 165. A. Katchalsky, H. Eisenberg, J. Polym. Sci., 6, 145 (1951). 166. I. A. Katime Amashta, G. Sanchez, Europ. Polym. J., 11,223 (1975). 167. H. Kaye, H. J. Cou, J. Polym. Sci., Polym. Phys. Ed., 13,477 (1975). 168. W. Kern, D. Braun, Makromol. Chem., 27, 23 (1958). 169. J. B. Kinsinger, L. E. Ballard, J. Polym. Sci. B, 2, 879 (1964). 170. J. B. Kinsinger, L. E. Baliard, J. Polym. Sci. A, 3, 3963 (1965). 171. J. B. Kinsinger, R. E. Hughes, J. Phys. Chem., 67, 1922 (1963). 172. J. B. Kinsinger, R. A. Wessling, J. Am. Chem. Soc, 81, 2908 (1959). 173. R. Kirste, G. V. Schulz, Z. Physik. Chem. (Frankfurt/M.), 27, 310 (1960). 174. R. G. Kirste, G. V. Schulz, Z. Physik. Chem. (Frankfurt/M.), 30, 171 (1961).
Next Page
175. M. R. Knecht, R-G. Elias, Makromol. Chem., 157, 1 (1972). 176. A. Kokkiaris, C. Touloupis, N. Hadjichristidis, Polymer, 22, 63 (1981). 177. R. Koningsveld, Th. G. Schoolte, private communication. 178. T. Kotaka, H. Ohnuma, H. Inagaki, Polymer, 10, 517 (1969). 179. T. Kotaka, H. Ohnuma, H. Inagaki, ACS Polymer Preprints, 11, 660 (1970). 180. T. Kotaka, H. Ohnuma, Y. Murakami, J. Phys. Chem., 70, 4099 (1966). 181. T. Kotaka, T. Tanaka, H. Ohnuma, Y. Murakami, H. Inagaki, Polymer J., 1, 245 (1970). 182. A. Kotera, H. Matsuda, K. Konishi, K. Takemura, J. Polym. Sci. C, 23, 619 (1968). 183. A. Kotera, N. Onda, T. Saito, Rep. Progr. Polym. Phys. Japan, 17, 25 (1974). 184. A. Kotera, T. Saito, N. Yamaguchi, Annual Meeting Chem. Soc. Japan, 1962; cited in A. Kotera, N. Ise, A. Senuma, T. Hamada, IUPAC Symp. Macromol., Prague 1965, Preprint 232. 185. J. Kovaf, L. Mrkvickova-Vaculova, M. Bohdanecky, Makromol. Chem., 176, 1829 (1975). 186. P. Kratochvil, D. Strtakova, Makromol. Chem., 154, 325 (1972). 187. S. Krause, E. Cohn-Ginsburg, J. Phys. Chem., 67, 1479 (1963). 188. W. R. Krigbaum, D. K. Carpenter, J. Phys. Chem., 59, 1166 (1955). 189. W. R. Krigbaum, P. J. Flory, J. Polym. Sci., 11, 37 (1953). 190. W. R. Krigbaum, J. E. Kurz, P. Smith, J. Phys. Chem., 65, 1984 (1961). 191. W. R. Krigbaum, L. H. Sperling, J. Phys. Chem., 64, 99 (1960). 192. W. R. Krigbaum, J. D. Woods, J. Polym. Sci. A, 2, 3075 (1964). 193. S. Krozer, Plaste Kautschuk, 15, 175 (1968). 194. S. Krozer, A. Pastusiak, IUPAC Symp. Macromol., Prague 1965, Preprint 609. 195. K. Kubo, K. Ogino, Rep. Progr. Polym. Phys. Japan, 10,111 (1967). 196. K. Kubo, K. Ogino, T. Nakagawa, Rep. Progr. Polym. Phys. Japan, 10, 7 (1967). 197. Z. Kuciikyavuz, A. Kuc,iikyavuz, Europ. Polym. J., 14, 867 (1978). 198. A. M. Kulakova, I. K. Nekrasov, Vysokomol. Soedin. A, 18, 127 (1976); Polym. Sci. USSR, 18, 146 (1976). 199. M. Kurata, H. Utiyama, K. Kamada, Makromol. Chem., 88, 281 (1965). 200. N. Kuwahara, S. Higashida, M. Nakata, K. Kaneko, J. Polym. Sci. A-2, 7, 285 (1969). 201. N. Kuwahara, M. Kaneko, Makromol. Chem., 82 205 (1965). 202. N. Kuwahara, T. Miyake, M. Kaneko, J. Furuichi, Rep. Progr. Polym. Phys. Japan, 5, 1 (1962). 203. N. Kuwahara. S. Saeki, S. Konno, M. Kaneko, Macromolecules, 6, 589 (1973). 204. N. Kuwahara, S. Saeki, S. Konno, Polymer, 15, 66 (1974).
205. D. Lath, M. Bohdanecky, J. Polym. Sci.-Letters Ed., 15, 555 (1977). 206. H. T. Lee, D. W. Levi, J. Polym. Sci., 47, 449 (1960). 207. L. M. Leon, J. Galaz, L. M. Garcia, M. S. Anasagasti, Europ. Polym. J., 16, 921 (1980). 208. D. W. Levi, H. T. Lee, R. J. Valles, J. Polym. Sci., 62, S163 (1962). 209. J. Lilie, J. Springer, K. Ueberreiter, Kolloid-Z., 226, 138 (1968). 210. F. C. Lin, S. S. Stivala, J. A. Biesenberger, J. Appl. Polym. Sci., 17, 3465 (1973). 211. M. Lippay. Ph.D. Thesis, ETH Zurich, 1963. 212. J. Llopis, A. Albeit, P. Usobiaga, Europ. Polym. J., 3, 259 (1967). 213. T. Lucas, Bull. Liaison Lab. (Lab. Prof. Peint)., 20, 15 (1967). 214. N. V. Makletsova, I. V. Epel'baum, B. A. Rozenberg, Ye. B. Lyudvig, Vysokomol. Soedin., 7, 70 (1965); Polym. Sci. USSR, 7, 73 (1966). 215. L. Mandelkern, P. J. Flory, J. Am. Chem. Soc, 74, 2517 (1952). 216. P. V. Mangalam, V. P. Kalpagam, J. Polym. Sci.-Polym. Phys. Ed., 20, 773 (1982). 217. V. P. Mardykin, K. B. Martinovich, A. I. Volozhin, N. M. Denisyuk, Vysokomol. Soedin. B, 16, 23 (1974); CA 81: 1390Or (1974). 218. J. E. Mark, Diss. Abstr., 23, 1205 (1962). 219. J. E. Mark, P. J. Flory, J. Am. Chem. Soc, 87, 1423 (1965). 220. R. M. Masegosa, M. G. Prolongo, I. Hernandez-Fuentes, A. Horta, Macromolecules, 17, 1181 (1984). 221. T. Matsumoto, N. Nishioka, H. Fujita, J. Polym. Sci. A-2,10, 23 (1972). 222. M. Matsumoto, Y. Ohyanagi, J. Polym. Sci., 46, 441 (1960). 223. M. Matsumoto, Y. Ohyanagi, J. Polym. Sci., 50, Sl (1961). 224. K. Matsumura, Polym. J., 1 322 (1970). 225. M. Matsushima, M. Fukatsu, M. Kurata, Bull. Chem. Soc Japan, 41, 2570 (1968). 226. A. Mattiussi, E. Conto, G. B. Gechele, Europ. Polym. J., 8, 429 (1972). 227. W. L. Mattice, L. Mandelkern, Macromolecules, 4, 271 (1971). 228. R. M. May, R. E. Wetton, cited in [84]. 229. H. W. McCormick, J. Polym. Sci., 36, 341 (1959). 230. D. Mclntyre, J. H. O'Mara, B. C. Konouck, J. Am. Chem. Soc, 81, 3498 (1959). 231. R. A. Mendelson, J. Polym. Sci., 46, 493 (1960). 232. G. Meyerhoff, Makromol. Chem., 37, 97 (1960). 233. G. Meyerhoff, in: J. W. Williams (Ed.), "Ultracentrifugal Analysis in Theory and Practice". Academic Press, New York, 1963. 234. R. Meza, L. Gargallo, Europ. Polym. J., 13, 235 (1977). 235. S. Miyamoto, Y. Ishii, H. Ohnuma, Makromol. Chem., 182, 483 (1981). 236. J. Moacanin, J. Appl. Polym. Sci., 1, 272 (1959). 237. J. Moacanin, A. Rembaum, R. K. Laudenslager, ACS Polymer Preprints, 4/2, 179 (1963).
Previous Page
Table 2. cont'd Polymer (mol/mol)
Theta temp. (0C)
Theta solvent (v/v) Methylcyclopentane Nitroethane/toluene (25.9/74.1) Nitromethane/toluene (18.9/81.1) Nitropropane/toluene (36/64) n-Nonane rc-Octane Perfluorooctane/tetrachlorodifluoroethane (33.2/66.8; w/w) Phenetole
K-Propyl acetate Styrene Toluene Xylene Poly(methylphenylsiloxane) Poly(phenylsilasesquioxane)
Di-/-butylamine 1,2-Dichloroethane
Poly(Y-trifluoropropyl methyl siloxamer)
Mesitylene/toluene (30/70) Cyclohexyl acetate Methyl hexanoate
-98.2 25 25 25 -113.2 -143.2 22.5 83.0 83.0 89.3 89.5 -28.2 35 -30 -33.2 -47 -48.2 30.4 50.5 56 25 25 72.8
Method VM CP CP CP VM VM A, PE PE A VM A VM A A VM A VM VM VM A VM VM
Refs. 201 94 94 94 201 201 67 111 202 201 309 201 429 202 201 202 201 487 138,431 276 185 38 38
2.8. PHOSPHORUS-OXYGEN CHAINS Poly(phosphate)
LiBr/water (1.80mol/l) LiCl/water (0.40mol/l) NaBr/water (0.415 mol/1)
25 20 25
A A A
326 297 327
C. REFERENCES 1. M. Abe, H. Fujita, Rep. Progr. Polym. Phys. Japan, 7, 42 (1964). 2. M. Abe, H. Fujita, J. Phys. Chem., 69, 3263 (1965). 3. M. Abe, K. Sakato, T. Kageyama, M. Fukatsu, M. Kurata, Bull. Chem. Soc. Japan, 41, 2330 (1968). 4. P. Adamski, Vysokomol. Soedin. A, 13, 709 (1971); Polym. Sci. USSR, 13, 803 (1973). 5. P. Adamski, Vysokomol. Soedin. B, 13, 666 (1971). 6. P. Adamski, Zesz. Nauk Politech. Lodz, 23, 5 (1971). 7. P. Adamski, M. Kryshevski, IUPAC Symp. Macromolecules, Toronto, 1968. 8. A. M. Afifi-Effat, J. N. Hay, M. Wiles, J. Polym. Sci. B, 11, 87 (1973). 9. S. M. AIi, M. B. Huglin, Makromol. Chem., 84, 117 (1965). 10. G. Allen, C. Booth, C. Price, Polymer, 7, 167 (1966). 11. F. J. Ansorene, L. M. Revuelta, G. M. Guzman, J. J. Iruin, Europ. Polym. J., 18, 19 (1982). 12. M. Asahina, M. Sato, Bull. Chem. Soc. Japan, 35, 630 (1962). 13. F. E. Bailey, Jr., R. W. Callard, J. Appl. Polym. Sci., 1, 56 (1959). 14. W. Banks, C. T. Greenwood, Makromol. Chem., 67, 49 (1963); Carbohydrate Res., 7, 349 (1968). 15. W. Banks, C. T. Greenwood, J. Sloss, Makromol. Chem., 140, 109 (1970). 16. J. M. Barrales-Rienda, D. C. Pepper, Polymer, 8,337 (1967).
17. J. M. Barrales-Rienda, C. Romero Galicia, J. F. Freire, A. Horta, Macromolecules, 16, 337 (1983). 18. T. W. Bates, J. Biggins, K. J. Ivin, Makromol. Chem., 87,180 (1965). 19. T. W. Bates, K. J. Ivin, Polymer, 8, 263 (1967). 20. B. J. Bauer, N. Hadjichristidis, L. J. Fetters, J. E. L. Roovers, J. Am. Chem. Soc, 102, 2410 (1980). 21. U. Baumann, H. Schreiber, K. Tessmar, Makromol. Chem., 36, 81 (1960). 22. A. Bazuaye, M. B. Huglin, Polymer, 20, 44 (1979). 23. H. C. Beachell, J. C. Peterson, J. Polym. Sci. A-I, 7, 2021 (1969). 24. M. Becerra, D. Radic, L. Gargallo, Makromol. Chem. 179, 2241 (1978). 25. D. R. Beach, C. Booth, J. Polym. Sci. A-2, 7, 575 (1969). 26. G. C. Berry, J. Chem. Phys., 44, 4550 (1966). 27. G. C. Berry, H. Nomura, K. G. Mayhan, J. Polym. Sci. A-2, 5, 1 (1967). 28. G. C. Berry, H. Nakayasu, T. G. Fox, J. Polym. Sci., Polym. Phys. Ed., 17, 1825 (1979). 29. M. N. Berger, B. M. Tidswell, J. Polym. Sci.-Symp., 42, 1063 (1973). 30. U. Bianchi, V. Magnasco, C. Rossi, Ric. Sci., 28, 1412 (1958). 31. U. Bianchi, V. Magnasco, C. Rossi, Chim. Ind. (Milan), 40, 263 (1958).
32. M. Bohdanecky, Coll. Czech. Chem. Commun., 29, 876 (1964). 33. M. Bohdaneckv, V. Petrus, B. Sedlacek, Makromol. Chem., 184, 2061 (1983). 34. M. Bohdaneck>>, Z. Tuzar, Coll. Czech. Chem. Commun., 34, 3318 (1969). 35. C. Booth, R. Orme, Polymer, 11, 626 (1970). 36. E. A. Boucher, P. M. Hines, J. Polym. ScL, Polym. Phys. Ed., 16, 501 (1978). 37. J. Brezinski, B. Czamecka, Polimery Tworzywa, 14, 117 (1969). 38. R. R. Buch, H. M. Klimisch, O. K. Johannson, J. Polym. Sci. A-2, 7, 563 (1969). 39. W. Burchard, Habilitation Thesis, University of Freiburg, Germany. 40. W. Burchard, Makromol. Chem., 64, 110 (1963). 41. W. Burchard, Z. Physik. Chem. (Frankfurt/M.), 43, 265 (1964). 42. F. Candau, C. Strazielle, H. Benoit, Makromol. Chem., 170, 165 (1973). 43. H. -J. Cantow, Makromol. Chem., 30, 169 (1959). 44. D. K. Carpenter, J. H. Hsieh, ACS Polymer Preprints, 13, 981 (1972). 45. B. Chew, A. Couper, J. Chem. Soc. Faraday Soc, [1], 72,382 (1976). 46. R. Chiang, J. Phys. Chem., 69, 1645 (1965). 47. S. N. Chinai, J. Polym. Sci., 25, 413 (1957). 48. S. N. Chinai, J. Polym. Sci., 44, 475 (1959). 49. S. N. Chinai, C. W. Bondurant, J. Polym. Sci., 22, 555 (1956). 50. S. N. Chinai, R. A. Guzzi, J. Polym. Sci., 21, 417 (1956). 51. S. N. Chinai, A. L. Resnick, H. T. Lee, J. Polym. Sci., 33,471 (1958). 52. S. N. Chinai, R. J. Samuels, J. Polym. Sci., 19, 463 (1956). 53. S. N. Chinai, P C. Scherer, C. W. Bondurant, D. W. Levi, J. Polym. Sci., 22, 527, (1956). 54. S. N. Chinai, R. J. Valles, J. Polym. 39, 363 (1959). 55. D. S. Chiu, Y. Takahashi, J. E. Mark, Polymer, 17, 670 (1976). 56. A. Ciferri, M. Lauretti, Ann. Chim. (Rome), 48, 198 (1958). 57. E. Conn-Ginsberg, T. G. Fox, H. F. Mason, Polymer, 3, 97 (1962). 58. C. F. Cornet, H. van Ballegooijen, Polymer, 7, 293 (1966). 59. B. J. Cottam, J. M. G. Cowie, S. Bywater, Makromol. Chem., 86, 116(1965). 60. J. P. Cotton, D. Decker, H. Benoit, B. Farnoux, J. Higgins, G. Jannink, R. Ober, J. des Cloizeaux, Macromolecules, 7, 863 (1974). 61. J. M. G. Cowie, Makromol. Chem., 59, 189 (1963). 62. J. M. G. Cowie, J. Polymer. Sci. C, 23, 267 (1968). 63. J. M. G. Cowie, S. Bywater, J. Polym. Sci. A-2, 6, 499 (1968). 64. J. M. G. Cowie, S. Bywater, D. J. Worsfold, Polymer, 8, 105 (1967). 65. J. M. G. Cowie, A. Maconnachie, R. J. Ranson, Macromolecules, 4, 57 (1971). 66. J. M. G. Cowie, I. J. McEwen, Polymer, 16, 933 (1975).
67. V. Crescenci, P. J. Flory, J. Am. Chem. Soc, 86, 141 (1964). 68. A. Czuppon, IUPAC Symp. Macromolecules, Prague 1965, Preprint 459. 69. F. Danusso, G. Moraglio, Atti Accad. Nazi. Lincei Rend. Classe Sci. Fis. Mat. Nat., [8], 25, 509 (1958). 70. F. Danusso, G. Moraglio, G. Gianotti, J. Polym. Sci., 51,475 (1961). 71. J. V. Dawkins, M. Hemming, Makromol. Chem., 155, 75 (1972). 72. J. V. Dawkins, G. Taylor, Colloid Polym. Sci., 258, 79 (1980). 73. A. de Chirico, Chim. Ind. (Milan), 42, 248 (1960). 74. A. de Chirico, Chim. Ind. (Milan), 46, 53 (1964). 75. D. Decker, Makromol. Chem., 125, 136 (1969). 76. G. Delmas, D. Patterson, Polymer, 7, 513 (1966). 77. F. E. Didot, S. N. Chinai, D. W. Levi, J. Polym. Sci., 43, 557 (1960). 78. H. Dietschy, Ph.D. Thesis, ETH Zurich 1966. 79. H. A. Dieu, J. Polym. Sci., 12, 417 (1954). 80. J. Dohany, Ph.D. Thesis, ETH Zurich 1963. 81. A. Dondos, Makromol. Chem., 135. 181 (1970). 82. A. Dondos, H. Benoit, J. Polym. Sci. B, 7, 279 (1969). 83. A. Dondos, H. Benoit, Macromolecules, 4, 279 (1971). 84. P. Dreyfus, M. P. Dreyfus, Adv. Polym. Sci., 4, 528 (1967). 85. E. T. Dumitru, L. H. Cragg, Cited in ref. [110], p. 615. 86. K. Dusek, M. Bohdanecky, E. Prokopova, Eur. Polym. J., 10, 239 (1974). 87. H. Eisenberg, D. Woodside, J. Polym. Phys. 36,1844 (1962). 88. K. H. Elgert, PhD Thesis, Techn. Univ. of Munich, 1963. 89. H.-G. Elias, Makromol. Chem., 33, 140 (1959). 90. H.-G. Elias, Makromol. Chem., 50, 1 (1961). 91. H.-G. Elias, Makromol. Chem., 54, 78 (1962). 92. H.-G. Elias, "Makromolekiile", Hiithig and Wepf, Basle, Fourth Ed. 1981, p. 200; "Macromolecules", Plenum, New York, Second Ed. 1984, Vol. I., p. 232. 93. H.-G. Elias, in: L. H. Tung, (Ed.), 'Tractionation of Synthetic Polymers", Dekker, New York, 1977. 94. H.-G. Elias, G. Adank, Makromol. Chem., 69, 241 (1963). 95. H.-G. Elias, O. Etter, Makromol. Chem., 66, 56 (1963). 96. H.-G. Elias, O. Etter, Makromol. Chem., 89, 228 (1965). 97. H.-G. Elias, O. Etter, J. Makromol. Chem., 1, 431 (1966). 98. H.-G. Elias, U. Gruber, Makromol. Chem., 78, 72 (1964). 99. U. Gruber, H. -G. Elias, Makromol. Chem., 86, 168 (1965). 100. H. -G. Elias, F. W. Ibrahim, Makromol. Chem., 89, 12 (1965). 101. H. -G. Elias, R. Schumacher, Makromol. Chem., 76, 23 (1964). 102. V. E. Eskin, L. N. Andreeva, Vysokomol. Soedin., 3, 435 (1961); cited in J. Polym. Sci., 56, S 39 (1962). 103. V. E. Eskin, K. Z. Gumargalieva, Vysokomol. Soedin., 2, 265 (1960). 104. V. E. Eskin, O. Z. Korothina, Vysokomol. Soedin,, 2, 272 (1960); J. Polym. Sci. USSR, 2, 247 (1961). 105. J. M. Evans, M. B. Huglin, Makromol. Chem., 127, 141 (1969). 106. J. M. Evans, M. B. Huglin, Europ. Polym. J., 6, 1161 (1970).
107. J. M. Evans, M. B. Huglin, cited in [84]. 108. W. W. Everett, J. F. Foster, J. Am. Chem. Soc, 81, 3459, 3464 (1959). 109. J. Feisst, H.-G. Elias, Makromol. Chem., 82, 78 (1965). 110. P. J. Flory, "Principles of Polymer Chemistry", Cornell Univ. Press, Ithaca, NY, 1953. 111. P. J. Flory, L. Mandelkern, J. B. Kinsinger, W. B. Shultz, J. Am. Chem. Soc, 74, 3364 (1952). 112. T. G. Fox, Polymer, 3, 111 (1962). 113. T. G. Fox, P. J. Flory, J. Am. Chem. Soc, 73, 1909 (1959). 114. T. G. Fox, P. J. Flory, J. Am. Chem. Soc, 73, 1915 (1959). 115. T. G. Fox, J. B. Kinsinger, H. F. Mason, E. M. Schuele, Polymer, 3, 71 (1962). 116. D. M. French, A. W. Casey, C. I. Collins, P. Kirchner, ACS Polymer Preprints, 7, 447 (1966). 117. D. Froelich, Ph.D. Thesis, Univ. of Strasbourg, 1966; cited in [83]. 118. D. Froelich, H. Benoit, Makromol. Chem., 92, 224 (1966). 119. M. Fukuda, M. Fukutomi, Y. Kato, T. Hashimoto, J. Polym. Sci.-Polym. Chem. Ed., 12, 871 (1974). 120. C. Garbuglio, L. Crescentini, A. MuIa, G. B. Gechele, Makromol. Chem., 97, 97 (1966). 121. L. Gargallo, J. Niezzette, V. Desreux, Bull. Soc Roy. Sci. Liege, 1-2, 82 (1977); cited in [122]. 122. L. Gargallo, D. Radic, I. Katime, Europ. Polym. J., 16, 383 (1980). 123. G. B. Gechele, L. Crescentini, J. Polym. Sci. A, 3, 3599 (1965). 124. H. Geerissen, B. A. Wolf, Makromol. Chem., Rapid Commun., 3, 17 (1982). 125. G. Gianotti, U. Bonicelli, D. Borghi, Makromol. Chem., 166, 235 (1973). 126. C. Gonzalez, F Zamora, G. M. Guzman, L. M. Leon, Makromol. Chem., 185, 339 (1984). 127. T. B. Grimley, Proc Roy. Soc. [London] A, 212, 339 (1952). 128. U. Gruber, Ph.D. Thesis, ETH Zurich, 1964. 129. N. Hadjichristidis, Polymer, 16, 848 (1975). 130. N. Hadjichristidis, J. E. L. Roovers, J. Polym. Sci., Polym. Phys. Ed., 12, 2521 (1974). 131. J. Hakozaki, J. Chem. Soc Japan, Pure Chem. Sect. (Nippon Kagaku Zasshi), 82, 158 (1961). 132. F. Hamada, K. Fujisawa, A. Nakajima, Polym. J., 4, 316 (1973). 133. K. Hanafusa, A. Teramoto, H. Fujita, J. Chem. Phys., 70, 4004 (1966). 134. J. N. Hay, A. M. Afifi-Effat, Brit. Polym. J., 9, 1 (1977). 135. J. N. Hay, P A. Fitzgerald, J. Polym. Sci., Polym. Chem. Ed., 18, 1079 (1980). 136. J. N. Hay, M. Wiles, Brit. Polym. J., 10, 181 (1978). 137. W. Hayduk, H. A. Bromfield, J. Appl. Polym. Sci., 22, 149 (1978). 138. T. E. Helminiak, C. L. Benner, W. E. Gibbs, ACS Polymer Preprints, 8, 284 (1967). 139. I. Hernandez-Fuentes, M. G. Prolongo, Europ. Polym. J., 15, 571 (1979). 140. F. K. Herold, B. A. Wolf, Makromol. Chem., 184, 2539 (1981).
141. J. Herold, G. Meyerhoff, Europ. Polym. J., 15, 525 (1979). 142. M. Heskins, J. E. Guillet, J. Macromol. Sci. A, 2, 1441 (1968). 143. T. Hirosye, Y. Einaga, H. Fujita, Polym. J., 11, 819 (1979). 144. T. Homma, K. Kawahara, H. Fujita, M. Ueda, Makromol. Chem., 67, 132 (1963). 145. T. Homma, K. Kawahara, H. Fujita, J. Appl. Polym. Sci., 8, 2853 (1964). 146. F. Hooshmand-Mozaffar, M. K. Hoseinalizadeh-Khorasani, M. B. Huglin, Polymer, 21, 413 (1980). 147. F. Horii, Y Ikada, I. Sakurada, J. Polym. Sci., Polym. Chem. Ed., 12, 323 (1974). 148. N. Howard, M. B. Huglin, R. W. Richards, J. Appl. Polym. Sci., 16, 1525 (1972). 149. A. J. Hyde, R. B. Taylor, Polymer, 4, 1 (1963). 150. T. Ikeda, H. Kawaguchi, Rep. Progr. Polym. Phys. Japan, 9, 23 (1966). 151. H. Inagaki, A. Nakazawa, T. Kotaka, Bull. Inst. Chem. Res. Kyoto Univ., 43, 135 (1965). 152. H. Inagaki, T. Miyamoto, S. Ohta, J. Phys. Chem., 70, 3420 (1966). 153. H. Inagaki, H. Suzuki, M. Fujii, T Matsuo, J. Phys. Chem., 70, 1718 (1966). 154. K. J. Mn, H. A. Ende, G. Meyerhoff, Polymer, 3,129 (1962). 155. M. Iwama, H. Utiyama, M. Kurata, J. Macromol. Chem., 1, 701 (1966). 156. Y. Izumi, Y Miyake, Polym. J., 3, 647 (1972). 157. Y Izumi, Y. Miyake, Polym. J., 4, 205 (1973). 158. Y. Izumi, S. Otsuka, Y Miyake, Rep. Progr. Polym. Phys. Japan, 12, 13 (1969). 159. R. Jerome, V. Desreux, Europ. Polym. J., 6, 411 (1970). 160. R. M. Johnson, J. L. Schrag, J. D. Ferry, Polym. J., 1, 742 (1970). 161. M. Kalfus, J. Mitus, J. Polym. Sci. A-I, 4, 953 (1966). 162. K. Kamada, H. Sato, Polym. J., 2, 593 (1971). 163. K. Kamide, T. Terekawa, Makromol. Chem., 155,25 (1972). 164. Ye. A. Kanevskaya, P. I. Zubov, L. V. Ivanova, Yu. S. Lipatov, Vysokomol. Soedin., 6, 981 (1964); Polym. Sci. USSR, 6, 1080 (1964). 165. A. Katchalsky, H. Eisenberg, J. Polym. Sci., 6, 145 (1951). 166. I. A. Katime Amashta, G. Sanchez, Europ. Polym. J., 11,223 (1975). 167. H. Kaye, H. J. Cou, J. Polym. Sci., Polym. Phys. Ed., 13,477 (1975). 168. W. Kern, D. Braun, Makromol. Chem., 27, 23 (1958). 169. J. B. Kinsinger, L. E. Ballard, J. Polym. Sci. B, 2, 879 (1964). 170. J. B. Kinsinger, L. E. Baliard, J. Polym. Sci. A, 3, 3963 (1965). 171. J. B. Kinsinger, R. E. Hughes, J. Phys. Chem., 67, 1922 (1963). 172. J. B. Kinsinger, R. A. Wessling, J. Am. Chem. Soc, 81, 2908 (1959). 173. R. Kirste, G. V. Schulz, Z. Physik. Chem. (Frankfurt/M.), 27, 310 (1960). 174. R. G. Kirste, G. V. Schulz, Z. Physik. Chem. (Frankfurt/M.), 30, 171 (1961).
175. M. R. Knecht, R-G. Elias, Makromol. Chem., 157, 1 (1972). 176. A. Kokkiaris, C. Touloupis, N. Hadjichristidis, Polymer, 22, 63 (1981). 177. R. Koningsveld, Th. G. Schoolte, private communication. 178. T. Kotaka, H. Ohnuma, H. Inagaki, Polymer, 10, 517 (1969). 179. T. Kotaka, H. Ohnuma, H. Inagaki, ACS Polymer Preprints, 11, 660 (1970). 180. T. Kotaka, H. Ohnuma, Y. Murakami, J. Phys. Chem., 70, 4099 (1966). 181. T. Kotaka, T. Tanaka, H. Ohnuma, Y. Murakami, H. Inagaki, Polymer J., 1, 245 (1970). 182. A. Kotera, H. Matsuda, K. Konishi, K. Takemura, J. Polym. Sci. C, 23, 619 (1968). 183. A. Kotera, N. Onda, T. Saito, Rep. Progr. Polym. Phys. Japan, 17, 25 (1974). 184. A. Kotera, T. Saito, N. Yamaguchi, Annual Meeting Chem. Soc. Japan, 1962; cited in A. Kotera, N. Ise, A. Senuma, T. Hamada, IUPAC Symp. Macromol., Prague 1965, Preprint 232. 185. J. Kovaf, L. Mrkvickova-Vaculova, M. Bohdanecky, Makromol. Chem., 176, 1829 (1975). 186. P. Kratochvil, D. Strtakova, Makromol. Chem., 154, 325 (1972). 187. S. Krause, E. Cohn-Ginsburg, J. Phys. Chem., 67, 1479 (1963). 188. W. R. Krigbaum, D. K. Carpenter, J. Phys. Chem., 59, 1166 (1955). 189. W. R. Krigbaum, P. J. Flory, J. Polym. Sci., 11, 37 (1953). 190. W. R. Krigbaum, J. E. Kurz, P. Smith, J. Phys. Chem., 65, 1984 (1961). 191. W. R. Krigbaum, L. H. Sperling, J. Phys. Chem., 64, 99 (1960). 192. W. R. Krigbaum, J. D. Woods, J. Polym. Sci. A, 2, 3075 (1964). 193. S. Krozer, Plaste Kautschuk, 15, 175 (1968). 194. S. Krozer, A. Pastusiak, IUPAC Symp. Macromol., Prague 1965, Preprint 609. 195. K. Kubo, K. Ogino, Rep. Progr. Polym. Phys. Japan, 10,111 (1967). 196. K. Kubo, K. Ogino, T. Nakagawa, Rep. Progr. Polym. Phys. Japan, 10, 7 (1967). 197. Z. Kuciikyavuz, A. Kuc,iikyavuz, Europ. Polym. J., 14, 867 (1978). 198. A. M. Kulakova, I. K. Nekrasov, Vysokomol. Soedin. A, 18, 127 (1976); Polym. Sci. USSR, 18, 146 (1976). 199. M. Kurata, H. Utiyama, K. Kamada, Makromol. Chem., 88, 281 (1965). 200. N. Kuwahara, S. Higashida, M. Nakata, K. Kaneko, J. Polym. Sci. A-2, 7, 285 (1969). 201. N. Kuwahara, M. Kaneko, Makromol. Chem., 82 205 (1965). 202. N. Kuwahara, T. Miyake, M. Kaneko, J. Furuichi, Rep. Progr. Polym. Phys. Japan, 5, 1 (1962). 203. N. Kuwahara. S. Saeki, S. Konno, M. Kaneko, Macromolecules, 6, 589 (1973). 204. N. Kuwahara, S. Saeki, S. Konno, Polymer, 15, 66 (1974).
205. D. Lath, M. Bohdanecky, J. Polym. Sci.-Letters Ed., 15, 555 (1977). 206. H. T. Lee, D. W. Levi, J. Polym. Sci., 47, 449 (1960). 207. L. M. Leon, J. Galaz, L. M. Garcia, M. S. Anasagasti, Europ. Polym. J., 16, 921 (1980). 208. D. W. Levi, H. T. Lee, R. J. Valles, J. Polym. Sci., 62, S163 (1962). 209. J. Lilie, J. Springer, K. Ueberreiter, Kolloid-Z., 226, 138 (1968). 210. F. C. Lin, S. S. Stivala, J. A. Biesenberger, J. Appl. Polym. Sci., 17, 3465 (1973). 211. M. Lippay. Ph.D. Thesis, ETH Zurich, 1963. 212. J. Llopis, A. Albeit, P. Usobiaga, Europ. Polym. J., 3, 259 (1967). 213. T. Lucas, Bull. Liaison Lab. (Lab. Prof. Peint)., 20, 15 (1967). 214. N. V. Makletsova, I. V. Epel'baum, B. A. Rozenberg, Ye. B. Lyudvig, Vysokomol. Soedin., 7, 70 (1965); Polym. Sci. USSR, 7, 73 (1966). 215. L. Mandelkern, P. J. Flory, J. Am. Chem. Soc, 74, 2517 (1952). 216. P. V. Mangalam, V. P. Kalpagam, J. Polym. Sci.-Polym. Phys. Ed., 20, 773 (1982). 217. V. P. Mardykin, K. B. Martinovich, A. I. Volozhin, N. M. Denisyuk, Vysokomol. Soedin. B, 16, 23 (1974); CA 81: 1390Or (1974). 218. J. E. Mark, Diss. Abstr., 23, 1205 (1962). 219. J. E. Mark, P. J. Flory, J. Am. Chem. Soc, 87, 1423 (1965). 220. R. M. Masegosa, M. G. Prolongo, I. Hernandez-Fuentes, A. Horta, Macromolecules, 17, 1181 (1984). 221. T. Matsumoto, N. Nishioka, H. Fujita, J. Polym. Sci. A-2,10, 23 (1972). 222. M. Matsumoto, Y. Ohyanagi, J. Polym. Sci., 46, 441 (1960). 223. M. Matsumoto, Y. Ohyanagi, J. Polym. Sci., 50, Sl (1961). 224. K. Matsumura, Polym. J., 1 322 (1970). 225. M. Matsushima, M. Fukatsu, M. Kurata, Bull. Chem. Soc Japan, 41, 2570 (1968). 226. A. Mattiussi, E. Conto, G. B. Gechele, Europ. Polym. J., 8, 429 (1972). 227. W. L. Mattice, L. Mandelkern, Macromolecules, 4, 271 (1971). 228. R. M. May, R. E. Wetton, cited in [84]. 229. H. W. McCormick, J. Polym. Sci., 36, 341 (1959). 230. D. Mclntyre, J. H. O'Mara, B. C. Konouck, J. Am. Chem. Soc, 81, 3498 (1959). 231. R. A. Mendelson, J. Polym. Sci., 46, 493 (1960). 232. G. Meyerhoff, Makromol. Chem., 37, 97 (1960). 233. G. Meyerhoff, in: J. W. Williams (Ed.), "Ultracentrifugal Analysis in Theory and Practice". Academic Press, New York, 1963. 234. R. Meza, L. Gargallo, Europ. Polym. J., 13, 235 (1977). 235. S. Miyamoto, Y. Ishii, H. Ohnuma, Makromol. Chem., 182, 483 (1981). 236. J. Moacanin, J. Appl. Polym. Sci., 1, 272 (1959). 237. J. Moacanin, A. Rembaum, R. K. Laudenslager, ACS Polymer Preprints, 4/2, 179 (1963).
238. J. Moacanin, A. Rembaum, R. K. Laudenslager, R. Adler, J. Macromol. Sci., Chem., A: 1, 1497 (1967). 239. R. B. Mohite, S. Gundiah, S. L. Kapur, Makromol. Chem., 108, 52 (1967). 240. L. D. Moore, Jr., J. Polym. Sci., 36, 155 (1959). 241. W. R. Moore, M. Uddin, Europ. Polym. J., 5, 185 (1969). 242. G. Moraglio, Europ. Polym. J., I1 103 (1965). 243. G. Moraglio, J. Brzenzainski, J. Polym. Sci. B, 2, 1105 (1964). 244. G. Moraglio, G. Gianotti, U. Bonicelli, Europ. Polym. J., 9, 623 (1973). 245. G. Moraglio, G. Gianotti, F. Danusso, Europ. Polym. J., 3, 251 (1967). 246. G. Moraglio, G. Gianotti, F. Zoppi, U. Bonicelli, Europ. Polym. J., 7, 303 (1971). 247. U. Moritz, G. Meyerhoff, Makromol. Chem., 139,23 (1970). 248. G. A. Morneau, P. I. Roth, A. R. Shultz, J. Polym. Sci., 55, 609 (1961). 249. J. Naghizadeh, J. Springer, Kolloid-Z. Z. Polym., 215, 21 (1967). 250. R. Naito, Chem. High Polym. Japan (Kobunshi Kagaku), 16, 7 (1959). 251. A. Nakajima, H. Fujiwara, F. Hamada, J. Polym. Sci. A-2,4, 507 (1966). 252. A. Nakajima, F. Hamada, Rep. Progr. Polym. Phys. Japan, 9, 41 (1966). 253. A. Nakajima, K. Kato, Makromol. Chem., 95, 52 (1966). 254. A. Nakajima, K. Okazaki, Chem. High Poiym. Japan (Kobunshi Kagaku), 22, 791 (1965). 255. A. Nakajima, H. Saijyo, J. Polym. Sci. A-2, 6, 735 (1968). 256. A. Nakajima, K. Tanaami, Polym. J., 5, 248 (1973). 257. D. H. Napper, Trans. Faraday Soc, 64, 1701 (1968). 258. D. H. Napper, Kolloid-Z., 234, 1149 (1969). 259. D. H. Napper, J. Colloid Interface Sci., 32, 106 (1970). 260. D. H. Napper, J. Colloid Interface Sci., 33, 384 (1970). 261. D. W. Nash, C. C. Pepper, Polymer, 16, 105 (1975). 262. P. Neuenschwander, P. Pino, Makromol. Chem., 181, 737 (1980). 263. S. Newman, W. R. Krigbaum, C. Laugier, P. J. Flory, J. Polym. Sci., 14, 451 (1954). 264. J. Niezette, N. Hadjichristidis, V. Desreux, Europ. Polym. J., 13, 41 (1977). 265. A. Nikolaev, N. V. Daniel, A. M. Torotseva, I. Varga, N. V. Ivanova, Vysokomol. Soedin., 6, 292 (1964); Polym. Sci. USSR, 6, 336 (1964). 266. I. Noda, K. Mizutani, T. Kato, T. Fujimoto, N. Nagasawa, Macromolecules, 3, 787 (1970). 267. H. Ohnuma, Y. Murakami, T. Kotaka, Rep. Progr. Polym. Phys. Japan, 10, 63 (1967). 268. R. Okada, Y. Toyoshima, H. Fujita, Makromol. Chem., 59, 137 (1963). 269. T. A. Orofino, A. Ciferri, J. Phys. Chem., 68, 3136 (1964). 270. T. A. Orofino, J. W. Mickey, Jr., J. Chem. Phys., 38, 2512 (1963). 271. R. Okada, Y. Toyoshima, H. Fujita, Makromol. Chem., 59, 137 (1963).
272. S. Okamura, T. Higashimura, Y. Imanishi, Chem. High Polym. Japan (Kobunshi Kagaku), 16, 244 (1959). 273. J. Oth, V. Desreux, Bull. Soc. Chim. Beige, 63, 285 (1954). 274. P. Outer, C. I. Carr, B. H. Zimm, J. Chem. Phys., 18, 830 (1950). 275. C. G. Overberger, E. M. Pearce, N. Mayes, J. Polym. Sci., 34, 109 (1959). 276. O. Quadrat, Coll. Czech. Chem. Commun., 35, 2564 (1970). 277. O. Quadrat, M. Bohdanecky, J. Polym. Sci. A-2, 5, 1309 (1967). 278. O. Quadrat, M. Bohdanecky, L. Mrkvickova, Makromol. Chem., 182, 445 (1981). 279. O. Quadrat, M. Bohdaneckv, P. Munk, J. Polym. Sci. C, 16, 95 (1967). 280. M. Pissoli, G. Ceccorulli, G. Stea, Makromol. Chem., 164, 273 (1973). 281. M. Pizzoli, G. Stera, G. Ceccorulli, G. B. Gechele, Europ. Polym. J., 6, 1219 (1970). 282. I. Ya. Poddubnyi, V. A. Grechanovskii, M. I. Mosevitskii, Vysokomol. Soedin, 5, 1049 (1963); Polym Sci. USSR, 5, 105 (1964). 283. I. Ya. Poddubnyi, V. A. Grechanovskii, M. I. Mosevitskii, A. V. Podalinskii, Vysokomol. Soedin, 5, 1042 (1963); Polym. Sci. USSR, 5, 97 (1964). 284. I. Ya. Poddubnyi, V. A. Grechanovskii, A. V. Podalinskii, J. Polym. Sci. C, 16, 3109 (1968). 285. I. Ya. Poddubnyi, A. V. Podalinskii, V. A. Grechanovskii, Polym. Sci. USSR, 8, 1715 (1966). 286. R. Puffr, Z. Tuzar, L. Mrkvickova, J. Sebenda, Makromol. Chem., 184, 1957 (1983). 287. D. Radic, L. Gargallo, Makromol. Chem., 180, 1329 (1979). 288. D. Radic, L. Gargallo, Polymer, 22, 410 (1981). 289. C. Reiss, H. Benoit, Compt. Rend. Acad. Sci. (Paris), 253, 268 (1962). 290. C. Reiss, H. Benoit, J. Polym. Sci. C, 16, 3079 (1968). 291. R. W. Richards, Polymer, 18, 114 (1977). 292. R. W. Richards, G. Disselhoff, Angew. Makromol. Chem., 66, 221 (1978). 293. A. Roig, I. Katime, V. C. Ramiro, L. M. Leon, An. Quim., 69, 965 (1973). 294. J. Roovers, Polymer, 20, 843 (1979). 295. R. Rossi, A. Mattiussi, G. B. Gechele, D. Damiani, Chim. Ind. (Milan), 53, 350(1971). 296. S. Saeki, S. Konno, N. Kuwahara, M. Nakata, M. Kaneko, Macromolecules, 7, 521 (1974). 297. G. Saini, L. Trossarelli, J. Polym. Sci., 23, 563 (1957). 298. Y. Sakaguchi, J. Nishino, K. Tsugawa, Chem. High Polym., Japan (Kobunshi Kagaku), 20, 661 (1963). 299. I. Sakurada, A. Nakajima, K. Shibetani, J. Polym. Sci. A, 2, 3345 (1964). 300. I. Sakurada, A. Nakajima, O. Yoshizaki, K. Nakamae, Kolloid-Z., 186, 41 (1962). 301. I. Sakurada, Y. Sakaguchi, S. Kokuryo, Chem. High. Polym. Japan (Kobunshi Kagaku), 17, 227 (1960). 302. R. J. Samuels, Polymer, 18, 452 (1977). 303. M. Sato, Y. Koshishi, M. Asahina, J. Polym. Sci. B, 1, 233 (1963).
304. K. S. Sastry, R. D. Patel, Europ. Polym. J., 5, 79 (1969). 305. P. R. Saunders, J. Poiym. Sci., 57, 131 (1961). 306. W. Scholtan, H. Lange, R. Casper, U. Pohl, D. Wendisch, R. Mayer-Mader, Angew. Makromol. Chem., 27, 1 (1972). 307. G. V. Schulz, H. Baumann, Makromol. Chem., 60,120 (1963). 308. G. V. Schulz, H. J. Cantow, Z. Elektrochem., 60, 517 (1956). 309. G. V. Schulz, A. Haug, Z. Physik. Chem. (Frankfurt/M.), 34, 328 (1962). 310. G. V. Schulz, A. MuIa, Makromol. Chem., 44/46, 479 (1961). 311. G. V. Schulz, W. Wunderlich, R. Kirste, Makromol. Chem., 75, 22 (1964). 312. K. Sedlak, D. Lath, Makrotest sb, Prednasek, Celustatni Kof., 5, 71 (1978); CA 89, 180549e (1978). 313. V. S. Shazka, G. A. Fomin, G. V. Tarasova, I. G. Kirillova, V. M. Yamshchikov, A. Ye. Grishchenko, I. A. Shefer, I. S. Alekseyeva, Polym. Sci. USSR, 15, 2903 (1973). 314. Y. Shiokawa, H. Takeo, K. Takamizawa, T. Oyama, Rep. Progr. Polym. Phys. Japan, 7, 49 (1964). 315. A. R. Shultz, Ph.D. Thesis, Cornell Univ., cited in [HO]. 316. A. R. Shultz, J. Am. Chem. Soc, 76, 3422 (1954). 317. A. R. Shultz, C. R. McCullough, J. Polym. Sci. A-2,7, 1577 (1969). 318. L. Simek, J. Hrncirik, M. Mladek, Angew. Makromol. Chem., 92, 33 (1980). 319. G. Sitaramaiah, D. Jacobs, Makromol. Chem., 164, 237 (1973). 320. V. S. Skazka, R. A. Zobov, A. Moshpauenko, Vysokomol. Soedin., 4, 1257 (1962). 321. E. M. Sorvik, J. Appl. Polym. Sci., 21, 2769 (1977). 322. T. Spychaj, D. Lath, D. Berek, Polymer, 20, 437 (1979). 323. K. S. V. Srinivasan, M. Santappa, Polymer, 14, 5 (1973). 324. C. J. Stacy, R. L. Arnett, J. Phys. Chem., 69, 3109 (1965). 325. C. J. Stacy, J. E Foster, J. Polym. Sci., 20, 56 (1956). 326. U. P. Strauss, P Ander, J. Phys. Chem., 66, 2235 (1962). 327. U. P. Strauss, R L. Wineman, J. Am. Chem. Soc, 80, 3266 (1958). 328. C. Strazielle et al., cited in J. P. Cotton, D. Decker, H. Benoit, B. Farnoux, J. Higgins, G. Jannink, R. Ober, C. Picot, J. des Cloizeaux, Macromolecules, 7, 863 (1974). 329. C. Strazielle, H. Benoit, O. Vogl, Europ. Polym. J., 14, 331 (1978). 330. H. Suzuki, K. Kamide, M. Saitoh, Europ. Polym. J., 18, 123 (1982). 331. H. Suzuki, Y Muraoka, M. Saitoh, K. Kamide, Brit. Polym. J., 14, 23 (1982). 332. H. Suzuki, Y. Muraoka, M. Saitoh, K. Kamide, Europ. Polym. J., 18, 831 (1982). 333. K. Takamizawa, Y. Kambara, T Oyama, Rep. Progr. Polym. Phys. Japan, 10, 85 (1967). 334. S. Tani, F. Hamada, A. Nakajima, Polym. J., 5, 86 (1973). 335. J. O. Threkeld, H. A. Ende, J. Polym. Sci. A-2,4,663 (1966). 336. M. Tricot, J. P. Bleus, J.-P. Riga, V. Desreux, Makromol. Chem., 175, 913 (1974). 337. M. Tricot, C. Mertens, R Collete, V. Desreux, Bull. Roy. Soc. Liege, 43, 502 (1974).
338. S. Tsuchiya, Y. Sakaguchi, I. Sakurada, Chem. High. Polym. Japan (Kobunshi Kagaku), 18, 346 (1961). 339. T Tsuji, H. Fujita, Polym. J., 4, 409 (1973). 340. V. N. Tsvetkov, L. N. Andreyeva, Ye. V. Korneyeva, R N. Lavrenko, N. A. Plate, V. R Shibayev, B. S. Petrukhin, Vysokomol. Soedin. A, 14, 1944 (1972). 341. V. N. Tsvetkov, L. N. Andreyeva, Ye. V. Komeyeva, P. N. Lavrenko, N. A. Plate, V. P Shibayev, B. S. Petrukhin, Vysokomol. Soedin. A, 13, 2226 (1971); Polym. Sci. USSR, 13, 2501 (1971). 342. V. N. Tsvetkov, G. V. Tarasova, Ye. L. Vinogradov, N. Kuprianova, V. M. Yamshchikov, V. S. Kozka, V. S. Ivanov, V. K. Smirnova, 1. I. Migunova, Vysokomol. Soedin. A, 13, 620 (1971); Polym. Sci. USSR, 13, 705 (1971). 343. Z. Tuzar, P. Kratochvil, Coll. Czech. Chem. Comm., 32, 3358 (1967). 344. Z. Tuzar, V. Vosicky, M. Bohdanecky, J. Jalovecky, Makromol. Chem., 180, 1399 (1979). 345. M. Ueda, K. Kajitani, Makromol. Chem., 108, 138 (1967) 346. M. Uhniat, M. Rubaj, T. Marciniak, J. Bankiewicz, Polimery, 17, 141 (1972); CA 77: 153493c (1972). 347. I. R. Urwin, M. Girolamo, Makromol. Chem., 150, 179 (1971). 348. R. van Leemput, R. Stein, J. Polym. Sci. A, 2, 4039 (1964). 349. P. Vasudevan, M. Santappa, Makromol. Chem., 137, 261 (1970). 350. J. Valickovic, V. Juranicova, J. Filipovic, Angew. Makromol. Chem., 24, 77 (1972). 351. H. Volker, F-J. Luig, Angew. Makromol. Chem., 12, 43 (1970). 352. H. L. Wagner, P J. Flory, J. Am. Chem. Soc, 74,195 (1952). 353. H. L. Wagner, C. A. J. Hoeve, J. Polym. Sci.-Symp., 54, 327 (1976). 354. R. A. Wessling, Diss. Abstr., 23, 1536 (1962). 355. G. R. Williamson, A. Cervenko, Europ. Polym. J., 10, 295 (1974). 356. B. A. Wolf, H. F. Bieringer, J. W. Breitenbach, Polymer, 17, 605 (1976). 357. E. Wolfram, Kolloid-Z. Z. Polym., 227, 86 (1968). 358. K. Yamamoto, N. Bessho, T. Shiibashi, E. Maekawa, Polym. J., 13, 555 (1981). 359. M. M. Zafar, R. Mahmood, Makromol. Chem., 175, 903 (1974). 360. E. A. Zavaglia, F. W. Billmeyer, Jr., Official Digest, 36, 221 (1964). 361. G. Gianotti, U. Bonicelli, D. Borghi, Makromol. Chem., 166, 235 (1973). 362. M. Abe, Y. Murakami, H. Fujita, J. Appl. Polym. Sci., 9, 2549(1965). 363. J. Mays, H. Hadjichristidis, L. J. Fetters, Macromolecules, 17, 2723 (1984). 364. K. Kajiwara, H. Suzuki, H. Inagaki, M. Maeda, T. Tsuruta, Makromol. Chem., 187, 2251 (1986). 365. Z. Kiic.ukyavuz, S. Kugiikyavuz, Makromol. Chem., 187 2469 (1986). 366. J. Roovers, J. Polym. Sci., Polym. Phys. Ed., 23, 1117 (1985).
367. S. Arichi, N. Sakamoto, S. Himura, M. Miki, M. Yoshida, Polymer, 26, 1175(1985). 368. G. C. Berry, E. F. Casassa, P.-Y. Liu, J. Polym. Sci., Polym. Phys. B, 25, 673 (1987). 369. O. Vogl, M. Malanga, W. Berger, in W. J. Bailey, T. Tsuruta, Eds., "Contemporary Topics in Polymer Science", Vol. 4, Plenum, New York 1984, p. 35. 370. J. W. Mays, W. M. Ferry, N. Hadjichristidis, W. G. Funk, L. J. Fetters, Polymer, 27, 129 (1986). 371. R. W. Richards, A. Maconnachie, G. Allen, Polymer, 22,153 (1981). 372. J. L. Roovers, P. M. Toporowski, Macromolecules, 14, 1174 (1981). 373. J. L. Roovers, P. M. Toporowski, Macromolecules, 16, 843 (1983). 374. B. A. Wolf, H. J. Adam, J. Chem. Phys., 75, 4121 (1981). 375. P. Vidakovic, F. Rondelez, Macromolecules, 18,700 (1985). 376. W. Brown, P. Stepanek, Macromolecules, 21, 1791 (1988). 377. H. Geerissen, J. Roos, B. A. Wolf, Makromol. Chem., 186, 753 (1985). 378. S. Arichi, Bull. Chem. Soc. Japan, 39, 439 (1966). 379. P. V. Mangalam, V. P. Kalpagam, Polymer, 23, 991 (1982). 380. F. Horkay, H. B. Stanley, E. Geissler, S. M. King, Macromolecules, 28, 678 (1995). 381. P. Sakellariou, Polymer, 33, 1339 (1992). 382. S. Fujishige, Polymer J., 19, 297 (1987). 383. P. Gregory, M. B. Huglin, M. K. H. Khorasani, P. M. Sasia, Brit. Polym. J., 20, 1 (1988). 384. K. Kamide, Y. Miyazaki, H. Kobayashi, Polymer J., 17, 607 (1985). 385. K. Kamide, Y Miyazaki, H. Kobayashi, Polymer J., 14, 591 (1982). 386. L. Gargallo, D. Radic, A. Leon, Makromol. Chem., 186, 1289 (1985). 387. W. Scholtan, H. Marzolph, Makromol. Chem., 57,52 (1962). 388. V. P. Shibaev, Habilitation Thesis, Moscow State University, 1974; cited by N. A. Plate, V. P. Shibaev, "Comb-Shaped Polymers and Liquid Crystals", Plenum, New York, 1987. 389. M. P. Breton, Diss. Abstracts International B, 42/11, 4446 (1982). 390. K. Kubota, S. Fujishige, I. Ando, Polymer J., 22, 15 (1990). 391. S. R. Gooda, M. B. Huglin, Macromolecules, 25, 4215 (1992). 392. K. Sivadasan, S. Gundiah, Polymer, 28, 1426 (1987). 393. K. Nomiama, M. Kaneko, Rep. Progr. Polym. Phys. Japan, 24, 15 (1981). 394. N. M. Wiederbora, A. R. Brown, J. Polym. Sci., 8, 651 (1952). 395. N. Hadjichristidis, C. Touloupis, Makromol. Chem., 183, 611 (1982). 396. N. Hadjichristidis, J. Mays, W. Ferry, L. J. Fetters, J. Polym. Sci.-Polym. Phys. Ed., 22, 1745 (1984). 397. J. W. Mays, W. Ferry, N. Hadjichristidis, L. J. Fetters, Macromolecules, 18, 2330 (1985). 398. N. Hadjichristidis, Makromol. Chem., 178, 1463 (1977). 399. M. Krakovyak, T. Ananieva, E. Anufrieva, T. Nekrasova, G. Sinitsina, Makromol. Chem., 186, 1075 (1985).
400. H. Inagaki, S. Kawai, Makromol. Chem., 79, 42 (1964). 401. X. Zhongde, N. Hadjichristidis, L. J. Fetters, Macromolecules, 17, 2303 (1984). 402. H. G. Ohm, R. G. Kirste, R. C. Oberthiir, Makromol. Chem., 189, 1387 (1988). 403. M. Nakata, Y Nakano, K. Kawate, Macromolecules, 21, 2509 (1988). 404. E. Siakali-Kioulafa, N. Hadjichristidis, J. W. Mays, Macromolecules, 22, 2059 (1989). 405. J. W. Mays, N. Hadjichristidis, J. S. Lindner, ACS Polymer Preprints, 32/1, 148 (1991). 406. M. Ricker, M. Schmidt, ACS Polymer Preprints, 31/2, 122 (1990) Makromol. Chem. 192, 679 (1991). 407. Y. Tamai, T. Konishi, Y. Einaga, M. Fujii, H. Yamakawa, Macromolecules, 23, 4067 (1990). 408. G. M. Burnett, P. Meares, C. Paton, Trans. Faraday, Soc, 58, 737 (1962). 409. M. Guaita, O. Chiantore, W. Burchard, Makromol. Chem., 192, 2333 (1991). 410. T. Yoshizaki, H. Hayashi, H. Yamakawa, Macromolecules, 26, 4037 (1993). 411. L. Gargallo, N. Hamidi, D. Radic, Polymer, 31, 924 (1990). 412. S. P. Nunes, B. A. Wolf, H. E. Jeberien, Macromolecules, 20, 1948 (1987). 413. Y Matsushita, K. Shimizu, Y Nakao, H. Chashi, I. Noda, M. Nagasawa, Polym. J., 18, 361 (1986). 414. I. Katime, J. R. Quintana, Polym. Bull, 6, 455 (1982). 415. M. J. R. Cantow, R. B. Larrabee, E. M. Barrall II, R. S. Butner, P. Cotts, F. Levy, T. Y Ting, Makromol. Chem., 187, 2475 (1986). 416. P. Gregory, M. B. Huglin, Makromol. Chem., 187, 1745 (1986). 417. M. Ataman, Colloid Polym. Sci., 265, 19 (1987). 418. W. F. Polik, W. Burchard, Macromolecules, 16, 978 (1983). 419. T. Amu, Polymer, 23, 1775 (1982). 420. Ye. A. Gladkova, S.-S. A. Pavlova, L. V. Dubrovina, V. V. Korshak, Vysokomol. soyed. A, 26,53 (1984); Polymer Sci. USSR, 26, 59 (1984). 421. M. B. Huglin, M. A. Radwan, Polymer, 32, 1293 (1991). 422. P. R. Saunders, J. Polym. Sci. A, 2, 3765 (1964). 423. W. Brown, Arkiv Kemi, 18, 227 (1961). 424. H. L. Griffin, S. R. Erlander, F. R. Senti, Die Starke, 1, 8 (1967). 425. V. P. Shanbhag, J. Ohman, Arkiv Kemi, 29, 163 (1968). 426. K. Kamide, S. Matsuda; cited in K. Kamide, M. Saito, Adv. Polym. Sci., 83, 1 (1987). 427. T. Konishi, Y. Yoshizaki, H. Yamakawa, Macromolecules, 24, 5614 (1991). 428. G. Allen, J. McAnish, C. Strazielle, Europ. Polym. J., 5, 319 (1969). 429. A. Lapp, C. Strazielle, Makromol. Chem.-Rapid Comm., 6, 591 (1985); Makromol. Chem., 188, 2921 (1987). 430. L. A. Tartarova, T G. Ermakova, N. F. Kedreena, B. A. Kasekeen, D. D. Novekov, B. A. Lopirev, Vysokomol. Soedin., 24, 697 (1982). 431. T. E. Helminiak, C. L. Benner, W. E. Gibbs, ACS Polymer Preprints, 8/1, 284 (1967).
432. P. J. Flory, L. Mandelkern, J. B. Kinsinger, W. B. Shultz, J. Am. Chem. Soc., 74, 3364 (1952). 433. A. Haug, G. Meyerhoff, Makromol. Chem., 53, 91 (1962). 434. H. Rios, L. Gargallo, D. Radic, J. Polym. ScL, B: Polym. Phys. 24, 2421 (1986). 435. P. P. Shah, J. Macromol. Sci. A: Chem. 21, 547 (1984). 436. L. V. Dubrovina, S.-S. A. Pavlova, M. A. Ponomareva, Vysokomol. Soyed. A, 27, 780 (1985); Polym. Sci. USSR, 27, 875 (1985). 437. J. I. Egaiazabal, J. Areizaga, J. J. Iruin, G. M. Guzman, Europ. Polym. J., 21, 711 (1985). 438. I. H. Park, J.-H. Kim, T. Chang, Macromolecules, 25, 7300 (1992). 439. C. Strazielle, H. Benoit, Macromolecules, 8, 203 (1975). 440. J. M. G. Cowie, I. J. McEwen, Polymer, 25, 1107 (1984). 441. A. Kanda, M. Duval, D. Sarazin, J. Francois, Polymer, 26, 406 (1985). 442. T. Schwartz, J. Sabbadin, J. Francois, Polymer, 22, 609 (1981). 443. O. Quadrat, L. Mrkvickova, Europ. Polym. J., 17, 1155 (1981). 444. E. A. Bekturov, S. L. Kudaibergenov, J. Macromol. Sci. B: Phys. 25, 133 (1986). 445. J. M. G. Cowie, I. J. McEwen, Brit. Polym. J., 18, 387 (1986). 446. K. Matsuo, W. H. Stockmayer, G. F. Needham, J. Polym. Sci., Polym. Symp., 71, 95 (1984). 447. N. Hadjichristidis, Z. Zhongde, L. J. Fetters, J. Roovers, J. Polym. Sci., Polym. Phys. Ed., 20, 743 (1982). 448. A. Nakajima, H. Fujiwara, J. Polym. Sci. A-2, 6, 723 (1968). 449. T. M. Birshtein, Europ. Polym. J., 13, 375 (1977). 450. N. Hadjichristidis, M. Devaleriola, V. Desreux, Europ. Polym. J,, 8, 1193 (1972). 451. G. C. Berry, J. Chem. Phys., 46, 1338 (1967). 452. A. Takahashi, S. Yamori, I. Kagawa, J. Chem. Soc. Japan, Ind. Chem. Section., 83, 11 (1962); cited in A. Takahashi, M. Nagasawa, J. Am. Chem. Soc, 86, 543 (1964). 453. J. W. Mays, L. J. Fetters, Macromolecules, 22, 921 (1989). 454. Xu Zhongde, J. Mays, C. Xuexin, N. Hadjichristidis, F. C. Schilling, H. E. Bair, D. S. Pearson, L. J. Fetters, Macromolecules, 18, 2560 (1985). 455. T. Norisuye, K. Kawahara, A. Teramoto, H. Fujita, J. Chem. Phys., 49, 4330 (1968). 456. J. W. Mays, N. Hadjichristidis, L. J. Fetters, Macromolecules, 18, 2231 (1985). 457. Xu Zhongde, N. Hadjichristidis, L. J. Fetters, Macromolecules, 17, 2303 (1984). 458. Xu Zhongde, N. Hadjichristidis, J. M. Carella, L. J. Fetters, Macromolecules, 16, 925 (1983). 459. J. G. Zilliox, J. E. L. Roovers, S. Bywater, Macromolecules, 8, 573 (1975). 460. S. Saeki, N. Kuwahara, S. Konno, M. Kaneko, Macromolecules, 6, 589 (1973). 461. A. M. Afifi-Effat, J. N. Hay, Brit. Polym. J., 8, 91 (1976). 462. W. R. A. D. Moore, W. Millns, Brit. Polym. J., 1, 81 (1969).
463. A. L. Izyumnikov, L. V. Mineyev, V. A. Maslennikov, L. S. Sidorina, O. S. Samsonova, A. D. Abkin, Polym. Sci. USSR, 30, 1062 (1988). 464. S. Ya. Magarik, A. P. Filippov, N. V. D'yakonova, Polym. Sci. USSR, 29, 772 (1987). 465. S. Kiiguiikyavuz, Z. Kuguukyavuz, Polym. Commun., 31,35 (1990). 466. A. Karandinos, J. W. Mays, H. Hadjichristidis, Polym. Bull., 24, 251 (1990). 467. L. Gargallo, N. Hamidi, D. Radic, Polym. Internat., 24, 1 (1991). 468. B. Simionescu, S. loan, M. Bercea, C. I. Simionescu, Europ. Polym. J., 27, 589 (1991). 469. L. Gargallo, E. Soto, F. R. Diaz, L. H. Tagle, D. Radic, Europ. Polym. J., 23, 571 (1987). 470. M. Yazdani-Pedram, L. Gargallo, D. Radic, Europ. Polym. J., 21, 461 (1985). 471. S. Arichi, M. Y. Pedram, J. M. G. Cowie, Europ. Polym. J., 15, 113 (1979). 472. G. Moraglio, G. Gianotti, Europ. Polym. J., 5, 781 (1969). 473. A. George, W. W. Wilson, J. S. Lindner, J. W. Mays, Polymer, 35, 600 (1994). 474. A. Kuntman, B. M. Baysal, Polymer, 34, 3723 (1993). 475. S. R. Gooda, M. B. Huglin, Polymer, 34, 1913 (1993). 476. A.-A. A. Abdel-Azim, M. B. Huglin, Polymer, 24, 1429 (1983). 477. Y. -Z. Chen, J. W. Mays, N. Hadjichristidis, J. Polym. Sci., Polym. Phys. Ed., 32, 715 (1994). 478. J. W. Mays, N. Hadjichristidis, J. S. Lindner, J. Polym. Sci., Polym. Phys. Ed., 28, 1881 (1990). 479. J. W. Mays, N. Hadjichristidis, W. W. Graessley, L. J. Fetters, J. Polym. Sci., Polym. Phys. Ed., 24, 2553 (1986). 480. N. Hadjichristidis, Xu Zhongde, L. J. Fetters, J. Roovers, J. Polym. Sci., Polym. Phys. Ed., 20, 743 (1982). 481. N. Hadjichristidis, J. W. Mays, R. D. Vargo, L. J. Fetters, J. Polym. Sci., Polym. Phys. Ed., 21, 189 (1983). 482. M. Ataman, E. A. Boucher, J. Polym. Sci., Polym. Phys. Ed., 20, 1585 (1982). 483. J. Ansorena, J. J. Iruin, G. M. Guzman, J. Polym. Sci., Polym. Phys. Ed., 18, 173 (1980). 484. S. H. Oh, M. S. John, J. Polym. Sci., Polym. Chem. Ed., 27, 1731 (1989). 485. A. Nakajima, F. Hamada, S. Hayashi, J. Polym. Sci. C, 15, 285 (1966). 486. C. Tsitslianis, E. Pierri, A. Dondos, J. Polym. Sci., Polym. Letters Ed., 21, 685 (1983). 487. R. R. Buch, H. M. Klimisch, O. K. Johannoson, J. Polym. Sci. A-2, 8, 541 (1970). 488. T. Altares, D. P. Wyman, V. R. Allen, J. Polym. Sci. A, 2, 4533 (1964). 489. S. N. Chinai, R. A. Guzzi, J. Polym. Sci., 41, 475 (1959). 490. U. Bianchi, V. Magnasco, J. Polym. Sci., 41, 177 (1959). 491. T. Hirao, A. Teramoto, T. Sato, T. Norisuye, T. Masuda, T. Higashimura, Polym. J., 23, 925 (1991). 492. R. Chiang, J. Phys. Chem., 70, 2348 (1966). 493. T. A. Orofino, F. Wenger, J. Phys. Chem., 67, 566 (1963).
494. G. Tanaka, S. Imai, H. Yamakawa, J. Chem. Phys., 52, 2639 (1970). 495. K. Kawahara, T. Norisuye, H. Fujita, J. Chem. Phys., 49, 4339 (1968). 496. P. R. Sundarajan, in: J. E. Mark, (Ed.), "Physical Properties of Polymers Handbook", AIP Press, American Institute of Physics, Woodbury. NY, 1996, p. 197. 497. J. W. Mays, N. Hadjichristidis, J. Macromol. Sci.-Rev. Macromol. Chem. Phys. C, 28, 371 (1988). 498. H. -G. Elias, Polymere, Huthig and Wepf, Zug (Switzerland) 1996, p. 204; Polymers, VCH Publ., Weinheim (Germany) 1997, p. 209. 499. K. Akasaka, Y. Nakamura, T. Norisuye, A. Teramoto, Polym. J., 26, 363 (1994). 500. Y H. Park, D. C. Lee, Polymer (Korea), 12,749 (1988); cited in (496). 501. I. A. Ronova, M. A. Ponomareva, L. V. Dubrovina, et al., Int. Polym. Sci. Techn., 13, T 90 (1986); cited in (496). 502. I. Noda, T. Horikawa, T. Kato, T. Fujimoto, M. Nagasawa, Macromolecules, 3, 795 (1970). 503. M. Bohdanecky, D. Berek, Macromol. Chem., Rapid Commun., 6, 275 (1985). 504. D. Pateropoulou, E. Siakali-Kioulafa, N. Hadjichristidis, Macromol. Chem. Phys., 195, 173 (1994). 505. A.-A. A. Abdel-Azim, Macromol. Chem. Phys., 195, 159 (1994). 506. L. Fritz, J. Springer, Makromol. Chem., 194, 2047 (1993). 507. M. M. Zafar, R. Mahmood, S. A. Wadood, Makromol. Chem., 160, 313 (1972). 508. T. Hama, K. Yamaguchi, T. Suzuki, Makromol. Chem., 155, 283 (1972). 509. H. Liitje, G. Meyerhoff, Makromol. Chem., 68, 180 (1963). 510. H. M. Tan, A. Hiltner, E. Baer, Macromolecules, 16, 28 (1983). 511. T. Yoshizaki, K. Hayashi, H. Yamakawa, Macromolecules, 27, 4259 (1994). 512. F. Abe, K. Horita, Y Einaga, H. Yamakawa, Macromolecules, 27, 725 (1994). 513. Y. Takaeda, T. Yoshizaki, H. Yamakawa, Macromolecules, 26, 3742 (1993). 514. P. Hattam, S. Gauntlett, J. W. Mays, N. Hadjichristidis, R. N. Young, L. J. Fetters, Macromolecules, 24,6199 (1991).
515. J. W. Mays, S. Nan, D. Whitfield, Macromolecules, 24, 315 (1991). 516. J. W. Mays, S. Nan, W. Yunan, J. Li, N. Hadjichristidis, Macromolecules, 24, 4469 (1991). 517. F. Abe, Y. Einaga, H. Yamakawa, Macromolecules, 24,4423 (1991). 518. A. Karandinos, S. Nan, J. W. Mays, N. Hadjichristidis, Macromolecules, 24, 2007 (1991). 519. F. Fujii, Y. Tamai, T. Konishi, H. Yamakawa, Macromolecules, 24, 1608 (1991). 520. H. M. Petri, N. Schuld, B. A. Wolf, Macromolecules, 28, 4975 (1995). 521. J. B. Kinsinger, R. E. Hughes, J. Phys. Chem., 63, 2002 (1959). 522. F Strehle, Th. Dorfmuller, D. Samios, Macromolecules, 25, 3569 (1992); N. Pesce da Silveira, D. Samios, F. Strehle, Th. Dorfmiiller, Macromol. Chem. Phys., 197, 1945 (1996). 523. W.-M. Kulicke, M. Prescher, Makromol. Chem., 185, 2619 (1984). 524. J.-G. Zilliox, Makromol. Chem., 156, 121 (1972). 525. F. Abe, Y. Einaga, H. Yamakawa, Macromolecules, 27, 3262 (1994). 526. A.-A. A. Abdel-Azim, M. B. Huglin, Europ. Polym. J., 18, 735 (1982). 527. R. Jenkins, R. S. Porter, Adv. Polym. Sci., 36, 1 (1980). 528. J. W. Mays, N. Hadjichristidis, J. Macromol. Sci. Rev.Macromol. Phys. C, 28, 371 (1988). 529. A. R. Shultz, P. J. Flory, J. Am. Chem. Soc, 74, 4760 (1952). 530. G. Talamini, G. Bidotto, Makromol. Chem., 110, 111 (1967). 531. H.-G. Elias, M. Dobler, H.-R. Wyss, J. Polym. Sci., 46, 264 (1960). 532. D. H. Napper, Polymer, 10, 181 (1969). 533. D. H. Napper, Polymeric Stabilization of Colloidal Dispersions, Academic Press, London 1983. 534. S. Q. Zhou, S. Y Fan, S. T. F. An-yeung, C. Wu, Polymer, 36, 1341 (1995). 535. F. Dobert, A. Pfennig, M. Stumpf, Macromolecules, 28, 7860 (1995). 536. D. H. Napper, in: C. A. Finch, (Ed.), Chemistry and Technology of Water-Soluble, Polymers, Plenum, New York 1983.
S o l v e n t s
a n d
N o n
S o l v e n t s
f o r
P o l y m e r s
D a n i e l R. B l o c h Lakeshore Research, 5536 W. Branch Trail Racine, Wl, USA 53402
A. Introduction VII-498 B. Abbreviations VII-498 C. Tables of Solvents and Nonsolvents VII-499 Table 1. Main-Chain Acyclic Carbon Polymers VII-499 1.1. Poly(dienes), Poly(acetylenes) VII-499 1.2. Poly(alkenes) VII-500 1.3. Poly(acrylics), Poly(methacrylics) VII-501 1.3.1. Poly(acrylic acids) VII-501 1.3.2. Poly(acrylates) VII-501 1.3.3. Poly(methacrylates) VII-501 1.3.4. Poly(disubstituted esters) VII-502 1.3.5. Poly(acrylamides), Poly(methacrylamides) VII-503 1.4. Poly(vinyl ethers) VII-503 1.5. Poly(vinyl alcohols), Poly(acetals), Poly(vinyl ketones) ' VII-504 1.6. Poly(vinyl halides) VII-505 1.7. Poly(vinyl nitrites) VII-506 1.8. Poly(vinyl esters) VII-506 1.9. Poly(styrenes) VII-507 1.10. Other Compounds VII-508 Table 2. Main-Chain Carbocyclic Polymers VII-509 2.1. Poly(phenylenes) VII-509 2.2. Other Compounds VII-510 Table 3. Main-Chain Carbonyl Polymers VII-510 Table 4. Main-Chain Acyclic Heteroatom Polymers VII-511 4.1. Main-Chain - C - O - C Polymers VII-511 4.1.1. Poly(oxides) VII-511 4.1.2. Poly(carbonates) VII-513 4.1.3. Poly(esters) VII-513 4.1.4. Poly(anhydrides) VII-515 4.1.5. Poly(urethanes) VII-515 4.2. Main-Chain - O - Heteroatom Polymers VII-515 4.2.1. Poly(sulfonates) VII-515 4.2.2. Poly(siloxanes) VII-516
4.3.
Table 5.
Table 6. Table 7.
Main-Chain - C - S - C - and - C - S - N - Polymers 4.3.1. Poly(sulfides) 4.3.2. Poly(sulfones) 4.3.3. Others 4.4. Main-Chain - C - N - C Polymers 4.4.1. Poly(amides) 4.4.2. Poly(hydrazides) 4.4.3. Poly(ureas) 4.4.4. Poly(carbodiimides) 4.4.5. Other Compounds 4.5. Poly(phosphazenes) and Related Compounds 4.6. Poly(silanes), Poly(silazanes) Main-Chain Heterocyclic Polymers 5.1. Poly(benzoxazoles), Poly(oxadiazoles), Poly(oxadiazolidines) 5.2. Poly(dithiazoles), Poly(benzothiazoles) 5.3. Poly(imides) 5.3.1. Poly(benzimides) 5.3.2. Poly(pyromellitides) 5.3.3. Others 5.4. Poly(quinoxalines) 5.5. Poly(benzimidazoles) 5.6. Poly(piperazines) 5.7. Poly(anhydrides) 5.8. Poly(thiophenes) 5.9. Others Formaldehyde Resins Natural Polymers and Modified Natural Polymers 7.1. Natural Rubber and Derivatives 7.2. Cutta Percha 7.3. Cellulose and Derivatives 7.3.1. Cellulose 7.3.2. Cellulose Ethers
VII-516 VII-516 VII-517 VII-518 VII-518 VII-518 VII-520 VII-521 VII-521 VII-521 VII-522 VII-522 VII-523 VII-523 VII-524 VII-524 VII-524 VII-525 VII-525 VII-526 VII-526 VII-526 VII-527 VII-527 VII-527 VII-528 VII-528 VII-528 VII-529 VII-529 VII-529 VII-529
7.3.3. Cellulose Esters VII-530 7.3.4. Cellulose Nitrate and Sulfate VII-531 7.4. Starch and Derivatives VII-531 7.5. Other Poly(saccharides) VII-531 7.6. Natural Resins VII-532 Table 8. Inorganic Polymers VII-532 Table 9. Poly(electrolytes) VII-533 Table 10. Block Polymers VIJ-533 Table 11. Dendrimers VII-534 D. References VII-536
A.
INTRODUCTION
The tables contain qualitative solubility data for a selected number of polymers. Since no standard definition for solvent-nonsolvent systems has been used in most of the original sources, the recognition of a certain compound as a solvent or nonsolvent is to some extent influenced by personal interpretation. No attempt has been made to edit the original information. Division into only two classes, solvents and nonsolvents, is dictated by the practical point of view. For more quantitative information, the user is referred to the tables of theta solvents and fractionation of polymers in this Handbook. The arrangement of polymers into classes is based on chemical structure. Since properties change gradually within a series of homologs, polymers are arranged according to increasing complexity, as regards the size of the monomer unit, and the kind and number of substituents. Only when this principle could not be applied was an alphabetical listing chosen. We believe that a typical solution behavior of similar polymers may be recognized more easily by this arrangement. When formulas are given, they refer to the main structures present in the polymers. Polymers are named in a manner thought to be most recognizable to the reader. IUPAC or common names (and sometimes both) are used. The table has nearly doubled in size since the last edition. New polymer categories include copolymers, mainchain carbonyl polymers, block copolymers and dendrimers, emphasizing recently developed materials. Copolymers are generally named with the dominant monomer given first, but the reader should check alternate names, since each polymer is listed only once. Solubility of copolymers generally resemble more or less the properties of the dominating monomer, although they often exhibit higher solubilities than the corresponding homopolymers. The solubility of block copolymers may reflect the solubilizing/dispersing power of one of the polymer segments rather than true solubility of all segments. Dendrimers are shown as the repeating monomer unit, with the terminal unit specified when known.
Solubility normally increases with rising temperature. However, negative temperature coefficients in some solvents are observed. This is particularly true for cellulose and poly(ethylene oxide)s. Increasing molecular weight generally reduces solubility. Increased branching increases the solubility compared to a linear polymer of the same molecular weight. Certain combinations of two or more solvents may become nonsolvents. Conversely, mixtures of two or more nonsolvents may sometimes become solvents. These possibilities should be considered if new solvent-nonsolvent combinations are to be examined. It is recommended that the reader consults the solubility parameter section in this Handbook. The classification of a certain compound as a nonsolvent does not necessarily imply its ability to act as a precipitant since this is also influenced by the nature of the particular solvent of a solvent-nonsolvent pair. However, most nonsolvents combine both properties. The list of solvents and nonsolvents for each polymer is arranged alphabetically. If class names are used, they refer to the most common compounds. Less common compounds, although falling into a class already mentioned, are additionally cited. Water is a nonsolvent for most polymers and is, therefore, often not mentioned or only mentioned if similar polymers or derivatives are water soluble. The data refer to room temperature unless otherwise stated. Homologs and closely related compounds generally have similar solubility properties. When specific solvents or nonsolvents are cited, it is done so with the understanding that homologs and compounds with similar structures can be expected to exhibit similar properties.
B.
ABBREVIATIONS
bzn. DMA DMF DMSO HMPT TMS THF W aqu. cone. DS degrad. dil. mol. wt. rt SC sw temp.
Benzene /V,/V-Dimethylacetamide Af,N~Dimethylformamide Dimethyl sulfoxide Hexamethylphosphoric triamide Tetramethylene sulfone Tetrahydrofuran Water Aqueous Concentrated Degree of substitution Degradation Diluted Molecular weight Room temperature Substituent content Swelling Temperature
C. TABLES OF SOLVENTS AND NONSOLVENTS TABLE 1. MAIN-CHAIN ACYCLIC CARBON POLYMERS Polymer 1.1.
Solvents
Nonsolvents
Refs.
POLY(DIENES), POLY(ACETYLENES) (see also 6.1, 6.2)
Poly(dienes) unsubstituted Poly(allene) PoIy(1,2-butadiene) 57% 1,2PoIy(1,3-butadiene)
98% cis-, 2% 1,295% cis-, 1% trans100% cis97% trans-, 3% 1,2Poly(isoprene), cis-, with chlorosulfonylisocyanato groups Poly(dienes) substituted Poly(2-terf-butyl-l,3-butadiene) Poly(dicyclopentadiene) Poly(5,7-dimethyl-1,6-octadiene) PoIy(I-methoxybutadiene), crystalline
Bzn., halogenated hydrocarbons Toluene Chloroform Higher aliphatic ethers, hydrocarbons, higher ketones, THF Bzn., toluene Cyclohexane Bzn., heptane/hexane (1/1) Cyclohexane, toluene See PoIy(1,3-butadiene) Toluene Bzn., carbon disulfide, carbon tetrachloride, chloroform, diethyl ether, heptane Toluene See Poly(2-terf-butyl-1,3-butadiene)
Poly(2-chlorobutadiene), chloroprene
Bzn., carbon tetrachloride, chlorinated hydrocarbons, cyclohexane/toluene, cyclohexanone, dioxane, ethyl * acetate, pyridine 1,4-dsBzn., chloroform, ether, hexane, THF Poly[2-(chloromethyl)butadienej Dichloromethane, THF, toluene Poly(perfluoro-1,4-pentadiene) Hexafluorobenzene Poly(2,5-diheptyl~l,4-phenylenehexa-l,3,5-triene-l,6~diyl) Acetone, bzn., chloroform PoIy(1,5-pentamethyl-2-enediyl) Methylene chloride Poly(butadiene-c-styrene) (7:3-95:5) Bzn., cyclohexane, toluene Buna-S GR-S SBR rubber Poly(acetylenes) Poly(acetylene) Aniline, DMF, isopropylamine Poly(phenylacetylene) low mol. wt. high mol. wt.
Alcohol, dil. acids, dil. alkalies, hypochlorite solutions, lower ketones and esters, nitromethane, propionitrile, W
Chloroform, cyclohexane, dioxane
Poly[bis(alkylthio)acetylene]
Aromatic hydrocarbons, halogenated hydrocarbons Chloroform, hexane, THF
Poly[3-(^rr-butoxycarbonylmethyleneiminocarbonyloxy)8-(5-pyrimidyl)-oct-5-yn-7-ene-l,8-diyl] Poly[2-(dodecyloxycarbonyl) 1,4-phenyleneethynylene] THF (hot) Dichlorobenzene Poly(9,9-dipropargylfluorene),
Diethyl ether, hexane Acetone, alcohol
8 9,10
Methanol
11
Acetone, bzn., dioxane, heptane, methanol Alcohols, aliphatic hydrocarbons, hydrogen fluoride, ketones, mineral oils, nonoxidizing cone, acids incl. hydrogen fluoride, toluene (sw), W Acetone, ethanol, methanol Ethanol, methanol
12
Acetone, bzn., carbon tetrachloride, cyclohexane, methanol, methylene chloride, pyridine
Methanol
4-7,13
14 686 16 17 7
Methanol
18
19,20 19-21 22
23 24 Methanol
DMF/pyridine
W
Dioxane, pyridine
Methanol
Acetone, bzn., chloroform
1 2 3 4-6
7 7 7 7
Acetone, carbon tetrachloride, methanol Bzn., cyclohexane (hot), toluene Methanol
Poly(diphenyldiacetyiene), poly- r(№ (1,4-diphenyl-1,3-butadiene), — Q~ Q— I C=CC 6 H 5
Poly (1 -propynyleneoxy-1,4-phenyleneisopropylidene1,4-phenyleneoxy-2-propynylene) Poly(ethynylene-1,4-phenyleneoxy1,4-phenyleneethynylene) Poly(butadiene-c-acrylonitrile)
Hexane, methanol
25 26
27,247 28 7
References page VII - 536
TABLE 1. cont'd Polymer 1.2.
Solvents
Nonsolvents
Refs.
POLY(ALKENES)
Poly(methylene) Polyethylene high density
low density chlorinated, 40% Cl
chlorinated, 60% Cl
chlorosulfonated, 30% Cl, 1.5% S Poly(ethylene g-maleic anhydride) (97:3) Poly(ethylene-o?-propylene) (3:2) Poly(ethylene-co-acryiic acid) (6:1) Poly(vinyl chloride-co-ethylene) (1:9) Poly(ethylene-C0-propylene-c0-5-methylene2-norbornene) (40:55 :5), PoIyEPDM Polypropylene) atactic
isotactic PoIy(I-butene) atactic isotactic Poly(isobutene)
Poly(4-methyl-l-pentene), isotactic Poly(2-methyl-3-hydroxy-1,4-butylene) PoIy(I -hexene) Poly(cyclopentylethylene) Poly(cyclohexylethylene) atactic stereospecific
Poly(cyclohexylalkenes) Poly(cyclohexenylethylene) atactic isotactic Poly(pentenamer), Poly(cyclopentene) -f CH = CH(CH2 ) 3f~ Poly(3,4-dicarboxypent-l-ene-l,5-diyl)
See Polyethylene Above 8O0C: 1,2,4-trichlorobenzene, decalin, di-rt-amyl ether, halogenated hydrocarbons, higher aliphatic esters and ketones, hydrocarbons, xylene As above, but temperature 20-3O0C lower, depending on degree of branching At elevated temperature: chlorobenzene, cyclohexanone, tetrachloroethane, tetrahydronaphthalene, toluene, xylene At elevated temperature: acetone/ carbon disulfide (1/1), aromatic hydrocarbons, chloroform, cyclohexane, THF Chlorinated hydrocarbons, MEK, THF, toluene Toluene, xylene Bzn., xylene (hot) Xylene Cyclohexanone (hot), nitrobenzene/chloroform (1 /1) 1,2,4-Trichlorobenzene
All common organic solvents at room temperature, more polar organic solvents even at elevated temperatures, inorganic solvents
Bzn., chlorinated hydrocarbons at rt, cyclohexane, diethyl ether, ethylcyclohexane, hydrocarbons, isoamyl acetate, toluene See Polyethylene
More polar organic solvents with small hydrocarbon group even at elevated temperature
4-7,13, 29,30
As above
5,7
Acetone, butanol, chloroform, dioxane, MEK, methanol, methyl acetate, THF
31
Acetone, aliphatic and cycloaliphatic hydrocarbons, ethanol, methanol, methyl acetate
31
32,33 W
34 32 32 127 32 5,7
7,32 Bzn., chloroform, decalin, ethylcyclohexane, toluene See Polyethylene, ethylcyclohexane Aliphatic ethers, anisole, carbon Lower alcohols, lower ketones disulfide, chlorinated hydrocarbons, and esters, nitromethane, di(2-chloroethyl) ether, diethylsumde, lower organic acids, propionitrile higher alcohols, higher esters, hydrocarbons, THF See Polyethylene THF Chloroform, THF Chloroform, diethyl ether, toluene Methanol Chlorinated hydrocarbons, Alcohols, ethers, dioxane, esters, ketones hydrocarbons, THF At elevated temperature: bzn., Heptane, MEK, nitrobenzene chlorobenzene, decahydronaphthalene, o-dichlorobenzene, methylcyclohexane, tetrahydronaphthalene, xylene Chloroform, diethyl ether (partially), Methanol toluene Aliphatic hydrocarbons Acetone, ethanol Aromatic hydrocarbons, Acetone, aliphatic hydrocarbons, halogenated hydrocarbons (partially) diethyl ether, ethanol Chlorinated hydrocarbons, Alcohols, aliphatic ketones, ethers hydrocarbons Chloroform, methanol Diethyl ether
7 5,6,13, 30,35
36 37 38 39 40
41 42 42 43 44
TABLE 1. cont'd Polymer Poly(3,4-dihydroxypent-l-ene-l,5-diyl) PoIy(I, l-diphenyl-2-vinylcyclopropane) Poly(/?-anthrylphenylethylene) PoIy(I-methylbicyclo-[2.2.1]-hept-2-ene) Poly(vinylborazine) Poly(methylene-a/r-5-hydroxycyclohexene-l,3-diyl) Poly(ethylene-ctf-1,4-hexadiene) (97:3) Poly(ethylene-ctf-l-cyano-l,4-butylene) (1:2) Poly(isobutylene-c0-4-methylstyrene) (95:5) Poly[hexene-c<9-Af,N-di(isopropyl)amino-l-pentene] (2: 3)
Solvents
Nonsolvents
Refs.
DMSO, methanol Chloroform Bzn., chlorobenzene, methylene chloride Chlorobenzene, /7-xylene Bzn. Hexanes Toluene Acetone (hot), chloroform, DMA, DMSO Chloroform Hexane
Ethanol Methanol Methanol, ethanol, hexane, W
44 45 46
Methanol Pentane
47 48 49 50 51
Alcohols, dil. alkali solutions, formamide, DMF, W Dioxane/water (80/20)
Dioxane (hot) (sw), esters, hydrocarbons, ketones Dioxane
Alcohols, aqu. hydrogen chloride (0.002 M, >30°C), dil. aqu. sodium hydroxide, W W(partially) THF DMF, methanol, W
Carboxylic acids, esters, hydrocarbons, ketones
Aromatic hydrocarbons, chlorinated hydrocarbons, esters, ketones, THF See General, acetone, bzn., ethyl acetate, glycol ester ethers, phosphorus trichloride See General, acetone, butanol, bzn., glycol ether, methanol, THF, /?-xylene Methanol, W See General, butanol, turpentine
Aliphatic hydrocarbons, hydrogenated naphthalenes, diethyl ether Alcohols, carbon tetrachloride
Methanol
52 53
1.3. POLY(ACRYLICS), POLY(METHACRYLICS) 1.3.1. POLY(ACRYLIC ACIDS) Poly(acrylic acid) atactic isotactic Poly(methacrylic acid) atactic isotactic, syndiotactic Poly(acrylic acid-c-9-vinylphenanthrene) (3:2) Poly(itaconic acid)
Acetone, aniline, bzn., carbon disulfide, chloroform, ethanol, ethyl acetate, THF
4-6, 13,54 55 4,5 56 57 58
1.3.2. POLY(ACRYLATES) General Poly(methyl acrylate) Poly(ethyl acrylate) Poly(2-hydroxyethyl acrylate) Poly(/i-butyl acrylate) Poly(ter/-butyl acrylate) Poly(4-hydroxybutyl acrylate) Poly(isobornyl acrylate) Poly(cyclohexyl acrylate) Poly(2-ethylhexyl acrylate) Poly(benzyl acrylate) Poly(5-cyano-3-thiapentyl acrylate) Poly[l-(/V-ethyl-AMl,4,7,10,13-pentaoxacyclopentadecyl)carbamoyl)ethylenej Poly(pentachlorophenyl acrylate) Poly(4-10,15,20-triphenylporphorin-21H,23H-5-ylphenyl acrylate) Poly(vinylcyclohexane-a?-methyl acrylate) (9: 1)
Aliphatic alcohols C >4, cyclohexanol, tetrahydrofurfuryl alcohol Cyclohexyl acetate, ethanol, ethyl acetate, methanol
5,7, 30,59 5,7, 30,59 32 30
Acetone, methanol Isopropanol THF Bzn., THF, toluene Esters, ketones, THF, toluene Bzn., THF, toluene Acetone, acetonitrile, dioxane, pyridine Solvents of low solubility parameter Bzn., chloroform Hexane
7 32 60 32 32 32 61 62
Bzn., THF Bzn., chloroform, THF, trifluoroacetic acid THF
Hexane, methanol, W Acetone, ethanol, hexane, methanol, W
63 64
W
65
1.3.3. POLY(METHACRYLATES) General
Acetic acid, acetone, bzn., chlorobenzene, chloroform, cyclohexanol (hot), cyclohexanone, cyclohexyi acetate, dioxane, 2-ethoxyethanol, ethyl acetate, isobutanol (hot), isobutyric acid, MEK, methylene chloride, xylene
Castor oil, cyclohexane, diethyl ether, ethylene glycol, formamide, gasoline, glycerol, hexane, methanol, nujol
References page VII - 536
TABLE 1. cont'd Polymer Poly(methyl methacrylate) atactic
isotactic syndiotactic Poly(methyl methacrylate-co-2-acrylamido-2-methyl1-propanesulfonic acid) (95 :5) Poly(ethyl methacrylate)
Poly(2-hydroxyethyl methacrylate) Poly(w-propyl methacrylate)
PoIy(^-butyl methacrylate) and Poly(isobutyl methacrylate)
Poly (butyl methacrylate-o?- /-butyl methacrylate) (1:1) Poly(n-hexyl methacrylate) Poly(cyclohexyl methacrylate) Poly(cyclohexylmethyl methacrylate) Poly(n-octyl methacrylate) Poly(2-ethylhexyl methacrylate) Poly(rc-decyl methacrylate) Poly(rc-lauryl methacrylate) Poly(phenyl methacrylate) Poly(benzyl methacrylate) Poly(4-ter/-butylphenyl methacrylate) Poly[(4-(terf-butyoxycarbonyloxy)phenyl) methacrylate] Poly(bornyl methacrylate) Poly(isobornyl methacrylate) Poly[2-(dimethylamino)ethyl methacrylate] Poly[(2-trimethylsiloxy)ethyl methacrylate] Poly[2-(/V-carbazoyl)ethyl methacrylate], crystalline Poly(cyanomethyl methacrylate) Poly[2-(4-phenylazophenyl)ethyl methacrylate] Poly[(methacryloyloxyundecyloxycarbonyldecyl)2-(trimethylamino)ethyl phosphate] Poly[4-(4-methoxyphenyloxycarbonyl) phenoxyhexamethylene methacrylate] Poly[2-(dimethylamino)ethyl methacrylate-coacrylamide] (4 : 1 to 2: 3)
Solvents
Nonsolvents
Refs.
See General, ethanol/water, Butylene glycol, carbon ethanol/carbon tetrachloride, tetrachloride, m-cresol, diethyl isopropanol/MEK (1/1) above 25°C, ether, ethanol (absolute), higher formic acid, nitroethane esters, hydrogenated naphthalenes, linseed oil, turpentine Acetone, acetonitrile, bzn., MEK, THF See isotactic Bzn., toluene
4,5,13, 30,66,67
See General, carbon tetrachloride, Alcohols, cyclohexane ethanol (hot), ethyl ether, ethyl acetate, formic acid, isopropanol above 37°C, tetralin, turpentine (hot) DMF, methanol, methyl CellosolveQ See General, carbon tetrachloride, Formic acid castor oil (hot), cyclohexane (hot), diethyl ether, ethanol, gasoline (hot), Unseed oil (hot), turpentine See General, carbon tetrachloride, Ethanol (cold), formic acid castor oil (hot), cyclohexane, diethyl ether, ethanol (hot), gasoline, hexane, isopropanol above 23.7°C, linseed oil (hot), nujol (hot), turpentine Acetone, MEK, methylene chloride, THF, toluene Isopropanol above 33°C, MEK Bzn., dioxane, THF Bzn., THF Methanol n-Butanol, MEK Bzn., MEK, THF Bzn., THF n-Pentanol above 29°C, Ethyl acetate, methanol isopropyl acetate, MEK Bzn., MEK, THF, toluene Bzn., chloroform, dioxane, THF Acetone Bzn. Bzn. Methanol Bzn., THF, toluene Bzn., toluene THF Aniline (hot, partially), diphenyl MEK ether (hot), nitrobenzene (hot) Acetone, acetonitrile, ethyl acetate, Bzn., chloroform, methanol THF THF Methanol Ethanol (hot), methanol Acetone, bzn.
5,7,67,68
Chloroform, THF, bzn., methylene chloride, o-dichlorobenzene, W
Hexane, methanol
Acetone, acetonitrile, bzn., DME, furfurol, halogenated hydrocarbons, methyl acetate, nitrobenzene, nitromethane, THF Acetone, amyl acetate, dioxane, ethanol, halogenated hydrocarbons, hydrocarbons, methyl acetate, THF Bzn., chloroform, dioxane, DMF, ethyl acetate, THF
Aliphatic hydrocarbons, carbon tetrachloride, diisopropyl ether, ethanol, ethyl acetate, methanol, propylene carbonate, toluene, W Acetonitrile, DMF, furfurol, methanol, nitrobenzene, nitromethane, propylene carbonate
7,32 32 A32
32 67
5,13,30, 67-69
32 5 32 70 5 32 32 5,71 32 32 5 696 72 32 32 73 74 75 76 77 78 79
1.3.4. POLY(DISUBSTITUTED ESTERS) Poly(dimethyl itaconate)
Poly(di-«-butyl itaconate) Poly(diphenyl itaconate)
80-82
81,82 83
TABLE 1. cont'd Polymer Poly(diamyl fumarate) Poly (methyl terr-butyl fumarate)
Solvents Chloroform, THF, toluene Bzn., chloroform, methanol, THF
Nonsol vents Hexane, W Hexane, W
Refs. 84 85
1.3.5. POLY(ACRYLAMIDES), POLY(METHACRYLAMIDES) Polyacrylamide
Ethylene glycol (partially), morpholine, W
Alcohols, diethyl ether, DMF, 4,5,13 esters, higher glycols, hydrocarbons, nitrobenzene, propylene glycol, THF W (hot) 86,87 W (sw) 5 88 W (sw) 89 32
Poly(AMsopropylacrylamide) W (cold) Poly(WV-dimethylacrylamide) Methanol, W (400C) Poly(WV-diethylacrylamide) THF Poly[N-(l,l-dimethyl-3~oxobutyl) acrylamide] Butanol, MEK, toluene Poly(2-acrylamido-2-methyl-l-propanesulfonic acid), W PoIyAMPS Poly(N-terf-butyl-N-allylacrylamide) Chloroform Petroleum ether Poly(N-dodecylacrylamide-co-iV-vinylcarbazole) Chloroform Acrylonitrile (15:1 to 2:1) Polymethacrylamide Acetone, ethylene glycol, methanol, W Diethyl ether, hydrocarbons PolyyV-carbazolylcarbonylethylene), Poly(9-acryloylcarbazole) atactic Bzn. (partially) Methanol tactic Chloroform (partially), cone, or moderately cone, sulfuric acid Poly(morpholinocarbonylethylene), DMF Poly(/V-acryloylmorpholine) Poly(piperidinocarbonylethylene), DMF Poly(acryloylpiperidide)
90 91 4,5,13 92 5 5 5
1.4. POLY(VINYL ETHERS) General Unsubstituted Poly(methoxyethylene), Poly(methyl vinyl ether) amorphous crystalline Poly(ethoxyethylene), Poly(ethyl vinyl ether), Poly(propoxyethylene), crystalline Poly(propyl vinyl ether) Poly(isopropoxyethylene), crystalline, Poly(isopropyl vinyl ether) Poly(butoxyethylene), Poly (butyl vinyl ether) Poly(isobutoxyethylene), Poly(isobutyl vinyl ether) amorphous
crystalline
Poly(terf-butoxyethylene), Poly(ferf-butyl vinyl ether) amorphous crystalline Poiy(neopentyloxyethylene), Poly(neopentyl vinyl ether), crystalline Poly(cyclohexyloxyethylene), Poly(cyclohexyl vinyl ether) Poly(benzyloxyethylene), Poly(benzyl vinyl ether) atactic
Bzn., rc-butanol, cyclohexanone, halogenated hydrocarbons, MEK
Heptane
See General, acetone, ethanol, ethyl acetate, methylene chloride, THF, W (cold)
Diethyl ether, ethylene glycol, 4,5,13,30,93-95 hexane, W (hot) Acetone, methanol, W
95,96
See Poly(methoxyethylene) Acetone, heptane
95
See Poly(propoxyethylene) See General, bis(2-ethoxy ethyl) ether, Ethanol, 2-ethoxyethanol cyclohexane, diethyl ether, n-heptane See General, aliphatic alcohols C>2, bis(2-ethoxyethyl) ether, carbon disulfide, cyclohexane, diethyl ether, ^-heptane, isopropyl acetate, MEK, methylene chloride Chloroform above 500C
Ethanol 2-ethoxyethanol, methanol
Heptane, bis(2-ethoxyethyl) ether, bzn. (sw at 200C), chloroform (sw at 200C), isopropanol (hot), MEK
Acetone, MEK
4,13,30, 93,98,99
95
95,98 95,98 95
Bzn., heptane Bzn., heptane Methylene chloride Acetone, bzn., toluene
95,97
100 Ethanol, methanol, W
101
References page VII - 536
TABLE 1. cont'd Polymer Substituted Poly(carbomethoxymethoxyethylene) Poly[2-(methoxyethoxy)ethylene], crystalline Poly[2-(chloroethoxy)ethylene], crystalline Poly(2,2,2-trifluoroethoxyethylene), crystalline Poly(methyl vinyl ether-a/Mnethyl tricyanoethylenecarboxylate) Poly(phenyl vinyl ether-a/f-2-phenyl1,1-dicyanoethylene)
Solvents
Chloroform, methylene chloride W Bzn., dioxane, heptane DMA, DMF, nitromethane Acetone, carbon tetrachloride, chloroform, DMF, DMSO, THF
Nonsol vents
Diethyl ether Diethyl ether Acetone
Refs.
Diethyl ether
102 95 95 95 103
Hexane methanol
104
1.5. POLY(VINYL ALCOHOLS), POLY(ACETALS), POLY(VINYL KETONES) Poly(vinyl alcohol) atactic
syndiotactic 12% acetyl 35% acetyl Poly(vinyl alcohol-co-ethylene) (1:1) Poly(vinyl alcohol-a?-rnaleic anhydride) (1:1) Poly(allyl alcohol) lower mol. wt. high mol. wt. (DP > 350) Poly(vinyl formal)
Poly(vinyl acetal)
high degree of acetalization Poly(vinyl butyral) acetalization 70% acetalization 77% acetalization 83% Poly(vinyl alcohol-covinyl pentanal) Poly(2-vinyl-4,7-dihydro-1,3-dioxepine),
Poly(vinyl cyclohexanone ketal),
Acetamide, DMF, DMSO (hot), formamide, glycerol (hot), glycols (hot), HMTP, piperazine, triethylenediamine, W
Carboxylic acids, chlorinated hydrocarbons, esters, hydrocarbons, ketones, lower alcohols, cone. aqu. salt solutions, THF
1,3-Propandiol above 1600C, W above 1600C W (cold) Carboxylic acids, esters, halogenated hydrocarbons, hydrocarbons, ketones, W (hot) Alcohols, aqu. sol. of tetraalkylW ammonium bromide and iodide DMF (hot), DMSO (hot) Methylene chloride, THF Acetone Cresol, dioxane, glycerol, methanol, pyridine, THF Mixtures of cone, hydrochloric acid and dioxane, methanol, THF Acetic acid, benzyl alcohol, bzn./alcohol (70/30), carbon tetrachloride/alcohol (70/30), 2-chloroethanol, chloroform, cyclohexanone, dichloroethylene/ diacetone alcohol (50/50), dioxane, DMF, furfurol, THF, toluene Acetone, benzyl acetate, bzn./ethanol (1/1), bzn., butanol, carbon tetrachloride, 2-chloroethanol, chloroform, chloroform/methanol (9/1), cyclohexanone, dioxane, ethanol, ethyl acetate, ethylene glycol, THF Acetic acid (glacial), dioxane, ethanol, ethylene dichloride, methanol, nitromethane, pyridine
4-6,13, 30,105
106 4 38 107 108 13
Most organic solvents, W Acetone (sw), aliphatic hydrocarbons, aromatic hydrocarbons (sw), dilute acids, dioxane, esters, ethanol, methanol, pyridine (sw), W
DiI. acids, aliphatic hydrocarbons, diethyl ether (sw), pyridine (sw), W
Acetone, bzn.
13 4,6,30
6,30
4
Alcohols, cyclohexanone, ethyl glycol acetate, ethyl lactate Acetone, alcohols, cyclohexanone, lower esters, methylene chloride Alcohols, lower esters, ketones, methylene chloride Bzn., chloroform Acetone, 2-buten-1,2-diol
Aliphatic ketones, hydrocarbons, methylene chloride, most esters, W Higher esters, hydrocarbons, methyl isobutyl ketone Higher esters, hydrocarbons, methanol
109 109
Methanol W
110 111
Butanol, chloroform, cyclohexanone, ethanol, ethylene glycol, ethylene chloride, THF
Aliphatic hydrocarbons, carbon tetrachloride (sw), diethyl ether (sw)
109
30
TABLE 1. cont'd Polymer Poly(vinyl methyl ketone) Poly(methyl isopropenyl ketone)
Solvents
Nonsolvents
Acetic acid, acetone, chloroform, dioxane, DMF, ethyl acetate, pyridine, THF Acetone, dioxane, esters
Alcohol, carbon tetrachloride, diethyl ether, petroleum ether, W Alcohol, petroleum ether, W
Refs. 4,6,13 6,13
1.6. POLY(VINYL HALIDES) Poly (vinyl chloride) high mol. wt.
Acetone/carbon disulflde, chlorobenzene, cyclohexanone, cyclopentanone, DMF, DMSO, MEK, nitrobenzene, THF
lower mol. wt.
chlorinated, 63% Cl
Poly(vinylidene chloride)
Poly(vinyl bromide) Poly (vinyl fluoride) chlorinated, 30% Cl chlorinated, 60% Cl Poly(vinylidene
, fluoride)
PoIy(1,2-difluoroethylene) PoIy(I-chloro-1-fluoroethylene) Poly(chlorotrifluoroethylene)
Poly(tetrafluoroethylene) Poly(3,3,3-trifluoropropylene) Poly(hexafluoropropylene) Poly(3,3,4,4,5,5,5-heptafluoro-l-pentene) Poly(vinylidene chloride cyanide-a/M,3-cyclohexadiene) Poly(cnlorotrifluoroethyIene-c0-vinylidene fluoride) (3:1) Poly(tetrafluoroethylene-o?-hexafluoropropylene) (4:1) Poly[tetrafluoroethylene-o>-4,5-difluoro-2,2bis(trifluoromethyl)-l,3-dioxole] (13: 87 and 35:65)
Acetic anhydride (sw), 4-7,13, acetone (sw), nonoxidizing acids, 30,112 alcohols, cone, alkalies, aniline (sw), carbon disulflde, carboxylic acids, esters, hydrocarbons, nitroparaffins (sw), vinyl chloride Acetone/carbon disulflde, cyclohexanone, 4-6,13,30 1,2-dichlorobenzene, diisopropyl ketone, dioxane, DMF, ethylene chloride, HMPT, isophorone, mesityl oxide, nitrobenzene, perchloroethylene/acetone, toluene, tricresyl phosphate Acetone, aromatic hydrocarbons, Aliphatic and cycloaliphatic 6 butyl acetate, chlorobenzene, hydrocarbons, carbon tetrachloride, chloroform, cyclohexanone, dioxane, methyl acetate, nitromethane, DMF, DMSO, nitrobenzene, THF organic and inorganic acids Benzonitrile, butyl acetate, Cone, and moderately cone, acids 4,6,30, cyclohexanone, 1,2-dichlorobenzene, and alkalies (except ammonia), 113,114 dioxane, DMA, DMF, NMP, alcohols, carbon disulflde, tetrahydrofurfuryl alcohol, tetralin chloroform, cyclohexanone (hot), THF (hot), trichloroethane (cold, sw), dioxane (cold, sw), ethyl bromide, hydrocarbons, phenols, THF (cold, sw) Cyclohexanone, THF DMF, ethanol, HMPT, 5 hydrocarbons, methanol Cyclohexanone (hot), dinitrile, Aliphatic, cycloaliphatic, and 115 DMA (hot), DMF, DMSO (hot) aromatic hydrocarbons DMF Aliphatic, cycloaliphatic, and 115 aromatic hydrocarbons Carbon tetrachloride Aliphatic, cycloaliphatic, and 115 aromatic hydrocarbons y-Butyrolactone, cyclohexanone, Acetone, alcohols, aliphatic and 116-119 DMA, DMF, DMSO, ethylene cycloaliphatic hydrocarbons, carbonate, NMP chlorinated solvents, methyl isobutyl ketone Acetone, DMF, methyl isobutyl ketone Ethanol, hydrocarbons, methanol 118 Toluene 120 2,5-Dinitrotrifluorobenzene (1300C), Common organic solvents at RT 4,5,13, bzn. (2000C), carbon tetrachloride 121,674 (114°C), cyclohexane (235°C), 1,2-dichlorotrifluorobenzene, HMPT, mesitylene (14O0C), toluene (142°C), 1,1,1-trichloroethane (1200C), 1,2,3-trifluoropentachloropentane Perfluorokerosene (3500C), no other 4,13,122,123 solvent known Acetone, hexafluorobenzene Ethanol, hydrocarbons, methanol 124 Hexafluorobenzene, 125 perfluorodibutylamine, perfluorodibutyl ether Perfluorohexane 126 Chloroform Pentane 128 MEK Amyl acetate 129 Carbon dioxide (>200°C) Hexafluorobenzene, perfluorooctane
130 131
References page VII - 536
TABLE 1. cont'd Polymer 1.7.
Solvents
Nonsolvents
Refs.
POLY(VINYL NITRILES)
Polyacrylonitrile
ultrahigh MW Poly(2-fluoroacrylonitrile) Poly(acrylonitrile-a?-vinyl acetate) (98:2) Poly(acrylonitrile-a//-1,3-isoprene) Poly(vinylidine fluoride-co-ethyl vinyl ether) (1:1) Poly(acrylonitrile-a?-butadiene) (2:3 to 1:4) Polymethacrylonitrile
Acetic anhydride, y-butyrolactone, e-caprolactam, bis(2-cyanoethyl)ether, bis(4-cyanobutyl)sulfone, chloroacetonitrile/water, chloroacetonitrile, cyanoacetic acid, dimethyl phosphite, dimethyl sulfone, dioxanone, DMA, DMF, DMSO, ethylene carbonate, A^formylhexamethyleneimine, 2-hydroxyethyl methyl sulfone, Af-methyl-p-cyanoethylformamide, methylene dithiocyanate, Af-methyl-a,a,a,~trifluoroacetamide, l-methyl-2-pyridone, 3-,4-nitrophenol, nitromethane/W (94:6), Af-nitrosopiperidine, 2-oxazolidone, 1,3,3,5-tetracyanopentane, tetramethylene sulfoxide, l,i,l-trichloro-3-nitro-2-propane, sulfuric acid, nitric acid, p-phenol sulfonic acid, cone. aqu. sodium thiocyanate, molten quat. ammonium salts and their aqu. solutions DMF (10O0C) DMF DMF 1,2-Dichloroethane THF MEK, THF (partially), toluene Acetic anhydride, acetone, benzonitrile, cyanoacetic acid, cyclohexanone, dinitriles, DMF (>20°C), DMSO, ethylene carbonate, furfural, HMPT, methylene chloride, nitromethane, pyridine
Acetonitrile (sw), 5,6,13,132, acrylonitrile, alcohols, aliphatic 133,675 nitro compounds, bis(2-hydroxyethyl) sulfoxide, chlorinated hydrocarbons, 3,4-dimethyl sulfolane, diethyl ether, diethyl sulfone (sw), diethyl sulfoxide, diethylformamide, dimethylmalomtrile, dimethyloxamide, 1,1 -dimethylsuccinonitrile, ethylene urea, formamide, hexamethylene dithiocyanate, 1,6-hexanediamine, hydrocarbons, 1-hydroxypropionitrile, ketones, methanol, methoxyacetamide, methoxyacetonitrile, methyl thiocyanate, 1-nitrophenol, propyl formate
THF Methanol Aliphatic hydrocarbons, alcohols, esters, methacrylonitrile, toluene
134 135 136 137 135 32 4,5
1.8. POLY(VINYL ESTERS) Poly(vinyl acetate) atactic
syndiotactic Poly(vinyl trifluoroacetate) Poly(vinyl propionate) Poly(vinyl n-butyrate) Poly(vinyl isobutyrate) Poly(vinyl pivalate) Poly(vinyl caproate)
Acetic acid, acetone, acetonitrile, allyl DiL acids, dil. alkalies, carbon 4,5,13 alcohol, benzyl alcohol, bzn., carbon tetrachloride (sw), carbon disulfide, tetrachloride/ethanol, chlorobenzene, cyclohexanol, diethyl ether (anhydrous, chloroform, dichloroethylene/ethanol alcohol free), higher esters C>5, (20/80), 2,4-dimethyl-3-pentanol, ethanol (anhydrous, sw), ethylene dioxane, DMF, DMSO, lower glycol, saturated hydrocarbons, aliphatic esters, ethanol/W, glycol mesitylene, W (sw) ether esters, glycol ethers, methanol, nitromethane, tetrahydrofurfuryl alcohol, THF, toluene Chlorobenzene, chloroform Acetone, bzn. 106 Acetone, chloroform, ethyl acetate, 138 hexamethyldisiloxane See Poly(vinyl acetate) See Poly(vinyl acetate), amyl alcohol, 31 cyclohexane, hexyl acetate See Poly(vinyl acetate), amyl alcohol, 31 cyclohexane, hexyl acetate Acetone, butanone, bzn., ethyl Hexane, methanol, W 139 acetate, toluene Bzn. 5
TABLE 1. cont'd Polymer Poly(vinyl caprylate) Poly(vinyl laurate) Poly(vinyl benzoate), Poly(vinyl chloroacetate)
Poly(vinyl acetylacetate)
Pory(vinyl-A'-octadecylcarbamate) Poly(vtnyl acetate-fl/f-N-alkyl/arylmaleimide)
1.9.
Solvents
Nonsol vents
Acetone, aliphatic and aromatic hydrocarbons Aliphatic and aromatic hydrocarbons See Poly(vinyl acetate) Chlorobenzene, chloroform, cyclohexanone, dioxane, ethyl acetate, pyridine Acetic acid, acetone, chloroform, dioxane, DMF, ethyl acetate, pyridine, THF, saturated aqu. sol. of magnesium perchlorate Toluene (hot) Bzn., chloroform
Lower alcohols
Bzn., carbon disulfide, lower chlorinated aliphatic hydrocarbons, chloroform, cyclohexane (above 35°C), cyclohexanone, cyclohexane/acetone, decahydronaphthalene/diethyl oxalate, dimethyl phthalate, dioxane, ethyl acetate, ethylbenzene, glycol formal, MEK, methylene chloride, NMP, 1-nitropropane, phenol/acetone, phosphorus trichloride, THF, tributyl phosphate Bzn., chloroform, o-dichlorobenzene, toluene n-Tetradecane/dec any dronaph thai ene (2/1) THF See Polystyrene MEK, THF, toluene Bzn., THF, toluene Acetone, acetonitrile, DMF, DMSO, nitromethane Bzn., THF Bzn., dioxane, THF Ethyl acetate/ethanol (15/1) toluene THF Methanol and higher alcohols, methyl acetate, THF, THF/chloroform (1/1) MEK, toluene Bzn., toluene, chloroform Chloroform Acetone, bzn., chlorohexane, DMF, methylene chloride THF
Acetic acid, acetone, alcohols, diethyl ether, diols, ethylene chlorohydrin, glycol ethers, saturated hydrocarbons, isobutyl phthalate, phenol, 1,2,3, 4-tetrafluorobenzene (lower than 100C), tri(chloroethyl) phosphate, tricresyl phosphate
Refs. 4
Lower alcohols, acetone
4 5,87 4
Acetone (sw), saturated hydrocarbons
Alcohols, bzn., diethyl ether, W
140
Petroleum ether
327 142
POLY(STYRENES)
Poly(styrene) atactic
isotactic syndiotactic Poly(4-acetoxystyrene) Poly(a-methylstyrene), Poly(2-,3-, or 4-chlorostyrene) Poly(chloromethylstyrene) Poly(4-cyanostyrene) Poly(2 ,3-, or 4-bromostyrene) Poly(4-iodostyrene) Poly(2,5-dichlorostyrene) Poly(2,4,6-tribromostyrene) Poly(4-hydroxystyrene), Poly(/?-hydroxyphenylethylene)
Poly(4-methoxystyrene) Poly(2,5-dimethoxystyrene) Poly(3,4-dimethoxystyrene) Poly(ter/-butyl-4-vinyl perbenzoate) Poly(4-formylphenyl)ethylene, Poly(/>formylstyrene) Poly(styrenesulfonic acid) Poly(styrene-co-styrenesulfomc acid) (95:5) sodium salt Poly(4-trimethylsilylethynylenestyrene) Poly(styrene-c0-allyl alcohol) (94:6) Poly(styrene-c-acrylonitrile) (3 : 2) Poly(styrene-ctf-tert-butoxycarbonyloxystyrene) (4:5) Poly(styrene-o?-butyl methacrylate) (1:1) Poly(styrene-<:/-2,4-diamino-6-vinyl-l,3,5-tnazine)
4,5,7, 13,30,143
7 144 Mechanol
144
Bzn., carbon tetrachloride, ethyl acetate, diethyl ether, hexane, methanol
32 32 146 5,32 5,32 5 32 147,148
Chloroform, toluene
Hexane
5 149 150 141
Hexane, methanol, W
151
Hexane, methanol
Ethanol, lower glycols, W DMF, methylene chloride, THF Lower glycols, W THF Alcohols, aromatic hydrocarbons, esters, THF Chloroform, MEK, methylene chloride, Methanol THF THF, pyridine Methanol, W MEK, toluene DMSO, hexafiuoroisopropanol
32 152 153 154 32 7,32,155 156 32 157
References page VII - 536
TABLE 1.
cont'd
Polymer Poly(styrene-C0-maleic anhydride) (9:1) (1:1) Poly(styrene-a/Mnaleimide) Poly(styrene-cc?-4-thiomethylstyrene) (95:5) Poly(styrene-c0-4-vinylpyridine) (1:1)
Solvents
Cyclohexane/ethyl acetate (3/2) Acetone, acetonitrile, MEK THF THF DMF, THF
Nonsol vents
Methanol Ethanol, hexane
Refs.
65 32,158 157 159 32
1.10. OTHER COMPOUNDS (alphabetically ordered) Polyacrolein, (redox polymerization)
Polyacrolein (ionic polymerization), See 3.1.1 Poly(anthrylethylene) Poly(7V-benztriazolylethylene) Poly(biphenylyethylene) Poly(7V-carbazolyethylene), Poly(/V-vinylcarbazole)
Poly[6-(/V-carbazolyl)hexylethylene] Poly(diallyldimethylsilane) Poly(3,6-dichloro-Af-carbazolylethylene) Poly(2,4-dimethyl-6-triazinylethylene) Poly(diphenylphosphinylideneethylene), Poly(vinyldiphenylphosphine oxide) Poly(diphenylthiophosphinylideneethylene), Poly (vinyldiphenylphosphine sulfide) Poly(2-methyl-5-pyridylethylene) Poly(3-morpholinylethylene) PoIy(I-nitropropylene) Poly(2-pyridylethylene), Poly(2-vmylpyridine)
crystalline Poly(4-pyridylethylene), Poly(4-vinylpyridine)
Poly(/V-pyrrolidonylethylene), Poly(Af-vinylpyrrolidone)
Above 60 0 C: pyridine/water (55/45 to 90/10), above 1300C: nitrobenzene, sat. stannous chloride solution, y-butyrolactone (160-170 0 C), ethylene carbonate (130-135 0 C), DMF(153°C), DMSO (160-170 0 C), divinyl sulfone(150-155°C), TMS (160-165 0 C)
Lower alcohols, hydrocarbons, chlorinated hydrocarbons, diethyl ether, esters, aromatic ketones
Methylene chloride Chlorinated hydrocarbons, cyclohexanol, DMF, glacial acetic acid Bzn., dimethoxyethane, toluene Benzyl acetate, bzn., chlorobenzene, chloroform, cyclohexanone, dioxane, cone, nitric acid, cone, sulfuric acid, tetrachloroethane
Methanol Alcohols, esters, hydrocarbons, ketones, W
Acetone, methanol (partially), NMP (123°C) Bzn. Dichloroethane Alcohols, bzn., esters, ketones, W (cold) Bzn., ethanol, methanol, toluene Bzn., chloroform
Methanol Acetals, alcohols, dil. alkalies, dil. carboxylic acids, chlorohydrin, 1-chlorotoluene (sw), diethyl ether, dimethyltetrahydrofuran, diols, aliphatic esters, glycol monoethers, aliphatic ketones, saturated hydrocarbons, trichloroethylene (sw), W Methanol Methanol Aliphatic hydrocarbons, W (ppt. below 73°C) Hexane, W Methanol
Methanol, DMF W DMF (partially) Acetone, alcohols/water, bzn., Carbon tetrachloride toluene, chloroform, dioxane, ethanol, W (sw) glacial acetic acid, aqu. mineral acids, nitroethane, pyridine, THF Aromatic hydrocarbons (reflux), Aliphatic hydrocarbons (reflux), chlorinated solvents, methanol diethyl ether, MEK Acetone/W (1/1), benzyl alcohol, Acetone, diethyl ether, dioxane, bzn., cyclohexanol, dioxane/W ethyl acetate, MEK, petroleum (1/1), ethanol/water (92/8), ether, W isopropanol/MEK (86/14), methanol, aqu. mineral acids, nitromethane, pyridine, THF (solubility depending on small Acetic esters, acetone, acid amounts of W): acetone, dil. acids, esters, carbon tetrachloride, aromatic alcohols, chloroacetic acid 1-chlorotoluene, diethyl ether, esters, chloroform, chlorohydrins, hydrocarbons, methoxybutyrate ethanol, glacial acetic acid, esters, nitomethane/W methanol, nitromethane, pyridine
160,161
15 162 163 4,6,13, 30,164
165,166 167 168 169 170,171 171 5 172 173 4,13,35, 174,175
5,13,175
4-6,13,30
TABLE 1. cont'd Polymer
Solvents
PoIy(N-I,2,4-triazolylethylene)
Glacial acetic acid, DMF, DMSO, W
PolyyV-vinylthiopyrrolidone) Poly(5-vinyl-l,3-benzodioxole) Poly(2-vinylthiophene) Poly(vinyl sulfate) Poly(vinylsulfofluoride) Poly(vinylsulfonic acid) sodium salt Poly(vinyl sulfoxide) Poly(vinyl 4-methoxyphenyl sulfoxide) Poly(/V-vinylpyrrolidone-a>acrylic acid) (3 : 1 to 1: 3)
DMF Chloroform Chloroform Aqu. NaCl (0.5 M), W Acetone, DMF, ethyl acetate, THF Acetone, dioxane, ethanol, W Methanol, W, aqu. NaCl (0.5M) Chloroform, DMSO, methanol, W THF Acetone/W (1/1), isopropanol/W (1/1), NMP Butanol, DMSO, ethylene glycol, formamide, methanol, W DMSO, ethylene glycol (partially), formamide, W Saturated hydrocarbons Bzn., dioxane, THF Ethanol, isopropanol Ethanol Isopropanol, W DMF, DMSO (partially), NMP
Poly(vinyl amine), Poly(aminoethylene) Poly(vinylformamide) Poly(/V-vinylpyrrolidone-co-i-hexadecene) (1 :2) Poly(vinylnaphthalene) Poly(Af-vinylpyrrolidone-co-vinyl acetate) (1 :4 to 3 :2) PoIy(ZV-vinylpyrrolidone-co vinyl alcohol) (13: 1) PoIy(N-vinylpyrrolidone-covinyl acetate) (1:1) Poly(A^vinylformamide-o?-methyl 3-phenyl2-cyanopropenoate) (1:1) Poly(2-vinylpyridine-costyrene) (7:3) Poly(4-vinylpyridine-cfl-styrene) (3:2)
TABLE 2.
Alcohols, chlorinated hydrocarbons, esters, hydrocarbons ketone Butanol, hydrocarbons, MEK, W Methanol Diethyl ether Esters, hydrocarbons, ketones Acetone, methanol Acetone, bzn. Diethyl ether Methanol, MEK, THF
Refs. 162 176 150 177 5 13 4,13,179 13,179 180,181 182 183 179,184,185
Acetone, isopropanol /7-Propanol, W
Diethyl ether Chloroform, diethyl ether, ethyl acetate, methylene chloride
Bzn., chloroform, MEK, THF DMF, THF
179,185 186 32 186 187 32,681 697 32 32
MAIN-CHAIN CARBOCYCLIC POLYMERS
Polymer 2.1.
Nonsol vents
Solvents
Nonsolvents
Refs.
POLY(PHENYLENES)
Poly(2-hydroxy-l,4-phenylene) Poly(dihydroxyl-1,4-phenylene), Polyhydroquinone
Methylene chloride DMF (partially)
Poly(2.5-dw7-butoxy-l,4-phenylene)
1,2-Dichloroethane, methylene chloride, nitrobenzene Toluene Acetic acid, chloroform, DMF, ethanol Toluene
Poly(2,5-di-rc-decyl-l,4-phenylene) Poly(A^,A^-dimethy!aniline) Poly(2,l': 4 ' , 1 " : 4",1 "'-quaterphenylene-1,4), Poly [2-(phenyl-1,4-phenylene-1,4-phenylene)1,4-phenylene] Poly(2-benzoyl-l,4-phenylene), Poly(2,5-benzophenone) Poly(nitrophenylene) Poly[2-(4-methylbenzoyl)-l ,4-phenylene] Poly(2,5-dihydroxy-l,4-phenylenethenylene) PoIy(1,4-benzophenone-/V-phenyloxime) Poly(2,5-dimethoxy-l,4-phenylenethenylene) Poly(2,5-dimethyl-l,4-phenylenethenylene) low mol. wt. Poly(2,5-dimethyl-l,4-phenylenemethylene) low mol. wt. PoIy(1,4-phenyleneethenylene), Poly(phenylenevinylene) Poly( 1,4-phenylene-1,2-diphenylethenylene) PoIy[1,4-phenyleneethenylene-1,4-phenyleneethynylene2,5-(dodecyloxy)-1,4-phenyleneethynylene] Poly[3-nitro-l,4-phenyleneethenylene-2-(dihexylamino)1,4-phenyleneethenylene]
m-Cresol, DMA, methylene chloride, NMP
Acetone, chloroform, ethanol
188 181
Methanol
189
Acetone Aqu. sodium hydroxide Methanol
190 191 192
Methanol
193,194
All common organic compounds DMA Common organic solvents, aqu. potassium hydroxide DMA, NMP Bromoform Common organic solvents Chloroform, 1,2-and 1,4-dichlorobenzene Chloroform, 1,2- and 1,4-dichlorobenzene (hot) Biphenyl, benzyl benzoate, chlorinated biphenyls, diphenyl ether, nitrobenzene Chloroform Methanol Chloroform, THE toluene Chloroform, 1,2-dichloroethane, THF
195 196 197 194 197,198 199 199 197,200 201 202 203
References page VII - 536
TABLE 2. cont'd Polymer Poly(tetramethyl-l,4-phenylenethenylene) Poly(5-«-dodecyloxy-l,4-phenylene) Poly(2,5-di-n-decyloxy-1,4-phenylene) Poly(2,5-di-n-decyloxy-4,4/-biphenylylene) Poly[2-bis(methoxycarbonyl)-1,4-phenylenethenylene] Poly[l,4-phenylene-l,2-di(4-phenoxyphenyl)ethenylene] Poly [2-(2-phenylethenyl)~ 1,4-phenyleneethenylene] Poly(6-rc-hexyl-l,4-naphthalenediylethenylene) Poly(2,6-naphthalenediylethenylene)
Solvents
Nonsolvents
Refs.
Bzn., 1-chloronaphthalene (sw), ethanol DMA, DMF THF THF Methylene chloride Chlorobenzene, chloroform, toluene DMF Chloroform Tetrachloroethylene (partially)
Methanol Methanol Methanol Methanol
197 204 205 205 206 207 208 209 210
2.2. OTHER COMPOUNDS (alphabetically ordered) Poly(acenaphthylene) Poly[//-(3-bromophenyl)norbornenedicarboximide] PoIy(1,3-cyclohexadiene) Poly( 1,3-cyclohexy leneethenylene) PoIy(1,5-cyclooctadiene) Poly(cyclopentadiene), T V ^ - T — \ \
Bzn., carbon tetrachloride, chloroform, 1,2-dichloroethane (>30°C), THF, toluene 1,2-Dichloroethane, methylene chloride Bzn., xylene Bzn. Aromatic hydrocarbons, chlorinated hydrocarbons, diethyl ether (partially) methanol (oligomers) Bzn., chloroform, dioxane, THF
Poly( 1,3-cyclophenylenemethylene) Poly(erafo-dicyclopentadiene) Poly(2,3-dimethoxycarbonyl-2,5-cyclohexadien1,4-diylethenylene), Poly(dimethyl barrelene2,3-carboxylate) Poly(l,2-dihydronaphthalene)
Toluene (hot) Bzn., carbon disulfide, chlorobenzene Bzn.
Poly(dimethylfulvene)
Acetone, bzn., chlorinated hydrocarbons, diethyl ether, hexane Aromatic chlorinated hydrocarbons, diethyl ether, dioxane, drying oils, ketones, pyridine Bzn., carbon disulfide, chloroform, THF Acetone, acetonitrile, bzn., chloroform, DMF, DMSO, THF
Poly(indene) PoIy(I-isopropylidene3a,4,7,7a-tetrahydroindene) Poly[l,4-phenylene-l,2-dicyanol,2-bis(propoxycarbonyl)ethenylene]
Bis(phenoxyphenyl) ether (above 2900C)
Acetone, acids, alcohols, dimethoxyethane, ethers
4,32,211
Methanol Methanol Methanol Methanol
212 213 214 215
Ether, hexane, methanol, petrol
216
Acetone, hexane, methanol Methanol
217,218 219 206
Amyl acetate, chloronaphthalene, diphenyl ether, tetrachloroethane, tetrahydronaphthalene Alcohol
220
Acids, aliphatic hydrocarbons (sw), alkalies, lower alcohols, W
6
221
Acetone, cyclohexane, ethanol, hexane
222
Diethyl ether, hexane, methanol
164
TABLE 3. MAIN-CHAIN CARBONYL POLYMERS Polymer Poly(carbonylethylene) Poly(carbonyl-l,2-propylene) Poly(carbonylethylene-cc>-carbonyH,2-propylene) (7:3) Poly(carbonyl-l-furfuryltrimethylene) Poly(carbonylphenylethylene), Poly(carbon monoxideco-styrene) Poly(carbonyl-1-phenyltrimethylene) Poly(carbonyl-l,4-cyclohexan-3-onediyl) Poly(carbonyl-l,4-cyclohexan-3-onediylmethylene) Poly[carbonyl-2,3-di(ethoxycarbonyl)bicyclo[2.2.2] hepta-2,5-diene-5,6-diyl] Poly(carbonyl-4,4/-biphenylylene) Poly(carbonyl-l,4-phenyleneoxy-l,4-phenylene)
Solvents ra-Cresol Hexafluoroisopropanol Cresol, hexafluoropropylene, methylene chloride Acetone, dioxane Chlorobenzene, hexafluoroisopropanol, MEK (hot), methylene chloride Chloroform Chloroform Chloroform Acetone, common organic solvents Chloroform, DMA, 1,1,2,2-tetrachloroethane
Nonsolvents
Methanol Chloroform, ethanol, W Methanol
Refs. 328 329 330,331 332 333-335
Alkyl hydrocarbons
336 337 338 339
DMA, NMP MEK, methanol, toluene
194 340
Methanol
TABLE 3. cont'd Polymer
Solvents
Poly(carbonyl-1,3-pheny leneoxy-1,4-phenylene) Poly [carbonyl-l,4-phenyleneoxy-2-(methoxy methylene)1,4-phenyleneoxy-1,4-phenylenej Poly(carbonyl-l,3-phenylenecarbonyl-l,4-phenyleneoxy1,4-phenylene), PEKK Poly(carbonyl-1,4-phenytenecarbony 1-1,4-phenyleneoxy1,4-phenylene), PEKK Poly(carbonyl-1,3-phenylenecarbonyt-1,4-phenyleneoxy1,3-phenylenemethylene-1,3-phenyleneoxy-1,4-phenylene) Poly(carbonyl-l,4-phenylenecarbonyl-l,4-phenyleneoxy1,4-phenylene-2-pentylidene-1,4-phenyleneoxy1,4-phenylene) Poly(carbonyl-1,4-phenyleneoxy-1,4-phenyIeneoxy1,3-pyridinediyloxy -1,4-phenyleneoxy-1,4-phenylene) Poly (carbony 1-1,4-phenyleneoxy-4,4'-biphenylyleneoxy1,4-phenylene-c-carbonyl-1,4-phenyleneoxy1,4-phenyleneoxy-1,4-phenylene) (1:1 to 1:3) Poly(carbonyl-l,3-phenylenecarbonyl-l,4-phenyleneoxy1,3-pheny lenemethylene-1,3-phenyleneoxy1,4-phenylene)
TABLE 4.
Nonsolvents
Refs.
-Chlorophenol Chloroform, THF
341 342
Pentafluorophenol (80°)
343,344
Pentafluorophenol
344
DMA, DMF, NMP
345
DMA
Methanol
346
DMA
347
Sulfuric acid, 0.1 wt.%
348
DMA, DMSO, NMP
345
MAIN-CHAIN ACYCLIC HETEROATOM POLYMERS
Polymer
Solvents
Nonsolvents
Refs.
4.1. MAIN-CHAIN - C - O - C - POLYMERS 4.1.1. POLY(OXIDES) Unsubstituted Poly(oxymethylene), Poly formaldehyde
Poly(oxyethylene), Polyethylene glycol), Poly(ethylene oxide)
Poly(oxyethylidene), Polyacetaldehyde amorphous crystalline Poly(oxypropylene), PoIy(1,2-propylene glycol), Poly(propylene oxide), crystalline Poly(oxypropylidene), crystalline Poly(oxyisopropylidene), Polyacetone PoIy(1,3-dioxolane) Poly(oxytetramethylene), Poly(tetrahydrofuran) Poly(oxycyclopentenylene) Poly(oxycyclohexenylene) Poly(oxymethylenecyclopropylidenemethyleneoxyhexamethylene) Poly(oxy- 1,3-phenylene)
At elevated temp.: aniline, benzyl Lower alcohols, diethyl ether, 4,224,225 alcohol, benzyl benzoate, lower esters, hydrocarbons bromobenzene, y-butyrolactone, chlorophenols, diphenyl ether, DMF, ethylene carbonate, formamide, malodinitrile, phenol Acetonitrile, alcohols, bzn., Aliphatic hydrocarbons, ethers, dioxane 4,5,13 chloroform, cyclohexanone, esters, (sw), W (hot) DMF, W (cold), aqu. K 2 SO 4 (0.45 M above 35°C), aqu. Mg2SO4 (0.39 x M above 45°C) Alcohols, aromatic hydrocarbons, chloroform, esters, ketones Chloroform (partially) Acetone, bzn., chloroform, dioxane, DMF, ethanol, methanol (hot), THF Chloroform (partially) Acetone, chloroform Methylene chloride, W (700C) Bzn., chloroform, ethanol, THF Bzn., carbon disulfide, chloroform Aliphatic hydrocarbons, Chinese wood oil, methyl acetate, toluene Methylene chloride Benzophenone, bzn., diphenyl ether. DMF, DMSO, nitrobenzene, 3-pentanol, pyridine
Aliphatic hydrocarbons
226
Alcohols, esters, hydrocarbons, ketones 2-Aminoethanol, diethyl ether (sw), ethyl acetate (sw) Common organic solvents
226 13
Hexane, methanol, petroleum ether, W Methanol Acetone, ethanol, 2-ethoxyethanol
227 228 229 230-233 677 13
Hexanes
234
Methanol
235
References page VII - 536
TABLE 4. cont'd Polymer
Solvents
Substituted Polyepichlorohydrin, Poly(oxy-3-chloro-l,2-propylene) Poly(oxy-2-chloroethylidene) amorphous crystalline Poly(oxy-2-methyltetramethylene) Poly(oxy-2,2,2-trichloroethylidene), crystalline Polychloral Poly[oxy-2,2-bis(chloromethyl)trimethylene, Poly (oxy-2,6-dimethyl-1,4-phenylene), Poly(2,6-dimethyl-1,4-phenylene oxide) amorphous crystalline Poly(oxy-2,6-dichloro-1,4-phenylene) Poly(oxy-l,4-phenylene-l,2-cyclopropylene1,4-pheny leneoxymethylene) Poly(oxy-4,4/-biphenylylene-l,2-propylene1,4-phenyleneoxydodecamethylene) PoIy(I-propynylene-l,3-diyloxy-l, 4-phenyleneisopropylidene-1,4-phenyleneoxy2-propynylene 1,3-diyl) Poly[oxyethylene-co-oxy(chlorornethyl)ethylene] (1:1) Poly[oxy-3,5-bis(4-carboxyphenyl)-l,4-phenylene-a?oxy-3,5-bis(phenyl)-l,4-phenylene] (13: 87 to 62:38) Poly(oxy-l,4-phenyleneisopropylidine-l,4-phenyleneoxya/f-2-hydroxy-l,3-propylene), Poly(Bisphenol A), epoxy resin Polymeric structures, not 100% specific Poly(dimethylketene), -f OC-)-
Nonsolvents
Refs. 32,94,236,237 32,94, 236,237
Acetone, bzn., chloroform, diethyl ether, MEK, THF, toluene
Methanol
Chloroform
Cyclohexanone
Methanol Chloroform, methanol Methanol Chloroform, methanol, other common solvents Methanol
a-Pinene (hot) Bzn., chlorobenzene, chloroform, toluene 2-Methoxymethanol Chloroform, DMA, NMP
a-Pinene (cold), methanol, ethanol Ethanol, methanol, nitromethane, oc-pinene (hot) Methanol Methanol
Bzn., Cloroform
238 238 239 227 237,240 241 - 244 241-244 241-244 688 245
Chloroform
246
Toluene
247
Chloroform DMF, DMSO
Methanol Chloroform, toluene
Esters, ethers, ketones
237 248 249
C(CH3)2 low mol. wt. higher mol. wt. Polyacrolein, (ionic polymerization) -f OCH+-
Diethyl ether Bzn., carbon tetrachloride Acetone, bzn., dioxane, THF, DMF
Methanol Chloroform (partially) Methanol, petroleum ether
Aniline, y-butyrolactone, DMF, nitrobenzene, pyridine
Alcohols, hydrocarbons
250,251 250, 251 252
CH=CH2 Polyacrolein, (redox polymerization) see 1.10 Poly(a-methylacrolein)
13
Poly[l,2-di(epoxyethyl)benzene],
Chloroform, THF
Poly(phenyl glycidyl ether)
1,2-Dichlorobenzene (hot), DMF (hot), xylene (hot)
Common organic solvents at rt
Bzn., chloroform, diethyl ether, THF
Petroleum ether, W
Methylene chloride, THF, pyridine
Bzn., (partially)
Chloroform, diethyl ether, dioxane, THF Bzn., chloroform, diethyl ether, THF, dioxane Bzn., chloroform, hexane
Petroleum ether, W
133,197, 255,256 133,197, 255,256 255
Petroleum ether, W
255
Methanol
257
Poly(glutardialdehyde) low mol. wt. high mol. wt. Poly(p-methylglutardialdehyde), low mol. wt. Poly(p-phenylglutardialdehyde), low mol. wt. VoXy {trans-1,2-cyclohexanedicarb-
253 254
oxaldehyde),
Poly(2-formyl- A 5-dihydropyran)
Aromatic hydrocarbons, chloroform, pyridine, THF
258
TABLE 4. cont'd Polymer
Solvents
Nonsolvents
Refs.
4.1.2. POLY(CARBONATES) Poly(oxycarbonyloxypropylene) Poly(oxycarbonyloxyhexamethylene) Poly(oxycarbonyloxy-2,4-dihydroxy-l,4-butylene) Poly(oxycarbonyloxy-l,4-butyleneoxycarbonyloxy1,4-cyclohexylene) Poly(oxycarbonyloxymethylene-l,2-cylcohex4-enylenemethylene) Poly(oxycarbonyloxy-l,3-phenylene) Poly(oxycarbonyloxy-l,4-phenylene) Poly(oxycarbonyloxy-1,4-phenyleneisopropylidene-l,4-phenylene), Poly(Bisphenol A carbonate) chlorinated (8% Cl and more) Poly(oxycarbonyloxy-1,4-phenylene2-pentylidene-1,4-phenylene) Poly(carbon dioxide-co-propylene oxide) (1:1) Polypropylene carbonate-co-propylene oxide) (9:1) Poly(oxycarbonyloxy-l,2-cyclohexyleneoxy1,2-cylclohexylene)
Dioxane, methylene chloride Acetone, bzn., chloroform, toluene Methylene chloride Chloroform, THF
Methanol, W Ethanol, ether Ethanol
678 13 260 261
Chloroform
Chloroform, ra-cresol, cyclohexanone, dioxane, DMF, pyridine, THF
262 Common organic solvents Common organic solvents Acetone, carbon tetrachloride, lower esters, hydrocarbons, styrene
Bzn., methyl methacrylate, styrene Bzn., chloroform, ethyl acetate THF Chlorobenzene Methylene chloride, THF
13 13 13,263-265 265 13
Methanol Methanol
266 267 268
4.1.3. POLY(ESTERS) (alphabetically ordered) Polyethylene terephthalate), see Poly(oxyterephthaloyloxyethylene) Poly(oxyadipoyloxyethylene, Poly(ethylene adipate) Poly(oxyadipoyloxy-1,4-phenylene-1,2-propenylene1,4-phenylene) Poly(oxyadipoyloxytetramethylene), PoIy(1,4-butylene adipate) Poly(oxyadipoyloxytrimethylene), Poly(l,3-propylene adipate) Poly(oxyazelaoyloxyethlylene), Poly(ethylene azelate) Poly(oxycarbonyl-4,4'-biphenylylenecarbonyloxyhexamethylene) Poly(oxycarbonyl-1,4-cyclohexylenecarbonyloxyoctamethylene), cis and trans Poly(oxycarbonyldodecamethylenecarbonyloxy4,4 '-biphenylylene) Poly(oxycarbonylethylene), Poly((3-propiolactone) Poly(oxycarbonyiethyleneoxyethylene) Poly(oxycarbonylethylidene), Poly(DL-lactic acid) Poly (oxycarbonylethynylene-1,4-phenyleneethynylenecarbonyltetramethylene) Poly(oxycarbonyl-2,6-naphthalenediylcarbonyloxybutylene, Poly(butylene 2,6-naphthalate) Poly(oxycarbonyl-2,6-naphthalenediylcarbonyloxyethylene, Poly(ethylene 2,6-napthalenedicarboxylate) Poly(oxycarbonyl-2,6-naphthalenediyl-c6>-oxycarbonyl1,4-phenylene) (1:3) Poly(oxycarbonyloctadecamethylenecarbonyloxyethylene) Poly(oxycarbonylpentamethylene), Poly(e-caprolactone), Poly(oxyhexanoyl) Poly(oxycarbonylpentamethylene-co-oxycarbonyl3-hydroxypentamethylene) (9:1 to 1:9), Poly(5-hydroxyvaleric acid-co-4-hydroxyvaleric acid) Poly(oxycarbonyl-1,4-phenylene), Poly(4-hydroxybenzoic acid) Poly(oxycarbonyl-1,4-phenyleneoxyhexamethyleneoxy1,4-phenylene)
Bzn., THF Chloroform Chloroform, DMF, THF
32 269 Methanol
32,270
Chloroform, MEK, THF
32
Bzn., THF
32
Pentafluorophenol/methylene chloride (3/1), THF Chloroform
271,272 5
Phenol/tetrachloroethane (3/2)
273
Chloroform, formic acid
Hydrocarbons
274,275
THF, toluene Acetone, chloroform, toluene
Ethanol
278 276,277
DMA
Methanol
Methylene chloride
Chloroform THF
279 280,281
Hexafluoroisopropanol
282
Pentafiuorophenol/hexafluoroisopropanol Toluene Chloroform, methylene chloride, THF, toluene Methylene chloride
283
No known solvent Phenol//?-chlorophenol/ trichloroethylene (25/40/35)
Methanol Hexane, methanol Methanol (cold)
284 285-287 288 32 289
References page VII - 536
TABLE 4. cont'd Polymer Poly(oxycarbonyl-1,4-phenyleneoxyterephthaloyloxytetramethylene) (7 : 3 to 2:3), Poly(butylene terephthalate-co-4-hydroxybenzoic acid) Poly(oxycarbonyl-2-phenyl-l,3-propylene) Poly(oxycarbonylpolyethylenecarbonylpolyethylene) Poly(oxycarbonyl-l,2-propylene), Poly(3-hydroxybutyric acid) Poly(oxycarbonyl-l,3-propylene), Poly(y-butyrolactone), Poly(4-hydroxybutyric acid) Poly(oxycarbonyl-1,2-propylene-cooxyethylenecarbonyloxyethylene) (9:1 to 1:9) Poly(oxycarbonyltetradecamethylene) Poly(oxycarbonyltrimethyleneoxyethylene-co-methyl vinyl ether) (1:2 to 4: 1) Poly(oxycarbonyl-l-vinylethylene), Poly(p-vinyl-P-propiolactone) Poly(oxy-a,a-dibutylsebacoyloxyhexamethylene) Poly(oxydodecanedioyloxy-l,4-phenylene2-methylethenylene-1,4-phenylene) Poly(oxyfumaroyloxyhexamethylene) Poly(oxyfumaroyloxytetramethylene) Poly(oxyglutaroyloxyhexamethylene) Poly(oxyglutaroyloxypropylene), Poly(l,3-propylene glutarate) Poly(oxyisophthyloyloxy-4,4'-biphenylylene) Poly(oxyisophthaloyloxy-1,4-phenylene), Poly(phenylene isophthalate)
Poly(oxyisophthaloyloxy-1,4-phenylenefluorenylidene-1,4-phenylene) Poly(oxyisophthaloyloxy-l,l,3-trimethylindan -3,5-diyl-l,4-phenylene) Poly(oxymaleoyloxyhexamethylene), Poly(hexamethylene malonate) Poly(oxymaleoyloxytetramethylene), Poly(butylene malonate) Poly(oxyoxalyloxyethylene), Poly(ethylene oxalate) Poly(oxyoxalyloxyhexamethylene), Poly(hexamethylene oxalate) Poly(oxy-1-oxo-3-methyltrimethlylene-cc?-oxy3-ethyltrimethylene) (9:1), Poly(3-hydroxybutryic acid-cc-3-hydroxyvaleric acid) Poly(oxy-l-oxo-3-methyltrimethylene-co-oxy1-oxotrimethylene) (1:0 to 3 :1), Pory(3-hydroxybutyric acid-co-3-hydroxypropionic acid) Poly(oxy-1-OXO-1,2-propylene), Poly(lactic acid) Poly (oxy- 1-oxo-1,2-propylene-co-oxycarbonylmethylene), Poly (lactic acid-co-glycolic acid) (1:1 to 1:3) Poly(oxysuccinoyloxy-2,2-dimethyl-l,3-propylene) Poly(oxysuccinoyloxydoeicosan-10,12-diyne-l,22-diyl) Poly(oxysebacoyloxyhexamethylene), Poly(hexamethylene sebacate) Poly(oxysebacoyloxyhexadecamethylene) Poly(oxysuccinoyloxyhexamethylene), Poly(hexamethylene succinate) Poly(oxysuccinoyloxymethylene-l,4-cyclohexylenemethylene) Poly(oxysuccinoyloxynonamethylenebutadyne1,3-diylnonamethylene)
Solvents
Nonsolvents
/?-Chlorophenol/tetrachloroethane, trifluoroacetic acid Chloroform Cyclohexane Chloroform
Refs. 291
Hexane
290 292 7
Carbon tetrachloride, chloroform, dichloroethylene, trifluoroethanol Chloroform
Diethyl ether/hexane (1 :3)
295
Chloroform Bzn.
Diethyl ether
296 297
Butyrolactone, chlorinated hydrocarbons, DMF Bzn. Chloroform
293,294
298 Hexane, W
Chloroform Chloroform, NMP Methanol, W Bzn., chlorobenzene, chloroform, THF Chloroform, MEK, THF, toluene See poly(oxyisophthaloyloxy-1,4-phenylene) At elevated temp.: benzophenone, Common organic solvents halogenated biphenyls, halogenated diphenyl oxides, halogenated naphthalenes, m-terphenyl, 2,4,6-trichlorophenol Dichloroethane Methanol, W Chloroform, DMF, m-cresol, NMP, nitrobenzene, pyridine, THF Bzn., chloroform, THF
DMSO, hexane, methanol
Chloroform, NMP, THF
Methanol
Chlorobenzene, chloroform, dioxane, nitromethane, toluene Chloroform
302
303 304
300
Bzn., Chlorobenzene, chloroform, THF 301 Bzn., methanol, toluene, THF 301,305 306
Hexane, methanol
Acetone, chloroform, dioxane, DMF, methylene chloride, pyridine Chloroform
Ethanol, hexane, methanol
307
276,277,308,690 309
Bzn., chloroform, THF Chloroform, THF Bzn., chlorobenzene, chloroform, THF
Chloroform, THF
5 300 301 32
5
Chloroform
Chloroform Bzn., chlorobenzene, chloroform, nitromethane, THF Bzn., chloroform, THF (hot)
5 299
32 310 5,301 Methanol
5 5,301,305 32 310
TABLE 4. cont'd Polymer Poly(oxysuccinoyloxytetramethylene), Poly(tetramethylene succinate) Poly(oxysuccinoyloxytrimethylene), Poly( 1,3-propylene succinate) Poly[oxyterephthaloyloxy-l,4-(2-rc-alkyl)phenylene] Poly(oxyterephthaloyloxytetramethylene), Poly(butylene terephthalate) Poly[oxyterephthaloyloxybutyIene-C(?-oxycarbony2,6-naphthanenediylcarbonylpoly(oxyethylene)] (1:1) Poly(oxyterephthaloyloxyethylene), crystalline, Polyethylene terephthalate), Poly(oxyethyleneoxyterephthaloyl)
Poly(oxyterephthaloyloxyethylene-a?-oxyhexanoyl) (1:1), Poly(ethylene terephthalate-coe-caprolactone) Poly(oxyterephthaloyloxyethylene-c<9-oxycarbonylnaphthalene-2,6-diylcarbonyloxyethylene) ( < 4 : 1, > 4 : 1) Poly(oxyterephthaloyloxy- 1,4-phenylenecarbonyloxy tetraethylene) ( 2 : 1 : 1 ) Poly(oxyundecanoyl)
Solvents Chloroform, toluene
Nonsolvents
Refs.
Diethyl ether
311
Chloroform, MEK, THF, toluene /?-Chlorophenol, methylene chloride Phenol/tetrachloroethane
32 Acetone, ethanol, hexane
312 313
m-Cresol
314
Chloral hydrate, chlorophenol, Aliphatic alcohols, carboxylic DMSO (hot), halogenated aliphatic esters, chlorinated hydrocarbons, carboxylic acids, anhydrous ethers, hydrocarbons, ketones hydrogen fluoride, nitrobenzene, phenol/2,4,6-trichlorophenol (10/7), phenol, phenol/tetrachloroethane ( l / l ) Chloroform Methanol
4,5,315, 316
317
Phenol/tetrachloroethane (3/2)
318
p-Chlorophenol/tetrachloroethane, trifluoroacetic acid Bzn., chloroform
291 5
4.1.4. POLY(ANHYDRIDES) Poly(oxysebacoyl) Poly(oxyterephthaloyl)
Chloroform DMF
276 319,320
4.1.5. POLY(URETHANES) (alphabetically ordered) Poly(urethanes) (general) Poly(oxy-l,4-butyleneoxycarbonylimino1,4-phenylenemethylene-1,4-phenyleneiminocarbonyl), Poly(butanediol-#/f-diphenyl methane-1,4-diisocyanate) Poly(oxy-l,4-cyclohexyleneoxycarbonylimino1,4-phenylenemethylene-1,4-phenyleneiminocarbonyl) Poly(oxyethyleneoxycarbonyliminoethylene~ iminocarbonyl) Poly(oxyethyleneoxycarbonyliminohexamethyleneiminocarbonyl) Poly(oxyethyleneoxycarbonylimino~ 1,3-phenyleneiminocarbonyl) Poly(oxytrimethyleneiminocarbonyl)
4.2.
Phenol, m-cresol, formic acid, sulfuric acid DMA
Alcohols, diethyl ether, saturated hydrocarbons
Dioxane (hot), DMF, THF
1,1,2-Trichloroethane
322
Chloroform, formic acid, methylene chloride Diethyl ether
323
ra-Cresol DMF m-Cresol (hot), DMSO, sulfuric acid
4 321
Chlorobenzene, chloroform, cyclohexanone (sw), DMF (sw), xylene
DMSO
324 325 326
MAIN-CHAIN - O - HETEROATOM POLYMERS
4.2.1. POLY(SULFONATES) Poiy(aryl sulfonates) DMF
Methanol
349
DMA, DMF, NMP
Chloroform, methanol, methyl ethyl ketone, tetrahydrofuran
676
References page VII - 536
TABLE 4. cont'd Polymer
Solvents
Nonsolvents
Refs.
4.2.2. POLY(SILOXANES) (ordered according to increasing complexity) Poly(siloxanes) (general) fluids and greases
Aromatic and chlorinated hydrocarbons, esters
Moderately cone, acids and alkalies, 6 lower alcohols, W rubbers Aromatic and chlorinated hydrocarbons 6 (sw), esters (sw) Poly(oxydimethylsilylene), Poly(dimethylsiloxane) Amyl acetate, chlorobenzene, Acetone, acetonitrile, acetophenone, 4,5 chloroform, cyclohexyl acetate, aniline, benzyl alcohol, benzyl acetate, dichlorobenzene, 1,2-dimethoxybromobenzene, y-butyrolactone, ethane, ethyl bromide, Carbitol ~, cyclohexanone, cyclohexanol, ethyl acetate, ofluorotoluene, 1,4-dibromobutane, 1,2-dichloroethane, hydrocarbons, hydrogenated xylene, di(chloroethyl) ether, dichlorobenzene, isopropyl acetate, MEK (above 200C), dimethylnaphthalene, dioxane, octylamine, phenetol diphenyl oxide, ethyl formate, ethyl (above 13°C), trichloroethylene benzoate, 2-isopropoxyethanol, mesityl oxide, methanol, nitrobenzene, 1 -nitropropane Poly(oxydiethylsilylene), Poly(diethylsiloxane) Toluene W 32 Poly(oxyhydrophenylsilylene) THF 351 Poly(oxymethylphenylsilylene), Poly(methylphenylsiloxane) Acetone (hot), butanol, chloroform, Ethanol, ethylene glycol, methanol 352 diethyl ether, ethyl acetate, toluene Poly(oxymethylhexadecylsilylene) Chloroform, THF, toluene W 32 Poly(oxyalkylmethylsilylene)-co-4-(4-cyanobenzoyl)phenoxy DMF, toluene Hexane, methanol 353 Poly(oxydiphenylsilylene), Poly(diphenylsiloxane) Acetone (hot) Acetone (cold) 352 Poly[oxybis(3,4-dichlorophenyl)silylene] Acetone, bzn. 354 Poly(oxydimethylsilyleneethyleneoxydimethylsilylene) Toluene 355 Poly(oxydimethylsilyleneoxydimethylsilyleneTHF 356 1,4-phenylenedimethylsilylene) Poly [oxymethy 1(5-f-butoxycarbonyloxy-2-norbornyl)silylene] Chloroform, toluene Methanol 357,358 Poly(oxydimethylsilylene-c-oxyalkylmethylsilylene), Aliphatic hydrocarbons, aromatic Ethanol, W 359 Poly(dimethylsiloxane-co-alkylmethylsiloxane) hydrocarbons, isopropanol Poly(oxydimethylsirylene-a?-oxycarbonylBzn., carbon tetrachloride, 360 l,4-phenyleneisopropylidene-l,4~phenylene) (1:3 to 1:1) chloroform, methylene chloride, pyridine, THF 4.3. MAIN-CHAIN - C - S - C - AND -C-S-N-POLYMERS 4.3.1.POLY(SULFIDES) (alphabetically ordered) Poly(2,5-dioxopyrrolidine-1,3-diylthio-1,4-phenylene)
Tricresol
Methanol
Poly(dithioethyleneoxyethylene)
1,1,2-Trichloroethane (partially), other chlorinated hydrocarbons (partially)
liquid polymers Poly(tetrathioethylene)
Bzn., ethylene dichloride No solvent known
Poly(tetrathioethyleneoxyethylene)
1,1,2-Trichloroethane (partially), other chlorinated hydrocarbons (partially) Bzn., ethylene dichloride Biphenyl, dichlorobiphenyl, dimethyl-/?-terphenyl Chloroform/methanol
DiI. acids, alcohols, dil. alkalies, 6,178 bzn. (sw), carbon disulfide, carbon tetrachloride (sw), gasoline (sw), turpentine (sw) 6,178 DiI. acids, alcohols, dil. alkalies, 6,178 bzn. (sw), carbon tetrachloride, carbon disulfide, gasoline Dil. acids, alcohols, dil. alkalies, 6,178 bzn. (sw), carbon tetrachloride, carbon disulfide, gasoline 6,178 362
liquid polymers Poly(thio-4,4-biphenylylene) Poly(thiodifluoromethylene) Poly(thio-2,5-dimethyl-l,4-phenylene) Poly(thiomethylene-l,4-frafls-cyclohexylenemethylenethiomethylene) Poly(thio-1,4-phenylene), Poly(phenylene sulfide)
Cone, nitric acid (reflux), aqu. sodium hydroxide (10%, reflux)
Hexane, methylene chloride Bzn., chloroform
Methanol, W
Biphenyl, ra-dichlorobenzene, dichlorobiphenyl, dimethyl/7-terphenyl, hexachlorobiphenyl
At reflux temp.: 2,4-lutidine, phenyl sulfide, phenyl oxide, pyridine, toluene
361
363 364 365 362,366, 367
TABLE 4.
cont'd
Polymer
Solvents
Poly (thio-l,4-p.henylenecarbony 1-1,4-phenyleneisopropylidene-1,4-phenylenecarbonyl-1,4-phenylene) Poly(thio-l,4-phenyleneiminocarbonyl-l,4-phenyleneoxy carbonylethylene) Poly(thio-l,4-phenyleneoxymethyleneoxy-l,4-phenylene) Poly(thio-1,4-phenyleneoxy-1,4-phenylene) Poly(thiotetramethyl-1,4-phenylene) O C
^ ~\T^)C
Nonsolvents
Refs.
Chloroform, NMP
Methanol
368
Chloroform, NMP
Hexane, methanol
369
Chloroform, methyiene chloride Hexane, methyiene chloride Durene
Methanol
364 364 364
O S
^V"
CNH
lf':\~NH^
DMA DMF NMP
'
'
Methanol
370
4.3.2. POLY(SULFONES) (ordered according to increasing complexity) Poly(ethylene-a?-sulfur dioxide) Poly(propylene-o?-sulfur dioxide) PoIy(I -butene-co-sulfur dioxide)
No solvent known Cone, nitric acid, cone, sulfuric acid Acetone, cyclohexanone
Poly(butylethylene-cosulfur dioxide) PoIy(1,3-hexadiene-o?-sulfur dioxide) (1 : <3) Poly(dimethylbutadiene-cc>-sulfur dioxide) PoIy(I-pentyne-co-sulfur dioxide) PoIy(I -hexyne-co-sulfur dioxide) PoIy(I-heptyne-co-sulfur dioxide) Poly[4-(terf-butoxycarbonyloxy)styrene-co-sulfur dioxide] (5:1) PoIy(1,4-phenyleneoxymethyleneoxy1,4-phenylenesulfonyl) PoIy(1,4-phenylenesulfonyl) Poly(oxy-l,4-phenylenesulfony 1-1,4-phenylene)
Bzn., chloroform, dioxane Acetone, chloroform, DMA, DMF, THF Cone, nitric acid, cone, sulfuric acid Common organic solvents Dioxane Acetone, dioxane Acetone, dioxane Toluene
7 371 13 13 13 13 372
Chloroform
364
Poly (thio-1,4-phenylenesulfonyl-1,4-phenylene) Poly(carbonyl-l,3-phenylenemethylene1,4-phenylenesulfonyl-1,4-phenylene) Poly(thio-1,4-phenylenesulfonyl-1,4-phenylenethio1,4-phenyleneisopropylidine-1,4-phenylene) Poly(3-amino-l,4-phenylenesulfonyl-2-amino1,4-phenyleneoxy-1,4-phenyleneisopropylidene1,4-phenylene) Poly(2,5-thiophenediylsulfonyM ,4-phenyleneoxy1,4-phenyleneisopropylidene-1,4-phenyleneoxy) PoIy(1,4-phenylenesulfony 1-1,4-phenyleneoxy4,4'-biphenylyleneoxy) PoIy(1,4-phenylenesulfonyl-1,4-phenyleneoxy1,4-phenylenecarbonyl-1,4-phenyleneoxy1,4-phenyleneoxy) PoIy(1,4-phenylenesulfonyl-1,4-phenyleneoxy1,3-phenyleneethenylene -1,3-phenyleneoxy) PoIy(1,4-phenylenesulfonyM,4-phenyleneoxy1,4-phenylenevinylidene-1,4-phenylene) Poly (1,4-phenylenesulfonyl-1,4-phenyleneoxy1,4-phenyleneoxy-1,3-pyridinediyloxy-1,4-phenyleneoxy) PoIy(1,4-phenylenesulfonyl-1,4-phenyleneoxy1,4-phenylenemethylphosphineoxide-1,4-phenyleneoxy)
Poly(l,3,4,6-tetraoxyperhydrocyclopentene-(l,2-c: 3,4-c')dipropyl-2,5-diylethylenesulfonylethylene)
Aniline, DMA, pyridine Aniline, aromatic amines, DMF, DMSO, methyiene chloride, NMP, pyridine DMF, DMSO, NMP No known solvent
Common organic solvents Paraffins, cycloparaffins, aromatic hydrocarbons
Methanol Alcohols, halogenated hydrocarbons, hydrocarbons, silicone oil Acetone, DMF, THF, toluene
DMA/toluene
13,178 13,178 13
373 32,373-375 376 377 378
THF
Ethanol/W (1:1)
379
DMA, methyiene chloride, THF
Methanol, W
380
Aniline, DMA, pyridine Chloroform, sulfolane
373 Methanol
381
DMA
382
Chloroform, DMA
181
DMA
347
DMA
Methanol/W
383
Dichlorobenzene
Isopropanol, methanol
384
DMF, DMSO, formic acid, NMP, sulfuric acid
Hexane
385
References page VII-536
TABLE 4.
cont'd
Polymer
Solvents
Nonsolvents
Refs.
4.3.3. OTHERS Poly(trimethylenesulfite)
Methylene chloride
386
4.4. MAIN-CHAIN - C - N - C - POLYMERS 4.4.1. POLY(AMIDES) Poly(amides) 1 Poly(N-ethyliminocarbonyl), Poly (ethyl isocyanate) Poly(N-butyliminocarbonyl) Poly(butyl isocyanate) Poly(A/r-n-hexyliminocarbonyl), Poly(n-hexyl isocyanate) Poly(N-m-tolyliminocarbonyl) Poly(A/'-vinyliminocarbonyl) Poly (amide) 1,5 Poly(iminoglutaroyliminomethylene) Poly(amide) 1,6 Poly(iminoadipoyliminomethylene), Poly(methylene adipamide) Poly(amide) 1,12 Poly(iminododecanoyliminomethylene) Poly(amides) 2 Poly(7-benzyl glutamamide) Poly(lysine-co-lactic acid) (1:19) Poly(amides) 3 Poly[imino-(l-oxo-2,2-dimethyl-3-phenyltrimethylene)], Poly(3,3-dimethyl-4-phenylazetidine-2-one) Poly[imino-(l-oxo-3-methyltrimethylene)], Poly (4-methylazetidine-2-one) optical activity < 75% optical activity > 80% Poly[imino-(l-oxotrirnethylene)]
Poly(aspartic acid-co-lactic acid) (1:9) Poly(amides) 4 Poly[imino-(l-oxotetramethylene)], Polypyrrolidone
Poly(iminooxalyliminotetramethylene) Poly(imino-l-carboxy-l,3-propylenecarbonyl), Poly (y-glutamic acid) Poly(amide) 4,6 Poly(iminoadipoyliminotetramethylene), Poly(butylene adipamide) Poly(amides) 5,5 Poly(iminoglutaroyliminopentamethylene), Poly (1,5-pentamethylene glutaramide) Poly (amide) 5,6 Poly(iminoadipoyliminopentamethylene), Poly (pentamethylene adipamide) Poly(amides) 6 Poly[imino-(l-oxohexamethylene)], Poly (e-caprolactam) chlorinated
Sulfuric acid, trifluoroacetic acid Bzn., carbon tetrachloride, THF Bzn., chloroform, DMF DMF DMA, DMF, DMSO, pyridine
Methanol Alcohols, carbon disulfide, chloroform, dioxane
1,4-Butanediol, dichloroacetic acid
387 387,388 389-391 387 392 393,394
1,4-Butanediol
394
2-Methyl-2,4-pentanediol
394
m-Cresol, DMF Chloroform
Methanol
Phenol, sulfuric acid, trifluoroethanol
Chloroform, HMPT, methanol, sol. OfCa(CNS)2 in methanol
Formic acid, phenol, sulfuric acid, sol. of Ca(SCN) 2 in methanol Chlorobenzene/trichloroacetic acid (1/1), dichloroacetic acid, formic acid/trichloroacetic acid (3/7) Aqu. chloral hydrate, aqu. sol. of CaBr2 or FeCU, chloroacetic acid, cyanoacetic acid, formic acid, glycerol (hot), nitric acid, nitrophenols, phenol (hot), sulfuric acid, W>140°C Methylene chloride
Chloroform, HMPT* methanol, trifluoroethanol Formic acid, sulfuric acid
395,396 397 399 399,691
a-Pyrrolidone (hot), acetic acid (hot), aqu. sol. of Ca(CNS)2, benzyl alcohol (hot), 0-chlorophenol, m-cresol, dichloroacetic acid, formic acid, methanol, sulfuric acid Dichloroacetic acid, sulfuric acid, trifluoroacetamide W
Most organic solvents, dilute bases and acids, DMF, DMSO, phenol (cold)
691 13,400,401
402 DMF, formamide, W
403, 404
Formic acid, phenol, W
405
Ethanol
406
Hexafluoroisopropanol
407
Dichloroacetic acid
408
Dichloroacetic acid, trifluoroethanol
Methanol
409,410
Acetic acid, chlorophenol, m-cresol, ethylene carbonate, formic acid, HMPT, phosphoric acid, sulfuric acid, trichloroacetic acid o-Chlorophenol, DMSO, sulfuric acid
Alcohols, chloroform, esters, ethers, hydrocarbons, ketones
4,5
Formic acid
411
TABLE 4. cont'd Polymer Poly[imino-(l-oxohexamethylene)], partially N-trifluoroacetic acid substituted Poly[imino-( l-oxohexamethylene)-cY;-imino(1-oxyundecamethylene)] (1:1) Poly[imino-(l-oxohexamethylene)-o?-iminosuccinoyl], (9 : 1 to 2: 8) Poly(amide) 6,6 Poly(iminoadipoyliminohexamethylene), Poly(hexamethylene adipamide)]
Poly(amide) 6,9 Poly(iminoazelaoyliminohexamethylene) Poly(amide) 7 Poly[imino-(1 -oxohepamethylene)-o?-imino(1-oxodedecamethylene)], (1 : 1) Poly(amide) 8,6 Poly(iminoadipoyliminooctamethylene) Poly (amide) 10,6 Poly(iminoadipoyliminodecarnethylene), Poly(decamethylene adipamide) Poly(amide) 11 Poly[imino-(l-oxoundecamethylene)], PoIy(I I-aminoundecanoic acid) Poly(amide) 12 Poly[imino-(l-oxododecamethylene)], PoIy(12-aminododecanoic acid) Poly(amide) 12/2 Poly(iminocarbonylmethyleneiminocarbonylundecamethylene) Poly(amide) 12,6 Poly(iminoadipoylirmnododecamethylene) Poly (amide) 18 Poly[amino-(l-oxooctadecamethylene)], Poly (18-aminostearic acid) Other aliphatic poly (amides) Poly(iminotartronoyliminohexamethylene) Aromatic poly(amides) Poly(imino~l,4-phenylenecarbonyl-cc>-oxy-l,4-phenylenecarbonyl) (1 : 1 to 1 :9), Poly(/?-aminobenzoic acid-co-p-hydroxybenzoic acid) Poly(iminocarbonyl-l,4-phenyleneoxyterephthaloyloxy1,4-phenylenecarbonylimino-1,4-phenylenehexafluoroisopropylidene-1,4-phenylene) Poly(iminocarbonylpyridine-2,6-diyl-carbonylimino1,4-phenyleneoxy-l ,4-phenylene) Poly(iminoterephthaloyliminoethylene), Poly(ethylene terephthalamide) Poly(A^methyliminoterephthaloyl-/V-methyliminoethylene) Poly(/V-methyliminoterephthaloyl-
Solvents Acetone, chloroform, THF
Nonsolvents Hexane, W
Refs. 412
2,2,2-Trifluoroethanol/methylene chloride (3/2) Mesitylene/sulfolane
413 414
it: Chloral hydrate, chloroacetic Aliphatic alcohols, chloroform, acids, formic acid, HCl, HF, liquid diethyl ether, hydrocarbons, sulfur dioxide, methanol, phenols, aliphatic ketones, aliphatic esters phosphoric acid, sulfuric acid, trichloroethanol, trifluoroethanol, saturated solutions of: alcohol-soluble salts, e.g. calcium chloride, magnesium chloride in methanol, at 120-1800C: acetic acid, /V-acetylmorpholine, benzyl alcohol, 2-butene-l,4-diol, 1,3-chloropropanol, di(ethylene glycol), DMSO, ethylene chlorohydrin, formamide
13
m-Cresol
32
2,2,2-Trifluoroethanol/methylene chloride (3/2)
413 415
1,4-Butanediol, hot Chlorobenzene, diethyl succinate (790C)
5
Higher primary alcohols, DMF, DMSO, hexafluoropropanol
13,692
Cresol DMSO
416 Diethyl ether
398
Cresol
416
DMF, DMSO, pyridine
Hexane, methanol, W
417
Chloroacetic acid, DMSO
Acetone, hexane, methanol, W
418
Cone, sulfuric acid (decomp.)
Insoluble in all common solvents
419
NMP
693
NMP, sulfuric acid
Methanol
420
Sulfuric acid
Acetone, chloroform, m-cresol, DMF, ethanolAV (4/1), formamide, trifluoroacetic acid Ethanol/W (4/1)
421 421
Acetone, DMF
421
Acetone, chloroform, m-cresol, DMF, formamide, sulfuric acid, trifluoroacetic acid Chloroform, m-cresol (hot),
References page VII - 536
TABLE 4. cont'd Polymer Mmethyliminotetramethylene) Poly(immoisophthaloylimino-1,3-phenylene), N-methyl substituted Poly(iminoisophthaloyHmino-l,4-phenyleneoxy1,4-phenylene) Poly(iminoisophthaloylimino-2,4-pentylene) Poly(iminoisophthaioylimino-4,4'-biphenylylene)
Poly (iminoisophthaloylimino-1,4-phenylene) Poly(iminoterephthaloylirninoethylene oxyisophthaloyloxyethylene) Poly(iminoterephthaloyliminotetramethylene) Poly(butylene terephthalamide) Poly(iminoterephthaloylimino-2,4-pentylene) Poly(iminoterephthaloylimino-1,4-phenylene), Poly (p-phenylene tetrephthalamide) Poly(iminocarbonyl-l-methyl-4,5-imidazolediylcarbonyliminoethylene) Poly(iminocarbonyl-l,4-phenyleneiminocarbonylpentamethylene) Poly(iminoterephthaloylimino-3-methyl1,4-phenyleneoxyethyleneoxy-2-methyl-1,4-phenylene) Poly(iminocarbonyl-l,4-phenylenehexafluoroisopropylidene-1,4-phenylenecarbonylimino1,4-phenyleneoxy-1,4-phenylene) Poly(iminocarbonyl-l,4-phenyleneoxyterephthaloyloxy1,4-phenylenecarbonylimino-1,4-phenylenehexafluoroisopropylidene-1,4-phenylene) Poly(imino-3-alkylisophthaloylimino-1,4-phenylene) Poly(iminotetra(octylthio)terephthaloylimino1,4-phenylene) Poly(pyromellitic dianhydride-co-aromatic diamines), Poly(amic acids)
Solvents
Nonsolvents
Refs.
ethanol/W (4/1) (hot), formamide, sulfuric acid DMSO, sulfuric acid
Hexane, W
422
NMP, sulfuric acid
Methanol
420
DMF, DMSO, methanol, Hexane, methanol trifluoroacetic acid, trifluoroethanol Cone, sulfuric acid ra-Cresol (hot), DMA (sw), DMF (sw), DMSO (sw), formic acid (85%) (sw), glacial acetic acid (sw), methanol, NMP (sw) HMPT DMSO, NMP, trifluoroacetic acid Methanol, DMF DMF, formamide, sulfuric acid, trifluoroacetic acid LiCl, sulfuric acid, trifluoroacetic acid DMF/LiCl, NMP
Acetone, chloroform, m-cresol DMF, DMSO, trifluoroethanol, W
423 424
425 426 421 423 427,428
Chloroform, DMF, methylene chloride, NMP Ethyl acetate
429
Tetrachloroethane
431
DMA
430
Methanol
NMP NMP Methylene chloride/methanesulfonic acid DMF, DMA, DMSO, tetramethylurea
432 693
Chlorobenzene, chloroform, dioxane, THF, trifluoroacetic acid
433 434 435
Sulfur and phosphorus containing poly(amides) Poly(iminoadipoyliminotrimethylene-1,4-phenylenephosphinidene-l,4-phenylenetrimethylene)
Aqu. hydrochloric acid (5%), cresol, DMF, ethanol, formic acid
Poly(iminoethyleneiminocarbonyl- 1,4-phenylenesulfonyl-1,4-phenylenecarbonyl)
Formic acid, tetrachloroethane/phenol (2/3), 1,1,2-trichloroethane/formic acid (3/2) Cresol, DMF, ethanol, C-7 fluoroalcohol, formic acid
Poly(iminohexamethyleneiminocarbonylethylene1,4-phenylenephosphinylidene1,4-phenyleneethylenecarbonyl) Poly(iminohexamethyleneiminocarbonylethylenethioethylenecarbonyl) Poly(iminoisophthaloylimino-l,3-phenylenesulfonyl-1,3-phenylene) Poly (iminoterephmaloylimino-1,3-phenylenesulfonyl-1,3-phenylene) Poly(iminoterephthaloylimino-1,4-phenylenesulfonyl-1,4-phenylene) Poly(iminoterephthaloyliminotrimethylene1,4-phenylenephosphinidene1,4-phenylenetrimethylene
Acetone, acetonitrile, chiorobenzene, chloroform, C-7 fluoroalcohol, hexane (sw), W 2-Chloroethanol, m-cresol, DMF
436 437
DMA, DMF, NMP
Acetone, acetonitrile, aqu. hydrochloric acid (5%, sw), chlorobenzene, chloroform (sw), HX, W (sw) Acetone, acetonitrile, aqu. hydrochloric 436 acid (5%), chlorobenzene, chloroform, ethanol, C-7 fluoroalcohol (sw), hexane, W 438
DMA, DMF
NMP
438
Sol. of LiCl in DMF (5%)
DMF, NMP
438
Cresol, DMF, formic acid, hydrochloric acid (5% sw)
Acetone, acetonitrile, chlorobenzene, chloroform, ethanol (sw), hexane, W
436
Chloroform, odichlorobenzene, nitrobenzene, THF
Acetone, hexane, methanol
439
Cresol, DMF, formic acid
4.4.2. POLY(HYDRAZIDES) Poly[diazo-l,4-phenylenecarbonyltri(oxyethylene)oxycarbonyl-1,4-phenylene]
TABLE 4. cont'd Polymer Poly(hydrazoadipoylhydrazoisophthaloyl) Poly(hydrazoadipoylhydrazosuccinoyl) Poly(hydrazoisophthaloylhydrazoterephthaloyl)
Poly(4,4'-benzaldehydeazineoxy-l,4-phenyleneisopropylidene-1,4-phenyleneoxy)
Solvents
Nonsol vents
DMSO, HMPT m-Cresol, dichloroacetic acid (degrad.), DMA, DMSO (cold), formic acid (degrad.), NMP, sulfuric acid (degrad.), trifluoroacetic acid (degrad.), trifluoropropanol Toluene
DMSO (sw) Chloroform, nitrobenzene, trichloroethane (sw), trifluoropropanol, W
Methanol
Refs. 440 440 441
442
4.4.3. POLY(UREAS) Poly(ureas) (general) Poly(iminocarbonylirninononamethylene), Poly(ureylenenonamethylene) Poly(iminocarbonylimino-l,3-phenyleneiminocarbonylirnino-2-methyl-5-sulfo-1,3-phenylene), Poly(ureylene-1,3-phenyleneureylene-2-methyl5-sulfo-1,3-phenylene)
m-cresol, formic acid, phenol, sulfuric acid Sulfuric acid (60% and 95%) Aqu. NaOH
Alcohols, diethyl ether m-Cresol (sw), glacial acetic acid, aqu. NaOH (45%, sw) W
30 679 443
4.4.4. POLY(CARBODIIMIDES) (arranged according to increasing complexity) NR
Poly(diethylcarbodiimide) ** Poly(diallylcarbodiimide) Poly(di-rc-butylcarbodiimide) Poly(diisobutylcarbodiimide) Poly(methylhexylcarbodiimide) Poly(di-rc-hexylcarbodiimide) Poly(diphenylcarbodiimide) -N=C=N-RPoly(hexamethylenecarbodiimide) Poly(4,4'-biphenylylenemethylenecarbodiimide) Poly(3-methyl-l,4-phenylenecarbodiimide) Poly(l,3-xylylenecarbodiimide)
Poly(2,2'-dimethyl-4,4'-biphenylylenecarbodiimide) Poly(2,2/-dimethoxy-l,4-biphenylylenecarbodiimide) PoIy(1,5-naphthylenediylcarbodiimide)
Formic acid, aqu. mineral acids Formic acid Formic acid Formic acid Toluene Formic acid, rc-heptane, toluene Formic acid
Heptane Heptane Heptane
444 444 444 444 445 445,446 444
No solvent known m-Cresol, trichlorophenol/phenol (7/10) No solvent known No solvent known Chlorobenzene, chloroform, cyclohexanone, DMF, DMSO, ethylene chiorohydrin, formic acid, trichloroethylene, xylene No solvent known No solvent known No solvent known
447 447 447 447
447 447 447
4.4.5. OTHER COMPOUNDS Poly(N-propanoyliminoethylene), Poly(2-ethyl-2-oxazoline) Poly[AKperfluorooctylethylenecarbonyl)iminoethylene] Poly(/V-benzoyliminoethylene) Poly[AH(9-carbazolyl)acetyl)iminoethylene] Poly[N-2-((9-carbazolyl)propanoyl)iminoethylene] Polysuccinimide Poly(ter?-butylmaleimide) Poly(phenylmaleimide) Poly(m-aniline) Polyaniline, camphorsulfonic acid doped Poly|7V-(p-tert-butylbenzoyi)aniline] Poly(2-pentadecylaniline) Poly(3-trifluoromethylaniline) Poly(4-amino-3-sulfoaniline)
Ethanol, W Hexafluoroisopropanol Chloroform Chloroform, THF Chloroform, THF Mesitylene sulfolane Bzn., carbon tetrachloride, DMF, THF DMF, DMSO DMF, DMSO, methylene chloride (partially), NMP Benzyl alcohol, chloroform, m-, p-cresol, DMF, NMP Acetone (partially), chloroform (partially), DMSO, THF Chloroform, THF Acetone, acrylonitrile, toluene Methanol, W
Methanol Diethyl ether Ethanol, diethyl ether Ethanol, diethyl ether Hexane Bzn., hexane
448,449 450 451 452 452 453 454 454 455 456,457 458 459 460 461
References page VII - 536
TABLE 4. cont'd Polymer Poly[yV-(p-sulfophenyl)imino-3-hydroxymethyll,4-phenyleneimino-l,4-phenylene] Poly[N-(4-methylphenyl)-6-iminohexamethylenecarbonyl1,4-phenylene] Poly(imino-l,4-phenylenecarbonyloxy1,4-phenyleneoxycarbonyl-l,4-phenylene) Poly[/V-(methyl)imino-3-phenyltriazine-l,5-diyl] Poly (9-nitriloanthraquinone-10-nitrilo-l,4-phenylene) Poly(9-nitriloanthraquinone- 10-nitrilo-1,4-phenylenemethylene-1,4-phenylene) Poly[carbonyliminocarbonyl-1,4-phenylenecarbonyliminocarbonyloxy-2,2-(dimethyl) tetramethyleneoxy] Poly(oxy-3-methyl-l,4-phenylene-<9MV-azoxy2-methyl-1,4-phenyleneoxy-1,12-dodecanoyl),
Solvents DMF (partially), DMSO (partially), NMP (partially), W Methylene chloride, THF
Nonsolvents
Refs. 462
Diethyl ether, methanol
463
m-Cresol, DMA (partially), DMSO (partially), NMP (partially), sulfuric acid Bzn., cresols, phenols Chlorobenzene, chloroform Chlorobenzene
Chloroform, hexane
464
Hexane Hexanes
465 466 467
DMA
Diethyl ether
468
Chloroform
Poly[/V-(acetyl)irninoethylene-c-Af(3-thiopheneylcarbonyl)iminoethylene]
469
Acetone, acetonitrile, DMF, DMSO, THF
470
4.5. POLY(PHOSPHAZENES) AND RELATED COMPOUNDS Poly(dichlorophosphazene) Poly[bis(trifluoroethoxy)phosphazene] Poly(dimethoxyphosphazene) Poly(dihexyloxyphosphazene) Poly(methylphenylphosphazene) Poly(diphenoxyphosphazene) Poly(4-nitrophenoxyphenoxyphosphazene) Poly[(phenylthiophosphonoyl)trirnethyene]
Acetonitrile, cyclohexane, 682 methylene chloride, THF Acetone, cyclohexanone (hot), Diethyl ether, dioxane, ethanol, 471-473 dimethyl ether, ethyl acetate, hydrocarbons, W glycol, methanol (hot), THF Acetonitrile, chloroform, Acetone, bzn., diethyl ether, ethanol, W 471 dimethoxyethane, dioxane, DMF, methanol, pyridine, THF Bzn. 7 THF 474 Bzn. (hot), chlorobenzene, DMF, THF Acetone, DMSO, ethanol, hexane, W 471 Dioxane, THF Hexane, methanol, W 475 Acetone (partially), acetonitrile Toluene, ethyl acetate, methanol, W 476 (partially), chloroform, DMF, DMSO
Chloroform
Methanol/W (9/1)
477
Methylene chloride
Diethyl ether
478
Aromatic hydrocarbons, carbon tetrachloride, cyclohexane Aromatic hydrocarbons Diethyl ether, THF Toluene Isooctane Chloroform Carbon tetrachloride Toluene THF Toluene Toluene Chloroform, diethyl ether Bzn., THF
Acetone (partially), DMSO (partially)
479
4.6. POLY(SILANES), POLY(SILAZANES) Poly(alkyltrisilazane) Poly(dimethylsilylene-1,4-phenylene) Poly(dimethlylsilylenetrimethylene) Poly(;z-pentyl-n-hexylsilylene) Poly(di-rc-hexylsilylene) Poly(methylphenylsilylene) Poly(phenylchlorosilylene) PoIy(1,1,2,2-tetramethyldisilylenemethylene) Poly (diethoxysilylene-1,4-phenylene) Poly(octamethyltetrasilylenedimethylsilylene) Poly(octamethyltetrasilylenemethylene) Poly(dihydrosilylene-1,4-phenylene) Poly(hydrophenylsilyleneethynylene1,3-phenyleneethynylene)
Aliphatic hydrocarbons, ethanol Isopropanol/ethyl acetate
Ethanol Chloroform/me thanol Methanol Methanol Ethanol Hexane, methanol
480 481 482 483 484 485 486 487 488 488 489 490,491
Next Page
TABLE 4. cont'd Polymer Poly(dibutylsilylene-1,4-phenyleneethenylene1,4-phenyleneethenylene-1,4-phenylene) Poly(hexamethylcyclotrisilazane) Poly(dihexylsilyleneferrocenediyl) Poly(dimethyisilylene-N-methylimino) Poly(dimethylsilyleneiminoethyleneimino) Poly(dimethylsilylene-co-1,3-dihydro1,3-dimethyldisilazane) (1:1 to 3: 1)
Solvents
Nonsolvents
Refs.
Chloroform
THF
492
Carbon tetrachloride, hydrocarbons THF THF Xylene Decaline, toluene
Acetone, DMSO
493 680 494 495 496
Toluene
Methanol
497
TABLE 5. MAIN-CHAIN HETEROCYCLIC POLYMERS Polymer
Solvents
Nonsolvents
Refs.
5.1. POLY(BENZOXAZOLES), POLY(OXADIAZOLES), POLY(OXADIAZOLIDINES) Poly(benzoxazoles) Poly(2,5-benzoxazolediyl) Poly(2,6-benzoxazolediyl) Poly(dibenzothiazoles)
Sulfuric acid Sulfuric acid
498 498 499
R = 1,3-phenylene R = 1,4-phenylene R = octamethylene R = 1,4-cyclohexylene
Sulfuric acid Sulfuric acid m-Cresol, formic acid, sulfuric acid Sulfuric acid
R = tetramethylene
Chloroform, m-cresol, DMF (hot), Benzyl alcohol, formic acid pyridine (hot), sulfuric acid (hot), tetrachloroethane (hot), THF (hot) Benzyl alcohol (hot), chloroform, DMF (partially), formic acid (partially) m-cresol (hot), pyridine, sulfuric acid, tetrachloroethane (hot), THF Chloroform, m-cresol, Benzyl alcohol, DMF, pyridine, formic acid (hot), sulfuric acid (hot) tetrachloroethane, THF
R = 1,3-phenylene
R = l ,4-phenylene
Organic solvents Organic solvents Acetic acid, DMA, DMF, DMSO, formamide, NMP
Polyphosphoric acid
DMA, NMP
499 499,500 500 501
502 502
502 503
Methanol
504-506
Poly( 1,3,4-oxadiazoles)
R = octamethylene
R = methylene to eicosamethylene
Bzn., chloroform, m-cresol, dichloroethylene, DMA (hot), DMF, DMSO (hot), NMP (hot), sulfuric acid DMA (hot), DMSO (hot), NMP (hot), DMSO (sw), NMP (sw) sulfuric acid (95%)
507-509
509
References page VII - 536
Previous Page
TABLE 4. cont'd Polymer Poly(dibutylsilylene-1,4-phenyleneethenylene1,4-phenyleneethenylene-1,4-phenylene) Poly(hexamethylcyclotrisilazane) Poly(dihexylsilyleneferrocenediyl) Poly(dimethyisilylene-N-methylimino) Poly(dimethylsilyleneiminoethyleneimino) Poly(dimethylsilylene-co-1,3-dihydro1,3-dimethyldisilazane) (1:1 to 3: 1)
Solvents
Nonsolvents
Refs.
Chloroform
THF
492
Carbon tetrachloride, hydrocarbons THF THF Xylene Decaline, toluene
Acetone, DMSO
493 680 494 495 496
Toluene
Methanol
497
TABLE 5. MAIN-CHAIN HETEROCYCLIC POLYMERS Polymer
Solvents
Nonsolvents
Refs.
5.1. POLY(BENZOXAZOLES), POLY(OXADIAZOLES), POLY(OXADIAZOLIDINES) Poly(benzoxazoles) Poly(2,5-benzoxazolediyl) Poly(2,6-benzoxazolediyl) Poly(dibenzothiazoles)
Sulfuric acid Sulfuric acid
498 498 499
R = 1,3-phenylene R = 1,4-phenylene R = octamethylene R = 1,4-cyclohexylene
Sulfuric acid Sulfuric acid m-Cresol, formic acid, sulfuric acid Sulfuric acid
R = tetramethylene
Chloroform, m-cresol, DMF (hot), Benzyl alcohol, formic acid pyridine (hot), sulfuric acid (hot), tetrachloroethane (hot), THF (hot) Benzyl alcohol (hot), chloroform, DMF (partially), formic acid (partially) m-cresol (hot), pyridine, sulfuric acid, tetrachloroethane (hot), THF Chloroform, m-cresol, Benzyl alcohol, DMF, pyridine, formic acid (hot), sulfuric acid (hot) tetrachloroethane, THF
R = 1,3-phenylene
R = l ,4-phenylene
Organic solvents Organic solvents Acetic acid, DMA, DMF, DMSO, formamide, NMP
Polyphosphoric acid
DMA, NMP
499 499,500 500 501
502 502
502 503
Methanol
504-506
Poly( 1,3,4-oxadiazoles)
R = octamethylene
R = methylene to eicosamethylene
Bzn., chloroform, m-cresol, dichloroethylene, DMA (hot), DMF, DMSO (hot), NMP (hot), sulfuric acid DMA (hot), DMSO (hot), NMP (hot), DMSO (sw), NMP (sw) sulfuric acid (95%)
507-509
509
References page VII - 536
TABLE 5. cont'd Polymer R = 1,4-cyclohexylene R = 1,3-cyclohexylene R = 1,2-phenylene R = 1,3-phenylene
Solvents Formic acid (80%), sulfuric acid DMA, DMSO, formic acid (80%), NMP, sulfuric acid Sulfuric acid Sulfuric acid, trifluoroacetic acid
Nonsolvents
Refs.
DMA, DMSO, NMP
Chloroform, m-cresol, DMF, nitrobenzene, tetrafluoropropanol
510 510 511 512-514
Poly(oxadiazolidines)
R=l,3-phenylene
DMSO
Methanol
515
Diethyl ether, diphenyl ether, diphenylmethane, DMA, DMF, DMSO, ethanol, formic acid, quinoline
516
5.2. POLY(DITHIAZOLES), POLY(BENZOTHIAZOLES) Poly(dithiazoles)
R = 1,4-phenylene R = l ,4-phenylenehexamethylene-1,4-phenylene Mw = 11000 Mw = 12000 Mw = 27000 Poly(benzothiazoles)
Sulfuric acid (cold) Sulfuric acid (cold) DMF (cold) DMF (hot)
DMF (hot)
516 516 516 516
R = 1,4-phenylene R = 5-alkoxy-l,3-phenylene R = l,4-bicyclo[2.2.2]octane R = 1,4-phenylene and 1,4-phenyleneimino1,4-phenylene
Methanesulfonic acid Methanesulfonic acid Methanesulfonic acid, sulfuric acid Methanesulfonic acid, polyphosphoric acid
517 433 518 519
R = 1,3-phenylene R = 3,5-pyridinediyl R = 1,4-phenyleneoxy-1,4-phenylene R = 1,4-phenylenecarbonyl-1,4-phenylene R = 1,4-phenylene R = 1,6-anthracenediyl Poly(2,6-benzothiazolediyl)
Cone, sulfuric acid Cone, sulfuric acid Cone, sulfuric acid Cone, sulfuric acid Cone, sulfuric acid Sulfuric acid (partially) Sulfuric acid
520 520 520 520 500 521 498
5.3. POLY(IMIDES) 5.3.1. POLY(BENZIMIDES)
R = 1,4-phenylenecarbonyloxyethyleneoxyethyleneoxycarbonyl R = poly(isobutylene)iminocarbonyl rc-Butyl R = 1,4-phenyleneoxy-1,4-phenyleneiminocarbonyl R = 4,4/-biphenylyleneiminocarbonyl R = 1,4-phenylenemethylene-1,4-phenyleneiminocarbonyl R = 1,4-phenylenecarbonyloxymethyleneoxycarbonyl R = 1,4-phenyleneoxy-1,4-phenyleneiminocarbonyl R = 1,4-phenyleneoxy-1,4-phenylenecarbonylimino1,4-phenyleneoxy-1,4-pheny leneiminocarbony 1
Methylene chloride/trifluoroacetic acid (4/1) acetate, diethyl ether NMP NMP/xylene DMA5DMSO, NMP m-Cresol (1500C), trichlorobenzene (reflux) DMA DMA, NMP
Methanol Ethanol, methanol
Methanol Methanol
522 313 523 524 525,539 526 527 528
TABLE 5. cont'd Polymer R = 1,4-phenylene R' = 5-oxy-1,4-phenyleneisopropylidene1,4-phenylene-5 '-oxy R = hexamethylene R'-5,5'-oxy R = 2,2/-di(trifluoromethyl)-4,4/-biphenylylene R' = S^'-hexafluoroisopropylidene R = 1,4-phenyleneoxy-1,4-phenylene R' = 5,5 '-phenylphosphineoxide R = 2,2/-ditrifluoromethyl-4,4/-biphenylylene R' = 5,5'-idyl R = 1,4-phenyleneoxy-l, 4-phenylene R' = 5,5'-carbonyl R = 1,3-phenylene R' = S^'-oxy-l^-phenyleneisopropylidene1,4-phenyleneoxy
Solvents
Nonsolvents
Refs.
DMA
529
Cone, sulfuric acid
530
Acetone, chloroform, m-cresol
531
NMP
532
m-Cresol (hot)
533
DMA
534
NMP
535
5.3.2. POLY(PYROMELLITIMIDES)
R = nonamethylene R = 1,3-phenylene; 1,4-phenylene R = 4,4'-biphenylylene R = 1,4-phenylenemethylene-l,4-phenylene; 1,4-phenyleneisopropylidene-1,4-phenylene R = 1,4-phenyleneoxy-1,4-phenylene amic acid R = 1,4-phenylenethio-l,4-phenylene R = 1,4-phenylenesulfonyl-l,4-phenylene R = l,3-phenylenesulfonyl-l,3-methylene R = pentaerythrityl R —4-hydroxy-l,3-phenyleneisopropylidene4-hydroxy-1,3-phenylene R = ethylidenecarbonyloxysebacoyloxycarbonylethylidene, <40% imide R = hexa-2,4-diyne-l,6-diyl R = l,3-phenyleneoxy-l,3-phenyleneoxy-1,3-phenylene
m-Cresol Cone, sulfuric acid Fuming nitric acid Cone, sulfuric acid
Common Common Common Common
solvents solvents solvents solvents
13,540 13,540 13,540 13,540
DMA, iV-methylcaprolactone, fuming nitric acid DMA, DMF, DMSO Fuming nitric acid Cone, sulfuric acid Cone, sulfuric acid No solvent known DMF, DMA, DMSO, nitrobenzene, tetramethylene sulfone Chloroform
Common organic solvents
13,540, 541 542 13,540 13,540 13,540 543 223
DMSO DMA
organic organic organic organic
Common organic solvents Common organic solvents Common organic solvents
544 W
545 525
DMA (partial), DMSO (partial), NMP (partial)
546
Cresol, DMA, DMF, DMSO, NMP
536
4-Butyrolactone
537
No known solvent
538
5.3.3. OTHERS
References page VII - 536
TABLE 5. cont'd Polymer 5.4.
Nonsolvents
Refs.
POLY(QUINOXAHNES)
Poly(quinoxaline-2,6-diylquinoxaline-6,2-diyl1,4-phenylene) Poly(quinoxalines) several different compositions
5.5.
Solvents
Sulfuric acid
547
13-Dichloro-l,l,3,3-tetrafluoro2,2-dihydroxypropane, methanesulfonic acid
548,549
POLY(BENZIMIDAZOLES)
Poly(benzimidazoles)
R = tetramethylene R = 1,4-phenylene R = 1,3-phenylene Poly(dibenzimidazoles)
R = tetramethylene to eicosane-l,20-diyl R = cyclohexylene R = 1,3-phenylene
R = 1,4-phenylene R = 2,2/-biphenylylene R = 4,4'-biphenylylene R = 3,5-pyridyenediyl R = 2,5-furandiyl R = l,4-phenyleneiminocarbonyl-R'-carbonylimino1,4-phenylene; R' = octamethylene; 1,4-phenylene; 1,3-phenylene
5.6.
DMSO (partially), formic acid Formic acid (partially)
m-Cresol, formic acid (85%), DMA, DMSO, NMP, cone. sulfuric acid Acetic acid, m-cresol, DMF, DMSO, formic acid, NMP, sulfuric acid DMA, DMSO, formic acid, NMP, cone, sulfuric acid Formic acid (2-3% soluble) DMF, DMSO, formic acid Formic acid (partially) DMF (partially), DMSO, formic acid (partially) DMF, DMSO, formic acid (partially) DMA, DMF, DMSO, NMP, cone. sulfuric acid
DMF DMF, DMSO, formic acid DMF, DMSO
550 550 550
Glacial acetic acid, DMF (sw)
551 501
Glacial acetic acid, m-cresol, DMF (partially), formic acid (85%, sw) DMF, DMSO DMF, DMSO
Glacial acetic acid (sw), m cresol (sw), formic acid (sw), methanol
550,551
550,551 550,551 550,551 550,551 550,551 550,551
POLY(PIPERAZINES)
Poly(2,5-diketo-l,4-piperazinediy 1-1,4-phenylene sulfonyl-1,4-phenylene) Poly(2,5-dimethyl-l,4-piperazinediylcarbonyl1,4-phenylenesulfonyl-1,4-phenylene) Poly(l,4-piperazinediylcarbonylethylene1,4-phenylenephosphinylidene1,4-phenyleneethylenecarbonyl) Poly(piperazinediylcarbonyloxym-cyclohexyleneoxycarbonyl) Poly(l,4-piperazinediylcarbonyl2,5-pyridinediylcarbonyl) PoIy(1,4-piperazinediyl-2-hydroxytrimethyleneoxy1,4-phenyleneisopropylidene-1,4-phenyleneoxy1 -hydroxyethylene) PoIy(1,4-piperazinediylcarbonyl-2,5-norbornadiene2,3-diylcarbonyl)
Dichloroacetic acid, formic acid, DMA, DMF, DMSO 552 trifluoroacetic acid DMF, svm-tetrachloroethane/phenol Methanol, W 13 (2/3) Chloroform, cresol, DMF, ethanol, Acetone, acetonitrile (sw), chlorobenzene, 436 C-7 fluoroalcohol, formic acid, aqu. hexane hydrochloric acid (5%) Chloroform, m-cresol, formic acid 323 m-cresol, formic acid, cone. aqu. HCl, phenol, sulfuric acid DMF Chloroform, o-cresol
553 554 Methanol
555
TABLE 5.
cont'd
Polymer 5.7.
Solvents
Refs.
POLY(ANHYDRIDES)
Poly(maleic anhydride)
PolyCacrylic anhydride)
Acetic anhydride, acetonitrile, acetophenone, lower aliphatic alcohols, butanone, dioxane, DMF, ethers, ketones, nitroparaffins DMF, DMSO
Poly(methacrylic anhydride)
DMF, DMSO
Poly(itaconic acid anhydride)
Acetic acid, acetone, cyclohexanone, THF THF
Poly(maleic anhydride-a/f-2-cyclohexylenel,3-dioxepin-5-ene)
Poly(maleic Poly(maleic Poly(maleic Poly(maleic Poly(maleic
anhydride-fl//-isopropenylisocyanate) anhydride-a/f-2-propenylisocyanate) anhydride-co-styrene) (3:1) anhydride-a/r-methyl vinyl ether) anhydride-tf/r-1-octadecene)
Poly(maleic anhydride -co-N-vinylforrnamide) (1 :1) 5.8.
Nonsolvents
Acetone, DMF MEK Acetone, MEK MEK, THF Acetone, bzn., carbon tetrachloride, ethyl acetate THF
Hydrocarbons, most chlorinated hydrocarbons
Alcohols, bzn., diethyl ether
Aliphatic hydrocarbons, diethyl ether, methanol, W Chloroform, diethyl ether Hexenes
556
13
557,558 687,700 559
560 561 153 Carbon tetrachloride, diethyl ether, hexane 186 Ethanol 562 Bzn.
563
POLY(THIOPHENES)
Poly(3-alkyl-2,5-thiophenediyl) Poly(3-hexyl-2,5-thiophenediyl) Poly(3-hexyloxycarbonyl-2,5-thiophenediyl) Poly(3,4-oxyethyleneoxy-2,5-thiophenediyl) Poly(2,5-thiophenediyl-co-3-undecyl-2,5-thiophenediyl) (1:1) Poly(3-rnethyl-2,5-thiophenediyl-c<73-oligodimethylysiloxane-2,5~thiophenediyl) Poly(2,5-thiophenediylethylene) Poly(2,5-thiophenediyl-co-dimethylsilylene) (3:1 to 3 : 2) Poly(2,5-thiophenediyl-co-/V-tt-dodecyl-2,5-pyrrolediyl) (4:1) Po]y(2,5-thiophenediyl-l,2-dirnethoxyethenylene) Poly(2,5-thiophenediylethynylene-2,5-dioctyloxy1,4-phenylene) Poly(2,5-thiophenediylethynylene-l,4-tetrafluoro phenyleneethynylene) Poly(thieno[3.2-b]thiophene-2,5-diyl) Poly(2,5-thiophenediylcarbonyl-1,4-phenyleneoxy1,4-phenyleneisopropylidene-1,4-phenyleneoxy) Poly(4,4/-diphenyl-2,2/-bisthiazole-5,5'-diyl)
Chloroform, methylene chloride, THF (partially) THF, toluene Chloroform, DMF Chloroform Nitrobenzene, THF
564 Methanol Methanol Methanol
Chloroform THF Dimethoxyethane THF Chloroform Chloroform, THF, toluene
7 565 566 567 568
Methanol Hexane
Chloroform, THF, toluene
569 570 571 572 573 573
Chloroform Chloroform, DMA, NMP
Methanol Methanol
574 575-577
Hexane
Methanol
578
Chloroform
579
5.9. OTHERS Poly(2,3-dihydrofuran-3,4-diyl) Poly(2,5-furandiylethylene) Poly(3,5-dicarboxytetrahydropyran-3,5-diylmethylene)
Toluene THF DMSO
Methanol Acetone
580 569 581
References page VII - 536
TABLE 5. cont'd Polymer Poly(Ar-rt-butylitaconimide) Poly(iV-phenylmaleimide) Poly(2,5-pyridinediylethenylene) Poly(#-2-ethylhexyl-3,6-carbazolediylethenylene) Poly^-methyleneimidazoleimide-l^-diyl) Poly(3-phenyl-3,5-triazolediyl-l,4-phenyleneoxy1,4-phenyleneisopropylidene-1,4-phenyleneoxy1,4-phenylene) Poly[3-(2'-pyridyl)-l,2,4-triazine-5,6-diyll,4-phenyleneoxy-4,4'-biphenylyleneoxy1,4-phenylene] Poly(3,5-pyrazolediyl-l,4-phenyleneoxy1,4-phenylenecarbonyl-1,4-phenyleneoxy1,4-phenylene)
Solvents
Nonsolvents
Refs.
Bzn., THF, toluene DMF, DMSO, THF Methanol Formic acid, sulfuric acid 1M LiCl in NMP Methanol DMA (partially), sulfuric acid (partially) Toluene Methanol
7 582 583 584 585 586
Chlorobenzene, NMP
Methanol
587
DMA, NMP
Chloroform, methanol
588
TABLE 6. FORMALDEHYDE RESINS Polymer Aniline-formaldehyde resins low mol. wt. high mol. wt. Melamine-formaldehyde resins very low mol. wt. intermediate mol. wt. final resin, high mol. wt. Phenol-formaldehyde resins Novolaks and low mol. wt. 4-terf-butylphenol and 4-phenylphenol polymers final resins
Solvents Methylcyclohexanone No solvent known
final resin, high mol. wt. Phenyl glycidyl ether-formaldehyde resins, low mol. wt.
Alcohols, aniline (sw), hydrocarbons Aniline, chlorinated hydrocarbons (sw)
Refs. 6 6
Alcohol, W DiI. and cone, acids, formalin, formic acids, pyridine No solvent known
6 6
Acetone, diethyl ether, esters, hydrocarbons Drying oils Molten phenols (with some decomposition)
6
fully cured resins /7-Toluenesulfonamide-formaldehyde resins Urea-formaldehyde resins very low mol. wt. intermediate mol. wt.
Nonsolvents
Alcohols, bzn., esters, ethers, ketones
6
Most common organic compounds
6 6
DiI. acids (sw), dil. alkalies (sw), alcohol, 6 W(sw) Aliphatic hydrocarbons, W 6,589
Alcohol, W DiI. and cone, acids, formalin, formic acid, pyridine No solvent known Acetone, MEK, methyl isobutyl ketone
6 6 6 590
TABLE 7. NATURAL POLYMERS AND MODIFIED NATURAL POLYMERS Polymer
Solvents
Nonsolvents
Refs.
7.1. NATURAL RUBBER AND DERIVATIVES (see also 1.1) Natural rubber
cyclic
Bzn., chlorinated hydrocarbons, cyclohexane, hydrocarbons, methyl isobutyl ketone (low mol. wt.), w-propyl ketone (above 14.5°C), toluene (low mol. wt.) Aromatic and chlorinated hydrocarbons
hydrochlorinated chlorinated
Chlorinated hydrocarbons Aromatic and chlorinated hydrocarbons, hydrogenated naphthas
dichlorocarbene modified
Chloroform
Acetone, alcohols, carboxylic acids
Acetone, acids, alcohol, alkalies, diethyl ether, aliphatic hydrocarbons, oils (sw), W Alcohol, W Cone, acids, oxidizing acids, acetone (sw), alcohol, moderately cone, alkalies, aliphatic hydrocarbons, diethyl ether (sw), W Methanol
4,5,7, 591
6 6 6
592
TABLE 7. cont'd Polymer
Solvents
Nonsolvents
Refs.
7.2. GUTTA PERCHA Gutta percha
Bzn., cloroform, hot petroleum ether
Alcohol, W
6
7.3. CELLULOSE AND DERIVATIVES 7.3.1. CELLULOSE Cellulose
/V-Ethylpyridinium chloride/DMF DiI. aqu. alkalies, hydrocarbons, (1/1), /V-ethylpyridinium mineral oils, W (sw) chloride/pyridine (1/1), trifluoroacetic acid, aqu. solutions of: alkalies (ice-cold), beryllium perchlorate, calcium thiocyanate, cupriammonium hydroxide, cupriethylenediamine, sodium xanthate, tetramethylammonium hydroxide, zinc chloride/hydrochloric acid (cold), zinc chloride (hot), cone, phosphoric acid, cone, sulfuric acid. See also table on cellulose in this Handbook
4-6, 593,594
7.3.2. CELLULOSE ETHERS Methyl cellulose SC = 3-10% = 22-32% = > 40% Ethyl cellulose DS = 0.5-0.7 = 1.0-1.5 =2 = 2.3
=3 Isopropyl cellulose DS = 0.5 = 2.5
Butyl cellulose DS = 0.8 = 1.9 Benzyl cellulose DS = 1.65 =2
Aqu. alkalies Aqu. alkali, N-ethylpyridinium chloride/DMF, methanol/methylene chloride, W (cold) Acetone, chloroform, cyclohexanone, esters, pyridine
W Diethyl ether, methanol, methylene chloride, W (hot)
Aqu. alkali Acetic acid, cuoxam, formic acid, pyridine, W (cold) Chloroform, chlorohydrins, dichloroethylene, ethanol, methylene chloride, THF Acetic esters, alcohols, alkyl halides, bzn., carbon disulfide, furan derivatives, ketones, nitromethane Alcohols, bzn., esters, methylene chloride
W (cold) Ethanol
Aliphatic hydrocarbons, diethyl ether, ethanol, W
6,595 6,594,595 6,595 5,6,30, 595,596
Alcohols, diethyl ether, esters, hydrocarbons, ketones, tetrachloroethylene, W Acetone (cold), ethylene glycol
Carbon tetrachloride, diols, di-n-propyl ether, hydrocarbons, tetrahydrofurfuryl alcohol
W (cold) Acetone, butanol, bzn., chloroform, cyclohexanone, dichloroethane, dioxane, glycol formal, methyl acetate, methylcyclohexanone, THF
W (hot) Ethanol, ethanol/diethylether (1/3), hydrocarbons, methanol, propanol
595 30
Polar organic solvents Aromatic hydrocarbons, polar organic solvents
Hydrocarbons, W Aliphatic hydrocarbons, W
595 595
Methylene chloride, methyl ether glycol acetate, nitrobenzene Acetates (< C5), acetone, bzn./acetone, bzn./alcohol, chlorobenzene, chlorohydrins, dichloroethylene, ethanol/carbon tetrachloride (1/1), MEK, methylene chloride, pyridine, tetrahydrofurfuryl alcohol, tetralin, trichloroethylene
Bzn., chlorobenzene, butyl acetate
210
Alcohols, (> C5), carbon tetrachloride, o-chlorotoluene, diethyl ether, dioxane, dipropyl ketone, hydrocarbons
6,30
References page VII - 536
TABLE 7.
cont'd
Polymer DS = 3
Hydroxyethyl cellulose SC = <30% = 35-55% = >55% Hydroxypropyl cellulose Carboxymethyl cellulose SC = 5-10% = 15-30% = high Cyanoethyl cellulose SC = 8-12% = 24-32% = >50%
Solvents
Nonsolvents
Acetone, butyl acetate, chlorobenzene, Aliphatic hydrocarbons, aromatic chloroform, cyclohexanone, hydrocarbons (sw), carbon ethyl acetate, MEK tetrachloride, diethyl ether, dioxane, ethanol Alkali Ethylene chlorohydrin, DMSO, formic acid, W Bzn./acetone, bzn./alcohol, chloroform, pyridine, esters Cellosolve", dioxane, ethanol, methanol, W (<45°C)
Refs. 199
Cellosolve", hexane, methanol, toluene
597
Acetone, bzn., methanol (sw), methyl acetate, THF W (>45°C)
597
Alkali W (sodium salt) Acetone, bzn./acetone, bzn./alcohol, chloroform, esters, pyridine 6 Alkali W Acetone, bzn./acetone, bzn./alcohol, chloroform, esters, pyridine
7.3.3. CELLULOSE ESTERS Cellulose triformate Cellulose acetate DS = 0.6-0.8 = 1.3-1.7 = 2-2.3
Cellulose triacetate
Cellulose acetate hydrogen phthalate Cellulose tripropionate Cellulose tributyrate
Cellulose tricaproate
Cellulose tricaprylate Cellulose stearate DS = 3
Formic acid, pyridine W 2-Methoxyethanol Acetic acid (glacial), acetone, aniline, benzyl alcohol, chloroform/methanol, cyclohexanone, diethanolamine, dioxane, ethyl acetate/nitrobenzene, ethylene glycol ethers, formic acid, glycol monoethyl ether acetate, methyl acetate, methylene chloride/methanol (4/1), nitromethane, phenols, pyridine Acetone/W (4/1), chloroform/alcohol, chloroform, dioxane, ethyl acetate, ethylene glycol ether acetates, ethylene carbonate, methyl acetate, methylene chloride/ethanol (4/1), methylene chloride, THF, trichloroethane Acetone Acetone, bzn., chlorobenzene, dichloroethane, ethyl acetate Acetone, amyl acetate, bzn., chlorobenzene, chloroform, cyclohexanone, dodecane/tetralin (3/1 above 1300C), ethanol (hot), ethyl acetate, nitrobenzene, THF, xylene (hot) Acetone, bzn., chlorobenzene, chloroform, cyclohexanone, diethyl ether, dioxane, DMF, ethanol (hot), ethyl acetate, glacial acetic acid (hot), hexane, nitroethane, THF, xylene DMF (above 14O0C), 3-phenylpropanol (above 48°C), toluene bzn., tetrachloroethane, toluene
30 Acetone, W Aliphatic ethers, hydrocarbons, weak mineral acids
Acetone (partially), aliphatic hydrocarbons, aliphatic ethers, bzn., chlorobenzene, c-chlorotoluene, dichloroethane, ethanol (absolute), glycol ethers, methyl /-butyl ketone, weak mineral acids o-Chlorotoluene, ethanol, hydrocarbons
595 4,6
4-6,30, 598,599
32 30
2 Ethylhexanol, cyclohexane, diethyl ether, hexane, methanol
595
2-Hydroxyethyl acetate, formamide, methanol, nitromethane
595
5 Acetone, butyl acetate, dichloroethane, ethyl acetate
595
TABLE 7. cont'd Polymer Cellulose acetate butyrate DS (acetate) — 0.5 DS (butyrate) = 2.35 DS (acetate) - 2 . 1 DS (butyrate) = 0.7 Cellulose tricarbanilate
Propyl cellulose benzoate
Hydroxypropyl cellulose perfluorooctanoate DS = 3 (ester), DS = 4 (ether)
Solvents
Nonsolvents
Refs.
Acetone, amyl acetate, bzn., Aliphatic hydrocarbons, diethyl ether, chloroform, cyclohexanone, dioxane, ethanol, methanol esters, methanol (hot), nitroethane, tetrachloroethane, toluene (hot) Acetone, chloroform, cyclohexanone, Amyl acetate, bzn./methanol dichloroethane, dioxane, (1/4 and 4/1), carbon tetrachloride, ethyl acetate, nitroethane diethyl ether, ethanol, hydrocarbons, methanol, W Acetone, bzn., chloroform, dioxane, Methanol, W DMF, iV-ethylpyridinium chloride/DMSO (1/1), iV-ethylpyridinium chloride/pyridine (1/1), pyridine, THF Acetone, bzn., chloroform, dioxane, DMA, ethyl acetate, pyridine, TMF, toluene, xylene Acetone Ethanol
595
595
7,594, 595
600
601
7.3.4. CELLULOSE NITRATE AND SULFATE Cellulose nitrate N = 6.8% N = 10.5-12% N = 12.7%
Cellulose sulfate, sodium salt DS=I
W 602 Acetic acid (glacial), acetone, Higher alcohols, higher carboxylic 4,6,595 alcohol/diethyl ether, alcohol (lower), acids, higher ketones, amyl acetate, ethylene glycol ethers tricresyl phosphate Acetone, cyclohexanone, ethanol/ DiI. carboxylic acids, aliphatic 4-6,595 diethyl ether, ethyl lactate, hydrocarbons, aromatic ethyl butyrate, ethylene carbonate, hydrocarbons (sw), diethyl ether, ethylene glycol ether acetates, ethylene glycol, higher alcohols (sw), furan derivatives, halogenated lower alcohols, W hydrocarbons, methyl acetate, methyl amyl ketone, nitrobenzene W
Ethanol
595
Ethylenediamine, /V-ethylpyridinium chloride/pyridine (1/1), DMSO, nitromethane, W (hot), aqu. KOH, aqu. KCl (0.33 M, above 25°C) Chloroform, methyl acetate, nitromethane Acetone, dioxane, pyridine W, W/butanol Bzn., chloroform, dioxane, DMF, DMSO, THF Liquid ammonia, aqu. sol. of cupriethylenediamine, fused chloral hydrate, N-ethylpyridinium chloride/pyridine (1 /1), W (hot, pressure)
w-Butanol, diethyl ether
7.4. STARCH AND DERIVATIVES Amylose
Amylose acetate DS = 2 Amylose tricarbanilate Amylopectin Benzyl amylose DS = 3 Starch
Starch, methyl ether DS = 0.5-2 DS = 3
5,7,363,594,595,603
W
5
Acetone, diethyl ether, ethanol Ethanoi, methanol, W Alkali (sw), diethyl ether, W (sw)
W (cold) Chloroform
W (hot)
Aqu. alkalies, aqu. sodium carbonate, W (sparingly)
DiI. acids, aqu. calcium salt solutions, hydrophilic organic compounds (sw), hydrophobic organic compounds Organic hydrophobic compounds Organic hydrophobic compounds
5 604 605 6,363, 594,595
595 595
7.5. OTHER POLY(SACCHARIDES) Alginic acid alkali and ammonium salts magnesium and ferrous salts
Aqu. alkali, W W
6,363 6
References page VII - 536
TABLE 7.
cont'd
Polymer calcium salts copper, zinc, aluminum salts beryllium, chromium, ferric salts ^-Carrageenan Chitin Chitosan N-[Q '-hydroxy-2',3 '-dicarboxy)ethyl]chitosan Glycogen Gum arabic Gum tragacanth, Tragacanthin, tragacanthic acid 2,3-Di-0-benzyl-(l,5)-ot-D-furanan Heparin Konjac glucomannan Pectin Pullulan Xanthan gum
Solvents Weak aqu. alkali Aqu. ammonium hydroxide W Formic acid, cone. mineral acids (degrad.) Acetic acid, W (pH < 6.5) W DiI. trichloroacetic acid W (warm) W o-Dichlorobenzene (hot) DiL alkali solution, alkaline solution of ammonium sulfate, W W DiI. acids, W W W
Nonsolvents
Refs.
Organic hydrophobic compounds, W Organic hydrophobic compounds, W Aqu. alkali, organic hydrophobic compounds DiI. acids, organic solvents
694 363
Alcohol Alcohol Acetone, alcohol
606 607 363 363 363
Acetone, cyclohexanone, ethyl acetate, hexane, methanol Acetic acid, acetone, alcohol
608 363 609 363 609 610
Alcohol
7.6. NATURAL RESINS Colophony
Copal
Shellac
Zein a
Acetone, aromatic hydrocarbons Aliphatic hydrocarbons (partially), carbon tetrachloride, chloroform, diethyl ether, ethanol, ethyl acetate, methanol Acetone (25-90%)", bzn. (35-60%)", carbon tetrachloride (15-40%)°, chloroform (30-90%)*, diethyl ether (10-90%)fl, ethanol (20-100%)°, hydrocarbons (10-55%)°, methanol (20-70%)° Acetone (50-80%)*, bzn. (10-20%)°, Aliphatic hydrocarbons carbon tetrachloride (5-15%)°, chloroform (25-40%)°, diethyl ether (10-25%)°, ethanol (85-98%)°, methanol (100%) Aqu. alcohols, glycols, DMF
30
30
30
32
Percentage soluble, depending on source.
TABLE 8. INORGANIC POLYMERS Polymer Poly(phosphorus nitrile chloride) Poly(sodium-m-phosphate) Poly(tri-/i-butyl tin fluoride) Poly(phosphoryldimethylamide) Poly(2,5-selenienylene) PoIy[Tj 5-(vinylcyclopentadienyl)tricarbonylmethyltungsten] Poly(n-dibutyl stannane)
Solvents Bzn., carbon tetrachloride, chloroform, cyclohexane Aqu. sol. of LiCl, NaCl or NH4Cl Aliphatic hydrocarbons Carbon tetrachloride (hot), W Chloroform, THF Bzn., chloroform, THF Chloroform, THF, toluene
Nonsolvents
Refs.
Aliphatic hydrocarbons
611
Acetone, ethanol, W
612 259 613 614 615 616
Acetone Methanol, W Hexane Methanol
TABLE 9. POLY(ELECTROLYTES) Polymer Poly(allyammonium chloride) Poly(allylammonium phosphate) Poly (dial lyldimethylammonium chloride) Poly(benzyltrimethylammonium chloride) Poly(diallyldimethylamrnonium chloride-cc-Afisopropylacrylamide), (2:98) Poly (sodium trimethyleneoxyethylenesulfonate) Poly[dimethyldodecyl(2-acrylamidoethyl) ammonium bromide] Poly(4-/V-butylpyridiniumethylene bromide)
Solvents
Nonsolvents
Refs.
W HCl, W W W W
Methanol Methanol, W
617 617 618 32 619
DMSO, W W
Bzn., hexane
620 701
Bzn., hexane
621
Methylene chloride tert-Butyi methyl ether Ethyl acetate
687 583 622 623
Diethyl ether
624
Hexane, methanol, THF, toluene
625
Benzyl alcohol, DMSO, nitromethane, W Poly(2-/V-methylpyridiniumethylene iodine) Methanol, W Poly(Af-methylpyridinium-2,5-diylethenylene) DMF, DMSO, NMP, W Poly(4,4/-bipyridiniumdiyl-N,A^/-decamethylene dibromide) DMF/methanol, W PoIy(1,4-pyridiniumdiyl-A'r,A^/-tetramethyleneEthanol 4,1 -pyridiniumdiylethenylene methylsulfate) Poly(2,6-diphenyl-l,4-pyridiniumdiyl-yV,A^/DMA, DMF, DMSO, NMP 1,4-phenylene-4,1 -pyridiniumdiyl-1,4-phenylene) Poly|ethyldipropargyl-4-sulfobutyl ammonium betainej Formic acid, W
TABLE 10. BLOCK COPOLYMERS (alphabetically listed) Polymer Poly(f-butyl methacrylate)-b-polystyrene-b-poly(f-butyl methacrylate) ( 1 : 6 : 1 ) Poly(f-butyl methacrylate)-b-poly(oxytetramethylene)b-poly(butyl methacrylate) ( 2 : 6 : 2 to 4 : 2 : 4 ) Poly(butyl acrylate)-b-poly[3-(pentamethyldisiloxy)propyl methacrylate] (3:1) Poly(butyl vinyl ether)-b-poly(2-ethyloxazoline) Poly(2-cinnamoylethyl methacrylate)-bpoly(acrylic acid) (4:5) Poly(e-caprolactone)-b-poly(oxytetramethylene)b-poly(e-caprolactone) (4: 2 : 4 to 1:3:1) Poly(dimethylsiloxane)-b-poly(6-aminohexanoic acid) (1:2) Poly(2-ethyl-2-oxazoline)-b-poly(lactic acid) (3 :2 to 2 :4), Poly (Af-proponyliminoethylene)-b-poly (oxy-1 -oxo2-methylethylene) Poly(3-hydroxybutyric acid)-b-poly(e-caprolactone) ( 3 : 5 to 2 : 1 ) Polyisobutylene-b-poly(a-tnethylstyrene) (9: 1) PolyOmethacrylic acid)-b-polystyreneb-poly(methacrylic acid) ( 1 : 8 : 1 ) Poly(3-methyl-2,5-thiophenediyl)b-poly(2-vinylpyrrolidone) Poly(oxy-2,2-di(chloromethyl)trimethlylene)b-poly(oxytetramethylene)-b-poiyoxy2,2-di(chloromethyl)trimethylene (7 : 86:7) Poly(oxytetramethylene)-b-poly(e-caprolactone) (1:4) Polystyrene-b-polybutadiene-b-polystyrene) ( 7 : 8 6 : 7 to 15:70: 15) Polystyrene-b-poly(terr-butyl methacrylate) (2: 3 to 4 : 1 ) Polystyrene-b-poly(dimethylsiloxane) (1:1) (1 :9 to 7:3)
Solvents Dioxane
Nonsolvents Hexane
Refs. 626
Toluene
627
THF
628
Chlorobenzene, THF Methanol, methylene chloride
Hexanes Isopropanol/hexane (3/7)
629 630
THF, toluene
631
2,2,2-Trifluoroethanol
632
Chlorobenzene
Hexane
633
Chloroform
Methanol
634
Chloroform Dioxane
Methanol Hexane
635 626
Anisole
636
Methylene chloride
637
THF, toluene Toluene
638 639
Dioxane THF Bzn./2-methoxyethyl ether, dioxane
Hexane Methanol Methanol, W
626 350 640
References page VII - 536
TABLE 10. cont'd Polymer Polystyrene-b-poly(ethylene/butylene)-b-polystyrene ( 1 : 8 : 1 to 1:3:1) Polystyrene-b-poly(ethylene/propylene) (3:7) Polystyrene-b-(/v*-ethyl-2-ethynylpyridinium trifluoromethanesulfonate) ( 8 : 1 ) Polystyrene-b-poly(hexyl isocyanate) (1:4) Polystyrene-b-poly(hydroxyethyl methacrylate) (2:3) Polystyrene-b-polyisoprene (1:1) Polystyrene-b-polyisoprene-b-polystyrene (1 : 12: 1 to 2 : 1: 2)
Polystyrene-b-poly(methyl methacrylate) (7:3) Polystyrene-b-poly(methylphenylsiloxane) (3:2) Polystyrene-b-poly(methyl vinyl ether) (2:1) Polystyrene-b-poly(4-vinylpyridine) (5:1) Polystyrene-b-poly(2-vinylpyridine) ( 1 : 1 to 6 : 1 ) Polystyrene-b-poly(vinylpyridine) (1:1) Polypropylene-b-poly(methacrylic acid) (2:1)
Solvents
Nonsolvents
Toluene
Refs. 641,642
THF Diethyl ether/petroleum ether (1/1), THF Carbon tetrachloride, chloroform, toluene DMF, THF Dioctyl phthalate MEK/isobutyl isobutyrate, methylcylcohexane/methylene chloride (3/2), methyl amyl ketone, methylene chloride, xylene Toluene Cyclohexane Methylene chloride THF Bzn. THF Dioxane, THF, toluene
643 644 645 646 647 639, 548-650
Hexanes Hexane/methanol (8/2) Hexane Methanol
7,698 651 652 653 654 655 653,626
Nonsolvents
Refs.
TABLE 11. DENDRIMERS Polymer
Solvents DMSO, methanol, THF (partially), W
656
THF
657
Methylene chloride, most organic solvents Acetone, DMSO
Hexane, W
689
Toluene
hyperbranched
Lower alcohols, ethyl acetate, W Alcohol, glycols, W Acetone, chloroform
659
Hydrocarbons
W THF, toluene
Bzn., chloroform, cyclohexane, methylene chloride
658,684
683 660
661,685 Methanol
662
287
TABLE 11.
cont'd
Polymer
Solvents
Nonsolvents
Refs.
THF
Methanol
663
THF
Methanol
664
DMF, NMP, THF
665 666,667
Chloroform
Methanol
668
THF
Methanol
669
THF
Ethyl acetate, chloroform, DMF, DMSO, methylene chloride, THF, toluene
670
DMF, DMSO, THF Methylene chloride
671 524
THF
Diethyl ether, W
672
DMF
673
NMP, THF
695
References page VII - 536
D.
REFERENCES
1. W. P. Baker, J. Polym. Sci. A, 1, 655 (1963). 2. A. A. Arest-Yakubovich et al., ACS Polymer Preprints 37 (2), 634 (1996). 3. T. Yasuyuki et al., Macromolecules, 26, 5253 (1993). 4. H. Dexheimer, O. Fuchs, in: R. R. Nitsche, K. A. Wolf, (Eds.), "Struktur und Physikalisches Verhalten der Kunststoffe", vol. 1, Springer, Heidelberg, 1961. 5. M. Kurata W. H. Stockmayer, in: Adv. Polym. Sci. vol. 3, Springer, Heidelberg, 1963, p. 196. 6. W. J. Roff, in: "Fibers, Plastics, and Rubbers", Academic Press, New York, 1956. 7. Y. Du et al., in: J. E. Mark (Ed.), "Physical Properties of Polymers Handbook", Ch. 17, AIP Press, New York, 1996. 8. L. van der Does, J. F. van Duijd et al., J. Polym. Sci. Chem. Ed., 17, 53 (1980). 9. W. Marcony, A. Mazzei, S. Cucinella, M. J. Cesari, Polym. Sci. A, 2, 4261 (1964). 10. Jr. J. M. Wilbur, C. S. Marvel, J. Polym. Sci. A, 2, 4415 (1964). 11. T. A. Davidson et al., Macromolecules, 29, 786 (1996). 12. R. F. Heck, D. S. Breslow, J. Polym. Sci., 41, 521 (1959). 13. Houben-Weyl, in: "Methoden der Organischen Chernie", Band XIV/1, 2, 4, Auflage, ThiemeVerlag, Stuttgart, 1961. 14. Jr. C. A. Aufdermarsh, R. Pariser, J. Polym. Sci. A, 2, 4727 (1964). 15. R. H. Michel, J. Polym. Sci. A, 2, 2533 (1964). 16. Y. Sonoda et al., Macromolecules, 29, 288 (1996). 17. J-i. Sugiyama et al., Macromolecules, 27, 5543 (1994). 18. Y. Tabata, B. Saito, H. Shibano, H. Sobue, K. Oshima, Makromol. Chem., 76, 89 (1964). 19. S. Kambara, H. Noguchi, Makromol. Chem., 73, 24 (1964). 20. I. M. Paushkin, S. A. Nizova, J. Poiym. Sci. A, 2, 2783 (1964). 21. A. Teramoto, ACS Polymer Preprints, 31 (2), 135 (1990). 22. P. Teyssie, A. C. Korn-Girard, Polym. Sci. A, 2, 2849 (1964). 23. H.-KK. Roth, H. Gruber, Synthetic Metals, 37, 151 (1990). 24. W. H. Kim et al., Macromolecules, 27, 1819 (1994). 25. M. Moroni, J. LeMoigne, Macromolecules, 27, 562 (1994). 26. G. J. Tregre, L. J. Mathias, ACS Polymer Preprints, 36 (2), 310 (1995). 27. S. Dirlikow et al., ACS Polymer Preprints, 33 (1), 483 (1992). 28. E. W. Kwock et al., ACS Polymer Preprints, 34 (1), 900 (1993). 29. K. J. Saunders, "Organic Polymer Chemistry", 2nd ed., Chapman and Hall, New York, 1988, p. 56. 30. K. Thinius, in: "Analytische Chemie der Plaste", Springer, Heidelberg, 1952. 31. O. Fuchs, unpublished results. 32. Scientific Polymer Products, Inc. Catalog 1996/97, Ontario, NY. 33. K. J. Saunders, "Organic Polymer Chemistry", 2nd ed., Chapman and Hall, New York, 1988; p. 61. 34. Trade literature, AlliedSignal Inc., Morrestown, NJ,
35. S. Arichi, H. Matsuura, Y Tamimoto, H., Murata, Bull. Chem. Soc. (Japan), 39, 434 (1966). 36. S. Sanganeria, ACS Polymer Preprints, 34 (2), 378 (1993). 37. G. N. Babu et al., Macromolecules, 27, 3383 (1994). 38. S. Saito, J. Polym. Sci. A-I, 7, 1789 (1969). 39. H. G. Elias, O. Etter, J. Polym. Sci. A l , 5, 947 (1967). 40. W. H. McCarty, G. Parravano, J. Polym. Sci. A-I, 3, 4029 (1965). 41. Y. Iwakura, K. Uno, K. Ichikawa, J. Polym. Sci. A, 2, 3387 (1964). 42. W. Marconi, S. Cesca, G. Delia Fortuna, J. Polym. Sci. B, 2, 301 (1964). 43. G. Dall'Asta, G. Natta, G. Mazzanti, Chem. Eng. News, 42 (14), 42 (1964). 44. M. Perrott, B. M. Novak, Macromolecules, 29, 1817 (1996). 45. I. Cho, J. Y Lee, Makromol. Chem. Rapid Commun., 5, 263 (1984). 46. A. Mukoh, H. Morishita, J. Polym. Sci. Letters, 18, 35 (1980). 47. J. G. Hamilton, K. J. Ivin, J. J. Rooney, Brit. Polym. J., 16,21 (1984). 48. K. Su et al., ACS Polymer Preprints, 32 (3), 481 (1991). 49. K. M. Stein et al., ACS Polymer Preprints, 35 (1), 480 (1994). 50. T. C. Chung et al. Macromolecules, 27, 7533 (1994). 51. C D . Eisenbach, B. Sperlich, Macromolecules, 29, 7748 (1996). 52. S. A. Haque et al., ACS Polym. Mater. Sci. Eng., 76, 87 (1997). 53. A. Mogstad et al., ACS Polymer Preprints, 34 (1), 211 (1993). 54. P. J. Flory, J. E. Osterheld, J. Phys. Chem., 58, 653 (1954). 55. M. L. Miller, K. O'Donnell, J. Skogman, J. Colloid Sci., 17, 649 (1962). 56. E. M. Loebl, J. O'Neill, J. Polym. Sci., 45, 538 (1960). 57. D. J. Diserow et al., ACS Polymer Preprints, 33 (1), 810 (1992). 58. H. Nakamoto, Y Ogo, T. Imoto, Makromol. Chem., Ill, 104 (1968). 59. G. F. L. Ehlers, J. Polym. Sci. A, 2, 4989 (1964). 60. S. Coca et al., ACS Polymer Preprints, 38 (1), 689 (1997). 61. J. Prager, R. M. McCurdy, G. B. Rathmann, J. Polym. Sci. A, 2, 1941 (1964). 62. Y. Nakatsuji, S. Furuyoshi, M. Okahara, Makromol. Chem., 87, 105 (1986). 63. C. Potin, A. Pleurdeau, C. M. Bruneau, Angew. Makromol. Chem., 138, 75 (1986). 64. M. Kamachi, H. Akimoto, S. Nozakura, J. Polym. Sci. Letters Ed., 21, 693 (1983). 65. J.-S. Kim et al., Macromolecules, 27, 814 (1994). 66. C. Simionescu, D. Feldman, I. Theil, Plaste Kautschuk, 15, 714 (1968). 67. D. E. Strain, R. G. Kennelly, H. R. Dittmar, Ind. Eng. Chem., 31, 382 (1939). 68. Trade literature, ICI Acrylics, St. Louis, MO.
69. Trade literature, Rohm Tech, Maiden, MA. 70. L. Gargallo, I. Mendez, D. Radic, Makromol. Chem., 184, 1053 (1983). 71. I. Reynolds et al., Macromolecules, 28, 7845 (1995). 72. M. Imoto, T. Otsu, K. Tsuda, T. Ito, J. Polym. Sci. A, 2, 1407 (1964). 73. Y. Nagasaki et al., ACS Polymer Preprints, 38 (1), 514 (1997). 74. G. Natta, P. Longi, E. Pellino, Makromol. Chem., 71, 212 (1964). 75. M. Ueda, T. Suzuki et al., J. Polym. Sci. Chem. Ed., 21,2997 (1983). 76. A. Natansohn et al., Macromolecules, 28, 4179 (1995). 77. A. Furukawa, T. Nakaya, M. Imoto, Makromol. Chem., 187, 311 (1986). 78. J. Springer, F. W. Weigelt, Makromol. Chem., 184, 1489 (1983). 79. S. H. Yuk, ACS Polym. Mater. Sci. Eng., 76, 231 (1997). 80. R. D Calleja et al., Macromolecules, 28, 6963 (1995). 81. J. Velickovic, Vukajlovic-Fiiipovic, J. Angew. Makromol. Chem., 13, 79 (1970). 82. J. Velickovic, J. Juranicova, J. Filipovic, IUPAC Intern. Symp. Macromolecules; Leiden, vol. I, 289 (1970). 83. J. Velickovic, M. Plavsic, Eur. Polym. J., 19, 1171 (1983). 84. T. Otsu, K. Shiraishi, A. Matsumoto et al., Polym. Commun., 26, 367 (1985). 85. N. Toyoda, T. Otsu, J. Macromol. Sci. A, 19, 1011 (1983). 86. J. S. Scarpa, D. D. Mueller, I. M. Klotz, J. Am. Chem. Soc, 89, 6024 (1967). 87. C. K. Chiklis, J. M. Grasshoff, J. Polym. Sci. A-2, 8, 1617 (1970). 88. S. Nakahama et al., ACS Polym. Mater. Sci. Eng., 76, 11 (1997). 89. L. E. Coleman, J. F. Bork, D. P. Wyman, ACS Polymer Preprints, 5, 250 (1964). 90. T. Kodaira et al., Macromolecules, 27, 1320 (1994). 91. R. Miyashita et al., Macromolecules, 27, 513 (1994). 92. J. Heller, C. B. Kingsley, Makromol. Chem., 78, 47 (1964). 93. O. Nuyken et al., ACS Polymer Preprints, 37 (1), 343 (1996). 94. A. Alegria et al., Macromolecules, 28, 8819 (1995). 95. E. J. Vandenberg, R. F. Heck, D. S. Breslow, J. Polym. Sci., 41, 519 (1959). 96. G. F. L. Ehlers, J. D. Ray, J. Polym. Sci. A, 2, 4989 (1964). 97. C. E. Schildknecht, S. T. Gross, H. R. Davidson, J. M. Lambert, A. O. Zoss, Ind. Eng. Chem., 40, 2104 (1948). 98. R. J. Kern, J. J. Hawkins, J. D. Calfee, Makromol. Chem., 66, 127 (1963). 99. G. Natta, G. Mazzanti, P Longi, F. Bernardini, J. Polym. Sci., 31, 181 (1958). 100. H. Cramail, A. Deffieux, Macromolecules, 27, 1401 (1994). 101. H. Yuki, K. Hatada, S. Murahashi, K. Hibino, Polym. J., 1, 271 (1970). 102. D. D. Coffman, G. H. KaIb, A. B. Ness, J. Org. Chem., 13, 223 (1948). 103. T. Yokozawa, E. Tsuruta, Macromolecules, 29, 8053 (1996).
104. G. B. Dharas et al., ACS Polymer Preprints, 33 (1), 211 (1992). 105. K. Saunders, J. Organic Polymer Chemistry, 2nd ed., Chapman and Hall, New York, 1988, p. 121. 106. M. Sumi, K. Matsumura, R. Obno, S. Nozakura, S. Murahashi, Chem. High Polymers (Tokyo), 24, 606 (1967). 107. D. Y. Sogah, J. F. Harris, ACS Polymer Preprints, 32 (1), 435 (1991). 108. B. M. Novak, A. K. Cederstav, ACS Polymer Preprints, 36 (1), 548 (1995). 109. Brochure "Mowital" of Hoechst AG, Frankfurt/M., 1971. 110. T. Hayashi et al., Macromolecules, 27, 2270 (1994). 111. H. Rittner, R. Sperber, Macromolecules, 27, 5919 (1994). 112. Skillicorn et al., J. of Vinyl Technology, 15 (2), 105 (1993). 113. R. A. Wessling, J. Appl. Polym. Sci., 14, 1531 (1970). 114. R. A. Wessling, J. Appl. Polym. Sci., 14, 2263 (1970). 115. G. H. KaIb, D. D. Coffman, T. A. Ford, F. L. Johnston, J. Appl. Polym. Sci., 4, 55 (1960). 116. R. Advincula et al., ACS Polymer Preprints, 38 (1), 912 (1997). 117. Trade literature, Elf Atochem, Philadelphia, PA. 118. W. S. Durrell, G. Westmoreland, M. G. Moshonas, J. Polym. Sci. A, 3, 2975 (1965). 119. E. L. Gal'perin et al., Vysokomol Soedin. A, 12, 1654 (1970). 120. R L. Rinaldi, ACS Polymer Preprints, 38 (1), 770 (1997). 121. H. T. Hall, J. Am. Chem. Soc, 71, 68 (1952). 122. R. C. Doban, A. C. Knight, J. J. Peterson, C. A. Sperati, Am. Chem. Soc. Meeting Atlantic City, 1956. 123. N. K. I. Symons, J. Polym. Sci., 51, S21 (1961). 124. D. Mclntyre, D. R. Valentine, ACS Polymer Preprints, 7, 1133 (1966). 125. R. E. Lowry, D. W. Brown, L. A. Wall, J. Polym. Sci. A-1,4, 2229 (1966). 126. D. W. Brown, R. E. Lowry, L. A. Wall, J. Polym. Sci. A-I, 8, 2441 (1970). 127. D. Lopez et al., Macromolecules, 27, 7415 (1994). 128. V Panchalingam et al., ACS Polymer Preprints, 32 (3), 185 (1991). 129. Trade literature, 3M Industrial Chemicals, St. Paul, MN. 130. W. Tuminello et al., Macromolecules, 28, 1506 (1995). 131. Dupont Specialty Polymers, Wilmington, DE. 132. S. M. Jo et al., ACS Polymer Preprints, 38 (1), 697 (1997). 133. Jr. W. W. Moyer, D. A. Grev, J. Polym. Sci. B, 1, 29 (1963). 134. A. Yamane et al., Macromolecules, 30, 4170 (1997). 135. M. Victor et al., ACS Polymer Preprints, 33 (1), 1162 (1992). 136. M. Ulbricht, G. Belfort, ACS Polymer Preprints, 36 (1), 135 (1995). 137. M. G. Mikhael et al., Macromolecules, 27, 7499 (1994). 138. G. L. Eian, ACS Polymer Preprints, 36 (1), 459 (1995). 139. H. Hopff, J. Dohany, Makromol. Chem., 69, 131 (1963). 140. H. Staudinger, M. Haeberle, Makromol. Chem., 9, 52 (1953). 141. K. Schaefers, C. Schneider, J. Polym. Sci. Chem. Ed., 23, 2879 (1985).
142. 143. 144. 145. 146. 147. 148. 149. 150. 151. 152. 153. 154. 155. 156. 157. 158. 159. 160. 161. 162. 163. 164. 165. 166.
167. 168. 169. 170. 171. 172. 173. 174. 175. 176. 177. 178.
T. M. Pyriadi, ACS Polymer Preprints, 36 (1), 245 (1995). R. C. Schulz, R. Wolf, Makromol. Chem., 99, 76 (1966). M. Tosaka et al., Macromolecules, 30, 4132 (1997). P. Lu et al., Macromolecules, 29, 8583 (1996). T. Ishizone et al., Macromolecules, 30, 761 (1997). P. Xing et al., Macromolecules, 30, 2726 (1997). Trade literature, Hoechst Celanese, Dallas, TX. H. Kamogawa, H. G. Cassidy, J. Polym. Sci. A, 2, 2409 (1964). T. Ishizone, Macromolecules, 28, 3787 (1995). A. Hirao, Y. Ishino, S. Nakahama, Makromol. Chem., 187, 141 (1986). Y. Fu, R. A. Weiss, ACS Polymer Preprints, 38 (1), 270 (1997). Trade literature, ALCO Chemical, Chattanooga, TN. T. Ishizone et al., ACS Polymer Preprints, 35 (2), 540 (1994). D. Liu et al., Macromolecules, 28, 622 (1995). B. D. Edgecombe et al., ACS Polym. Mater. Sci. Eng., 75, 478 (1996). R. F. M. Lange, E. W. Meijer, Macromolecules, 28, 782 (1995). R. A. Sanayei et al., Macromolecules, 27, 5577 (1994). J. B. Schlenoff et al., Macromolecules, 28, 4290 (1995). R. C. Schulz, J. Kovacs, W. Kern, Makromol. Chem., 52,236 (1962). R. Hank, Makromol. Chem., 52, 108 (1962). H. Hopff, M. Lippay, Makromol. Chem., 66, 157 (1963). J. Moacanin, A. Rembaum, R. K. Laudenslager, ACS Polymer Preprints, 4, 179 (1963). G. Sitaramaiah, D. Jacobs, Polymer, 11, 165 (1970). J. Heller, D. J. Lymann, W. A. Hewett, Makromol. Chem., 73, 48 (1964). Y. L. Getter, International Series of Monographs on Organic Chemistry, Vol. 6, "Organophosphorus Monomers and Polymers", Pergamon Press: New York, 1962. G. B. Butler, Proc. Conf. "High Temperature Polymer and Fluid Research", Dayton, Ohio, 1962, p. 53. J. Pielichowski, A. Romaniszyn, J. Polym. Sci. Letters Ed., 22, 395 (1984). A. T. Coscia, R. L. Kugel, J. Pellon, J. Polym. Sci., 55, 303 (1961). H. R. Allcock, J. Polym. Sci. A, 2, 4087 (1964). R. Rabinowitz, R. Marcus, J. Pellon, J. Polym. Sci. A, 2, 1233 (1964). Br. Patent 849038. A. V. Topchiev, V. P. Alaniya, J. Polym. Sci. A, 1, 559 (1963). G. Natta, G. Mazzanti, G. Dall'Asta, P. Longi, Makromol. Chem., 37, 160 (1960). P. Grosius, Y. Gallot, A. Skoulios, Makromol. Chem., 136, 191 (1970). L. E. Coleman, J. F. Bork, J. Polym. Sci. A-1,8,2073 (1970). R. M. O'Malley et al., Macromolecules, 27, 5107 (1994). N. Gaylord, in: "Polyethers, Polyalkylene Sulfides and Other Polythioethers", High Polymers, vol. XIII, Part III, Interscience, New York-London, 1962.
179. Trade literature, Air Products and Chemicals, Allentown, PA. 180. K. Imai, T. Shiomi et al., J. Macromol. Sci. A, 22, 1347 (1985). 181. A. Patil, ACS Polym. Mater. Sci. Eng., 75, 287 (1996). 182. A. Bader, J. R. Wunsch, Macromolecules, 28, 3794 (1995). 183. J. C. Hornby et al., Soap/Cosmetics/Chemical Specialities June 1993, p. 40. 184. L. A. Belfiore, ACS Polym. Mater. Sci. Eng., 76, 97 (1997). 185. R. J. Badesso et al., ACS Polym. Mater. Sci. Eng., 69, 251 (1993). 186. Trade literature, ISP Technologies, Wayne, NJ. 187. F. Shi, R. Subramanian, ACS Polymer Preprints, 37 (1), 637 (1996). 188. Q. Pei et al., ACS Polymer Preprints, 36 (I), 213 (1995). 189. T. Okada et al., Macromolecules, 29, 7645 (1996). 190. T. F. McCarthy, Macromolecules, 28, 8350 (1995). 191. R. Zhang et al., Macromolecules, 29, 7627 (1996). 192. M. Pomerantz, J. Wang, ACS Polymer Preprints, 35 (1), 210 (1994). 193. Trade literature, Maxdem Inc., San Dimas, CA. 194. R. W. Phillips et al., Macromolecules, 27, 2354 (1994). 195. H. O. Wirth, R. Mueller, W. Kern, Makromol. Chem., 77, 90 (1964). 196. A. J. Pasquale et al., ACS Polymer Preprints, 38 (1), 170 (1997). 197. C. Aso, Y. Aito, Makromol. Chem., 58, 195 (1962). 198. L. D. Taylor, H. S. Kolesinski, J. Polym. Sci. B, 1, 117 (1963). 199. J. A. Moore, ACS Polymer Preprints, 5, 250 (1964). 200. J. R. Schaefgen, J. Polym. Sci., 41, 133 (1959). 201. B. R. Hsich, ACS Polym. Mater. Sci. Eng., 67, 252 (1992). 202. W. Chen et al., ACS Polymer Preprints, 36 (1), 495 (1995). 203. M. Pan et al., ACS Polymer Preprints, 36 (1), 618 (1995). 204. J. L. Reddiger, J, R. Reynolds, ACS Polymer Preprints, 37(1), 530 (1996). 205. Y. Fu, ACS Polymer Preprints, 38 (1), 410 (1997). 206. M. Wagaman, R. H. Grubbs, Macromolecules, 30, 3978 (1997). 207. Y. Baek, G. I. Stegeman, ACS Polym. Mater. Sci. Eng., 75, 221 (1996). 208. J.-I. Jin et al., Macromolecules, 27, 5239 (1994). 209. L. Pu et. al., Macromolecules, 29, 1138 (1996). 210. C-S. Wang, Y-M. Sun, ACS Polymer Preprints, 36 (1), 197 (1995). 211. R. Kulkarni, ACS Polymer Preprints, 32 (1), 128 (1991). 212. J. Asrar, Macromolecules, 27, 4036 (1994). 213. D. A. Frey, M. Hasegawa, C. S. Marvel, J. Polym. Sci. A, 1, 2057 (1963). 214. J. Konzelman, K. B. Wagener, ACS Polymer Preprints, 33 (2), 110(1992). 215. R. Reichel, C. S. Marvel, R. Z. Greenley, J. t>olym. Sci. A, 1, 2935 (1963). 216. S. P. Yen, ACS Polymer Preprints, 4, 82 (1963). 217. G. W. Coates, R. W. Waymough, ACS Polym. Mater. Sci. Eng., 67, 92 (1992).
218. G. W. Coates et al., ACS Polymer Preprints, 33 (1), 1230 (1992). 219. S. Cesca, A. Priola, G. Santi, J. Polym. Sci. B, 8, 573 (1970). 220. L. A. Wall, L. J. Fetters, S. Straus, J. Polym. Sci. B, 5, 721 (1967). 221. H. Mains, J. H. Day, J. Polym. Sci. B, 1, 347 (1963). 222. S. Cesca, A. Roggero, N. Palladino, A. De Chivico, Makromol. Chem., 136,23 (1970). 223. V. V. Korshak, S. M. Tseitlin, V. I. Azarov, A. I. Parlov, Izv. Akad. Nauk SSSR, Ser. Chim., 1, 226 (1968). 224. R. G. Alsup, J. O. Punderson, G. F. Leverett, J. Appl. Polym. Sci., 1, 185 (1959). 225. N. G. Gaylord, Polyethers; Interscience: New York, Part I, p. 46. 226. J. Furukawa, T. Saegusa, H. Fujii, A. Kawasaki, T. Tatano, Makromol. Chem., 33, 32 (1959). 227. J. Furukawa, T. Saegusa, H. Fujii, Makromol. Chem., 44/46, 398 (1961). 228. J. Furukawa, T. Saegusa, in: "Polymerization of Aldehydes and Oxides", Polymer Reviews, Interscience, New York, Vol. 3, 1963. 229. A. Benkhira et al., Macromolecules, 27, 3963 (1994). 230. K. Weissermel, E. Noelken, Makromol. Chem., 68, 140 (1963). 231. V. N. Kuznetsov, S. D. Vogman et al., Vysokomol. Soedin. A, 12, 2635 (1970). 232. R. C. Schulz, R. Wolf, Makromol. Chem., 99, 76 (1966). 233. T. Saegusa, S. Matsumoto, Y. Hashimoto, Macromol., 3,735 (1970). 234. M. E. Wright, G. D. Allred, ACS Polymer Preprints, 33 (1), 1123 (1992). 235. G. B. Brown, A. Goldman, ACS Polymer Preprints, 4 (2), 39 (1963). 236. S. Brochu, G. Ampleman, Macromolecules, 29, 5539 (1996). 237. J.-C. Lee et al., Macromolecules, 30, 3766 (1997). 238. T. Iwata, G. Wasai, T. Saegusa, Furukawa, J. Makromol. Chem., 77, 229 (1964). 239. E. Riande, J. Guzman, L. Garillo, Macromolecules, 17, 1234 (1984). 240. I. Penczek, S. Penzcek, Makromol. Chem., 67, 203 (1963). 241. W. A. Butte, C. C. Price, R. E. Hughes, J. Polym. Sci., 61, 528 (1962). 242. G. F. Endres, A. S. Hay, J. W. Eustance, J. Org. Chem., 28, 1300 (1963). 243. G. D. Staffin, C. C. Price, J. Am. Chem. Soc, 82, 3632 (1960). 244. J. M. Barrales-Rienda, D. C. Pepper, Eur. Polym. J., 3, 535 (1967). 245. R. W. Phillips et al., Macromolecules, 27, 3451 (1994). 246. R.-M. Ho et al., Macromolecules, 30, 3349 (1997). 247. Z. Chen et al., ACS Polym. Mater. Sci. Eng., 70, 40 (1994). 248. M. E. Denker, F. W. Harris, ACS Polymer Preprints, 35 (1), 521 (1994). 249. K. J. Saunders, "Organic Polymer Chemistry", 2nd ed., Chapman and Hall, New York, p. 275.
250. G. F. Pregaglia, M. Binaghi, M. Cambini, Makromol. Chem., 67, 10 (1963). 251. G. Natta, G. Mazzanti, G. F. Pregaglia, M. Binaghi, M. Cambini, Makromol. Chem., 51, 148 (1962). 252. R. C. Schulz, W. Passmann, Makromol. Chem., 60, 139 (1963). 253. C. Aso, Y. Aito, Makromol. Chem., 73, 141 (1964). 254. A. Takahashi, S. Kambara, Makromol. Chem., 72,92 (1964). 255. K. Meyersen, R. C. Schulz, W. Kern, Makromol. Chem., 58, 204 (1962). 256. C. G. Overberger, S. Ishida, H. Ringsdorf, J. Polym. Sci., 62, 51 (1962). 257. C. G. Overberger, S. Ishida, ACS Polymer Preprints, 5, 210 (1964). 258. H. Ohse, H. Cherdron, F. Korte, Makromol. Chem., 76, 147 (1964). 259. P. Dunn, D. Oldfield, J. Macromol. Sci. A, 4, 1157 (1970). 260. M. Acemoglu et al., Macromolecules, 28, 3030 (1995). 261. J. Labadie, ACS Polymer Preprints, 36 (1), 735 (1995). 262. X. Chen et al., Macromolecules, 30, 3470 (1997). 263. W. R. Moore, M. Uddin, Eur. Polym. J., 5, 185 (1969). 264. W. R. Moore, M. Uddin, Eur. Polym. J., 6, 121 (1970). 265. G. S. Kolesnikov et al., Vysokomol. Soedin. B, 12, 548 (1970). 266. C-S. Tan, T.-I. Hsu, Macromolecules, 30, 3147 (1997). 267. J. M. Bronk, J. S. Riffle, ACS Polymer Preprints, 35 (1), 915 (1994). 268. M. Super et al., Macromolecules, 30, 368 (1997). 269. P. Cebe, J. Carbeck, ACS Polymer Preprints, 33 (1), 331 (1992). 270. J. P. Penning, R. St. John Manley, ACS Polymer Preprints, 36 (1), 330 (1995). 271. M. Tokita et al., Macromolecules, 29, 1345 (1996). 272. X. Li, F. Brisse, Macromolecules, 27, 7718 (1994). 273. Y. Maeda, J. Watanabe, Macromoiecules, 28, 1661 (1995). 274. S. Inoue, Y. Tomoi, T. Tsuruta, J. Furukawa, Makromol. Chem., 48, 229 (1961). 275. H. Cherdron, H. Ohse, F. Korte, Makromol. Chem., 56, 179, 187 (1962). 276. K. M. Shakesheff et al., ACS Polymer Preprints, 36 (1), 71 (1995). 277. S. M. Li et al., ACS Polymer Preprints, 37 (2), 133 (1996). 278. A. Lofgren et al., Macromolecules, 27, 5556 (1994). 279. S. Oi et al., Macromolecules, 29, 2694 (1996). 280. P. Hubbard et al., Macromolecules, 29, 8304 (1996). 281. P. Wilson, W. J. Brittain, ACS Polymer Preprints, 36 (2), 136 (1995). 282. C. Spies, R. Gehrke, Macromolecules, 30, 1701 (1997). 283. A. Romo-Uribe, A. H. Windle, Macromolecules, 28, 7085 (1995). 284. C. G. Bauch et al., ACS Polymer Preprints, 32 (1), 377 (1991). 285. Y. Wei et al., ACS Polymer Preprints, 36 (2), 241 (1995). 286. H.-L. Chen et al., Macromolecules, 30, 1718 (1997). 287. H. A. Al-Maullen, D. M. Knauss, ACS Polymer Preprints, 38 (1), 68 (1997).
288. D. Tian et al., Macromolecules, 30, 406 (1997). 289. J.-H. Chang et al., ACS Polymer Preprints, 36 (1), 829 (1995). 290. K. Belfield, G. Zhong, ACS Polymer Preprints, 36 (2), 269 (1995). 291. F. Ignatious et al., ACS Polymer Preprints, 34 (2), 586 (1993). 292. B.-H. Chang, J. Kwiatek, ACS Polymer Preprints, 36 (2), 146 (1995). 293. S. Davies, B. Tighe, ACS Polymer Preprints, 36 (1), 103 (1995). 294. R. H. Marchessault, K. Okamura, C. J. Su, MacromoL, 3, 735 (1970). 295. Y. Hori, A. Yamaguchi, Macromolecules, 28, 406 (1995). 296. K. S. Bisht et al., Macromolecules, 30, 2705 (1997). 297. Y. Hiragui, Y. Tokiwa, Macromolecules, 30, 3691 (1997). 298. H. Ohse, H. Cherdron, Makromol. Chem., 95, 283 (1966). 299. A. Roviello, A. Sirigu, Makromol. Chem., 181,1799 (1980). 300. N. Lacoudre, A. Leborgue et al., Makromol. Chem., 187, 341 (1986). 301. H. Batzer, H. Lang, Makromol. Chem., 15, 211 (1955). 302. R. Nitsche, K. A. Wolf, US Patent 3 036990, 3 036991, 1962. 303. J. Lo, S. N. Lee, E. M. Pearce, J. Appl. Polym. ScL, 29, 35 (1984). 304. Y. Imai, S. Tassavori, J. Polym. Sci. Chem. Ed., 22, 1319 (1984). 305. J. H. Pawlow et al., ACS Polymer Preprints, 37 (2), 198 (1996). 306. J. Hori et al., Macromolecules, 26, 4388 (1993). 307. E. Shimamura, Macromolecules, 27, 4429 (1994). 308. H. R. Kricheldorf, J. M. Jonte, Polym. Bull., 9, 276 (1983). 309. A. G. Shard et al., ACS Polymer Preprints, 36 (1), 74 (1995). 310. R. C. Schulz et al., ACS Polymer Preprints, 31 (2), 402 (1990). 311. YK. Sung, D. K. Song, ACS Polymer Preprints, 37 (2), 107 (1996). 312. J. Majnusz, J. Catala, R. W. Lenz, Eur. Polym. J., 19, 1043 (1983). 313. Trade literature, Amoco Chemical Co., Chicago, IL. 314. J. Jager et al., ACS Polymer Preprints, 37 (1), 236 (1996). 315. K. J. Saunders, "Organic Polymer Chemistry", 2nd ed., Chapman and Hall, New York, 1988, p. 256. 316. H. Prueckner, Erdoel, Kohle, Erdgas, Petrochemie, 16, 188 (1959). 317. C. Wu et al., Macromolecules, 27, 6055 (1994). 318. A. S. Jones et al., ACS Polymer Preprints, 37 (1), 229 (1996). 319. Y-H. So, ACS Polymer Preprints, 35 (1), 819 (1994). 320. F. H. Henglein, H. E. Tarrach, Kunststoffe-Plastics, 6, 5 (1959). 321. S. Nomula, S. L. Cooper, ACS Polymer Preprints, 38 (1), 78 (1997). 322. D. J. Lyman, J. Polym. Sci., 55, 507 (1961). 323. E. L. Wittbecker, M. Katz, J. Polym. Sci., 40, 367 (1959). 324. T. M. Gricenko et al., KMm. Volokna, 5, 18 (1970). 325. D. J. Lyman, J. Polym. Sci., 45, 49 (1960).
326. S. Neffgen et al., Macromolecules, 30, 1289 (1997). 327. Trade literature, Anderson Development Co., Adrian, MI. 328. J. C. Wittmann et al., ACS Polymer Preprints, 36 (I), 257 (1995). 329. S. Bronco, Macromolecules, 27, 4436 (1994). 330. Z. Jiang et al., ACS Polymer Preprints, 35 (1), 676 (1994). 331. J. G. Bonner, A. K. Powell, ACS Polym. Mater. Sci. Eng., 76, 108 (1997). 332. A. A. Patel, S. R. Patel, Eur. Polym. J., 19, 17 (1983). 333. M. Barsacchi et al., ACS Polym. Mater. Sci. Eng., 67, 63 (1992). 334. M. Brookhart et al., ACS Polymer Preprints, 35 (2), 530 (1994). 335. R. A. Koster, R. H. Birk, ACS Polymer Preprints, 37 (2), 525 (1996). 336. S. Murtuza, A. Sen, ACS Polymer Preprints, 37 (2), 194 (1996). 337. S. L. Borkowsky, R. M. Waymouth, Macromolecules, 29, 6377 (1996). 338. S. L. Borkowsky, R. M. Waymough, ACS Polymer Preprints, 35 (1), 792 (1994). 339. A. L. Safir, B. M. Novak, ACS Polymer Preprints, 36 (1), 227 (1995). 340. M. F. Teasley, B. S. Hsiao, Macromolecules, 29, 6432 (1996). 341. M. Teasley etal., ACS Polymer Preprints, 38(1), 125 (1997). 342. F. Wang, J. Roovers, ACS Polym. Mater. Sci. Eng., 69, 44 (1993). 343. R.-M. Ho et al., Macromolecules, 27, 5787 (1994). 344. R.-H. Ho et al., ACS Polymer Preprints, 36 (1), 338 (1995). 345. S. Ahmed etal., ACS Polymer Preprints, 38 (I), 172(1997). 346. U. Hoffmann et al., Macromolecules, 27, 3575 (1994). 347. J. V. Facinelli et al., ACS Polymer Preprints, 36 (1), 759 (1995). 348. Z. Wu et al., ACS Polymer Preprints, 36 (2), 215 (1995). 349. D. W. Thomson, G. F. L. Ehlers, J. Polym. Sci. A, 2, 1051 (1964). 350. A. Mochizuki et al., Macromolecules, 28, 365 (1995). 351. J. V. Beach, ACS Polym. Mater. Sci. Eng., 72, 205 (1995). 352. B. A. Kiselov, I. A. Stepina, Z. P. Ablekova, Soviet Plastics, 13 (1970). 353. G. W. Gray, D. Lacey et al., Makromol. Chem. Rapid Commun., 7, 71 (1986). 354. J. B. Ganci, F. A. Bettelheim, J. Polym. Sci. A, 2, 4011 (1964). 355. P. R. Dvornic et al., Macromolecules, 27, 7575 (1994). 356. P. R. Dvornic, R. W. Lenz, Macromolecules, 27, 5833 (1994). 357. P. R. Dvornic, V. V. Gerov, Macromolecules, 27, 1068 (1994). 358. R. Puyerbrock et al., ACS Polym. Mater. Sci. Eng., 72, 110 (1995). 359. Trade literature, GE Silicones, Waterford, NY. 360. H. Zhuang, Jr., J. A. Gardella, Macromolecules, 30, 3632 (1997).
361. A. Sergeyev, V. I. Ness'kin, S. S. Arustamyan, Polymer Commun., 26, 365 (1985). 362. Phillips Petroleum US Patent 3 380951. 363. B. Jirgensons, in: "Natural Organic Polymers", Pergamon Press, New York, 1962. 364. K. Yamamoto et al., Macromolecules, 27, 4312 (1994). 365. J. L. de Ia Pena, E. Riande, J. Guzman, Macromolecules, 18, 2739 (1985). 366. S. S. Wu et al., ACS Polymer Preprints, 36 (1), 267 (1995). 367. H. A. Smith, C. E. Handlovits, Proc. Conf. High Temperature Polymer and Fluid Research, Dayton, Ohio, 1962, p. 123. 368. M. L. Cameron et al., ACS Polymer Preprints, 31 (1), 297 (1990). 369. M. Ueda, T. Okada, Macromolecules, 27, 3449 (1994). 370. R. A. Johnson, L. J. Mathais, Macromolecules, 28, 79 (1995). 371. J. D. Davies, W. H. Daley, ACS Polymer Preprints, 37 (1), 745 (1996). 372. M. P. Bohrer, D. A. Mixon, ACS Polymer Preprints, 34 (1), 455 (1993). 373. K. J. Saunders, "Organic Polymer Chemistry", 2nd ed., Chapman and Hall, New York,' 1988; p. 283. 374. H. A. Vogel, J. Polym. Sci. A-I, 8, 2035 (1970). 375. M .E. A. Cudby, R. G. Feasy, B. E. Jennings, M. E. B. Jones, J. B. Rose, Polymer, 6, 589 (1965). 376. A. Bhatnager, ACS Polymer Preprints, 38 (1), 111 (1997). 377. A. Pandya et al., Macromolecules, 27, 1367 (1994). 378. S. G. Gaynor, S. Z. Edelman, ACS Polymer Preprints, 38 (1), 703 (1997). 379. M. D. Guiver et al., Macromolecules, 28, 7612 (1995). 380. R. S. Achibald et al., ACS Polym. Mater. Sci. Eng., 69, 293 (1993). 381. Y-K. Han et al., Macromolecules, 28, 916 (1995). 382. C. Gao, A. S. Hay, ACS Polymer Preprints, 36 (2), 102 (1995). 383. D. J. Riley et al., ACS Polymer Preprints, 37 (1), 489 (1996). 384. T. M. Moy et al., ACS Polymer Preprints, 33 (1), 489 (1992). 385. M. Russo, S. Hara, Chem. High Polymers (Tokyo), 27, 661 (1970). 386. N. Azuma, Macromolecules, 28, 7331 (1995). 387. V. E. Shashoua, W. Sweeny, R. F. Tietz, J. Am. Chem. Soc, 82, 866 (1966). 388. W. Buchard, Makromol. Chem., 67, 182 (1963). 389. A. Ohshima et al., Macromolecules, 28, 6095 (1995). 390. Y Jimbo et al., Macromolecules, 27, 6080 (1994). 391. C. Khatri et al., ACS Polymer Preprints, 33 (2), 200 (1992). 392. R. C. Schultz, R. Stenner, Makromol. Chem., 12, 202 (1964). 393. L. Franco et al., ACS Polymer Preprints, 33 (1), 325 (1992). 394. L. Franco et al., Macromolecules, 27, 4284 (1994). 395. J. A. Muller et al., ACS Polymer Preprints, 36 (1), 166 (1995). 396. J. Helfrich et al., Macromolecules, 27, 472 (1994). 397. D. Barrera et al., Macromolecules, 28, 425 (1995). 398. M. Bermudez et al., Macromolecules, 27, 6325 (1994).
399. R. Graf, G. Lohaus, K. Boerner, E. Schmidt, H. Bestian, Angew. Chem., 74, 523 (1962). 400. J. Masamoto, Y Kaneko, K. Sasaguri, H. Kobayashi, J. Soc. Fiber Sci. Technol. Japan, 25, 525 (1969). 401. J. Masamoto, K. Sasaguri, C. Ohizumi, H. Kobayashi, J. Polym. Sci. A-2, 8, 1703 (1970). 402. S. Jin, K. E. Gonsalves, ACS Polym. Mater. Sci. Eng., 76, 15 (1997). 403. C-W. Ng et al., ACS Polym. Mater. Sci. Eng., 69, 345 (1993). 404. H. Sekiguchi, Bull. Soc. Chim. France, 1839 (1960). 405. R. J. Gaymans, V. S. Venkatraman, J. Schuijer, J. Polym. Sci. Chem. Ed., 22, 1373 (1984). 406. S. A. Giannos, ACS Polym. Mater. Sci. Eng., 62, 236 (1990). 407. K. L. L. Eerisels et al., Macromolecules, 29, 6744 (1996). 408. E. Navarro et al., Macromolecules, 29, 5406 (1996). 409. E. Navarro et al., Macromolecules, 28, 8742 (1995). 410. S. Steadman, L. J. Mathias, ACS Polymer Preprints, 37 (2), 256 (1996). 411. G. Reinisch, K. Dietrich, Eur. Polyrn. J., 6, 1269 (1970). 412. K. Weiskopf, G. Meyerhoff, Polymer, 24, 72 (1983). 413. C. G. Johnson, L. J. Mathias, ACS Polymer Preprints, 34 (2), 348 (1993). 414. T. KakuchietaL, ACS Polymer Preprints, 37(1), 561 (1996). 415. M. J. Hill, E. D. T. Atkins, Macromolecules, 28, 604 (1995). 416. Trade literature, HuIs, Marl, Germany. 417. G. Cojazzi, A. M. Drusiani et al., Eur. Polym. J., 17, 1241 (1981). 418. N. Ogata, K. Sanui et al., J. Polym. Sci. Chem. Ed., 22, 793 (1984). 419. H. R. Dricheldorf et al., Macromolecules, 27, 1669 (1994). 420. M. Ueda, A. Mochizuki, Macromolecules, 18, 2353 (1985). 421. V. E. Shaskoua, W. M. Eareckson, J. Polym. Sci., 40, 343 (1959). 422. A. C. Karydas, M. Kapuscinska, E. M. Pearce, Eur. Polym. J., 19, 935 (1983). 423. C. G. Overberger, C. X. Lu, C. C. Chen, J. Polym. Sci. Chem. Ed., 24, 75 (1986). 424. Y Iwakura, K. Uno, Y Imai, M. Fukui, Makromol. Chem., 77, 41 (1964). 425. K. J. Saunders, "Organic Polymer Chemistry", 2nd ed., Chapman and Hall, New York, 1988; p. 210. 426. C. X. Lu, Q. Li, J. Pan, J. Polym. Sci. Chem. Ed., 23, 30 (1985). 427. D. J. Schaefer et al., ACS Polymer Preprints, 35 (1), 118 (1994). 428. K. J. Saunders, "Organic Polymer Chemistry", 2nd ed., Chapman and Hall, New York, 1988; p 209. 429. K. J. Bouck, P G. Rasmussen, ACS Polymer Preprints, 34 (1), 463 (1993). 430. J. Rosch, R. Mulhaupt, ACS Polymer Preprints, 33 (1), 370 (1992). 431. D. Lin et al., ACS Polymer Preprints, 33 (1), 335 (1992). 432. P E. Cassidy et al., ACS Polymer Preprints, 31 (2), 582 (1990). 433. K. Kimura et al., Macromolecules, 27, 1303 (1994).
434. H. Kricheldorf, A. Domschke, Macromolecules, 27, 1509 (1994). 435. C. E. Sroog, S. V. Abramo, C. E. Berr, W. M. Edwards, A. L. Endrey, K. L. Olivier, ACS Polymer Preprints, 5(1), 132; J. Polym. Sci. A, 3, 1373 (1965). 436. J. Pellon, W. G. Carpenter, J. Polym. Sci. A, 1, 863 (1963). 437. B. L. Kwolek, P. W. Morgan, J. Polym. Sci. A, 2,269 (1964). 438. S. A. Suncket, W. A. Muiphey, S. B. Spenk, J. Polym. Sci., 40, 389 (1959). 439. K. Iimura, N. Koide et al, Makromol. Chem., 182, 2563 (1981). 440. A. H. Frazer, F. T. Wallenberger, J. Polym. Sci. A, 2, 1137 (1964). 441. A. H. Frazer, F. T. Wallenberger, J. Polym. Sci. A, 2, 1147 (1964). 442. K. R. Carter, J. L. Hedrich, ACS Polymer Preprints, 34 (1), 521 (1993). 443. H. Rinke, E. Istel, in: E. Mueller (Ed.), "Houben-Weyl Methoden der Organischen Chemie", vol. 14 (2), 412 ed., Georg Thieme, Stuttgart, 1963. 444. G. C. Robinson, J. Polym. Sci. A, 2, 390 (1964). 445. A. Goodwin, B. M. Novak, Macromolecules, 27, 5520 (1994). 446. K. Shibayama et al., Macromolecules, 30, 3159 (1997). 447. D. J. Lyman, N. Sadri, Makromol. Chem., 67, 1 (1963). 448. C. H. Chen et al., Macromolecules, 27, 6376 (1994). 449. Trade literature, Polymer Chemistry Innovations, Tuscon, AZ. 450. J. M. Rodriguey-Parada et al., Macromolecules, 27, 1571 (1994). 451. M. A. Mitchell et al., ACS Polym. Mater. Sci. Eng., 68, 22 (1993). 452. K. S. Arora, C. G. Overberger, J. Polym. Sci. Chem. Ed., 24, 37 (1986). 453. T. Nakato et al., ACS Polymer Preprints, 37 (1), 555 (1996). 454. O. Takayuki, A. Tatsumi, A. Matsumoto, J. Polym. Sci. Letters Ed., 24, 113 (1986). 455. A. Ito et al., Macromolecules, 28, 5618 (1995). 456. Y. Xia, A. G. MacDiarmid, Macromolecules, 27, 7212 (1994). 457. M. R. Majidi et al., ACS Polymer Preprints, 36 (2), 51 (1995). 458. M. G. Mikheal et al., ACS Polymer Preprints, 37 (1), 523 (1996). 459. T. E. Herold, R. S. Duran, ACS Polymer Preprints, 36 (1), 576 (1995). 460. W. E. Rudzinski et al., ACS Polymer Preprints, 34 (1), 449 (1993). 461. K. Shirdhara et al., Macromolecules, 30, 4024 (1997). 462. M. T. Nguyen, A. F. Diaz, Macromolecules, 27, 7003 (1994). 463. T. Tsuda, A. Tobisawa, Macromolecules, 28, 1360 (1995). 464. J. Gopal, M. Srinivasan, Makromol. Chem., 187, 1 (1986). 465. G. F. L. Ehlers, J. D. Ray, J. Polym. Sci. A, 2, 4989 (1964). 466. H. K. Hall, Jr., ACS Polym. Mater. Sci. Eng., 72, 129 (1995). 467. H. K. Hall et al., Macromolecules, 28, 1 (1995).
468. T. Endo et al., Macromolecules, 27, 3694 (1994). 469. A. Nakai et al., Macromolecules, 27, 6963 (1994). 470. B. M. Culbertson, X.-L. Want, ACS Polymer Preprints, 37 (2), 279 (1996). 471. H. R. Allcock, R. L. Kugel, K. J. Valan, Inorg. Chem., 5, 1709 (1966). 472. G. Allen, C. J. Lewis, S. M. Todd, Polymer, 11, 31 (1970). 473. G. Allen, C. J. Lewis, S. M. Todd, Polymer, 11, 44 (1970). 474. G.-F. Xu, P. Wilsian-Neilson, ACS Polymer Preprints, 36 (1), 219 (1995). 475. H. R. Allcock, P. E. Austin, Macromolecules, 14, 1616 (1981). 476. S. Kobayashi, M. Suzuki, T. Saegusa, Macromolecules, 19, 462 (1986). 477. E. Bonaplata et al., ACS Polym. Mater. Sci. Eng., 70, 405 (1994). 478. J. Gruneich, P. Wisian-Neilsen, ACS Polymer Preprints, 37 (1), 611 (1996). 479. L. W. Breed, R. L. Elliott, A. F. Ferris, J. Polym. Sci. A, 2, 45, 1964; J. Org. Chem., 27, 1114 (1962). 480. K. A. Andrianov, V. I. Pachomov, V. M. Gel'perina, Dokl. Akad. Nauk SSSR, 162, 79 (1965). 481. K. Matsumota, H. Yamaoka, Macromolecules, 28, 7029 (1995). 482. B. M. Klemann et al., Macromolecules, 29, 198 (1996). 483. M. M. Despotopoulou et al., Macromolecules, 29, 5797 (1996). 484. T. Hiraoka et al., ACS Polymer Preprints, 37 (1), 483 (1996). 485. J. P. Banovetz et al., ACS Polymer Preprints, 34 (1), 228 (1993). 486. H. Isaka et al., Macromolecules, 28, 4733 (1995). 487. J. Ohshita et al., Macromolecules, 30, 1540 (1997). 488. H. Isaka et al., Macromolecules, 30, 344 (1997). 489. J. Ohshita et al., Macromolecules, 27, 5583 (1994). 490. M. Itoh et al., Macromolecules, 30, 694 (1997). 491. M. Itoh et al., Macromolecules, 27, 7917 (1994). 492. M.-K. Ryu et al., ACS Polym. Mater. Sci. Eng., 75, 408 (1996). 493. C. R. Krueger, E. G. Rochow, J. Polym. Sci. A, 2, 3179 (1964). 494. H. Tang et al., Macromolecules, 30, 1400 (1997). 495. R. Minne, E. G. Rochow, J. Am. Chem. Soc, 82, 5625 (1960). 496. J. P. Pillot et al., ACS Polymer Preprints, 34 (1), 562 (1993). 497. Y. Pang, ACS Polymer Preprints, 37 (2), 382 (1996). 498. Y. Imai, K. Uno, Y. Iwakura, Makromol. Chem., 83, 17 (1965). 499. T. Kubota, R. Nakanishi, J. Polym. Sci. B, 2, 655 (1964). 500. Y. Imai, I. Kaoka, K. Uno, Y. Iwakura, Makromol. Chem., 83, 167 (1965). 501. S. Inoue, Y. Imai, K. Uno, Y. Iwakura, Makromol. Chem., 95, 236 (1966). 502. V. V. Korshak, G. M. Tseitlin, A. I. Pavlow, Vysokomol. Soedin., 8, 1599 (1966). 503. D. M. Husband et al., ACS Polymer Preprints, 36 (1), 221 (1995).
504. W. D. Joseph et al., ACS Polymer Preprints, 34 (1), 397 (1993). 505. R. J. Parry, B. K. Wilson, Macromolecules, 27, 40 (1994). 506. W. D. Joseph et al., ACS Polymer Preprints, 35 (1), 551 (1994). 507. A. W. Frazer, W. Sweeny, F. T. Wallenberger, J. Polym. Sci. A, 2, 1157 (1964). 508. M. Hasegawa, T. Unishi, J. Polym. Sci. B, 2, 237 (1964). 509. Y Iwakura, K. Uno, S. Hara, Makromol. Chem., 94, 103 (1966). 510. Y. Iwakura, K. Uno, S. Hara, Makromol. Chem., 95, 248 (1966). 511. C J . Abshire, C. S. Marvel, Makromol. Chem., 44/46, 388 (1961). 512. A. H. Frazer, W. Sweeny, F. T. Wallenberger, J. Polym. Sci. A, 2, 1157 (1964). 513. M. Hasegawa, R. Huiski, J. Polym. Sci. B, 2, 237 (1964). 514. Y. Iwakura, K. Uno, S. Hara, J. Polym. Sci. A, 3, 45 (1965). 515. A. H. Frazer, F. T. Wallenberger, J. Polym. Sci. A, 2, 1181 (1964). 516. D. T. Longone, H. H. Un, J. Polym. Sci. A, 3, 3117 (1965). 517. M. Srinivasarao, ACS Polymer Preprints, 33 (1), 777 (1992). 518. M. Dotrong et al., ACS Polymer Preprints, 32 (3), 201 (1991). 519. K. R. Srinivansan et ah, ACS Polymer Preprints, 36 (2), 249 (1995). 520. P. Hergenrother, W. Wrasidlo, H. H. Levine, ACS Polymer Preprints, 5, 153 (1964). 521. H. Kokelenberg, C. S. Marvel, J. Polym. Sci. A-I, 8, 3235 (1970). 522. H. R. Kircheldorf et al., Macromolecules, 27, 2540 (1994). 523. V. N. Sekharipuram et al., ACS Polymer Preprints, 34 (1), 618 (1993). 524. P. Cebe, ACS Polymer Preprints, 37 (1), 140 (1996). 525. D. C. Rich et al., ACS Polymer Preprints, 38 (1), 414 (1997). 526. R. Pardey et al., Macromolecules, 27, 5794 (1994). 527. R. J. Perry et al., Macromolecules, 28, 2607 (1995). 528. R. J. Perry et al, Macromolecules, 27, 4058 (1994). 529. S.-H. Hsiao et al., Macromolecules, 30, 165 (1997). 530. K. Itoya et al., Macromolecules, 27, 4101 (1994). 531. A. E. Hoy It, S. J. Haung, ACS Polymer Preprints, 35 (1), 343 (1994). 532. Y-N. Lin et al., ACS Polymer Preprints, 34 (1), 515 (1993). 533. D. Cheng et al., ACS Polymer Preprints, 34 (2), 718 (1993). 534. R. E. Southwark et al., ACS Polym. Mater. Sci. Eng., 76,183 (1997). 535. B. Conger et al., Macromolecules, 30, 4049 (1997). 536. T. Matsumoto, T. Kurosaki, Macromolecules, 28, 5684 (1995). 537. N. A. J. M. van Aerie, A. J. W. ToI, Macromolecules, 27, 6520 (1994). 538. K. Itoya et al., Macromolecules, 27, 7231 (1994). 539. Trade literature, Amoco Performance Products, Ridgefield, CT.
540. C. E. Sroog, S. E. Abramo, C. E. Berr, W. M. Edwards, A. L. Endrey, K. L. Olivier, ACS Polymer Preprints, 5, 132 (1964). 541. J. W. Yu et al., Macromolecules, 30, 1845 (1997). 542. K. J. Saunders, "Organic Polymer Chemistry", 2nd ed., Chapman and Hall, New York, 1988, p. 217. 543. J. Heller, J. H. Hodgkin, F. J. Martinelli, J. Polym. Sci. B, 6, 153 (1968). 544. K. E. Uhrich et al., Macromolecules, 28, 2184 (1995). 545. A. N. Thuo, H. W. Beckman, ACS Polymer Preprints, 36 (2), 274 (1995). 546. J. W. Park et ai., Macromolecules, 27, 3459 (1994). 547. J. K. Stille, J. R. Williamson, J. Polym. Sci. A, 2, 3867 (1964). 548. J. K. Stille, E. L. Mainen, Macromolecules, 1, 36 (1968). 549. F. De Schryver, C. S. Marvel, J. Polym. Sci. A, 1, 5, 545 (1967). 550. H. H. Levine, J. K. Kjeller, C. G. Delano, ACS Polymer Preprints, 5, 160 (1964). 551. Y Iwakura, K. Uno, Y Imai, Makromol. Chem., 77, 33 (1964). 552. Y Iwakura, S. I. Izawa, F. Hayano, J. Polym. Sci. A-I, 6, 1097 (1968). 553. V. P. Sarzevskaja et al., Ukr. Khim. Zh., 35, 390 (1969). 554. J. E. White et al., ACS Polymer Preprints, 34 (1), 904 (1993). 555. T. Nishikubo et al., Macromolecules, 27, 1087 (1994). 556. J. L. Lang, W. A. Pavelich, H. D. Clarey, J. Polym. Sci. A, 1, 1123 (1963). 557. J. C. L. Hwa, W. A. Fleming, L. Miller, J. Polym. Sci. A, 2, 2395 (1964). 558. F. Xi, O. Vogl, J. Macromol. Sci. A, 20, 139 (1983). 559. J. L. Ding, R. M. Ottenbrite, ACS Polymer Preprints, 34 (2), 508 (1993). 560. W. Mormann, K. Schmalz, ACS Polymer Preprints, 33 (1), 968 (1992). 561. W. Mormann, K. Schmalz, Macromolecules, 27, 7115 (1994). 562. Trade literature, Chevron Chemical Co., Houston, TX. 563. Y Chang, C. L. McCormick, Macromolecules, 26, 4814 (1993). 564. Trade literature, Rieke Metals, Lincoln, NE. 565. M. Pomerantz et al., ACS Polym. Mater. Sci. Eng., 72, 271 (1995). 566. A. Kumar, S. R. Reynolds, ACS Polymer Preprints, 37 (2), 337 (1996). 567. J. Kowalik et al., ACS Polym. Mater. Sci. Eng., 72, 325 (1995). 568. S. Arnold et al., ACS Polym. Mater. Sci. Eng., 72, 170 (1995). 569. Y-H. Lu et al., Macromolecules, 29, 5546 (1996). 570. J. Parakka et al., Macromolecules, 29, 1928 (1996). 571. J. K. Herrema et al., Macromolecules, 28, 8102 (1995). 572. L. D. Peeters et al., Macromolecules, 29, 4216 (1996). 573. Y Pang et al., ACS Polymer Preprints, 37 (2), 333 (1996). 574. D. R. Rutherford et al., ACS Polymer Preprints, 31 (2), 643 (1990).
575. V. V. Sheares et al., ACS Polymer Preprints, 33 (2), 170 (1992). 576. V. V. Sheares et al., ACS Polym. Mater. Sci. Eng., 69, 236 (1993). 577. V. V. Sheares, ACS Polym. Mater. Sci. Eng., 73,258 (1995). 578. M. D. Curtin et al., ACS Polymer Preprints, 36 (1), 191 (1995). 579. J. Kastner et al., Macromolecules, 28, 2922 (1995). 580. F. Sanda, M. Matsumoto, Macromolecules, 28, 6911 (1995). 581. T. Tsuda, L. J. Mathias, ACS Polymer Preprint, 34 (2), 346 (1993). 582. A. Saito, D. A. Tirrell, ACS Polymer Preprints, 34 (1), 152 (1993). 583. M. J. Marsella, T. M. Swager, ACS Polymer Preprints, 33 (1), 1196(1992). 584. S.-W. Park et al., ACS Polymer Preprints, 36 (2), 259 (1995). 585. Y.-K. Kim et al., ACS Polymer Preprints, 32 (3), 590 (1991). 586. K. R. Carter et al., ACS Polymer Preprints, 34 (1), 481 (1993). 587. M. Strukilj, J. C. Hedrick, Macromolecules, 27,7511 (1994). 588. R. G. Bass, K. R. Srinivasan, ACS Polymer Preprints, 32 (1), 619 (1991). 589. Trade literature, AKZO, Dobbs Ferry, NY. 590. Trade literature, Dow Chemical Co., Midland, MI. 591. Trade literature, Hardman Inc., Belleville, NJ. 592. J. H. Bradbury, M. C. S. Perera, Brit. Polym. J., 18, 127 (1986). 593. H. Valdsar, R. Dunlap, Am. Chem. Soc. Meeting, Atlantic City, N. J., Sept. 1952. 594. E. Husemann, E. Siefert, Makromol. Chem., 128, 288 (1969). 595. E. Ott, H. M. Spurlin, (Eds.), "Cellulose and Cellulose Derivatives" Interscience, New York, 2nd ed., 1954. This book contains additional references. 596. A. Muenster, H. in: A. Stuart (Ed.), "Physik der Hochpolymeren", vol. II, Springer, Heidelberg, 1953, p. 193. 597. Trade literature, Hercules, Inc., Wilmington, DE. 598. Trade literature, Eastman Chemical Co., Kingsport, TN. 599. P. Howard, R. S. Pankh, Polym. Sci. A-I, 6, 537 (1968). 600. S. N. Bhadani, D. G. Gray, Makromol. Chem. Rapid Commun., 3, 449 (1982). 601. F. Guittard et al., Macromolecules, 27, 6988 (1994). 602. C. E. Schildknecht (Ed.), "Polymer Processes", Interscience: New York, 1956, p. 427. 603. C. T. Greenwood, D. J. Hourston, A. R. Proeter, Eur. Polyrn. J., 6, 293 (1970). 604. K. R. Meyer, Angew. Chem., 63, 155 (1951). 605. G. Keilich, N. Frank, E. Husemann, Makromol. Chem., 143, 275 (1971). 606. Trade literature, Pronova Biopolymers, Portsmouth, NH. 607. J. V. Gruber et al., Macromolecules, 28, 8865 (1995). 608. A. Hagino, S. Yoshida et al., Macromolecules, 19, 1 (1986). 609. C. L. Yue et al., ACS Polymer Preprints, 36 (1), 416 (1995). 610. Trade literature, Kelco, Chicago, IL. 611. R. Knoesel, J. Perrod, H. Benoit, Compt. Rend., 251, 2944 (1960).
612. J. F. McCullough, I. R. Van Walzer, E. J. Griffith, J. Am. Chem. Soc, 78, 4528 (1956). 613. E. Schwarzmann, I. R. Van Walzer, J. Am. Chem. Soc, 82, 6009 (1960). 614. H. Guenther, M. D. Bezoavi, P. Kovacic, J. Polym. Sci. Letters Ed., 22, 65 (1984). 615. C V . Pittman, R. D. Priester, T. V. Jagaramann, J. Polym. Sci. Chem. Ed., 19, 3351 (1981). 616. W. K. Zou, N.-L. Yang, ACS Polymer Preprints, 33 (2), 188 (1992). 617. S. Harada, S. Hasegawa, Makromol. Chem. Rapid Commun., 5, 27 (1984). 618. Trade literature, CPS Chemical Co., Old Bridge, NJ. 619. Y. Deng, R. Pelton, Macromolecules, 28, 4617 (1995). 620. J. C. Gahin, J. Appl. Polym. Sci., IS, 213 (1970). 621. M. Tricot, F. Debeauvais, C. Houssier, Eur. Polym. J., 11, 589 (1975). 622. L. P. Meier et al., Macromolecules, 29, 718 (1996). 623. P. Cheng et al., ACS Polymer Preprints, 32 (1), 138 (1991). 624. S. A. X. Haung, F. W. Harris, ACS Polymer Preprints, 35 (1), 519 (1994). 625. D.-C. Choi et al., Macromolecules, 30, 176 (1997). 626. A. Qin et al., Macromolecules, 27, 120 (1994). 627. R. Nomura et al., Macromolecules, 28, 86 (1995). 628. A. H. Gabor, C. K. Ober, ACS Polym. Mater. Sci. Eng., 72, 104 (1995). 629. O. Liu et al., ACS Polymer Preprints, 33 (1), 215 (1992). 630. F. Henselwood, G. Liu, Macromolecules, 30, 488 (1997). 631. R. Numora, T. Endo, Macromolecules, 28, 5372 (1995). 632. X. Chen, J. A. Gardella, ACS Polymer Preprints, 33 (2), 312 (1992). 633. C. Kim et al., ACS Polymer Preprints, 37 (2), 159 (1996). 634. M. S. Reeve, ACS Polym. Mater. Sci. Eng., 67, 182 (1992). 635. D. Li, R. Faust, Macromolecules, 28, 1383 (1995). 636. J. Li et al., ACS Polymer Preprints, 36 (2), 388 (1995). 637. G.-H. Hsiue et al., ACS Polymer Preprints, 33 (2), 212 (1992). 638. R. Nomura, T. Endo, Macromolecules, 28, 1754 (1995). 639. Trade literature, Shell Chemical Co., Houston, TX. 640. J. H. Chu et al., ACS Polymer Preprints, 36 (2), 122 (1995). 641. M. Motomatsu et al., ACS Polymer Preprints, 37 (2), 579 (1996). 642. B. S. Pinheiro, K. I. Winey, ACS Polymer Preprints, 36 (1), 174 (1995). 643. D. Hajduk et al., Macromolecules, 27, 490 (1994). 644. L. Balogh, L. A. Blumstein, ACS Polymer Preprints, 36 (2), 211 (1995). 645. J. T. Chen et al., Macromolecules, 28, 1688 (1995). 646. S. Nakahama et al., ACS Polymer Preprints, 36 (1), 57 (1995). 647. X. Jin, T. Lodge, ACS Polymer Preprints, 36 (1), 168 (1995). 648. R. F. Story, D. W. Baugh, ACS Polymer Preprints, 36 (1), 414 (1995). 649. Z. Fodor, R. Faust, ACS Polymer Preprints, 36 (2), 176 (1995). 650. X. Chen et al., ACS Polymer Preprints, 38 (1), 715 (1997).
651. 652. 653. 654. 655. 656. 657. 658. 659. 660. 661. 662. 663. 664. 665. 666. 667. 668. 669. 670. 671. 672. 673. 674. 675.
S. J. Clarson et al., Macromolecules, 28, 674 (1995). T. Ohmura et al., Macromolecules, 27, 3714 (1994). D. Nguyen et al., Macromolecules, 27, 5173 (1994). Y. Gan, T. E. Hogen-Esch, ACS Polymer Preprints, 36 (1), 406 (1995). Y. Gan et al., ACS Polymer Preprints 1993,34 (1), 69 (1993). T. K. Bera et al., ACS Polym. Mater. Sci. Eng., 77, 126 (1997). H. R. Allcock et al., Macromolecules, 30, 3184 (1997). I. Ihre, A. HuIt, ACS Polym. Mater. Sci. Eng., 77,71 (1997). S. Rannard, N. Davis, ACS Polym. Mater. Sci. Eng., 77, 63 (1997). Trade literature, DSM Fine Chemicals, Heerlen, NL. L. J. Hobson et al., ACS Polym. Mater. Sci. Eng., 77, 220 (1997). Y. H. Kim, ACS Polym. Mater. Sci. Eng., 73, 175 (1995). C. Kim et al., Macromolecules, 29, 6353 (1996). P. Lu et al., ACS Polymer Preprints, 37 (2), 342 (1996). C. J. Hawker, F. Chu, Macromolecules, 29, 4370 (1996). C. J. Hawker, ACS Polym. Mater. Sci. Eng., 76, 152 (1997). J. P Kampf, ACS Polymer Preprints, 38 (1), 908 (1997). M. R. Leduc et al., ACS Polym. Mater. Sci. Eng., 77, 1 (1997). W. Hayes et al., ACS Polym. Mater. Sci. Eng., 77, 143 (1997). E. W. Kwock et al., ACS Polymer Preprints 1991,32 (3), 635 (1991). F. Walter et al., ACS Polymer Preprints, 34 (1), 79 (1993). S. R. Turner et al., Macromolecules, 27, 1611 (1994). C. Wu et al, Macromolecuies, 29, 228 (1996). DBP 926. 163; 928, 793; 929, 931; 929. 932; 1955, Hoechst AG, O. Fuchs et al., Chem. Z. 1169, 1956; 3756, 1958. G. E. Ham, Ind. Eng. Chem., 46, 390 (1954).
676. 677. 678. 679. 680. 681. 682. 683. 684. 685. 686. 687. 688. 689. 690. 691. 692. 693. 694. 695. 696. 697. 698. 699. 700. 701.
S. Petitjean et al., Macromolecules, 27, 4127 (1994). R. Bacskai, J. Polym. Sci. A, 1, 2777 (1963). W. Kuran, P. Gorecki, Makromol. Chem., 184, 907 (1983). T. Ikemura, Chem. High Polymers (Tokyo), 26, 845 (1969). M. T. Nguyen et al., ACS Polym. Mater. Sci. Eng., 70, 22 (1994). Y. Xhong, P. Wolf, ACS Polymer Preprints, 36 (2), 370 (1995). H. R. Allcock et al., Macromolecules, 29, 7740 (1996). Trade literature, BASF, Rensselaer, NY. E. Malstrom, A. HuIt, Macromolecules, 29, 1222 (1996). Trade literature, Dendritech Inc., Midland, MI. J. F. Klebe, J. Polym. Sci. A, 2, 2673 (1964). K. I. Lee, H. Japson, P Choleva, Internat. Polym. Sci. Technol., 8, 143 (1981). M. Kubo et al., Macromolecules, 29, 4447 (1996). E. Malstrom et al., ACS Polym. Mater. Sci. Eng., 77, 151 (1997). H. R. Kricheldorf, A. Serra, Polym. Bull., 14, 497 (1985). E. Schmidt, Angew. Makromol. Chem., 14, 185 (1970). N. Tsutsumi et al., Macromolecules, 30, 1637 (1997). M. Bruma et al., ACS Polymer Preprints, 36 (1), 727 (1995). K. Vanneste et al., Macromolecules, 27, 7496 (1994). S. C. E. Backson et al., ACS Polymer Preprints, 34 (1), 50 (1993). B. A. Howell, B. Pan, ACS Polym. Mater. Sci. Eng., 76,401 (1997). M. Eaker et al., ACS Polymer Preprints, 36 (1), 473 (1995). K. Char et al., Macromolecules, 26, 4165 (1993). S. Hadjikyriacou, R. Foust, Macromolecules, 28, 7893 (1995). S. Nagai, Bull. Chem. Soc. Japan, 37, 369 (1964). Y. Chang et al., Macromolecules, 27, 2145 (1994).
S p e c i f i c o f
R e f r a c t i v e
P o l y m e r s
i n
I n d e x D i l u t e
I n c r e m e n t s S o l u t i o n *
S. M i c h i e l s e n School of Textile and Fiber Engineering, Georgia Institute of Technology, Atlanta, GA, USA
A. B. C. D.
Introduction VU-547 Introduction from the Third Edition VII-547 Refractometric Calibration Data VII-550 Tables of Specific Refractive Index Increments of Polymer Solutions VII-551 Table 1. Main-Chain Acyclic Carbon Polymers VII-551 1.1. Poly(dienes) VII-551 1.2. Poly(alkenes) VII-553 1.3. Poly(acrylic acid) and Derivatives VII-557 1.4. Poly(methacrylic acid) and Derivatives VII-561 1.5. Other a- or p-Substituted Poly(acrylics) and Poly(methacrylics) VII-573 1.6. Poly(styrenes) VII-574 1.7. Other Compounds VII-588 Table 2. Main-Chain Cyclic Carbon Polymers VII-594 Table 3. Main-Chain Heteroatom Polymers VII-594 3.1. C - O - C Polymers (Poly(oxides), Poly(esters), and Others) VII-594 3.2. C-S-C Polymers (Poly(sulfones) and Others) VII-599 3.3. C - N - C Polymers (Poly(amides), Poly(isocyanates), Poly(urethanes), and Others) VII-600 3.4. Poly(amino acids) VII-604 3.5. Poly(silanes) and Poly(silazanes) Vll-606 3.6. Poly(heterocyclics) and Others VII-608 Table 4. Cellulose and Derivatives VII-609 Table 5. Poly(saccharides) VII-611 E. References VII-615
trend of using XQ = 633 nm from the HeNe laser continues and thus the 633 nm data has been given its own column in this compilation. As in the previous edition, most copolymer data has not been included. Perhaps the most significant change since the previous edition is the coupling of size exclusion chromatography (SEC) with multiple detectors, largely eliminating the need for v for obtaining molecular weights. In addition, the measurement of the specific refractive index increment has become so routine that many authors no longer report the results of these measurements. These two factors combine to reduce the number of new entries to a mere 46 new references and about 160 new entries. Finally, the excellent introduction written by Huglin for the third edition has been retained in its entirety and follows this brief introduction. B.
INTRODUCTION FROM THE THIRD EDITION
This is the limiting value at c — 0 of the quantity (n — no)/c, where n and no are the refractive indices of the solution and solvent, respectively, and c (g/ml) denotes the concentration of the polymer in solution. Conditions of constant pressure p, constant temperature T, and a fixed wavelength of light in vacuum, Ao, are implied. Specific refractive index increments are required to determine the weight-average molecular weight, Af w , of a polymer and the second virial coefficient, Aj, of a polymer in solution, using the light scattering equation. (Al) where (A2)
A.
INTRODUCTION
This section presents a compilation of the specific index of refraction increments, v = dn/dc, of polymer solutions. This table has been updated since the third edition. The * Based on a table by M. B. Huglin in the 3rd ed. of the Polymer Handbook.
Here, c is the concentration of the polymer in solution (g/ml) RQ (cm" 1 ) is the reduced intensity at an angle 0, P(O), is the particle scattering function, A2 is expressed in molcrnVg 2 , /VA (mol" 1 ) is the Avogadro number. Because
u appears as a squared term, an error of E% in v will result in an error of 2E% in the derived molecular weight, and consequently an accurate determination of v is imperative. Examination of reported data discloses that about 20 different values of Ao have been used by different workers, this increase over the earlier more restricted number being due to growing use of various laser light sources. The values of the constant K appropriate to nine common values of Ao are as follows: 1 0 7 X A 0 (cm)
366 403 436 488 514 546 578 633 1086
10 6 x K (cm~ 4 mol)
Vp, = i/B- However, it is not possible to derive the molecular weights M A and M B of the constituent portions or the heterogeneity parameters P and Q. If vA / isB, an apparent value of M is obtained. Tuzar et al. (8) have summarized the criteria for the most sensitive characterization of a copolymer:
Quantity to be determined
Criterion
M
vA and ^B fr°tn large and of same sign;
MA MB Q
V A large and i/B = 0 ^ B large and z/A = 0 i/ = 0
Of UA = ^B
18.3 12.4 9.07 5.78 4.69 3.69 2.94 2.04 0.236
For a copolymer comprising monomers A and B or a terpolymer comprising units A, B and C, the specific increment is an additive function of the composition of the polymer expressed in terms of weight fractions w. Thus,
Equations (A3) and (A4) have been verified with copolymer samples of known composition (5,6). In studies on terpolymerization, Kambe and Honda (7,897) have found that the value of v, from monomer feeds other than the azeotropic composition, changes with conversion, on account of a composition distribution. On the other hand, a constant value of v, independent of conversion, is yielded for the azeotropic case in which feed and polymer have the same composition. When vA and vB differ appreciably in a given solvent, Eq. (A3) affords a convenient means of estimating composition from the measured value of v. If this is not the situation, it is possible to introduce changes in the specific increment by using mixed solvents. The appropriate specific increment to be utilized in light scattering is then v^ that is, one at constant potential of low molecular weight solvent. V11 is measured after dialysis equilibrium between solution and pure mixed solvent, v and V11 allow one to obtain the coefficient of preferential adsorption 71 (ml/g) of the liquid (solvent 1) in the binary solvent mixture, which has a greater affinity for the polymer: (A5) In Eq. (A5), dno/d(/) 1 is the variation of the refractive index of the mixed solvent, with its composition expressed in terms of the volume fraction \ of liquid 1. For a copolymer derived from A and B, light scattering always yields the true value of the molecular weight M if
Normally, these conditions cannot be satisfied by using single solvents alone, and recourse must be made to using mixed solvents and employing i/M, (v^)^ and (y^)fi of the appropriate composition to satisfy them. The concentration dependence of v is expressed by the coefficient a2, in Eq. (A6). (A6) Lorimer (1) has derived an expression for coefficient a 2 in terms of no, v, and the concentration dependence of the partial specific volume of the polymer in solution, V2. However, within the range of c normally used to measure v, the value of a2 is usually close to zero. Expressions have also been formulated for v in terms of HQ, VI, and the refractive index of the polymer in solution, n2. These afford an indirect means of obtaining TJ2 from an experimental value of v (see Refs. 2-5). Actually v2 can now be measured to a very high level of accuracy with the Kratky digital densimeter, provided there is an appreciable difference between the densities of polymer and solvent. The main uncertainty or difficulty lies in the value of n 2 , when one wishes to calculate v via v2. 1.
Measurement and Calibration
Experimental methods and refinements have been summarized elsewhere (4). The main approaches are given below. lnterferometry In this absolute method, light beams of identical geometrical paths traverse two different optical paths and the number (/) of displaced fringes is measured by an optical compensator. If / is the length of the troughs, (n — no) is given by (A7) When (n — TIQ) is very small, for example, in extremely dilute solutions, the accuracy can be enhanced by increasing the trough length. A range of troughs of different lengths is normally available with a commercial instrument. The slope of a plot/versus c, when multiplied by (//A 0 ),
yields the value of v. Baltog et al. (10) have developed an improved cell which prevents the formation of a liquid film at the central surface with the trough, thus enabling accurate measurements to be made with volatile liquids. Differences in the dispersion of the refractive index of the solvent and the solute can lead to discontinuities in the plot of / versus c. This problem can be overcome by measuring / for a large number of solutions of gradually increasing concentration, i.e., by the dropwise addition of concentrated polymer solution to pure solvent (5,11). Differential Refractometry This relies on the image displacement AX of beams from the light source, which traverse pure solvent and polymer solution in a divided cell. Adequate temperature control is necessary and it is essential to utilize a stoppered cell to prevent solvent "creep". The method is not an absolute one and necessitates calibration with solutions of accurately known (ft - fto), so that the calibration constant k can be determined for the apparatus:
A0 = 633 nm and C in g salt/100 g water (Ref. 942):
Also, for Ao = 1086 nm and C expressed in g salt/100 ml solution, the following holds at 20 0 C (Ref. 943):
Mandel and coworkers (722) have calibrated the Chromatix differential refractometer for Ao = 633 nm and have also indicated the range over which AX is directly proportional to (ft — fto). Values of the latter quantity were interpolated to Ao = 633 nm via a Cauchy dispersion from the values at other wavelengths in Section C. Within the interval 3.6>C>0.46g salt/100g water, the following polynomial was found for aq. NaCl at 633 nm
(A8) In Eq. (A8), n is the refractive index of the solution of calibrant, and fto that of the solvent. The value of k decreases slightly with increase in Ao and must therefore be re-determined if measurements are to be conducted at a different wavelength. A selection of useful calibration data (all involving aqueous solutions) has been gathered from several sources in the literature and is given in Section C. The Brice-Phoenix differential cell is satisfactory for liquids having refractive indices not in excess of about 1.60. At higher values than this, the slit image disappears from the field of vision because of total reflection in the glass partition dividing the cell. Kratochvil and Babka (9) have described a useful modification whereby the partition is replaced with glass of a higher refractive index. This extends the useful range of the different refractometers so that even such highly refractive liquids as 1-bromonaphthalene can be accomodated. The calibration data at A o = 436 nm for aq. KCl in Section C have been fitted by Abdel-Azim and Huglin (676) to the following polynomial in which C is the concentration expressed is g salt/100 g water (ft - ft0) x 10 6 - 1.862 + 1415.8C - 17.699C 2 + 0.428C 3 Some light scattering and refractometric data relating to wavelengths different from those in Section C have been summarized elsewhere (833). The most common light source for recent light scattering studies is probably the He-Ne laser affording Ao = 633 nm. At this Ao, directly measured specific refractive index increments for certain aqueous salt solutions have been reported. On the assumption of direct proportionality between (ft — fto) and concentration, these may be represented as follows for
Abbreviations/Symbols Used Arochlor (B) Cadoxen Calgon Cuoxam Cuoxen DCA DMA DMSO DN DS EDTA FeTNa Freon 113 GHCl Halothane HEMA HMP / M MEK MMA TEAB TFP THF Versene (/u)
(approximately) Chlorinated diphenyl Branched polymer Triethylenediamine cadmium hydroxide Sodium hexametaphosphate Cuprammonium hydroxide Cupriethylenediamine hydroxide Dichloroacetic acid /V,N-Dimethylacetamide Dimethyl sulfoxide Degree of neutralization (also a) Degree of substitution Ethylenediamine tetraacetic acid Iron-tartaric acid-sodium complex solution l-Fluorodichloro-2-chlorodifluoroethane Guanidine hydrochloride 1,1,1 -Trifluoro-2-chloro-2-bromoethane 2-Hydroxyethyl methacrylate Hexamethyl phosphoramide Ionic strength Relative molar mass (M) or molarity (M), according to context Methyl ethyl ketone Methyl methacrylate Tetraethyl ammonium bromide 2,2',3,3 '-Tetrafluoropropanol Tetrahydrofuran Sodium salt of EDTA Specific increment measured at dialysis equilibrium
References page VII-615
C.
REFRACTOMETRIC CALIBRATION DATA (n - n0 ) ( x 106 )
Concentration Solute NaCl
NH4NO3
Na2SO4
SrCl2
KCl
Sucrose
(g/100 g water)
Temp* (0C)
0.0938 0.1034 0.3362 0.5602 0.6866 0.9090 1.1240 1.6465 2.0327 3.7307 6.7405 0.07878 0.1671 0.3433 1.0314 2.8884 5.8417 0.09566 0.2198 0.2686 0.3939 0.7508 1.2640 1.5417 2.5322 5.7875 0.08474 0.1749 0.2430 0.3580 0.0696 0.1067 0.2799 0.5964 1.0794 1.4911 2.9821 3.9969 4.4732 5.9642 6.4680 0.100
0.09412 0.1037 0.3375 0.5627 0.6900 0.9142 1.1311 1.6595 2.0513 3.7854 6.9092 0.07906 0.1677 0.3450 1.0408 2.9479 6.0732 0.09595 0.2205 0.2694 0.3952 0.7536 1.2693 1.5488 2.5471 5.8500 0.08506 0.1755 0.2437 0.3591 0.0699 0.1070 0.2812 0.5994 1.0869 1.5037 3.0250 4.0703 4.5647 6.1217 3.6526 0.100
0.200
0.200
0.300
0.301
0.400
0.402
0.500
0.502
0.600
0.604
0.701
0.705
0.801
0.806
0.902
0.9082
1.002
1.010
1.506
1.523
25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 20 28 20 28 20 28 20 28 20 28 20 28 20 28 20 28 20 28 20 28 20
(g/100 ml solution)
436 n m
546 n m
173 190 614 1019 1246 1645 2028 2954 3634 6583 11673 103.5 218.9 448.5 1336 3702 7410 153.1 349.0 425.3 620.1 1168 1940 2352 3796 8309 159.8 328.5 455.5 669.2 100 153 399 845 1521 2093 4135 5500 6136 8105 8763 _ _ _ _ -
_ _
166 184 592 982 1202 1586 1956 2848 3504 6345 11247 98.77 208.9 428.0 1275 3531 7066 151.0 344.1 419.3 611.5 1151 1913 2319 3744 8195 155.1 318.9 442.2 649.6 96 148 386 817 1469 2022 3994 5314 5926 7828 8465 -
_
_
_
_ _
_ _
_ _
-
578 n m
589 n m
165 182 588 976 1194 1576 1943 2830 3481 6306 11174 96 147 383 812 1460 2009 3969 5281 5890 7781 8414 -
165 182 587 974 1191 1572 1939 2824 3474 6293 11151 97.73 206.7 423.5 1262 3494 6992 150.5 343.0 417.9 609.4 1148 1906 2311 3731 8168 154.1 316.7 439.1 645.1 96 146 382 810 1457 2005 3962 5271 5879 7766 8398 140 140 290 290 430 430 580 570 720 720 860 860 1010 1000 1150 1140 1300 1290 1440 1430 2160
-
-
-
(n - no) ( x 106)
Concentration Solute
(g/100 ml solution)
2.012
2.041
3.030
3.093
3.52 4.056
4.167
5.089
5.263
6.14 7.181
7.527
8.240
8.696
9.306
9.890
10.6 16.3
D.
Temp. (0C)
(g/100 g water)
436 n m
28 20 28 20 28 25 20 28 20 28 25 20 28 20 28 20 28 25 25
-
546 n m
5100 8900 15400 23600
578 n m
589 n m 2150 2890 2870 4340 4300
5000 5810 5760 7280 7220 8800 10270 10190 11780 11680 13300 13190 15200 23200
TABLES OF SPECIFIC REFRACTIVE INDEX INCREMENTS OF POLYMER SOLUTIONS
TABLE 1. MAIN-CHAIN ACYCLIC CARBON POLYMERS dw/dc (ml/g) Polymer
Solvent
A0 = 436nm
X0 = 546nm
A0 = 633nm
Others
T (0C)
Refs.
1.1. POLY(DIENES) PoIy(1,3-butadiene)
Benzene 0.0117 0.022 Bromoform 1-Bromonaphthalene Chloroform Cyclohexane
pure 1,4 pure 1,2
hydroxyl terminated and acetyl terminated 98% cis 1,4 98% trans 1,4 7% vinyl-99% vinyl high 1,4; M = 0.96 x 103 to 90.6 xlO 3 hydroxyl terminated and acetyl terminated
Diethyl ketone w-Heptane THF Chloroform Chloroform Cyclohexane Cyclohexane Cyclohexane Cyclohexane Cyclohexane Cyclohexane Cyclohexanone 1,2-Dichloroethane n-Heptane Hexane Isobutyl acetate MEK 5-Methyl-2-hexanone 3-Pentanone THF Toluene
0.144 0.126 0.121 0.092 0.156 0.151
0.011 0.0086 0.021 — 0.115 —0.185 0.083
20 25
0.118 0.113 0.087
0.092 0.096
0.141 0.132 0.087 0.093
0.127
0.118
25 25 25
0.106 0.111 0.110 0.110-0.087 0.094-0.Ill 0.092 0.157 0.177 0.149 0.165 0.125 0.145
0.081 0.088 0.150 0.169 0.143 0.159 0.120 0.139
0.034
0.031
0.130
25 37 20 25 30 30 30 30 25 25 25 35 20.5 26 12.6 10.3 23 25
57 58 647 58 58 58 59,60 61 62 62 63 61 57 859 859 835 647 836 836 836 836 647 647 859 859 859 859 859 859 830 647
References page VII - 615
TABLE 1. cont'd dn/dc (ml/g) Polymer
Poly(chloroprene)
Solvent
n-Butyl acetate Carbon tetrachloride trans-Dccalm MEK
A 0 = 436 nm
0.146 0.0976 0.0799 0.0820 0.0777 0.160 0.162
Poly(cyclopentadiene) Poly(isoprene) 97.8% cis 1,4 73-80% cis 1,4 Poly(isoprene) anionically polymerized
Benzene Bromobenzene Carbon tetrachloride
0.0143
Chloroform oChlorotoluene Cyclohexane
0.100
Others
T( 0 C)
25 25 25 40 10 25 25
0.0394 0.125
21 21
0.0194 -0.041
20 20 25
58 73 964
25 20 20 23
68 73 73 34 59 74,75 69 69 69 68 68 68 68 70 70 69 73 68 73 7374 70 70 71 34 73 68 72 655 655 655 704 835
0.156
0.095 -0.003 0.104 0.1034
0.117
Cyclohexene
0.0988 0.0992 0.0953 0.0914
Decalin w-Hexane
0.0669
(non-extracted) (extracted) 0.1886 73-80% cis 1,4 cyclic cw 1,4
Methyl isobutyl ketone THF
70-75% cw 1,4 73-80% cis 1,4
Toluene
chlorinated synthetic high cis natural hevea natural guayule
MEK Chloroform
0.131 0.1238 0.124 0.117 0.0943 0.0947 0.0909 0.0869 0.145 0.0946 0.0605 0.168 0.1802 0.139 0.156 0.128 0.128
25 27 7 25 27 17 7 20 20 25 20 25 20 20 20 19-21 35 20 25 35 25 25 25 35 20
0.160 (calc.)
Cyclohexane
0.0308 0.131 0.104 0.106 0.108 0.117
0.0308 0.028 0.0339 0.100 0.104 0.101 0.106
trans \A star branched 93% 1,4- M = 0.9 x 103 - 10.1 x 103 93% 1,4- M> 19.5 XlO 3 synthetic high cis n-Hexane natural hevea natural guayule THF synthetic, high cis natural hevea natural guayule synthetic Toluene natural hevea natural guayuie Poly(trichlorobutadiene) Benzene
Refs.
64 64 64 64 64 64 65 66 66 67 67
0.082
0.1305
73-80% cis 1,4
A0 = 633 nm
0.152 0.138
THF Benzene Carbon tetrachloride
73-80% cis 1,4 73-80% cis 1,4 70-75% cis 1,4 trans cyclic
A0 = 546 nm
0 U 7
30
838
0.06
25 25 25 25 25 25 20 25 25 25 25 25 25 25
833 833 833 655 655 655 835 655 655 655 655 655 655 76
0.104-0.113 0.093-0.105 0.106 0.192 0.200 0.198
0.191 0.198 0.193
0.153 0.160 0.157 0.030 0.034 0.033
0.148 0.156 0.153 0.028 0.032 0.030
0.124
TABLE 1. cont'd dn/dc (ml/g) Polymer
Solvent
A0 = 436nm
A0 = 546 nm
X0 = 633 nm
Others
T (0C)
Refs.
1.2. POLY(ALKENES) PoIy(I-butene) isotactic
n-Nonane 1-Chloronaphthalene
0.092 0.108 -0.206
35 80 135 135 135 25
13 13 867 867 867 621
-0.078
-0.107(403) -0.085(578) -0.101(403) -0.080(578)
35 35 35 35 35 135 135 123.2 135 135 135 135
767 767 767 767 767 867 867 14 863 863 863 863
-0.205
-0.207(578)
135 135
863 863
-0.187 -0.183(578) -0.177
Cyclohexane Cyclohexane/n-propanol (10/90, v/v) (20/80, v/v) (30/70, v/v) (35/65, v/v) 1,2,4-Trichlorobenzene
0.074
- 0.120
0.068 0.072 0.072 0.075 0.079 - 0.108 -0.103
Poly(ethylene)
Biphenyl Bromobenzene
-0.101
-0.174 -0.089 -0.083
B B B
-0.095 1-Bromonaphthalene
B B B B
-0.083 -0.208
-0.210 -0.208(578) -0.206 -0.076
(?-Chlorobenzene 1-Chloronaphthalene
-0.195 -0.199 -0.198 -0.197 -0.188 -0.195 -0.1957 -0.193 -0.192 -0.195 -0.191 -0.214 - 0.245
Mn=
- 0.127 (403) -0.105(578)
12300 13500 18300 25200 110000 112000
-0.1967 -0.1955 -0.191 -0.1931 -0.1929 -0.1932 -0.1916 -0.1883 -0.1879 -0.190 -0.1956 -0.1961 -0.191 -0.189 -0.1967 -0.187 -0.1943 -0.193 -0.192 -0.191 -0.191
135 863 135 863 135 863 135 863 65-80 15 90 16,17 90 18 100 19 105 20,21 110 19 114 23 120 19 125 24 125 25,18 125 16 125 26 125 27 127 23 128 23 130 19 135 22 135 22 135 22 135 22 135 22 135 22 135 17,28 139 23 140 23 140 25 140 19 145 23 150 19 151 23 115 832,917 120 931 125 931 127 610
References page VII - 615
TABLE 1. cont'd dn/dc (ml/g) Polymer
Solvent
A0 = 436nm -0.215
increase with M B B B
-0.212
n-Decane
0.114
A0 = 546nm
A0 = 633nm
-0.192 -0.183 -0.192 -0.191 -0.193 -0.196 -0.188 to-0.193 0.195 to-0.192 -0.193 to-0.188 -0.189 -0.178 -0.190 -0.196 -0.177 -0.195 0.0881 0.0890 0.0901 0.0917 0.0870 0.0881 0.095 0.0915 0.0922 0.0937 0.0955 0.0971 0.0985 0.0979 0.0995 0.113
0.121
0.117
0.126
0.121
0.132
0.126
0.117
0.114
0.120
0.118
0.112 B B
0.116
Others -0.188(578)
-0.184(578)
0.114(404) 0.112(577) 0.119(404) 0.116(577) 0.123(404) 0.120(577) 0.130(404) 0.124(577) 0.119(403) 0.113(578) 0.122(403) 0.117(578)
T (0C)
Refs.
135 863,867 135 866 135 932 135 832,917,934 135 631 135 815,914 135 933 135 914 135 863,867 135 863,867 140 935,936 145 934 145 864 937,938 65 15 70 15 75 15 80 15 111 23 114 23 115 24 120 23 125 23 130 23 138 23 139 23 143 23 146 23 149 23 106 632 106 632 106 632 106 832 106 832 106 832 106 832 106 832 135 863 135 863 135 863 135 863
B p-Dibromobenzene
- 0.179
0.098 - 0.162
-0.176
-0.159
140 135 135 135 135
935 863 863 863 863
-0.165
-0.215(403) -0.172(578) -0.212(403) -0.169(578)
120 120 135 135 135 135 135 123 127 127 127 127
939 29 864 863 863 863 863 939 863 863 863 863
-0.163
-0.209(403) -0.168(578)
135 135
863 863
-0.155 B B
-0.153
- 0.184 (403) -0.159(578) -0.182(403) -0.157(578)
B 0-Dichlorobenzene
-0.078 0.078 -0.056 -0.095
-0.083 -0.078
B
-0.091
-0.081
-0.202
-0.174 -0.176
B
Diphenyl
-0.166 B B B
-0.199 -0.195
-0.173 -0.172
-0.101(403) -0.080(578) -0.099(403) -0.078(578)
TABLE 1. cont'd dw/dc (ml/g) Polymer
Solvent
B B B
;vO = 436nm -0.192
^0 = 546 nm
A0 = 633 nm
-0.167
863 863
-0.155(403) -0.127(578) -0.142(403) -0.118(578)
142 142 142 142 142
863 866 863 863 863
0.049 (403) 0.046(578) 0.050(403) 0.047 (578)
137 137 137 137
863 863 863 863
-0.220(403) -0.172(578) -0.211(403) -0.164(578)
135 135 135 135
863 863 863 863
-0.001(403) -0.001(578) 0.001 (403) 0.001 (578)
135 135 135 135
863 863 863 863
-0.075
120
931
-0.074 -0.094 -0.094 - 0.077 -0.074
- 0.091 (403) -0.075(578)
125 125 129 135 135
931 940 941 863 863
- 0.071
-0.089(403) - 0.073 (578)
135 135
863 863
50 80 81.5 81.5 95 95 100 104 105 105 105 105 105 110 116 119 125 128 138 144 135 135 135 135 135 135 135 135
15 15 30,20 25 23 23 23 23 25 21* 29* 29* 29* 23 23 23 15 23 23 23 631 746,900 863,867 863,867 864 866 863,867 863,867
-0.146
-0.129 -0.126
-0.135
-0.120 -0.116
i-Dodecanol
0.048
0.046 0.045
B B B
0.049
0.047 0.047
1 -Methylnaphthalene
-0.206
-0.177 -0.167
B B B
-0.199
-0.170 -0.159
Paraffin oil
-0.001
-0.001 -0.001
B B B
0.001
0.001 0.001
Tetralin
- 0.087 B B B
-0.085
-0.075 -0.0834 -0.0811
0.104 -0.0887
-0.0805
1,2,4-Trichlorobenzetie -0.125
-0.075 -0.0910 -0.0918 - 0.0903 -0.893 -0.0691 -0.100 -0.078 -0.072 -0.083 -0.088 -0.0866 -0.0858 -0.075 - 0.0837 -0.0813 -0.0801 -0.106 -0.116 -0.107 -0.104
B B
-0.177
Refs.
135 135
-0.126 B B B
T( 0 C)
-0.207(403) -0.163(578)
-0.158(633) Diphenylmethane
Others
-0.111 -0.105 -0.102
-0.109(488) -0.130(403) -0.108(578) -0.122(403) -0.103(578)
* Values reported erroneously as positive in these references.
References page VII-615
TABLE 1.
cont'd dn/dc (ml/g)
Polymer B increase with M Mn= 2000 18400 34000 77000 110000 Poly(hexene-l) Poly(isobutylene)
Solvent
A0 = 436nm
X0 = 546nm
A0 = 633nm
Others
- 0.109 to - 0.106 -0.1085 -0.1085 -0.1082 -0.1073 -0.1063 Cyclohexane Toluene Benzene Cyclohexane
-0.063 -0.042 -0.007
Cyclohexane Cyclohexane
0.067 0.0285 + 2.08 0.0198 + 2.29 XlO" 4 T(K) x 10" 4 7(K) 0.0991 0.0966 -0.146 -0.131 0.043 0.0374 0.1036 0.124 0.167 0.135 0.140 0.1422 0.1008 0.155 0.1066 0.1091 0.1129 0.140
0.105 0.099
Cyclohexane 1-Chloronaphthalene Decalin rc~Decane Dibutyl ether n-Heptane rt-Hexane Isoamyl isovalerate Isooctane
0.135 0.139 Toluene 1,2,4-Trichlorobenzene PoIy(I-octene) frans-poly(pentenamer) Poly(propylene)
0.001 - 0.066
Bromobenzene n-Hexane Benzene Bromobenzene n-Butyl chloride n-Butyl propionate Carbon tetrachloride 1-Chloronaphthalene
-0.122
-0.128(578)
-0.051
- 0.070 (403) -0.053(578)
- 0.054 -0.105
0.175
-0.228
0.171 -0.0497 -0.1125 - 0.0599 -0.1082 0.1101 0.0112 -0.227 -0.195
-0.227 -0.231 isotactic -0.2275 -0.195 isotactic syndiotactic
Cyclohexane Decalin n-Heptane
p-Xylene 1-Chloronaphthalene
-0.200(365) 0.023
0.1105 0.1077
n-Hexane Methylcyclohexane Toluene atactic
-0.189 -0.188 -0.2157 -0.184 0.0570
-0.211
0.1152 0.0652 -0.0368 - 0.0027 -0.0380 -0.188
-0.177
-0.183(578)
T (0C)
Refs.
135 135 135 135 135 135 25 25 25 20 25 25
914 22 22 22 22 22 858 858 956 31 32 872 956
25 135 25 35 22.5 120 25 25 25 25 25 15 25 40 25.5 25 25 135 25 135 135 30
957 867 33 34 35 35 36 37 38 38 872 38 38 38 39 32 40 867 872 867 867 41
25 25 40 25 25 25 25 125 140 145 145 125 140 145 150 25 120 30 30 25 25 25 25 25 135
894 42 42 43 43 43 43 44 25 27 45 46 28,47 48 49 42 50 51 52 42 42 42 43 43 867
TABLEI. cont'd dn/dc (ml/g) Polymer isotactic atactic
Solvent
X0 = 436 nm
1,2,4-Trichlorobenzene
A0 = 546 nm
A0 = 633 nm
-0.205 -0.123
-0.184 -0.111
-0.173
-0.121
-0.107
-0.105 isotactic
-0.102 -0.092 to -0.094
Others -0.180(578) -0.130(403) -0.109(578) -0.128(403) -0.105(578)
PoIy(I-phenyl-1-propyne)
Toluene 0.1861 0.1656 Cyclohexane 0.264 + 5.3 x 10-4(T°C-30) 0.234 + 4.7 x 10~4(T°C-30) Poly(trifiuorochloroethylene) Mesitylene 0.026 Poly(vinylcyclohexane) Cyclohexane 0.101 Cyclohexane/dioxane 0.103 (50.1/49.9, v/v) Cyclohexane/MEK 0.138 (64.6/35.4, v/v) Decalin/dioxane 0.078 (50.6/49.4, v/v) Decalin/MEK 0.075 (59.7/40.3, v/v) rt-Heptane/dioxane 0.147 (56.8/43.2, v/v) K-Heptane/MEK 0.167 (82.6/17.4, v/v) n-Hexane 0.170 THF 0.131
T( 0 C)
Refs.
135 135 135 135 135 145 25 30-45 145 25 25
867 867 867 867 867 646 979 979 53 305 305
25
305
25
305
25
305
25
305
25
305
25 25
305 305
25 25 25 25 25 25 25 25 30 65 25 25 65 25 25 25 RT 20 25 20 20 20
627 627 627 657 657 620 627 627 898 928 627 928 928 728 728 728 674 714 926 714 714 929 927 899 980 714 77 78 79 80 714 639 639 657 728 845 785 657
1.3. POLY(ACRYLIC ACID) AND DERIVATIVES Poly(acrylamide)
Acetic acid DMSO Ethanolamine Ethylene glycol
Formamide Formic acid Aq. 1% LiCl Aq. 5% LiCl Aq. IMMg(ClO 4 )I Aq. 2.8 M Mg(ClO 4 ) 2 Aq. 3 M Mg(ClO4) 2 Aq. IMNaCl Aq. IMNaCl Aq. IMNaCl Aq. 0.2MNaCl Aq. 0.2MNaCl Aq. 0.1 M NaCl Aq. 0.1 M NaCl Aq. IMNaNO 3 Aq. 0.02MNa 2 SO 4 Water
0.199 0.091 0.093
0.117 0.109 0.103 0.172
0.194 0.089 0.089 0.177 0.095-0.110 0.084 0.113 0.109
0.192 0.089 0.088
0.111 0.109
0.127 0.169
0.166 0.181
0.110 0.165 0.145 0.138 0.175 0.175 (fi) 0.156-0.159 0.186
0.182 0.172 (/x) 0.17 0.164
0.182
30 25 20 20-65
0.1869 0.185
0.182 0.149 0.163 0.195(589) 0.179
0.167
0.173 (/x) 0.160 0.187 0.183 0.170 0.169 0.162
0.172(405) 0.157 (579)
30 20 25 25 25 25 25 25 25
References page VII-615
TABLE 1. confd d/t/dc (ml/g) Polymer
Solvent
A0 = 436 nm
vt0 = 546 nm
A0 = 633 nm
Others
0.161
T ( 0 C) 25 25 25
0.185 0.146 0.142
25 23 23 25
804 926 888 927 627 924 925 620
0.149(488)
53.7
604
0.209
25
944
0.158 0.179 0.261
30 30 30 25 25
85 85 85 86 86 87 77 80 617 617 617 617 617 617 617 617 617 617 617 617 617 617 617 617 617 617 617 617 617 617 617 743 743 743 743 743 743 743 617 617 617 617 617 617 617 617 617 617 617
0.183 0.18 0.165 0.193
On aging Water containing carboxyl groups Water
0.187
0.197-0.326
Poly [N-( 1,1 -dimethyl-3-imidazolylpropyl)acrylamide] O.OlMTetrabutylammonium Poly(acrylic acid) DN = 0.102,/ = 0.10 Aqueous NaCl 0.335,0.10 0.994,0.10 Dioxane
0.090 0.088 0.140(589) 0.146 0.137
HCl 0.1 N 0.2 N Water Water/dioxane (90/10, v/v) (80/20, v/v) (60/40, v/v) (50/50, v/v) (40/60, v/v) (35/65, v/v) (30/70, v/v) (25/75, v/v) (10/90, v/v) (5/95, v/v) (1.5/98.5, v/v) - , lithium salt
- , sodium salt
Methanol a — 0 0.04 0.09 0.21 0.40 0.60 0.69 Water Water/dioxane (90/10, v/v) (80/20, v/v) (60/40, v/v) (50/50, v/v) (40/60, v/v)
Refs.
0.156 0.160 0.112 0.164 0.105 0.171 0.119 0.174 0.117 0.178 0.117 0.166 0.112 0.159 0.101 0.141 0.079 0.204 0.138 0.092 0.075 0.078 0.084
(^) (M)
00 (/z) 00 00 00 00 (At) 00 (fi) 0.191 0.198 0.199 0.233 0.235 0.251 0.224
0.231 0.246 0.126 0.258 0.100 0.238 0.073 0.219 0.082 0.203 0.069
00 {ii) 00 00 (it)
20-65 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 20 20 20 20 20 20 20 25 25 25 25 25 25 25 25 25 25 25
TABLE 1. cont'd dn/dc (ml/g) Polymer
Solvent
^0 = 436 nm (30/70, v/v)
DN = 0.2 DN-0.2 DN-0.6 DN = 0.6 DN-I DN-I DN=I Poly(benzyl acrylate)
(20/80, v/v) Aq. 0.3 M NaCl Aq. 1M NaCl Aq. NaBr (Af = COl, 0.025, 0.1) (Af = 0.5) (Af = 0.01. 0.025, 0.1) (Af = 0.5) (Af = 0.01, 0.025, 0.1) (M = 0.5) (M = 1.5) Benzene DMF
MEK
Poly(w-butyl acrylate)
Poly(rm-butyl acrylate) Poly(l,l-dihydroperfluorobutyl acrylate) Poly(WV-dimethylacrylamide) Poly(ethyl acrylate)
Acetone Benzene Chlorobenzene Cyclohexanone Dioxane n-Hexane MEK THF
X0 = 546 nm 0.184 0.066 Ox) 0.223
0.128 (/x) 0.122 0*) 0.156 Ox) 0.138(At) 0.183 Oz) 0.166 (/x) 0.140(Ai) 0.062 0.124
0.062 0.119
0.1760 0.1746 0.1746
0.1665 0.1665
A0 = 633 nm
Others
617 617 617 678 678 711
25 25 25 25 25 25 20 20 20 20 20 20 20 20 20 20 20 30 30 30 30 30 30 30
711 711 711 711 711 711 6 6 6 6 6 88 6 5 5 5 89 84 84 729 729 84 729 84 803 84 90 91 91 83 83 10,92,93 89 10 10 729 10 10,93 729 10 10 5 729 5 5 10,93 94 10 95 982 982 982 982 982
0.132(365) 0.118(578) 0.117(589) 0.116(644) 0.1653 (578) 0.1647 (589) 0.1623 (644)
-0.0292 -0.0525 0.021 (488) 0.043 (488) 0.0885 0.088(488) 0.0651 0.062 -0.0239 0.0818 0.30 0.0311 0.194 0.150
Methanol Water Acetone
1.107 0.109
Benzene Chloroform Cyclohexanone Dichloroethane Dioxane
-0.042 0.0363 0.017 (488) 0.23 0.036 0.045 (488)
DMF Ethyl acetate MEK
Poly(2-ethylhexyl acrylate)
n-Methylpyrrolidone Water Butanone rc-Heptane Tetrahydrofuran Toluene Chlorobenzene
Poly(isopropyl acrylate) isotactic, syndiotactic and Bromobenzene atactic
0.0870
0.032 0.0916 0.0856
0.0854(578) 0.088 (488) 0.0853 (589) 0.0852 (644)
0.086 0.1407 -0.027 0.131
30 25 25 25 25 25 25 20 25 25 30 25 25 30 25 25 20 30 20 20 25 30 25 25
0.101 0.096 0.070 -0.040 -0.072 -0.103
-0.0870
Refs.
25 25 25 0.159 (\x) (488) 25 0.152 (u) (488) 25 25
0.112
Toluene MEK Benzotrifluoride
T( 0 C)
60
101
References page VII-615
TABLE 1. cont'd dn/dc (ml/g) Polymer
isotactic and atactic Poly (methyl acrylate)
Solvent
TFP Acetone Acetonitrile
Benzene o-Chlorophenol m-Cresol 1,2-Dibromoethane
Dioxane
Ethyl acetate
Isoamyl acetate MEK
TFP TFP/o-chlorophenol (10/90, v/v) (26/74, v/v) (32/68, v/v) (40/60, v/v) (50/50, v/v) (70/30, v/v) (90/10, v/v) Poly(n-octadecyl acrylate)
Toluene Benzene n-Butyl acetate Carbon tetrachloride Chlorobenzene Cyclohexane n-Hexane
A0 = 436 nm
A0 = 546 nm
X0 = 633 nm
Others
0.124 0.113 0.120 0.121 0.122 0.123 0.123 0.127 -0.019 -0.056 -0.035 -0.0606 -0.0598 -0.0578 -0.0579 -0.062 0.0503 0.052 0.055 0.0524 0.0533 0.0547 0.0566 0.0940 0.0989 0.0967 0.100 0.102 0.102 0.105 0.077 0.090 0.0938
0.118 0.119 0.120 0.122 0.125
-0.560 -0.0528 -0.0532 -0.0523 0.0497 0.0515 0.0526 0.0537 0.0562 0.0920 0.0967 0.0964 0.101 0.103 0.0923
0.097 0.090 0.126 -0.050 -0.050 (M) -0.014 -0.004Gu) -0.005 - 0.016 (/i) 0.004 0.029 (/i) 0.043 0.064 Qi) 0.075 0.123 Qi) 0.102 0.135 Qi) -0.009 - 0.0505 - 0.0269 -0.0363 0.0883 0.0114 -0.0682 -0.0489 -0.0563 0.0175 0.1096 0.1292
0.0921 (578) 0.0919 (589) 0.0915 (644)
T ( 0 C)
Refs.
25 20 25 32 40 48 30 56 30 30 30 25 32 40 48 30 25 30 30 32 40 48 56 19.5 25 32 30 35 40 48 30 RT 20 20 20 30 35 30
101 89 96 96 96 96 96 96 97 916-918 916-918 96 96 96 96 916-918 96 96 97 96 96 96 96 96 96 96 96 98 96 96 97 99 5 5 5 97,100 72 916-918
30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30
916-918 916-918 916-918 916-918 916-918 916-918 916-918 916-918 916-918 916-918 916-918 916-918 916-918 916-918 97 84 84 84 84 84 84 84 84 84 84 84
TABLE 1. cont'd dn/dc (ml/g) Polymer
Solvent
A0 = 436nm
THF
A0 = 546 nm
A0 = 633 nm
T (0C)
Others
0.0702
30
84
30 30 30
84 84 84
0.1102
30 30
634 94
0.154
RT
674
0.0508 (589)
25
982
0.123
12
922 81 82 105 89 106 107 106,107 106 911 106 789
0.0898 0.0723 -0.0425
Toluene Poly(phenyl acrylate) MEK Poly(rc-propyl acrylate) MEK Poly(trimethylammoniumethyl chloride acrylate) Aq. IMNaCl
Refs.
0.183
1.4. POLY(METHACRYLIC ACID) AND DERIVATIVES Poly(allyl methacrylate) Carbon tetrachloride Poly(benzyl methacrylate-co-cyclohexylmethyl methacrylate) (1/1, (mol/mol) Di-isobutyl ketone Poly(N-terf-butylacrylamide) Methanol 0.249 0.234 0.234 Poly(/i-butyl methacrylate) Acetone 0.1249 0.1236 0.122 Benzene -0.023 -0.014 -0.024 0.015 Bromobenzene -0.084 -0.073 Bromoform -0.129 0.118 n-Butyl chloride 0.085 Carbon tetrachloride 0.026 0.027 m-Cresol/rt-heptane 0.155 (30/70, v/v) 0.358 (M) DMF Isopropanol 0.102 0.102 0.1059 0.1066 0.1068 0.1076 0.1097 MEK 0.103 0.102 0.1059 0.1046 0.104
0.1257(366)
0.016
0.1064(366) 0.097
0.100 0.169
TFP
0.067 -0.024
Toluene -0.017 Poly(terf-butyl methacrylate) n-Butyl acetate Poly(p-te/t-butylphenyl Acetone methacrylate) Chloroform/THF (90/10, v/v) (70/30, v/v) (50/50, v/v) (30/70, v/v) (10/90, v/v) Water/THF (2/98, v/v) (4/96, v/v) (7/93, v/v) (9/91, v/v)
0.09 0.183 0.110 0.107 0.120 0.100 0.130 0.129 0.133 0.206 0.164 0.266 0.142 0.124 0.208 0.143 0.177 0.194 0.192 0.205
(/x) (M) (M)
(M) (M) (M) (M) (M)
(M)
20 25 20 25 25 25 25 25 25 25 25 20 23 20 23.7 25 31 45 25 25 23 20 25 25 20 20 25
25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25
789 769 108 109 109 109 109 109 106,107 105 108 869 807 789 869 869 911 110 111 665 655 665 665 665 665 665 655 665 655 796 796 796 796 796 796 796 796
References page VII-615
TABLE 1.
cont'd dn/dc (ml/g)
Polymer Poly(cetyl methacrylate)
Poly(2-chloroethyl methacrylate) Poly(4-chlorophenyl methacrylate) Poly(cyclohexyl methacrylate)
Poly(decahydro-(3-naphthyl methacrylate) Poly(n>decyl methacrylate)
Solvent
A0 = 436 nm
Benzene rc-Butyl acetate Carbon tetrachloride w-Heptane THF
Poly(ethyl methacrylate)
Poly(n-hexyl methacrylate) Poly(2-hydroxyethyl methacrylate)
A0 = 633 nm
Others
T( 0 C)
0.02 0.095
21 30
112 113 112 112 749
25 - 0.015 0.114 0.096
Refs.
Benzene
0.0758
25
114
n-Butyl alcohol
0.098
25
762
25 25 25 25
911 115 911 856
0.054
30 25
744 744
0.163 0.157
RT RT
680 680
0.119
25 25 25 29 35 50 65 75 85 25-48 31 30 25
679 116 116 116 116 116 116 116 116 116 744 744 117
Ai-Butyl chloride Cyclohexane Toluene Cyclohexane
Cyclohexane Ethyl acetate Poly- [2-(2-diethylaminoethoxy)ethyl methacrylate] Methanol Poly(dimethylaminoethyl Methanol methacrylate) Poly(N,N-dimethylarninoethyl methacrylate Af-oxide) Aq. 0.1M NaCl Poly(«-docosyl methacrylate) o-Dichlorobenzene Tetralin
Poly(2~ethylbutyl methacrylate)
X0 = 546 nm
THF n-Amyl acetate Cyclohexane Isopropanol
0.116 0.0845 0.019 0.104 0.115
0.102 0.094 0.0935 0.093 0.091 0.088 0.084 0.076 0.0745 0.090
0.090 0.084
0.109
0.105
0.104 0.087 0.109 0.113
0.102
25 25
117 911 122 122
0.104 0.101 0.107 0.075
23 25 23 25 25 23 32.6 25 25
123 807 123 807 911 124 124 616 807 120 119 119 119 119 119 119 119 119 119 119 119 119
0.082 0.081 0.077 0.070 0.068 0.0745 0.054
MEK n-Butyl chloride Ethyl acetate Ethyl acetate/ethanol (1/4.5 - 1/6, v/v) MEK
MEK/isopropanol (1/7, v/v) Methyl cellusolve Toluene -0.009 MEK 0.105 Isopropanol 0.108 2-Chloroethanol DMF Dioxane/water (90/10, v/v) (80/20, v/v) (60/40, v/v) (40/60, v/v) (20/80, v/v) Ethanol/water (80/20, v/v)
0.105 0.106 0.048 0.076 0.076 0.083 0.066 (/it) 0.086 0.071 (/x) 0.095 0.100 (M) 0.108 0.120 Ot) 0.123 0.130(/Lt) 0.124 0.121 (At)
25 25 25 25 25 25 25 25 25 25 25 25
TABLE 1. cont'd dn/dc (ml/g) Polymer
Solvent
A0 = 436 nm (70/30, v/v) (60/40, v/v) (40/60, v/v) (30/70, v/v)
Formamide rc-Heptane/m-cresol (50/50, v/v) (50/50, v/v) Methanol Methanol/HEMA (25/75, v/v) (25/75, v/v) (35/65, v/v) (35/65, v/v) (50/50, v/v) (50/50, v/v) (62.5/37.5, v/v) (75/25, v/v) (87.5/12.5, v/v) 2-Methoxy ethanol Methyl cellusolve rc-Propanol/dioxane (85/15, v/v) (70/30, v/v) (60/40, v/v) (40/60, v/v) (30/70, v/v) rc-Propanol/water (95/5, v/v) (90/10, v/v) (80/20, v/v) (75/25, v/v) (70/30, v/v) (60/40, v/v) (50/50, v/v) (40/60, v/v) (30/70, v/v) (20/80, v/v) TFP/HEMA (50/50, v/v) Toluene/methanol (42/58, v/v) Toluene/isopropanol (38/62, v/v)
X0 = 546nm
A0 = 633 nm
Others
T (0C)
0.121 0.119 (Ai) 0.120 0.120 (jj) 0.123 0.127 (M) 0.125 0.132 Ox) 0.045 0.033 0.361 (Ai) 0.162 0.078 0.070(/Lt) 0.090 0.081 00 0.110 00 0.093 00 0.120 0.107 (M) 0.135 0.122 (Ai) 0.151 0.140 (AX) 0.091 0.095
25 25 25 25 25 25 25 25
0.105 0.108(Ai) 0.100 0.103(Ai) 0.096 0.097(Ai) 0.091 0.090(Ai) 0.087 0.086 (M) 0.110 0.105 (Ai) 0.113 0.105 (Ai) 0.115 0.106 (Ai) 0.103 00 0.119 0.109 (Ai) 0.122 0.110(Ai) 0.125 0.123 (/i) 0.128 0.138 (M) 0.131 0.149 (M) 0.135 0.153 (M) 0.105 0.083 OO 0.101 0.063 (M) 0.087 0.064 (M)
25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25
25 25 25 25 25 25 25 25 25 25 25 25 25 25 25
25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25
Refs. 119 119 119 119 119 119 119 119 120 698 698 120 726 726 726 726 726 726 726 726 726 726 726 726 769 807 119 119 119 119 119 119 119 119 119 119 121 121 121 121 121 121 120 121 121 121 121 121 121 121 121 121 121 121 121 726 726 118 118 118 118
References page VII-615
TABLE 1. cont'd dn/dc (ml/g) Polymer
Solvent
A0 = 436nm
Water/2-chloroethanol (80/20, v/v) (72/25, v/v) (70/30, v/v) (60/40, v/v) (50/50, v/v) (40/60, v/v) (20/80, v/v) Water/Hema (20/80, v/v)
(60/40, v/v)
Poly [l(2-hydroxyethyl)pyridinium methacrylate]], benzenesulfonate Aq. 0.5MKBr 0.136Ox) 0.5 M KCl 0.122(Ai) IMKCl 0.118(Ai) 2MKC1 0.113 (AX) 3MKC1 0.104 Oi) 1.86MKSCN 0.05MNaF 0.123 (Ai) 0.05MNaI 4MNaI Poly [l(2-hydroxyethyl)pyridinium methacrylate], toluenesulfonate Benzyl alcohol Benzyl alcohol/methyloc-naphthyl ether (45/55, v/v) DMF
A0 = 546nm
0.031 0.131 (M) 0.046 0.127 (/i) 0.023 0.120 Oi) 0.015 0.101 (u) 0.016 0.103 Oi) 0.020 0.091 0 0 0.034 0.066(At)
A0 = 633 nm
Others
T (0C)
25 25 25 25 25 25 25 25 25 25 25 25 25 25
Refs.
616 616 616 616 616 616 616 616 616 616 616 616 616 616
0.068
25
726
0.049 (At) 0.069 0.051 (Ai) 0.071 0.053 (At) 0.074 0.055 (Ai) 0.076 0.057 (Ai) 0.079 0.059 (Ai) 0.103
25 30 30 40 40 50 50 60 60 70 70 25
726 726 726 726 726 726 726 726 726 726 726 726
0.143 Oi) 0.104 0.144(At) 0.107 0.147(Ai) 0.109 0.149 (M) 0.111 0.151 (Ai) 0.114 0.154(At)
25 30 30 40 40 50 50 60 60 70 70
726 726 726 726 726 726 726 726 726 726 726
0.178 0.129(Ai) 0.178 0.117 Ou) 0.174 0.114 (/i) 0.167 0.108(At) 0.161 0.100(Ai) 0.119 (At) 0.118 (Ai) 0.183 0.155 (At) 0.121 0.119(Ai)
25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25
818 813 818 813 818 813 818 813 818 813 813 813 818 818 818 818
0.039 0.000
25 25
813 813
0.130
25
813
TABLE 1. cont'd d/i/dc (ml/g) Polymer
Solvent
A0 = 436nm
X0 = 546nm
0.182 0.181 0.129 Oz) 0.5 M KCl 0.182 0.121 (/*) 0.114 00 IMKCl 0.178 0.117 0 0 0.111 00 2MKC1 0.171 0.109(/u) 0.105(At) 3 M KCl 0.163 0.100(Ai) 0.097 (/i) Methanol 0.209 Methanol + 0.5MLiCl 0.205 0.5MNaF 0.186 4MNaI 0.121 0.116(Ai) 7MNaI 0.072 n-Propanol 0.159 Tetrahydrofurfuryl alcohol 0.106 TFP 0.196 Water 0.187 Poly [ 1 (2-hydroxyethyl)trimethylammonium methacrylate], benzene sulfonate Aq. 0.5 M KCl 0.101 (^) Poly[l(2-hydroxyethyl)tximethylammonium methacrylate], toluene sulfonate Aq, 0.5 M KCl 0.095 00 Poly(/V-2-hydroxypropyl methacrylamide) Aq. 0.1 M KCl 0.166 Poly(isobutyl methacrylate) Acetone 0.122 0.117 n-Butyl chloride 0.084 Toluene -0.021 Poly(isooctyl methacrylate) ^-Heptane Poly(n-lauryl methacryiate) n-Amyl alcohol 0.0744 0.0781 n-Butyl acetate 0.092 0.090 Isopropyl acetate 0.107 0.104 Poly(methacrylamide) Aq. 0.4 M Mg perchlorate 0.180 0.180 OO Water Poly(methacrylic acid) Water 0.175 Water/dioxane (95/5, v/v) 0.170 0.179 Ox) (90/10, v/v) 0.165 0.180 (JJ) (80/20, v/v) 0.163 0.200 (Ai) (70/30, v/v) 0.150 0.191 (M) (60/40, v/v) 0.150 0.196(Ai) (50/50, v/v) 0.139 0.169(Ai) (40/60, v/v) 0.134 0.155 (Ai) (35/65, v/v) 0.148 (JJ) (25/75, v/v) 0.125 0.122 (15/85, v/v) 0.115 0.109 (M) Dimethyl formamide/ 0.099 1,4-dioxane (5:7, v/v) Alcoholic LiBr 0.154 Ethanol 0.154 HCl 0.1 N 0.5N 0.137
A0 = 633nm
Others
Ethanol Aq. 0.5MKBr
T (0C) 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25
813 813 818 813 813,818 813 813,818 813 813,818 813 813,818 813 813 813 813 818 813 813 813 813 813
25
813
25
813
25 25 25 25
755 103,104 911 911 168 125 126 126 775 775 77 628 628 628 628 628 628 628 628 628 628 628 628 628 628 628 628 628 628 628 628 977
0.109 23 13 25 25 20-65 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 26.9
0.209
Refs.
25 25 0.159(589) 25
127 127 87 128
References page VII-615
TABLE 1. cont'd dn/dc (ml/g) Polymer
Solvent
A0 = 436 nm
A0 = 546 nm
A0 = 633 nm
0.045 N 0.02 N 0.001 N Methanol NaBr 0.1 M
0.140 0.134
NaCl 0.1 M NaF 0.1 M NaI 0.1 M Na 2 SO 4 0.1 M (NH4)IMo7O24O-OlM Water
0.142
Poly(methacrylie acid), sodium salt Water Water/dioxane (95/5, v/v) (90/10, v/v) (80/20, v/v) (75/25, v/v) (70/30, v/v)
0.260 0.256 0.230 (jjL) 0.240 0.189 (M) 0.250 0.154 (M) 0.252 0.121 (M) 0.238 0.108 (M)
Poly(methoxybiphenyl methacrylate) THF 0.196 50/50 Poly(methoxy-biphenyl methacrylate-co-methoxybiphenyl ethylene oxide methacrylate) THF 0.194 Poly(methoxybiphenyl ethylene oxide methacrylate) THF 0.212 50/50 Poly(methoxy-biphenyl ethylene oxide methacrylate-co-methoxy-biphenyl bis(ethylene oxide)methacrylate) THF 0.188 Poly(methoxybiphenyl bis(ethylene oxide) methacrylate THF 0.205 Poly(methoxybiphenyl methacrylate-comethoxybiphenyl tris(ethylene oxide)methacrylate) THF 0.170 Poly(methoxybiphenyl tris(ethylene oxide)methacrylate) THF 0.181 50/50 poly(methoxybiphenyl methacrylate-co-methoxybiphenyl tetrakis(ethylene oxide) methacrylate THF 0.153 Poly(methoxybiphenyl tetrakis(ethylene oxide) methacrylate) THF 0.171 Poly(methoxybiphenyl methacrylate) CHCl3 0.163 Poly(methoxybiphenyl ethylene oxide methacrylate) CHCl3 0.180 50/50 Poly(methoxybiphenyl ethylene oxide methacrylate-co-methoxybiphenyl bis(ethylene oxide)methacrylate) CHCl3 0.153 Poly(methoxybiphenyl bis(ethylene oxide) methacrylate) CHCl3 0.167 Poly(methoxybiphenyl tris(ethylene oxide) methacrylate) CHCl3 0.152 Poly(methoxybiphenyl tetrakis(ethylene oxide) methacrylate) CHCl3 0.152 Poly(2-methacryloyloxyethyl trimethylammonium chloride) 1M aqueous NaCl 0.157 Poly(2-methoxyethyl Halothane 0.125 methacrylate) MEK 0.108
J( 0 C)
Refs.
0.156(560) 20 0.162 (M) (560) 20 0.158 20-65 25 25 0.234(560) 20 0.209 (/it) (560) 20 0.213 (M) (560) 20 0.229(560) 20 0.219(^X560) 20 0.197 (M) (560) 20 0.210 (M) (560) 20 0.227 20 0.169 (/*) (560) 20 25 0.153
129 129 77 128 128 129 129 129 129 129 129 129 129 129 128 80
Others
25 25 25 25 25 25 25 25 25 25 25
628 628 628 628 628 628 628 628 628 628 628 958 958 958 958 958 958 958 958 958 958 958 958 958 958 958
25 25
971 589 589,902
TABLE 1. cont'd d/t/dc (ml/g) Polymer
Poly(methyl methacrylate)
Solvent
X0 = 436 nm
Nitrobenzene THF Toluene 1,2,4, Trichlorobenzene Acetone
A0 = 546 nm
A0 = 633
rnn
Others
-0.058 0.078 0.000 -0.067 0.1391 0.107 0.137 0.129
0.134
T( 0 C)
Refs.
25 25 25 25 27 27 23 ± 2
589 589 589 653 130 131 132 133 134
0.131
0.1313 0.136
0.1293 0.134
0.134(366)
25 25
0.132 0.132 0.1305
0.1312 Acetone
0.132
20 20 20 20 20
0.135 0.1292 0.1330 0.135
20 20 25 25
0.1285
0.1281 (578) 0.1279(589) 0.1276(644)
25 25 20 25 25 25 25 25
137,138 139 140,141 759 618 689 947 142 141 141 141 141 141
0.1170 0.1005 0.091 0.0861 0.0734
25 25 25 25 25 20
140 140 140 140 140 626
0.133 0.137
25 20 44
721 136 947
0.094 0.078 (/J,) 0.100 0.085 (/x) 0.110 0.097 (iji) 0.119 0.113(/i)
25 25 25 25 25 25 25 25 25
726 726 726 726 726 726 726 726 726
0.034 0.033 (IJ,)
25 25
726 726
0.074 0.115(A*) 0.059 0.104 (At) 0.044 0.084 (Ai) 0.027 0.050 (Ai)
25 25 25 25 25 25 25 25
825 825 825 825 825 825 825 825
0.130 0.129 M w >5060 isotactic
Af w >10 4
Acetone Acetone Acetone/benzene (88/12, (76/24, (64/36, (52/48, (40/60, Acetone/chloroform (80/20, v/v) (60/40, v/v) (52/48, v/v) (40/60, v/v) (20/80, v/v) Acetone/water (62.2/37.8, mol) Acetonitrile Acetonitrile Acetonitrile/MMA (17/83, v/v) (32/68, v/v) (50/50, v/v) (68/32, v/v) Acetophenone/MMA (50/50, v/v) Acetophenone/isopropanol (30/70, v/v) (40/60, v/v) (50/50, v/v) (60/40, v/v)
0.134 0.136 v/v) v/v) v/v) v/v) v/v)
0.134 0.1170 0.1005 0.0861 0.0734 0.0590
0.136 0.140 0.144
135 10,136 92 89 5 5 5 93
References page VII-615
TABLE 1. cont'd dn/dc (ml/g) Polymer
Solvent
A0 = 436 nm
(70/30, v/v)
XQ = 546 nm
A0 = 633 nm
Others
0.017 0.030 (/x) 0.001 0.005 Ox) -0.012 -0.012Ox)
(80/20, v/v) (90/10, v/v) Arochlor Benzene
-0.124 0.0398
T( 0 C)
Refs.
25 25 25 25 25 25 20 27
25 20 30 25 25 25 25 25 25 25 25 25
825 825 825 825 825 825 144 130 145 146 139 147 148 10 6 677 689 726 726 726 726 726 726 726 726
25 25 25 25 25 25 25 25 25 25 25 25
782 782 782 782 782 782 782 782 782 782 782 782
25 25 25 25 25 25 25 25 25 25 25 25 25 25
-0.010 0.002 0.0039
25 25
0.0110 0.004 -0
0.001 0.006
-0.016 0.007 0.015
Benzene/MMA (30/70, v/v) (50/50, v/v) (70/30, v/v) Benzyl alcohol/MMA (50/50, v/v) Benzyl alcoholM-butanol (90/10, v/v)
0.061 0.054 0.046 0.044 0.033 0.032 0.026 0.027 -0.036 -0.034 0.012 0.017 0.016 0.024 0.030 0.043 0.041 0.060 0.057 0.084
(80/20, v/v) (70/30, v/v) (60/40, v/v) (50/50, v/v) (40/60, v/v) Benzyl alcohol/sec-butanol (90/10, v/v)
00 00 (/x) (/Lt)
0*) (/x) (/x) (/x) (M) Ox)
-0.037 - 0.070 (/x) 0.011 -0.012 (AX) 0.012 0.013 00 0.029 0.082 (M) 0.040 0.160 Ox) 0.056 0.254 Ox) 0.074 0.316 Ox) — 0.058
(80/20, v/v) (70/30, v/v) (60/40, v/v) (50/50, v/v) (40/60, v/v) (30/70, v/v) Bromobenzene
0.056
25 25
782 782 782 782 782 782 782 782 782 782 782 782 782 782 145 624 825
0.196 Ox) 0.036 0.166 (M) 0.019 0.136 (M)
25 25 25 25 25
825 825 825 825 825
- 0.050 Bromoform/isopropanol (30/70, v/v) (40/60, v/v) (50/50, v/v)
TABLE 1. cont'd d/t/dc (ml/g) Polymer
Solvent
^ 0 = 436 nm
(60/40, v/v) (70/30, v/v) (80/20, v/v) (90/10, v/v) Bromoform/acetophenone/ isopropanol 1 -Bromonaphthalene 2-Butanol n-Butyl acetate
X0 = 546 rim
0.002 0.092 -0.017 0.034 00 -0.036 -0.031 00 -0.059 - 0.067 00 Values for numerous solvent ratios given in reference - 0.147 -0.148 0.0802 + 0.0004 * T (0C) 0.0987 0.0970 0.0986 0.0969 0.1 0.0970 0.097
syndiotactic rc-Butyl acetate/chloroform (20/80, v/v) (40/60, v/v) (60/40, v/v) (80/20, v/v) (90/10, v/v) n-Butyl chloride 0.0913 0.0948 0.0984
/I 0 = 633 nm
Others
fa)
0.063 0.070 0.073 0.083 0.094 0.0898 0.0934 0.0970 0.096
0.098 0.0931 0.1021 0.1001 0.0902 0.0965
syndiotactic isotactic n-Butyl chloride/toluene (83/17, v/v) (56.9/43.1, v/v) (32.1/67.9, v/v) (20/80, v/v) Carbon tetrachloride
Refs.
25 25 25 25 25 25 25 25
825 825 825 825 825 825 825 825 825
25 55 < T < 76 0.101 (366) 25 25 25 25 25 0.096 25 0.096 25 0.097 25
0.093 atactic
T ( 0 C)
0.0914 0.1001 0.0986 0.0875 0.0954
0.080 0.058 0.035 0.026
25 25 25 25 25 20 30 40 40 25 40 25 50 50 25 50
802 802 802 802 802 143 143 143 615 721 731 150 150 150 150 150
25 25 25 25
911 911 911 911 145 677 145 697 689 146 148 955 135 134
0.023 0.033
Chlorobenzene
30 -0.026
- 0.004 -0.010 -0.018
35 25 25
- 0.026 1-Chlorobutane Chloroform
0.098 0.0631
0.0629
0.0630
0.0628
0.0635 (366) 0.056
40 25
25 0.050
0.059 0.056 Cyclohexanone o-Dichlorobenzene
0.062 0.059 0.046 -0.037
145 9 954 135 139 113 149 670 689 802 742
25 30 25 25 30 25
139 148 10,140 677 689 802 729 689
References page VII - 615
TABLE 1. cont'd dn/dc (ml/g) Polymer
Solvent
A0 = 436 nm
1,2-Dichloroethane
0.050 0.050
A0 = 546 nm
A0 = 633 nm
Others
0.051 30 0.050 0.046 0.079
Dioxane 0.0720
T( 0 C)
0.075 0.0707 0.068 0.071
0.050
25 30 25
0.074(366)
25
0.0703 (589)
25 25 25
0.07 0.070 0.066 0.0707 0.072 (488) 0.068 0.069 Dioxane/water (95/5, v/v) (90/10, v/v) (85/15, v/v)
(82/18, v/v) DMF
0.0600
0.070 0.072 0.076 (/z) 0.076 0.083 Oi) 0.079 0.072 0.090(Ai) 0.090 0.082 (^) 0.096 OLO 0.0614
0.0617 (578) 0.0168 (589) 0.0619 (644) 0.055 (365)
0.055 0.069 0.095
25 25 30 25 25 25 25 25 25 25 25 25 30 25 25 20 20 20 20 25 30 90
0.042 0.060
0.058 0.086 0.058 0.063
Polymer modified with RCH 2 Li R = SC 6 H 5 R = SO 2 CH 3 R = SO 2 N(CH 3 ) 2 Ethyl acetate
0.079-0.096 0.1200
0.070-0.081 0.075-0.107 0.1180
0.123(366) 0.1174 (589)
0.118
20 30 25 25 25 25 25 25 25 25
0.118 isotactic
0.117 Furfuryl alcohol H-Heptane/m-cresol (50/50, v/v) Isoamyl acetate
0.0931 0.0945 0.0959 0.0974
MEK
0.138 0.116 0.010 0.040 0.349 (/x) 0.0911 0.0926 0.0942 0.0957 0.111 0.112
25 30 25 30 25 25 20 30 40 50 RT
0.093 0.111
Refs. 151 152 147 10 826 689 154 135,139 145 93 155 121,147 148 10 156,157 729 618 689 807,822 121 121 121 121 121 118 118,121 158 121 121 5,6 5,6 5,6 6 10 159 159 148 897 826 807 689 700 700 700 135,139 155 10 618 771 826 720 691 698 698 143 143 143 143 154 160 131 134
TABLE 1. cont'd dn/dc (ml/g) Polymer
Solvent
A0 = 436 nm
A0 = 546 nm
A0 = 633 nm
Others
0.1173
RT RT
0.100 0.1131
0.1112
0.113
0.111 0.117
0.110 0.1110(578) 0.1107(589) 0.1102(644)
0.111 0.111 0.110 0.108 0.01385 0.111(488) 0.114
30 30
0.059 0.131 0.113 0.1147
35 35 25 25 30 20 10 20 30 40 30 30 30 20
0.113 0.111
atactic syndiotactic isotactic
(55/54, v/v) MEK/2-propanol (43.6/56.4, mol/mol) 2-Methoxy ethanol Methyl cellusolve MMA/styrene (50/50, v/v)
0.110 0.1090 0.1130 0.1167 0.1208 0.1169 0.1165 0.1167 0.109
2-Propanol/isopropylamine (5.6/94.4, mol/mol) TFP TFP/water (92/5, v/v)
40 25 25 25 30 25
0.082 0.025 0.025 (/a) 0.075 0.0176 0.100 0.094
25 20
0.109
(90/10, v/v) (80/20, v/v) (70/30, v/v) (65/35, v/v) THF
0.112 0.134 0.108 0.1075 0.1114 0.1153 0.1192 0.1153 0.1155 0.1152
0.089
Methyl methacrylate /V-Methylpyrrolidone Nitroethane
0.0887 0.0886
20 20 20 23db2 25 25 25 25 25 27 28
0.113 0.111
0.113
MEK/isopropanol
T( 0 C)
0.141 0.141 0.140 (M) 0.139 0.137 (M) 0.135 0.131 (M) 0.133 0.124 (/i) 0.132 0.121 (ILL) 0.0871 0.0870 0.0902
0.091 (366)
25 25 25 25 25 25 25 25 25 25 25 25 25 36
0.09 0.087 0.098 0.086
25 25
Refs. 163 99 148 5,6,88 5 5 132 162 146 132,161 10,93 165 130 134 151 145 152 164 153 147 34 72 689 807 826 897 143 143 143 143 150 150 150 626 731 807 726 726 158 10 154 161 626 121 121 121 121 121 121 121 121 121 121 121 135 139 34 166 618 637 689
References page VII-615
TABLE 1. contfd dw/dc (ml/g) Polymer
Solvent
A0 = 436 nm
A0 = 546 nm
M v v >10 4 atactic isotactic varying tacticities
A0 = 633 nm
Others
0.110-0.114 0.084 0.086 0.084-0.088 THF/cyclopentane (65.7/34.3, mol/mol) Toluene
0.089
25 25 25 20
0.004 0.010 0.0094
30 25 25
0.0157 0.004 0.005 0.003
0.004 0.009 0.014 -0.003 0.001 0.003 0.007 0.010 0.007 0.014
atactic syndiotactic isotactic Toluene/methanol (42/58, v/v) Toluene/isopropanol (38/62, v/v) Toluene//?-cymene (73.4/26.6, w/w) (49.7/503, w/w) Benzene
0.094 0.152 (/x) 0.096 0.154 (M) 0.073 0.121 (/i) 0.006 0.008 0.133
Poly(o-methylphenylthio methacrylate Poly((3-naphthyl Benzene methacrylate) Poly(nonyloxy-1,4-phenyleneoxycarbonylphenyl methacrylate) Carbon tetrachloride Poly(//-octadecylacrylamide) Benzene Chlorobenzene Cyclohexane rc-Hexane
Poly(rc-octyl methacrylate) Poly(4-phenylbutyl1 -methacrylate) Poly(2-phenylethyl1-methacrylate) Poly(phenyl methacrylate)
THF Toluene rc-Butanol MEK 1-Chloroundecane
0.083 0.107
0.133 0.142 0.096
Poly(phenylthiol 0.142 methacrylate) Poly[2-(3-sodium sulfonato-2-methylpropyl) methacrylamide] Aq. 0.05MNaCl 0.142 (/x) Aq. 5 M NaCl 0.097 (jx) Poly(3-sodium sulfonatopropyl methacrylate) Aq. 0.01 M NaCl 0.11 Aq. 0.1 M NaCl 0.13 Poly(n-stearyl methacrylate) Cyclohexane rt-Propyl acetate 0.107
Refs. 984 811 811 686 626
152 146 139 153 147 30 691 30 697,699,834 50 699 70 699 15 834 20 834 25 834 25 911 25 146 25 146 25 146 25 118 25 118 25 167 25 167 25 118 25 118 30 30 35
699 699 666
25
856 890 84 84 84 84 84 84 84 169 169 965
0.100
0.105(488)
24 30 30 30 30 30 30 30 16.8 28 23
0.128
0.134(488)
27.5
965
25 35
170 115 666
RT RT
701 701
25 25 20 36
824 824 744 744
0.0269 0.0489 0.0651 0.1292 0.1168 0.0898 0.0154 0.080 0.107
1-Chloroheptane Acetone MEK Benzene
T( 0 C)
0.234 0.182
0.054
TABLE 1. cont'd d/i/dc (ml/g) Polymer
Solvent
A0 = 436nm
Poly(tetrahydro-4H-pyranyl- THF 2-methacrylate) Poly(rc-tridecyl methacrylate) Ethyl acetate THF Poly(3-trimethylammonium ethyl chloride methacrylate) Aq. IMNaCl
A0 = 546nm
A0 = 633nm
Others
T (0C)
Refs.
0.092
20
840
0.083
27 30
744 744
0.121 0.157
0.155
0.154
25
882
0.158 (/Lt)
0.155(AX)
0.154(/Lt)
25
882
25
770
Poly[2-(triphenylmethoxy)ethyl methacrylate] Dioxane
0.180
1.5. OTHER a OR p SUBSTITUTED POLY(ACRYLICS) AND POLY(METHACRYLICS) Poly[bis(phenylethyl) itaconate] Poly[bis(phenyl-«-propyl) itaconate] Poly(ter/-butyl crotonate)
MEK
0.180
20
738
MEK
0.173
20
738
0.083 0.111 0.074 -0.035 0.018 0.036 0.102 0.096 -0.027 0.183 0.109 0.074 -0.030 0.020 -0.050 0.036 0.101 -0.021 0.101 0.096 0.112 -0.077 -0.023 0.109 0.126 0.058 -0.005 0.132 0.017 0.079 -0.041 0.015 -0.032 0.074 -0.018 0.024 0.100 0.096 -0.014 0.075 -0.037 -0.036 0.017 0.035 0.102 0.102
25 25 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20
718 718 102 102 102 102 102 102 102 738 102 102 102 102 102 102 102 102 102 102 102 102 102 763 763 763 763 763 763 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102
H-Butyl chloride Ethyl acetate Poly(di-fi-amyl itaconate) rc-Amyl acetate Benzene Carbon tetrachloride Chloroform Ethyl acetate MEK Toluene Poly(dibenzyl itaconate) MEK Poly(di-rc-butyl itaconate) Acetone n-Amy\ acetate Benzene Carbon tetrachloride Chlorobenzene Chloroform Ethyl acetate Ethylbenzene N-Hexane MEK Methyl acetate Styrene Toluene Poly(di-cyclohexyl itaconate) n-Amyl acetate H-Butyl acetate Carbon tetrachloride Chlorobenzene K-Propyl acetate Toluene Poly(di-K-decyl itaconate) n-Amy\ acetate Benzene Carbon tetrachloride Toluene Poly(diethyl itaconate) w-Amyl acetate Benzene Carbon tetrachloride Ethyl acetate MEK Toluene Poly(di-n-heptyl itaconate) w-Amyl acetate Benzene Benzene Carbon tetrachloride Chloroform Ethyl acetate Ethyl acetate
References page VII - 615
TABLE 1. cont'd dn/dc (ml/g) Polymer
Poly(dimethylitaconate)
Solvent MEK MEK Toluene Toluene Acetone Benzene Chlorobenzene Chloroform MEK Methyl acetate MEK
A0 = 436 nm
PoIy(AM,1-dimethyl3-oxobutylacrylamide) Poly(di-n-nonyl itaconate) rc-Amyl acetate Benzene Toluene Poly(di-rc-octyl itaconate) rc-Amyl acetate Benzene Carbon tetrachloride Chloroform Ethyl acetate MEK Toluene Poly(diphenyl itaconate) Benzene Chlorobenzene Ethyl acetate MEK Styrene Toluene Poly(di-n-propyl itaconate) n-Amyl acetate Benzene Carbon tetrachloride Chloroform MEK Toluene Poly(di-n-undecyl itaconate) n-Amyl acetate Benzene Carbon tetrachloride Chlorobenzene Chloroform Ethyl benzene rc-Hexane Styrene Toluene Poly(methyl a-chloroacrylate) Chloroform Poly(methyl n-butacrylate) n-Butanol MEK Poly(methyl ethacrylate) Diisobutyl ketone MEK 1.6.
A0 = 546 nm
A0 = 633 nm
Others
T( 0 C)
Refs.
0.095 0.095 -0.029 -0.028 0.118 0.000 -0.022 0.041 0.096 0.110 0.137
20 20 20 20 20 20 20 20 20 20 25
102 102 102 102 102 102 102 102 102 102 622
0.079 -0.030 -0.039 0.078 -0.039 0.016 0.033 0.105 0.096 -0.030 0.083 0.060 0.191 0.189 0.040 0.087 0.074 -0.025 0.021 0.036 0.096 -0.019 0.079 -0.042 0.014 -0.064 0.030 - 0.030 0.112 -0.088 -0.032 0.072 0.0878 0.1192 0.0791 0.1357
20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 13 30 11.4 30
102 102 102 102 102 102 102 102 102 102 768 768 768 768 768 768 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 707 286 286 286 286
0.139
25
654
0.0643
25
974
0.0344
25
974
0.0368
25
974
0.0391
25
974
0.0443
25
974
POLY(STYRENES)
Poly(4-acetoxystyrene) Dioxane Poly(4-acetoxymethyl styrene) Toluene Poly(0.05 wt.% 4-acetoxymethyl styrene-co-0.95 Toluene Poly(0.10 wt.% 4-acetoxymethyl styrene-c-0.90 Toluene Poly(0.20 wt.% 4-acetoxymethyl styrene-co-0.80 Toluene Poly(0.35 wt.% 4-acetoxymethyl styrene-co-0.65 Toluene
wt.% tert-butyloxy carbonyloxy styrene) wt.% terf-butyloxy carbonyloxy styrene) wt.% tert-butyloxy carbonyloxy styrene) wt.% terf-butyloxy carbonyloxy styrene)
TABLE 1. cont'd d/i/dc (ml/g) Polymer
Solvent
X0 = 436nm
X0 = 546nm
PoIy(0.50 wt.% 4-acetoxymethyl styrene-co-0.50 wt.% tert-buiy\oxy carbonyloxy styrene) Toluene Poly(/?-?m-butylstyrene) Cyclohexane 0.139 1-Nitropropane 0.162 Poly(tf-chlorostyrene) MEK 0.191 Poly(/?-chlorostyrene) Benzene 0.095 Chloroform 0.157 Dioxane 0.164 MEK 0.207 0.197 Toluene 0.121 PolyOModostyrene) Dioxane 0.156 0.144
14% iodine 27% iodine Poly(p-isopropylot-methylstyrene) Poly(/7-isopropylstyrene)
Poly(p-isopropylstyrene) hydroperoxide Poly (p-methoxy styrene)
Poly(a-methylstyrene)
A0 = 633nm
0.0486
Chloroform MEK THF MEK THF Benzene/cyclohexanol (61.19/38.81, v/v) Benzene/methanol (73.69/26.31, v/v) Chloroform/cyclohexane (36.08/63.92, v/v) Chloroform/methanol (66.49/33.51, v/v) MEK/n-heptane (80.01/19.99, v/v) MEKAi-propanol (80.64/19.36, v/v) Toluene Toluene/cyclohexanol (62.8/37.2, v/v) Benzene
0.084 0.134 0.198 0.177 0.195-0.203 0.177
0.105
0.124 0.186 0.167 0.184-0.197 0.167 0.112
Carbon tetrachloride Cyclohexane
1,2-Dichloroethane Toluene
Toluene Acetone/cyclohexane (26.6/73.4, v/v)
776 187 187 188 187 189 175
0.163
175
0.190
175
0.211
175
0.215
175
0.101 0.113
0.168
0.193(366)
0.192
0.219(366)
0.126
0.135(366) 0.129 0.137
0.137 Poly(;?-methylstyrene) Poly(styrene)
974 778 778 765 171 171 171 172 173 174 174 174 174
175
0.1165 0.131 0.1307 0.130
Refs.
0.125
0.138
Poly(a-methylstyrene)
20 35 20 20 20 20 874 874 25 25 25 25 25 25
0.1238 0.134 0.131 0.178 0.206 0.208 0.199 0.200 0.1967 0.210 0.212 0.214 0.204 0.1764
T (0C)
25 35 35 25
0.166(365) 0.143 (578) 0.142(589) 0.140(644) 0.032 0.050
Bromoform Toluene
Others
0.093 0.192
25
176 175
25 25 30 30 23 32 36 37 39 39 40 45 50 35 25 23 25 25 23 25 25 20
177 178 179 180 181 183 183 182 179 177 183 183 183 181 177 34 184 177 181 185 186 613 976
25
783
References page VII - 615
TABLE 1. confd dn/dc (ml/g) Polymer
Solvent (38.2/61.8, v/v) (49.1/50.9, v/v) (59.1/40.9, v/v) (68.4/31.6, v/v) (77.2/22.8, v/v) Isoamyl acetate n-Amy\ acetate Arochlor Benzene
A0 = 436 nm
A0 = 546 nm
A0 = 633 nm
Others
0.202 0.207 0.214 0.220 0.225
T( 0 C) 25 25 25 25 25 30 20
0.205 0.205 -0.017 0.1151 0.111 0.1066 0.113 0.1066
0.115 0.108 0.109 0.112
0.1034 0.1034
0.1030(578) 0.1028(589) 0.1021 (644)
0.105 0.105 0.109 0.107(589)
0.109 0.110
20 20 20 20 20 20 25 25 25 25 25
0.115 0.108 0.1025 0.108 0.1094
25 25 25
0.1062 0.106 0.105
25 25 25
0.111 0.106 0.113
28 30
0.109 0.106 0.101 0.115 0.1123 0.112 0.131 0.107
0.103 0.111 0.105
0.109
0.106 0.103 0.106 0.109(488)
increase with M: M = 1.3 x 103 - 1.3 x 105 M> 1.05 XlO 6 star shaped star shaped comb shaped
0.093-0.109 0.091-0.106 0.108 0.104 0.126 0.104-0.109 0.102 0.116 0.113 0.112
30 30 30 35 70 20 25 25 25 25 25 25 25 25 25 25 35 25 30 30 30 35
0.105 Benzene Benzene/bromoform (95/5, v/v) (90/10, v/v) (85/15, v/v)
0.0495 -f 2.20 x 10 " 4 T(K) 0.101 0.096 0.099
25 25 25
Refs. 783 783 783 783 783 97 102,190 144 191 102 6 203 5 5 5 205 106 107 32 206 193 194 57 195 146,197 139 148 10 198 145,196, 199,201 192 204 147 97 200 84 202 203 709 664 593,705 779,751 774 890,647 812 648 612 612 612 683 612 671 677 821 683 618 962 198 198 198
TABLE 1. cont'd d/i/dc (ml/g) Polymer
Solvent
X0 = 436 nm
(75/25, v/v) (50/50, v/v) (25/75, v/v) Benzene/(CH 2C1)2CHOH (33/67, v/v) Benzene/cyclohexane (82.9/18.1, mol/mol) (65.3/34.7, mol/mol) (44.8/55.2, mol/mol) (23.6/76.4, mol/mol) (10/90, mol/mol) (4.8/95.2, mol/mol) (90/10, v/v) (80/20, v/v)
0.083 0.074 0.036
0.137 0.155 0.155 0.172 0.170 0.186 0.183 0.197 0.189 0.202 0.191 0.116 0.126 0.138 0.142 {(i) 0.135 0.144
(50/50, v/v)
0.151
v/v) v/v) v/v) v/v)
(10/90, v/v) Benzene/cyclohexanol (61.6/38.4, v/v) (81.8/18.2, mol/mol)
A0 = 633 nm
Others
T ( 0 C)
25 25 25 0.112
(75/25, v/v) (70/30, v/v) (60/40, v/v)
(40/60, (35/65, (30/70, (20/80,
A0 = 546 nm
0.150 0.159 (M) 0.158 0.165 0.171 0.166 0.175 (/i) 0.175
0.121 0.134 (90.9/9.1, mol/mol) 0.119 (99.628/0.372, mol/mol) 0.124 0.134 Benzene/rc-docosane (98.7/1.3, mol/mol) 0.122 0.140 (95.7/4.3, mol/mol) 0.135 0.147 (90.3/9.7, v/v) 0.147 0.150 Benzene/rt-dodecane (96.2/3.8, mol/mol) 0.123 0.139 (92.7/7.3, mol/mol) 0.131 0.145 (86.4/13.6, mol/mol) 0.140 0.149 Benzene/1 -dodecanol (98.1/1.9, mol/mol) 0.116 (94.6/5.4, mol/mol) 0.122 (89.7/10.3, mol/mol) 0.132
0.113 0.120 0.124 0.129 0.135 0.137 0.142 0.145 0.148 0.153 0.154 0.158 0.162 0.162 0.108
Refs.
198 198 198 207
20 70 20 70 20 70 20 70 20 70 20 20 20 30 30 25 20 20 25 20 25 30 30 20 25 20 20 25 30 30 20
208 208 208 208 208 208 208 208 208 208 208 709 709 692 692 751 709 709 751 709 751 692 692 709 751 709 709 751 692 692 709
25 20 70 20 20 70
209 208 208 208 208 208
20 70 20 70 20 70
210 210 210 210 210 210
20 70 20 70 20 70
210 210 210 210 210 210
20 20 20
210 210 210
References page VII - 615
TABLE 1. cont'd dn/dc (ml/g) Polymer
Solvent
X0 = 436 nm
Benzene/ethanol (70.4/29.6, v/v) (70.4/29.6, v/v) (94.3/5.7, v/v) (89.1/10.9, v/v) (62.1/37.9, v/v) BenzeneM-heptane (44/56, v/v) (90/10, v/v) (50/50, v/v) (60/40, v/v) BenzeneM-hexane (88/12, mol/mol) (78.6/21.4, mol/mol) (63.2/36.8, mol/mol) (55.1/44.9, mol/mol) Benzene/1 -hexanol (92.7/7.3, mol/mol) (84.9/15.1, mol/mol) (76.6/23.4, mol/mol) (67.8/32.2, mol/mol) Benzene/MEK (25.1/74.9, mol/mol) (50.2/49.8, mol/mol) (75.1/24.9, mol/mol) Benzene/methanol (70.9/29.1, mol/mol) (83.9/16.1, mol/mol) (92.4/7.6, mol/mol) (22.2/77.8, v/v) (76.6/23.4, v/v) (80/20, v/v) (74.7/25.3, v/v) (95/5, v/v) (80/15, v/v) (83/17, v/v) (80/20, v/v) (78/22, v/v) (76.8/23.2, v/v) (76.8/23.2, v/v) (75/25, v/v) Benzene/1-octadecanol (99.15/0.85, mol/mol) Benzene/poly(oxyethylene) 420 (95.9/4.1, mol/mol) 2100 (99.41/0.59, mol/mol) Benzene/isopropanol (35.8/64.2, v/v) (65/35, v/v) (61/39, v/v) (64/36, v/v)
A0 = 546 nm
A0 = 633 nm
Others
T( 0 C)
Refs.
0.156 0.155 0.115 0.119 0.131 0.162 0.151
19.6 25 20 20 70 20 70
611 611 210 210 210 210 210
0.130 0.124
35 35 25 25
211 202 751 751
0.141 0.160 0.174 0.188 0.199 0.197 0.205
20 20 70 20 70 20 70
210 210 210 210 210 210 210
0.119 0.126 0.135 0.136 0.148 0.144
20 20 70 20 20 70
210 210 210 210 210 210
0.210 0.224 0.178 0.193 0.145 0.162
20 70 20 70 20 70
203 203 203 203 203 203
0.154 0.124 0.114
20 20 20 25 25
0.116 0.134
35 25 25 25 25 25 16.7 25 25 20 70
208 208 208 209 193 207 211 751 751 751 751 751 611 611 751 210 210
0.125
20
210
0.120
20
210
25
212 207 211 692 692
0.157 0.152
0.145 0.122 0.137 0.159 0.114 0.127 0.132 0.136 0.141 0.190 0.187 0.144
0.159 0.154 0.142 0.150 0.216 (jui)
35 30 30
TABLE 1. cont'd dn/dc (ml/g) Polymer
Solvent
X0 = 436nm
Benzene/rc-propanol (63.7/36.3, v/v) Bromobenzene
0.131 0.130 0.0492 0.043 0.0495
X0 = 546nm
A0 = 633nm
Others
0.042 0.0485 0.0455
0.042
Bromoform
- 0.005 0.012
611 611 213 106 107 214
25
0.012
1-Bromonaphthalene
30 -0.051 -0.091 -0.0517 0.1997 0.2018
25 25 25 20 25
0.156 0.161 0.159 0.160
0162 0.159
0.144 0.146 0.147 0.150 0.1518 0.148
0.145 (589)
0.148 015
0.162 Poly(styrene) anionically polymerized
21.7 29.7 18 25
25 30
0.014
n-Butyl chloride rc-Butyl propionate Carbon tetrachloride
Refs.
25 25
0.047 0.015 0.014
T (0C)
Carbon tetrachloride Carbon tetrachloride/ 0.176 n-butanol (65/35, v/v) Carbon tetrachloride/ 0.189 rc-heptane (53/47, v/v) Carbon tetrachloride/ methanol (18.3/81.7, v/v) Chlorobenzene 0.0833 0 082
O145
25 25 30 30 35 25 25 30
145,215 624 57 106 216 874 216,919 145 57 9 43 43 102 217 154 145 106 206 84 204 202
647 651 677
oc
¥\ ^??
is
911
0.162
9c
onQ
0 079 '
IR
25
^
S
Jn
213
Z
0.079
0.0848
Il 0.079
°081
0.083 Chlorobenzene/isopropyl ether (68/32, v/v) 1 -Chlorodecane l-Chlorodecane/3-methylcyclohexanol
(782/21.S1V(V) (75/25, v/v) (49.5/50.5, v/v) (10/90, v/v) Chloroform
2
H 148
„
™ 697
0192 '
25
209
6 2
661
0.165
228
66.
0.168 0.166 0.155
35 59 6 87;8
0.165 '
0.158 0.1554 0.165
I8 20 25
0.169 0.152 0.161 0.157
25 30
^
1
661
^1 57 213 102 26 148 146 677
References page VII-615
TABLE 1. cont'd dn/dc (ml/g) Polymer
Solvent Cyclohexane
M w = 2.18 XlO 3 2.92 XlO 3 4.69 XlO 3 11.8 x l O 3 22.2 XlO 3 167 x l O 3
A0 = 436 nm 0.1795 0.1798 0.1801 0.1804 0.1810 0.168 0.171 0.174 0.177 0.180 0.181 0.1825 0.181 0.1840
A0 = 546 nm
A0 = 633 nm
Others
0.1682 0.1685 0.1687 0.1690 0.1695 0.156 0.160 0.163 0.165 0.167 0.167 0.1709 0.1723 0.171 0.179 0.1738 0.1752 0.181 0.163
0.179 0.181
M = 1.2 x 103 - 1.07 x 105 star shaped after photoisomerization: trans —> cis
0.191 0.181 0.181
0.166 0.170 0.169 0.171 0.169 0.156-0.168 0.157-0.163 0.100
0.181 0.171 0.175 (488) 0.181 0.184 0.161 0.168 0.170 Cyclohexane Cyclohexane/cyclohexanol (75.3/24.7, v/v) -0.043 -0.044 -0.045 -0.046 -0.047 (37.3/62.7, v/v) -0.048 -0.049 -0.050 -0.051 Cyclohexane/ethanol 0.065 (97/3, v/v) 0.064 Cyclohexane/ethyl acetate (10/90, v/v) 0.229 (20/80, v/v) 0.226 (30/70, v/v) 0.223 (40/60, v/v) 0.219 (50/50, v/v) 0.216 (60/40, v/v) 0.211 (70/30, v/v) 0.206
0.187 0.191 0.195
0.216 0.213 0.210 0.206 0.202 0.197 0.191
Refs.
20 21 22 23 25 25 25 25 25 25 25 30 34.5 35 35 35 40 40 45 50
0.181 0.1855 0.1870 0.188
T( 0 C)
219 219 219 219 139,219 220 220 220 220 220 220 219 221 219 209 202,222 218 219 219 223 224 618 20 709 25 647 25 751 30 677 34.5 712,705 34.5 809 34.5 732 34.5 737 28 736 34.8 611 34.8 664 35 642 35 659,694,704 35 661 35 671 35 683 35 683 30 943 40 943 50 943 36 38 44 52.2 58.2 65.1 74 82 86 29.2 39.8
611 611 611 611 611 611 611 611 611 611 611
20 20 20 20 20 20 20
709 709 709 709 709 709 709
TABLE 1. cont'd dit/dc (ml/g) Polymer
Solvent (80/20, v/v) (90/10, v/v) Cyclohexane/methanol (95.5/4.5, v/v) Cyclohexane/w-propanol (97.6/2.4, v/v) Cyclohexane/styrene (15/85, v/v)
A0 = 436nm 0.198 0.189 0.099 0.098 0.041 0.040
(40/60, v/v) (50/50, v/v) (60/40, v/v) (70/30, v/v) (85/15, v/v)
Cyclohexanone Cyclohexene Decalin
A0 = 633nm
Others
0.184 0.176
0.075 0.086 0.092 0.112 0.104 0.129 0.120 0.152 0.129 0.160 0.138 0.166 0.155 0.173
(30/70, v/v)
Cyclohexanol
A0 = 546nm
(M) (/i) Cu) (M) (M) (M)
(ji)
0.165 0.141 0.169 0.169 0.151 0.151 0.151 0.165 0.129 0.129 0.118 0.137 0.138 0.143 0.147 0.152 0.155 0.120 0.125
0.119 0.137 0.141 0.120 0.120 0.120 50 bar pressure 50 bar pressure 50 bar pressure cw-Decalin Decalin, 50% trans
0.124
1,2-Dibromoethane
0.065
0.123(579)
0.110 0.130 0.110 0.127 0.111 0.128 0.111 0.130 0.132 0.119 0.120 0.121 0.122 0.123 0.115 0.115 0.116 0.117 0.118
0.125 (579) 0.126(579) 0.128(579) 0.130(579)
T (0C)
Refs.
20 20 29.2 39.8 28.2 37.8
709 709 611 611 611 611
25 25 25 25 25 25 25 25 25 25 25 25 25 25 84.2 87.8 92.5 100 30 25 30 25 24 25 25 52 60 87 104 123 139 20 20
726 726 726 726 726 726 726 726 726 726 726 726 726 726 611 661 611 611 216 647 216,919 23 217 215 23 23 23 23 23 23 23 615,713 625
20 20.4 22.8 25 30 30 40 40 50 60 20 30 40 50 60 12 20 30 40 50 60 30
827 809 661 827 625 827 625 827 625 625 625 625 625 625 625 221 885 885 885 885 885 216,919
References page VII-615
TABLE 1.
coned dn/dc (ml/g)
Polymer
Solvent
A0 = 436nm
Dibutyl phthalate 1,2-Dichloroethane
A0 = 546nm
A0 = 633nm
Others
0.108 0.120 0.155 0.155 0.161
0.168 0.168
T (0C) 25 135 25
30 30
863 863 647 151 218 152 147 152 200 826
25 25 25 25 25 25 59.6
693 693 693 693 693 693 661
20 30
0.168 0.168 0.168 0.166 0.158 Diethyl ether/methylcyclohexane (70/30, v/v) 0.215 (65/35, v/v) 0.220 (60/40, v/v) 0.215 (50/50, v/v) 0.225 (40/60, v/v) 0.240 (35/65, v/v) 0.245 Diethyl oxalate 0.195 Diethyl fumarate/CH2ClCH2OH (80/20, v/v) Dioxane
0.185
0.152 0.171 0.176 0.168 0.172 0.173
0.1852
0.1731
0.193
0.182
0.204(365) 0.171 (578) 0.170(589) 0.168(644) 0.1702 (589) 0.176(589) 0.170
0.181 0.190
20 20 20 20 25 25 25 35 35
0.184 0.166 0.170 0.173 0.181 star shaped deuterated polymer
star shaped
Dioxane/1-bromonaphthalene (96/4, v/v) 0.134 (90/10, v/v) 0.075 (83/17, v/v) 0.000 (81.5/18.5, v/v) - 0.010 (50/50, v/v) -0.298 Dioxane//i-heptane 0.212 (41.5/58.5, v/v) Dioxane/methanol (28.6/71.4, v/v) (66.5/33.5, v/v) 0.218 Dioxane/methanol (71.4/28.6, v/v) (71.4/28.6, v/v) Dioxane/isopropanol 0.212 (51.5/48.5, v/v) Dioxane/styrene (15/85, v/v) (15/85, v/v) (30/70, v/v)
0.170 0.195 0.164 00 0*) 00 00 (/i)
25 25 30 35 35 30 30 30 30 30 35
0.191 0.222 0.197
0.076 0.084 00 0.092 0.102 OO
Refs.
207 154 225 145 196 174 174 174 174 139 155 206 148 97 202 147 618 807,822 751 671 683 683 645 216,919 216,919 216,919 216,919 216,919 211
25 35 25 35 35 35
209 211 683 683 211
25 25 25 25
726 726 726 726
TABLE 1. cont'd dn/dc (ml/g) Polymer
Solvent
X0 = 436 nm
(40/60, v/v)
A0 = 633 nm
Others
0.104 0.112 (/*) 0.116 0.129 (M) 0.126 0.138 (M) 0.137 0.147 Oi) 0.155 0.163 Oi)
(50/50, v/v) (60/40, v/v) (70/30, v/v) (85/15, v/v) DMF
A0 = 546 nm
0.1703 0.1739
0.1648
0.1632(578) 0.1625 (589) 0.1604(644) 0.145 0.189(365)
0.165 0.175
T (0C) 25 25 25 25 25 25 25 25 25 25 18 20 20 20 20 25 25
0.166 0.171 0.165 0.168 Microgel DMF/tetralin (35.2/64.8, v/v) Ethyl acetate
0.158 0.166 0.178 0.174 0.119 (/x) 0.119
25 80 18 20 25 20 25 30
0.2310 0.234 0.231
20 20 25 30
0.2231 0.218 0.223 0.226 0.216
Ethyl acetate/ethanol (94.81/5.19, v/v) (91.76/8.24, v/v) (89.34/10.66, v/v) Ethylbenzene
0.2196 0.2210 0.2238 0.1 Il 0.093 0.093 0.096 0.102 0.114 0.128 0.117
Ethylcyclohexane Furfuryl alcohol n- Heptane/sty rene (10/90, v/v) (20/80, v/v) (30/70, v/v) (40/60, v/v) (50/50, v/v) (60/40, v/v) MEK
0.2258 0.2275 0.2290 0.2287
0.075 0.089 (M) 0.091 0.109(M) 0.106 0.136 (M) 0.122 0.162 (p) 0.137 0.191 (M) 0.154 0.195 (M) 0.2138 0.2155 0.2167
Refs. 726 726 726 726 726 726 726 726 726 726 213 5,6 5,6 5,6 148 6 215 146 658 658 869 897 638 826 608 638 638 213 102 226 709 779 826 618
25 25 25 25 20 30 40 50 60 70 30
226 226 226 102 885 885 885 885 885 806 691
25 25 25 25 25 25 25 25 25 25 25 25 7.5 15 18 20
726 726 726 726 726 726 726 726 726 726 726 726 219 219 213 219
References page VII-615
TABLE 1. cont'd dn/dc (ml/g) Polymer
Solvent
A0 = 436nm 0.2296
A0 = 546nm
A0 = 633 nm
Others
0.2170 0.214
T (0C) 20 20 20
0.243 0.232 0.229 0.228 0.2296
0.2170
0.2298
0.2175
0.2150 (578) 0.2143 (589) 0.2110(644) 0.2146 (589)
0.2298
0.229 0.226 0.231 0.231
0.2165 0.2178 0.214 0.220
20 20 20 20 20 25 25 25 25 25
25 25
0.220 0.218
0.208(589) 0.220 (589)
0.226
25 0.220
0.227
0.219 0.230 0.215
25 25 0.210*
0.229
0.217
0.232 0.238 0.232 0.223 0.229
0.223
0.2309 0.227 0.2321 0.2333 0.2345
0.2189
0.222 (437) 0.216(589)
25 25 30 30 30
0.170
30 30 35 35 40 45 67 70
0.219
0.2201 0.2213 0.2225 0.230
0.254 0.212 0.222 0.214 0.225
0.230 increase with M
0.207 0.217 0.220 0.217 0.218 0.207-0.211 0.220
0.238 0.235 0.240
randomly branched branched with divinyl benzene MEK/(CH 2C1)2CHOH (46/54, v/v) MEK/1-dodecanol (95.4/4.6, mol/mol)
* Given erroneously as 0.110 in journal.
20 20 25 25 25 25 25 30 30 35
0.165 0.238 0.253
Refs.
6 227 203 153 88,231 102,190 5 5 5 139 155 165 219 195 145,154,196 146 217 212 151,232 232 228 148 215 147 106 224 107 233 206 216 152 229 230 164 219 97 219 219 219 218 203 618 891 869 897 751 807 809 902 648 826 216,919 599 598 207
20 70
203 203
TABLE 1. cont'd d#*/dc (ml/g) Polymer
Solvent
J ( 0 C)
Refs.
0.232 0.248
20 70
203 203
0.241 0.238 0.251 0.234 0.249
20 20 70 20 70
203 203 203 203 203
0.214 0.211
25 25
209 209
0.219 0.140 0.149 (/*) 0.188
25 25
207 726 726 26
22 22 22 22 22 22 22 22 22 98.4
234 234 234 234 234 234 234 234 234 661
22.8 35 59.6 87.8
661 661 661 661
98.4 98.4 98.4 98.4 98.4 35
903,676 903,676 903,676 903,676 903,676 202
35 35 25 20 34.5 98.4
202 211 146 102 903 676,903
34.5 34.5 34.5 34.5 34.5 34.5 34.5 34.5 30 30
903 903 903 903 903 903 903 903 216 84 235 57 166 236 236 236
XQ = 436 nm
(91.2/8.8, mol/mol) MEK/1-hexanol (93.3/6.7, mol/mol) (84.8/15.2, mol/mol) (73.7/26.3, mol/mol) MEK/methanol (11.3/88.7, v/v) MEK/isopropanol (11.4/88.6, v/v) (85/15, v/v) MEK/styrene (50/50, v/v)
Methylcyclohexane Methylcyclohexane/acetone (17/83, v/v) 0.242 (22.2/77.8, v/v) 0.242 (28/72, v/v) 0.239 (39/61, v/v) 0.231 (50/50, v/v) 0.228 (61/39, v/v) 0.223 (72/28, v/v) 0.222 (83/17, v/v) 0.217 (88.3/11.7, v/v) 0.210 3-Methyl cyclohexanol 0.154 3-Methyl cyclohexanol/1 -chlorodecane (21.8/78.2, v/v) 0.165 (25/75, v/v) 0.168 (50.5/49.5, v/v) 0.166 (90/10, v/v) 0.155 3-Methylcyclohexanol/tetralin (23.2/76.8, v/v) 0.096 (43.4/56.6, v/v) 0.115 (49.5/50.5, v/v) 0.112 (61/39, v/v) 0.131 (77/23, v/v) 0.145 Nitropropane 0.208 NitropropaneM-heptane (42/58, v/v) 0.216 0.218 Phenylcyanide 0.0775 Styrene 0.054 Tetralin 0.072 0.075 Tetraiin/cyclohexane (89.4/10.6, v/v) 0.082 (^) (88/12, v/v) 0.087 (81/19, v/v) 0.093 (79.4/20.6, v/v) 0.095 (^) (69.7/30.3, v/v) 0.119 (A0 (59.7/40.3, v/v) 0.139 (fj) (39.6/60.4, v/v) 0.159 (/*) (20/80, v/v) 0.173 (M) THF 0.195
/I0 = 546nm
X0 = 633nm
Others
0.1926 0.190 0.198 Mw=
2.4 x l O 4 5.31 x 104 16.5 xlO 4
0.194 0.205 0.202 0.207
0.193 0.189 0.194
25 25 25
References page VII - 615
TABLE 1. cont'd dn/dc (mi/g) Polymer
Solvent 54.1 x 104 15OxIO 4 57OxIO 4
A0 = 436nm 0.208 0.209 0.211
A0 = 546nm
A0 = 633nm
Others
0.195 0.196 0.198
25 25 25 0.186 0.193 0.192 0.186
0.195 0.208 0.186 0.190 0.193
100% mol deuterated 62% mol deuterated 25% mol deuterated THF/methanol (28.7/71.3, v/v) Toluene
0.111 0.112
0.193 0.171 0.177 0.182
20 23 25 30 RT RT RT RT
0.188 0.165 0.172 0.178
0.179 0.109 0.104
0.112 0.1113
0.112 0.195
0.109 0.1079
0.1073(578) 0.1071 (589) 0.1060(644) 0.113
20 20 23 25
0.111 0.112
0.111 0.112 0.1150
25 RT 12 20 20 20 20 20 20
0.108 0.110
0.1188 0.1129
T (0C)
0.109 0.1079 0.1091 0.1130 0.110 0.111
25 25 25 25 25 25 25 25 28
0.1111 0.111 0.110
0-U3 0.118 0.114
30 30 35 45 65
0.118 0.125 0.110 0.118
67 0.106 0.101
0.113 0-115 0.111 0.103(1086) M = 1.2 x 103 - 1.07 x 103 star shaped polymer
0.089-0.105 0.103 0.105(1086) 0.113
0.109 0.111 0.110 0.H2 0.105 0.110-0.112 0.093-0.109 0.112
increase with M increase with M: 0-117
0.107-0.110
15 20 20 20 20 20 25 25 25 25 25 25 25 25 25 25
Refs. 236 236 236 618,798 869 830 637 216,919 630 630 630 630 209 232 221 31,227 102 238 5 5 5 153 230 231 240 237 239 225 241 242 43 243 240 217,228 146 139 29 147 152,216 229 97 243 243 244 218 618 842 834 834 869 915 732 737 915 647 751 601 613 633 635 648 664 834
TABLE 1. confd dn/dc (ml/g) Polymer
Solvent
A0 = 436 nm
X0 = 546 nm
4
A/>2xlO star branched
A0 = 633 nm
Others
0.108 0.103-0.106 0.107-0.112 0.108 0.110
M = 2 x 103 - 18 x 105
0.125 0.126 isotactic M w =0.02 x 10 s - 0.5 x 105 Toluene Mw = l . l 0 x l 0 5 Toluene M w = 1.60 x l O 5 Toluene M w = 2.00 x K)5 - 8.67 x 105Toluene M w = 18 x 105 Toluene M w = 1.25 x 105 - 2.5 x 105 Toluene dispersion Water latex sulfonated
0.111 0.101-0.107 0.106 0.107 0.110-0.117 0.118 0.117 0.250 0.241 0.256 0.257
Neutralization equiv. = 0.9 mEq/g: 0.05 M NaCl 1.8mEq/g: 0.056MNaCl 2.0 mEq/g: 0.10 M NaCl 2.7 mEq/g: 0.10 M NaCl Toluene//>cymene (73.4/26.6 w/w) 0.115 (49.7/50.3 w/w) 0.117 Trichlorobenzene Water/THF (1 /99, v/v)
0.212 0.207 0.195 0.205
25 25 25 25
247 247 247 247
0.124 0.128 (M) 0.152 Ox) 0.122 (/x)
30 30 25 25 25 25 25 25 25 25 25 25 30 25 25 25 25
699 699 653 796 796 796 796 796 796 796 796 249 85 675 675 879 879
0.198
25
753
0.164
35
814
0.122 0.124 0.125
25 40 55
795 795 795
25 25
675 675
0.028 0.183 0.166 Oi) 0.192 0.183 Ox) 0.180 0.177 Ox) 0.180 0.188(At)
(3/97, v/v) (4.5/95.5, v/v) (7/93, v/v) Poly(styrene-p-sulfonic acid) Aq. KCl 2.5 M -, K-salt, DN= 1.0 Aq. KCl; / = 0.10 - , Na-salt THF/ethanol (76/24, v/v) Aq. 0.1 M Na 2 SO 4 Aq. 1M Na 2 SO 4 Poly(styrene-co-acrylonitrile), (1/1, mol/mol) MEK Poly(styrene-c<9-/?-butyl methacrylate) (1/1, mol/mol) MEK Poly(styrene-c0-/?-cnlorostyrene), ( ~ l / l , mol/mol) Cumene Poly(styrene-a?-ethylene-a7-butene) (Kraton G) THF THF/ethanol (94/6, v/v) (88/12, v/v)
Refs.
25 833 25 833 23-27 652 30 671 30 691 30 697,699,216 30 834 30 837 35 659 35 704 50 699 70 699 80 638 90 609 30 245 30 962 30 962 30 962 30 962 30 962 30 962 25 95 246 25 247 248
0.113 0.118 0.101-0.118 0.113 0.114 0.119 0.125
M = 2 x 103 - 18 x 105
T (0C)
0.0347* 0.197
0.116 0.118 0.120 00 0.120 0.124Ou)
25
675
25 25
675 675
* Expressed in 1/g-segment.
References page VII-615
TABLE 1. cont'd d/i/dc (ml/g) Polymer 1.7.
Solvent
A0 = 436nm
A0 = 546 nm
A0 = 633 nm
Others
T (0C)
Refs.
OTHER COMPOUNDS
Poly(acrylonitrile)
y-Butyrolactone Dimethylacetamide Chlorobenzene DMF
0.0767
0.079 0.078 0.0769
25 30 25 0.00
0.080 0.085 0.870
18 20 20 20 20 20 25 25
0.082 0.0874 0.0877 0.0914 0.0924 0.196 0.083 0.089 0.080
0.085 DMSO
0.029
DMSO/acrylonitrile (65/35, v/v) (73/27, v/v) (82/18, v/v) (91/9, v/v)
0.084 0.087 0.084 0.078 0.031 0.043 0.092 0.0263
25 25 25 20 25 25 25 140 25
0.061 0.067 0.055 0.062 0.048 0.053 0.040 0.044
25 25 25 25 25 25 25 25 0.132
726 726 726 726 726 726 726 726 891
0.174(580) 0.198(580) 0.228 (580)
644 644 644
(/i) (JJL) (jj.) Ox)
MEK
276 277 278 891 643 891 213 238 281 283 283 283 284 215,276, 278,280 279 282 277 10 897 985 278 285 278 284
Poly(diacetylenes) =c-c=c-c= (CH2)9
(CH2)9
O-COR O-COR R = isopropyl Chloroform R = benzyl R = 1-methylene naphthalene R = 1-methylene naphthalene 1,2-Dichloroethane
0.267
0.220(578)
RT RT 25
740 740 715 577
0.091
25
663
0.180
25
663
0.088
25 30
663 896
25
733
25
679
25 25
269 269
0.190 Poly(terf-butyl vinyl ketone) sec-Butyl alcohol Poly(N-isobutyl maleimide) Chlorobenzene Poly(maleic acid-c-ethyl vinyl ether) (1/1, mol/mol) THF Poly(maleic acid-a?-ethyl vinyl ether) (1/1 mol), sodium salt Aq. 0.18MNaCl Poly(maleic anhydride-co-ethyl vinyl ether (1/1, mol/mol) THF Acetone 0.133 Poly(maleic anhydride-co-octadecene) (1/1, mol/mol) Ethyl acetate Poly(2-methyl 5-vinylpyridine; iV-oxide) Methanol Poly(2-methyl-5-vinylpyridine) rc-Butyl acetate 0.200 MEK 0.212
0.097 0.01
0.119 0.262 0.188 0.202
TABLE 1. contd dn/dc (ml/g) Polymer
Solvent Methanol
A0 = 436 nm 0.273
A0 = 546 nm
A0 = 633 nm
Others
0.257
Benzene Acetone
0.102 0.095 0.104 0.116 0.104 0.104 0.105 0.1021
Acetonitrile Benzene
0.104 0.030 -0.0225 0.0716 -0.0426
n-Butyl acetate Chlorobenzene
- 0.049 0.028 0.087 0.095 0.080
Dioxane Ethyl acetate Ethyl formate MEK 0.080 0.080
0.080 0.083 0.080 0.080 0.075 Methanol
0.107 0.130 0.132 0.124 0.132 0.1319 0.119 0.130
Methyl isobutyl ketone Methyl isopropyl ketone/ 0.075 ^-heptane (3/1-6/1, v/v) THF
0.132
0.128 (366) 0.068
0.075 0.0582
Refs.
25 RT 25 20
0.250 Poly(phenyl vinyl ketone) Poly(vinyl acetate)
T( 0 C)
270 680 759 238 287 25 32 25 289 25 288 25 201 35 34 290 194 30 84 30 84 30 84 25 32 290 25 32 290 15 32 291 252,287,292 25 32,293 25 205 25 289 35 32 618 25 287 25 288 25 205,294 25 32 289 34-38 295 618 881 290 25 252 30
84 618
0.057
25
0.054
25 34-38
637 803 865 296
25 25 25 25 25 25 25 25 25 25 25 25 26 40
297 297 297 289 289 289 289 289 289 289 289 289 289 289 289 823 823
0.050 Poly(vinyl acetate) 0.059 Trichlorobenzene Poly(vinyl acetate) (partially hydrolyzed) Deg. of Hydrolysis = 0.840 Water 0.883 0.964 0.008 Acetone 0.029 0.049 0.119 0.008 MEK 0.029 0.049 0.119 0.008 Methanol 0.029 0.049 0.119 Poly(9-vinyl adenine) Aq. 0.1 M NaCl+Na cacodylate
0.1030 0.151 0.155 0.161 0.103 0.101 0.098 0.090 0.083 0.087 0.092 0.110 0.128 0.115 0.107 0.071 0.326 0.331
References page VII-615
TABLE 1. cont'd dn/dc (ml/g) Polymer Poly(vinyl alcohol)
Solvent
A0 = 436nm
Water/n-propanol (98/2, w/w)
0.134
0.135
0.145
0.147
0.158
0.160
Water
Poly (vinyl bromide)
0.164
Water Benzene Carbon tetrachloride Dioxane Ethylene glycol dimethyl ether Ethylene glycol dimethyl ether/ethylene glycol monomethyl ether (56/44, v/v) THF
X0 = 633 nm
Others
T (0C)
Refs.
0.128(366) 0.133 (404) 0.142(366) 0.144 (404) 0.151 (366) 0.153 (404)
25 25 40 40 70 70 20 20 30
881 881 881 881 881 881 298 299 287 948 948 948 300 300 300 300
0.150 0,144 0.168
M w = 39900 M w -120000 M w = 160000 Poly(vinylbiphenyl)
/I0 = 546nm
0.164(578) 0.151 0.153 0.153
0.182 0.220 0.257 0.301
0.165 0.207 0.233 0.277
25 25 25 24 24 24 24
0.297-0.301
0.271-0.275
30
300
25
251 252 250
0.155 0.190 0.195 0.198 0.201 0.204 0.207 0.232 0.185 0.262
25 25 25 25 25 20 20 25 25 30 35 40 45 25 25 25
880 880 880 880 880 301 302 304 303 303 303 303 303 304 304 304
0.128
25
781
0.113 0.174 0.138
25 25 20 20
800 800 238 682 253 682 259 259 255,256 206 10 254,257 258 259 259 259 259
0.112 0.112(644)
Poly(vinyl n-butyl ether) MEK Poly(vinyl butyral) - acetylated Acetone Acetonitrile rc-Butyl acetate n-Butyl chloride THF Poiy(vinyl n-butyrate) MEK Poly(vinyl carbanilate) Dioxane PoIy(N-vinylcarbazole) Benzene
0.0792 0.119 0.130 0.084 0.075 0.071 0.0684 0.159 0.210 0.219 0.222 0.225 0.228 0.231 0.268 0.214 0.282
Chloroform Tetrachloroethane THF Poly(9-vinylcarbazole-c0-diethyl fumarate) Benzene Poly (N- vinyl- 3,6-dibromocarbazole) o-Dichloroenzene THF Poly (vinyl chloride) Acetone iso-Amyl acetate Aq. NH4OH; pH 9-10 (latex) «-Butyl acetate Cyclohexanone 0.0718 0.0723 0.079
0.0739 0.0758 0.0764 0.0767
0.098 0.200 0.112 0.0705 0.0714 0.0840 0.077 0.075 0.074 0.0727 0.0742 0.0746 0.0756
0.0701 (578) 0.0708 (578) 0.076(589) 0.078 0.0716(578) 0.0740 (578) 0.0745 (578) 0.0753 (578)
20 15.5 20 25 25 25 25 25 25 30 35
TABLE 1. cont'd dnldc (ml/g) Polymer
Solvent
I0 = 436 nm
A0 = 546nm
A0 = 633 nm
Others
0.0905 0.0840 0.0900 0.0970 0.0940 0.075 0.074 0.0380
Di-n-butyl phthalate Diethyl adipate Di-2-ethylhexyl phthalate
0.085 0.0435 0.0465 0.0494 0.0518
Diethyl malonate Diethyl oxalate Diethyl succinate Di-2-heptylnoyl phthalate Di-fl-hexyl phthalate
0.094 0.103 0.094 0.0420 0.0250 0.0260 0.0280 0.0300 0.0260 0.0900 0.0925
Dimethyl phthalate Dioxane
0.107 M w = 2.04 x iO6 1.78 x l O 6
0.107(589)
0.0850 0.0865 0.0395 0.069 0.078 0.0875 0.095
Di-rc-propyl phthalate DMF
0.084 0.0816 Ethyl heptanoate Tetrachloroethane
THF
0.104 0.11
0.0810
0.0813 (578) 0.102
0.1040 0.115
0.0432 0.0450 0.0540 0.0630 0.1017 0.110
0.1010(578)
T (0C) 50 50 75 75 95 20 25 25 20 25 50 80 105 20 20 20 25 25 50 70 105 25 25 25
255 256 256 255 256 682 851 256 682 256 256 256 256 682 682 682 256 256 256 256 256 256 256 260
25 25
206 261
28.5 28.5 25 25 50 75 95
262 262 256 256 256 256 256 258 259 682 255 255 255 255 259 265 258 266 263 261 256 206 267 259 259 259 259 34 264 682 637 851 267 255 255 255 255 255
25 20 20 25 50 75 16.5 RT
0.102 0.106 0.1124 0.119 0.1079 0.1067 0.1093 0.1118
0.105 0.1123 0.116 0.1065 0.1052 0.1053 0.1064 0.1087 0.1045 0.1065
0.115(589) 0.1068(578) 0.1046(578) 0.1059(578) 0.1093(578) 0.111 0.102
-, chlorinated 56.4, 58.3, 61.5, 63.4, 66.6,
wt.% wt.% wt.% wt.% wt.%
THF/water (91/9, v/v) Cl Tetrachloroethane Cl Cl Cl Cl
0.112 (/x)
0.106 0.1085 (^) 0.045 0.0424 0.525 0.0606 0.073
Refs.
20 25 25 25 25 25 25 30 35 35 20 25 25 25 25 25 25 25 25
References page VII-615
TABLE 1. confd dn/dc (ml/g) Polymer Poly(vinyl dimethylamylsilane) Poly(vinyl dimethylheptylsilane) Poly(vinyl dimethy lpheny lsilane) Poly(vinylidene chloride) Poly(vinyl ethyl ether) Poly(vinyl fluoride) Poly(vinylidene fluoride)
PoIy(N-vinyl-imidazole) incr. with mol. wt.
Poly(vinyl isopropyl ether) Poly(vinyl methyl ether)
Poly(a-vinylnaphthalene)
Poly(P-vinylnaphthalene)
Poly(2~vinylpyridine)
Solvent
X0 = 436 nm
A0 = 546 nm
A0 = 633 nm
Others
Refs.
Cyclohexane
0.070
25
884
Cyclohexane
0.085
25
884
Cyclohexane
0.142
25
884
l-Methyl-2-pyirolidone Tetramethylene sulfoxide MEK 0.0736 DMF DMA DMF DMSO AW-dimethylethyleneurea Hexamethylphosphoric triamide //-methyl pyrrolidone 3-methyltetramethylene sulfone Tetramethylurea
0.080 0.049
RT RT 25 25 25 25 25 25 25 25 25
695 695 250 268 986 986 986 986 986 986 986 986
0.235 0.224
25 25 25
887 719 719
0.224 (^)
25
719
0.0827 0.0944
25 25
Ethanol Methanol Tetrabutyl ammonium bromide Tetrabutyl ammonium bromide MEK MEK Chloroform THF Toluene Benzene Ethylene dichloride Ethylene glycol dimethyl ether Toluene Benzene Carbon tetrachloride Ethylene glycol dimethyl ether Ethylene glycol dimethyl ether/ethylene glycol monomethyl ether (56/44, v/v) Aniline Benzene rc-Butanol 2-Butanol Chloroform
«0.02 -0.033 -0.023 -0.062 -0.055 - 0.046 -0.052 - 0.064 -0.042
-0.031 -0.021 -0.060 -0.053 - 0.044 -0.50 - 0.063 -0.040
0.180-0.192
0.192 0.239 0.268
0.175 0.217 0.248
24 24 24
250 250 842 842 842 300 300 300
0.162-0.192 0.182-0.197 0.215 0.309
0.167-0.181 0.194 0.284
24 24 24 24
300 300 300 300
0.283
0.258
24
300
25 25 25 25 23 25 35 25 25 25 25
907 907 907 907 34 907 39 907 907 907 907 271 271 797
0.044 0.063 0.001
0.023 0.107 0.209 0.216 0.1372 0.168 0.1215
Cyclohexanone 1,2-Dichloroethane Dioxane DMF
0.144 0.148 0.175 0.165
atactic isotactic
0.157 0.163 DME/methacrylic acid (95/5, v/v) Ethanol
atactic isotactic isotactic
F( 0 C)
Ethanol -f 0.1M sodium acetate
0.187(589)
20
0.195 (fj.) (589) 20 25
0.245 0.221 0.221 0.222
797 907 271 271 271
Next Page
TABLE 1. cont'd dn/dc (ml/g) Polymer
Solvent
A0 = 436 nm
MEK Methanol Af = 2.1 x 103-22.9 x 103 Poly(vinyl-2-pyridine) 0.950 Nitromethane/0.050 0.900 Nitromethane/0.100 0.800 Nitromethane/0.200 0.750 Nitromethane/0.250 0.700 Nitromethane/0.300 0.625 Nitromethane/0.375 0.565 Nitromethane/0.435 0.500 Nitromethane/0.500 0.470 Nitromethane/0.530 0.400 Nitromethane/0.600 0.250 Nitromethane/0.750 0.214 Nitromethane/0.786 Nitroethane n-Propanol 2-Propanol 1,1,2,2-Tetrachloroethane THF
X0 = 546 nm
A0 = 633 nm
Others
0.215
25 RT 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25
0.254 0.270 0.259-0.263 carbon tetrachloride carbon tetrachloride carbon tetrachloride carbon tetrachloride carbon tetrachloride carbon tetrachloride carbon tetrachloride carbon tetrachloride carbon tetrachloride carbon tetrachloride carbon tetrachloride carbon tetrachloride 0.197 0.215 0.221 0.109 0.195
T (0C)
0.2020 0.1989 0.1918 0.1889 0.1847 0.1793 0.1740 0.1705 0.1684 0.1560 0.1525 0.1500
0.182 Poly(4-vinylpyridine)
1,1,1-Trichloroethane Chloroform DMF
0.162 0.150 0.160
25 25 25 0.153 0.153
Ethanol Ethanol/water (95/5, wAv) Isopropanol MEK/isopropanol (85/15, w/w) (86/14, w/w) Methanol Nitromethane Phenyl cyanide Poly(2-vinylpyridine 1-oxide) Aq. IMNaCl 2-Propanol Poly(4-vinylpyridine ;V-oxide)Aq. 0.1 M NaCl Poly(vinylpyrrolidone) Chloroform Methanol
25 25
0.224 0.267
25 25 0.180 0.159 0.152
0.052 0.209 0.241 0.108
0.185 0.181 0.180 0.179 0.179
Poly(vinyltrimethyl silane)
0.108 0.183 0.176 0.135 0.185 0.176 0.176 0.175 0.174
Water
KCl 0.35 M 0.65 M Carbon tetrachloride Cyclohexane Cyclohexane
25 25 25 25
0.220
Water
Mw=IOlOO Mw = 35100 Mw =46400 Mw = 1540000 Poly(vinylsulfonic acid), potassium salt
RT
0.231 0.231 0.224 0.221
25 25 25 0.176(578) 0.175 (578) 0.174(578) 0.173 (578) 0.181 0.181 0.185 0.179
0.01664 (/*)* 0.01638 (^)* 0.048 0.083 0.087
20 25 30 35 25 25 25 25 23 23 25
Refs. 907 680 907 909 967 967 967 967 967 967 967 967 967 967 967 967 907 907 907 907 907 272 907 146 146 658 680 273 273 274 274 274 274 275 275 275 146 679 640,987 679 306 201 193 193 306 792 792 792 792 948 948 948 948 308 308 307 307 884
* Expressed in i/g-segment.
References page VII-615
P a r t i c l e i n
S c a t t e r i n g
R a y l e i g h
F a c t o r s
S c a t t e r i n g
E d w a r d F. C a s a s s a Department of Chemistry, Carnegie-Mellon University, Pittsburgh, PA, USA
A. Introduction: General Relations for a Homogeneous Solute B. Scattering Factors for Various Molecular Models C. Effects of Dispersion in Molecular Weight D. Determination of Molecular Weight and Radius of Gyration E. Calculation of Scattering Factors F. Particle Scattering Factors and Dissymmetries Table 1. Dissymmetries for Monodisperse Systems Table 2. Dissymmetries for Monodisperse and Polydisperse Coils G. References
VII-629
where M is the molecular weight of the solute, c is the concentration in units of mass/volume, Ai is the second virial coefficient, and q is an angle variable
VII-630 VII-631
(A2)
VII-632 VII-633 VII-633 VII-634 VII-634 VII-635
A. INTRODUCTION: GENERAL RELATIONS FOR A HOMOGENEOUS SOLUTE (1,2)
h denoting the refractive index of the solution, and A the vacuum wavelength of the incident radiation. In the optical constant (assuming incident radiation polarized perpendicular to the plane containing angle 9) (A3) dh/dc is the specific refractive index increment at constant pressure and temperature, and NA is Avogadro's number. The intensity R(q, c) is that due to the solute; the (relatively weak) background solvent scattering is assumed to be that measured for the pure solvent. The first term on the right-hand side of Eq. (Al) contains the intramolecular interference function, or particle scattering factor, defined by (4,5)
When electromagnetic radiation interacts with any fluid medium, inhomogeneities in refractive index (dielectric constant) arising from microscopic thermal fluctuations in density and composition cause scattering of a small fraction of the incident radiation. If scattering elements are spatially correlated over distances of the order of magnitude of the wavelength of the exciting radiation, the scattering is subject to optical interferences that affect the angular intensity distribution. This distribution can provide information on the size and shape of macromolecular solutes or suspended colloidal particles: in principle, the molecular radius of gyration is determinable unambiguously, and calculated scattering distributions for idealized models can be compared with experimental data to infer an acceptable molecular conformation. However, an experimental scattering distribution does not permit a unique model assignment in the absence of additional information or supposition. The limiting dilute-solution behavior of the reduced intensity R(q, c) (Rayleigh's ratio) of light scattered through an angle 9 is given by (3)
the superscript zero denoting the limit of infinite dilution. Thus the intensity distribution P(q) is normalized to unity at zero scattering angle. Unless particle dimensions are infinitesimally small compared with A, P(q) is less than unity for q < 0; and for particles of less than colloidal dimensions, it is almost always a monotonously decreasing function of q throughout the accessible range of q with visible light. The second term of Eq. (Al) contains the effects of pairwise interactions between solute molecules (and, implicitly, of interactions involving solvent). The dimensionless angle factor, Q(q), is a function generally unknown, dependent on both intermolecular and intramolecular correlations (3,6). Like P(q) it is normalized to unity at 9 = 0, but usually the approximation is made that Q(q) is unity at all angles so that
(Al)
(A5)
(A4)
replaces Eq. (Al). In all that follows, Eq. (A5), which is Zimm's "single contact" approximation (4), is assumed to hold for any macromolecular species in solution. At 6 = 0, Eqs. (Al) and (A5) revert to a thermodynamic equation of a state in virial form. A scattering entity (polymer molecule, particle) may be represented by n optically isotropic point scattering centers whose spatial arrangement in any given conformation is specified by n(n — l)/2 « n2 J2 vectors r,y, separating pairs of scattering centers ij. The scattering function P(q) is then
where (B4) is Dawson's integral, for which tabulations are available (9). The variable u is defined as in the first equality in Eq. (B2), so that in this case u — 2q2R2ori since the meansquare radius R\sin% is nb2/12. For flexible regular-star branched molecules with / identical arms (/ random-flight chains starting from a common node), P(q) is given by (10,11)
(A6) The vector q is the difference between vectorial wave numbers of incident and scattered rays such that |q| —
(B5) The mean-square radius of the star model is [ ( 3 / - 2)/f2][nb2/6\. Scattering functions have also been calculated for certain random-flight comb-shaped models of flexible backbones with uniform side chains (11). Provided q2R2g < 2, a good approximation to P(q) for a variety of branched chains and for the ring model is afforded by the form of Eq. (Bl) for a linear chain with u replaced by gu, g denoting the ratio of the mean-square radius of the nonlinear structure to that of the linear chain of the same mass (2,10). Strictly, Eqs. (B1-B5) apply only to flexible chain molecules in a theta solvent. To account approximately for the chain expansion in a good solvent, the most obvious expedient is to increase the statistical mean-square segment length b2 by the same factor as that for the increase of the overall mean-square radius over the unperturbed value and assume that the foregoing equations still apply. Several derivations (12-15) however, recognize the non-Gaussian character of the segment distribution perturbed by the excluded volume effect. Scattering factors have also been obtained for another type of modification of the random flight, the "wormlike" chain of Kratky and Porod, which introduces a persistence length to account for chain "stiffness'' (1,16). For thin cylindrical rods of length L, P(q) is (7,17,18)
B. SCATTERING FACTORS FOR VARIOUS MOLECULAR MODELS (1,2)
The scattering factor P{q) has been calculated for a number of simple molecular geometries. For monodisperse randomflight (Gaussian) coils it is given by (7)
(B6)
(Bl) (B2) (B7) where n is the number of equivalent statistical segments of root-mean-square length b in the chain. For a flexible-ring model (a long chain of Gaussian segments constrained to have ends joined), P(q) is given by (8) (B3)
The "sine integral" function Si(^) is given in standard tabulations (9). For large v this P(q) function asymptotically approaches {n/2y) - (l/2y 2 ); and, in fact, the asymptotic relation is less than 1% in error for v > 4. The four terms of the series form given in Eq. (B6) are within 1% of the correct value for y < 2.
For spheres of diameter D, P(q) is (7,18)
Series expansion of PX{Q) gives an average over the mean-square radii of gyration R2gi of the solute species (C5) (B8)
where v = qD/2; and for thin disks of diameter D, the function is (18) (B9) with w - qD/2, and J\(x), the Bessel function of the first kind, of order one (9). Scattering factors have been calculated for a variety of more complicated particles; e.g., oblate and prolate ellipsoids, cylinders of finite thickness, shells of different forms, particles of nonuniform density, and assemblages of simple geometrical shapes (see Ref. 19 and citations therein). C. EFFECTS OF DISPERSION IN MOLECULAR WEIGHT (2)
(C6) The average R\ is sometimes called the Z-average meansquare radius (for a distribution of random-flight chain species R\ is proportional to the so-called Z-average molecular weight (C7) Angular scattering functions Px{4) have been calculated for various molecular size distributions. In particular, distributions of linear random-flight chains have been studied for the exponential weight-fraction distribution of Schulz and Zimm (20) (C8)
For a mixture of solutes all having the same specific refractive increment, e.g., a polymer heterogeneous in molecular weight, the reciprocal scattering function in Eq. (A5), for the single-contact approximation, is replaced by (2, 20-22) (Cl) Here, M w denotes the weight-average molecular weight Y^jMjWi, Mj being the molecular weight of the /th solute and Wj its weight fraction in the solute mixture; c is the total solute concentration. The measured particle scattering factor is the average (C2) where Pt(q) is the scattering factor for the ith polymer. The quantity i42.app is an apparent, angle-dependent second virial coefficient
with b = (h + 1)/M W ~ h/Mn, F(x) the gamma function, and the dispersion parameter h — 1/[M W /M n ) — I]. For a system of random flight chains with this distribution, the averaged scattering factor is
(C9)
where Ux = Q2R\- For a monodisperse polymer, h is infinite; and for increasing dispersion in molecular weight it decreases towards zero. It is unity for the "most probable" distribution (characteristic of the products of step-growth polymerization at high conversion and of free-radical polymerization at low conversion with chain transfer). In this special case, Px{q) for random-flight linear chains is given by the very simple relation (20) (ClO)
(C3) where By is the virial coefficient for interaction between components i and j (Ba is just A2 for a solution of component / alone). At the limit 9 —» 0, A2,app reduces to a true thermodynamic quantity: (C4) which might be described as a "light-scattering-average" second virial coefficient (to distinguish it from the analogous average obtained from an osmotic pressure experiment).
Plots of [Px{q)\~{ versus Ux for h < 1 curve upward, and for h > 1 curve downward. The asymototic dependence of [Px(q)]~l for heterogeneous chains at large q is (23) (CU) so that, in principle, this dependence could provide information on M n . In practice, the experimental limit on q imposed by the upper bound on 8 of 180° makes it difficult to ascertain whether the asymptotic behavior is accessible, even for polymers of high molecular weight. Calculations for branched monodisperse Gaussian chain models and for systems with certain distributions of References page VII-635
(C12) where yw = (q/2) £VL,-w,-, L{ being the length of the ith rod species. For large qL, the asymptotic dependence of [Kc/R(9)]° on q (not q2) for rods of uniform diameter and density is linear, and the slope of the plot is (L,/M/)/7r: i.e., the slope yields the linear density or mass per unit rod length, independent of any dispersion in L (28). If the rods are heterogeneous in diameter, the limiting slope is k E i ^ ^ i / ^ ' ) ] " • Unlike the asymptotic behavior for Gaussian coils, this asymptotic dependence for rods is manifested in practical situations with both synthetic polymers and biopolymers. Some care in interpretation is needed, however. For thin oblate ellipsoids ("needles"), a model seemingly scarcely different from thin cylinders, the asymptotic dependence of [(Kc/R(O)]0 on q is also linear but with slope 5/6 that for the cylinder system (28). D. DETERMINATION OF MOLECULAR WEIGHT AND RADIUS OF GYRATION In general, information from a light scattering experiment on a polymer/solvent system consists of an array of intensity data determined at a number of concentrations and a number of angles. These are usually represented as values of the reciprocal intensity function KcZR(O1C). The form of Eq. (A5) suggests use of the popular Zimm plot: i.e., the values of Kc/R(O, c) are plotted against Cic + C2 sin2(0/2), with C\ and C2 being arbitrary constants chosen merely to separate data points conveniently, to form a gridlike pattern (4,20). In conformity with Eq. (A5), a homogeneous polymer gives contours at constant angles (0) that form a family of parallel straight (or nearly parallel and straight) lines, and contours at constant concentrations that form another family of curves of similar shape, displaced from one another by translations. This representation, shown schematically in Figure 1, facilitates simultaneous extrapolations of angular data to
Slope Kc I R(q,c)
branching and molecular weight suggest as a reasonable approximation for such heterogeneous systems in general, the Px(q) obtained by replacement of the variable u in Eq. (Bl) by (ux)xR2x/(R2x)v where (ux){ and ( ^ ) 1 denote ux and Rx, as defined above, for the system of linear chains with the same weight distribution as the structurally heterogeneous system. Derivations of P(q) for randomly branched systems have been based on cascade models and moment generating functions (24-26). Branching and molecular-weight dispersion have opposing effects on the P(q) function and in randomly branched systems are largely compensatory (2,26). Interestingly, however, the asymptotic behavior of P(q) for Gaussian chains is unaffected by chain branching; it depends only on molecular weight and weight distribution (10). Px(q) has been obtained in closed analytical form for systems of thin rodlike (cylindrical) particles distributed in length (and therefore in mass) according to Eq. (C8) for integral values of the parameter h (27). For A = I , the result is
q 2 + const x c
Figure 1. Schematic Zimm plot for a solute polydisperse in molecular weight, illustrating empirical determination of averaged molecular weight MW/ scattering factor Px{cj), and radius of gyration Rx according to Eq. 19. The filled circles simulate experimental data; the open circles represent extrapolations to zero scattering angle and zero concentration. zero concentration and concentration data to zero angle, and extrapolation of both limiting dependences to a common intercept [Kc/R(0,c)]°. In general, the ratio of the initial slope to the intercept of the angular plot extrapolated to c ~ 0 is 167r2rc2/?|/3A2; the slope of the concentration dependence extrapolated to (9 = 0 is twice the averaged second virial coefficient A2 , and the double limit [Kc/R(0,c)]° is M~l. The dominant cause of lack of parallelism of the contours in experimental Zimm plots is dispersion in molecular weight (cf. Eqs. C19, C21). If both the molecular architecture of a polymer in solution and its molecular weight dispersion are known, the scattering function Px(q) is known (in principle) and can be combined with limited angular scattering data to deduce Mw and R\. Thus, in the "dissymmetry" method (7) scattered intensities at 90° and the ratio of intensities at 45° and 135° (or another pair of complementary angles) are measured for each concentration. Then the extrapolated transverse scattering function [Kc/R(qgo)}° and the extrapolated dissymmetry ratio (Dl) determine the molecular weight and radius of gyration, given the Px(q) function. Tables correlating Z45 with P~l(#90) and the molecular dimensions have been compiled for monodisperse coils (5,29), rods (5,29), spheres (5,29), and disks (5,29,30), and for polydisperse coils (5,31). Except for routine characterization of systems of well known character exhibiting low dissymmetry, the dissymmetry method cannot be recommended if a photometer is available that is capable of a full complement of angular readings. Apart from the desirability of determining Mw and R\ without assumptions, it is
helpful to have the maximum amount of information as an aid in detecting any spurious angular dependence of scattering due to instrumental artifacts or to contamination by "dust". In current practice, photometers that do not provide scattering measurements over a continuous angular range, are typically dedicated to the limited task of monitoring the output stream in size exclusion chromatography, perhaps on line with other detection modes. In this application, passage of the polymer through the chromatographic column effectively eliminates the problem of contamination by foreign particulate matter. One popular instrument of this kind reads scattering only at right angles and at 15°.
The Bessel function J1(Jc) for x > 3 (Ref. 34):
E. CALCULATIONS OF SCATTERING FACTORS Figure 2 and Tables 1 and 2 illustrate some quantitative comparisons among scattering factors for several molecular models and the effects of dispersion in molecular weight for Gaussian coils. Tables of P{q) and Z45 in the older literature are much more extensive and reflect the needs of a time without widely available computer technology. Today, for careful work to compare experimental R(q, 0) data with theoretical scattering functions, investigators will find it preferable to return to the mathematical functions and write computer routines to do calculations for data analysis rather than to routinely interpolate in tables. For those who may wish to use a traditional programming language such as FORTRAN, the following rational approximation formulas will facilitate accurate calculation of the special functions that appear in the various expressions for P(q). The sine integral Si(x) for x < 1 (Refs. 32,33):
Modern mathematics programs such as Mathematica and Maple constitute higher level languages that make possible direct operations with special functions on a personal computer (35,36). F. PARTICLE SCATTERING FACTORS AND DISSYMMETRIES
sphere disk ring
llP{q)
4-star
coil rod
The Bessel function Jx(x) for 0 < x < 3 (Ref. 34):
Figure 2. Reciprocal scattering factors yP{q) versus q2R2 for monodisperse systems of the models indicated. R2 is: nb2/6 (linear Gaussian coil); 5nb2/48 (4-branch regular star); nb2/M (flexible ring); L2/12 (thin rod); D2/8 (disk); 3D2/20 (sphere). References page VII-635
TABLE 1. DISSYMMETRIES FOR MONODISPERSE SYSTEMS Z45 and P- 1 C^o) R%h/ X
Coil
4-Starfl
Rod
Disk
Sphere
0.00 0.01 0.02 0.03 0.04
1.000 (1.000) * 1.004(1.003) 1.015(1.011) 1.034(1.024) 1.060(1.043)
1.000 (1.000) 1.004(1.003) 1.015(1.011) 1.034(1.024) 1.061(1.043)
1.000 (1.000) 1.004(1.003) 1.015(1.011) 1.034(1.024) 1.060(1.043)
1.000 (1.000) 1.004(1.003) 1.015(1.011) 1.034(1.024) 1.061(1.043)
1.000 (1.000) 1.004(1.003) 1.015(1.011) 1.034(1.024) 1.062(1.043)
0.05 0.06 0.07 0.08 0.09
1.094 (1.067) 1.136(1.097) 1.186(1.133) 1.245(1.175) 1.311 (1.224)
1.095 (1.067) 1.139(1.098) 1.191(1.135) 1.253(1.178) 1.325 (1.229)
1.093 (1.067) 1.137(1.097) 1.187(1.133) 1.245(1.176) 1.311 (1.225)
1.097 (1.068) 1.143(1.099) 1.200(1.138) 1.268(1.183) 1.351 (1.237)
1.098 (1.068) 1.146(1.100) 1.204 (1.139) 1.277 (1.186) 1.365 (1.242)
0.10 0.11 0.12 0.13 0.14
1.386(1.280) 1.469(1.342) 1.559(1.412) 1.657(1.490) 1.761(1.575)
1.407(1.287) 1.500(1.353) 1.604(1.428) 1.720(1.512) 1.848(1.607)
1.384(1.280) 1.463(1.343) 1.546(1.412) 1.632(1.488) 1.717(1.570)
1.448(1301) 1.564(1.374) 1.700 (1.459) 1.859(1.558) 2.044(1.671)
1.473(1.308) 1.604(1.386) 1.765(1.477) 1.963(1.584) 2.208(1.710)
0.15 0.16 0.17 0.18 0.19
1.872(1.669) 1.987 (1.771) 2.108(1.881) 2.231 (2.001) 2.357 (2.129)
1.987(1.712) 2.138 (1.828) 2.299(1.957) 2.470 (2.098) 2.650 (2.253)
1.801(1.659) 1.879 (1.753) 1.951(1.853) 2.013 (1.956) 2.067 (2.063)
2.258(1.800) 2.504 (1.949) 2.783(2.120) 3.096 (2.315) 3.439 (2.538)
2.514(1.858) 2.901 (2.034) 3.397(2.242) 4.045 (2.490) 4.906 (2.789)
0.20 0.21 0.22 0.23 0.24
2.485(2.266) 2.613 (2.413) 2.741(2.568) 2.868 (2.733) 2.993(2.906)
2.837(2.422) 3.030 (2.606) 3.277(2.806) 3.427 (3.022) 3.627(3.254)
2.110(2.171) 2.145 (2.279) 2.173(2.387) 2.195 (2.493) 2.212(2.597)
3.807(2.791) 4.190 (3.079) 4.574(3.403) 4.942 (3.768) 5.278(4.174)
6.080(3.149) 7.724 (3.589) 10.112(4.130)
0.25 0.26 0.27 0.28 0.29
3.116(3.089) 3.236(3.280) 3.353 (3.481) 3.466 (3.690) 3.576 (3.908)
3.826(3.502) 4.022(3.768) 4.214 (4.051) 4.400 (4.350) 4.579 (4.667)
2.226(2.698) 2.238(2.796) 2.249 (2.892) 2.259 (2.985) 2.268 (3.076)
5.566(4.622) 5.797(5.112) 5.970 (5.640) 6.089 (6.202) 6.163 (6.788)
a b
Regular star with four arms. Entries in parentheses indicate P~l(qg0) values.
TABLE 2.
DISSYMMETRIES FOR MONODISPERSE AND POLYDISPERSE COILS*
P-(^)
Z45
p =l
/t> = 1 . 2
and ( ^
(*^ 2 )
/7 = 1 . 5
p = 2.0
p = 5.0
1.00 1.02 1.04 1.06 1.08
1.000(O)6 1.014(23) 1.028 (33) 1.042 (40) 1.056(46)
1.000(0) 1.014(21) 1.028 (30) 1.042 (37) 1.056(43)
1.000(0) 1.014(20) 1.028 (29) 1.042 (35) 1.056(40)
1.000(0) 1.014(19) 1.028 (27) 1.042 (33) 1.056(38)
1.000(0) 1.014(17) 1.028 (24) 1.042 (30) 1.056(35)
1.10 1.12 1.14 1.16 1.18
1.070 (51) 1.085(56) 1.099(61) 1.113(65) 1.128(69)
1.070 (48) 1.085(53) 1.099(57) 1.114(61) 1.129(65)
1.071 (45) 1.086(49) 1.100(53) 1.115(57) 1.130(61)
1.071 (43) 1.086(47) 1.101(51) 1.116(54) 1.131(58)
1.071 (39) 1.087(43) 1.102(47) 1.116(50) 1.133(53)
1.20 1.22 1.24 1.26 1.28
1.142(72) 1.157(76) 1.171(79) 1.186(82) 1.201(85)
1.143(68) 1.159(71) 1.173(75) 1.189(78) 1.204(80)
1.145(64) 1.161(67) 1.176(71) 1.191(73) 1.207(76)
1.146(61) 1.162(64) 1.177(67) 1.193(70) 1.210(73)
1.148(56) 1.164(59) 1.180(62) 1.196(65) 1.213(68)
TABLE 2. conf'c/ P ^ 9 0 ) and ( ^ Z45
P= I
p = 1.2
(Rl)1J^
p = 1.5
p = 2.0
p = 5.0
1.30 1.40 1.50 1.60 1.70
1.215(88) 1.290(102) 1.366(113) 1.444(124) 1.524(134)
1.219(83) 1.297(97) 1.377(109) 1.460(119) 1.546(129)
1.222(79) 1.303(92) 1.387(104) 1.473(115) 1.564(125)
1.225(76) 1.308(88) 1.394(100) 1.484 (111) 1.578(121)
1.229(70) 1.314(82) 1.404(93) 1.498(104) 1.597(114)
1.80 1.90 2.00 2.10 2.20
1.607 (144) 1.693(152) 1.781(161) 1.874(169) 1.969(178)
1.636 (139) 1.729(149) 1.826(158) 1.927(167) 2.032(175)
1.659 (135) 1.758(145) 1.861(154) 1.971(163) 2.084(172)
1.677 (131) 1.782(141) 1.890(150) 2.007(160) 2.128(169)
1.703 (125) 1.815(134) 1.932(144) 2.058(154) 2.190(163)
2.30 2.40 2.50 2.60 2.70
2.069 (185) 2.174(194) 2.283 (201) 2.397 (209) 2.517 (217)
2.143 (184) 2.260(192) 2.382 (201) 2.510 (209) 2.645 (218)
2.205 (181) 2.332(190) 2.466 (199) 2.607 (209) 2.757 (218)
2.257 (178) 2.393(188) 2.538 (198) 2.691 (207) 2.855 (217)
2.332 (173) 2.484(183) 2.645 (193) 2.817 (203) 3.003 (214)
2.80 2.90 3.00 3.50 4.00
2.643 2.776 2.916 3.755 4.948
2.788 2.939 3.099 4.070 5.488
2.916 3.085 3.264 4.375 6.044
3.029 3.215 3.414 4.665 6.601
3.202 (225) 3.416 (236) 3.648 (247) 5.145 (312) 7.588 (397)
11 b
(225) (233) (240) (283) (333)
(227) (235) (244) (292) (349)
(227) (236) (246) (299) (364)
(227) (237) (247) (305) (377)
Polydisperse systems characterized by the Schulz-Zimm distribution: p — A/ w /A/,,. Entries in parentheses denote weight-average value of R2%.
G. REFERENCES 1. H. Yamakawa, "Modern Theory of Polymer Solutions", Harper and Row, New York, 1971, Ch. 5. 2. E. F. Casassa, G. C. Berry, in: P. E. Slade Jr., (Ed.), "Polymer Molecular Weights", Marcel Dekker, New York, 1975, C. 5. 3. A. C. Albrecht, J. Chem. Phys., 27, 1014 (1957). 4. B. H. Zimm, J. Chem. Phys., 16, 1093 (1948). 5. P. Doty, R. F. Steiner, J. Chem. Phys., 18 1211 (1950). 6. E. F. Casassa, J. Polym. Sci., Polym. Phys. Ed., 17, 2077 (1979). 7. P. Debye, J. Phys. Colloid Chem., 51, 18 (1947). 8. E. F. Casassa, J. Polym. Sci. A, 3, 605 (1965). 9. M. Abramovitz, I. A. Stegun (Eds.), "Handbook of Mathematical Functions with Formulas, Graphs, and Mathematical Tables", National Bureau of Standards Applied Mathematics Series 55, US Government Printing Office, Washington DC, 10th printing, 1972. 10. H. Benoit, J. Polym. Sci., 11, 507 (1953). 11. E. F. Casassa, G. C. Berry, J. Polym. Sci. A-2, 4, 881 (1966). 12. H. Benoit, Compt. Rend., 245, 2244 (1957). 13. O. B. Ptitsyn, Zh. Fiz. Khim., 31, 1091 (1957). 14. A. J. Hyde, J. H. Ryan, F. T Wall, J. Polym. Sci., 33, 129 (1958). 15. P. J. Flory, R. L. Jernigan, J. Am. Chem. Soc, 90, 3128 (1968). 16. A. Peterlin, in: M. Kerker, (Ed.), "Electromagnetic Scattering", Pergamon Press, New York, 1963, p. 357.
17. T. Neugebauer, Ann. Phys., 42, 509 (1943). 18. O. Kratky, J. Porod, J. Colloid Sci., 4, 35 (1949). 19. M. Kerker, "The scattering of Light and other Electromagnetic Radiation", Academic Press, New York, 1969, Ch. 8. 20. B. H. Zimm, J. Chem. Phys., 16, 1099 (1948). 21. J. G. Kirkwood, R. J. Goldberg, J. Chem. Phys., 18, 54 (1950). 22. W. H. Stockmeyer, J. Chem. Phys., 18, 58 (1950). 23. H. Benoit, J. Polym. Sci., 11, 507 (1953). 24. A. H. Dautzenberg, C. Ruscher, J. Polym. Sci. C, 16, 2913 (1967). 25. K. Kajiwara, W. Burchard, M. Gordon, Brit. Polym. J., 2, 110(1970). 26. W. Burchard, Macromolecules, 10, 919 (1977). 27. M. Goldstein, J. Chem. Phys., 21, 1255 (1953). 28. E. F. Casassa, J. Am. Chem. Soc, 78, 3980 (1956). 29. W. H. Beattie, C. Booth, J. Phys. Chem., 64, 696 (1960). 30. P. Becher, J. Phys. Chem., 63, 1213 (1959). 31. W. H. Beattie, C. Booth, J. Polym. Sci., 44, 81 (1960). 32. M. Abramovitz, I. A. Stegun (Eds.), "Handbook of Mathematical Functions with Formulas, Graphs, and Mathematical Tables", National Bureau of Standards Applied Mathematics Series 55, US Government Printing Office, Washington DC, p. 232. 33. C. Hastings, Jr., "Approximations for Digital Computers", Princeton University Press, Princeton, 1955, pp. 197, 199.
34. M. Abramovitz, I. A. Stegun (Eds.), "Handbook of Mathematical Functions with Formulas, Graphs, and Mathematical Tables", National Bureau of Standards Applied Mathematics Series 55, US Government Printing Office, Washington DC, p. 370.
35. S. Wolfram, The Mathematica Book, Wolfram Media, Champaign, Illinois, 1996. 36. B. W. Char, K. O. Geddes, K. H. Gonnet, B. L. Leong, M. B. Monagan, S. M, Watt, "First Leaves: ATutorial Introduction to Maple V", Springer, New York, 1992.
D i p o l e
M o m e n t s
o f
P o l y m e r s
i n
S o l u t i o n
J. F. Salort C/Azalea 200, 28109-Madrid, Spain C. Salom Escuela Tecnica Superior de lngenieros Aeronauticos, Universidad Politecnica, Madrid, Spain E. Riande lnstituto de Ciencia y Tecnologfa de Polfmeros, Consejo Superior de Investigaciones Cientfficas, Madrid, Spain
A. Introduction VII-637 B. Dipole Moments of Polymers In Solution VII-638 Table 1. Polyoxides (Polyethers) VII-638 Table 2. Polysulfides (Polythioethers) VII-639 Table 3. Hydroxyl Terminated Oxide/Sulfide Copolymers VII-640 Table 4. Polyesters Derived from Aromatic Diacids VII-640 Table 5. Aliphatic and Cycloaliphatic Polyesters VII-641 Table 6. Polycarbonates VII-641 Table 7. Vinyl Polymers VII-642 Table 8. Acrylic Polymers VII-643 Table 9. Methacrylic Polymers VII-644 Table 10. ltaconate Polymers VII-644 Table 11. Polydienes VII-644 Table 12. Silicon Based Polymers VII-645 Table 13. Styrene Copolymers VII-645 C. References VII-646
A.
INTRODUCTION
Each conformation of a polymer chain has a dipole moment, \x, in Debye units D (=10 ~18 x u.e.e. x 1 cm or 3.338 x 10" 30 C x m), equal to the vectorial sum of the moments of Af dipolar groups along the chain, that is, }JL(Q = Ylimi> where ra, is the dipole moment associated with the skeletal bond / in the conformation (. The mean-square dipole moment {JJL1) can be written as (22,91)
(Al)
where ra, and m; are the dipole moments associated with the skeletal bonds i and j , respectively, and the brackets mean averages. For a freely jointed chain, the last term in Eq. (Al) averages to zero, and the corresponding meansquare dipole moment is given by (A2) The values of the mean-square dipole moment are currently expressed in terms of the dipole moment ratio, Dn — (/i 2 )/ Yl mh o r ^ e dipolar correlation coefficient, g, by means of the following expression: (A3) Debye (13) pioneered the theories which allow calculation of the dipole moments of molecules in the vapor or gas phase. Other theories (23,32,53) developed to determine the dipole moments of molecules in the liquid state were not so successful because of the difficulties involved in defining the internal field in a polar, condensed medium. This problem was circumvented by calculating the dipole moment of polymers and polar liquids in very dilute solutions using nonpolar solvents. In this way, the solute molecules are separated from one another by nonpolar molecules, and the dielectric behavior of the system resembles that of a gaseous condition. The method developed by Guggenheim (27) and Smith (106), based on this approach, permits calculation of the mean-square dipole moments of polymers by means of the following equation: (A4)
where k% and NA are, respectively, the Boltzmann constant and Avogadro's number, M is the molecular weight of the solute, T the absolute temperature, p and e \ the density and the dielectric permitivity of the solvent, respectively. The term de/dw (proportional to the total polarization of the solute) can be obtained from plots of the dielectric permitivity of the solution, e, against the weight fraction of solute w, in the limit w —» 0. The values of dn2/dw (proportional to the electronic polarization) can be obtained from the increments of the indices of refraction of the solution n with respect to that of the solvent n \, also in the limit w —> 0. A shortcoming of this equation is that a ficticious atomic polarization (instead of the true one) is assumed. However, with the exception of the silicones, the atomic polarization for most systems is less than 10% of the electronic polarization and, consequently, the error involved in the determination of (IJL2) with Eq. (A4) is negligible. The mean-square dipole moment presents some advantages over other more traditional conformation-dependent properties such as the mean-square end-to-end distance (r 2 ) 0 . For
example, since the skeletal bonds change much more in polarity than they do in length, (fj,2) is usually more sensitive to structure than {r2}0. Moreover, with the exception of a relatively few number of polymers that have dipole moments in their structure with a component parallel and the other perpendicular to the chain contour, excluded volume effects are negligible. In the tables, the dipole moments are expressed in terms of either the dipolar correlation coefficient g, or the meansquare dipole moment per repeating unit, {JJL2)/X. For relatively long chains in which dipole contributions of the end groups are not important, (^2}/x and g are related by (A5) where x is the degree of polymerization, and ^Q is the sum of the squares of the dipole moments associated with the repeating unit. Below the generic name of each family of polymers, the dipole moments associated with the backbone are indicated.
B. DIPOLE MOMENTS OF POLYMERS IN SOLUTION TABLE 1. POLYOXIDES (POLYETHERS)* Polymer Poly(oxymethylene) Polyformaldehyde With x = l With x = 2 With x = infinite Poly(oxyethylene) Poly(ethylene oxide) x = 2-6 M n = 4000 X= 1-6 x = 4.0-176.2 x = 4.1-153.0 x = 1-33,6 M n = 4000 x = 1-7 x = 2-227 Poly(oxypropylene) Poly(propylene oxide) x = 6.6-69.0 Poly(oxytrimethylene) Poly(trimethylene oxide) Poly[oxy(2,2-dimethyltrimethylene)] Poly(3,3 -dimethyloxetane) M n = 8500 Mn = 19000 Mn = 35000 Poly [oxy( 1 -methyltrimethylene)] Poly(2~methyloxetane) Mn = 13000 Poly[oxy(2-methyltrimethylene)] Poly(3-methyloxetane) Mn = 125000
Solvent
Temp. (0C)
gorDn
(/J2)/JC, D 2
Remarks
0.1 0.29 0.3
Refs.
Benzene Benzene Melt
25 25 202
109 109 56
Benzene Benzene Benzene Benzene Benzene Benzene Benzene Dioxane Benzene
20 20-60 25 25 25 20 20-60 25 20-30
Benzene Benzene Dioxane
25 25 25
0.54 0.49
Benzene
25
0.41
50
Benzene Benzene Benzene
20-60 30-60 30-60
0.25-0.30 0.20-0.22 0.21-0.23
94 25 25
Cyclohexane
30-60
0.36-0.41
78
Cyclohexane
30-60
0.35-0.38
77
1.32-1.23 0.603-0.644 1.30-1.14 2.82-1.28 2.59-1.28 1.99-1.19 0.621-0.693
End groups: -OC 2 H 5 m(CH 2 -O) = 0.99Z) End groups: -OC 2 H 5
W(CH2-O) = 0.99D 2.82-1.66 2.13-1.14 1.96-1.04 Isotactic Isotactic
47 59 34 46 2 45 4 110 47 45 1 1
*If not indicated otherwise, the dipole moments associated with the skeletal bonds used in the calculation of g were m(CH 2 -0) = 1.07D, m(CH 2 -CH 2 ) = 0£>, and m(O-H)= 1.7D.
TABLE 1. cont'd Polymer
Solvent
Temp. (0C)
Poly(oxytetramethylene) Polytfetramethylene oxide) M n =2500 Benzene Mn-408000 Benzene Poly[oxy(2-methyltetramethylene)] Poly(3-methyltetrahydrofuran) M n = 6700 Benzene Poly(oxyhexamethylene) Poly(hexamethylene oxide) M n = 5500 Benzene Mn = 2460 Benzene Poly(oxydecamethylene) Polyidecam ethy Ien e oxide) M n = 2000 Benzene Poly(oxyethyleneoxyrnethylene) Poly(l,3-dioxo!ane) M n = 12000 Benzene M n =16000 Benzene M n =42000 Benzene Poly(oxytetrarnethyleneoxymethylene) PoIy ( 1,3-dioxepane) M n = HOOO Benzene Poly(oxypentamethyleneoxymethylene) Poly( 1,3 -dioxocane) M n = 1850 Benzene Mn = 2560 Benzene M n = 3700 Benzene Poly(oxyhexamethyleneoxymethylene) Poly( 1,3 -dioxonane) M n =4020 Benzene Mn = 2600 Benzene Poly(7/rm.s-oxymethylene-1,4-cyclohexyIeneoxymethylene) Poly( trans-1,4-cyclohexane dimethanol alt-formaldehyde) Mn =6500 Benzene ' Poly(oxypropyleneoxy methylene) Poly [(4-methyl)-1,3-dioxolane] M n =40000 Benzene M n =48000 Benzene Poly(fra/is-7-oxabicyclo-[4.3.0Jnonane) Poly(trans-7-oxabkyclo-[4.3.0]nonane) Benzene
g or Dn
(n2)/x, D2
ra(CH 20-60 20-60
Remarks 2 -O) =
Refs. 0.99D
0.60-0.65 0.59-0.65
30-60
61 4
0.52-0.55
81
ra(CH 35-60 35-60
2 -O) =
0.99D
0.65-0.68 0.64-0.67
59 80
ra(CH 35-60
2-O) =
0.99D
0.64-0.68
61 Polyformals: alternating copolymer of methylene oxide and alkylene oxide
20-60 20-60 20-60
0.160-0.204 0.164-0.213 0.177-0.227
62 62 62
25-60
0.160-0.190
63
20-60 20-60 20-60
0.190-0.232 0.183-0.207 0.168-0.207
64 64 64
20-60 20-60
0.190-0.230 0.180-0.217
64 64
20-60
0.17-0.21
71
20-60 20-60
0.237-0.281 0.216-0.256
73 73
30-60
0.63-0.66
111
TABLE 2. POLYSULFIDES (POLYTHIOETHERS)* Polymer Poly(thiotrimethylene) PoIy(trimethylene su lfide) M n = 14000 Poly(thiopentamethylene) Poly(pentamethylene sulfide) M n = 3200
Solvent
Temp. (0C)
g or Dn
Benzene
20-60
0.60-0.63
Benzene
20-60
0.75-0.78
Benzene Carbon tetrachloride Benzene Carbon tetrachloride Benzene Carbon tetrachloride Benzene
20-60 20-60 20-60 20-60 20-60 20-60 20-60
0.434-0.449 0.362-0.407 0.429-0.458 0.325-0.347 0.448-0.460 0.357-0.389 0.386-0.420
(n2)/x,D2
Remarks
Refs.
75
End bonds: CH 2 -Br; m(CH 2 -Br)=1.96D
74
Poly(thiopropylene) Polyipwpylene sulfide) Mn Mn Mw Mn Mn Mn
= 5000000 =5000000 = 1.6 x l O 6 =5000 =6000 =1.6 x l O 6
Isotactic
Isotactic
67 68 68 68 67 67 68
* Wt(CH2-CH2) = 0A m(CH 2 -S)=1.2LD, m(6-H) = 1.7D.
References page VII - 646
TABLE 2. cont'd Polymer
Solvent
Poly[thio(2,2-dimethyltrimethylene)] Poly {3,3-dimethylthietane) M n = 8200 Benzene Poly(thiopentamethylenethioethylene) Poly(ethylene sulfide-alt-pentamethylene sulfide) Mn = 3800 Benzene
Temp, (0C)
gorDn
30-60
0,62-0.63
30-60
0.64-0.67
Poly(thiopentamethylenethiomethylene) PoIy(1,3-dithiocane) Mn = 14000 Benzene 20-60 Poly(thiomethylene-1,4-cyclohexylenemethylenethiomethylene) trans Mn = 8000 Benzene 30-60
0.26-0.31
TABLE 3. Polymer
(fi2)/x,D2
Remarks
Refs.
72
End bonds: CH 2 -Br, m(CH 2 -Br)=1.96D Alternating copolymer of pentamethylene sulfide and methylene sulfide
0.176-0.207
70
112 54
HYDROXYL TERMINATED OXIDE/SULFIDE COPOLYMERS0 Solvent
Poly(thioethyleneoxyethylene) Poly(thiodiethylene glycol) M n = 13000 Benzene M n = 8000 Benzene Poly(thiomethyleneoxymethylenethiopentamethylene) Poly(3-oxa-1,5-dithiadeca-methylene) M n = 5200 Benzene Poly(oxymethyleneoxyethylenethioethylene) PoIy(1,3-dioxa-6-thiocane) M n = 2500 Benzene M n = 3000 Benzene Poly(oxymethyleneoxyethylenethiomethylenethioethylene) Alternating copolymer of 1,3-dioxolane and 1,3-dithiolane Benzene
Temp. (0C)
g or Dn
Remarks Alternating copolymer of ethylene sulfide and methylene sulfide
Refs.
20-60 20-60
0.607-0.648 0.627-0.659
66 66
30-60
0.323-0.358
84
20-60 20-60
0.419-0.432 0.419-0.432
65 65
30
0.26
66
fl
m(CH2-CH2) = 0Z), m(CH 2 -0)= 1.07D, m(CH2-S)= 1.21D.
TABLE 4. Polymer
POLYESTERS DERIVED FROM AROMATIC DIACIDS* Solvent
Poly[di(oxyethylene) oxyterephthaloyl] Poly(diethyleneglycol terephthalate) M n = 2500 Benzene Poly[di(oxyethylene) oxyisophthaloyl] Poly(diethyleneglycol isophthalate) M n = 5900 Benzene Poly[di(oxyethylene) oxyphthaloyl) Poly(diethyleneglycol phthalate) M n = 10300 Benzene Poly(oxypropyleneoxyterephthaloyl) Poly(propyleneglycol terephthalate) M n = IlOOO Benzene Poly[di(oxypropylene) oxyterephthaloyl) Poly(dipropyleneglycol terephthalate) M n = IOOOO Benzene Poly(tri(oxytrimethylene) oxyterephthaloyl) Poly(triethyleneglycol terephthalate) M n =7800 Benzene Poly[di(oxytrimethylene) oxyterephthaloyl] Poly(ditrimethyleneglycol terephthalate) Mn =15500 Benzene (Poly(thioethyleneoxyethyleneoxyterephthaloyl) Poly(thiodiethyleneglycol terephthalate) M n = 6400 Dioxane
Temp. (0C)
g or Dn
35-60
0.688-0.692
60
30-60
0.691-0.692
79
30-60
0.637-0.679
86
30-60
0.582-0.609
87
30-60
0.715-0.750
14
30-60
0.677-0.695
82
30-60
0.805-0.798
26
40-70
0.540-0.552
Remarks
m(CH 2 -S) = 1.21D
'Hydroxyl terminated polyesters m(C6H5COOCH2) = 1.98Z); m(CH2-O) (ether)= 1.07D; m(CH2-CH2) = 0D; m(O-H) = LlD.
Refs.
69
TABLE 5. ALIPHATIC AND CYCLOALIPHATIC POLYESTERS* Polymer
Solvent
Poly[oxy (2,2-dirnethyltrimethylene) oxysuccinoyl] Poly(neopentylglycol succinate) M n = 6900 Benzene Poly(oxysuccinoyloxymethylene-1,4-cyclohexylenemethylene) trans Poly(trans-l,4-cyclohexane dimethanol succinate) M n = 5800 Dioxane Poly[oxy(2,2-dimethyltrimethylene) oxyadipoyl] Poly(neopentylglycol adipate) M n =5500 Benzene Poly(oxyadipoyloxymethylene-1,4-cyclohexylenemethylene) cis Poly(cis-1,4-cyclohexane dimethanol adipate) M n = IlOOO Benzene M n = IlOOO Dioxane Poly(oxy adipoyloxymethylene-1,4-cyclohexylenemethylene) trans Poly(trans-1,4-cyclohexane dimethanol adipate) M n = IOOOO Dioxane Poly(oxysebacoyloxymethylene-1,4-cyclohexylenemethylene) trans Poly(trans-1,4-cyclohexane dimethanol sebacate) M n =4600 Benzene Poly[oxy(2,2-dimethyltrimethylene) oxyhexafluoroglutaroyl] Poly(neopentylglycol hexafluoroglutarate) M n = 3640 Benzene Poly[oxy(2,2-dimethyltrimethylene) oxyglutaroyl] Poly(neopentylglycol glutarate) M n =4500 Benzene Poly(oxysebacoyloxymethylene-1,4-cyclohexylenemethylene) cis Poly(cis-1,4-cyclohexane dimethanol sebacate) M n = 5200 Benzene Poly[di(oxyethylene) oxycarbonyl-1,4-cyclohexylenecarbonyl] trans Poly(diethyleneglycol-1,4-trans-cyclohexane dicarboxylate) M n = 5300 Benzene
Temp. (0C)
g or Dn
(fi2)/x
30-60
0.548-0.586
88
70
0.454
90
30-60
0.653-0.688
85
30-60 30-60
0.950-0.972 0.914-0.959
90 90
50-70
0.596-0.65
90
30-60
0.631-0.709
83
Refs.
30-60
9.16-9.78
58
30-60
4.26-4.52
58
300-60
0.983-1.04
83
30-60
0.585-0.608
89
* Hydroxyl terminated polyesters m(CH2COOCH2)= 1.89D. TABLE 6.
POLYCARBONATES
Polymer
Solvent
Temp. (0C)
(p2)/x,D2
Remarks
Refs.
Poly(oxycarbonyloxy-1,4-phenylene-1 -(R)-1 -methylmethylene-1,4-phenylene) Polycarbonate x = 97 JC = 88 x — 73
Benzene Benzene Benzene
25 25 25
9.36 11.70 17.64
R = 3-chlorophenyl R = 4-chlorophenyl
28 28 28
Benzene 25 1,4-Dioxane 25 1,4-Dioxane 25 Benzene 25 Benzene 25 2,2/-bis(4-hydroxylphenyl)propane) 2,2/-bis(4-hydroxylphenyl)propane) 1,4-Dioxane 25 l,l/-bis(4-hydroxyphenyl)-l-(3-chlorophenyl)ethane) l,l/-bis(4-hydroxyphenyl)-l-(3-chlorophenyl)ethane) Benzene 25 l,l/-bis(4-hydroxyphenyl)-l-(4-chlorophenyl)ethane) 1,17-bis(4-hydroxyphenyl)-1-(4-chlorophenyl)ethane) Benzene 25
1.69 1.88 2.07 2.76 2.13
R = isobutyl R= H R = phenyl R= H R = ethyl
21 21 21 21 21
Poly(thiocarbonate) Poly(thiocarbonate) x= 128 x = 75 JC = 2 8 0 JC = 7 5 x = 49 Poly(thiocarbonate Poly(thiocarbonate M n =9400 Poly(thiocarbonate Poly(thiocarbonate With JC = 97 Poly(thiocarbonate Poly(thiocarbonate With x = 88
of of of of of of
0.92
97
7.40
99,28
6.05
99,28
References page VII - 646
TABLE 6. cont'd Polymer
Solvent
Temp. (0C)
(fi2)/x,D2
Poly(thiocarbonate of l,l/-bis(4-hydroxyphenyl)-l-(3,4-dichlorophenyl)ethane) Poly(thiocarbonate of 1, l/-bis(4-hydroxyphenyl)~l-(3,4-dichlorophenyl)ethane) With x = 73 * Benzene 25
Remarks
Refs.
12.25
99,28
TABLE 7. VINYL POLYMERS* Polymer Poly (1 -phenylethylene) Poly(styrene) Atactic Atactic Isotactic Poly(2-bromophenylethylene) Poly(o-bromostyrene)
Solvent
Toluene Carbon tetrachloride Toluene
Temp. (0C)
g or Dn
38.4 25 38.4
0.36 0.56 0.53
(n2)/x9D2
Remarks
M0 = 0.60D /i 0 = O.35D /.to = 0.60D
0.50 1.21
Poly(4-bromophenylethylene) Poly(p-bromostyrene) PPBSI /?-Dioxane PPBSI Carbon tetrachloride PPBSII /7-Dioxane Poly( 1 -phenylethylene/(4-pyridyl) ethylene) Poly {sty rene/4-vinylpyridine) Benzene Poly[ 1 -methyl-1 -(4-fluorophenyl) ethylene] Poly(p-fluoromethylstyrene) Benzene Benzene Poly[(4-methoxyphenyl) ethylene] Poly(p-methoxystyrene) Toluene Benzene Benzene Poly[(4-fluorophenyl) ethylene] Poly(p-fluorostyrene) Benzene Benzene Poly[(2-chlorophenyl) ethylene] Poly(o-chlorostyrene)
20-50 20-50 20-50 0.73
25 25
0.62 0.27
25 25 25 25 25
108 108 108 Mo = 2.65D
5
0.89
Mo = 1.82D /*0 = 1-82D
6 5
0.54 0.72 0.64
0.78 1.06 0.94
no = l.2W no = \.2\D /x0 = 1.21D
31 5 6
0.62 0.51
2.05 1.69
Mo = 1.82D Mo = 1-82D
6 5
2.85 Poly[(3-chlorophenyl) ethylene] (Poly(m-chlorostyrene) Poly[(4-chlorophenyl) ethylene] Poly(p-chlorostyrene)
57
Toluene
25
0.63
1.61
Mo = 1-60D
Xylene
30 30-50 30 50 20-50 25 25-65 30 30-90 30-60 25 25 30 20-90 25 30 30 25 30-90 15-70
0.71 0.42-0.56 0.56
2.00
Mo = 1.68
2.10 1.89 2.11-2.46 1.82 1.87-1.73 2.17 2.06-1.98 2.09-2.12
Mo = 1^3
Benzene Carbon tetrachloride /?-Dioxane Toluene Cumene Toluene Isopropylbenzene Toluene Benzene Toluene Isopropylbenzene K-Propylbenzene Carbon tetrachloride Benzene Benzene Toluene Isopropylbenzene Benzene
35 37 35 57 57
2.20-2.49 2.12-2.54 2.44-2.72
25
Refs.
0.77 0.73-0.70 0.74-0.75 0.64 0.53 0.436-0.499 0.57 0.60 0.493-0.520 0.599-0.562
1.65 1.50 1.641-1.878
M0 = ^0 = Mo = Mo =
1.68 1.68 1 68 2.0
Mo =1-68 Mo = 1 88D
1.49 1.49 1.59 11.854-1.956 2.373-2.224
Isotactic Mo = 1 63
93 11 57 12 108 108 113 113 11 9 9 5 31 Il 114 6 55 55 93 114 114
*In vinyl polymers the dipolar correlation coefficient is expressed by g = (M 2 ) AMO> w h ^re x is the degree of polymerization and MO is the dipole moment of a model compound of the repeating unit.
TABLE 7. cont'd Polymer
Solvent
Poly( 1 -acetoxyethylene) Poly(vinyl acetate)
Poly( 1 -bromoethylene) Polyivinyl bromide) Several fractions
Poly( 1 -chloroethylene) Poly(vinyl chloride) Atactic fraction Atactic fraction Atactic fraction Eight fractions (atactic) Syndiotactic fraction Mn = 26000 (atactic) Mn =47000 (atactic) Poly(isobutoxyethylene) Poly(vinyl isobuts'lether) Isotactic fraction Atactic fraction Isotactic fraction Atactic fraction Poly(carbazolylethylene) Poly(vinyl carbazole)
Temp. (0C)
g or Dn
(fi2)/x,D2
Remarks
Refs.
25 20
0.89 and 0.94 0.84 0.75-0.80
2.59-2.89 2.89
/X0 = 1-80D ^ 0 = 1.86
38 101 107
1.97-3.20 2.29-2.38
^o = 1.93D /x0 = 2.08D ^o = 2.08D
40 95 95
2.65 2.79-3.06 1.716 1.72-1.67 2.59-2.82 1.93 2.72-2.60
/i O = Mo = /xo = /x0 = ^0 = /U0 = /i 0 =
2.80-2.72
^ 0 = 2.00D
33 29 33 33 39 33 8 12 8
1.345 and 1.464
^ 0 = 1.22Z) /xo = 1.22D
107 107 55 55
Benzene and CCl4 Benzene
/>Dioxane p-Dioxane 1-Methylnaphthalene
/?-Dioxane /?-Dioxane Tetrahydrofuran Tetrahydrofuran p-Dioxane Tetrahydrofuran /7-Dioxane
25 30-60 30-60
20 and 40 20-65 40 20 and 40 25 20 25-55
/7-Dioxane
Benzene Benzene Benzene Benzene
25-55
0.59 0.70-0.75 0.64-0.62 0.66-0.72 0.71 0.68-0.65 0.75 0.70-0.68
2.12D 2.00D 1.64D 1.64D 2.00D 1.64D 2.00D
25 and 50 25 30 30
0.90 and 0.98 0.77 and 0.83 0.98
0.98 0.96
25 30-60
0.36 0.41-0.44
3.71 3.52-3.78
/x0 = 3.21D /x0 = 2.93D
30 102
20-50
1.10-1.06
2.34-2.26
^ 0 = 1.46D
100
25
0.28
1.21
/x0 = 2.08D
6
Toluene /7-Dioxane
Poly(ethylenethiophenylene) Pofyfvinylphenyl sulfide) Benzene Poly[ 1 -methyl-1 -(4-bromophenyl) ethylene] Po/vfp-fcroma-a-methylstyrene) Benzene
TABLE 8.
0.53-0.86 0.45-0.46
ACRYLIC POLYMERS*
Polymer Poly[ 1 -methoxycarbonyl) ethylene] Poly(methyl aery late)
Solvent
Benzene Benzene
Temp. (0C)
20 25
Poly[2-(biphenyloxycarbonyl) ethylene] Poly(2-biphenyl acrylate) Benzene 30-60 Poly[ 1 -(cyclohexyloxycarbonyl) ethylene] Poly(cyclohexyl acrylate) Benzene 30-60 PoIy[I -(ethoxycarbonyl) ethylene] Poly(ethyl acrylate) Atactic fraction Benzene 30 Syndiotactic fraction Benzene 30 Poly[ 1 -(phenoxycarbonyl) ethylene] Polyiphenyl acrylate) Benzene 30-60 PoIy[I-((3-chloro) phenoxycarbonyl) ethylene] Polyim-chlorophenyl acrylate) Benzene 30-60 PoIy[I -((2-chloro) phenoxycarbonyl) ethylene] Poly(o-chlorophenyl acrylate) Benzene 30-60 PoIy[I-((4-chloro) phenoxycarbonyl) ethylene] Polyip-chlorophenyl aaylate) Benzene 30-60 PoIy[I-((4-benzoyl) phenoxycarbonyl) ethylene] Poly(4-benzoylphenyl acrylate) 1,4-Dioxane 30-60 PoIy[I-(4-phenoxy) phenyloxycarbonyl) ethylene] Poly(4-phenoxyphenyl acrylate) Benzene 30-60 PoIy[I -(hydroxyethylenedi(oxyethylene) oxycarbonyl) ethylene] Poly(triethyleneglycol acrylate) Benzene 30-60
g or Dn
(n2)/x,D2
Remarks
Refs.
0.717 0.64-0.67
2.22 1.99-2.07
/xo = l-76D /x0 = 1.76D
51 43
0.69-0.74
2.05-2.22
/i 0 = 1.723- 1.732D
16
0.75-0.81
2.79-3.01
/i 0 = 1.93D
15
1.04 1.04
55 55
0.62-0.66
1.73-1.91
/U0 = 1-669-1.700D
98
0.57-0.61
1.85-2.02
/I0 = 1.800- 1.824D
98
1.09-1.09
3.30-3.97
^ 0 = 1.74-1.91D
98
MO = 2 . 5 9 O - 2 . 6 9 4 D
98
^ 0 = 3.561-3.521/)
17
^ 0 =2.10-2.1 ID
18
0.524-0.501 0.81-0.84
10.27-10.41
0.82-0.84
3.61-3.74 7.97-8.16
92
* /to is the dipole moment of a model compound of the side group.
References page VII - 646
TABLE 9. METHACRYLIC POLYMERS* Polymer
Temp. (0C)
Solvent
Poly [ 1 -methoxycarbonyl)-1 -methylethylene] Poly(methyl methacrylate) Atactic fraction Five solvents Atactic fraction Benzene Atactic fraction Benzene Syndiotactic fraction Toluene Isotactic fraction Toluene Syndiotactic fraction Benzene Atactic fraction Benzene Isotactic fraction Benzene Isotactic fraction Benzene Atactic fraction Benzene Atactic fraction Toluene Syndiotactic fraction Benzene Atactic fraction p-Dioxane Poly[l-(ethoxycarbonyl)-l-methylethylene] Poly(ethyl methacrylate) 1,4-Dioxane Carbon tetrachloride Toluene Benzene Poly [ 1 -(propoxycarbonyl)-1 -methylethylene] Poly(propyl methacrylate) Poly [ 1 -(isopropoxycarbonyl)-1 -methylethylene] Poly(isopropyl methacrylate) Poly(butyl methacrylate) Poly(butyl methacrylate) Four solvents Poly(phenylmethacrylate) Poly(phenylmethacrylate) Poly(p-chlorophenylmethacrylate) Poly(p-chlorophenylmethacrylate) Poly(dichlorophenylmethacrylate) Poly(dichlorophenylmethacrylate)
25 25 25 30-90 25-65 25-65 25-65 25-65 30 30 25-65 30 23
0.62 0.53-0.66 0.55-0.72 0.67-0.79 0.65-0.75 0.70-0.78 0.69-0.78 0.77-0.81 0.67 0.56-0.61 0.66-0.78 0.53
25 25 25
0.58 0.54 0.62 0.59-0.62 0.58
25
(fi2)/x,D2
gorD,,
Remarks
^o = 1.73D 1.77-2.31 1.72-2.01 1.66-1.93 1.79-1.99 1.77-1.99 1.96-2.07 2.00 1.66-1.82 1.69-1.99 1.61 2.25
/i 0 = /x0 = ^0 = /^0 = ^0 = ^0 = Mo = /i 0 = /*0 = ^t0 =
1-80D 1-60D 1-60D 1.60D 1-60D 1-60D 0.73D 1.73D 1-60D 1-73D
2.00 1.87 2.14
/i 0 = 1-86D /^0 = 1-86D / i 0 = 1-86D
2.00
/I0 = 1.86D
48 57,107 42 105 105 105 105 105 3 3 105 3 10 36 36 36 57
0.56-0.59
57
0.61-0.66
57 1..93-2.72
23
Refs.
0.55-0.59
10 57
0.55
57
0.35
57
0.38
52
*}IQ is the dipole moment of a model compound of the side group.
TABLE 10. ITACONATE POLYMERS Polymer
Temp. (0C)
Solvent
Poly[ 1 -(cyclohexylmethylene oxycarbonylmethylene)-1 -(carboxy)ethylene] Poly(monocyclohexylmethylene itaconate) 1,4-Dioxane 20-50 Poly[ 1 -(cyclohexylmethyleneoxycarbonylmethylene)-1 -(cyclohexylmethyleneoxycarbonylmethylene) ethylene] Poly(dicyclohexylmethylene itaconate) Benzene 30-60 Poly[ 1 -benzyloxycarbonylmethylene)-1 -(carboxy) ethylene] Poly(monobenzyl itaconate) 1,4-Dioxane 25 Poly [ 1 -(benzyloxycarbonylmethylene)-1 -(benzyloxycarbonylmethylene)ethylene] Polyidibenzyl itaconate) 1,4-Dioxane 25-33
(n2)/x,D2
Refs.
5.75-5.70
20
6.89-7.00
19
3.84
96
2.31-2.79
24
TABLE 11. POLYDIENES
Polymer Poly( 1 -methyl-1 -butenylene) Poly(isoprene) cis 1,4 trans 1,4 Poly( 1 -chloro-1 -butenylene) Poly(chloroprene)
Temp. (0C)
gorD,,
Benzene Benzene
25 25
0.70 0.82
Benzene
20
2.70
Solvent
Remarks
^o = 0.34D ^ 0 = 0.34D
Refs.
41 41 101
TABLE 12. SILICON BASED POLYMERS* Polymer
Solvent
Linear Poly(dimethylsiloxane) Linear Poly(dimethylsiloxane) x+) =188 " A = 9.85 A = I , 102 x = 4, 95.0 .x = 69.6 JC= 14.8 A = 70.55 jc= 15.8 x~ 10.5 A+1=239 A-+1=97 A + 1 = 1038 A+1=239 A + 1 = 188 A+1=97 A + 1 = 1038 Poly (1,1 -dimethylsilazane) PoIy(IJ -dimethylsilazane) M n = 750
Undiluted Cyclohexane, benzene Undiluted
Temp. (0C)
g or Dn
10-60 30 25
0.306-0.297 0.18-0.21
Undiluted Cyclohexane, Cyclohexane, Cyclohexane, Cyclohexane, Cyclohexane, Undiluted Undiluted Cyclohexane Cyclohexane Cyciohexane Cyclohexane Undiluted
(?*2)/x, D2
Cyclic PDMS Linear PDMS; {fi2)1/2 = 2.07D, 14.4D Cyclic PDMS; (/i 2 ) l / 2 = 1.50D, 14.3D
25 benzene benzene benzene benzene benzene
30 30 30 30 30 10-60 10-60 10-60 10-60 10-60 10-60 10-60
Cyclohexane Hexamethyldisilazane Hexane Carbon tetrachloride Benzene
20-50 25 20 20-50 20-50
Poly(methylphenyl siloxane) Poly(methylphenyl siloxane) Mn = 45000 Cyclohexane Poly(dimethyl siloxane-co-methylphenyl siloxane) (35.7/54.3) Poly(dimethyl siloxane-co-methylphenyl siloxane) (35.7/54.3) Mn = 4200 Cyclohexane Poly(dimethylsiloxane-c-methylphenylsiloxane) (90.5/9.5) Poly(dimethylsiloxane'Co-methylphenylsiloxane) (90.5/9.5) Mn = 6400 Cyclohexane Poly(methylsilmethylene) Poly(methylsilmethylene) Cyclohexane
Remarks
0.20,0.33 0.21,0.28 0.21,0.30 0.19,0.26 0.18,0.27 0.305-0.297 0.314-0.306 0.398-0.444 0.377-0.412 0.377-0.369 0.387-0.407 0.308-0.301
Cyclic PDMS
0.370-0.326 0.246 0.330 0.310-0.310 0.342-0.359
Refs.
44 76 7 7 76 76 76 76 76 44 44 44 44 44 44 44 104 104 104 104 104
25
0.31
103
25
0.22
103
25
0.27
103
20
0.391
m(Si-C) = 0.50D
49
fl
m(Si-O) = 0.60D.
TABLE 13.
STYRENE COPOLYMERS*
Polymer
Solvent
Temp. (0C)
g or Dn
(n2)/x,D2
Remarks
Refs.
Poly[ 1 -phenylethylene-c0-(4-methoxyphenyl) ethylene] Poly(styrene-co-p-methoxystyrene) Ap =0.157 .
/i 0 = 121D; (M 2 )/A is referred to the polar unit
Toluene
25
1.07
1.56
3130
Ap =0.328 Toluene Ap =0.480 Toluene A P =0.721 Toluene Ap = 1 Toluene Poly( 1 -phenylethylene-c0-carbazolylethy Iene) Poly(styrene-co-vinykarbazole) AP =0.074 Toluene AP = 1.00 Toluene A P =0.368 Toluene A P =0.665 Toluene PoIy[I -phenylethylene-c0-(4-pyvidyl) ethylene] Poly(styrene-co-4-\nnylpyridine) Ap = 0.028 Toluene A P =0.183 Toluene A P =0.154 Toluene
25 25 25 25
0.84 0.74 0.69 0.54
1.23 1.08 1.01 0.78
25 25 25 25
0.53 0.36 0.53 0.39
/X0 = 3.21Z)
30 30 30 30
25 25 25
0.31 0.50 0.34
/U0 = 2.655D
30 30 30
3130 3130 3130 31 30
* AP is the molar fraction of polar comonomer and /Lto is the dipole moment of the polar repeating unit.
References page VII - 646
TABLE 13. cont'd Polymer
Solvent
JCp = 0.118 Toluene Xp =0.051 Toluene xp = 0.082 Toluene PoIy[I -phenylethylene-co-(4-chlorophenyl) ethylene] Poly(styrene-co-p-chlorostyrene) x p = 0.247 Toluene x p =0.802 Toluene x p = 1.00 Toluene
C.
Temp. (0C)
g or Dn
25 25 25
0.29 0.29 0.23
25 25 25
0.67 0.44 0.41
(fi2)/x,D2
Remarks
Refs. 30 30 30
2.67 1.76 1.4
/z0 = 2.0D
31,30 31,30 31,30
REFERENCES
1. A. Abe, T. Hirano, T. Tsuruta, Macromolecules, 12, 1092 (1979). 2. M. Aroney, R. J. W. Le Fevre, G. M. Parkins, J. Chem. Soc. 2890 (1960). 3. R. Bacskai, H. A. Pohl, J. Polym. Sci., 42, 151 (1960). 4. K. Bak, G. Elefante, J. E. Mark, J. Phys. Chem., 71, 4007 (1967). 5. B. M. Bay sal, H. Yu, W. H. Stockmayer, "Dielectric Dispersion in Dilute Solutions of Several Parasubstituted Polystyrenes", in: F. E. Karasz (Ed.), "Dielectric Properties of Polymers", 1972: p. 329. Plenum Press, New York, 1971. 6. B. M. Baysal, L. Aras, Macromolecules, 18, 1693 (1985). 7. M. S. Beevers, S. J. Mumby, S. J. Carlson, A. J. Semlyen, Polymer, 24, 1565 (1983). 8. F. Blasco-Cantera, E. Riande, J. P. Almendro, E. Saiz, Macromolecules, 14, 138 (1981). 9. F. Blasco, E. Riande, J. Polym. Sci., Polym. Phys. (Ed.), 21, 835 (1983). 10. L. de Brouckere, M. Mandel, "Dielectric Properties of Dilute Polymer Solutions", in: I. Prigogine 1(Ed.), "Advances in Chemical Physics", Interscience, New York, 1958, p. 77. 11. L. L. Burshtein, T. P. Stepenova, Polym. Sci. USSR, 11,2885 (1969). 12. P. Debye, F. Bueche, J. Chem. Phys., 19, 589 (1951). 13. P. Debye, Phys. Z., 13, 97 (1912); "Collected papers, Polar Molecules", Wiley Interscience, New York, 1954, p. 173. 14. R. Diaz-Calleja, E. Riande, J. Guzman, Macromolecules, 22, 3654 (1989). 15. R. Diaz-Calleja, E. Riande, J. San Roman, Macromolecules, 25, 2875 (1992). 16. R. Diaz-Calleja, E. Riande, J. San Roman, J. Phys. Chem., 96, 6843 (1992). 17. R. Diaz-Calleja, E. Riande, J. San Roman, J. Phys. Chem., 97, 4848 (1993). 18. R. Diaz-Calleja, E. Riande, J. San Roman, Polymer, 34,3456 (1993). 19. R. Diaz-Calleja, E. Riande, L. Gargallo, D. Radic, Macromolecules, 26, 3795 (1993). 20. R. Diaz-Calleja, E. Riande, L. Gargallo, D. Radic, J. Polym. Sci., Part B: Polym. Phys., 32, 1069 (1994). 21. M. J. Fabre, I. Hernandez-Fuentes, L. Gargallo, D. Radic, Polymer, 33, 194 (1992).
22. P. J. Flory, "Statistical Mechanics of Chain Molecules", Wiley-Interscience, New York, 1969. 23. H. Frohlich, Trans. Faraday Soc, 44,238 (1948); "Theory of Dielectrics", Oxford University Press, London, 1958. 24. L. Gargallo, M. Yazdani-Pedram, D. Radic, I. HernandezFuentes, Makromol. Chem., 189, 145 (1988). 25. L. Garrido, E. Riande, J. Guzman, J. Polym. Sci., Polym. Phys. Ed., 20, 1805 (1982). 26. C. Gonzalez, E. Riande, A. Bello, J. M. Perena, Macromolecules, 21, 3230 (1988). 27. E. A. Guggenheim, Trans. Faraday Soc, 45, 714 (1949); ibid. 47, 573 (1951). 28. I. Hernandez-Fuentes, F. Rey-Stolle, L. Hernan Tagle, E. Saiz, Macromolecules, 25, 3291 (1992). 29. Y. Imamura, J. Chem. Soc. Japan, 76, 217 (1955). 30. Z. Kuciikyavuz, B. M. Baysal, Macromolecules, 21, 2287 (1988). 31. K. Kuciikyavuz, B. M. Baysal, Polymer, 32, 3418 (1991). 32. J. G. Kirkwood, J. Chem. Phys., 7, 911 (1939). 33. A. Kotera, M. Shima, N. Fujisaki, T. Kobayashi, Bull. Chem. Soc. Japan, 35, 1117 (1962). 34. A. Kotera, K. Suzuki, K. Matsumura, T. Nakano, Y. Oyama, U. Kabayashi, Bull. Chem. Soc Japan, 35, 797 (1962). 35. W. R. Krigbaum, A. Roig, J. Chem. Phys., 31, 544 (1959). 36. A. Kuntman, I. Bahar, B. M. Baysal, Macromolecules, 23, 4959 (1990). 37. C. G. Le Fevre, R. J. W. Le Fevre, G. M. Parkins, J. Chem. Soc, 1468 (1958). 38. C. G. Le Fevre, R. J. W. Le Fevre, G. M. Parkins, J. Chem. Soc, 1814 (1960). 39. R. J. W. Le Fevre, K. M. S. Sundaram, J. Chem. Soc, 1494 (1962). 40. R. J. W. Le Fevre, K. M. S. Sundaram, J. Chem. Soc, 4003 (1962). 41. R. J. Le Fevre, K. M. S. Sundaram, J. Chem. Soc, 3547 (1963). 42. R. J. W. Le Fevre, K. M. S. Sundaram, J. Chem. Soc, 1880 (1963). 43. R. J. W. Le Fevre, K. M. S. Sundaram, J. Chem. Soc, 3188 (1963). 44. S. C. Liao, J. E. Mark, J. Chem. Phys., 59, 3825 (1973). 45. G. D. Loveluck, J. Chem. Soc, 4729 (1961). 46. V. Magnasco, G. Dellepiane, C. Rossi, Makromol. Chem., 65, 16 (1963).
47. 48. 49. 50. 51. 52. 53. 54. 55. 56. 57. 58. 59. 60. 61. 62. 63. 64. 65. 66. 67. 68. 69. 70. 71. 72. 73. 74. 75. 76. 77. 78. 79. 80. 81. 82.
J. Marchal, H. Benoit, J. Polym. ScL, 23, 223 (1957). J. Marchal, C. Lapp, J. Polym. ScL, 27, 571 (1958). J. E. Mark, J. H. Ko Macromolecules, 8, 869 (1975). J. E. Mark, D. S. Chiu, J. Chem. Phys., 66, 1901 (1977). R. M. Masegosa, I. Hernandez-Fuentes, E. A. Ojalvo, E. Saiz, Macromolecules, 12, 862 (1979). G. P. Mikhailov, J. Polym. ScL, 30, 605 (1958). L. Onsager, J. Am. Chem. Soc., 7, 911 (1936). J. L. de Ia Pefla, E. Riande, J. Guzman, Macromolecules, 18, 2739 (1985). H. A. Pohl, H. H. Zabusky, J. Phys. Chem., 66, 1390 (1962). C. H. Porter, J. H. Lawler, R. H. Boyd, Macromolecules, 3, 308 (1970). O. B. Ptitsyn, Soviet Phys.-Usp. (English transl.), 2, 797 (1960). R. C. Reis-Nunes, E. Riande, N. Chavez, J. Guzman, Macromolecules, 29, 7989 (1996). E. Riande, J. Polym. ScL, Polym. Phys. Ed., 14, 2231 (1976). E. Riande, J. Polym. ScL, Polym. Phys. Ed., 15,1397 (1977). E. Riande, Makromol. Chem., 178, 2001 (1977). E. Riande, J. E. Mark, Macromolecules, 11, 956 (1978). E. Riande, J. E. Mark, J. Polym. ScL, Polym. Phys. Ed., 17, 2013 (1979). E. Riande, J. E. Mark, Polymer, 20, 1188 (1979). E. Riande, J. Guzman, Macromolecules, 12, 1117 (1979). E. Riande, J. Guzman, Macromolecules, 12, 952 (1979). E. Riande, S. Boileau, P. Hemery, J. E. Mark, J. Chem. Phys., 71, 4206 (1979). E. Riande, S. Boileau, P. Hemery, J. E. Mark, Macromolecules, 12, 702 (1979). E. Riande, J. Guzman, J. San Roman, J. Chem. Phys., 72, 5263 (1980). E. Riande, J. Guzman, Macromolecules, 14, 1234 (1981). E. Riande, J. Guzman, E. Saiz, Polymer, 22, 465 (1981). E. Riande, J. Guzman, E. Saiz, J. de Abajo, Macromolecules, 14, 608 (1981). E. Riande, M. Garcia, J. Mark, J. Polym. ScL, Polym. Phys. Ed., 19, 1739 (1981). E. Riande, J. Guzman, W. J. Welsh, J. E. Mark, Makromol. Chem., 183, 2555 (1982). J. Guzman, E. Riande, W. J. Welsh, J. E. Mark, Makromol. Chem., 183, 2573 (1982). E. Riande, J. E. Mark, Eur. Polym. J., 20, 517 (1984). E. Riande, J. G. de Ia Campa, J. Guzman, J. de Abajo, Macromolecules, 17, 1431 (1984). E. Riande, J. G. de Ia Campa, J. Guzman, J. de Abajo, Macromolecules, 17, 1891 (1984). E. Riande, J. Guzman, J. de Abajo, Makromol. Chem., 185, 1943 (1984). E. Riande, J. Guzman, L. Garrido, Macromolecules, 17, 1234 (1984). E. Riande, J. Guzman, L. Garrido, Macromolecules, 17, 134 (1984). E. Riande, J. Guzman, J. Polym. ScL, Polym. Phys. Ed., 23, 1235 (1985).
83. E. Riande, J. Guzman, J. G. de Ia Campa, J. de Abajo, Macromolecules, 18, 1583 (1985). 84. E. Riande, J. Guzman, H. Addabo, Macromolecules, 19, 2567 (1986). 85. E. Riande, J. E. Mark, Macromolecules, 19, 2956 (1986). 86. E. Riande, J. Guzman, J. G. de Ia Campa, J. de Abajo, J. Polym. ScL, Polym. Phys. Ed., 25, 2403 (1987). 87. E. Riande, J. G. de Ia Campa, D. D. Schlereth, J. de Abajo, J. Guzman, Macromolecules, 20, 1641 (1987). 88. E. Riande, J. Guzman, J. Chem. Soc. Perkin Trans., 2, 299 (1988). 89. E. Riande, J. Guzman, J. G. de Ia Campa, Macromolecules, 21, 2128 (1988). 90. E. Riande, J. Guzman, J. de Abajo, Macromolecules, 22, 4026 (1989). 91. E. Riande, E. Saiz, "Dipole Moments and Birefringence of Polymers", Prentice Hall, Englwood Cliff, NJ, 1992. 92. E. Riande, J. Guzman, Macromolecules, 29, 1728 (1996). 93. A. Roig, I. Hernandez-Fuentes, An. Quim., 70, 668 (1974). 94. E. Saiz, E. Riande, J. Guzman, J. de Abajo, Chem. Phys., 73, 958 (1980). 95. E. Saiz, E. Riande, M. P. Delgado, J. M. Barrales-Rienda, Macromolecules, 15, 1152 (1982). 96. E. Saiz, A. Horta, L. Gargallo, I. Hernandez-Fuentes, D. Radic, Macromolecules, 21, 1736 (1988). 97. E. Saiz, M. J. Fabre, L. Gargallo, D. Radic, I. HernandezFuentes, Macromolecules, 22, 3660 (1989). 98. E. Saiz, E. Riande, J. San Roman, E. L. Madruga, Macromolecules, 23, 785 (1990). 99. E. Saiz, C. Abradelo, J. Mogin, L. Hernan Tagle, I. Hernandez-Fuentes, Macromolecules, 24, 5594 (1991). 100. E. Saiz, C. Mijangos, E. Riande, D. Lopez, Macromolecules, 27, 5716 (1994). 101. I. Sakurada, S. Lee, Z. Phys. Chem. B, 43, 245 (1939). 102. M. Salmeron, J. M. Barrales-Rienda, E. Riande, E. Saiz, Macromolecules, 17, 2728 (1984). 103. C. Salom, J. J. Freire, I. Hernandez-Fuentes, Polymer., 20, 1109(1988). 104. C. Salom, E. Riande, I. Hernandez-Fuente, R. Diaz-Calleja, J. Polym. ScL, Part B: Polym. Phys., 31, 1591 (1993). 105. R. Salovey, J. Polym. ScL, 50, S7 (1961). 106. E. A. Smith, Trans. Faraday Soc, 46, 394 (1950). 107. M. Takeda, Y. Imamura, S. Okamura, T. Higashimura, J. Chem. Phys., 33, 631 (1960). 108. A. E. Tonelli, L. A. Belfiore, Macromolecules, 16, 1740 (1983). 109. T. Uchida, Y. Kurita, M. Kubo, J. Polym. ScL, 19,365 (1956). 110. T. Uchida, Y. Kurita, N. Koizumi, M. Kubo, J. Polym. ScL, 21, 313 (1956). 111. S. Vega, E. Riande, J. Guzman, Macromolecules, 23, 3573 (1990). 112. W. J. Welsh, J. E. Mark, J. Guzman, E. Riande, Makromol. Chem., 183, 2562 (1982). 113. N. Yamaguchi, M. Sato, E. Ogawa, M. Shima, Polymer, 22, 1464 (1981). 114. F. Yilmaz, B. M. Baysal, J. Polym. ScL, Part B: Polym. Phys., 30, 197 (1992).
H e a t ,
E n t r o p y ,
a n d
V o l u m e
P o l y m e r - L i q u i d
C h a n g e s
f o r
M i x t u r e s
Robert A. O r w o l l Department of Chemistry, College of William and Mary Williamsburg, VA, USA
A. Introduction 1. Scope of the Table 2. Experimental Methods B. Key for the Tables C. Tables of Literature References for Heat, Entropy, and Volume Changes for Polymer-Solvent Mixtures Table 1. Main-Chain Carbon Polymers 1.1. Poly(dienes) 1.2. Poly(alkenes) 1.3. Poly(acrylics) 1.4. Vinyl Polymers 1.5. Poly(styrenes) 1.6. Other Compounds Table 2. Main-Chain Carbon Heteroatom Polymers 2.1. Poly(oxides) and Poly(esters) 2.2. Poly(amides) 2.3. Poly(siloxanes) 2.4. Derivatives of Cellulose 2.5. Other Compounds D. References
A.
VII-649 VII-649 VII-649 VII-650
VII-650 VII-650 VII-650 VII-651 VII-654 VII-655 VII-657 VII-659 VII-659 VII-659 VII-661 VII-661 VII-662 VIJ-663 VII-663
INTRODUCTION
Tabulated below are references to the studies of the enthalpy, entropy, and volume changes that occur when polymer and solvent are mixed to form a homogeneous liquid solution. This bibliography follows closely the form employed by C. Booth (Manchester) in his contribution under the same title in the second edition of this Handbook. With several exceptions, references to work reported before 1972 were compiled by Professor Booth for the second edition. 1. Scope of the Table This table includes literature citations to studies from which the thermodynamic properties named in the title can be
deduced. The experimental methods utilized are also identified. This tabulation is limited to reports of measurements on solutions that contain only one nonelectrolyte homopolymer; solutions with a copolymer, polyelectrolyte, or polymer mixture have been excluded. Solvents for the solutions in this compilation are liquids comprising single molecular entities; i.e., references to studies in which the solvent is a binary or ternary mixture or a mixture of oligomers are not included. Most studies whose primary goal is to characterize the individual polymer molecule and its interaction in an infinitely dilute solution will not be found in this table. However, references to studies of dilute solutions are presented in some of the other tables of Part VII ("Solution Properties")- Most of the reports of changes in free energy on mixing or on dilution cited here have been limited to those that also provide sufficient data to determine the change in the enthalpy (or entropy). References to measurements of solvent activities which can yield information about changes in free energy can be found in "Polymer-Solvent Interaction Parameters". These references were collected without regard for the quality of data. 2. Experimental Methods Heat Several different kinds of enthalpy changes are recognized in the formation of solutions. The integral heat of mixing or integral heat of solution, (Al) is the heat absorbed when pure solvent and pure polymer are combined to form a solution at constant temperature and pressure. Here AT80Int # ? , and H\ are the molar enthalpies of solution, pure solvent, and pure solute respectively; and n\ and n2 the number of moles of each component. The value of AHmiX is dependent on the degree of crystallinity for semicrystalline polymers and, usually to a lesser extent, on the thermal history of glassy polymers. However, if a
polymer solution already exists and more solvent is added, the accompanying enthalpy change, which is called the integral heat of dilution, is independent of any crystalline or glassy aspect of the pure polymeric solute. The integral heats, both of mixing and of dilution, are usually determined calorimetrically. The latter is often preferable for experimental reasons, because its measurement is not complicated by the long dissolution times usually required in the direct measurements of integral heats of solution. The partial or differential heat of solution, AH2, is the change in enthalpy when a very small amount of pure solute is added to a large amount of either solution or pure solvent. In the latter instance, the resultant quantity which is properly identified as the partial heat of solution at infinite dilution is sometimes referred to more simply as the heat of solution. For polymer solutions, AHj is often expressed as the heat absorbed per unit mass of solute added and can be found as the derivative of the integral heat of mixing: (A2) Here ni2 is the mass of polymeric solute. Values of AH\ at infinite dilution for some polymer-solvent systems are listed in "Heats of Solution of Some Common Polymers". The partial or differential heat of dilution AH\ differs from AH2 in that it is a consequence of adding solvent, rather than solute, to a solution and is almost always expressed as the heat per mol of added solvent. Accordingly,
(A3) It can also be obtained from the variation with concentration of the integral heat of dilution. Or it may be determined from the temperature dependence of the activity a\ of solvent according to the Gibbs-Helmholtz equation (A4) I turn, the activity a \ of solvent in a polymer solution has a variety of sources including the osmotic pressure of the solution, the vapor pressure of solvent above the solution relative to that of the pure solvent, the gas-chromatographic retention volumes of volatile solvent on columns with polymeric solute as the stationary phase, swelling equilibria for polymer networks, the concentration dependence of Rayleigh scattering, and sedimentation equilibria. The first three methods are the ones used most frequently. Entropy The entropy of mixing pure polymer with pure solvent can be obtained from the difference between the integral heat of mixing and the free energy of mixing (A5) Free energies of mixing can be determined by integrating concentration-dependent functions of the chemical potential of the solvent.
More often, the partial molar entropy of solvent (A6) is reported, using the temperature dependence of the activity of solvent (A7) Volume Volume changes reported in the literature cited below are measured directly (dilatometry) or from density determinations. B. KEY FOR THE TABLES The following abbreviations are used to identify the experimental methods utilized for the studies cited: CD CM D DL GC LS OS SD SW VP XS
Calorimetry: integral heat of dilution Calorimetry: integral heat of mixing Density Dilatometry Gas chromatography with polymeric stationary phase Rayleigh light scattering Osmotic pressure Sedimentation equilibrium Swelling of polymer network Vapor pressure including manometry, isopiestic distillation, vapor phase osmometry, etc. X-ray scattering
A Chemical Abstracts Service registry number accompanies most of the polymers named in the table. Although some polymers have more than one registry number owing to particular stereochemistries, different terminal groups, etc., only the most common number appears in the table for each polymer. C. TABLES OF LITERATURE REFERENCES FOR HEAT, ENTROPY, AND VOLUME CHANGES FOR POLYMER-SOLVENT MIXTURES TABLE 1. MAJN-CHAIN CARBON POLYMERS Polymer-Solvent 1.1. POLY(DIENES) Poly(l,3-butadiene) [9003-17-2] Benzene
ds-Bicyclo[4.4.0]decane rran5-Bicyclo[4.4.0]decane 1,3-Butadiene Butane
Method
Refs.
CD CM GC VP CM CM DL GC DL GC
140 19,84 308,327 73 293 293 374 327 374 327
TABLE 1. cont'd Polymer-Solvent PoIy(1,3-butadiene) cont'd 1-Butene dj-2-Butene tmns-2-Butene Carbon dioxide Carbon tetrachloride 1-Chlorobutane Chloroform Cyclohexane Cyclooctane Cyclopentane Decane 3,3-Diethylpentane 2,2-Dimethylbutane 2,2-Dimethylpentane 2,3-Dimethylpentane 2,4-Dimethylpentane 3,3-Dimethylpentane 1,4-Dioxane Dodecane Ethane Ethylbenzene Ethylene 3-Ethylpentane 2,2,4,4,6,8,8-Heptamethylnonane Heptane Hexadecane Hexane 2-Methylbutane 3-Methylhexane 2-Methylpropane 2-Methylpropene Nonane Octane 1-Octene 2,2,4,6,6-Pentamethylheptane Pentane 2,2,4,4-Tetramethylpentane 2,3,3,4-Tetramethylpentane Toluene 1,3,5-Trimethylbenzene 2,2,4-Trimethylpentane w-Xylene Water Poly(chloroprene) [9010-98-4] Benzene Butyl alcohol Carbon tetrachloride 2-Chloro-l,3-butadiene 1-Chlorobutane Chloroform Decane Octane 1-Octene 2-Pentanone
TABLE 1. cont'd Method
Refs.
DL DL DL SW GC GC GC VP CM GC CM CM GC GC CM GC CM CM CM CM VP CM GC SW GC SW CM CM CM GC CM GC GC CM DL GC DL CM GC CM GC GC CM GC CM CM CD GC GC CM GC SW
374 374 374 350 308 308 308 119 293 327 293 293 327 327 293 327 293 293 293 293 165 294 327 350 327 350 293 294 294 327 294 327 327 293 374 327 374 294 327 294 308,327 308 294 308,327 293,294 293 140 308,327 327 294 327 388
CM GC GC GC VP GC GC GC GC GC GC
19 308 308 308 126 308 308 308 308 308 308
Polymer-Solvent
Method
Refs.
PoIy(Cw-1,3-isoprene) [9003-31-0] and [104389-31-3] Acetone SW 9,120 VP 120 Benzene CM 6,8,55 DL 5,166 OS 5,166 SW 9,121,130 VP 5,8,74,130,166 Butane VP 46 2-Butanone DL 120 SW 9,120 VP 120 Butyl acetate SW 9 Butyl butyrate SW 9 Carbon disulfide SW 9 Carbon tetrachloride SW 9 Chloroform SW 9 Cyclohexane SW 9 2,4-Dimethyl-3-pentanone SW 9 2,2-Dimethylpropane VP 46 Ethyl acetate DL 120 SW 9,120 VP 63,120 Heptane CM 6 SW 9 Hexane VP 59 Isoprene VP 126 Methyl acetate SW 9,120 Methyl alcohol VP 6 2-Methylbutane VP 46 2-Methylpropane VP 46 Octane VP 177 Pentane SW 9 VP 46 2-Pentanone SW 120 Propyl acetate SW 9 Toluene OS 1 SW 9 VP 1 2,2,4-Trimethylpentane VP 177 Polygons-1,3-isoprene) [9003-31-0] and [104389-32-4] Octane VP 177 Toluene OS 2 2,2,4-Trimethylpentane VP 167,177 1.2. POLY(ALKENES) PoIy(I-butene) [9003-28-5J ds-Bicyclo[4.4.0]decane rra/w-Bicyclo[4.4.0]decane Cyclohexane Cyclooctane Cyclopentane Decane 3,3-Diethylpentane 2,2-Dimethylpentane 2,3-Dimethylpentane 2,4-Dimethylpentane 3,3-Dimethylpentane Dodecane 3-Ethylpentane 2,2,4,4,6,8,8-Heptamethylnonane Heptane Hexadecane
CM CM CM CM CM CM CM CM CM CM CM CM VP CM CM CM CM
293 293 293 293 293 248 293 293 293 293 293 248 107 293 294 248 248
References page VII - 663
TABLE 1. confd Polymer-Solvent Hexane 3-Methylhexane Nonane Octane 2,2,4,6,6-Pentamethylheptane Pentane Tetradecane 2,2,4,4-Tetramethylpentane 2,3,3,4-Tetramethylpentane 2,2,4-Trimethylpentane Poly(l-decene) [25189-70-2] Toluene PoIy(I-dodecene) [25067-08-7] Toluene Poly(ethylene) [9002-88-4] Benzene Bromomethane 2-Butanone Butyl acetate Butyl alcohol Carbon tetrachloride Chlorobenzene 1-Chlorobutane Chloroform 1-Chlorohexane 1-Chloronaphthalene Cyclohexane Cyclohexanol Cyclohexanone Cyclohexyl chloride Cyclopentane Decahydronaphthalene Decane 2,6-Di-rerf-butyl-4-methylphenol 1,5-Dichloropentane /V,N-Dimethylacetamide WV-Dimethylformamide 1,2-Dimethylnaphthalene 1,3-Dimethy !naphthalene 1,4-Dimethylnaphthalene 1,5-Dimethylnaphthalene 1,6-Dimethylnaphthalene 1,7-Dimethylnaphthalene 1,8-Dimethylnaphthalene 2,3-Dimethylnaphthalene 2,6-Dimethylnaphthalene 2,7-Dimethylnaphthalene 2,4-Dimethylpentane Dodecane 1-Ethylnaphthalene 2-Ethylnaphthalene Ethyl propionate 2,2,4,4,6,8,8-Heptamethylnonane Heptane Hexadecane Hexane 2-Methylbutane 1-Methylnaphthalene 2-Methylnaphthalene
TABLE 1. Method
Refs.
CM CM CM CM VP CM CM CM GC CM CM CM
248 293 248 248 102 294 248 248 281 293,294 293 294
VP
195
VP
195
GC VP GC GC GC GC GC GC GC GC CM CM GC GC GC GC CM CD CM DL GC VP GC GC GC GC GC GC GC GC GC GC GC GC GC CM VP GC GC GC CM GC VP CM VP CM GC GC
299 87 351 351 299 299 299,351 351,299 299,351 351 151,367 367 299,351 299 299,351 299 367 246 367,369 252 299,351 361 351 351 351 234 234 234 234 234 234 234 234 234 234 367 100,107,351 234 234 351 367 351 38 367 87 367 234 234
confd
Polymer-Solvent
Method
Methyl sulfoxide Nonane Octacosane Octane 1-Octene 2-Pentanone Phenol Phenyl ether Propyl ether Propyl sulfide 1,1,2,2-Tetrachloroethane Tetradecane 1,2,3,4-Tetrahydronaphthalene Toluene 1,2,4-Trichlorobenzene 1,1,2-Trichloroethane /7-Xylene PoIy(I-heptene) [25511-64-2] Toluene Poly(isobutene) [9003-27-4], polyisobutylene Benzaldehyde Benzene
m-Bicyclo[4.4.0]decane fra^Bicyclo[4.4.0]decane Butane 2-Butanone Butyl ether Butyl propionate Carbon tetrachloride
Chlorobenzene
Chloroform Cyclohexane
Cyclooctane Cyclopentane Decahydronaphthalene Decane Decyl alcohol 0-Dichlorobenzene p-Dichlorobenzene 3,3-Diethylpentane
Refs.
GC GC SW GC GC GC GC VP GC GC GC GC CM GC CM GC VP
351 299 93 281,351 299 299 299 180 351 351 351 281 151 351 367 351 131
VP
195
GC CD CM
291 72,98 19,88,94,116, 141,157,184,278 73,82,128,211,254 69,137,159,184 263,287,291,378 61,159 56,73,159,259,318 293 293 35 291 95 105 104 104,116,278 254 105 98 88,94,184 82,254 137,184 96 254 291 255 88,94,104,116, 184,278,293 128 137,155,184 263,378 158 61 26,56,105,155 293 293 254 94 254 137,160 291 254 254 293
D DL GC OS VP CM CM VP GC CM VP CD CM D VP CD CM D DL OS D GC CD CM D DL GC LS OS VP CM CM D CM D DL GC D D CM
TABLE 1. cont'd Polymer-Solvent 2,2-Dimethylbutane 2,3-Dimethylbutane 2,2-Dimethylhexane 2,5-Dimethylhexane 2,2-Dimethylpentane 2,3-Dimethylpentane 2,4-Dimethylpentane 3,3-Dimethylpentane 2,2-Dimethylpropane Dodecane Ethyl acetate Ethylbenzene Ethyl decanoate Ethyl ether Ethyl heptanoate Ethyl hexadecanoate Ethyl hexanoate Ethyl nonanoate Ethyl octanoate 3-Ethylpentane Ethyl tetradecanoate Heptadecane 2,2,4,4,6,8,8-Heptamethylnonane Heptane
Hexadecane Hexane
Hexyl ether Methyl alcohol 2-Methylbutane Methy lcyclohexane 2-Methylheptane 4-Methylheptane 2-Methylhexane 3-Methylhexane 2-Methylpentane 3-Methylpentane 2-Methylpropane Naphthalene Nitrobenzene Nonane Octane
2,2,4,6,6-Pentamethylheptane Pentanal
TABLE 1. cont'd Method
Refs.
GC GC GC GC CM GC CM GC CM GC CM VP CM D GC CM CM CM CM CM CM CM CM CM CM D CM CM
378 378 378 378 293 378 293 378 293 378 293 35 94,278,294 254 291 88,297,378 95 94,95 95 95 95 95 95 293 95 254 294 19,88,94,116,157, 184,278,294 69,137,160,184 263,378 221 94,278,294 160 94,184 254 137,160,184 263,378 221 95 105 94 35 94,116,184 137,184 378 378 378 293 378 378 94 378 35 291 291 94,294 291,378 94,294 254 160 263,378 160 294 291
DL GC OS CM DL CM D DL GC OS CM VP CM VP CM DL GC GC GC CM GC GC CM GC VP GC GC CM GC CM D DL GC OS CM GC
Polymer-Solvent Pentane
Pentyl ether Propyl alcohol Propyl ether Pyridine Tetradecane 1,2,3,4-Tetrahydronaphthalene 2,2,4,4-Tetramethylpentane 2,3,3,4-Tetramethylpentane Toluene
Tridecane 2,2,4-Trimethylpentane
2,3,4-Trimethylpentane Undecane PoIy(I-octadecene) [25511-67-5] Toluene Poly(propylene) [9003-07-0] Benzene ds-Bicyclo[4.4.0]decane rranj-Bicyclo[4.4.0]decane Carbon tetrachloride
Chloroform 1-Chloronaphthalene Cyclohexane Cyclooctane Cyclopentane Decane 3,3-Diethylpentane 2,2-Dimethylpentane 2,3-Dimethylpentane 2,4-Dimethylpentane 3,3-Dimethylpentane 2,4-Dimethyl-3-pentanone Dodecane Ethylbenzene 3-Ethylpentane 2,2,4,4,6,8,8-Heptamethylnonane
Method
Refs.
CD 255 CM 94,278 D 254,338 DL 97,160 GC 263,378 LS 238 OS 221 VP 35,97,156 CM 95 GC 291 CM 95 GC 291 CM 94 D 254 CM 293,294 CM 293 CD 98,104 CM 19,104,184 D 254 DL 69,137,184 GC 291,378 VP 105 CM 94 CM 19,94,104,157,294 D 211 DL 69 GC 287,378 LS 145,158,238 VP 14,237,259 GC 378 CM 94 VP
195
CM D VP CM CD CD CM D VP CD CM D CM CM D CM CM CM GC CM CM CM CM CM VP CM GC VP CM CM CM
315 315 101 293 293 280 315 315 216 280 315 315 151 293,315 315 293 293 315 281 293 293 293 293 293 123 294 281 125,171 315 293 294
References page VII - 663
TABLE 1. cont'd Polymer-Solvent Heptane
Hexadecane Hexane 3-Methylhexane Nonane Nonyl alcohol Octane 2,2,4,6,6-Pentamethylheptane Pentane 3-Pentanone Tetradecane 1,2,3,4-Tetrahydronaphthalene 2,2,4,4-Tetramethylpentane 2,3,3,4-Tetramethylpentane Toluene 2,2,4-Trimethylpentane m-Xylene 0-Xyiene p-Xy lene 1.3.
TABLE 1. cont'd Method
Refs.
CM D VP CM CM D VP CM CM VP CM CM CM D VP VP GC CM CM CM CM CM VP CM CM CM
294,315 315 101,217 294 315 315 101 293 294,315 134 294,315 294 315 315 217 117,123 281 151 293,294 293 315 294 101 315 315 315
CD D
313 196,313
CM CM CD D CD CM CD CM CD CM D VP
381 381 343 343 292 292 292 292 233,292,343 292,381 196,343 366
GC CM GC GC GC GC GC GC GC GC CM GC GC GC GC GC GC GC GC GC
307 55 307 307 307 307 307 307 307 307 260 307 307 307 307 307 307 307 307 307
POLY(ACRYLICS)
Poly(acrylamide) [9003-05-8] Water Poly (acrylic acid) [9003-01-4] Butyl alcohol A^Dimethylformamide Ethyl alcohol Ethylene glycol Formamide Water
Poly(butyl methacrylate) [9003-63-8] Benzene Butyl acetate Butyl alcohol Butylbenzene terf-Butylbenzene Butylcyclohexane Carbon tetrachloride Chlorobenzene 1-Chlorobutane Chloroform Cyclohexane Cyclohexanol Decane Dichloromethane Octane 2-Pentanone 3,4,5-Trimethylheptane 2,2,4 ~ -Trimethylpentane
Polymer-Solvent Poly(WV-dimethylacrylamide) [26793-31 -0] Water Poly(ethyl methacrylate) [9003-42-3] Acetone Acetonitrile Acrylonitrile Benzene Bromobenzene 1-Bromobutane 2-Butanone Butyl acetate Butyl alcohol Butylamine Butyraldehyde Carbon tetrachloride Chlorobenzene Chloroform Cyclohexane Decane Ethane Ethylbenzene Ethylcyclohexane Ethylene Heptane Methylcyclohexane Nitroethane Nitromethane 1-Nitropropane Nonane Octane 1-Octene Pentyl alcohol Propane Propionic acid Propionitrile Propyl acetate Propyl alcohol Propyl ether Toluene Poly(N-isopropylacrylamide) [25189-55-3] Acetic acid Butyl alcohol 1-Chloronaphthalene Hexadecane Naphthalene Water Poly(methacrylic acid) [54193-36-1] Water Poly(Af-methylacrylamide) [25722-14-9] Water Poly(methyl acrylate) [9003-21-8] Benzene Butylbenzene ferr-Butylbenzene Butylcyclohexane Cyclohexane ds-Decahydronaphthalene frans-Decahydronaphthalene Decane Dodecane Ethylbenzene Naphthalene
Method
Refs.
CD D
313 313
CD CD CD CD CD CD CD CD CD CD CD CD CD CD CD CD D CD CD D CD CD CD CD CD CD CD CD CD D VP CD CD CD CD CD CD
284 284 284 284 284 284 284 284 284 284 284 284 284 284 284 284 360 284 284 360 284 284 284 284 284 284 284 284 284 360 341 284 284 284 284 284 284
GC GC GC GC GC CM OS
198 198,281 198 198 198 353 368
CM
381
CD D
313 313
GC GC GC GC GC GC GC GC GC GC GC
282 282 282 282 282 282 282 282 282 282 282
TABLE 1. cont'd Polymer-Solvent Octane Tetradecane 1,2,3,4-Tetrahydronaphthalene 3,3,4,4-Tetramethylhexane Toluene 3,4,5-Trimethylheptane 2,2,5-Trimethylhexane 2,2,4-Trimethylpentane Poly(methyl methacrylate) [9011-14-7] Acetone
Benzene
2-Butanone Butyl acetate Carbon dioxide Carbon tetrachloride Chlorobenzene Chloroform
Cyclohexane 0-Dichlorobenzene Dichloroethane 1,2-Dichloroethy lene 1,4-Dioxane Ethyl acetate Methyl isobutyrate 3-Pentanone Tetrahydrofuran Toluene
m-Xylene 1.4. VINYL POLYMERS Poly(acrylonitrile) [25014-41-9] Acrylonitrile Benzene WV-Dimethytformamide Poly(vinyl acetate) [9003-20-7] Acetone
TABLEI. cont'd Method
Refs.
GC GC GC GC GC GC GC GC
282 282 282 282 282 282 282 282
CD D OS VP CD CM D OS VP D OS D OS DL VP D CD D CD CM D DL OS OS CD CM D CM VP OS CD D OS D OS CM VP D OS D OS CD D DL OS D OS
148,161 60,178 31,178,261 220 162,186 224 60,178 31,178,261 220 60 261 60 36 387 387 60 162 60 212 193 60 210 31 261 162 266 60 83 83 149 148 60 31,149 60 36,261 83 83 60 31 60 31 148,212 60 210 31,261 60 31
VP CM VP CM
126 47 47 47
CM DL
75,184,345 184
Polymer-Solvent
Acetonitrile Benzene
2-Butanone
Butyl acetate Butyl alcohol Butylbenzene Butylcyclohexane Carbon tetrachloride Chlorobenzene
1-Chlorobutane Chloroform l-Chlorohexane 1-Chloropropane 3-Chloropropene Cyclohexane Cyclohexanol Cyclohexanone Cyclohexyl chloride c/i-Decahydronaphthalene Decane Dichloroethane 1,2-Dichloroethane 1,5-Dichloropentane Diethyl adipate Diethyl malonate Diethyl oxalate Diethyl sebacate Diethyl succinate A^Dimethylacetamide MiV-Dimethylformamide 1,4-Dioxane Dodecane Ethyl acetate
Method
Refs.
GC LS OS VP GC CD CM GC OS VP CD CM DL GC LS OS CM DL GC GC GC GC CM D GC LS GC CM GC GC VP VP GC OS GC GC GC GC GC CD CM GC GC CD D CD D CD D CD D CD D GC GC CM GC GC CM D DL GC LS OS VP
354 158 261 37,75 354 170 41,224 288,295,299,354 261 37,76,85 170 184 184 354 158 15,261 55,184 184 299 288 288 299,354 41 49,82 299,354 158 299 41,345 299,354 354 37 37 288,295,299,354 261 299 299 299 288 288,299 232 41 295,354 354 27 27 27 27 27 27 27 27 27 27 354 354 342 295,354 288 30,184 211 184 354 158 261 237
References page VII - 663
TABLE 1. cont'd Polymer-Solvent Heptane 3-Heptanone Hexane Isopropyl alcohol Isopropylamine Methyl acetate Methyl alcohol
Methyl sulfoxide Nonane 1-Octene 2-Pentanone Propyl acetate Propyl alcohol Propylamine Propyl ether Propyl sulfide 1,1,2,2-Tetrachloroethane Tetrahydrofuran 1,2,3,4-Tetrahydronaphthalene 3,3,4,4-Tetramethylhexane Toluene
1,2,3-Trichloropropane Undecane Vinyl acetate Water Poly(vinyl alcohol) [9002-89-5] Carbon tetrachloride Chloroacetic acid 1,4-Dioxane Ethyl alcohol Water
PoIy(iV-vinylcarbazole) [25067-59-8] Benzene Poly(vinyl chloride) [9002-86-2] Benzene Cyclohexane Cyclohexanone
Cyclopentanone Dibutyl phthalate Dichloroethane 1,2-Dichloroethane Diethyl phthalate Dioctyl phthalate 1,4-Dioxane Dodecane Heptane
TABLEI. Method
Refs.
GC CM DL GC GC VP CM DL CD CM D LS GC GC GC CM DL GC CM DL VP VP GC GC CM GC GC GC CD CM GC OS OS GC VP CM
295,354 141,184 184 354 295 37 184 184 271 41,48,345 211,271 158 354 288,299 299 184 184 299 184 184 37 37 354 354 41,48 354 288 288 64,232 41 295,354 261 15 288 85 342
CM CM CD CM CD CM LS VP
359 112 342 30 57,58 30,55,342 219 86,219
CD VP
161 124
GC GC CD CM D DL CD CM VP CM GC VP VP GC GC GC
295 295 231 106,231 273 106 243 243 250 55 295 250 250 295 281 295
cont'd
Polymer-Solvent Isopropyl alcohol Tetrahydrofuran Toluene Poly(vinylidene fluoride) [24937-79-9] Acetophenone 2-Butanone Butyl acetate Butylbenzene y-Butyrolactone Chlorobenzene 1-Chlorodecane 2-Chloroethyl ether 1-Chlorohexane 1-Chlorooctane Cyclohexanone ds-Decahydronaphthalene 1,2-Dichlorobenzene 1,2-Dichloroethane 1,5-Dichloropentane AW-Dimethylacetamide MN-Dimethylethyleneurea MN-Dimethylformamide AfyV-Dimethylpropyleneurea Dodecane Ethyl acetate Ethylbenzene Ethyl propionate Hexadecane Hexamethylphosphoramide l-Methyl-2-pyrrolidinone Methyl sulfoxide Pentachloroethane Propylene carbonate Propyl sulfide Pyridine 1,1,2,2-Tetrachloroethane Tetradecane Tetrahydronaphthalene Tetramethylene sulfone 1,1,3,3-Tetramethylurea Toluene 1,1,2-Trichloroethane m-Xylene Poly(vinyl methyl ether) [9003-09-2] Cyclohexane Ethylbenzene Toluene Water Poly(2-vinylpyridine) [25014-15-7] Benzene 2-Butanone Butyl alcohol Cyclohexanone 1,4-Dioxane Ethyl alcohol Methyl alcohol Propyl alcohol Poly(#-vinylpyrrolidone) [9003-39-8] Butyl alcohol
Method
Refs.
GC CD CM GC
295 244 244 295
GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC
354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354 354
VP CM D OS CM D OS CM
372 332 332 332 332 332 332 353
D D D D D D LS D D
267 267 267 267 267 267 111 267 267
CD
309
TABLE 1. cont'd Polymer-Solvent Chloroform
Ethyl alcohol Methyl alcohol Propyl alcohol Water
1.5.
TABLE 1. cont'd Method
Refs.
Polymer-Solvent
CD CM D CD CD CD CD CM D OS
330 174 174 309 269 309 269 174 174 214
Butane 2-Butanone
VP
103
GC VP GC GC GC GC GC GC VP
363 199 363 363 363 363 363 363 103
Butyl alcohol sec-Butyl alcohol Buty !benzene
CM VP VP VP
223 136 136,355 355
VP
103
GC CM D GC OS VP GC CD GC CD GC GC CD
306 29,34,43 43,60 306 261 51,220 306,354 279 306 135,279,286 336 306 28,70,81,147, 191,192,225 19,29,32,44,55, 90,184,192 222, 333 24,39,60,128,247, 283,296,329 12,69,184 235,282,305,306, 307,325,336,354 23,114,143, 145,158 12,33,147,261 147 13,28,32,147, 192,220 200 306 279 25
Butyl acetate
POLY(STYRENES)
Poly(p-bromostyrene) [24936-50-3] Toluene Poly(p-chlorostyrene) [24991 -47-7] Benzene Ethyl acetate Heptane Hexane Isopropylbenzene Pentane Propylbenzene Toluene Poly(ot-methylstyrene) [25014-31-7] Benzene Isopropylbenzene a-Methylstyrene Toluene Poly(p-methylstyrene) [24936-41 -2] Toluene Poly(styrene) [9003-53-6] Acetic acid Acetone
Acetonitrile Acetophenone Aniline Anisole Benzaldehyde Benzene
CM D DL GC LS OS SW VP Benzyl alcohol Benzyl ether Bromobenzene
XS GC CD D
terf-Butylbenzene Butylcyclohexane Carbon dioxide Carbon tetrachloride
Chlorobenzene
1-Chlorobutane Chloroform
1-Chlorohexane Cyclohexane
Method VP CD CM D DL GC OS VP CM D GC OS VP GC SW CM DL GC GC GC DL CD CM D GC LS OS VP CD CM D GC LS OS SW GC CD CM D GC OS SW VP GC CD CM D DL GC LS OS SD SW VP
Cyclohexanone Cyclohexene
CD GC CD CM VP
Refs. 337 135,249,255 29,68,146 24,39,45,60 12,207,256 235,306,354 12,18,33, 207,256,261 17 29 60 306 33 13 306 115 184 184 282,325 307 282 339 104,240 104,240 60 235,306,307 114 33 13,220 53 53,146 25,60,82 306,354 114 127 115 307 54,191,225 29 45,60,82 306,307,354 33 115 51 354 53,70,81,192,285 29,34,43,53, 184,192,359 43,45,60,189, 211,296,329 12,69,184, 189,209 282,306, 307,325,354 114,143,190,206 18,33,71,80,261 189,229 115 13,52,80, 192,237,259 289 306,354 192 29,192 201
References page VII - 663
TABLE 1. cont'd Polymer-Solvent Decahydronaphthalene
ds-Decahydronaphthalene frans-Decahydronaphthalene
Decane o-Dichlorobenzene 1,2-Dichloroethane Dichloromethane 1,5-Dichloropentane WV-Dimethylformamide 2,2-Dimethylpropane 1,4-Dioxane
1,3-Diphenylbutane Dodecane Ethane 2-Ethoxyethyl acetate Ethyl acetate
Ethyl alcohol Ethylbenzene
TABLE 1. Method CD CM D DL LS VP GC GC LS OS GC D GC GC GC GC GC VP CD CM D DL GC OS VP CD SW GC VP CM CD CM D DL GC OS VP GC CD CM
D DL GC LS OS SW VP Ethylene glycol Ethyl ether Formamide Heptane Hexadecane Hexane Hexyl alcohol Hexylbenzene Isobutyl alcohol Isopentyl alcohol Isopropyl alcohol
GC GC GC GC SW GC GC SW SW GC GC SW GC
Refs. 192 184,192,359 24 184 114,145 201 282 282 238 290 281,282,305,307 24,60 235 306,354 306,307 354 354 245 135 55,184 24,60 184 235,306,354 127 13 113,147 113,147 281,282 337 29 135,257 29,68 24,60,296 257 306 18,33,261 52 306 50,53,54,81,113, 147,192,228,255 30,44,53,78,90, 104,184,192, 228,264 24,39,113,147,211 69,184,208 235,325,336,354 114 113,147,208 113,115,147 50,90.113,147, 237,259 306 306 306 306,325,335,354 115 281,282 306,325,335,354 115 115 325 306 115 306
cont'd
Polymer-Solvent Isopropyl ether Methyl alcohol 2-Methylbutane 2-Methylheptane 2-Methylpentane 3-Methylpentane Naphthalene Nitrobenzene Nitromethane Nonane Octane
l-Octene c/^-2-Octene Octyl alcohol Pentane
3-Pentanone
Pentyl alcohol Pentylbenzene Propane Propyl acetate Propyl alcohol Propylbenzene
Propyl ether Propyl sulfide Pyridine Styrene
Tetradecane Tetrahydrofuran 1,2,3,4-Tetrahydronaphthalene 3,3,4,4-Tetramethylhexane Toluene
Method GC GC VP GC GC GC GC GC VP GC GC SW VP GC GC GC GC SW VP CD D VP GC GC VP VP GC SW CM DL GC GC VP GC GC CM GC VP GC D GC CM GC GC CD
CM
D DL GC LS OS SD SW VP
Refs. 306 306 245 325 325 325 282 306 13 305,325 305,306,307,325 115 13 325 325 306 306 115 245 319 60 13 306 325 337 51 306 115 184 184 325 354 13 354 306,336,354 10,29 235 126 281,282 60 306 192 282 282 28,53,54,81,135, 183,188,191,192, 225,228,240, 255,286 29,34,43,53,55,90, 146,154,184,192, 226,228,240, 264,332,333 11,24,39,43, 45,60,189,332 12,69,184, 189,210 235,305,306, 325,336,354 114,190 12,18,33,71,144, 203,261,332 189 115 13,17,28,52,103
TABLE 1. cont'd Polymer-Solvent Trichloroethylene 1,3,5-Trimethylbenzene
3,4,5-Trimethylheptane 2,2,4-Trimethylpentane Water m-Xylene
oXylene
1.6. OTHER COMPOUNDS Poly(nitro-l,4-phenylene) 1,4-Dioxane
TABLE 2. cont'd Method
Refs.
GC CM D DL GC GC GC GC CM D DL GC OS VP CM GC OS
306 29,184 60 184 305 307 306,307,325 306 29,184 60 184 305 33 13 29 235,306 33
VP
187
TABLE 2. MAIN-CHAIN CARBON HETEROATOM POLYMERS Polymer-Solvent
Method
2.1. POLY(OXIDES) AND POLY(ESTERS) Epoxy from bis(4-glycidylphenyl) propane and 1,6 hexanediamine Chloroform SW VP 1,4-Dioxane SW VP Poly(oxy-l,4-butanediyl) [25190-06-1], polytetrahydrofuran Acetone GC Acetonitrile GC Benzene GC 2-Butanone GC Butyl acetate GC Carbon tetrachloride GC Chlorobenzene GC Chloroform GC 1-Chlorohexane GC Cyclohexane GC Decane GC 1,2-Dichioroethane GC Dichloromethane GC 1,5-Dichloropentane GC 1,4-Dioxane GC Ethyl acetate GC Ethylbenzene GC Heptane GC Propyl ether GC Propyl sulfide GC Pyridine GC Tetrahydrofuran GC Toluene GC Poly(oxycarbonyloxy-1,4-phenyleneisopropylidene-1,4-phenylene) [24936-68-3J and [25037-45-0J, poly(bisphenol A carbonate), poly (carbonate) Acetone DL Benzene GC Butyl acetate GC Butylbenzene GC te/7-Butylbenzene GC
Refs.
110 110 110 110 376 376 376 376 376 376 376 376 376 376 376 376 376 376 376 376 376 376 376 376 376 376 376
386 362 362 362 362
Polymer-Solvent
Method
Refs.
Butylcyclohexane Carbon dioxide
GC 362 CM 377,385 DL 338,386 Chlorobenzene GC 310,362 Chloroform GC 362 Cyclohexanol GC 362 Cyclohexanone GC 362 Decane GC 310,362 o-Dichlorobenzene GC 310 Dichloromethane GC 362 1,4-Dioxane CD 161 Dodecane GC 362 Ethylbenzene GC 362 Methane DL 386 Methylcyclohexane GC 362 2-Pentanone GC 362 Propyl alcohol GC 362 1,1,2,2-Tetrachloroethane GC 362 Tetradecane GC 362 Toluene GC 362 Water DL 386 Poly(oxyethylene) [25322-68-3] and [9004-74-4], polyethylene glycol), poly(ethylene oxide) Acetone GC 268,302,317,376 Acetonitrile GC 268,320,376 Acetophenone GC 316 Aniline GC 239 Benzaldehyde GC 239 Benzene CD 262,312 CM 138,277,312 D 213,382 GC 239,268,274,276, 302,317,320,376 VP 175,213 Benzyl alcohol GC 239 p-Bromoacetophenone GC 316 2-Butanone GC 268,302,320,376 Butyl acetate GC 268,376 Butyl alcohol CD 218 GC 258,268,302 sec-Butyl alcohol GC 258,302 Carbon tetrachloride CM 129,185,277,357 DL 185 GC 268,302,376 VP 185,357 p-Chloroacetophenone GC 316 Chlorobenzene GC 239,317 Chloroform CD 230 CM 185,230 DL 185 GC 268,302,320,376 VP 117,185 1-Chlorohexane GC 376 Chloromethane CD 230 CM 230 Cyclohexane GC 302,317,320 Decane GC 239,302,320,376 1,2-Dichloroethane GC 268,376 Dichloromethane GC 276,376 1,5-Dichloropentane GC 376 1,2-Dimethoxyethane GC 320 1,2-Dimethylnaphthalene GC 234 1,3-Dimethylnaphthalene GC 234 1,4-Dimethylnaphthalene GC 234 1,5-Dimethylnaphthalene GC 234
References page VII - 663
TABLE 2.
TABLE 2. cont'd
contd
Polymer-Solvent
Method
Refs.
1-Methylnaphthalene 2-Methylnaphthalene c-Nitroacetophenone p-Nitroacetophenone Nitroglycerin Nitromethane Nonane Octane Octyl alcohol Pentane 2-Pentanol Pentyl alcohol Phenol Phenyl acetate Propyl alcohol Propyl ether Propyl sulfide Pyridine Tetrahydrofuran Toluene
GC GC GC GC GC GC CM GC GC GC GC CD CM GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC CD CM GC LS GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC
1,1,2-Trichloroethane
LS GC
234 234 234 234 234 234 129 302,320,376 239,302,320 317 276,317,320,376 218 138,277 258,276,302,317 320,376 302 234 234 316 316 239,302,320,376 302 302 258 239,276,302,317 258 258 302 258 316 316 258,320 316 316 320 302 316 316 218 138,277 258,268,274,317 242 234 234 316 316 346 302 239,302,344 239,302,317 258 302 258 258 239 239 258,317,320,344 376 376 302,320,376 268,376 268,302,317, 320,376 314 268
1,6-Dimethylnaphthalene 1,7-Dimethylnaphthalene 1,8-Dimethylnaphthalene 2,3-Dimethylnaphthalene 2,6-Dimethylnaphthalene 2,7-Dimethylnaphthalene 1,4-Dioxane Dodecane 2-Ethoxyethyl ether Ethyl acetate Ethyl alcohol Ethylbenzene Ethyl ether 1-Ethylnaphthalene 2-Ethylnaphthalene o-Fluoroacetophenone p-Fluoroacetophenone Heptane 3-Heptanone 1-Heptene Heptyl alcohol Hexane 2-Hexanol 3-Hexanol 1-Hexene Hexyl alcohol o-Hydroxyacetophenone /?-Hydroxyacetophenone Isopropyl alcohol 0-Methoxyacetophenone /?-Methoxyacetophenone 2-Methoxyethyl ether Methyl acetate oMethylacetophenone p-Methylacetophenone Methyl alcohol
Polymer-Solvent 2,2,2-Trifluoroet.hanol Undecane Water
Method GC GC CD
GC OS VP GC GC
320 239,302 150,230,303,312, 324,352,365 62,91,139,194, 230,311,312,324, 348,356 62,176,300, 365,382 268 214,368 62,176,375 302 268
GC GC GC GC GC GC GC GC GC GC CD CM D VP GC GC GC GC
234 234 234 231 234 234 234 231 234 234 265 132 265 132,165 234 234 234 234
CM D
m-Xylene o-Xylene Poly(oxyethyleneoxyadipoyl) [24937-05-1 ] 1,2-Dimethylnaphthalene 1,3-Dimethylnaphthalene 1,4-Dimethylnaphthalene 1,5-Dimethylnaphthalene 1,6-Dimethylnaphthalene 1,7-Dimethylnaphthalene 1,8-Dimethylnaphthalene 2,3-Dimethylnaphthalene 2,6-Dimethylnaphthalene 2,7-Dimethylnaphthalene 1,4-Dioxane
Refs.
1-Ethylnaphthalene 2-Ethylnaphthalene 1-Methylnaphthalene 2-Methylnaphthalene Poly(oxyethyleneoxysebacoyl) [26762-06-11 ] Butyl butyrate VP 197 1,4-Dioxane CM 132 VP 132 Poly(oxyethyleneoxysuccinyl) [25667-11-2] 1,4-Dioxane CM 132 VP 132 Poly(oxyhexamethyleneoxyadipoyl) [24937-10-8] 1,4-Dioxane CD 265 D 265 Poly(oxy- 1-oxopentamethylene) [26354-94-9] 1,4-Dioxane CD 265 D 265 Poly(oxypropylene) [25322-69-4], polypropylene glycol), poly(propylene oxide) Benzene CM 347,349 GC 331 VP 215 Butyl alcohol CM 118 DL 118 SW 118 ,sec-Butyl alcohol CM 118 SW 118 tert-Butyl alcohol CM 118 SW 118 Carbon tetrachloride CM 118,163,371 DL 163 SW 118 VP 163,371 Chloroform CM 163 DL 163 VP 163
TABLE 2. cont'd Polymer-Solvent Cyclohexane
Cyclohexene Ethyl alcohol
Heptane 1-Heptene 2-Heptene Hexane
1-Hexene cw-2-Hexene fra/w-2-Hexene Isobutyl alcohol Isopropyl alcohol Methyl alcohol
2-Methylhexane 2-Methylpentane Nonane 2-Pentanol Pentyl alcohol Propyl alcohol
Pyridine Water
TABLE 2. Method
Refs.
CM 118 GC 331 SW 118 GC 331 CM 118,347,348 DL 118 SW 118 GC 331 GC 331 GC 331 CD 241 CM 118,241 D 241 GC 331 SW 118 GC 331 GC 331 GC 331 CM 118 SW 118 CM 118 SW 118 CM 89 D 89 VP 89 GC 331 GC 331 GC 344 CM 118 SW 118 CM 118 SW 118 CM 118 GC 344 SW 118 CM 347 CD 241 CM 62,91,164,241,272, 311,322,348,353,373 D 62,241 VP 62,323
Poly(oxytrimethyleneoxyadipoyl) [36221 -42-8] 1,4-Dioxane CM VP
132 132
2.2. POLY(AMIDES) Poly[L~iminocarbonyl(benzyloxycarbony!ethyl) methylene] [25038-53-3], poly(y-benzyl-L-glutamate) Chloroform CD 179 Dichloroacetic acid CD 179 CM 142 1,2-Dichloroethane CM 142 D 133 VP 133 WV-Dimethylformamide VP 227 Pyridine D 133 VP 133 Poly[L-iminocarbonyl(benzyloxycarbonylmethyl) methylene] [25736-41-8], poly(y-benzyl-L-aspartate) Chloroform D 133 VP 133 Poly[imino(l-oxohexarnethylene)] [25038-54-4], nylon 6 Decyl alcohol VP 197 Water VP 370
cont'd
Polymer-Solvent
Method
Refs.
2.3. POLY(SILOXANES) Poly(oxydimethylsilylene) [9016-00-6], poly(dimethylsiloxane) Acetone SW 182 Benzene CD 253 CM 20,116,169 D 169 SW 182 VP 20,204 ds-Bicyclo[4.4.0]decane CM 293 /ra/?s-Bicyclo[4.4.0]decane CM 293 Bromocyclohexane CM 184 DL 184 Butane VP 99 2-Butanone CM 141,184,205,380 DL 184 GC 383 LS 380 SW 182 Butyl acetate CM 122 Butyl ether CM 122 Butyl propionate CM 122 Carbon dioxide CM 377 Carbon tetrachloride CM 116 Chlorobenzene CM 116 GC 310 OS 168 Cyclohexane CM 116,169,293 D 169 OS 168 Cyclopentane CM 293 Cyclooctane CM 293 Decane CD 253 CM 95 GC 270,310 Decyl acetate CM 122 tf-Dichlorobenzene GC 310 Diethoxymethane CM 122 3,3-Diethylpentane CM 293 1,2-Dimethoxyethane CM 122 2,3-Dimethylbutane GC 270 2,5-Dimethylhexane GC 270 2,2-Dimethylpentane CM 293 GC 270 2,3-Dimethylpentane CM 293 2,4-Dimethylpentane CM 293 3,3-Dimethylpentane CM 293 2,2-Dimethylpropane VP 99 Dodecane CM 95,294 Ethyl acetate CM 122,184,205 DL 184 Ethylbenzene CD 253 CM 169 D 169 VP 204 Ethyl butyrate CM 122 Ethyl decanoate CM 122 Ethyl dodecanoate CM 122 Ethyl ether CM 122,205 Ethyl heptanoate CM 122 Ethyl hexanoate CM 122 Ethyl nonanoate CM 122 Ethyl octanoate CM 122 3-Ethylpentane CM 293 Ethyl pentanoate CM 122
References page VII - 663
TABLE 2. confd Polymer-Solvent Ethyl propionate Ethyl undecanoate 2,2,4,4,6,8,8-Heptamethylnonane Heptane
Heptyl acetate Hexadecane Hexamethyldisiloxane Hexane
Hexyl acetate Hexyl alcohol Hexyl ether Isopropylbenzene Methyl alcohol Methyl butyrate Methylcyclohexane Methyl decanoate Methyl heptanoate 3-Methylhexane Methyl heptanoate Methyl nonanoate Methyl octanoate Methyl pentanoate 2-Methylpropane Methyl propionate Nonane Nonyl acetate Octamethylcyclotetrasiloxane Octamethyltrisiloxane Octane
Octyl acetate 2,2,4,6,6-Pentamethylheptane Pentane
2-Pentanone Pentyl acetate Pentyl ether Pentyl propionate Propyl acetate Propyl alcohol Propyl ether Propyl propionate Tetradecane 2,2,4,4-Tetramethylpentane
TABLE 2. cont'd Method
Refs.
CM CM CM CD CM D DL GC CM CM CD CM DL CD CM DL GC VP CM SW CM CM D SW CM CM D CM CM CM CM CM CM CM VP CM CM GC CM CM DL VP CD CD CM GC VP CM CM CD CM GC VP SW CM CM CM CM DL SW CM CM CD CM CM
122 122 294 253 95,116,169,184 169 184 270 122 95,294 253 181,184 184 253 95,184 184 270 204 122 182 122 169 169 182 122 169 169 122 122 293 122 122 122 122 99 122 95 270 122 40,184 184 40 253 253 95,294 270 204 122 294 253 95 270 99 182 122 122 122 122,184 184 182 122 122 253 95 293,294
Polymer-Solvent 2,3,3,4-Tetramethylpentane Toluene
Tridecane 1,3,5-Trimethylbenzene 2,2,4-Trimethylpentane Undecane m-Xylene -Xylene p-Xylene
2.4. DERIVATIVES OF CELLULOSE Cellulose acetate [9004-35-7J Acetone
Acetonitrile Aniline Chloroform Chlorornethane WV-Dimethylacetamide 1,4-Dioxane Ethyl alcohol Methyl acetate Methyl sulfoxide Phenol Pyridine Tetrachloroethane Cellulose nitrate [9004-70-0], nitrocellulose Acetone
Acetonitrile 2-Butanone Butyl acetate Cyclopentanone Dibutyl phthalate 2,4-Dimethyl-3-pentanone 1,4-Dioxane
Method
Refs.
CM CD CM D OS SW VP CM CM D CM GC CM CM D SW CM D SW CD CM D SW
293 253 169 169 168 182 204,372 95,205 169 169 294 270 95 169 169 182 169 169 182 253 169 169 182
D LS OS VP D D D VP D CM D VP DL D VP CM VP D OS VP D VP D OS
65,152 304 65 65,108 152 152 152 109 152 251 152 108 335 152 108 251 109 65 65 65 152 108 3 3
CD CM D OS VP VP D CM D VP CM VP VP
4,7 21,55 4,7,128 202 4,7,16,42,67,108 42 128 21,55 128 42 21,328,379 42 42
TABLE 2. cont'd Polymer-Solvent Ethyl acetate Ethyl propyl ether 2-Heptanone Methyl acetate Methyl alcohol 3-Methyl-2-butanone Nitroglycerin Nitromethane 2-Pentanone Pinacolone Propyl acetate Triacetin Tritolyl phosphate Ethyl cellulose [9004-57-3] Acetone Benzene Butane 2-Butanone Butyl acetate Carbon tetrachloride Chloroform Dichloromethane 2,2-Dimethylpropane Ethyl acetate Methyl alcohol 2-Methylbutane Pentane 1,1,1 -Trichloroethane Water Hydroxyethyl cellulose [9004-62-0] Water Hydroxypropyl cellulose [9004-64-2] Water Methyl cellulose [9004-67-5] Water Cellulose tricarbanilate [9047-07-8] Cyclohexanol 5-Nonanone
2.5. OTHER COMPOUNDS Dextran [9004-54-0] Ethanolamine Ethylene glycol Formamide Glycerol Methyl sulfoxide Water
Lignin [9005-53-2] N,N-Dimethylformamide 1,4-Dioxane Methyl sulfoxide Starch [9005-25-8] Water
D. Method
Refs.
CM D VP D D VP CM VP VP VP D VP VP D CM CM
21,22 128 42 128 128 108 22,55 42 384 42 128 42 42 128 326,334 21
D VP D VP VP D D D D GC GC VP D VP VP VP GC VP
172 66 172 66 77 172 172 172 172 364 364 77 172 66 77 77 364 79
OS
214
CM
353
CM
321,340
CD D CD D
271 271 271 271
CM CM CM CM CD CM CD CM OS VP
301 298,301 298,301 301 298,301 298,301 298,301 275,298,301 214,358 236,375
VP VP VP
153 153 153
VP
173
REFERENCES
1. K. H. Meyer, E. Wolff, C. G. Boissonas, HeIv. Chim. Acta, 23, 430 (1940). 2. E. Wolff, HeIv. Chim. Acta, 23, 439 (1940). 3. O. Hagger, A. J. A. van der Wyk, HeIv. Chim. Acta, 23, 488 (1940). 4. E. Calvet, Compt. Rend., 213, 126 (1941); 214, 767 (1942). 5. G. Gee, L. R. G. Treloar, Trans. Faraday Soc, 38, 147 (1942). 6. J. Ferry, G. Gee, L. R. G. Treloar, Trans. Faraday Soc, 41, 340 (1945). 7. E. Calvet, Bull. Soc. Chim., 12, 553 (1945). 8. G. Gee, W. J. C. Orr, Trans. Faraday Soc, 42, 507 (1946). 9. G. Gee, Trans. Faraday Soc, 42, 585 (1946). 10. D. E. Roberts, W. W. Walton, R. S. Jessup, J. Polym. Sci., 2, 420 (1947). 11. R. F. Boyer, R. S. Spencer, J. Polym. Sci., 3, 97 (1948). 12. J. W. Breitenbach, H. P. Frank, Monatsh., 79, 531 (1948). 13. E. C. Baughan, Trans. Faraday Soc, 44, 495 (1948). 14. A. A. Tager, V. A. Kargin, Kolloidn. Zh., 10, 455 (1948). 15. G. V. Browning, J. D. Ferry, J. Chem. Phys., 17,1107 (1949). 16. H. Campbell, P. Johnson, J. Polym. Sci., 4, 247 (1949). 17. C. E. H. Bawn, R. F. J. Freeman, A. R. Kamaliddin, Trans. Faraday Soc, 46, 677 (1950). 18. M. J. Schick, P. Doty, B. H. Zimm, J. Am. Chem. Soc, 72, 530 (1950). 19. A. A. Tager, V. Sanatina, Kolloidn. Zh., 12, 474 (1950); Rubber Chem. Technol., 24, 773 (1951). 20. M. J. Newing, Trans. Faraday Soc, 46, 613 (1950). 21. S. M. Lipatov, S. I. Meerson, Kolloidn. Zh., 12, 122 (1950). 22. S. M. Lipatov, S. I. Meerson, Kolloidn. Zh. 12, 427 (1950). 23. P. Debye, A. M. Bueche, J. Chem. Phys., 18, 1423 (1950). 24. D. J. Streeter, R. F. Boyer, Ind. Eng. Chem., 43,1790 (1951). 25. W. Heller, A. C. Thompson, J. Colloid Sci., 6, 57 (1951). 26. L. der Minassian, M. Magat, J. Chim. Phys., 48, 574 (1951). 27. P. Meares, Trans. Faraday Soc, 47, 699 (1951). 28. H. Tompa, J. Polym. Sci., 8, 51 (1952). 29. H. Hellfritz, Makromol. Chem., 7, 191 (1952). 30. A. A. Tager, V. A. Kargin, Kolloidn. Zh., 14, 367 (1952). 31. G. V. Schulz, H. Doll, Z. Elektrochem., 56, 248 (1952). 32. A. A. Tager, Zh. H Dombek, Kolloidn. Zh., 15, 69 (1953). 33. G. V. Schulz, H. Hellfritz, Z. Elektrochem., 57, 835 (1953). 34. K. von Guenner, G. V. Schulz, Naturwissensch., 40, 164 (1953). 35. S. Prager, E. Bagley, F. A. Long, J. Am. Chem. Soc, 75, 2742 (1953). 36. G. V. Schulz, H. Doll, Z. Elektrochem., 57, 841 (1953). 37. R. J. Kokes, A. R. DiPietro, F. A. Long, J. Am. Chem. Soc, 75, 6319 (1953). 38. J. H. van der Waals, J. J. Hermans, Rec Trav. Chim. PaysBas, 69, 971 (1953). 39. M. Griffel, R. S. Jessup, J. A. Cogliano, R. P. Park, J. Res. Nat. Bur. Std., 52, 217 (1954). 40. R. C. Osthoff, W. T. Grubb, J. Am. Chem. Soc, 76, 399 (1954).
41. H. Daoust, M. Rinfret, Can. J. Chem., 32, 492 (1954). 42. E. C. Baughan, A. L. Jones, K. Stewart, Proc. Roy. Soc, A, 225, 478 (1954). 43. G. V. Schulz, K. von Guenner, H. Gerrens, Z. Phys. Chem., NF, 4, 192 (1955). 44. A. A. Tager, R. V. Krivokorytova, P. M. Khodorov, Dokl. Akad. Nauk, SSSR, IGO, 741 (1955). 45. B. Rosen, J. Polym. ScL, 17, 559 (1955). 46. A. Aitken, R. M. Barrer, Trans. Faraday Soc, 51, 116 (1955). 47. A. A. Tager, L. K. Kosova, D. Y. Karlinskaya, I. A. Yurina, Kolloidn. Zh., 17, 315 (1955). 48. M. Parent, M. Rinfret, Can. J. Chem., 33, 971 (1955). 49. A. Horth, M. Rinfret, J. Am. Chem. Soc, 77, 503 (1955). 50. T. V. Gatovskaya, V. A. Kargin, A. A. Tager, Zh. Fiz. Khim., 29, 883 (1955). 51. C. E. H. Bawn, M. A. Wajid, Trans. Faraday Soc, 52, 1658 (1956). 52. K. Schmoll, E. Jenckel, Z. Elektrochem., 60, 756 (1956). 53. E. Jenckel, K. Gorke, Z. Elektrochem., 60, 579 (1956). 54. K. Amaya, R. Fujishiro, Bull. Chem. Soc. Japan, 29, 270 (1956). 55. S. I. Meerson, S. M. Lipatov, Kolloidn. Zh., 18, 447 (1956). 56. C. E. H. Bawn, R. D. Patel, Trans. Faraday Soc, 52, 1664 (1956). 57. K. Amaya, R. Fujishiro, Bull. Chem. Soc Japan, 29, 361 (1956). 58. K. Amaya, R. Fujishiro, Bull. Chem. Soc Japan, 29, 830 (1956). 59. V. A. Kargin, T. V. Gatovskaya, Zh. Fiz. Khim., 30, 1852 (1956). 60. G. V. Schulz, M. Hoffmann, Makromol. Chem., 23, 220 (1957). 61. P. J. Flory, H. Daoust, J. Polym. ScL, 25, 429 (1957). 62. G. N. Malcolm, J. S. Rowlinson, Trans. Faraday Soc, 53, 921 (1957). 63. C. Booth, G. Gee, G. R. Williamson, J. Polym. ScL, 23, 3 (1957). 64. H. J. L. Schuurmans, J. J. Hermans, J. Phys. Chem., 61,1496 (1957). 65. R. Jeffries, Trans. Farday Soc, 53, 1592 (1957). 66. R. M. Barrer, J. A. Barrie, J. Polym. ScL, 23, 331 (1957). 67. H. Takenaka, J. Polym. ScL, 24, 321 (1957). 68. A. A. Tager, L. A. Galkina, Nauch. Dokl. Vysshei Skoly, Khim. Khim. Tekhno., 1, 357 (1958). 69. A. A. Tager, A. Smirnova, N. Sysueva, Nauch. Dokl. Vysshei Skoly, Khim. Khim. Tekhnol., 1, 135 (1958). 70. K. Amaya, R. Fujishiro, Bull. Chem. Soc Japan, 31, 19 (1958). 71. G. Rehage, H. Meys, J. Polym. ScL, 30, 271 (1958). 72. M. A. Kabayama, H. Daoust, J. Phys. Chem., 62, 1127 (1958). 73. R. S. Jessup, J. Res. Nat. Bur. Std., 60, 47 (1958). 74. R. M. Barrer, R. R. Ferguson, Trans. Faraday Soc, 54, 989 (1958). 75. A. A. Tager, M. Iovieva, Zh. Fiz. Khim., 32, 1774 (1958).
76. A. F. Sirianni, R. Tremblay, I. E. Puddington, Can. J. Chem., 36, 543 (1958). 77. R. M. Barrer, J. A. Barrie, J. Slater, J. Polym. ScL, 27, 177 (1958). 78. A. A. Tager, M. M. Gur'yanova, Zh. Fiz. Khim., 32, 1958 (1958). 79. R. M. Barrer, J. A. Barrie, J. Polym. ScL, 28, 377 (1958). 80. W. R. Kiigbaum, D. O. Geymer, J. Am. Chem. Soc, 81, 1859 (1959). 81. G. V. Schulz, A. Horbach, Z. Phys. Chem., NF, 22, 377 (1959). 82. A. Horth, D. Patterson, M. Rinfret, J. Polym. ScL, 39, 189 (1959). 83. A. A. Tager, M. V. Tsilipotkina, V. K. Doronina, Zh. Fiz. Khim., 33, 335 (1959). 84. R. S. Jessup, J. Res. Nat. Bur. Std., 62, 1 (1959). 85. A. Nakajima, H. Yamakawa, I. Sakurada, J. Polym. ScL, 35, 489 (1959). 86. I. Sakurada, A. Nakajima, H. Fujiwara, J. Polym. ScL, 35, 497 (1959). 87. C. E. Rogers, V. Stanett, M. Szwarc, J. Phys. Chem., 63, 1406 (1959). 88. C. Watters, H. Daoust, M. Rinfret, Can. J. Chem., 38, 1087 (1960). 89. M. L. Lakhanpal, B. E. Conway, J. Polym. ScL, 46, 75 (1960). 90. S. I. Meerson, S. M. Lipatov, Kolloidn. Zh., 21, 531 (1959). 91. R. G. Cunninghame, G. N. Malcolm, J. Phys. Chem., 65, 1454 (1961). 92. G. Allen, G. Gee, J. P. Nicholson, Polymer, 2, 8 (1961). 93. P. J. Flory, A. Ciferri, R. Chiang, J. Am. Chem. Soc, 83, 1023 (1961). 94. G. Delmas, D., Patterson, T. Somcynsky, J. Polym. ScL, 57, 79 (1962). 95. G. Delmas, D. Patterson, D. Bohme, Trans. Faraday Soc, 58, 2116(1962). 96. J. Leonard, H. Daoust, J. Polym. ScL, 57, 53 (1962). 97. C. H. Baker, W. B. Brown, G. Gee, J. S. Rowlinson, D. Stubley, R. E. Yeadon, Polymer, 3, 215 (1962). 98. M. Senez, H. Daoust, Can. J. Chem., 40, 734 (1962). 99. R. M. Barrer, J. A. Barrie, N. K. Raman, Polymer, 3, 595 (1962). 100. T. V. Gatovskaya, G. M. Pavlyuchenko, V. A. Berestnev, V. A. Kargin, Dokl. Akad. Nauk, SSSR, 143, 590 (1962); Proc. Acad. Sci. SSSR, 143, 209 (1962). 101. K. P. Kwei, T. K. Kwei, J. Phys. Chem., 66, 2146 (1962). 102. G. M. Pavlyuchenko, T. V. Gatovskaya, V. A. Kargin, Dokl. Akad. Nauk, SSSR, 147,150 (1962); Proc Acad. Sci. USSR, 147, 790 (1962). 103. R. Corneliussen, S. A. Rice, H. Yamakawa, J. Chem. Phys., 38, 1768 (1963). 104. A. A. Tager, A. I. Podlesnyak, Vysokomol, Soedin. A, 5, 87 (1963); Polym. Sci. USSR, 4, 698 (1963). 105. A. A. Tager, M. V. Tsilipotkina V. Ye. Dreval, O. V. Nechayeva, Vysokomol. Soedin. A, 5, 94 (1963); Polym. Sci. USSR, 4, 706 (1963).
106. S. I. Meerson, I. M. Zagrayevskaya, Kolloidn. Zh., 25, 202 (1963). 107. T. V. Gatovskaya, G. M. Pavlyuchenko, V. A. Berestnev, V. A. Kargin, Vysokomol. Soedin. A, 5, 960 (1963); Polym. Sci. USSR, 5, 9 (1963). 108. W. R. Moore, R. Shuttleworth, J. Polym. Sci. A, 1, 733 (1963). 109. W. R. Moore, R. Shuttleworth, J. Polym. Sci. A, 1, 1985 (1963). 110. T. K. Kwei, J. Polym. Sci. A, 1, 2977 (1963). 111. A. J. Hyde, R. B. Taylor, Makromol. Chem., 62,204 (1963). 112. S. I. Meerson, I. M. Zagrayevskaya, Kolloidn. Zh., 25, 197 (1963). 113. J. Biros, K. Sole, J. Pouchly, Faserforsch. Textil., 15, 608 (1964). 114. A. A. Tager, V. M. Andreyeva, E. M. Evsina, Vysokomol. Soedin. A, 6, 1901 (1964); Polym. Sci. USSR, 6, 2107 (1964). 115. G. Rehage, Kolloid Z., 196, 97 (1964); 199, 1 (1964). 116. G. Delmas, D. Patterson, S. N. Bhattacharyya, J. Phys. Chem., 68, 1468 (1964). 117. G. Allen, C. Booth, G. Gee, M. N. Jones, Polymer, 5, 367 (1964). 118. B. E. Conway, J. P. Nicholson, Polymer, 5, 387 (1964). 119. C. Booth, G. Gee, M. N. Jones, W. D. Taylor, Polymer, 5,353 (1964). 120. C. Booth, G. Gee, G. Holden, G. R. Williamson, Polymer, 5, 343 (1964). 121. G. Butenuth, Rubber, Chem. Technol., 37, 326 (1964). 122. D. Patterson, J. Polym. Sci. A, 2, 5177 (1964). 123. W. B. Brown, G. Gee, W. D. Taylor, Polymer, 5, 362 (1964). 124. K. Ueberreiter, W. Bruns, Ber. Bunsenges. Phys. Chem., 68, 541 (1964). 125. G. M. Pavlyuchenko, T. V. Gatovskaya, V. A. Kargin, Vysokomoi. Soedin. A, 6, 1190 (1964); Polym. Sci. USSR, 6, 1309 (1964). 126. A. N. Gudkov, N. A. Fermor, N. I. Smirnov, Zh. Prikl. Khim., 37, 2204 (1964); J. Appl. Chem. USSR, 37, 2179 (1964). 127. J. Leonard, H. Daoust, J. Phys. Chem., 69, 1174 (1965). 128. W. R. Moore, B. M. Tidswell, Makromol. Chem., 81, 1 (1965). 129. M. L. Lakhanpal, M. LaI, R. K. Sharma, Indian J. Chem., 3, 547 (1965). 130. G. Gee, J. B. M. Herbert, R. C. Roberts, Polymer, 6, 541 (1965). 131. A. S. Michaels, R. W. Hausslein, J. Polym. Sci. C, 10, 61 (1965). 132. A. A. Tager, L. Ya. Kasas', Dokl. Akad. Nauk, SSSR, 165, 1122 (1965); Proc. Acad. Sci. USSR, 165, 892 (1965). 133. P. J. Flory, W. J. Leonard, J. Am. Chem. Soc, 87, 2102 (1965). 134. G. M. Pavlyuchenko, T. V. Gatovskaya, V. A. Kargin, Vysokomol. Soedin. A, 7, 647 (1965); Polym. Sci. USSR, 7, 714 (1965). 135. A. Kagemoto, S. Murakami, R. Fujishiro, Bull. Chem. Soc. Japan, 39, 15 (1966).
136. S. G. Canagaratna, D. Margerison, J. R Newport, Trans. Faraday Soc, 62, 3058 (1966). 137. C. Cuniberti, U. Bianchi, Polymer, 7, 151 (1966). 138. M. L. Lakhanpal, H. L. Taneja, R. K. Sharma, Indian J. Chem., 4, 12 (1966). 139. M. L. Lakhanpal, V Kapoor, R. K. Sharma, S. C. Sharma, Indian J. Chem., 4, 59 (1966). 140. A. Kagemoto, S. Murakami, R. Fujishiro, Bull. Chem. Soc. Japan, 39, 1814 (1966). 141. U. Bianchi, E. Pedemonte, C. Rossi, Makromol. Chem., 92, 114(1966). 142. G. Giacometti, A. Turolla, Z. Phys. Chem., NF, 51, 108 (1966). 143. H. Benoit, C. Picot, Pure Appl. Chem., 12, 545 (1966). 144. N. Kuwahara, T. Okazawa, M. Kaneko, J. Chem. Phys., 47, 3357 (1967). 145. A. A. Tager, V. M. Andreyeva, J. Polym. Sci. C, 16, 1145 (1967) 146. U. Bianchi, C. Cuniberti, E. Pedemonte, C. Rossi, J. Polym. Sci. A-2, 5, 743 (1967). 147. J. Pouchly, J. Biros, K. Sole, J. Vondrejsova, J. Polym. Sci. C, 16, 679 (1967). 148. A. Kagemoto, S. Murakami, R. Fujishiro, Bull. Chem. Soc. Japan, 40, 11 (1967). 149. J. Leonard, H. Daoust, Can. J. Chem., 45, 409 (1967). 150. A. Kagemoto, S. Murakami, R. Fujishiro, Makromol. Chem., 105, 154 (1967). 151. H. P. Schreiber, M. H. Waldman, J. Polym. Sci. A-2, 5, 555 (1967). 152. W. R. Moore, J. Polym. Sci. C, 16, 571 (1967). 153. W. Brown, J. Appl. Polym. Sci., 11, 2381 (1967). 154. G. Allen, R. C. Ayerst, J. R. Cleveland, G. Gee, C. Price, J. Polym. Sci. C, 23, 127 (1968). 155. B. E. Eichinger, P. J. Flory, Trans. Faraday Soc, 64, 2061 (1968). 156. B. E. Eichinger, P. J. Flory, Trans. Faraday Soc, 64, 2066 (1968). 157. A. A. Tager, A. I. Podlesnyak, L. V. Demidova, Vysokomol. Soedin. B, 10, 601 (1968). 158. A. A. Tager, A. A. Anikeyeva, V. M. Andreyeva, T. Ya. Gumarova, L. A. Chemoskutova, Vysokomol. Soedin. A, 10, 1661 (1968); Polym. Sci. USSR, 10, 1926 (1968). 159. B. E. Eichinger, P. J. Flory, Trans. Faraday Soc, 64, 2053 (1968). 160. P. J. Flory, J. L. Ellenson, B. E. Eichinger, Macromolecules, 1, 279 (1968). 161. W. Bruns, F. Mehdom, K. Mirus, K. Ueberreiter, Kolloid Z., 224, 17 (1968). 162. H. Daoust, A. Hade, Polymer, 9, 47 (1968). 163. R. W. Kershaw, G. N. Malcolm, Trans. Faraday Soc, 64,323 (1968). 164. M. L. Lakhanpal, H. G. Singh, H. Singh, S. C. Sharma, Indian J. Chem., 6, 95 (1968). 165. Yu. S. Lipatov, L. M. Sergeyeva, G. F. Kovalenko, Vysokomol. Soedin. B, 10, 205 (1968). 166. B. E. Eichinger, P. J. Flory, Trans. Faraday Soc, 64, 2035 (1968).
167. T. A. Bogayevskaya, T. V. Gatovskaya, V. A. Kargin, Vysokomol. Soedin. B, 10, 376 (1968). 168. N. Kuwahara, T. Okazawa, M. Kaneko, J. Polym. Sci. C, 23, 543 (1968). 169. S. Morimoto, J. Polym. Sci. A-I, 6, 1547 (1968). 170. A. Kagemoto, R. Fujishiro, Bull. Chem. Soc. Japan, 41,2201 (1968). 171. T. A. Bogayevskaya, T. V. Gatovskaya, V. A. Kargin, Vysokomol. Soedin. A, 10, 1357 (1968); Polym. Sci. USSR, 10, 1574 (1968). 172. W. R. Moore, Contribution to Chem. Soc. Symposium, "Solution Properties of Natural Polymers", Edinburgh 1968; Chem. Soc. Special Publication No. 23, 185 (1968). 173. M. Masuzawa, C. Stirling, J. Appl. Polym. Sci., 12, 2023 (1968). 174. J. Goldfarb, S. Rodriguez, Makromol. Chem., 116, 96 (1968). 175. M. L. Lakhanpal, H. G. Singh, S. C. Sharma, Indian J. Chem., 6, 436 (1968). 176. M. L. Lakhanpal, K. S. Chhina, S. C. Sharma, Indian J. Chem., 6, 505 (1968). 177. T. A. Bogayevskaya, T. V. Gatovskaya, Vysokomol. Soedin. B, 10, 555 (1968). 178. N. Kuwahara, T. Oikawa, M. Kaneko, J. Chem. Phys., 49, 4972 (1968). 179. A. Kagemoto, R. Fujishiro, Makromol. Chem., 114, 139 (1968). 180. R. Koningsveld, A. J. Staverman, J. Polym. Sci. A-2, 6, 325 (1968). 181. D. Patterson, S. N. Bhattacharyya, P. Picker, Trans. Faraday Soc, 64, 648 (1968). 182. R. D. Seeley, Rubber Chem. Technol., 41, 608 (1968). 183. G. Lewis, A. F. Johnson, J. Chem. Soc. A, 1816 (1969). 184. U. Bianchi, C. Cuniberti, E. Pedemonte, C. Rossi, J. Polym. Sci., A-2, 7, 855 (1969). 185. G. N. Malcolm, C. E. Baird, G. R. Bruce, K. G. Cheyne, R. W. Kershaw, M. C. Pratt, J. Polym. Sci. A-2, 7, 1495 (1969). 186. S. Takagi, R. Fujishiro, Rep. Prog. Polym. Phys. (Japan), 12, 39 (1969). 187. M. Hyodo, K. Kubo, K. Ogino, Rep. Prog. Polym. Phys. (Japan), 12, 21 (1969). 188. G. Lewis, A. F. Johnson, Polymer, 11, 336 (1970). 189. Th. G. Scholte, J. Polym. Sci. A-2, 8, 841 (1970). 190. Th. G. Scholte, Eur. Polym. J., 6, 1063 (1970). 191. S. Morimoto, Nippon Kagaku Zasshi, 91, 31, 117 (1970). 192. A. A. Tager, A. I. Podlesnayak, M. V. Tsilipotkina, L. V. Adamova, A. A. Bakhareva, L. V. Demidova, Vysokomol. Soedin. A, 12, 1320 (1970); Polym. Sci. USSR, 12, 1497 (1970). 193. C. Gerth, F. H. Mueller, Kolloid. Z., 241, 1071 (1970). 194. H. Nakayama, Bull. Chem. Soc. Japan., 43, 1683 (1970). 195. P. J. T. Tait, R J. Livesey, Polymer, 11, 359 (1970). 196. P. Roy-Chowdhury, K. M. Kale, J. Appl. Polym. Sci., 14, 2397 (1970).
197. T. A. Bogayavskaya, T. V. Gatovskaya, V. A. Kargin, Vysokomol. Soedin. A, 12, 243 (1970); Polym. Sci. USSR, 12, 279 (1970). 198. O. Smidsr0d, J. E. Guillet, Macromolecules, 2, 272 (1969). 199. K. Kubo K. Yamatsuta, K. Ogino, Rep. Prog. Polym. Phys. (Japan), 13, 19 (1970). 200. Y. Taru, K. Yosizaki, E. Wada, K. Kanamaru, Rep. Prog. Polym. Phys. (Japan), 13, 21 (1970). 201. S. Higashida, N. Kuwahara, M. Kaneko, Rep. Prog. Polym. Phys. (Japan), 13, 5 (1970). 202. T. Oikawa, N. Kuwahara, M. Kaneko, Rep. Prog. Polym. Phys. (Japan), 13, 9 (1970). 203. K. Kamada, H. Sato, Rep. Prog. Polym. Phys. (Japan), 13,47 (1970). 204. A. Muramoto, Polym. J., 1, 450 (1970). 205. S. Morimoto, Makromol. Chem., 133, 197 (1970) Rep. Prog. Polym. Phys. (Japan), 13, 29 (1970). 206. Th. G. Scholte, J. Polym. Sci. A-2, 9, 1553 (1971). 207. P. J. Flory, H. Hoecker, Trans. Faraday Soc, 67,2258 (1971). 208. H. Hoecker, P. J. Flory, Trans. Faraday Sco., 67, 2270 (1971). 209. H. Hoecker, H. Shih, P. J. Flory, Trans. Faraday Soc, 67, 2275 (1971). 210. G. Lewis, A. F Johnson, J. Chem. Soc. A, 3528 (1971). 211. A. A. Tager, L. V. Adamova, M. V. Tsilipotkina, G. I. Florova, Vysokomol. Soedin. A, 13, 654 (1971); Polym. Sci. USSR, 13, 745 (1971). 212. G. Lewis, A. F. Johnson, J. Chem. Soc. A, 3524 (1971). 213. C. Booth, C. J. Devoy, Polymer, 12, 309 (1971). 214. H. Vink, Eur. Polym. J., 7, 1411 (1971). 215. C Booth, C. J. Devoy, Polymer, 12, 320 (1971). 216. H. Ochiai, K. Gekko, H. Yamamura, J. Polym. Sci., A-2, 9, 1629(1971). 217. A. Takizawa, T. Negishi, K. Ishikawa, Sen-i Gakkaishi, 26, 567 (1971). 218. A. Kagemoto, Y. Itoi, Y Baba, R. Fujishiro, Makromol. Chem., 150, 255 (1971). 219. A. A. Tager, A. A. Anikeyeva, L. V Adamova, V. M. Andreyeva, T. A. Kuz'mina, M. V. Tsilipotkina, Vysokomol. Soedin. A, 13, 659 (1971); Polym. Sci. USSR, 13, 751 (1971). 220. K. Yamatsuta, K. Kubo, K. Ogino, Rep. Prog. Polym. Phys. (Japan), 14, 29 (1971). 221. T. Okazawa, M. Kaneko, Rep. Prog. Polym. Phys. (Japan), 14, 7 (1971); Polym. J., 2, 747 (1971). 222. S. Ichihara, A. Komatsu, T. Hata, Polym. J., 2, 644 (1971). 223. S. Ichihara, A. Komatsu, T. Hata, Polym. J., 2, 650 (1971). 224. S. Ichihara, A. Komatsu, T Hata, Polym. J., 2, 640 (1971). 225. S. Morimoto, Bull. Chem. Soc. Japan, 44, 879 (1971). 226. C. Price, R. C. Williams, R. C. Ayerst, "Amorphous Polymers", Wiley, London, 1972, p. 117. 227. J. H. Rai, W G. Miller, Macromolecules, 5, 45 (1972). 228. S. H. Maron, F. E. Filisko, J. Macromol. Sci., B, 6, 57 (1972). 229. B. J. Reitveld, Th. G. Scholte, J. P. L. Pijpres, Brit. Polym. J., 4, 109 (1972). 230. S. H. Maron, F. E. Filisko, J. Macromol. Sci., B, 6, 79 (1972).
231. S. H. Maron, F. E. Filisko, J. Macromol. Sci. B, 6, 413 (1972); S. H. Maron, M.-S. Lee, J. Macromol. Sci., Phys., 7, 29 (1973). 232. A. A. Tager, A. I. Suvorova, Yu. S. Bessonov, A. I. Podlesnyak, LA. Koroleva, L. V. Adarnova, M. V. Tsilipotkina, Vysokomol. Soedin. A, 13, 2454 (1971); Polym. Sci. USSR, 13, 2755 (1971). 233. J. P. Cartier, H. Daoust, Can. J. Chem., 49, 3935 (1971). 234. S. L. Mel'nikova, A. N. Korol, Zh. Fiz. Khim., 46, 30 (1972); Russian J. Phys. Chem., 46, 17 (1972). 235. F. H. Covitz, J. W. King, J. Polym. Sci. A-1,10 689 (1972). 236. K. Gekko, J. Sci. Hiroshima Univ., Ser. A-2, 35, 111 (1971). 237. A. A. Tager, L. V. Adamova, M. V. Tsilipotkina, R. K. Kuleshova, S. V. Fedotova, Vysokomol. Soedin. B, 14, 235 (1972). 238. M. D. Lechner, G. V. Schulz, B. A. Wolf, J. Colloid Interface Sci., 39, 462 (1972). 239. M. Mitooka, Buneski Kagaku, 21, 717 (1972). 240. P. Davalloo, J. L. Gainer, K. R. Hall, J. Chem. Thermodyn., 4, 691 (1972). 241. A. A. Tager, L. V. Adamova, Yu. S. Bessonov, V. N. Kuznetsov, T. A. Plyusnina, V. V. Soldatov, M. V. Tsilipotkina, Vysokomol. Soedin. A, 14, 1991 (1972); Polym. Sci. USSR, 14, 2233 (1972). 242. B. M. Fechner, C. Strazielle, Makromol. Chem., 160, 195 (1972). 243. S. H. Maron, M.-S. Lee, J. Macromol. Sci. Phys., 7, 47 (1973). 244. S. H. Maron, F. E. Filisko, J. Macromol. Sci. Phys., 6, 413 (1972); S. H. Maron, M.-S. Lee, J. Macromol. Sci. Phys., 7, 61 (1973). 245. H. Horacek, Kolloid-Z. Z. Polym., 250, 863 (1972). 246. D. A. Blackadder, T. L. Roberts, Angew. Makromol. Chem., 27, 165 (1972). 247. F. Candau, J. Francois, C. R. Acad. Sci., Ser. C, 276, 571 (1973). 248. G. Delmas, P Tancrede, Eur. Polym. J., 9, 199 (1973). 249. K. Tamura, S. Murakami, R. Fujishiro, Polymer, 14, 237 (1973). 250. A. Franck, Angew. Makromol. Chem., 29/30, 179 (1973). 251. E. M. Khalik, L. S. Gal'braikh, N. I. Ilieva, S. I. Meerson, Z. A. Rogovin, Vysokomol. Soedin. B, 15, 452 (1973). 252. R. A. Orwoll, J. A. Small, Macromolecules, 6, 755 (1973). 253. R. S. Chahal, W.-P. Kao, D. Patterson. J. Chem. Soc, Faraday Trans. I, 69, 1834 (1973). 254. T. N. Nekrasova, V. E. Eskin, Vysokomol. Soedin. A, 15, 2429 (1973); Polym. Sci. USSR, 15, 2749 (1973). 255. D. Gaeckle, W.-P. Kao, Patterson, M. Rinfret, J. Chem. Soc, Faraday Trans., I, 1849 (1943). 256. A. Nakajima, F. Hamada, K. Yasue, K. Fujisawa, T. Shiomi, Makromol. Chem., 175, 197 (1974). 257. Y. Baba, H. Katayama, A. Kagemoto. Makromol. Chem., 175, 209 (1974). 258. G. Castello, G. D'Amato, J. Chromatogr., 90, 291 (1974). 259. A. A. Tager, L. V. Adamova, V. V. Serpinskii, M. V. Tsilipotkina, Vysokomol. Soedin. A, 16,203 (1974); Polym. Sci. USSR, 16, 240 (1974).
260. Z. Masa, A. Zivny, J. Biros, Collect. Czech. Chem. Commun., 38, 3123 (1973). 261. H. Vink, Eur. Polym. J., 10, 149 (1974). 262. Y. Baba, H. Katayama, A. Kagemoto, Polym. J., 6, 230 (1974). 263. Y-K. Leung, B. E. Eichinger, Macromolecules, 7, 685 (1974). 264. F. E. Fiiisko, R. S. Raghava, G. S. Y. Yeh, J. Macromol. Sci. B: Phys., 10, 371 (1974). 265. G. Manzini, V. Crescenzi, R. Furlanetto, Macromolecules, 8, 198 (1975). 266. R. S. Raghava, F. E. Filisko, J. Appl. Phys., 45, 4155 (1974). 267. S. Arichi, M. Yoshida, Y. Ogawa, Bull. Chem. Soc. Japan, 48, 1417 (1975). 268. Y. H. Chang, D. C. Bonner, J. Appl. Polym. Sci., 19, 2439 (1975). 269. S. Murakami, F. Kimura, R. Fujishiro, Makromol. Chem., 176, 3425 (1975). 270. W. E. Hammers, B. C. Bos, L. H. Vaas, Y. J. W. A. Loomans, C. L. De Ligny, J. Polym. Sci., Polym. Phys. Ed., 13, 401 (1975). 271. A. A. Tager, Yu. S. Bessonov, Vysokomol. Soedin. A, 17, 2377 (1975); Polym. Sci. USSR, 17, 2734 (1975). 272. A. A. Tager, Yu. S. Bessonov, Vysokomol. Soedin. A, 17, 2383 (1975); Polym. Sci. USSR, 17, 2741 (1975). 273. E. Schroeder, U. Duesedau, J. T. Haponiuk, Faserforsch. Textiltech., 27, 67 (1976). 274. M. Kawakami, S. Kagawa, M. Egashira, Nagasaki Daigaku Kogakubu Kenkyu Hokoku, 6, 135 (1975). 275. V P. Kiselev, E. M. Shakhova, E. Z. Fainberg, A. D. Virnik, Z. A. Rogovin, Vysokomol. Soedin. B, 18, 847 (1976). 276. M. Kawakami, M. Egashira, S. Kagawa, Bull. Chem. Soc. Jpn., 49, 3449 (1976). 277. M. L. Lakhanpal, S. C. Sharma, B. Krishan, R. N. Parashar, Indian J. Chem. A, 14, 642 (1976). 278. D. D. Deshpande, C. S. Prabhu, Macromolecules, 10, 433 (1977). 279. Y. Baba, K. Fujimoto, A. Kagemoto, R. Fujishiro, Makromol. Chem., 178, 1439 (1977). 280. H. Ochiai, Y Nishihara, S. Yamaguchi, I. Murackami, J. Sci. Hiroshima Univ., Ser. A: Phys. Chem., 41, 157 (1977). 281. G. DiPaola-Baranyi, J. M. Braun, J. E. Guillet, Macromolecules, 11, 224 (1978). 282. G. DiPaola-Baranyi, J. E. Guillet, Macromolecules, 11, 228 (1978). 283. J. Francois, F. Candau, D. Sarazin, C. R. Hebd. Seances Acad. Sci., Ser. C, 286, 325 (1978). 284. K. A. Karim, D. C. Bonner, J. Appl. Polym. Sci., 22, 1277 (1978). 285. M. Okubo, K. Ueberreiter, Colloid Polym. Sci., 256, 941 (1978). 286. Y Baba, A. Kagemoto, Netsu Sokutei, 4, 57 (1977). 287. A. A. Tager, T. I. Kirillova, T. V. Ikanina, Vysokomol. Soedin. A, 20, 2543 (1978). 288. G. DiPaola-Baranyi, J. E. Guillet, J. Klein, H.-E. Jeberien, J. Chromatogr., 166, 349 (1978).
289. I. Fujihara, K. Tamura, S. Murakami, R. Fujishiro, Polym. J., 11, 153 (1979). 290. J. Roots, B. Nystrom, Eun Polym. J., 14, 773 (1978). 291. A. N. Korol, J. Chromatogr., 172, 77 (1979). 292. J. Klein, W. Scholz, Makromol. Chem., 180, 1477 (1979). 293. H. Phuong-Nguyen, G. Delmas, Macromolecules, 12, 746 (1979). 294. H. Phuong-Nguyen, G. Delmas. Macromolecules, 12, 740 (1979). 295. A. Heintz, R. N. Lichtenthaler, J. M. Prausnitz, Ber. Bunsenges. Phys. Chem., 83, 926 (1979). 296. T. M. Aminabhavi, P. Munk, Macromolecules, 12, 1186 (1979). 297. J.-G. Lee, M. Ono, F. Hamada, A. Nakajima, Polym. Bull. (Berlin), 1, 763 (1979). 298. A. M. Basedow, K. H. Ebert, J. Polym. Sci., Polym. Symp., 66, 101 (1979). 299. G. DiPaola-Baranyi, J. R Guillet, H.-E. Jeberien, J. Klein, Makromol. Chem., 181, 215 (1980). 300. K. Ueberreiter, Makromol. Chem., Rapid Commun., 1, 143 (1980). 301. A. M. Basedow, K. H. Ebert, W. Feigenbutz, Makromol. Chem., 181, 1071 (1980). 302. J. Klein, H. E. Jeberrien, Makromol. Chem., 181, 1237 (1980). 303. H. Schoenert, R Monshausen, Colloid Polym. Sci., 258, 578 (1980). 304. H. Suzuki, K. Kamide, Y. Miyazaki, Netsu Sokutei, 7, 37 (1980). 305. Y. Iwai, M. Nagafuji, Y. Arai, Sekiyu Gakkaishi, 23, 215 (1980). 306. S. Gunduz, S. Dincer, Polymer, 21, 1041 (1980). 307. G. DiPaola-Baranyi, Macromolecules, 14, 683 (1981). 308. J. E. G. Lipson, J. E. Guillet, J. Polym Sci., Polym. Phys. Ed., 19, 1199 (1981). 309. H. Ogawa, Y Baba, A. Kagemoto, Makromol. Chem., 182, 2495 (1981). 310. T. C. Ward, D. P. Sheehy, J. E. McGrath, J. S. Riffle, Macromolecules, 14, 1791 (1981). 311. Z. N. Medved, N. A. Starikova, Zh. Fiz. Khim., 55, 2438 (1981); Russian J. Phys. Chem., 55, 1380 (1981). 312. J. Roller, E. Killmann, Makromol. Chem., 182, 3579 (1981). 313. J. C. Day, I. D. Robb, Polymer, 22, 1530 (1981). 314. R Volatie, D. Sandulescu, Rev. Roum. Phys., 27, 81 (1982). 315. H. Ochiai, T. Ohashi, Y Tadokoro, I. Murakami, Polym. J. (Tokyo), 14, 457 (1982). 316. A. E. Habboush, N. S. Nassory, Iraqi J. Sci., 22, 362 (1981). 317. M. J. Fernandez-Berridi, T. R Otero, G. M. Guzman, J. M. Elorza, Polymer, 23, 1361 (1982). 318. M. J. Fernandez-Berridi, J. I. Eguiazabal, J. M. Elorza, J. J. Iruin, J. Polym. Sci., Polym. Phys. Ed., 21, 859 (1983). 319. I. Fujihara, T. Sakuta, A. Kagemoto, Makromol. Chem., 184, 1231 (1983). 320. M. Galin, Polymer, 24, 865 (1983); Polymer, 25, 1784 (1984). 321. T. Nagao, Hakodate Kogyo Senmon Gakko Kiyo, 17, 103 (1983).
322. Z. N. Medved, N. A. Starikova, Zh. Fiz. Khim., 57, 2590 (1983); Russian J. Phys. Chem., 57, 1563 (1983). 323. Z. N. Meved, N. I. Petrova, O. G. Tarakanov, Vysokomol. Soedin. B, 25, 764 (1983). 324. H. Daoust, D. St-Cyr, Macromolecules, 17, 596 (1984). 325. R. H. Schuster, H. Graeter, H.-J. Cantow, Macromolecules, 17, 596 (1984); Polym. Bull. (Berlin), 14, 379 (1985). 326. K. V. Kir'yanov, Termodin. Org. Soedin, 58 (1983). 327. S. Ituno, M. Ohzono, Y. Iwai, Y Arai, Kobunshi Ronbunshu, 42, 73 (1985). 328. I. B. Rabinovich, T. B. Khlyustova, A. N. Mochalov, Vysokomol. Soedin. A, 27, 525 (1985). 329. D. Sarazin, J. Francois, Macromolecules, 18, 1190 (1985). 330. E. Killmann, M. Bergmann, Colloid Polym. Sci., 263, 381 (1985). 331. K. Naito, N. Ohwada, S. Moriguchi, S. Takei, J. Chromatogr., 330, 193 (1985). 332. T. Shiomi, K. Kohno, K. Yoneda, T. Tomita, M. Miya, K. Imai, Macromolecules, 18, 414 (1985). 333. N. Aelenei, Mater. Plast. (Bucharest), 22, 92 (1985). 334. I. B. Rabinovich, T. B. Khlyustova, A. N. Mochalov, VysokomoL Soedin. A, 27, 1724 (1985). 335. B. A. Boiton, S. Kint, G. F. Bailey, J. R. Scherer, J. Phys. Chem., 90, 1207 (1986). 336. K. Inoue, R. Fujii, Y Baba, A. Kagemoto, C. L. Beatty, Makromol. Chem., 187, 923 (1986). 337. E. Casur, T. G. Smith, J. Appl. Polym. Sci., 31, 1425 (1986). 338. M. D. Sefcik, J. Polym. Sci., Polym. Phys. Ed., 24, 935 (1986). 339. M. D. Sefcik,J. Polym. Sci., Polym. Phys. Ed., 24,957 (1986). 340. T. Nagao, Hakodate Kogyo Koto Senmon Gakko Kiyo, 19, 161 (1985). 341. U. B. Goradia, H. G. Spencer, J. Appl. Polym. Sci., 33, 1525 (1987). 342. P. Schneider, A. Heintz, Thermochim. Acta, 119, 47 (1987). 343. H. Azuma, K. Hanada, Y Yoshikawa, Y Baba, A. Kagemoto, Thermochim. Acta, 123, 271 (1988). 344. H. Becker, R. Gnauck, J. Chromatogr., 410, 267 (1987). 345. M. Bender, A. Heintz, J. Solution Chem., 18, 1 (1989). 346. A. Edelman, A. Fradet, Polymer, 30, 324 (1989). 347. R. Parashar, H. G. Singh, S. C. Sharma, Indian J. Chem. A, 28, 317 (1989). 348. A. Zivny, J. Biros, J. Pouchly, Makromol. Chem., 190, 1345 (1989). 349. R. Parashar, S. C. Sharma, Indian J. Chem. A, 28, 1042 (1988). 350. Y Kamiya, Y Naito, K. Mizoguchi, J. Polym. Sci., Polym. Phys. Ed., 27, 2243 (1989). 351. M. Galin, Polymer, 30, 2074 (1989). 352. B. Andersson, G. Olofsson, J. Solution Chem., 18, 1019 (1989). 353. H. G. Schild, D. A. Tirrell, J. Phys. Chem., 94, 4352 (1990). 354. M. Galin, Macromolecules, 23, 3006 (1990). 355. A. Hamdouni, J. Leonard, V. T. Bui, Polym. Commun., 31, 258 (1990). 356. M. Labadie, J. C. Bollinger, Thermochim. Acta, 162, 445 (1990).
357. E. Killmann, F. Cordt, F. Moeller, Makromol. Chem., 191, 2929 (1990). 358. M. M. Selin, Khim.-Farm. Zh., 24, 72 (1990). 359. A. P. Safronov, A. A. Tager, Vysokomol. Soedin. A, 33,2198 (1991). 360. Y. Kamiya, D. Bourbon, K. Mizoguchi, Y. Naito, Polym. J. (Tokyo), 24, 443 (1992). 361. A. P. Mar'in, Yu. A. Shlyapnikov, A. Zh. Makhkamov, A. T. Dzhalilov, Int. J. Polym. Mater., 16, 37 (1992); Oxid. Commun., 20, 57 (1997). 362. G. DiPaola-Baranyi, C. K. Hsiao, M. Spes, P. G. Odell, R. A. Burt, J. Appl. Polym. Sci., Appl. Polym. Symp. 51, 195 (1992). 363. F. Yilmaz, O. G. Cankurtaran, B. M. Baysal, Polymer, 33, 4563 (1992). 364. J. Y. Wang, G. Charlet, Macromolecules, 26, 2413 (1993). 365. D. Eagland, N. J. Crowther, C. J. Butler, Polymer, 34, 2804 (1993); 35, 4704 (1994). 366. A. P. Safronov, A. A. Tager, E. S. Klyuzhin, L. V. Adamova, Vysokomol. Soedin. A, 35, 700 (1993). 367. H. Phuong-Nguyen, G. Delmas, J. Solution Chem., 23, 249 (1994). 368. K. Nagahama, H. Inomata, S. Saito, Fluid Phase Equilib., 96, 203 (1994). 369. H. Phuong-Nguyen, G. Delmas, Thermochim. Acta, 238, 257 (1994). 370. R. J. Hernandez, R. Gavara, J. Polym. Sci., Polym. Phys. Ed., 32, 2367 (1994). 371. E. Killmann, F. Cordt, F. Moeller, H. Zellner, Macromol. Chem. Phys., 196, 47 (1995).
372. H.-M. Petri, N. Schuld, B. A. Wolf, Macromolecules, 28, 4975 (1995). 373. M. Carlsson, D. Hallen, P. Linse, J. Chem. Soc, Faraday Trans., 91, 2081 (1995). 374. Y Kamiya, K. Terada, Y Naito, J.-S. Wang, J. Polym. Sci., Polym. Phys. Ed., 33, 1663 (1995). 375. C. Grossmann, R. Tintinger, J. Zhu, G. Maurer, Fluid Phase Equilib., 106, 111 (1995). 376. M. Galin, Polymer, 36, 3533 (1995). 377. T. Banerjee, M. Chhajer, G. G. Lipscomb, Macromolecules, 28, 8563 (1995). 378. R. C. Castells, L. M. Romero, A. M. Nardillo, Macromolecules, 29, 4278 (1996). 379. Y. N. Matyushin, T. S. Konkova, Int. Annu. Conf. ICT, 27th, 122.1 (1996). 380. S. A. Vshivkov, E. V. Rusinova, G. B. Zarubin, V. N. Dubchak, Vysokomol. Soedin., 38AB, 868 (1996). 381. A. P. Safronov, A. A. Tager, E. V. Koroleva, Vysokomol. Soedin., 38AB, 900 (1996). 382. E. Sabadini, E. M. Assano, T. D. Z. Atvars, J. Appl. Polym. Sci., 63, 301 (1997). 383. F. Yilmaz, O. Cankurtaran, Polymer, 38, 3539 (1997). 384. Y. M. Lotmentsev, D. V. Pleshakov, Propellants, Explos., Pyrotech., 22, 203 (1997). 385. T. Banerjee, G. G. Lipscomb, Polymer, 38, 5807 (1997). 386. P. Gotthardt, A. Grueger, H. G. Brion, R. Plaetschke, R. Kirchleim, Macromolecules, 30, 8058 (1997). 387. Y. Kamiya, K. Mizoguchi, K. Terada, Y. Fujiwara, J.-S. Wang, Macromolecules, 31, 472 (1998). 388. S. Erdal, I. Bahar, B. Erman, Polymer, 39, 2035 (1998).
H e a t s
o f
S o l u t i o n
o f
S o m e
C o m m o n
P o l y m e r s
Robert A . O r w o l l College of William and Mary, Williamsburg, VA, USA
A. Introduction B. Table of Heats of Solution C. References A.
VII-671 VII-671 VII-673
heat of solution for a glass is usually dependent on temperature and, to some extent, on the thermal history of the glass. The dissolving of a semicrystalline polymer (C) requires an additional amount of heat associated with the disordering of crystalline regions. Consequently its heat of solution is usually positive and depends on the extent of crystallinity of the sample. An amorphous polymer above its glass transition temperature (L) usually dissolves with the absorption of a small amount of heat but may also dissolve with the release of heat. Most of the references to measurements made before 1972 were collected by D. R. Cooper (Manchester) for the second edition of this Handbook. A more complete listing of references to heats of solution can be found in the chapter "Heat, Entropy, and Volume Changes for PolymerLiquid Systems."
INTRODUCTION
Heats of solution (at infinite dilution) are tabulated below for some common polymers dissolved in some common solvents. The values were determined calorimetrically and are reported here as the heat (in Joules) absorbed per gram of polymer as pure polymer and a large excess of pure solvent mixed isothermally to form a homogeneous solution. The state of the polymer before dissolution is indicated in the fourth column. It can significantly affect the heat of solution. An amorphous polymer below its glass transition temperature (G) often dissolves with release of heat. The B. TABLE OF HEATS OF SOLUTION Solvent Poly(butadiene) Benzene Cyclohexane /?-Hexadecane Poly(dimethyl siloxane) Benzene Carbon tetrachloride Cyclohexane Cyclohexane /?-Decane Ethyl ether n-Hexadecane /?-Hexadecane /r-Pentane Poly(ethylene) Cyclohexane 1,2,3,4-Tetrahydronaphthalene" 1,2,3,4-Tetrahydronaphthalene" 1,2,3,4-Tetrahydronaphthalene* 1,2,3,4-Tetrahydronaphthalene'7 Toluene Poly(isobutylene) Benzene Benzene
AH (J/g)
Temp. (0C)
State
MW x 10
4
(g/mol)
Refs.
13 5.4 4.9
27 25 25
L L L
8 -
5 23 24
14 2.4 5.1 5.2 3.9 -1.3 5.5 5.5 -0.9
25 25 25 25 25 25 25 25 25
L L L L L L L L L
10 10 10 2.0 10 8 10 2 10
11 11 11 23 7 10 7 24 7
205 39 560 88 1200 262
106 130 80 150 110 126
C L C L C C
90 67 67 14 14 90
32 12 12 12 12 32
19 19
25 30
L L
3 4.8
8 25
Solvent Benzene Carbon tetrachloride Carbon tetrachloride Cyclohexane Cyclohexane Cyclohexane rc-Decane Ethylbenzene Ethylbenzene Ethyl ether n-Hexadecane /i-Hexadecane n-Hexadecane rc-Pentane rc-Pentane Poly(isoprene) Benzene Poly(methyl methacrylate) Chloroform Chloroform Poly(oxyethylene) Benzene Carbon tetrachloridec Carbon tetrachlorided Chloroform Water Waterc Water* Water Water Water Poly(oxypropylene) Carbon tetrachloride Carbon tetrachloridec Carbon tetrachlorided Chloroform Methyl alcohol Poly(propylene) Benzene Carbon tetrachloride Carbon tetrachloride Chloroform Chloroform Cyclohexane Cyclohexane n-Decane Ethylbenzene rc-Hexadecane w-Pentane 1,2,3,4-Tetrahydronaphthalene Toluene Poly(styrene) Carbon tetrachloride Chloroform Cyclohexane Ethylbenzene Ethylbenzene Ethylbenzene Ethylbenzene Toluene Toluene Toluene Toluene Toluene Toluene Poly(vinyl acetate)
State
MW x 10 ~4 (g/mol)
Refs.
25 25 25 25 25 25 69 18 25 25 25 25 25 25
L L L L L L L L L L L L L L L
0.13 200 0.13 3 4.5 0.13 3 4.8 4.8 3 3 0.45 0.13 3 0.13
21 9 21 8 24 21 8 25 25 8 1 24 21 8 21
12
16
L
0.4
2
-84 -37
25 25
G C
170 16 -Yl 52 -120 -160 -200 10 24 40
30 30 30 30 80 25 25 25 30 30
C L L C L L L C C C
4.3 0.06 0.04 0.6 0.5 0.02 0.02 2 0.6 4.3
26 31 31 18 4 30 30 28 18 26
-20 -8 -14 -100 - 7
6 30 30 6 27
L L L L L
0.2 0.2 0.16 0.2 0.1
13 33 33 13 6
31 6.4 6.6 17 17 2.3 3.9 3.1 14 2.3 -4.7 320 16.5
25 25 25 25 25 25 25 25 25 25 25 120 25
L L L L L L L L L L L C L
1.8 1.8 1.8 1.8 1.8 0.6 1.8 1.8 1.8 0.6 1.8 1.8
27 22 27 22 27 23 27 27 27 24 27 12 27
- 20 -24 - 8.2 -6 -24 -22 -5 -3 -26 -22 -21 -7 -2.5
25 45 26 110 35 30 78 100 35 26 30 78 25
G G G L G G G L G G G G G
AH (J/g) 23 4.1 5.0 -0.7 -0.6 1.1 -0.5 3.5 9.3 2.8 0.04 0.9 1.0 -3.6 -3.2
Temp. (0C)
10 -
50 10 70 11 11 6 11 11 11 70 6 11
14 14
19 16 15 20 20 17 20 20 20 15 17 20 29
Solvent Benzene Chloroform Methyl alcohol 0 b c 1
A/f (J/g) 2.3 -45 28
Temp. (0C) 25 25 25
State
MW x 10 ~4 (g/mol)
G G G
14 14 14
Refs. 3 3 3
High-pressure poly(ethylene). Low-Pressure poly(ethylene). Hydroxy terminated. Methoxy terminated.
C. REFERENCES 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15.
16. 17. 18.
E. Calvet, Bull. Soc. Chim., 12, 553 (1945). G. Gee, W. J. C. Orr, Trans. Faraday Soc, 42, 507 (1946). H. Daoust, M. Rinfret, Can. J. Chem., 32, 492 (1954). G. N. Malcolm, J. S. Rowlinson, Trans. Faraday Soc, 53, 921 (1957). R. S. Jessup, J. Res. Natl. Bur. Std., 62, 1 (1959). M. L. Lakhanpal, B. E. Conway, J. Polym. Sci., 46, 75 (1960). G. Delmas, D. Patterson, D. Bohme, Trans. Faraday Soc, 58, 2116(1962). G. Delmas, D. Patterson, T. Somcynsky, J. Polym. Sci., 57, 79 (1962). A. A. Tager, A. I. Podlesnyak, Polym. Sci. USSR, 4, 698 (1963). D. Patterson. J. Polym. Sci. A, 2, 5177 (1964). G. Delmas, D. Patterson. S. N. Bhattacharyya, J. Phys. Chem., 68, 1468 (1964). H. P. Schreiber, M. H. Waidman, J. Polym. Sci. A-2, 5, 555 (1967). R. W. Kershaw, G. N. Malcolm, Trans. Faraday Soc, 64, 323 (1968). C. Gerth, F. H. Mueller, Kolloid-Z., 241, 1071 (1970). A. A. Tager, A. I. Podlesnayak, M. V. Tsilipotkina, L. V. Adamova, A. A. Bakhareva, L. V. Demidova, Polym. Sci. USSR, 12, 1497 (1970). S. Morimoto, Bull. Chem. Soc Japan, 44, 879 (1971). S. H. Maron, F. E. Filisko, J. Macromol. Sci. B, 6,57 (1972). S. H. Maron, F. E. Filisko, J. Macromol. Sci. B, 6,79 (1972).
19. P. Davalloo, J. L. Gainer, K. R. Hall, J. Chem. Thermodyn., 4, 691 (1972). 20. F. E. Filisko, R. S. Raghava, G. S. Y. Yeh, J. Macromol. Sci. B: Phys., 10, 371 (1974). 21. D. D. Deshpande, C. S. Prabhu, Macromolecules, 10, 433 (1977). 22. H. Ochiai, Y. Nishihara, S. Yamaguchi, I. Murakami, J. Sci. Hiroshima Univ. Ser. A: Phys. Chem., 41, 157 (1977). 23. H. Phuong-Nguyen, G. Delmas, Macromolecules, 12, 746 (1979). 24. H. Phuong-Nguyen, G. Delmas, Macromolecules, 12, 740 (1979). 25. J.-G. Lee, M. Ono, F. Hamad, A. Nakajima, Polym. Bull. (Berlin), 1, 763 (1979). 26. J. Koller, E. Killmann, Makromol. Chem., 182, 3579 (1981). 27. H. Ochiai, T. Ohashi, Y. Tadokoro, I. Murakami, Polym. J. (Tokyo), 14, 457 (1982). 28. H. Daoust, D. St-Cyr, Macromolecules, 17, 596 (1984) 29. S. Morimoto, Thesis, Osaka City Univ, 1970, as cited in T. Shiomi, K. Kohno, K. Yoneda, T. Tomita, M. Miya, K. Imai, Macromolecules, 18, 414 (1985). 30. J. Biros, J. Pouchly, A. Zivny, Makromol. Chem., 188, 379 (1987). 31. E. Killmannn, F. Cordt, F. Moller, Makromol. Chem., 191, 2929 (1990). 32. H. Phuong-Nguyen, G. Delmas, J. SoIn. Chem., 23, 249 (1994). 33. E. Killmannn, F. Cordt, F. Moller, H. Zellner, Makromol. Chem. Phys. 196, 47 (1995).
S o l u b i l i t y
P a r a m e t e r
V a l u e s
Eric A . G r u l k e Chemical and Materials Engineering, University of Kentucky, Lexington, KY, USA
A. Introduction VII-675 B. Miscibility of Solvents and Polymers VII-676 1. Cohesive Energy Density and the Solubility (Hildebrand) Parameter VII-676 2. Cohesive Energy Parameters for Polar Systems VII-677 3. Relationship Between Solubility Parameters and Other Thermodynamic Parameters VII-677 C. Solubility Parameter Measurements, Calculations, and Correlations VII-679 1. Solvents VII-679 2. Polymers VII-680 2.1. Indirect Measurements VII-680 2.2. Correlation Methods VII-682 Table 1. Selected Solvents for Use in Polymer Solvency Testing VII-683 Table 2. Group Contribution to Cohesive Energy Density VII-684 2.1. Carbon-Containing Groups VII-684 2.2. Oxygen-Containing Groups VII-684 2.3. Nitrogen-Containing Groups VII-684 2.4. Other Groups VII-684 2.5. Structural Features VII-685 Table 3. Contribution to Ecoh and V VII-685 Table 4. Solubility Parameter I: Component Group Contributions VII-686 Table 5. Solubility Parameter II: Component Group Contributions VII-686 Table 6. Equations to be Used for Hoy's System VII-687 D. Solubility Parameter Tables VII-688 Table 7. Solubility Parameters of Solvents in Alphabetical Order VII-688 Table 8. Solubility Parameters of Solvents in Increasing Order of 8 VII-694 Table 9. Hansen Solubility Parameters of Liquids at 25°C VII-698 9.1. Paraffinic Hydrocarbons VII-698 9.2. Aromatic Hydrocarbons VII-698
9.3. 9.4. 9.5. 9.6. 9.7. 9.8.
Halohydrocarbons Ethers Ketones Aldehydes Esters Nitrogen-Containing Compounds 9.9. Sulfur-Containing Compounds 9.10. Acid Halides and Anhydrides 9.11. Alcohols 9.12. Acids 9.13. Phenols 9.14. Water 9.15. Polyhydric Alcohols Table 10. Solubility Parameters of Polymers 10.1. Main Chain Carbon Polymers 10.2. Main Chain C-O Polymers 10.3. Main Chain C-N Polymers 10.4. Other Polymers E. References A.
VII-698 VII-699 VII-699 VII-699 VII-699 VII-700 VII-700 VII-700 VII-700 VII-701 VII-701 VII-701 VII-701 VII-702 VII-702 VII-708 VII-709 VII-710 VII-711
INTRODUCTION
Applications of solubility parameters include selecting compatible solvents for coating resins, predicting the swelling of cured elastomers by solvents, estimating solvent vapor pressure in polymer solutions for devolatilization and reaction systems (16), and predicting phase equilibria for polymer-polymer (107), polymer-binary (93), random copolymer (102), and multicomponent solvents (38, 98,108,109). Cohesive energy density and solubility parameters are defined in the section on miscibility of solvents and polymers (Section B). In addition, the applicability of solubility parameters to thermodynamic calculations and their limitations are discussed. Section C contains methods for measuring, calculating and correlating solubility parameters of solvents and polymers. Section D contains
alphabetical listings of solubility parameters (Table 7), a list of solubility parameters in rank order (Table 8), a list of three-component solubility parameters of solvents (Table 9), and a list of solubility parameters of polymers (Table 10). With the exception of Table 7, solubility parameter values are reported in MPa 1 / 2 units. The table showing solubility parameter value ranges for polymers (Table 3.4 in the third edition) has not been reproduced here. B. MISCIBILITY OF SOLVENTS AND POLYMERS
The solubility parameter can be interpreted as the "internal pressure" of the solvent (9-11). 5,- is called the Hildebrand parameter by some authors. Other researchers (13) prefer the term, "cohesion parameter", since it correlates with a large number of physical and chemical properties, and not just the miscibility of the components. The solubility parameter of a mixture is often taken as the sum of the products of the component solubility parameters with their volume fractions: (B5)
1. Cohesive Energy Density and the Solubility (Hildebrand) Parameter Dissolution of an amorphous polymer in a solvent is governed by the free energy of mixing (Bl) where AGm is the Gibbs free energy change on mixing, AHm is the enthalpy change on mixing, T the absolute temperature, and AS m is the entropy change on mixing. A negative value of the free energy change on mixing means that the mixing process will occur spontaneously. Otherwise, two or more phases result from the mixing process. Since the dissolution of a high molecular weight polymer is always connected with a small or modest increase in entropy, the enthalpy term (the sign and magnitude of A / / m ) is the deciding factor in determining the sign of the Gibbs free energy change. Solubility parameters were developed to describe the enthalpy of mixing of simple liquids (nonpolar, nonassociating solvents), but have been extended to polar solvents and polymers. Hildebrand and Scott (59) and Scatchard (101) proposed that (B2) where V is the volume of the mixture, AEJ the energy of vaporization of species /, Vj the molar volume of species /, and (j>i the volume fraction of / in the mixture. AEJ is the energy change upon isothermal vaporization of the saturated liquid to the ideal gas state at infinite volume (94). The cohesive energy density (CED), A£, v , is the energy of vaporization per cm 3 . The solubility parameter has been defined as the square root of the cohesive energy density and describes the attractive strength between molecules of the material. (B3)
Relation between S1 and AHm Equation (B2) can be rewritten to give the heat of mixing per unit volume for a binary mixture: (B6) Equation (B6) gives the heat of mixing of regular solutions in which the components mix with: (a) no volume change on mixing at constant pressure, (b) no reaction between the components, and (c) no complex formation or special associations (114). The heat of mixing must be smaller than the entropic term in E)q. (Bl) for polymer-solvent miscibility (AGm < 0). When 6\ = 62, the free energy of mixing will always be less than zero for regular solutions and the components will be miscible in all proportions. In general, the solubility parameter difference, (8\ — S2) must be small for miscibility over the entire volume fraction range. Relation between S1 and AHJ The energy change on isothermal vaporization can be related to the enthalpy of vaporization: (B7) where AHJ is the enthalpy of vaporization at standard conditions, AH^ the molar increase in enthalpy on isothermally expanding the saturated vapor to zero pressure, R the ideal gas constant, and ps the saturation vapor pressure at temperature, T. At pressures below 1 atm, the AHf0 and psVj terms are usually much less than the AHJ and RT terms, and Eq. (B7) reduces to Eq. (B8): (B8) The solubility parameter of volatile materials (solvents for example) can be determined by measuring their enthalpy of vaporization or using a correlation for this quantity, and using Eq. (B9):
The dimensions of <5/ are (B9)
(B4)
Equation (B9) should be used at pressures near 1 atm. Near the critical point, AHJ = 0, and Eq. (B8) incorrectly
predicts a negative value for the cohesive energy density while Eq. (B7) yields a small positive value.
permanent dipole-dipole interactions and hydrogen bonding forces:
Dissolution of crystalline polymers The free energy of mixing for crystalline polymers contains terms for the free energy of fusion for the crystalline volume fraction of the material. The free energy of fusion may contain terms that account for the loss of crystallite surface area and the mixing of amorphous material with oriented material. These terms would be added to Eq. (Bl). The enthalpy of mixing could still be modeled using Eqs. (B2) or (B6). Some crystalline polymers obey the solubility parameter model at temperatures near their melting point, T>0.9Tm (123). Solvent swelling experiments with crystalline polymers may fit Eq. (Bl), particularly if the solvent is a poor one for the polymer and does not significantly dissolve crystalline regions.
(BH)
2.
Cohesive Energy Parameters for Polar Systems
The solubility parameter describes well the enthalpy change on mixing of nonpolar solvents but does not always give reliable results when extended to polar systems. The free energy change of mixing for polar systems is dominated by hydrogen-bonding forces between various groups in the solvent and polymer. Hydrogen-bonding forces are much stronger than van der Waals or dipole forces and often dominate the free energy of mixing. Complete miscibility is expected to occur if the solubility parameters are similar and the degree of hydrogen bonding (p: poor, m: moderate and s: strong) is similar between the components. Hydrocarbons, chlorinated hydrocarbons and nitrohydrocarbons are considered to be poor hydrogen-bonding solvents. Ketones, esters, and glycol monoethers give moderate hydrogen bonding. Alcohols, amines, acids, amides and aldehydes are strong hydrogen-bonding solvents. Table 7 classifies materials using these categories (21-24). Alternative classifications have been given by Lieberman (69), Gardon (41,85,86) and Dyck and Hoyer (32). Other investigators have decomposed the Hildebrand parameter into several terms representing different contributions to the free energy of mixing. Hildebrand (59) used dispersive and polar solubility terms for solvents, with the complete parameter being given by (BlO) where S^ is the dispersive term and 6P the polar term. The additional term improved agreement between 6 and experimental data. Prausnitz and coworkers accounted for polar bonding by including parameters for permanent dipole interactions and dispersion type interactions. This approach has been applied to polymer solutions (15) and complex formation (57). Crowley et al. (26,27) proposed a three-parameter system. Hansen (49-53,56) and Hansen and Skaarup (54) assume that the cohesive energy arises from dispersive,
where <5h accounts for a variety of association bonds, including hydrogen bonds and permanent dipole-induced dipole (47). The values of these components for solvents were calculated from a large number of solubility data sets. Polymer solubility parameters can also be decomposed to a three-term set. The Hansen parameters give improved agreement with data but are still not completely accurate in predicting solutions thermodynamics for every system. Peiffer (172) has related dispersion, polar and induced solubility parameters to intermolecular forces and molecular size. The dispersive component increases with molecular size, while the polar component decreases with molecular size. Temperature effects The solubility parameter decreases with temperature. The individual terms have varied dependence on temperature, namely (Ref. 55)
(B12)
where a (K"1) is the volumetric thermal expansion coefficient. 3. Relationship between Solubility Parameters and other Thermodynamic Parameters
Hildebrand and Hansen parameters can be calculated using other thermodynamic quantities. This section contains some of the relationships for binary systems. Extensions to multicomponent systems are described by Flory (37) and Olabisi et al. (89). Activity coefficients Excess free energy calculations for regular solutions (93) can be used to relate solubility parameters and solvent activity coefficients: (B13) (B14) where 7, is the activity coefficient of component i. Equations (B 13) and (B 14) depend on the use of the geometric mean, 512 = (6\ x ^2)1//2. Funk and Prausnitz (40) show that there are deviations from this rule for aromatic hydrocarbons. Molar excess free energy of mixing The molar excess free energy of mixing for binary solutions is (B15) where Sj-i is the solubility term of group / for species j . References page VII - 711
Polymer-solvent interaction parameter The polymersolvent interaction parameter, x> is modeled as the sum of entropic and enthalpic components: (B16) where XH is the enthalpic component and Xs is the entropic component. Xs is usually taken to be a constant between 0.3 and 0.4 for nonpolar systems: Xs — 0-34 is often used (15,104). The enthalpic component can be related to the Hildebrand parameters: (B17) Substituting Eq. (B 17) into Eq. (B 16) (B18) Equation (B 18) permits only positive values of the interaction parameter. Since the Flory-Huggins criterion for complete solvent-polymer miscibility is x < 0-5, the enthalpic contribution must be small and the solubility parameters of the solvent and polymer must be similar (21). The molar volume of the solvent also affects miscibility and phase equilibria: a Hildebrand parameter needed for phase separation or miscibility cannot be specified without specifying Vi. Interchange energy density Equation (B 18) works well for nonpolar systems for which Eq. (B 17) is a good description of the enthalpic component of the interaction parameter. The geometric mean assumption of regular solution theory is not appropriate for polar systems, and better models include an extra term describing the interchange energy density for the solvent-polymer pair. For example (B19) with (B20) where I^ characterizes the intermolecular forces between molecules (rather than using the geometric mean assumption). Equation (B20) allows the modeling of specific interactions between components 1 and 2. Mixed solvents can be treated as a single solvent by determining the solubility parameter of the solvent mixture, and then using this value in Eq. (B 18). If both the solvents and the polymers interact, the description is more complicated. An alternative definition of An uses the two-component solubility parameter (Ref. 25) (B21) The Hansen parameters may also be used to model An-
Several recent theories for polymer solution thermodynamics include entropic, enthalpic and free-volume contributions to the free energy of mixing. The free-volume contributions modify the entropic components, and have the opposite temperature dependence from the combinatorial term, helping to explain the lower critical solution temperature. Since Eq. (B 18) assumes a constant value for the entropic component, it may not be valid over large temperature ranges. However, Eq. (B 18) will predict the upper critical solution temperature, and, from this standpoint, is adequate for a number of phase equilibria applications near this condition. The Lattice Fluid model (170) can be used to predict the solubilities of hydrocarbon and chlorinated hydrocarbons in nonpolar polymers. Three-dimensional solubility parameters can be used to provide an empirical correction to the geometric mean approximation (171). This correction predicts the solubility of polar and nonpolar solvents in polymers using only the pure component equation-of-state and solubility parameters. Guide to polymer solvent miscibility A region of solubility has been characterized by the distance between solvent and solute coordinates (Ref. 14)
(B22) A more general definition of the region of solubility is (B23) where a and b are empirical weighing factors. If the distance between the solvent and the solute Hansen coordinate position exceeds /?/,, the two components are not soluble, or swelling is less than expected. R(J reduces the need for three-dimensional plots. Some investigators have used two-dimensional plots for polar and hydrogen bonding terms, but the technique may be misleading for materials with large dispersion contributions. Barton (12) gives a number of models and contour map examples. As mentioned previously, Eqs. (B 17)-(B 19) suggest that the solvent molar volume can have a significant effect on miscibility. Zeller (131) reviewed graphical three-dimensional solubility parameter estimation methods (12,14,49,55,172,173) as applied to solvent swelling of crosslinked elastomers. In general, the graphical method (Eqs. B22 and B23) does not account for the known influence of molar volume and crosslink density of solubility, and incorrectly assumes a linear relationship between the solubility parameter difference and solubility. An improved method used the FloryRehner equation to modify the interaction parameter for the effects of crosslink density (132).
Guide to polymer-polymer miscibility In many polymer-polymer systems, miscibility can be predicted by comparing the solubility parameters (139). The following table proposes misciblity guidelines. Polymer-polymer miscibility is enhanced when hydrogen bonding is present.
correlations. When AHJ is known at the normal boiling point, it can be converted to the appropriate value at a second temperature using (126) (Cl)
0
TABLE OF MISCIBILITY GUIDELINES
Intermolecular Polymer blend interaction example
Critical value of the interaction parameter, Xcrit
Upper limit of the non-hydrogen bonded solubility parameter difference, A^ (MPa 1/2 )
Dispersive forces only Dipole-dipole interactions
Polyisoprene-Poly- < 0.002 (vinylethylene) Poly(methyl 0.002-0.001 methy aery late )poly(ethylene oxide) Weak hydrogen Poly(vinyl chloride)- 0.02-0.2 bonds polycaprolactone Moderate Poly(vinyl phenol)- 0.2-1.0 hydrogen poly (vinyl acetate) bonds Strong hydrogen Poly(vinyl phenol)- 1.0-1.5 bonds poly(vinyl methyl ether 0
<0.02 0.2-1.0 1.0-2.0 2.0-5.0 5.0-6.0
Ref. 139.
C.
SOLUBILITY PARAMETER MEASUREMENTS,
CALCULATIONS, A N D CORRELATIONS
Solubility parameters can be determined by direct measurements, indirect calculations, or correlations with other physical parameters. The solubility parameters of solvents usually can be determined directly by measuring the energy of vaporization. The solubility parameters of polymers can only be determined indirectly and may be affected by variations in their chemical constitutions, i.e., the number of crosslinks and the distribution of chain branches or substitutive groups along the polymer backbone. The methods presented in this section can be used to develop correlations of solubility parameters with other physical properties for specific commercial polymer products or to estimate the solubility parameters of new polymers. 1.
This corresponding state-type procedure gives estimates within 2% of experimental values over a wide range of temperatures (13). Hildebrand and Scott (59) proposed an empirical correlation between AHJ at 25°C and the normal boiling point, Tb\
Solvents
Calculation of the solubility term (5) by relating the enthalpy of vaporization to the energy of vaporization
Equation (B8) can be used to calculate AEJ when AHJ is available. The molar volume of the solute is needed to complete the calculation of 6, using Eq. (B3). This is the most direct and accurate method of determining the solubility parameter. However, <5's determined in this way may not give the best prediction of solution behavior. The solubility parameter values in Tables 7-9 reflect the solvent's behavior in a variety of systems. Correlations Both the enthalpy of vaporization and the molar volume of a solvent can be estimated from
(C2)
with enthalpy units of kcal/mol. Lawson (67) suggests different coefficients to include fluorocarbon liquids. The Clausius-Clapeyron equation can be applied if vapor pressure data are available. Eq. (C2) is reasonably accurate only for liquids that are not hydrogen bonded. The Hildebrand parameter calculated by Eq. (C2) should be adjusted as follows for different solvents (24): add 1.4 (cal/cm3)1/2 for alcohols, add 0.6 (cal/cm3)1/2 for esters, and add 0.5 (cal/cm3)1/2 for ketones if the boiling point is less than 1000C. Jayasri and Yaseen (64) suggest adding 1.7 (cal/cm3)1/2 for alcohols. Solvent molar volumes are available or can be calculated by group molar volume methods at 25°C (35,163-165). The molar volume for solids at 25°C can be extrapolated from liquid state values (the liquid is assumed to be subcooled). Thermodynamic coefficients defined as (Ref. 88)
The internal pressure, ?r, is
(C3)
where /J is the constant volume thermal pressure coefficient (the ratio of the coefficient of thermal expansion, a, to the isothermal compressibility, K). Since the external pressure is usually small with respect to TP, the internal pressure is approximated by (C4)
The Hildebrand parameter is the square root of the internal pressure. Eq. (C4) provides a method for scaling the Hildebrand parameter with temperature. This equation also provides a method for the direct estimation for 6 of polymers; a and K are measurable when AH] is not meaningful (B7). The thermal pressure coefficient (C4) can be evaluated from vapor-pressure data and is easier to apply than the Clausius-Clapeyron equation. For high pressure applications, such as phase equilibria in reverse osmosis membranes, the external pressure term in Eq. (C3) may not be negligible. Solubility parameters generally decrease with increasing pressure. References page VII - 711
van der Waals gas constant Tables are available in many Handbooks for the van der Waals correction constants to the ideal gas law, a and b, where a has units of l2/atm. For some liquids, these values may be at hand when other data are not available. They can be used to check Hildebrand parameter values obtained from other sources. (C5) The form of Eq. (C5) can be obtained by substituting the van der Waals equation of state into Eq. (C3). Critical pressure The solubility parameter is related to the critical pressure, Pc of a substance through the empirical equation (C6) where the critical pressure is expressed in atmospheres. Equation (C6) is not very accurate, but is simple to apply when critical pressure data are available. Surface tension Michaels (83) has shown that the surface tension can be related to the cohesive energy density: (CI) where *yL is the surface tension and A is a constant. Koenhen and Smolders (65) correlated surface tension and two Hansen parameters: (C8) <5h is probably not related to the liquid-vapor interfacial energy as these interactions do not involve breaking hydrogen bonds. Eq. (C8) does not describe cyclic compound, acetonitrile, carboxylic acids, polyfunctional alcohols, and other polar compounds well. Hildebrand and Scott (59) have proposed a different equation, which has been discussed by Lee (68). Index of refraction The dispersive Hansen parameter can be related to the index of refraction, no (65,105). (C9) The interaction energy between nonpolar molecules should depend on polarizability (London dispersion forces) and, therefore, on the index of refraction. Dipole moment Hansen and Skaarup (54) related the polar Hansen parameter to the dielectric constant, e, and the dipole moment, \x\ (ClO)
Beerbower and Dicky (14) proposed an empirical relationship: (CU) Kauri butanol values Proprietary hydrocarbon solvents are usually mixtures with boiling ranges and unknown molecular weights. Solubility parameter values may be estimated from Kauri butanol values (ASTM Method D1133-54T) using the equation 6 = 6.3 -f 0.03 KB
(C12)
2. Polymers Hildebrand parameters cannot be calculated for polymers from heat of vaporization data because of their nonvolatility. Indirect methods are described below. The solubility parameter values in Table 10 may only be representative of a given polymer since variations in compositions can lead to changes in 6. 2.1. Indirect Measurements Solvency testing (screening procedure) The classic method for determining solubility parameter of a commercial polymer is solvency testing, or the solvency screening procedure. This technique compares polymer solubility in solvent groups with different hydrogen bonding characteristics (poor, moderate and strong). The midpoints of the polymer's solubility range may be used as single-valued quantities for some purposes, but may not agree with values determined by other methods (43). A gram or two of solid polymer is placed in a test tube and an approximate amount of a selected solvent is added such that the final solution would have about the correct solid content for the expected commercial use, e.g., 50% for alkyds, 20% for vinyls, etc. The exact amount is often unimportant, except for poor solvents. A typical phase diagram for binary polymersolvent systems may show upper and lower critical solution temperatures. The one-phase region expands away from the UCST and LCST points, which often occur in the range of 20-80 wt.% polymer. The usual purpose of these experiments is to find good solvents for commercial product formulation, and this screening procedure will help identify such solvents. The mixture may be warmed and stirred to speed up solution, but it should be cooled and observed at room temperature. The resulting mixture should be a single phase, clear and free of gel particles or cloudiness, otherwise the polymer is judged insoluble. The solvents to be used are selected from Table 1. This grouping of solvents has been selected so that the Hildebrand parameter values increase by reasonably constant steps within each hydrogen bonding class. The object of using these solvent spectra is to establish a solubility parameter range for a polymer rather than a single-valued number. This range has the advantage of showing the difference, (6\ — ^ ) 2 (see Eqs. B13, B14 and
B18), which can be tolerated between the solubility values of the polymer and solvent for miscibility. Van Dyk et al. (120) have shown that the molar volume improves the correlation between solvency and the solubility parameters. A better measure of solubility might be the group, Vi(S1-S2)2. In carrying out the procedure, it is convenient to select the first trials about 1/2 and 2/3 of the way down the column; for example, in the poorly hydrogen bonded group, toluene and nitroethane would be chosen. If the polymer is soluble in both, there is no need to try intermediate solvents because experience has shown that the polymer will be soluble in every case. The solvents at the end of the spectrum should be tried next. If the polymer is soluble in one but not both of the initial trials, the third trial should be half-way between the two. By successive choices, sets of two adjacent solvents will be found, one of which dissolves the polymer and one that does not. The parameter values of the solvents which do dissolve the polymer mark the ends of the range. The procedure is repeated for the other two hydrogen bonding classes. Osmotic pressure Fedors (35) used the osmotic pressure of polymer solutions to determine solubility parameters. Swelling values Another method for measuring the solubility parameter of polymers is to prepare a sparsely crosslinked sample and immerse it in a series of liquids of varying 8 (166,167). The crosslinked material will swell to varying degrees, with the maximum amount of swelling occurring when the solvent has the same Hildebrand parameter as the polymer. The amount of swelling can be measured by length, weight, or volume changes. By inference, the soluble, uncrosslinked materials has the same value. An example of a crosslinked sample is styrene polymerized with 1% divinyl benzene. Turbidity Polymer can be precipitated from dilute solution by adding a non-solvent. The cloud point defines the onset of two phases. The enthalpic component of the interaction parameter, x#> can be related to the solubility parameter difference between the solvent and the polymer (Eq. B17). Two different non-solvents are used: one having a solubility parameter above that of the solvent, and another having a solubility parameter below that of the solvent. The enthalpic components of the interaction parameter for each phase are equal at the cloud point, which can be used to measure the solubility parameter of the polymer (116). The two expressions for XH &re
parameters of the mixed solvents. The mixture properties are calculated using (C14) (C15) where the subscripts, 1 and 3, refer to the solvent and the nonsolvent. Eq. (C 13) is simplified to determine the solubility parameter of the polymer:
(ci6) The volume fraction of the nonsolvent at the cloud point is used to compute the solvent mixture solubility parameter and molar volume. Cloud point experiments are done for a series of solvents with the two nonsolvents, generating a set of points, (6\, 82). The intersection of the line defined by this set of points with the line, 61 =62, determines the polymer's solubility parameter. Specific volume The specific volume of polymers varies with the solvent. Good solvents give higher values of the specific volume while poor solvents give lower values. A plot of the polymer specific volume as a function of solubility parameter gives a maximum value, which is taken to be the solubility parameter of the polymer. High precision density measurements at carefully controlled temperatures are needed for this method (168). The partial specific volume is defined as (C17) The specific volume of a nonideal two-component system is (C18) where V2 is the rate of change in volume of the solution when a very small amount of polymer is added. As the solvent volume fraction goes to one, the partial molar volume of solvent is constant and Eq. (C 18) becomes (C19) The maximum of the polymer partial specific volume is estimated by fitting a quadratic to the data (Ref. 142): (C20)
(C13)
where Vm\ and Vmh represent the molar volumes at the cloud points of the solvent-lower solubility parameter nonsolvent and solvent-higher solubility parameter nonsolvent, respectively. 8m\ and <5mh are the solubility
It is possible to estimate the polymer solubility parameter with only two reference solvents (168), but more reliable values are found by using a range of solvents. Intrinsic viscosity A number of researchers have used intrinsic viscosity to estimate Hildebrand parameters (74). References page VII-711
Flory (37) related intrinsic viscosity to polymer molecular weight and the chain-expansion factor. The chain-expansion factor can, in turn, be related to the polymer-solvent interaction parameter using the Flory-Huggins theory. Maximum coil extension should occur in solvents near the polymer's solubility parameter. A variety of models can be used to relate the interaction parameter to Hildebrand parameters (19,80,115,167-169). These equations are quadratic (Eq. C21) or take the form of a gaussian curve (Eq. C22): (C21) (C22) where [rj] is the intrinsic viscosity, [r?]max the maximum intrinsic viscosity, and A the constant. These researchers have shown that Eq. (C 14) gives a good correlation between solvency and Hansen parameters for methacrylate polymers. Inverse phase gas chromatography This method has been used by a number of investigators to measure infinite dilution weight fraction activity coefficients (6,2931,63,71,72,84,90,91,113). These coefficients can be related to Hildebrand parameters by using a thermodynamic theory for polymer solutions, such as Flory-Huggins theory. The polymer is the stationary phase in a gas chromatography column. Both binary and multicomponent equilibria (46,99,100) can be studied using this method. Chromatographic techniques have the advantage of rapid measurement of thermodynamic values once the columns have been made. The solubility parameter can be related to the specific retention volume of the solvent on the column. Both Vi and AHJ must be known at the temperature of the column. Molar volumes for the solvents can be determined by using literature density equations or generating equations from density data. Values for the enthalpy of vaporization can be determined at the experimental temperature (71). The inverse phase gas chromatography method has the advantage of providing values for the infinite dilution solubility parameter, Sf0, over a range of temperatures. This is particularly valuable for the prediction of phase equilibria at elevated temperatures. The value of 6f° at 25°C can be estimated by using the expected temperature dependence for x (Eq. B18) of (C23) One potential problem with this technique is that x *s known to be a function of concentration and the polymer Hildebrand parameter is determined at infinite dilution of solvent. For a number of binary systems, the change in \ with solvent weight fraction is the largest as u —» 0. The concentration dependence of the interaction parameter can be modeled using methods given in the chapter on interaction parameters in this Handbook.
2.2. Correlation Methods Refractive index Koenhen and Smolders (65) have predicted dispersive Hansen parameters from refractive index measurements of polymers. Wu (128) has suggested an effective cross-sectional area to relate the cohesive energy density and surface tension (C24) where n$ is the number of atoms in a segment, V,s the molar volume of a segment, and 7^ the dispersion contribution to the free surface energy of the polymer. Dipole moment Equation (ClO) has been applied to polymers by Koenhen and Smolders (65). The dipole moments of polymers are between 70% and 90% of those of the corresponding monomer units. Hydrogen-bonding parameter Hansen and Beerbower (55) compiled enthalpy data for hydrogen bonding groups. The following values are suggested: Group Alcohol Amide Ester Nitrile Ether Monochloro substituent Phenylene ring
Cohesive energy, E\x, (kj/mol) 20.9 16.3 5.2 2.1 2.3 0.4 0.4
Refs. 83 54 54 54 54 54
The hydrogen-bonding parameter is given by
*l=Y
(C25)
Group contribution methods These methods have been used to estimate the solubility parameter (17,20,28,33,35, 58,60,61,96,112,121,122). van Krevelen (123), Fedors (35), and Barton (12) have reviewed these techniques and given tables of group values. The molar volume of solvents and polymers can also be estimated by group contribution techniques (108). The sets of group constants of Small (112), Hoy (61) van Krevelen (121) and van Krevelen and Hoftyzer (122) seem to be most comprehensive. Table 2 gives the group molar attraction constants at 25°C. Small's values were derived from measurements of the heat of vaporization. Hoy's values were derived from vapor pressure measurements. The group contribution values of van Krevelen and Hoftyzer are based on cohesive energy data of polymers. The group contribution techniques are based on the assumption that the contributions of different functional groups to the thermodynamic property are additive. The energy of vaporization of a solvent or polymer is (C26)
where Aej is the energy of vaporization contribution of group jf, and ny the number of groups of type j in the molecule. The solubility parameter is obtained by combining Eqs. (B3) and (C26):
(C27)
Small (112) defined the molar attraction constant as (C28) that can be used to calculate the solubility parameter by
(C29)
where p{ is the polymer density and M/ is the polymer molecular weight. <5/ can be evaluated for polymer repeating group by using group contribution calculations for the molar volume and the cohesive energy density or molar attraction constant. Table 2 gives sets of molar attraction constants and the energy of vaporization provided by several different authors. It is preferrable to use parameters from only one set when determining the solubility parameter of a repeating unit. Table 3 gives the cohesive energy densities and group molar volumes determined by Fedors. This set may give less accurate estimates than those in Table 2, but it has value because it is more comprehensive and can be applied to more systems. Hansen parameters The terms in Eq. (BH) can be estimated by group contribution methods. In general, the resulting factors are known less accurately than the group molar attraction constants or energy of vaporizations. The interaction of structural groups within molecules may not follow simple additive rules. However, the estimate of Hansen parameters can be very useful. Under the method of Hoftyzer and van Krevelen (Table 4), the terms are estimated as
(C30)
The dispersive Hansen parameter treats the molar attraction constants as additive. The polar Hansen parameters also are additive, unless more than one polar group is present. Methods for treating additional polar groups are given in
the last three rows of Table 4: additional polar groups do not add linearly to the polar Hansen term. The molar attraction constant is not applied to the hydrogen-bonding Hansen parameter. Rather, a hydrogen bonding energy, E^, is used. Hoy (178-179) has an alternative group contribution method (Table 5). It includes a molar attraction function, Ftj a polar component of this function, Fp>;, the molar volume of the solvent or polymer structural unit, the Lyderson correction for solvent non-ideality, A J / , and a similar correction for polymer non-ideality, Bicerano (164) and Porter (165) have developed new group contribution techniques for a wide variety of polymer properties. These approaches consider how the different functional groups are connected in the molecule or in the polymeric repeating unit. Bicerano's method uses Fedor's (35) and van Krevelen's (123,163) group contribution values. Both references provide solubility parameter predictions of a number of polymers.
TABLE 1. SELECTED SOLVENTS FOR USE IN POLYMER SOLVENCY TESTING Solvent POORLY HYDROGEN BONDED rc-Pentane rc-Heptane Methylcyclohexane Solvesso 150 Toluene Tetrahydronaphthalene o-Dichlorobenzene 1-Bromonaphthalene Nitroethane Acetonitrile Nitromethane
<5 (MPa 1Z2)
14.3 15.1 16.0 17.4 18.2 19.4 20.5 21.7 22.7 24.1 26.0
MODERATELY HYDROGEN BONDED Diethyl ether Diisobutyl ketone n-Butyl acetate Methyl propionate Dibutyl phthalate Dioxane Dimethyl phthalate 2,3-Butylene carbonate Propylene carbonate Ethylene carbonate
15.2 16.0 17.4 18.2 19.0 20.3 21.9 24.8 27.2 30.1
STRONGLY HYDROGEN BONDED 2-Ethyl hexanol Methyl isobutyl carbinol 2-Ethyl butanol /?-Pentanol H-Butanol ;?-Propanol Ethanol Methanol
19.4 20.5 21.5 22.3 23.3 24.3 26.0 29.7
References page VII - 711
TABLE 2. GROUP CONTRIBUTIONS TO COHESIVE ENERGY DENSITY F[MPa1Z2CiIi3ZmOl] Small (112)
A£(v(J/mol)
van Krevelen (121)
Group
Hoy (61)
2.1. CARBON-CONTAINING GROUPS -CH 3 437 N
van Krevelen and Hoftyzer (163)
420
303
9630
CH2
272
280
269
4190
^CH-
57
140
176
420
-190 388 277 39 495 685 454 265
0 222 82
-5580
560 841 444 304
65 259 249 173 240 201 (479) (672) 497 421
(704)
724
(725)
583 454 1500 1350 2340
1380 1660 1520 1380 -
143 562 634 -
255 754 685 511 651 767 767
235 360 462 350 538 688 (998) (904) 1160
1120 982 1290 1480
464 368 125 (901) 725 (906) (1040)
-
_
734
164-205 460 644 (250) 552 695 870 307 561 900 900 1020 -77
140 460 164 471 614 -
- 103 (acidic dimer) 428
8800
84 420 528
4470 12990 15500
^C x ' = CH2 = CH= cf - C H = (aromatic) -C = (aromatic) -CH(CH3)-C(CH 3 ) 2 -CH = CH-C = CHCH 3 H N C=c' H-C = C -C =C Cyclopentyl Cyclohexyl Phenyl /7-Phenylene Naphthyl
2.2. OXYGEN-CONTAININGGROUPS - O - , ether - O - , epoxide -OH -OH, aromatic -(C = O ) -(C = O)-O-(C = O)-OH -0-(C = O)-O-(C = O)-O-(C = O ) -
2.3. NITROGEN-CONTAINING GROUPS -NH 2 -NH-N' -CH-CN (896) -CN 839 -(C = O)-NH-0-(C = O)-NH -
-N=C=O 2.4. OTHERGROUPS -H -S-SH -F -Cl (primary) -Br (primary) -I -CF2-CF 3 -O-N = O -NO2 -PO 4 -Si-
1300 1470 (1400) (1440)
(10060) (13700) 10200 4860 (14500)
31000 25140
6290 -
13410
25420 25000 60760
TABLE 2. cont'd F [MPa 1 / 2 cm 3 /mol] Small (112)
AE*(J/mo\)
van Krevelen (121)
Group 2.5. STRUCTURAL FEATURES Conjugation cw trans Ring, 4 member 5 member 6 member Subscription, ortho meta
41-61 215-235 194-215 -
-
E coh (J/mol)
-CH3 N CH
4710 4940
X
CH, CN =CH2
V(cm 3 /mol)
3430 1470 4310
-19.2 28.5
'
Group HCOO-, formate - C O 2 C O 2 - , oxalate -HCO 3 -COF -COCl _COBr ~CO1
-NH, -p/ H-C= 3850 -C7070 Phenyl 31940 Phenylene:,,m,p 31940 Phenyl (trisubstituted) 31940 (tetrasubstituted) 31940 (pentasubstituted) 31940 (hexasubstituted) 31940 Ring closure, 5 + atoms 1050 3 or 4 atoms 3140 Conjugation in ring for each double bond 1670 Halogen attached to carbon atom - 20% of Ecoh of with double bond halogen -F
-F, disubstituted trisubstituted - C F 2 - , perfluoro compounds -CF 3 , perfluoro compounds -Cl -Cl, disubstituted trisubstituted -Br -Br, disubstituted trisubstituted -I -1, disubstituted trisubstituted -CN -OH -OH, disubstituted or adjacent C atoms -O-CHO, aldehyde -CO-COOH -COO- C O 3 - , carbonate - C 2 O 3 - , anhydride
48 -15 -28 159 3 -48 20 14
-
TABLE 3. cont'd
33.5 16 1 ' -1.0
'
4
-
TABLE 3. CONTRIBUTIONS TO fcoh AND Va Group
van Krevelen and Hoftyzer (163)
Hoy (61)
27.4 6.5 71.4 52.4 33.4 14.4 -4.6 -23.6 16.0 18.0 —2.2 4.0
\ -N= "NHNH2 "N(NH 2 )H \ .Nx N H -N 2 , diazo -N = N ^C-N=N-C/ / X N _ r _ N ~M-<- ~ "
Ecoh (J/mol)
V (cm3/mol)
18000 26790 12560 13400 17580 24150
32.5 37.3 18.0 29.0 38.1 41.6
29300
487
,«.
,„
4190
-9.0
11720
50
21980 16740
16.0
16740
16.0
8370 4190 20090 11470 IRRZLO
23 r\ \
4190
18.0
-IN=L,
155W
Z^.i
3560 2300 4270 4270 11550 9630 7530 15490 12350 10670 19050 16740 16330 25530 29800 21850 3350 21350 17370 27630 18000 17580 30560
20^0 22.0 23.0 57.5 24.0 26.0 27.3 30.0 31.0 32.4 315 33^ 37.0 24.0 10.0 13.0 3.8 22.3 10.8 28.5 18.0 22.0 30.0
"NF2 rr^u PONH -LAJINH^ ^N^ C" ^ O ^\ ^ ^ C N H HCONH-NHCOO-NHCONHIl ^isrC^N^ , \ H Q Ii "N" ^N" i i NH 2 COO-NCO -ONH 2
7660 AVRZ VvM)
33.1 Ins o
W W 29510
~1J
27630
11.3
43950 26370 50230
27.0 18.5
4186
°
37000 28460 19050
35.0 20.0
References page VII - 711
TABLE 3. cont'd — Group
TABLE 4. SOLUBILITY PARAMETER I: COMPONENT GROUP CONTRIBUTIONS0 £COh (J/mol)
V(cm 3 /mo!)
— — — — r1^
^d/
HH
9S190
UH I -CH=: NOH -NO 2 , aliphatic -NO 2 , aromatic -NO 3 -NO 2 , nitrate -NHNO 2 -NNO-SH -S-S2-S3)s=O 503 504 -SO 2 Cl -SCN -NCS P PO 3
Structural Group 25120 29300 15360 20930 11720 39770 27210 14440 14150 23860 13400 39140 18840 28460 37070 20090 25120 9420 14230
^° -°
H
24.0 24.0 32.0 33.5 33.5 28.7 10.0 28.0 12.0 23.0 47.2 27.6 31.6 43.5 37.0 40.0 - 1.0 22.7
h
mol)
mol)
-CH 3 VH
420 270
0 0
0 0
CH\ , ^ -CH2 =CH= Q/ /—, -\_J / ^ -(Q) )=f " O " ^ ^ ^ J ^
80
/
2
^
0
0
~~ 400 200 70
° 0 0 0
° 0 0 0
1620
0
0
*10
°
1270
H 0
°
^ ^
550
400
143
°
'
7?'?
-CN
430
u0
3
-OH
210
500
!?J°
J
2
91770
5
SlS
IzS
Ge Sn Pb As Sb Bi Se Te Zn
8080 11300 17160 12980 16330 21350 17160 20090 14480
-1.5 1.5 2.5 7.0 8.9 9.5 16.0 17.4 2.5
Cd
n790
Hg
22810
0 ,-,O1n \H\l
, L _2; 20 4 Vn I "
-O-COH -C°-COOH H COO-
6 5
20000
40
3000
290
770
2000
° 800
530 390
NH?-
2500
°
10
° 470
-N"~ -Nx -NO2 -S=PO4Ring One plane of symmetry Two planes of symmetry More planes of symmetry _ ^
(J/mol)
10
vmn
SO 1' 0 ^ BO3 .. -
0
V
3
Po" OH 3
F pi
^J
111
4500
420
SS 160
: 210
20 500 440 740 190 -
10000
310
800 1070
° 5000 1500
1890
13000
0.50x 0.25 x Ox
Ox
R e t 163>
7.5
Ref. 35.
TABLE 5.
SOLUBILITY PARAMETER II: COMPONENT GROUP CONTRIBUTIONS 0
Group
Fa ((J cm^ 1 / 2 /mol)
Fpi ((J cm 3 ) 1 / 2 /mol)
V1 (cm 3 /mol)
-CH 3
303.5
0
21.55
0.023
0.022
X
CH 2
269.0
0
15.55
0.020
0.020
^CH-
176.0
0
9.56
0.012
0.013
^cf ^CH 2 = CH^c( CHaromatic C aromatic -HC = O
65.5 259 249 173 241 201 600
0 67 59.5 63 62.5 65 532
3.56 19.17 13.18 7.18 13.42 7.42 23.3
0 0.018 0.018 0 0.011 0.011 0.048
0.04 0.019 0.0185 0.013 0.018 0.015 0.045
An*
A£?
TABLE 5. cont'd Group
Fu ((Jcm 3 ) 1/2 /mol)
-CO-COOH -COO-CO-O-CO-CN -N = C= O -N(HCO)-CONH 2 -CONH-OCONH-OH-+H-bonded -OH, primary secondary tertiary phenolic - O - , ether acetal epoxide -NH2 -NH-
Fp,((J cm3)1/2/"!©!)
538 565 640 1160 725 736 1020 1200 1131 1265 485 675 591 (500) 350 235 236 361 464 368
525 415 528 1160 725 8.2 725 900 895 890 485 675 591 (500) 350 216 102 156 464 368
Vi (cm 3 /mol)
Ar/
A^
17.3 26.1 23.7 41.0 23.1 25.9 35.8 34.3 28.3 34.8 10.65 12.45 12.45 12.45 12.45 6.45 6.45 6.45 17.0 11.0
0.040 0.039 0.047 0.086 0.060 0.054 0.062 0.071 0.054 0.078 0.082 0.082 0.082 0.082 0.031 0.021 0.018 0.027 0.031 0.031
0.040 0.039 0.050 0.086 0.054 0.054 0.055 0.084 0.073 0.094 0.034 0.049 0.049 0.049 0.006 0.018 0.018 0.027 0.035 0.275
-N' -S-F -Cl, primary secondary aromatic
125 428 845 419.5 426 330
125 428 73.5 307 315 81.5
12.6 18.0 11.2 19.5 19.5 19.5
0.014 0.015 0.018 0.017 0.017 0.017
0.009 0.032 0.006 0.031 0.032 0.025
<
705
572
39.0
0.034
0.052
528 422 277 159 43 -48 92 47.5 -14.6 -27.6 20.2 13.5 83
123 100
25.3 25.3
0.010 0.010
0.039 0.031
Cl -Br, aliphatic aromatic Base value, B Ring, non-aromatic 4-member 5-member 6-mernber 7-member Conjugation, isomerism cis trans Aromatic substitution, ortho meta para
203 85 61 0 -19.8 -14.6 -27.6 -13.3 -24.3 -34.0
-
0 0 0
-
0.012 0.003 -0.0035 0.007 0.0035 -0.001 -0.002 0.0015 0.001 0.006
0 -
0 0 0 0 0 0
° Ref. (178-179).
TABLE 6. EQUATIONS TO BE USED FOR HOY'S SYSTEM ' Formulae Additive molar functions
Solvents Ft = E w /F/./
F
F
F
> ~ E' 7 '^/<
P = X>/Fp.,V = Ew1-V1Ar = E ^ A 7 , Tb
Auxiliary equations
Amorphous polymers
log a = 339
0.1585 - log V, T ci Tb — boiling point, TCi = critical temp.
( £ ) = 0.567+ Ar-(A,r-.
P =E " < / V v = E"/V,A = E»/A
n = 2±
Lyderson equation Expressions for b and 6-components
6, = ~
; B — 277
6, = — — ~ ; B — 277
References page VII - 711
Next Page TABLE 6. cont'd Formulae
a
Solvents
Amorphous polymers
In the equations given here, Ft is always combined with a Base value, a is the molecular aggregation number, and n the number of repeating units per polymer chain segment.
D.
SOLUBILITY PARAMETER TABLES
TABLE 7.
SOLUBILITY PARAMETERS OF SOLVENTS IN ALPHABETICAL ORDER
Solubility parameter 3 Solvent
CAS number
Acetaldehyde Acetic acid Acetic anhydride Acetone Acetonitrile Acetophenone Acetyl chloride Acetylmorpholine (AO Acetylpiperidine (AO Acetylpyrrolidine (AO Acrolein Acrylic acid Acrylonitrile AHyI acetate Allyl alcohol Allyl chloride Ammonia Amyl acetate (iso) (normal) (secondary) Amyl alcohol Amyl alcohol (normal) Amylamine (normal) Amyl bromide (1-bromopentane) Amyl chloride (1-chloropentane) Amylene (2-methyl-2-butene) Amyl ether (pentyl ether) Amyl formate (iso) (normal) Amyl iodide (1-iodopentane) Anethole (para) Aniline Anthracene Apco #18 solvent Apco #140 solvent Apco thinner Aroclor 1248 Benzaldehyde Benzene Benzonitrile Benzyl alcohol Bicyclohexyl Bromobenzene 1-Bromonaphthalene Bromostyrene (ortho) 1,3-Butadiene
75-07-0 64-19-7 108-24-7 67-64-1 75-07-8 98-86-2 75-36-5 1696-20-4 618-42-8 1072-83-9 107-02-8 79-10-7 107-13-1 591-87-7 107-18-6 107-05-1 7664-41-7 625-16-1 628-63-7 626-38-0 75-85-4 71-41-0 110-58-7 110-53-2 543-59-9 513-35-9 693-65-2 110-45-2 638-49-3 628-17-1 4180-23-8 65-53-3 120-12-7
12672-29-6 100-52-7 71-43-2 100-47-0 100-51-6 92-51-3 108-86-1 90-11-9 2039-88-5 106-99-0
(MPa1/2)
(cal/cm)1/2
21.1 20.7 21.1 20.3 24.3 21.7 19.4 23.7 22.9 23.3 20.1 24.6 21.5 18.8 24.1 18.0 33.4 16.0 17.4 17.0 20.5 22.3 17.8 15.6 17.0 14.1 14.9 16.4 17.2 17.2 17.2 21.1 20.3 15.3 14.9 16.0 18.0 19.2 18.8 17.2 24.8 17.4 20.3 21.7 20.1 14.5
10.3 10.2 10.3 9.9 11.9 10.6 9.5 11.6 11.2 11.4 9.8 12.0 10.5 9.2 11.8 8.8 16.3 7.8 8.5 8.3 10.0 10.9 8.7 7.6 8.3 6.9 7.3 8.0 8.5 8.4 8.4 10.3 9.9 7.5 7.3 7.8 8.8 9.4 9.2 8.4 12.1 08.5 09.9 10.6 9.8 7.1
H-bonding group m s s m p m m m s s s s p m s m s m m m s s s m m p m m m m m s p p p p p m p p s p p p p p
Previous Page TABLE 6. cont'd Formulae
a
Solvents
Amorphous polymers
In the equations given here, Ft is always combined with a Base value, a is the molecular aggregation number, and n the number of repeating units per polymer chain segment.
D.
SOLUBILITY PARAMETER TABLES
TABLE 7.
SOLUBILITY PARAMETERS OF SOLVENTS IN ALPHABETICAL ORDER
Solubility parameter 3 Solvent
CAS number
Acetaldehyde Acetic acid Acetic anhydride Acetone Acetonitrile Acetophenone Acetyl chloride Acetylmorpholine (AO Acetylpiperidine (AO Acetylpyrrolidine (AO Acrolein Acrylic acid Acrylonitrile AHyI acetate Allyl alcohol Allyl chloride Ammonia Amyl acetate (iso) (normal) (secondary) Amyl alcohol Amyl alcohol (normal) Amylamine (normal) Amyl bromide (1-bromopentane) Amyl chloride (1-chloropentane) Amylene (2-methyl-2-butene) Amyl ether (pentyl ether) Amyl formate (iso) (normal) Amyl iodide (1-iodopentane) Anethole (para) Aniline Anthracene Apco #18 solvent Apco #140 solvent Apco thinner Aroclor 1248 Benzaldehyde Benzene Benzonitrile Benzyl alcohol Bicyclohexyl Bromobenzene 1-Bromonaphthalene Bromostyrene (ortho) 1,3-Butadiene
75-07-0 64-19-7 108-24-7 67-64-1 75-07-8 98-86-2 75-36-5 1696-20-4 618-42-8 1072-83-9 107-02-8 79-10-7 107-13-1 591-87-7 107-18-6 107-05-1 7664-41-7 625-16-1 628-63-7 626-38-0 75-85-4 71-41-0 110-58-7 110-53-2 543-59-9 513-35-9 693-65-2 110-45-2 638-49-3 628-17-1 4180-23-8 65-53-3 120-12-7
12672-29-6 100-52-7 71-43-2 100-47-0 100-51-6 92-51-3 108-86-1 90-11-9 2039-88-5 106-99-0
(MPa1/2)
(cal/cm)1/2
21.1 20.7 21.1 20.3 24.3 21.7 19.4 23.7 22.9 23.3 20.1 24.6 21.5 18.8 24.1 18.0 33.4 16.0 17.4 17.0 20.5 22.3 17.8 15.6 17.0 14.1 14.9 16.4 17.2 17.2 17.2 21.1 20.3 15.3 14.9 16.0 18.0 19.2 18.8 17.2 24.8 17.4 20.3 21.7 20.1 14.5
10.3 10.2 10.3 9.9 11.9 10.6 9.5 11.6 11.2 11.4 9.8 12.0 10.5 9.2 11.8 8.8 16.3 7.8 8.5 8.3 10.0 10.9 8.7 7.6 8.3 6.9 7.3 8.0 8.5 8.4 8.4 10.3 9.9 7.5 7.3 7.8 8.8 9.4 9.2 8.4 12.1 08.5 09.9 10.6 9.8 7.1
H-bonding group m s s m p m m m s s s s p m s m s m m m s s s m m p m m m m m s p p p p p m p p s p p p p p
TABLE 7. cont'd Solubility parameter S Solvent >?-Butane 1,3-Butanediol 1,4-ButanedioI 2,3-Butanediol Butyl acetate (iso) Az-Butyl acetate sec-Butyl acetate Butyl acrylate (iso) M-Butyl acrylate Butyl alcohol (iso) (2-methyl-1-propanol) «-Butyl alcohol (1-butanol) sec-Butyl alcohol (2-butanol) terf-Butyl alcohol (2-methyl-2-propanoI) rc-Butylamine n-Butyl bromide (1-bromobutane) s
CAS number
(MPa 1/2 )
(cal/cm) l/2
106-97-8 107-88-0 110-63-4 513-85-9 540-88-5 123-86-4 105-46-4 1663-39-4 141-32-2 78-83-1 71-36-3 15892-23-6 75-65-0 109-73-9 109-65-9 78-76-2 539-90-2 109-21-7 507-20-0 4437-85-9 115-11-7 142-96-1 762-75-4 592-84-7 542-69-8 138-22-7 97-88-1 590-01-2 123-95-5 123-72-8 79-31-2 107-92-6 96-48-0 78-82-0 109-74-0 105-60-2 502-44-3 124-12-9 75-15-0 56-23-5
13.9 23.7 24.8 22.7 17.0 17.4 16.8 17.4 18.0 21.5 23.3 22.1 21.7 17.8 17.8 17.2 16.0 16.6 16.6 24.8 13.7 16.0 16.8 18.2 17.6 19.2 16.8 18.0 15.3 18.4 21.1 21.5 25.8 20.1 21.5 26.0 20.7 19.2 20.5 17.6 18.8 25.8 19.4 19.8 19.0 19.4 18.0 20.9 22.5 16.8 23.3 20.3 17.8 21.3 16.8 18.0 13.5 16.8 18.8 16.8 28.0 18.6 19.2
6.8 11.6 12.1 11.1 8.3 8.5 8.2 8.5 8.8 10.5 11.4 10.8 10.6 8.7 8.7 8.4 7.8 8.1 8.1 12.1 6.7 7.8 8.2 8.9 8.6 9.4 8.2 8.8 7.5 9.0 10.3 10.5 12.6 9.8 10.5 12.7 10.1 9.4 10.0 8.6 9.2 12.6 9.5 9.7 9.3 9.5 8.8 10.2 11.0 8.2 11.4 9.9 8.7 10.4 8.2 8.8 6.6 8.2 9.2 8.2 13.7 9.1 9.4
920-37-6 108-90-7 542-58-5 67-66-3 2039-87-4 106-43-4 108-39-4 14406-53-3 110-82-7 108-93-0 108-94-1 287-92-3 120-92-3 99-87-6 91-17-8 124-18-5 2156-96-9 123-42-2 107-70-0 18940-57-3 131-18-0 103-50-4
H-bonding group p s s s m m m m m s s s s s m m m m m m p m m m m m m m m m s s m p p m m p p p m p p m p p p s m p s m p m p p p m m m m m m
References page VII - 711
TABLE 7. cont'd Solubility parameter 5 Solvent Dibromoethane-1,2 Dibromoethylene-1,2 (cis and trans) Dibutoxyethyl phthalate (Kronisol) Dibutyiamine Dibutyl fumarate Dibutyl maleate Dibutyl phenyl phosphate Dibutyl phthalate Dibutyl sebacate Dichloroacetic acid Dichlorobenzene (ortho) Dichlorodifluoromethane (Freon 12) Dichloroethyl ether Dichloroethylene, cis-1,2 trans-1,2 Dichlorofluoromethane (Freon 21) Dichloropropane-1,2 Dichloropropane-2,2 Diethylacetamide (N3N) Diethylamine Diethyl carbonate Diethylene glycol Diethylene glycol monobutyl ether (normal) Diethylene glycol monobutyl ether Diethylene glycol monobutyl ether acetate Diethylene glycol monolaurate Diethyl ether Diethylformamide (N9N) Diethyl ketone Diethyl maleate Diethyl oxalate Diethyl phthalate Diethyl-2,2-propanediol-1,2 (heptylene glycol) Diethyl sulfone Difluorotetrachloroethane (Freon 112) Diformylpiperazine (NJN) Dihexyl ether Di-n-hexyl phthalate Diisobutylene Diisobutyl ketone Diisodecyl phthalate Diisopropyl ether Diisopropyl ketone Dimethylacetamide (N9N) Dimethylaniline Dimethyl-2,2-butanediol-l,2 (isobutylene glycol) Dimethyl-2,2-butanediol-l,3 Dimethyl carbonate Dimethyl ether Dimethylformamide (N,N) Dimethyl malonate Dimethylnitroamine (N,N) Dimethyl oxalate Dimethyl phosphite Dimethyl phthalate Dimethyl siloxane Dimethyl sulfide Dimethyl sulfoxide Dimethyltetramethylene sulfone Dioctyl adipate Dioctyl phthalate Dioctyl sebacate Dioxane-1,4
CAS number 106-93-4 540-49-8 117-83-9 111-92-2 105-75-9 105-76-0 2528-36-1 84-74-2 109-43-3 79-43-6 95-50-1 75-71-8 623-46-1 156-59-2 156-60-5 75-43-4 78-87-5 594-20-7 685-91-6 109-89-7 105-58-8 111-46-6 112-34-5 112-34-5 124-17-4 141-20-8 60-29-7 617-84-5 96-22-0 141-05-9 95-92-1 84-66-2 115-76-4 597-35-3 76-11-9 4164-39-0 112-58-3 108-83-8 107-39-1 108-83-8 26761-40-0 108-20-3 565-80-0 127-19-5 121-69-7 558-43-0 76-09-3 616-38-6 115-10-6 68-12-2 108-59-8 62-75-9 553-90-2 868-85-9 131-11-3 9016-00-6 75-18-3 67-68-5 1003-78-7 103-23-1 117-81-7 1222-62-3 123-91-1
(MPa1/2) 21.3 20.7 16.4 16.6 18.4 18.4 17.8 19.0 18.0 22.5 20.5 11.3 20.1 18.6 18.4 17.0 18.4 16.8 20.3 16.4 18.0 24.8 19.4 20.9 17.4 17.8 15.1 21.7 18.0 20.3 17.6 20.5 20.3 25.4 16.0 31.5 16.4 18.2 15.8 16.0 14.7 14.1 16.4 22.1 19.8 22.9 20.5 20.3 18.0 24.8 22.5 26.8 22.5 25.6 21.9 10.0-12.1 19.2 29.7 24.6 17.8 24.8 17.8 20.5
(cal/cm)1/2 10.4 10.1 8.0 8.1 9.0 9.0 8.7 9.3 9.2 11.0 10.0 5.5 9.8 9.1 9.0 8.3 9.0 8.2 9.9 8.0 8.8 12.1 9.5 10.2 8.5 8.7 7.4 10.6 8.8 9.9 8.6 10.0 9.9 12.4 7.8 15.4 8.0 8.9 7.7 7.8 7.2 6.9 8.0 10.8 9.7 11.2 10.0 9.9 8.8 12.1 11.0 13.1 11.0 12.5 10.7 4.9-5.9 9.4 14.5 12.0 8.7 12.1 8.7 10.0
H-bonding group p p m s m m m m m s p p m p p p p p m s m s m m m m m m m m m m s m p m m m p m m m m m m s s m m m m s m m m p p m m m m m m
TABLE 7. cont'd Solubility parameter 6 Solvent Dioxoiane-1,3 Dipentene Diphenyl ether Diphenyl 2-ethylhexyl phosphate Dipropylene glycol Dipropylene glycol monomethyl ether Dipropyl phthalate Dipropyl sulfone Dodecane Dodecanol-1 Epichlorohydrin Ethane Ethylacetamide (AO Ethyl acetate Ethyl acrylate Ethyl alcohol Ethylamine Ethyl amyl ketone (3-octanone) Ethylbenzene Ethyl benzoate Ethyl bromide (bromoethane) Ethyl-2-butanol-l Ethyl fl-butyrate Ethyl caprylate Ethyl chloride Ethyl cyanoacetate Ethylene bromide Ethylene carbonate Ethylene chlorohydrin (2-chloroethanol) Ethylene cyanohydrin (3-hydroxypropionitrile) Ethylenediamine Ethylene dichloride (1,2-dichloroethane) Ethylene glycol Ethylene glycol diacetate Ethylene glycol diethyl ether Ethylene glycol dimethyl ether Ethylene glycol methyl ether acetate Ethylene glycol monobenzyl ether Ethylene glycol monobutyl ether Ethylene glycol monoethyl ether (2-ethoxyethanol; Cellusolve) Ethylene glycol monomethyl ether (2-rnethoxyethanol) Ethylene glycol monophenyl ether Ethylene oxide Ethylene formamide (N) Ethyl formate Ethyl-2-hexanediol-l,3 (octylene glycol) Ethylhexanol Ethyl hexyl acrylate Ethylidene chloride Ethyl iodide (iodoethane) Ethyl isobutyl ether Ethyl isobutyrate Ethyl lactate Ethyl mercaptan (ethane thiol) Ethyl methacrylate Ethyl morpholine (AO Ethyl orthoformate (triethyl orthoformate) Ethyl propionate Fluorocarbons, aliphatic aromatic Formamide Formic acid
H-bonding group
CAS number
(MPa 1Z2)
(cal/cm)l'2
646-06-0 138-86-3 101-84-8 1241-94-7 110-98-5 34590-94-8 131-16-8 598-03-8 112-40-3 112-53-8 106-89-8 74-84-0 625-50-3 141-78-6 140-88-5 64-17-5 75-04-7 106-68-3 100-41-4 93-89-0 74-96-4 97-95-0 105-54-4 106-32-1 75-00-3 105-56-6 593-60-2 96-49-1 107-07-3 109-78-4 107-15-3 107-06-2 307-21-1 111-55-7 629-14-1 110-71-4 110-49-6 622-08-2 111-76-2 110-80-5
17.6 20.5 20.9 17.4 20.7 17.6 20.5 23.1 16.2 20-21 22.5 12.3 25.2 18.6 17.6 26.0 20.5 16.8 18.0 16.8 19.6 21.5 17.4 14.9 18.8 22.5 19.8 30.1 25.0 31.1 25.2 20.1 29.9 20.5 17.0 17.6 18.8 22.3 19.4 21.5
8.6 10.0 10.2 8.5 10.1 8.6 10.0 11.3 7.9 9.8 11.0 6.0 12.3 9.1 8.6 12.7 10.0 8.2 8.8 8.2 9.6 10.5 8.5 7.3 9.2 11.0 9.7 14.7 12.2 15.2 12.3 9.8 14.6 10.0 8.3 8.6 9.2 10.9 9.5 10.5
m m m p m m s m p s s p s m m s s m p m m s m m m m p m s s s p s m m m m m m m
11.4 11.5 11.1 13.9 9.4 9.4 9.5 7.8 8.9 9.4 7.5 7.9 10.0 9.2 8.3 8.9 8.3 8.4 5.5-6.2 7.5-8.2 19.2 12.1
m m m s m s s m p m m m m p m s m m p p s s
109-86-4 122-99-6 75-21-8 109-94-4 94-96-2 104-76-7 103-11-7 75-34-3 75-03-6 627-02-1 97-62-1 687-47-8 75-08-1 97-63-2 100-74-3 122-51-0 105-37-3 75-12-7 64-18-6
23.3 23.5 22.7 28.4 19.2 19.2 19.4 16.0 18.2 19.2 15.3 16.2 20.5 18.8 17.0 18.2 17.0 17.2 11.3-12.7 15.3-16.8 39.3 24.8
References page VII - 711
TABLE 7. cont'd Solubility parameter S Solvent
CAS number
Formylmorpholine (AO Formylpiperidine (AO Furan Furfural (2-furaldehyde) Furfuryl alcohol Glycerol Heptane (normal) Heptyl alcohol (normal) Hexamethylphosphoramide Hexane (normal) Hexanediol-2,5 Hexene-1 Hexyl alcohol (normal) Hydrazine Hydrogen Hydrogenated terphenyl (Monsanto HB-40) Hydrogen cyanide Iodobenzene Isophorone Isoprene Lauryl alcohol Low odor mineral spirits Maleic anhydride Malononitrile Mesitylene Mesityl oxide Methacrylic acid Methane Methanol Methoxy-4-methyl-4-pentanol-2 Methoxy-4-methyl-4-pentanone-2 Methylacetamide Methyl acetate Methyl acrylate Methylamine Methyl amyl acetate Methyl amyl ketone Methyl benzoate Methyl bromide Methyl n-butyl ketone Methyl n-butyrate Methyl caprolactone Methyl chloride Methylcyclohexane Methylcyclohexanone Methylene chloride Methylene glycolate Methylene iodide Methyl ethyl ketone Methyl ethyl sulfone Methylformamide (AO Methyl formate Methyl n-hexyl ketone Methyl iodide Methyl isoamyl ketone Methyl isobutyl carbinol Methyl isobutyl ketone Methyl isobutyrate Methyl isopropyl ketone Methyl isovalerate Methyl methacrylate Methyl nonyl ketone Methyl-2-pentanediol-l,3
4394-85-8 2591-86-8 110-00-9 98-01-1 98-00-0 56-81-5 142-82-5 111-70-6 680-31-9 110-54-3 2935-44-6 592-41-6 111-27-3 302-10-2 1333-74-0 74-90-8 591-50-4 78-59-1 78-79-5 112-53-8 108-31-6 109-77-3 108-67-8 141-79-7 79-41-4 74-82-8 67-56-1 107-70-0 79-16-3 79-20-9 96-33-3 74-89-5 108-84-9 110-43-0 95-58-3 74-83-9 591-78-6 623-42-7 74-87-3 10120-28-2 589-92-4 75-09-2 61192-32-3 75-11-6 78-93-3 594-43-4 123-39-7 107-31-3 111-13-7 74-88-4 110-12-3 108-11-2 108-10-1 547-63-7 563-80-4 624-24-8 80-62-6 112-12-9 149-31-5
MPa 1/2
(cal/cm) 1/2
26.6 23.5 19.2 22.9 25.6 33.8 15.1 21.7 21.5 14.9 21.2 15.1 21.9 37.3 6.9 18.4 24.8 20.7 18.6 15.1 16.6 14.1 27.8 30.9 18.0 18.4 22.9 11.0 29.7 17.4 17.0 29.9 19.6 18.2 22.9 16.4 17.4 21.5 19.6 17.0 18.2 18.2 19.8 16.0 19.0 19.8 25.4 24.1 19.0 27.4 32.9 20.9 17.0 20.9 17.2 20.5 17.2 17.0 17.4 16.2 18.0 16.0 21.1
13.0 11.5 9.4 11.2 12.5 16.5 7.4 10.6 10.5 7.3 10.3 7.4 10.7 18.1 3.0 9.0 12.1 10.1 9.1 7.4 8.1 6.9 13.6 15.1 8.8 9.0 11.2 5.4 14.5 8.5 8.3 14.6 9.6 8.9 11.2 8.0 8.5 10.5 9.6 8.3 8.9 8.9 9.7 7.8 9.3 9.7 12.4 11.8 9.3 13.4 16.1 10.2 8.3 10.2 8.4 10.0 8.4 8.3 8.5 7.9 8.8 7.8 10.3
H-Bonding Group m m m m s s p s s p s p s s p p s p m p s p s p p rn s p s s m s m m s m m rn m m m m m p m p m p m m s m m m m s m m m m m m s
TABLE 7. cont'd Solubility parameter S Solvent Methyl-2-pentanediol-2,4 Methyl-2-pentanediol monoethyl ether (Pentoxol) Methyl propionate Methyl propyl ketone Methyl propyl sulfone Methyl pyrrolidone-2 (l-methyl-2-pyrrolidinone) Methyl salicylate Methyl styrene (a) Methyltetramethylene sulfone Methyl n-valerate Morpholine Naphthalene Neopentane Neopentyl glycol Nitrobenzene Nitroethane Nitromethane Nitro-«-octane Nitro-1-propane Nitro-2-propane Nonyl phenol Octane (normal) Octyl alcohol (normal) Pentachloroethane Pentane (normal) Pentanediol-1,5 Pentanediol-2,4 Perchloroethylene Perfluoroheptane Perfluoromethylcyclohexane Phenanthrene Phenylhydrazine Pine oil Piperidine Piperidone Propane Propiolactone Propionic acid Propionic anhydride Propionitrile Propyl acetate (iso) Propyl acetate (normal) Propyl alcohol (2-propanol) Propyl alcohol (1-propanol) Propylbenzene (normal) Propyl bromide (l~bromopropane) Propyl butyrate Propyl butyrate (iso) Propyl chloride (2-chloropropane) Propyl chloride (1-chloropropane) Propylene-l,2-carbonate Propylene glycol (1,2-propanediol) Propylene glycol methyl ether (1,2-dimethoxypropane) Propylene oxide Propyl ether (di-, normal) Propyl ether (iso) Propyl formate Propyl propionate Pyridine Pyrone(y) Pyrrolidine (a) Quinoline Santicizer 8
CAS number 107-41-5 554-12-1 107-87-9 1977-37-3 872-50-4 119-36-8 98-83-9 624-24-8 110-91-8 91-20-3 463-82-1 126-30-7 98-95-3 79-24-3 75-52-5 108-03-2 79-46-9 25154-52-3 111-65-9 111-87-5 76-01-7 109-66-0 111-29-5 625-69-4 127-18-4 335-57-9 355-02-2 85-01-8 100-63-0 110-89-4 675-20-7 74-98-6 57-57-8 79-09-4 123-62-6 107-12-0 108-21-4 109-60-4 67-63-0 71-23-8 103-65-1 106-94-5 105-66-8 638-11-9 75-29-6 540-54-5 108-32-7 57-55-6 7778-85-0 75-56-9 111-43-3 108-20-3 110-74-7 106-36-5 110-86-1 504-31-4 123-75-1 00-02-2
(MPa1/2)
(cal/cm)1/2
19.8 17.4 18.2 17.8 25.6 23.1 21.7 17.4 26.4 16.2 22.1 20.3 12.9 22.5 20.5 22.7 26.0 14.3 21.1 20.3 19.2 15.6 21.1 19.2 14.3 23.5 22.1 19.0 11.9 12.3 20.1 25.6 17.6 17.8 27.8 13.1 27.2 20.3 20.5 22.1 17.2 18.0 23.5 24.3 17.6 18.2 17.2 16.2 16.6 17.4 27.2 25.8 20.7 18.8 16.0 14.5 18.8 17.4 21.9 27.4 30.1 22.1 24.3
9.7 8.5 8.9 8.7 12.5 11.3 10.6 8.5 12.9 7.9 10.8 9.9 6.3 11.0 10.0 11.1 12.7 7.0 10.3 9.9 9.4 7.6 10.3 9.4 7.0 11.5 10.8 9.3 5.8 6.0 9.8 12.5 8.6 8.7 13.6 6.4 13.3 9.9 10.0 10.8 8.4 8.8 11.5 11.9 8.6 8.9 8.4 7.9 8.1 8.5 13.3 12.6 10.1 9.2 7.8 7.1 9.2 8.5 10.7 13.4 14.7 10.8 11.9
H-bonding group s m m m m m m p m m s p p s p p p p P p s p s p p s s p p p p s p p s p m s s p m m s s p m m m m m m s m m m m m m s m s s m
References page VII - 711
TABLE 7. cont'd Solubility parameter S Solvent
CAS number
Shell Sol 72 Shell TS28 solvent Silicon tetrachloride Socal solvent No. 1 Socal solvent No. 2 Socal solvent No. 3 Solvesso 100 Solvesso 150 Styrene Styrene oxide Succinic anhydride Terpene B Tetrachloroethane-1,1,2,2 Tetrachloroethylene (perchloroethylene) Tetraethylene glycol Tetrahydrofuran Tetrahydronaphthalene (tetralin) Tetramethylene sulfone (sulfolane, tetrahydrothiophene 1,1-dioxide) Tetramethyloxamide Thiophene Toluene Tolylene diisocyanate (4-methy 1-1,3-phenylene diisocyanate) Tributylamine Trichloroethane-1,1,2 Trichloroethylene Trichlorofiuoromethane Trichlorotrifiuoroethane (1,1,2-trichlorotrifluoroethane) Tricresyl phosphate (tritolyl phosphate) Triethylamine Triethylene glycol Triethylenetetramine Trimethyl-3,5,5-hexanol (nonyl alcohol) Triphenyl phosphate Triphenyl phosphite Tripropylene glycol Tripropylene glycol methyl ether Turpentine Valeric acid (normal) Valeronitrile (normal) Varnolene (Varsol #2) Vinyl acetate Vinyl chloride Vinyl toluene V M & P naphtha Water Xylene (p-xylene)
100-42-5 96-09-3 108-30-5 79-34-5 127-18-4 112-60-7 109-99-9 119-64-2 126-33-0 110-02-1 108-88-3 584-84-9 102-82-9 79-00-5 79-01-6 75-69-4 76-13-1 1330-78-5 121-44-8 112-27-6 112-24-3 3452-97-9 115-86-6 101-02-0 24800-44-0 20324-33-8 8006-64-2 109-52-4 110-59-8 108-05-4 75-01-4 622-97-9 7732-18-5 106-42-3
TABLE 8. SOLUBILITY PARAMETERS OF SOLVENTS IN INCREASING ORDER OF 8 Solvent
_____ d (MPa1^2)
Hydrogen Dimethyl siloxane Methane Dichlorodifluoromethane (Freon 12) Fluorocarbons, aliphatic Perfluoroheptane Ethane Perfluoromethylcyclohexane Neopentane
6.9 10.0-12.1 1L0 11.3 11.3-12.7 11.9 12.3 12.3 12.9
H-bonding group
(MPa1/2)
(ca!/cm)1/2
14.7 15.1 15.1 16.6 16.2 15.8 17.6 17.4 19.0 21.5 31.5 17.2 19.8 19.0 20.3 18.6 19.4 27.4
7.2 7.4 7.4 8.1 7.9 7.7 8.6 8.5 9.3 10.5 15.4 8.4 9.7 9.3 9.9 9.1 9.5 13.4
p p p p p p p p p m s p p p s m p m
23.3 20.1 18.2 23.7 15.8 19.6 18.8 15.5 14.9 17.2 15.1 21.9 22.7 17.2 17.6 19.0 18.8 17.8 16.6 20.1 19.6 15.6 18.4 16.0 18.6 15.6 47.9 18.0
11.4 9.8 8.9 11.6 7.7 9.6 9.2 7.6 7.3 8.4 7.4 10.7 11.1 8.4 8.6 9.3 9.2 8.7 8.1 9.8 9.6 7.6 9.0 7.8 9.1 7.6 23.4 8.8
m m p s s p p p p m s s s s m m s m p s p p m m p p s p
TABLE 8. cont'd Solvent Propane Decane (normal) Butylene (iso) (2-methylpropene) w-Butane Amylene (2-methyl-2-butene) Diisopropyl ether Low odor mineral spirits Nitro-;?-octane Pentane (normal) 1,3-Butadiene
S(MPa 1/2 ) 13.1 13.5 13.7 13.9 14.1 14.1 14.1 14.3 14.3 14.5
TABLE 8. cont'd Solvent Propyl ether (iso) Diisodecyl phthalate Shell Sol 72 Amyl ether (pentyl ether) Apco #140 solvent Ethyl caprylate Hexane (normal) Trichlorotrifluoroethane (1,1,2-trichlorotrifluoroethane) Diethyl ether Heptane (normal) Hexene-1 Isoprene Shell TS28 solvent Silicon tetrachloride Triethylamine Apco #18 solvent Butyl stearate Ethyl isobutyl ether Fluorocarbons (aromatic) Trichlorofluoromethane Amyl bromide (1-bromopentane) Octane (normal) Varnolene (varsol #2) V M & P naphtha Diisobutylene Socal solvent No. 3 Tributylamine Amyl acetate (iso) Apco thinner Butyl (iso) butyrate (normal) Butyl ether Difluorotetrachioroethane (Freon 112) Diisobutyl ketone Ethyl hexyl aery late Methylcyclohexane Methyl nonyl ketone Propyl ether (di-, normal) Vinyl chloride Dodecane Ethyl isobutyrate Methyl isovalerate Methyl n-valerate Propyl butyrate (iso) Socal solvent No. 2 Amyl formate (iso) Dibutoxyethyl phthalate (Kronisol) Diethylamine Dihexyl ether Diisopropyl ketone Methyl amyl acetate Butyl (normal) butyrate (normal) Butyl chloride (iso) (2-chloro-2-methylpropane) Dibutylamine Lauryl alcohol Propyl chloride (2-chloropropane) Socal solvent No. 1 Turpentine sec-Butyl acetate Butyl formate (iso) Butyl methacrylate Cyclohexane Cymene {para) (2-isopropyl toluene) Decyl acrylate (iso) Diacetone alcohol methyl ether (Pentoxone) Dichloropropane-2,2
TABLE 8. cont'd 2
<5(MPa*/ ) 14.5 14.7 14.7 14.9 14.9 14.9 14.9 14.9 15.1 15.1 15.1 15.1 15.1 15.1 15.1 15.3 15.3 15.3 15.3-16.8 15.5 15.6 15.6 15.6 15.6 15.8 15.8 15.8 16.0 16.0 16.0 16,0 16.0 16.0 16.0 16.0 16.0 16.0 16.0 16.2 16.2 16.2 16.2 16.2 16.2 16.4 16.4 16.4 16.4 16.4 16.4 16.6 16.6 16.6 16.6 16.6 16.6 16.6 16.8 16.8 16.8 16.8 16.8 16.8 16.8 16.8
,5(MPa1/2)
Solvent Ethyl amyl ketone (3-octanone) Ethyl benzoate Ethyl benzoate (secondary) Amyl chloride (1-chloropentane) Butyl acetate (iso) Dichlorofluoromethane (Freon 21) Ethylene glycol diethyl ether Ethyl methacrylate Ethyl orthoformate (triethyl orthoformate) Methoxy-4-methyl-4-pentanone-2 Methyl «-butyl ketone Methyl rc-hexyl ketone Methyl isobutyrate Amylformates (normal) Methyl isobutyrate (normal) Amyl iodide (1-iodopentane) Anethole (para) Benzonitrile sec-Butyl bromide (2-bromobutane) Ethyl propionate Methyl isoamyl ketone Methyl isobutyl ketone Propyl acetate (iso) Propyl butyrate Terpene B Tricresyl phosphate (tritolyl phosphate) Trimethyl-3,5,5-hexanol (nonyl alcohol) Trimethyl-3,5,5-hexanol (normal) Bicyclohexyl n-Butyl acetate Butyl acrylate (iso) Diethylene glycol monobutyl ether acetate Diphenyl 2-ethylhexyl phosphate Ethyl n-butyrate Methoxy-4-methyl-4-pentanol-2 Methyl amyl ketone Methyl isopropyl ketone Methyl-2-pentanediol monoethyl ether (Pentoxol) Methyl styrene (a) Propyl chloride (1-chloropropane) Propyl propionate Solvesso 150 Butyl iodide (normal) (1-iodobutane) Carbon tetrachloride Diethyl oxalate Dioxolane-1,3 Dipropylene glycol monomethyl ether Ethyl acrylate Ethylene glycol dimethyl ether Pine oil Propylbenzene (normal) Solvesso 100 Triphenyl phosphate Amylamine (normal) «-Butylamine n-Butyl bromide (1-bromobutane) Cyclopentane Dibutyl phenyl phosphate Diethylene glycol monolaurate Dioctyl adipate Dioctyl sebacate Methyl propyl ketone Piperidine Tripropylene glycol methyl ether Aroclor 1248
16.8 16.8 17.0 17.0 17.0 17.0 17.0 17.0 17.0 17.0 17.0 17.0 17.0 17.2 17.2 17.2 17.2 17.2 17.2 17.2 17.2 17.2 17.2 17.2 17.2 17.2 17.2 17.4 17.4 17.4 17.4 17.4 17.4 17.4 17.4 17.4 17.4 17.4 17.4 17.4 17.4 17.4 17.6 17.6 17.6 17.6 17.6 17.6 17.6 17.6 17.6 17.6 17.6 17.8 17.8 17.8 17.8 17.8 17.8 17.8 17.8 17.8 17.8 17.8 18.0
References page VII - 711
TABLE 8.
TABLE 8. cont'd
cont'd
Solvent AUyI chloride rc-Butyl acrylate Butyl propionate Chlorotoluene (para) Decahydronaphthalene (cis and trans) (decalin) Dibutyl sebacate Diethyl carbonate Diethyl ketone Dimethyl ether Ethylbenzene Mesitylene Methyl methacrylate Propyl acetate (normal) Xylene (p-xylene) Butyl formate(normal) Di-/i-hexyl phthalate Ethylidene chloride Ethyl morpholine (normal) Methyl acrylate Methyl n-butyrate Methyl caprolactone Methyl propionate Propyl bromide (1-bromopropane) Toluene Butyraldehyde Dibutyl fumarate Dibutyl maleate Dichloroethylene trans-1,2 Dichloropropane-1,2 Hydrogenated terphenyl (Monsanto HB-40) Mesityl oxide Vinyl acetate Diamyl phthalate Dichloroethylene, as-1,2 Ethyl acetate Isophorone Tetrahydrofuran Vinyl toluene Allyl acetate Benzene Celanese solvent 601 Diacetone alcohol (4-hydroxy-4-methyl-2-pentanone) Ethyl chloride Ethylene glycol methyl ether acetate Ethyl mercaptan (ethane thiol) Propylene oxide Propyl formate Trichloroethylene Tripropylene glycol Chloroform Dibutyl phthalate Methylcyclohexanone Methyl ethyl ketone Perchloroethylene Styrene Tetrachloroethylene (perchloroethylene) Triphenyl phosphite Benzaldehyde Butyl lactate (normal) Capronitrile (heptyl cyanide) Dibenzyl ether Dimethyl sulfide Ethyl formate Ethyl-2-hexanediol-l,3 (octylene glycol) Ethyl iodide (iodoethane)
1 2
5 (MPa / ) 18.0 18.0 18.0 18.0 18.0 18.0 18.0 18.0 18.0 18.0 18.0 18.0 18.0 18.0 18.2 18.2 18.2 18.2 18.2 18.2 18.2 18.2 18.2 18.2 18.4 18.4 18.4 18.4 18.4 18.4 18.4 18.4 18.6 18.6 18.6 18.6 18.6 18.6 18.8 18.8 18.8 18.8 18.8 18.8 18.8 18.8 18.8 18.8 18.8 19.0 19.0 19.0 19.0 19.0 19.0 19.0 19.0 19.2 19.2 19.2 19.2 19.2 19.2 19.2 19.2
Solvent Furan Nonyl phenol Pentachloroethane Acetyl chloride Chlorobenzene Chlorostyrene (ortho or para) Diethylene glycol monobutyl ether (normal) Ethylene glycol monobutyl ether Ethylhexanol Tetrahydronaphthalene (tetralin) Ethyl bromide (bromoethane) Methyl acetate Methyl bromide Trichloroethane-1,1,2 Valeronitrile (normal) Chloroethyl acetate (P) Dimethylaniline Ethylene bromide Methyl chloride Methylene chloride Methyl-2-pentanediol-2,4 Tetrachloroethane-1,1,2,2 Dodecanol-1 Acrolein Bromostyrene {ortho) Butyronitrile (iso) Dichloroethyl ether Ethylene dichloride (1,2-dichloroethane) Phenanthrene Thiophene Valeric acid (normal) Acetone Anthracene Bromobenzene Cyclohexanone Diethylacetamide (N1N) Diethyl maleate Diethyl-2,2-propanediol-l,2 (heptylene glycol) Dimethyl carbonate Naphthalene Nitro-2-propane Propionic acid Tetraethylene glycol Amyl alcohol Carbon disulfide Dichlorobenzene (ortho) Diethyl phthalate Dimethyl-2,2-butanediol-1,3 Dioxane-1,4 Dipentene Dipropyl phthalate Ethylamine Ethylene glycol diacetate Ethyl lactate Methyl isobutyl carbinol Nitrobenzene Propionic anhydride Acetic acid Caprolactone (s) Dibromoethylene-1,2 (cis and trans) Dipropylene glycol Iodobenzene Propylene glycol methyl ether (1,2-dimethoxypropane) Cresol (meta) Diethylene glycol monobutyl ether
S (MPa1/*) 19.2 19.2 19.2 19.4 19.4 19.4 19.4 19.4 19.4 19.4 19.6 19.6 19.6 19.6 19.6 19.8 19.8 19.8 19.8 19.8 19.8 19.8 20-21 20.1 20.1 20.1 20.1 20.1 20.1 20.1 20.1 20.3 20.3 20.3 20.3 20.3 20.3 20.3 20.3 20.3 20.3 20.3 20.3 20.5 20.5 20.5 20.5 20.5 20.5 20.5 20.5 20.5 20.5 20.5 20.5 20.5 20.5 20.7 20.7 20.7 20.7 20.7 20.7 20.9 20.9
TABLE 8. cont'd Solvent Diphenyl ether Methyl formate Methyl iodide Acetaldehyde Acetic anhydride Aniline Butyric acid (iso) (2-methylpropionic acid) Methyl-2-pentanediol-1,3 Nitro-1 -propane Octyl alcohol (normal) Hexanediol-2,5 Cy clopentanone Dibromoethane-1,2 Acrylonitrile Butyl alcohol (iso) (2-methyl-1-propanol) Butyric acid (normal) Butyronitrile (normal) Ethyl-2-butanol-l Ethylene glycol monoethyl ether (2-ethoxyethanol; Cellusolve) Hexamethylphosphoramide Methyl benzoate Styrene oxide Acetophenone 1 -Bromonaphthalene terf-Butyl alcohol (2-methyl-2-propanol) Diethylformamide (N,N) Heptyl alcohol (normal) Methyl salicylate Dimethyl phthalate Hexyl alcohol (normal) Pyridine Triethylene glycol s
TABLE 8. cont'd 1 2
5(MPa / ) 20.9 20.9 20.9 21.1 21.1 21.1 21.1 21.1 21.1 21.1 21.2 21.3 21.3 21.5 21.5 21.5 21.5 21.5 21.5 21.5 21.5 21.5 21.7 21.7 21.7 21.7 21.7 21.7 21.9 21.9 21.9 21.9 22.1 22.1 22.1 22.1 22.1 22.1 22.3 22.3 22.5 22.5 22.5 22.5 22.5 22.5 22.5 22.7 22.7 22.7 22.7 22.9 22.9 22.9 22.9 22.9 23.1 23.1 23.3 23.3 23.3 23.3 23.3 23.5 23.5
Solvent
d (MPa1/2)
Pentanediol-1,5 Propyl alcohol (2-propanol) Acetylmorpholine (N) 1,3-Butanediol Tolylene diisocyanate (4-methyl-l,3-phenylene diisocyanate) AHyI alcohol Methylene iodide Acetonitrile Propyl alcohol (1-propanol) Santicizer 8 Acrylic acid Dimethyltetramethylene sulfone Benzyl alcohol 1,4-Butanediol Butylene-2,3 carbonate Diethylene glycol Dimethylformamide (Af5AO Dioctyl phthalate Formic acid Hydrogen cyanide Ethylene chlorohydrin (2-chloroethanol) Ethylacetamide (normal) Ethylenediamine Diethyl sulfone Methylene glycolate Dimethyl phosphite Furfuryl alcohol Methyl propyl sulfone Phenylhydrazine Butyrolactone (y) Chloroacetonitrile Propylene glycol (1,2-propanediol) Caprolactam (e) Ethyl alcohol Nitromethane Methyltetramethylene sulfone Formylmorpholine (N) Dimethylnitroamine (N1N) Propiolactone Propylene-1,2-carbonate Methyl ethyl sulfone Pyrone (y) Tetramethylene sulfone (sulfolane, tetrahydrothiophene 1,1-dioxide) Maleic anhydride Piperidone Diacetylpiperazine (N,N) Ethylene formamide (N) Dimethyl sulfoxide Methanol Ethylene glycol Methylacetamide Ethylene carbonate Pyrrolidine (a) Malononitrile Ethylene cyanohydrin (3-hydroxypropionitriIe) Diformylpiperazine (AW) Succinic anhydride Methylformamide (AO Ammonia Glycerol Hydrazine Formamide Water
23.5 23.5 23.7 23.7 23.7 24.1 24.1 24.3 24.3 24.3 24.6 24.6 24.8 24.8 24.8 24.8 24.8 24.8 24.8 24.8 25.0 25.2 25.2 25.4 25.4 25.6 25.6 25.6 25.6 25.8 25.8 25.8 26.0 26.0 26.0 26.4 26.6 26.8 27.2 27.2 27.4 21A 27.4 27.8 27.8 28.0 28.4 29.7 29.7 29.9 29.9 30.1 30.1 30.9 31.1 31.5 31.5 32.9 33.4 33.8 37.3 39.3 47.9
References page VII-711
TABLE 9. HANSEN SOLUBILITY PARAMETERS OF LIQUIDS AT 25°C Solubility parameters (MPa 1/2 ) Solvent
CAS Number
Molar volume (cm3/mol)
S^
^P
^h
^
9.1. PARAFFINIC HYDROCARBONS n-Butane n-Pentane Pentane(iso) rt-Hexane M-Heptane rc-Octane 2,2,4-Trimethylpentane rc-Nonane rc-Decane rc-Dodecane n-Hexadecane n-Eicosane Cyclohexane Methylcyclohexane ds-Decahydronaphthalene rrans-Decahydronaphthalene
106-97-8 109-66-0 78-78-4 110-54-3 142-82-5 111-65-9 540-84-1 111-84-2 124-18-5 112-40-3 544-76-3 112-95-8 110-82-7 108-87-2 493-01-6 493-02-7
101.4 116.2 117.4 147.4 147.4 163.5 166.1 179.7 195.9 228.6 294.1 359.8 108.7 128.3 156.9 159.9
14.1 14.5 13.7 14.9 15.3 15.6 14.3 15.8 15.8 16 16.4 16.6 16.8 16 18.8 18.8
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 0 0 0.2 1 0 0
14.1 14.5 13.7 14.9 15.3 15.6 14.3 15.8 15.8 16 16.4 16.6 16.8 16 18.8 18.8
9.2. AROMATIC HYDROCARBONS Benzene Toluene Naphthalene'7 Styrene o-Xylene Ethylbenzene 1-Methylnaphthalene Mesitylene Tetrahydronaphthalene Biphenyl /7-Diethylbenzene
71-43-2 108-88-3 91-20-3 1-42-5 95-47-6 1-41-4 90-12-0 108-67-8 119-64-2 92-52-4 105-05-5
89.4 106.8 111.5 115.6 121.2 123.1 138.8 139.8 136.0° 154.1 156.9
18.4 18 19 18.6 17.8 17.8 20.6 18 19.6° 21.5 18
0" 1.4 2 1 1 0.6 0.8 0 0 1 0
2 2 5.9 4.1 3.1 1.4 4.7 0.6 2.9 2 0.6
18.6 18.2 20 19 18 17.8 21.2 18 20 21.7 18
9.3. HALOHYDROCARBONS Methyl chloride Methylene dichloride Bromochloromethane Chlorodifluoromethane Dichlorofluoromethane Ethyl bromide 1,1-Dichloroethylene Ethylene dichloride Methylene diiodidec Chloroform 1,1-Dichloroethane Ethylene dibromide Bromoform rc-Propyl chloride Trichloroethylene Dichlorodifluoromethane Trichiorofluoromethane Bromotrifluoromethane Carbon tetrachloride 1,1,1-Trichloroethane Tetrachloroethylene Chlorobenzene rt-Butylchloride 1,1,2,2-Tetrachloroethane Bromobenzene o-Dichlorobenzene Benzyl chloride l,l,2,2-Tetrabromoethanec 1,2-Dichlorotetrafluoroethaner 1,1,2-Trichlorotrifluoroethane Cyclohexyl chloride
74-87-3 75-09-2 74-97-5 75-45-6 75-43-4 74-96-4 75-35-4 107-06-2 75-11-6 67-66-3 75-34-3 106-93-4 75-25-2 540-54-5 79-01-6 75-71-8 75-69-4 75-63-8 56-23-5 71-55-6 127-18-4 108-90-7 109-69-3 79-34-5 222-22-2 95-50-1 100-44-7 79-27-6 76-14-2 76-13-1 542-18-7
55.4 63.9 65 72.9 75.4 76.9 79 79.4 80.5 80.7 84.8 87 87.5 88.1 90.2 92.3 92.8 97 97.1 1.4 101.1 102.1 104.9 105.2" 105.3 112.8 115 116.8 117 119.2 121.3
15.3 18.2 17.4 12.3 15.8 16.6 17 19.0° 17.8 17.8 16.6 19.6 21.5" 16 18 12.3 15.3 9.6 17.8 17 19 19 16.4 18.8 20.5 19.2 18.8° 22.7 12.7 14.7 17.4
6.1 6.3 5.7 6.3 3 8 6.8 7.4 3.9 3.1 8.2 6.8 4.1 7.8 3.1 2 2 2.5 0 4.3 6.5" 4.3 5.5 5.1 5.5 6.3 7.2 5.1 1.8 1.6 5.5
3.9 6.1 3.5 5.7 5.7 5.1 4.5 4.1 5.5 5.7 0.4 12.1 6.1° 2 5.3 0 0 0 0.6 2 2.9" 2 2 9.4 4.1 3.3 2.7 8.2 0 0 2
17 20.3 18.6 14.9 17 19 18.8 20.9 19 19 18.4 23.9 22.7 17.8 19 12.5 15.5 10 17.8 17.6 20.3 19.6 17.4 21.7 21.7 20.5 20.3 24.8 12.9 14.7 18.4
TABLE 9. cont'd Solubility parameters (MPa 1/2 ) Solvent
CAS Number
1-Bromonaphthaiene Trichlorobiphenylf/ Perfluoromethylcyclohexane Perfluorodimethylcyclohexane Perfluoro-/7-heptane 9.4. ETHERS Furan Epichlorohydrin Tetrahydrofuran 1,4-Dioxane Methylal (dimethoxymethane) Diethyl ether Bis(2-chloroethyl) ether Anisolec Bis-(2-methoxyethyl) ether Dibenzyl etherc Di-(chloro-iso-propyl) ether Bis-(m-phenoxyphenyl) ether 9.5. KETONES Acetone Methyl ethyl ketone (2-butanone) Cyclohexanone Diethyl ketone (3-pentanone) Mestiyl oxide (4-methyl-3-pentene-2-one) Acetophenone Methyl iso-butyl ketone (2-hexanone) Methyl iso-amyl ketone Isophorone Di-iso-butyl ketone (2,6-dimethyl-4-heptanone) 9.6. ALDEHYDES Acetaldehyde 2-Furfuraldehyde (furfural) Butyraldehyde Benzaldehyde
Molar volume (cm3/mol)
#d
^P
^h
90-11-9 7012-37-5 355-02-2 335-27-3 335-57-9
140 187 196 217.4 227.3
20.3 19.2 12.5 12.5 12.1
3.1 5.3 0 0 0
4.1 4.1 0 0 0
20.9 20.5 12.5 12.5 12.5
110-00-9 106-89-8 109-99-9 123-91-1 109-87-5 60-29-7 107-30-2 100-66-3 111-96-6 103-50-4 108-60-1 748-30-1
72.5 79.9 81.7 85.7 88.8 104.8 117.6 119.1 142 192.7 146 373
17.8 19 16.8 19 15.1 14.5 18.8 17.8 15.8 17.4 19 19.6
1.8 10.2 5.7 1.8 1.8 2.9 9 4.1 6.1 3.7 8.2 3.1
5.3 3.7 8 7.4 8.6 5.1 5.7 6.8 9.2 7.4 5.1 5.1
18.6 21.9 19.4 20.5 17.6 15.8 21.7 19.4 19.2 19.2 21.3 20.5
67-64-1 78-93-3 108-94-1 96-22-0 141-79-7 98-86-2 591-78-6 78-59-1 108-83-8
74 90.1 104 106.4 115.6 117.4 125.8 142.8 150.5 177.1
15.5 16 17.8 15.8 16.4 19.6° 15.3 16 16.6 16
10.4 9 6.3 7.6 7.2 8.6 6.1 5.7 8.2 3.7
7 5.1 5.1 4.7 6.1 3.7 4.1 4.1 7.4 4.1
20.1 19 19.6 18.2 18.8 21.7 17 17.4 19.8 16.8
75-07-0 98-01-1 123-72-8 100-52-7
57.1 83.2 88.5 101.5
14.7 18.6 14.7 19.4
8 14.9 5.3 7.4
11.3 5.1 7 5.3
20.3 24.3 17.2 21.5
66 76.8 79.7 80.2 85
19.4 19 15.5 15.5 20.1
21.7 16.6 7.2 8.4 18
5.1 7.4 7.6 8.4 4.1
29.5 26.2 18.8 19.6 27.2
95.6 98.5 99.9 121 131.5 132.5 133.5 136.2 148.8 163 163 166.8 171 198 266 306 613 345
15.5 15.8" 16.8 16.6 15.8 15.8 15.1 16 15.3 15.1 18.6" 18.4 16.8 17.6 17.8° 19 19 16.4
10 5.3 16 3.1 14.7 3.7 3.7 4.7 3.1 2.9 10.8* 8.2 11.5 9.6 8.6 11.3 12.3 6.3
6.8 7.2* 10.2 6.1 7.2 6.3 6.3 10.6 7 5.9 4.9 4.1 9.2 4.5 4.1 3.1 4.5 4.3
19.6 18.2 25.4 18 22.7 17.4 16.8 19.6 17.2 16.6 22.1 20.5 22.3 20.5 20.3 22.3 23.1 18
9.7. ESTERS Ethylene carbonate (l,3-dioxolan-2-one) 96-41-9 y-Butyroiactone (4-hydroxybutryic acid 7-lactone) 96-48-0 Methyl acetate 79-20-9 Ethyl formate 109-94-4 Propylene carbonate (1,2-propanediol cyclic 108-32-7 carbonate) Ethyl chloroformate 541-41-3 Ethyl acetate 141-78-6 Trimethyl phosphate 512-56-1 Diethyl carbonate 105-58-8 Diethyl sulfate 64-67-5 n-Butyl acetate 123-86-4 Iso-butyl acetate 540-88-5 2-Ethoxyethyl acetate (Cellusolve acetate) 111-15-9 Iso-amyl acetate 628-63-7 Iso-butyl iso-butyrate 109-21-7 Dimethyl phthalate 131-11-3 Ethyl frans-cinnamate 103-36-6 Triethyl phosphate 78-40-0 Diethyl phthalate 84-66-2 Di-rc-butyl phthalate 84-74-2 n-Butyl benzyl phthalate 85-68-7 Tricresyl phosphate (tritolyl phosphate) 1330-78-5 Tri-n-butyl phosphate 126-73-8
S
References page VII - 711
TABLE 9. cont'd Solubility parameters (MPa 1/2 ) Solvent Iso-propyl palmitate c Di-n-butyl sebacate Methyl oleaterf Dioctyl phthalate (bis(2-ethylhexyl) phthalate) Di-butyl stearatec
CAS Number 2239-78-3 109-43-3 112-62-9 117 81-7
9.8. NITROGEN-CONTAINING COMPOUNDS Acetonitrile 75-05-8 Acrylonitrile 107-13-1 Propionitrile 107-12-0 Butyronitrile 109-74-0 Benzonitrile 100-47-0 Nitromethane 75-52-5 Nitroethane 79-24-3 2-Nitropropane 79-46-9 Nitrobenzene 98-95-3 Ethanolamine (2-aminoethanol) 141-43-5 Ethylene diamine 107-15-3 l,l-Dimethylhydrazine c 57-14-7 2-Pyrrolidone (2-pyrrolidinone) 616-45-5 Pyridine 110-86-1 rc-Propylamine 107-10-8 Morpholine 110-91-8 Aniline 62-53-3 Af-Methyl-2-pyrrolidone (1 -methyl872-50-4 2-pyrrolidinone) n-Butylamine 109-73-9 Diethylamine 109-87-7 Diethylenetriamine 111-40-0 Cyclohexylamine 108-91-8 Quinoline 91-22-5 Di-rc-propylamine 142-84-7 Formamide 75-12-7 Dimethylformamide 68-12-2 MN-Dimethylacetamide 127-19-5 1,1,3,3-Tetramethylurea 632-22-4 Hexamethyl phosporamidec (hexamethyl 680-31-9 phosphoric triamide)
Molar volume (cm 3 /mol)
— 8d
S9
5h
d
330 339 340 377 382
14.3 14.5 14.5 16.6 14.5
3.9 3.9 3.9 7 3.7
3.7 3.7 3.7 3.1 3.5
15.3 15.5 15.5 18.2 15.3
52.6 67.1 70.9 87 102.6 54.3 71.5 86.9 102.7 60.2 67.3 76 76.4 80.9 83 87.1 91.5 96.5
15.3 16.5 15.3 15.3 17.4 15.8 16 16.2 20.1 17.2 16.6 15.3 19.4 19 17 18.8 19.4 18
18 17.4 14.3 12.5 9 18.8 15.5 12.1 8.6 15.5 8.8 5.9 17.4 8.8 4.9 4.9 5.1 12.3
6.1 6.8 5.5 5.1 3.3 5.1 4.5 4.1 4.1 21.3 17 11 11.3 5.9 8.6 9.2 10.2 7.2
24.6 24.8 21.7 20.5 19.8 25 22.7 20.7 22.1 31.5 25.4 19.8 28.4 21.7 19.6 21.5 22.5 22.9
99 103.2 108 115.2 118 136.9 39.8 77 92.5 120.4 175.7
16.2° 14.9 16.8 17.4 19.4 15.3 17.2 17.4 16.8 16.8 18.4
4.5* 2.3 13.3 3.1 7 1.4 26.2 13.7 11.5 8.2 8.6
8 6.1 14.3 6.5 7.6 4.1 19 11.3 10.2 11 11.3
18.6 16.4 25.8 18.8 22.1 16 36.6 24.8 22.7 21/7 23.3
20.5 18.4 15.8 19 17
0 16.4 6.5 19.4 3.1
0.6 10.2 7.2 12.3 2
20.5 26 6 18.4 29 9 17.4
9.9. SULFUR-CONTAINING COMPOUNDS Carbon disulfide Dimethyl sulfoxide (methyl sulfoxide) Ethanethiolc (ethyl mercaptan) Dimethyl sulfoneb (methyl sulfone) Diethyl sulfide (ethyl sulflde)
75-15-0 67-68-5 75-08-1 67-71-0 352-93-2
60 71.3 74.3 75 108.2
9.10. ACID HALIDES AND ANHYDRIDES Acetyl chloride Succinic anhydride 6 Acetic anhydride
75-36-5 108-30-5 108-24-7
71 66.8 94.5
15.8 18.6 16.0"
10.6 19.2 11.7"
3.9 16.6 10.2°
19.4 31.5 22.3
67-56-1 64-17-5 109-78-4
40.7 58.5 68.3
15.1 15.8 17.2
12.3 8.8 18.8
22.3 19.4 17.6
29.7 26.6 30.9
107-18-6 71-23-8 67-63-0 627-30-5 98-00-0 71-36-3 4221-99-2
68.4 75.2 76.8 84.2 86.5 91.5 92
16.2 16 15.8 17.6 17.4 16 15.8
10.8 6.8 6.1 5.7 7*6 5.7 5.7
16.8 17 4 16.4 14.7 15*1 15 8 14 5
25 8 246 23.5 23 7 24*3 23 1 22 1
9.11. ALCOHOLS Methanol Ethano1
Ethylene cyanohydrin (hydracrylonitrile; 3-hydroxypropionitrile) Ally 1 alcohol (2-propen-l-ol) 1-Propanol 2-Propanol 3-Chloropropanol (trimethylene chlorohydrin) Furfuryl alcohol 1-Butanol (butyl alcohol) 2-Butanol
TABLE 9.
cont'd Solubility parameters (MPa 1/2 )
Solvent 2-Methyl-l-propanol (isobutyl alcohol) Benzyl alcohol Cyclohexanol 1-Pentanol 2-Ethyl-l-butanol Diacetone alcohol (4-hydroxy-4-methyl2-pentanone) 1,3-Dimethyl-l-butanol Ethyl lactate n-Butyl lactate Ethylene glycol monomethyl ether (2-methoxyethanol) Ethylene glycol monoethyl ether (2-ethoxyethanol) Cellusolve Diethylene glycol monomethyl ether (2-(2-methoxyethoxy)ethanol) Diethylene glycol monoethyl ether (2-(2-ethyoxyethyoxy)ethanol) Ethylene glycoi mono-rc-butyl ether (2-butoxyethanol) Butyl Cellusolve 2-Ethyl-l-hexanol 1-Octanol (capryl alcohol) 2-Octanol Diethylene glycol mono-n-butyl ether (2-(2-butoxyethoxy)ethanol) 1-Decanol Tridecyl alcohol* Nonylphenoxyethanol^ Oleyl alcohol' Triethylene glycol mono-oleyl ether 9.12. ACIDS Formic acid Acetic acid Benzoic acid* fi-Butyric acidc n-Octanoic acidc Oleicacid Stearicacid* 9.13. PHENOLS Phenol 1,3-Benzenediol*7 (resorcinol) m-Cresol 0-Methoxyphenol (guaiacol) Methyl salicylate Nonyl phenol' 9.14. WATER Waterc 9.15. POLYHYDRIC ALCOHOLS Ethylene glycol Glycerol Propylene glycol (1,2-propanediol) 1,3-Butanediol Diethylene glycol Triethylene glycol Hexylene glycol (2-methyl-2,4-pentanediol) Dipropylene glycol'
CAS Number
Molar volume (cm3/mol)
^d
78-83-1 100-51-6 108-93-0 71-41-0 97-95-0 123-42-2
92.8 103.6 106 109 123.2 124.2
105-30-6 687-47-8 138-22-7 109-86-4 111-15-9
dp
Sh
S
15.1 18.4 17.4 16 15.8 15.8
5.7 6.3 4.1 4.5 4.3 8.2
16 13.7 13.5 13.9 13.5 10.8
22.7 23.7 22.5 21.7 21.3 20.9
127.2 115 149 79.1
15.3 16 15.8 16.2
3.3 7.6 6.5 9.2
12.3 12.5 10.2 16.4
19.8 21.7 19.8 24.8
97.8
16.2
9.2
14.3
23.5
111-77-3
118
16.2
9.2
12.3
22.3
111-90-0
130.9
16.2
9.2
12.3
21.9
111-76-2
131.6
16
5.1
12.3
22.3
104-76-7 111-87-5 123-96-6 112-34-5
157 157.7 159.1 170.6
16 17 16.2 16
3.3 3.3 4.9 7
11.9 11.9 11 10.6
20.1 20.9 20.3 20.5
112-30-1 112-70-9 27986-36-3 143-28-2
191.8 242 275 316 418.5
17.6 14.3 16.8 14.3 13.3
2.7 3.1 10.2 2.7 3.1
10 9 8.4 8 8.4
20.5 17.2 21.3 16.6 16
64-18-6 64-19-7 65-85-0 107-92-6 124-07-2 112-80-1 57-11-4
37.8 57.1 100 110 159 320 326
14.3 14.5 18.2 14.9 15.1 14.3 16.4
11.9 8 7 4.1 3.3 3.1 3.3
16.6 13.5 9.8 10.6 8.2 5.5 5.5
25 21.3 21.9 18.8 17.6 15.8 17.6
108-95-2 108-46-3 108-39-4 90-05-1 119-36-8 25154-52-3
87.5 87.5 104.7 109.5 129 231
18 18 18 18 16 16.6
5.9 8.4 5.1 8.2 8 4.1
14.9 21.1 12.9 13.3 12.3 9.2
24.1 28.8 22.7 23.7 21.7 19.4
7732-18-5
18
15.5°
16.0"
42.4°
47.9
107-21-1 56-81-5 57-55-6 107-88-0 111-46-6 112-27-6 107-41-5 110-98-5
55.8 73.8 73.6 89.9 95.3 114 123 131.3
17 17.4 16.8 16.6 16.2 16 15.8 16
11 12.1 9.4 10 14.7 12.5 8.4 20.3
26 29.3 23.3 21.5 20.5 18.6 17.8 18.4
32.9 36.2 30.3 28.8 29.9 27.4 25.2 31.7
° Altered from previously published value. * Solid, treated as supercooled liquid. c Values uncertain. d Impure commercial product of this nominal formula.
References page VII - 711
TABLE 10. SOLUBILITY PARAMETERS OF POLYMERS Molar volume (cm3/gmol)
Polymer
Solubility parameters (MPa) 1/2 -—— — <5d <5P Sh <*
Method
J( 0 C)
Refs.
10.1. MAIN CHAIN CARBON POLYMERS 10.1.1. POLY(DIENES) Poly(butadiene)
3.42
1465 17.19 17.09 17.15 17.2-17.6 16.6 17.6 16.2 ±0.2 17.19 17.6 16.6 17.09 16.6 16.47 16.6 17.02 16.1 17.06 17.39 17.06 17.60 18
4.2
17.90-17.72 18.4 19.4 18.93 19.19 19.4 18.2 19.4 20.11-20.26 19.19 21.1 21.28-21.38 20.5 ±0.6 21
Emulsion Sodium Hydrogenated 16.98 PoIy(I f2-butadiene) Poly(3-methyl 1,2-butadiene) PoIy(I f3-butadiene) Poly(2,3-dimethyl 1,3 butadiene) Poly(cw-butadiene) elastomer (Bunahyls CBlO, Chemische Werke Huels) Poly(butadiene-co-acrylonitrile) BUNA N (82/18) (82/20)
-a
1.02
58.85 73.88 58.85 88.91 17.53
2.25
BUNA N (75/25)
(70/30) (61/39) Hycar (BFGoodrich) Poly(butadiene-co-styrene) BUNA S (94/6) (90/10) (87.5/12.5) (85/15)
(75/25)
18.6
8.8
16.45-16.64 17.13 16.39-16.57 16.55 17.6 17.31 17.19 17.35 17.4 17.39 17.41 17.39 17.5 17.29 17.47 16.55 16.49 16.6 17.5 17.56 17.5 17.6
CaIc. CaIc. Obs. IPGC
75
CaIc. Swelling Av. 129
Xe shift CaIc.HK" CaIc.HK CaIc.HK CaIc.HK
CaIc. Obs. CaIc. Obs. Obs.
25
IPGC
75
CaIc. Obs. CaIc. Obs. CaIc. Obs. Obs. CaIc. Obs.
28 66 110 112 112 118 72 70 79 79 62 104 75 75 75 98 152 3 3 3 3 56 19 66 66 112 42 104 118 79 19 43 19 19 70 56 19 110 19 43 104 112 110 112 112 79 66 66 104 UO 112 112 112 118 79 66 66 104
TABLE 10. cont'd Molar volume (cm3/gmol)
Polymer
Solubility parameters (MPa) 1 / 2 — — Sd £P ^h S
(71.5/28.5) (70/30) (60/40)
Poly(butadiene-co-styrene) (Polysar 5630, Polymer Corp.) Poly(butadiene-a?-vinylpyridine) Poly(chloroprene)
17.55
3.36
2.7
PoIy(1,4-cis-isoprene)
Poly(isoprene) elastomer (Cariflex IR 305, Shell) Natural Rubber
16.57
Guttapercha Chlorinated 10.1.2. POLY(ALKENES) Poly(2,3-dimethyl 1-butene) Poly(3,3-dimethyl 1-butene)
93.15 93.15
1.41
-0.82
16.55-16.72 17.51 17.35 17.5 17.7 17.74 17.74 17.76 17.74 17.8 18.07 19.13 18.42 16.59 19.19 16.74 18.93 17.6 16.8 18.8 16.6 17.6 17.54-17.74 15.18 18.0 ±0.4 17.6 15.18 16.64 16.68 16.57 20.46 16.47 16.47 16.57 16.68 16.6 16.4 16.47 16.82 16.68 16.2 16.33 17.09 16.2 16.65 16.2 16.6 16.68 17.09 17 16.6 16.4 17.09 16.33 16.6 16.42-16.49 16.2 16.6 19.2 18.05 18.05
Method
T(0C)
19 112 110 110 112 112 79 66 66 104 56
CaIc. Obs. CaIc. Obs.
25 CaIc. CaIc. Obs. Obs.
Swelling IPGC 129 Xe shift CaIc.
Swelling Av. Swelling Swelling CaIc. Swelling
75 25 25 35 35 35 35 35 35
Av. CaIc. Obs. Obs. Obs.
129 Xe shift CaIc.
Calc.HK CaIc.HK
Refs.
25 25
79 110 28 112 42 104 118 44 72 79 43 19 19 70 152 28 42 74 74 74 74 74 74 74 75 76 76 110 112 112 112 112 72 56 43 19 112 104 124 118 19,10 79 43 19 19 152 73 21-24 3 3
References page VII - 711
TABLE 10.
contd Solubility parameters (MPa) i / 2
Polymer Poly(3-methyl 1-butene) Poly(2-methyl 1-butene) Poly(2-methyl 2-butene) Polyethylene
Poly(ethylene) Poly(l,l-diphenyl ethylene) Poly(methylene) Poly(ethylene-co-vinyl acetate)
Molar volume (cm3/gmol)
<5d
Sp
Sh
78.12 78.12 78.12
33.03 166.29
Poly(isobutene)
Poly(isobutylene) (Lutonal IC/123, BASF)
14.53
2.52
4.66
Poly(isobutene-co-isoprene) butyl rubber Poly(propylene) Poly(propylene) 48.06 Poly(propylene), isotactic (Profax 6701, Hercules) Poly(propylene), chlorinated (Parlon PlO, Hercules) Poly(2-methyl propene) 63.09 10.1.3. POLY(ACRYLICS) AND POLY(METHACRYLICS) Poly(acrylic acid), butyl ester
Poly(acrylic acid), ethyl ester
17.19 20.26
6.32
5.4
5 17.76 17.92 17.68 15.76 16.6 16 16.2 17.09 16.4 16.2 16.2 16.8 16.2 18.4 17.99 16.96 19.93 14.3 18.6 ± 0.9 17.0 ±0.4 14.5 16.06 16 16.47 16.25 16.06 15.76 16.47 16.4 16.47 16.6 16 17 16.47 16.47 15.47 15 15.9-16.06 16.47 15.76 18.8 19.2 17.49 17.19 21.89 17.72 18 18.01 18.52 17.4 18.6 18.52 19.77 19.13 19.2 19.8 19.2 19.13 19.19 18.8 20.4
Method
T( 0 C)
Calc.HK CaIc.HK CaIc.HK CaIc.
CaIc. CaIc. Obs. 129 Xe shift CaIc. CaIc.HK Calc.HK Extrapol. IPGC IPGC CaIc. Av. Swelling Swelling
20 25 75 35
25 CaIc. Obs.
CaIc.
129
Xe shift
25 CaIc. CaIc.HK CaIc.HK 35 Av. Swelling CaIc. Swelling CaIc. Av. Swelling CaIc. Swelling CaIc. CaIc.
Refs. 3 3 3 110 112 58 97 8 124 118 72 97 73 152 119 3 3 45 71 70 28 74 74 74 19,10 110 112 112 58 104 21-24 19 124 72 79 56 152 19 104 112 58 124 3 81 56 3 75 75 75 75 77 77 119 75 75 75 77 77 45 62 119
TABLE 10. cont'd Molar volume (cm3/gmol)
Polymer
Solubility parameters (MPa)1/2 —— dd Sp Sh S
Poly(acrylic acid), isobornyl ester Poly(acrylic acid), methyl ester
Poly(acrylic acid), propyl ester Poly(a-chloroacrylic acid), methyl ester Poly(methacrylic acid), butyl ester
Poly(methacrylic acid), isobutyl ester Poly(methacrylic acid), sec-butyl ester Poly(methacrylic acid), ethoxyethyl ester Poly(methacrylic acid), ethyl ester Poly(ethyl methacrylate) (Lucite 2042, DuPont) Poly(methacrylic Poly(methacrylie Poly(methacrylic Poly(methacrylic
18.64
10.52
7.51
acid), n-hexyl ester acid), isobornyl ester acid), lauryl ester acid), methyl ester
Poly(methyl methacrylate) (Rohm and Haas) Poly (methacry lie acid), octyl ester Poly(methacrylic acid), propyl ester Poly(methacrylic acid), stearyl ester Poly(methacrylonitrile)
18.64
10.52
7.51
10.1.4. POLY(VINYL ALCOHOLS) Poly(vinyl alcohol)
10.1.5. POLY(VINYL ESTERS) Poly(vinyl acetate)
acetate) (Mowilith 50, Hoechst) acetate-co-vinyl alcohol) butyral) (Butvar B76, Shawinigan) propionate)
T(0C)
CaIc. Av. Swelling CaIc. Swelling Swelling Av. CaIc. CaIc. Swelling Swelling CaIc. IPGC IPGC IPGC Swelling
140 140 140
Swelling CaIc. 129 Xe shift CaIc.
CaIc. 25 Swelling CaIc. CaIc. CaIc. CaIc. CaIc. CaIc.
25.78 21.7 22.5
Poly(4-vinyl phenol)
Poly(vinyl Poly(vinyl Poly(vinyl Poly(vinyl
16.8 20.7 20.77 20.1 20.77 21.3 20.7 18.52 18.42 18.4 20.7 17.9 17.8 18.01 17.9 17 14.7 14.7 14.7 18.4 20.3 18.31 18.2 18.6 22.69 20.4 17.6 16.6 16.8 18.58 18.52-18.66 19.4 19.34 26.27 18.93 18.4-19.4 18.58 19.5 22.69 17.2 18 16 21 21.9
Method
20.93
11.27
9.66
18.6
4.36
13.03
19.62 19.13 20.93 19.2 18 22.61 19.2 19.2 25.66 21.94 23.12 18.01 18.52
Refs. 62 75 75 75 77 77 77 75 75 75 112 77 77 77 77 73 31 31 31 77 77 77 77 73 56 152 73 62 73 19 19 77 77 110 112 7 118 119 56 73 73 73 118 112 110 139 139
CaIc.
25 35
CaIc. CaIc. 25 CaIc. CaIc. 35 CaIc.
28 78 119 78 78 110 112 118 56 119 56 78 78
References page VII - 711
TABLE 10. cont'd Solubility parameters (MPa) 1 / 2 Polymer
Molar volume (cm 3 /gmol)
<5d
Sp
Sh
10.1.6. POLY(ALLYL ETHERS) AND POLY(VINYL ETHERS) Poly(allyl methyl ether) 70.79 Poly(allyl ethyl ether) 85.82 Poly(allyl propyl ether) 100.85 Poly(allyl isopropyl ether) 100.85 Poly(allyl phenyl ether) 122.39 Poly(allyl 2, tolyl ether) 137.41 Poly(allyl 3, tolyl ether) 137.41 Poly(allyl 4, tolyl ether) 137.41 Poly(diallyl ether) 96.61 Poly(vinyl methyl ether) 55.76 Poly(vinyl ethyl ether) 70.79 Poly(vinyl propyl ether) 85.82 Poly(vinyl butyl ether) 100.85 Poly(vinyl isopropyl ether) 85.82 Poly(vinyl isobutyl ether) 100.85 Poly(vinyl isoamyl ether) 115.88 Poly(vinyl-l-amyl methyl ether) 119.91 Poly(vinyl-2-ethyl hexyl ether) 160.96 Poly(vinyl-2-methoxyethyl ether) 93.52 Poly(vinyl phenyl ether) 107.36 Poly(vinyl-1 -phenyl methyl ether) 122.39 Poly(vinyl-1-methyl phenyl ether) 122.39 Poly(vinyl-1 -phenyl phenyl ether) 174.01 PoIy(I-methyl vinyl ethyl ether) 85.82 PoIy(I-ethyl vinyl ethyl ether) 100.85 PoIy(I-phenyl vinyl ethyl ether) 137.41 Poly(divinyl ether) 66.55
19.44 19.29 19.21 19.21 20.19 20.03 20.03 20.03 18.84 19.66 19.44 19.29 19.21 19.29 19.21 19.13 20.83 18.99 20.44 20.19 20.19 20.19 20.50 19.29 19.21 20.03 18.93
10.1.7. POLY(VINYL HALIDES) AND POLY(VINYL NITRILES) Poly(acrylonitrile)
18.21 Poly(allyl acetonitrile) Poly( 1-methyl acrylonitrile) Poly(2-methyl acrylonitrile) Poly(acrylonitrile-co-isopropyl methacrylate) Poly(tetrafluoroethylene)
16.16
6.75
81.13 66.09 66.09
Poly(vinyl bromide) Poly(vinyl chloride)
Poly(vinyl chloride) (Vipla KR, K = 50, Montecatini) Poly(vinyl chloride) Poly(vinyl chloride), high molecular weight
Poly(vinyl chloride), chlorinated
5
18.23 18.72 18.82
7.53 10.03 10.03
8.35 3.07 3.07
25.27 25.6 26.09 31.5 25.27 24.18 25.45 25.45 19.84 12.7 12.7 19.42 19.6 19.19-19.34 19.28 20.67 19.54 19.8 19.2 19.8 22.1 20.1 19.5 19.8 20.32 21.42 21.46 21.54 20.13 20.25 20.3 19
Method
T( 0 C)
CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK Calc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK
3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3
CaIc. CaIc.
25
CaIc. HK CaIc. HK CaIc. HK CaIc.
CaIc. CaIc. Obs.
CaIc.
Turbidity Swelling Vise. Vise.
Refs.
25
119 66 112 118 98 3 3 3 141 112 118 34 112 19 28 110 112 72 19 21-24 58 124 118 72 119 56 33 98 162 162 162 117
TABLE 10. cont'd Solubility parameters (MPa) 1 / 2 Polymer
Molar volume (cm3/gmol)
dd
dp
6h
Poly(vinyl chloride-co-vinyl acetate) (87/13) VYHH Poly(vinyl chloride-o?-vinyl acetate-comaleic acid) Poly(vinyl chloride-c-vinyl acetate-covinyl alcohol) Poly(allyl cyanide) 66.09 Poly(allyl isocyanide) 66.09 Poly(vinylidene chloride) Poly(vinylidene cyanide-o^-vinyl acetate) Poly(vinylidene fluoride)
17.2 16.6, 17.9 16.6 13.7
12.5
9.2
10.6
8.2
10.1.8. POLY(STYRENES) Poly(styrene)
Poly(styrene) (Polystyrene LG, BASF) Poly(o-methyl styrene) Poly(m-methyl styrene) Poly(/?-methyl styrene) PoIy(I-methyl styrene) Poly(methoxy styrene) PolyCcyano styrene) Poly(nitro styrene) Poly(2-nitro styrene) Poly(styrene-c<9-divinylbenzene) 5% crosslinking 10% crosslinking 20% crosslinking Poly(styrene-o?-rc-butyl methacrylate) Poly (sty rene-co-isobutyl methacrylate) Poly(4-chlorostyrene) Poly(a-methylstyrene-co-acrylonitrile) Poly(4-acetoxystyrene) Poly(4-hydroxystyrene)
21.28
5.75
4.3
114.69 114.69 114.69 114.69 122.39 124.28 113.29 113.29
17.6 17.8 17.6
6.1 9 10
4.1 8.4 13.7
d 21.7 21.3 20.42 20.44 20.77 25.45 25.45 25 22.67 23.2 23.2 19.2 24.6, 25.2
17.52 17.45-17.58 20.16 17.86-17.92 17.84-18.56 18.6 18.72 18.62 18.62 18.66 19.09 18.66 18.6 17.6-19.8 17.4 17.6 18.4 19.28 21.1 17.52 17.84 18.6 17.6-17.8 18.6 15.6 22.47 19.33 19.33 19.33 19.33 20.19 22.36 22.71 22.20 18.6 17.39 14.8 15.7 17.8 15.1 15.1 19.02 16.4 21.7 24.55
Method
T(0C)
CaIc.
28 21-24 119 119 119 3 3 21-24 128 147 147 147 147 149 148
CaIc. CaIc. CaIc. CaIc.HK CaIc.HK CaIc. Vise. Obs. CaIc. Refract, index Contact ang. Swelling
CaIc. Vise. 35 Av. Swelling CaIc. 25 CaIc. Obs. Obs.
CaIc. CaIc.
IPGC
Refs.
140
CaIc.HK CaIc.HK CaIc.HK CaIc.HK CaIc.HK CaIc.HK CaIc.s< CaIc. s Obs.
IPGC IPGC
140 140
IPGC
140
19 19 28 48 116 66 74 74 74 74 110 112 112 112 18 19 58 119 124 118 19,97 104 72 79 31 56 3 3 3 3 3 3 3 3 112 18 137 137 137 31 31 151 111 138 138
References page VII - 711
TABLE 10. confd Solubility parameters (MPa) 1 / 2 Polymer
Molar volume (cm 3 /gmol)
Poly(4-a-acetoxystyrene), -CH2-C-(OCOCH3)-(C6H5-OCOR)-, R = C H 3 , C 2 H 5 , W-C3H7, OCH 3 Poly(vinylidene cyanide-co-4-a-acetoxystyrene),
dh
5
Method
T( 0 C)
S6
dp
Refs.
15.7
10.2
7.4
21.9
161
21.5
11.3
7.2
25.3
161
17
13.5
6.5
23.5
161
17
12.1
8.2
22.4
161
17
11.9
7.2
21.9
161
-CH2-C(CN)2-CH2-C-(OCOCH3)-
(C6H5-OCOR)-, R = C H 3 Poly(vinylidene cyanide-cc-4-a-acetoxystyrene), R=OCOCH3 Poly(vinylidenecyanide-C(?-4-a-acetoxystyrene), R=OCOCH3 Poly(vinylidene cyanide-co-4-oc-acetoxystyrene), R=OCOCH3 10.2.
MAIN CHAIN C-O POLYMERS
10.2.1. POLY(VINYL ESTERS) Poly(vinyl acetate) Poly(allyl acetate) Poly(diethylaminoethyl acrylate)-palladium ion Poly(methyl acrylate) Poly(ethyl acrylate) Poly(allyl acrylate) Poly(butyl acrylate) Poly(isobutyl acrylate) Poly(2-ethyl hexyl acrylate) Poly(2-cyanoethyl acrylate) 0 Poly(benzyl acrylate) Poly(vinyl butyrate) Poly(dimethyl citraconate) Poly(diethyl citraconate) Poly(vinyl crotonate) Poly(methyl dimethyl fumarate) Poly(methyl diethyl fumarate) Poly(dimethyl fumarate) Poly(diethyl fumarate) Poly(dipropyl fumarate) Poly(di-n-butyl fumarate) Poly(di-H-amyl fumarate) Poly(di-isopropyl fumarate) Poly(di-isobutyl fumarate) Poly(di-isoamyl fumarate) Poly(dinitrile fumarate) Poly(diphenyl fumarate) Poly(vinyl-2-ethyl hexoate) Poly(dimethyl maleate) Poly(diethyl maleate) Poly(di-«-propyl maleate) Poly(di-n-butyl maleate) Poly(di-n-amyl maleate) Poly(di-isobutyl maleate) Poly(di-isoamyl maleate) Poly(diphenyl maleate) Poly(3-chloropropyl methacrylate) Poly(methyl methacrylate) Poly(ethyl methacrylate) Poly(propyl methacrylate) Poly(butyl methacrylate) Poly(hexyl methacrylate) Poly(allyl methacrylate) Poly(isopropyl methacrylate) Poly(isobutyl methacrylate) Poly(vinyl propionate)
74.25 89.28 74.25 89.28 100.07 119.34 119.34 179.46 89.36 140.88 104.31 130.5 160.58 100.07 130.5 160.56 115.47 145.53 165.58 205.65 235.71 165.58 205.65 235.71 46.32 217.67 157.83 115.47 145.53 165.58 205.65 235.71 205.65 235.71 217.67 89.28 110.9 119.34 134.37 191.91 115.1 119.34 134.37 89.32
18.21 18.27 20.50 18.21 18.27 17.94 20.42 18.37 18.45 31.77 19.38 18.33 18.58 18.58 17.94 18.58 18.58 18.56 18.58 19.72 18.60 18.60 19.72 18.60 18.60 48.45 19.91 19.21 18.56 18.58 19.70 18.60 18.60 18.60 18.60 19.91 19.60 18.27 17.25 18.37 18.41 15.80 17.51 18.39 18.39 18.27
CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK Calc. HK CaIc. HK CaIc. HK CaIc. HK CaIc. HK Calc. HK CaIc. HK CaIc. s CaIc. HK CaIc. HK CaIc. HK
3 3 136 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 160 3 3 3 3 3 3 3 3 3
TABLE 10.
cont'd Solubility parameters (MPa)1/2
Polymer
Molar volume (cm3/gmol)
<5d
<5P
Sh
S
Method
T(0C)
Refs.
10.3. MAIN CHAIN C-N POLYMERS 10.3.1. POLY(AMIDES) Poly(lactams) Nylon 3 Nylon 4 19.44
-a
14.12
Nylon 5 Nylon 6 Nylon 7 Nylon 8 Nylon 9 Nylon 10 Nylon 11 Nylon 12 Nylon 2-1 Nylon 34 Nylon 4-1 Nylon 5-1 Nylon 6-1 Nylon 61, poly(hexamethylene isophthalamide) Nylon 7-1 Nylon 8-1 Nylon 9-1 Nylon 10-1 Nylon 12-1 Nylon 66 Nylon 66 (Zytel, DuPont) Poly(iminohexamethylene iminoadipoyl) Poly(amide), thermoplastics (Versamid 930, General Mills) Poly(p-benzamide) Poly(/7-phenylene terephthalamide) Poly(/?-benzanilide terephthalamide) Poly(n-isopropyl acrylamide) Gel
18.62 18.62
5.11 0
12.28 14.12
17.43
- 1.92
14.89
11.9 11.9 11.9
7.9 7.9 7.9
18 18 18
10.3.2. CELLULOSE AND DERIVATIVES Benzyl cellulose Cellulose Cellulose Cellulose-alkylketene dimer treatment Cellulose acetate (56% acetate groups) (48% acetate groups) Cellulose acetate (Cellidore A. Bayer) Cellulose acetate Cellulose acetate butyrate Cellulose acetate propionate Cellulose diacetate
12.69 8.27 8.1
-a 8 12.35
22.3 13.88 7.96
18.6 15.55 15.75 15.75
12.73 -a -a -a
11.01 11.87 8.59 10.23
Cellulose nitrate (11.83% N)
(11.4% N) Cellulose nitrate (1/2 sec; H-23 Hagedon) Cellulose triacetate Cellulose tridecanoate Ethyl cellulose
15.41 15.55 19.85
14.73 -° -a
8.84 10.64 6.14
26.2 23.9 24.02 22.5 21.5 20.7 20.3 19.8 19.4 19.2 19 27.2 26 25 24.1 23.5 26.3 23.2 22.9 22.5 22.1 21.7 21.1 22.87 23.37 27.8 23.02 23 23 23 22.8 23.5
25.23 32.02 25.66 18.03 16.78 27.83 27.19 25.08 19.56 17.94 18.76 23.22 22.3 22.3 30.39 21.44 21.7 23.5 21.93 23.08 18.84 20.77 21.1
CaIc. CaIc. CaIc. CaIc. CaIc. CaIc. CaIc. CaIc. CaIc. CaIc. CaIc. CaIc. CaIc. CaIc. CaIc. CaIc.HK CaIc.H" CaIc. CaIc. CaIc. CaIc. CaIc.
Swelling Swelling Swelling CaIc. Swelling
CaIc.
139 139 81 139 139 139 139 139 139 139 139 139 139 139 139 139 150 150 139 139 139 139 139 98 56 118 56 143 143 143 154 153
110 110 81 140 140 110 110 56 81 81 18 112 118 72 110 112 72 21-24 72 56 81 81 21-24
References page VII - 711
TABLE 10. cont'd Solubility parameters (MPa) 1 / 2 Polymer 10.4. OTHER POLYMERS Alcohol soluble resin (Pentalyn 255, Hercules) Alcohol soluble rosin resin (Pentalyn 830, Hercules) Alkyd, short oil (coconut oil 34% phthalic anhydride, Plexal C34) Alkyd resin, medium oil length Alkyd, long oil (66% oil length, Plexal P65, Polyplex) Coumarone-indene resin (Piccoumarone 450L, Penn. Ind. Chem.) Epoxy resin Epoxy (Epikote 1001, Shell) Epoxy DBEBA-DDMe* DGEBA-DMM TGAP-DDMe TGAP-ANI TGAP-DDM TGAP-DDS Ester gum (ester gum BL, Hercules) Furfuryl alcohol resin (Durez 14383, Hooker Chemical) Hexamethoxymethyl melamine (Cymel 300, American Cyanimid) Pentaerythritol ester of rosin, modified (Cellolyn 102, Hercules) Petroleum hydrocarbon resin (Piccopale 110, Penn. Ind. Chem.) Phenolic resin (resole, Phenodur 373U Chemische Werke Albert) Phenolic resin (Super Beckacite 1001, Reichhold) Poly(2 acrylamide-2-methyl propane sulphonamide) (tested in formamide/water mixtures) Poly(3,3-dimethyl oxetane) Poly(3,3-diethyl oxetane) Poly(l,3-dioxolane) Poly(ether urethane)
Molar volume (cm 3 /gmol)
S9
^h
17.5
9.3
14.3
24.4
56
20
5.8
10.9
23.5
56
18.5
9.21
4.91
21.24
56
20.42
3.44
4.56
19.2 12.2
19.42
5.48
5.77
20.99
56
20.36
12.03
11.48
Method
Refs.
118 56 135 135 135 135 135 135 56 56
21-24 56
19.64 21.16
4.73 13.56
7.77 12.81
22.3 26.29 22 22.2 22.5 23.9 24.8 27.1 21.65 28.21
20.36
8.53
10.64
24.51
56
21.73
0.94
8.53
23.37
56
17.55
1.19
3.6
17.96
56
19.74
11.62
14.59
27.15
56
23.26
6.56
8.35
25.57
56
32 22 22.4
43.6
15.35 15.55
2.46 2.05
4.09 3.48
Poly(DL-lactic acid)
Poly(oxetane) Poly(oxydimethylsilylene)
d
T( 0 C)
5d
17.39
5.12
5.12
16.16 16.16 20.66 17.99 db.02 17.38 ± 0 . 1 6 17.20 ± 0 . 1 5 17.14±0.14 17.06 db 0.15 16.96 ±0.15 21.0 ± 0 . 3 20.5 ± 0 . 4 19.8 20.3 19.2 19.23 15.04 14.9 15.45 15.6 14.9 15.59 15.4 15 15.1
35 35 35 35 35 35
Vise.
Vise. Vise. Vise. IPGC IPGC IPGC IPGC IPGC IPGC Density Vise. CaIc. s CaIc. H CaIc. HK
25
25 25 100 120 130 140 150 25 25 25 25 25
Obs. Swelling Av.
25 Vapor sorp. IPGC
159
92 92 175 158 158 158 158 158 158 142 142 142 142 142 92 110 21-24 76 76 118 45 125 145 146
* DGEBA - diglycidyl ether of bisphenol A; DDMe - tetraethyl derivative of DDM; DDM - diamino diphenyl methane; TGAP - triglycidyl derivative of amino phenol; ANI aniline; DDS - diamino diphenylsulfone.
TABLE 10. cont'd Solubility parameters (MPa) 1 / 2 Polymer
Molar volume (cm3/gmol)
dd
dp
<5h
S1 = (15.7 - 0.026)f, t in 0 C Polyethylene adipate) Polyethylene oxide)
16.47
0.37
2.84
15.1 17.5 19.8±2 20.2 ±2 19.9 ±2.2 17.8 19.64 21.9 21.9 19.2 16.2 16.2 16.3 16.2 16.1 18.5±1.2 15.9 20.26 19.23 19.19 18.4 19.0 ± 1.0 20.5 20.5 22.9 16.5 25.6 22.92 22.14 19.52 20.28 16.72
20.81 17
8.29 10.3
12.71 6.1
25.74 20.8
16.3±2
6.1 ±0.5
9.4±0.1
17.3±2
3.0 ± 1
9.4±0.5
Poly(oxyethyleneoxyterephthaloyl) Poly(oxytrirnethylene) polyoxetane -3,3 dimethyl -3,3 diethyl Polypropylene oxide) 16.3 ± 1 Poly(sulfone), Bisphenol A (Udel) Poly(thioethylene)
19.03
4.7±0.5 0
7.4±0.5 6.96
Poly(thiophenylethylene) Poly(urethane) (unknown composition) Poly(urethane), amorphous Poly(vinyl ethylene) Poly(vinyl pyrroiidone) Poly(vinyi methyl ketone) Poly(vinyl ethyl ketone) Poly(vinyl methyl sulfide) Poly(vinyl phenyl sulfide) Teipene resin (Piccolyte S-1000, Penn. Ind. Chem.) Urea-formaldehyde resin (Plastopal H, BASF) Viton a
Altered ^Method 'Method rf Method
E.
S
66.59 81.58 66.63 118.35
Method
T(0C)
IPGC 129 Xe shift IPGC
25
CaIc. IPGC
70
Vise. Vise. Vise.
CaIc. Swelling Swelling Swelling Av. 129 Xe shift Vise. CaIc.HK Calc.HK CaIc.HK CaIc.HK
25 25 25 81 86 91
Refs. 144 152 157 31 157 157 176 118 112 31 92 92 156 156 156 157 157 81 110 43 43 87 76 76 155 152 177 3 3 3 3 56 56 130
from previously published value. of van Krevelen and Hoftyzee. of Small. of Hoy.
REFERENCES
1. H. Ahmad, M. Yaseen, J. Oil Chem. Assoc, 60, 488, (1977). 2. H. Ahmad, M. Yaseen, Farbe Lack, 85, 356, (1979). 3. H. Ahmad, M. Yaseen, Polym. Eng. SdL, 19 (2), 858 (1979). 4. H. Ahmad, J. Oil Col. Chem. Assoc, 63, 263 (1980). 5. H. Ahmad, J. Colour Soc, 20, 108 (1981). 6. P. Alessi, I. Kikic, G. Torriano, A. Papo, J. Coatings Technol., 51 (560), 62 (1979). 7. J. Alfrey, A. O. Goldberg, J. A. Price, J. Colloid ScL, 5, 251 (1950). 8. G. Allen, G. Geen, D. Mangaraj, D. Dims, G. J. Wilson, Polymer, 1, 467 (1960). 9. E. Bagley et al, J. Paint Tech., 41, 495 (1969). 10. E. B. Bagley, T. P. Nelson, J. W. Barlow, S. A. Chen, Ind. Eng. Chem. Fund., 9, 93 (1970). 11. E. Bagley et al., J. Paint Tech., 43, 35 (1971).
12. A. F. M. Barton, "CRC Handbook of Solubility Parameters and Other Cohesion Parameters", CRC Press, Boca Raton, FL, 1983, Ch. 15. 13. A. F. M. Barton, Pure Appl. Chem., 57 (7), 905 (1985). 14. A. Beerbower, J. R. Dickey, Am. Soc. Lubr. Eng., Trans., 12, 1 (1969). 15. R. G. Blanks, J. M. Prausnitz, Ind. Eng. Chem. Fund., 3 (1), 1 (1964). 16. R. F. Blanks, Polym.-Plast. Technol. Eng., 8 (1), 13 (1977). 17. S. T. Bowden, W. J. Jones, Phil. Mag., 39, 155 (1948). 18. R. F. Boyer, R. S. Spencer, "High Polymer Physics", Paper 5, Part III, Remoen Press, New York, 1948. 19. G. M. Bristow, W. F. Watson, Trans. Faraday Soc, 54, 1731 (1958). 20. C. W. Bunn, J. Polym. Sci., 16, 323 (1955). 21. H. Burrell, Interchem. Rev., 144, 3 and 31 (1955).
22. H. Burrell, Off. Dig., Fed. Paint Varn. Prod. Clubs, 27, 726 (1955). 23. H. Burrell, Off. Dig., Fed. Paint Varn. Prod. Clubs, 29, p. 1069, p. 1159 (1955). 24. H. Burrell, J. Paint Technol., 40, 197 (1968). 25. S. A. Chen, J. Appl. Polym. ScL, 15, 1247 (1971). 26. J. D. Crowley, G. S. Teague, J. W. Lowe, J. Paint Technol., 38 (496), 296 (1967). 27. J. D. Crowley, G. S. Teague, J. W. Lowe, J. Paint Technol., 39 (504), 19 (1967). 28. A. T. DiBenedetto, J. Polym. Sci. A, 1, 3459 (1963). 29. G. DiPaola-Baranayi, J. E. Guillet, Macromolecules, 11,228 (1978). 30. G. DiPaola-Baranayi, J. E. Guillet, J. Klein, H.-E. Jeberien, J. Chromatogr., 166, 349 (1978). 31. G. DiPaola-Baranayi, Macromolecules, 15, 622 (1982). 32. M. Dyck, P. Hower, Farbe Lack, 70, 522 (1964). 33. M. Dunkel, J. Phys. Chem. A, 138, 42 (1928). 34. D. Edelson, R. M. Fuoss, J. Am. Chem. Soc, 71,3548 (1949). 35. R. F. Fedors, Polym. Eng. Sci., 14 (2), p. 147, p. 472 (1974). 36. M. J. Fernandez-Berridi, T. F. Otero, G. M. Guzman, J. M. Elorza, Polymer, 23, 1361 (1982). 37. P J. Flory, "Principles of Polymer Chemistry", Cornell University Press, Ithaca, NY, 1953. 38. P. E. Froehling, L. T. Hillegers, Polymer, 22, 261 (1981). 39. P. E. Froehling, D. M. Koenhen, A. Bantjes, C. A. Smolders, Polymer, 17, 835 (1976). 40. E. W. Funk, J. M. Prausnitz, Ind. Eng. Chem., 62 (9), 8 (1970). 41. J. L. Gardon, J. Paint Technol., 38, 43 (1966). 42. G. Gee, Trans. Faraday Soc, 38, 418 (1942). 43. G. Gee, Trans. Inst. Rubber Ind., 18, 266 (1943). 44. G. Gee, Trans. Faraday Soc, 40, 468 (1944). 45. G. Gee, G. Allen, G. Wilson, Polymer (London), 1,456 (1960). 46. G. J. Glover, W. R. Lau, AIChE Jr., 29 (1), 73 (1983). 47. R. J. Good, in: R. L. Patrick (Ed.), "Treatise on Adhesion and Adhesives", Marcel Dekker, NY, 1967. 48. J. H. S. Green, Nature, 183, 818 (1959). 49. C. M. Hansen, Ind. Eng. Chem. Prod. Res. Dev., 8, 2 (1969). 50. C. M Hansen, Doctoral Dissertation, Technical University of Denmark, Danish Technical Press, Copenhagen, 1967. 51. C. M. Hansen, Farg Lack, 14 (1), 18;(2),23 (1968). 52. C. M.Hansen, J. Paint Technol., 39 (505), 104 (1967). 53. C. M. Hansen, J. Paint Technol., 39 (511), 505 (1967). 54. C. M. Hansen, K. Skaarup, J. Paint Technol., 39 (511), 511 (1967). 55. C. Hansen, A. Beerbower, Solubility Parameters, in: KirkOthmer (Ed.), "Encyclopedia of Chemical Technology", Supp. vol. (A. Standen (Ed.)),, 2nd ed., Interscience, New York, 1971, p. 889. 56. C. M. Hansen, Skaud. Tidskr. Faerg. Lack, 17, 69 (1971). 57. H. G. Harris, J. M. Prausnitz, Ind. Eng. Chem. Fundamentals, 8, 180 (1969). 58. R. A. Hayes, J. Appl. Polym. Sci., 5, 318 (1961). 59. J. H. Hildebrand, R. L. Scott, "The Solubility of Nonelectrolytes", (3rd ed.) Reinhold, NY 1959.
60. P. J. Hoftyzer, D. W. van Krevelen, Paper No. Ills-15, presented at International Symposium on Macromolecules of IUPAC, Lyden, 1970. 61. K. L. Hoy, J. Paint Technol., 42, 76 (1970). 62. I. J. Hughes, private communication to H. Burrell, "Polymer Handbook", 1st ed., J. Brandrup, E. H. Immergut (Eds.), Wiley, New York, 1966. 63. K. Ito, J. E. Guillet, Macromolecules, 12, 1163 (1979). 64. A. Jayasri, M. Yaseen, J. Oil Col. Chem. Assoc, 63, 61 (1980). 65. D. M. Koenhen, C. A. Smolders, J. Appl. Polym. Sci., 19, 1163 (1975). 66. M. Lautout, M. Magat, Z. Physik. Chem. (Frankfurt), 16, 292 (1958). 67. D. D. Lawson, Appl. Energy, 6, 241 (1980). 68. L.-H. Lee, J. Paint Technol., 42, 365 (1970). 69. E. P. Lieberman, Off. Dig., Fed Soc. Paint Technol., 349 (444), 30 (1962). 70. J. E. G. Lipson, J. E. Guillet, J. Polym. Sci. Polym. Phys. Ed., 19, 1199(1981). 71. J. E. G. Lipson, J. E. Guillet, J. Coatings Technol., 54 (684), 90 (1982). 72. M. Magat, J. Chem. Phys., 46, 344 (1949). 73. L. Mandelkern, private communcation to H. Burrell, "Polymer Handbook", 1st ed., J. Brandrup, E. H. Immergut (Eds.), Wiley, New York, 1966. 74. D. Mangaraj, S. K. Bhatnagar, S. B. Rath, Makromol. Chem., 67, 75 (1963). 75. D. Mangaraj, S. Patra, S. B. Rath, Makromol. Chem., 67, 84 (1963). 76. D. Mangaraj, Makromol. Chem., 65. 29 (1963). 77. D. Mangaraj, S. Patra, S. Rashid, Makromol. Chem., 65, 39 (1963). 78. D. Mangaraj, S. Patra, P C. Roy, S. K. Bhatnagar, Makromol. Chem., 84, 225 (1965). 79. H. Mark, A. V. Tobolsky, "Physical Chemistry of High Polymers", Interscience, New York, 1950, p. 263. 80. T. Matsuo, Preprints ACE/JSC, 20, 895 (1979). 81. T. Matsuura, P Blais, S. Sourirajan, J. Appl. Polym. Sci., 20, 1515 (1976). 82. A. McLellan, G. Pimentel, The Hydrogen Bond, Freeman, San Francisco, 1960. 83. A. S. Michaels, ASTM Technical Publications, 340, 1963, p. 3. 84. W. Merk, R. N. Lichtenthaler, J. M Prausnitz, J. Phys Chem., 84, 1694 (1980). 85. R. C. Nelson, R. W. Hemwall, G. D. Edwards, J. Paint Technol., 42 (550), 636 (1970). 86. R. C. Nelson, V. F. Figurelli, J. G. Walsham, G. D. Edwards, J. Paint Technol., 42 (550), 644 (1970). 87. A. Noshay, C. C. Price, J. Polym. Sci., 54, 533 (1961). 88. O. Olabisi, R. Simha, J. Appl. Polym. Sci., 21, 149 (1977). 89. O. Olabisi, L. M. Robeson, M. T. Shaw, "Polymer-Polymer Miscibility", Academic Press, NY, 1979. 90. D. Patterson, Macromolecules, 4, 30 (1971). 91. D. Patterson, Y B. Tewari, H. P. Schreiber, J. E. Guillet, Macromolecules, 4, 356 (1971).
92. E. Perez, M. A. Gomez, A. Bello, J.G. Fatou, J. Appl. Polym. ScL, 27, 3721 (1982). 93. S. Piccarolo, G. Titomanlio, Ind. Eng. Chem. Proc. Des. Dev., 22, 146 (1982). 94. J. M. Prausnitz, "Molecular Thermodynamics of Fluid Phase Equilibria", Prentice-Hall, Englewood Clifffs, NJ, 1969, p. 269. 95. J. Polak, Coll. Czech. Chem. Commun., 31, 1483 (1966). 96. A. E. Theineck, K. F. Lin, J. Paint Technol., 40, 611, (1968). 97. R. B. Richards, Trans. Faraday Soc, 42, 10 (1946). 98. Z. Ribgi, Polymer, 19, 1229 (1978). 99. W. A. Ruff, C. J. Glover, A. T. Watson, AIChE Jr., 32 (12), 1948 (1986). 100. W. A. Ruff, C. J. Glover, A. T. Watson, W. R. Lau, J. C. Holste, AIChE Jr., 32 (12), 1954 (1986). 101. G. Scatchard, Chem. Rev., 44, 7 (1949). 102. B. Schneier, Polym. Lett., 10, 245 (1972). 103. R. L. Scott, M. Magat, J. Chem. Phys., 13, p. 172, p. 178 (1945). 104. R. L. Scott, M. Magat, J. Polym ScL, 4, 555 (1949). 105. J. H. Sewell, R. A. E. Technical Report No. 66185, June, 1966. 106. J. H. Sewell. J. Appl. Polymer. ScL, 17, 1741 (1973). 107. M. T. Shaw, J. Appl. Polym. ScL, 18, 449 (1974). 108. Shell Chemicals, Solubility Parameters, 2nd Ed., Tech. Bull., ICS(X)/78/l, 1978. 109. Shell Chemicals, Solvent Systems Design, Tech. Bull. ICS (X)/78/2, 1987. 110. A. G. Shvarts, Kolloid Zh., 18, 755 (1956). 111. K. S. Siow, S. H. Goh, K. S. Yap,Polym. MaterialsSci. Eng., 51, 523 (1984). 112. P. A. Small, J. Appl. Chem., 3, 71 (1953). 113. C. Smidsrod, J. E. Guiilet, Macromolecules, 2, 272 (1968). 114. H. M. Spurlin, J. Polym. Sci., 3, 714 (1948). 115. W. H. Stockmayer, M. Fixman, J. Polym. Sci. C, I1 137 (1963). 116. K. W. Suh, D. H. Clarke, J. Polym. Sci. A-I, 5, 1671 (1967). 117. R. S. Tillaev, M. Khasaukhanova, S. A. Tashmukhamedov, Kk. U. Usmanov, J. Polym. Sci. C, 39, 107 (1972). 118. A. V. Tobolsky, "Properties and Structure of Polymers", Wiley, NY, I960, p. 64, p. 66. 119. Union Carbide Corp., private communication to H. Burrell, "Polymer Handbook", 1st ed., J. Brandrup, E. H. Immergut (Eds.), Wiley, New York 1966. 120. J. W. van Dyk, H. L. Frisch, D. T. Wu, Ind. Eng. Chem. Prod. Res. Dev., 24 (3), 473 (1985). 121. D. W. van Krevelen, Fuel, 44, 229 (1965). 122. D. W. van Krevelen, P. J. Hoftyzer, J. Appl. Polym. Sci., 11, 2189 (1967). 123. D. W. van Krevelen, P. H. Hoftyzer, Properties of Polymers. Correlations with Chemical Structure, Elsevier, NY, 1972, Chs. 6 and 8. 124. F. Vocks, J. Polym. Sci. A, 2, 5319 (1964). 125. H. Watanabe, T. Miyauchi, J. Chem. Eng. Japan, 6 (2), 109 (1973).
126. K. M. Watson, Ind. Eng. Chem., 23, 360 (1931); 35, 398 (1948). 127. S. Wu, J. Phys. Chem., 27, 3332 (1968). 128. J. A. Yanko, J. Polym. Sci., 22, 153 (1956). 129. T. Yamaguchi, S-I. Nakao, S. Kimura, Ind Eng. Chem. Res., 32, 848 (1993). 130. E. T. Zellers, J. Appl. Polym. Sci., 50, 513 (1993). 131. E. T. Zellers, G-Z. Zhang, J. Appl. Polym. ScL, 50, 531 (1993). 132. E. T. Zellers, D. H. Anna, R. Sulewski, X. Wei, J. Appl. Polym. Sci., 62 (12), 2069 (1996). 133. E. T. Zellers, D. H. Anna, R. Sulewski, X. Wei, J. Appl. Polym. Sci., 62 (12), 2081 (1996). 134. D. G. Peiffer, J. Appl. Polym. Sci., 25 (3), 369 (1980). 135. V. Bellenger, E. Morel, J. Verdu, J. Appl. Polym. ScL, 37 (9), 2563 (1989). 136. H. Jiadong, W. Ruofend, L. Lu, F. Peirong, J. Appl. Polym. Sci., 38(7), 1211 (1989). 137. L. A. Errede, J. Phys. Chem. 94 (1), 466 (1990). 138. S. Arichi, S. Himuro, Polymer, 30 (4), 686 (1989). 139. M. M. Coleman, C. J. Serman, D. E. Bhagwagar, P. C. Painter, Polymer, 31 (7), 1187 (1990). 140. H. L. Lee, P. Luner, J. Wood Chem. Technol., 11 (2), 247 (1991). 141. B. Bixamaiah, R. P. Raghunath, E. V. Sundaram, J. Appl. Polym. Sci., 44 (8), 1415 (1992). 142. U. Siemann, Europ. Polymer J., 28 (3), 293 (1992). 143. S. M. Aharoni, J. Appl. Polym. Sci., 45 (5), 813 (1992). 144. M. Roth, J. Polym. Sci., Phys. Ed., 28(13), 2715 (1990). 145. A. J. Ashworth, G. J. Price, Macromolecules, 19, 362 (1986). 146. G. J. Price, J. E. Guiilet, J. Solution Chem., 16, 605 (1987). 147. A. Bottino, G. Capannelli, S. Munari, A. Turturro, J. Polym. Sci., Polym. Phys., 26 (4), 785 (1988). 148. A. Chapiro, Z. Mankowski, N. Schmitt, J. Polym. Sci., Polym. Chem. Ed., 20, 1791 (1982). 149. C. M. Hansen, J. Paint Technol., 42, 660 (1970). 150. W. Liu, B. Breault, J. Brisson, J. Polym. Sci., Part B: Polym. Physics, 33 (4), 619 (1995). 151. Y. Izumi, Y Miyake, Polym. J., 3, 647 (1972). 152. J. B. Miller, J. H. Walton, C. M. Roland, Macromolecules, 26 (21), 5602 (1993). 153. Y. Yagi, H. Inomata, S. Saito, Macromolecules, 25 (11), 2997 (1992). 154. H. Ahmad, J. Macromol. Sci. A: Chem., 17, 585 (1982). 155. M. M. Coleman, J. Hu, Y. Park, P. C. Painter, Polymer, 29, 1659 (1988). 156. E. Morales, J. L. Acosta, Polymer J., 28 (2), 127 (1996). 157. R. Mieczkowski, Eur. Polym. J., 27 (4/5), 377 (1991). 158. A. M. Farooque, D. D. Deshpande, Eur. Polym. J., 28 (12), 1597 (1992). 159. S. R. Gooda, M. B. Huglin, Eur. Polym. J., 29 (2/3), 365 (1993). 160. S. M. Low, S. Y. Lee, S. H. Goh, Eur. Polym. J., 29 (8), 1075 (1993).
161. A. Belfkira, J.-R Montheard, J. Appl. Polym. ScL, 51 (11), 1849 (1994). 162. J. Zhang, C. Zheng, Y. Yang, Polymeric Mat. Sci. Eng. (China) [Gaofenzi Cailiao Kexue Yu Gongcheng], 10 (5), 50 (1994). 163. D. W. van Krevelen, "Properties of Polymers", 3rd ed., Elsevier, New York, 1990, Ch. 7. 164. J. Bicerano, "Prediction of Polymer Properties", 2nd ed., Marcel Dekker, New York, 1996, Ch. 5. 165. D. Porter, "Group Interaction Modeling of Polymer Properties", Marcel Dekker, New York, 1995. 166. M. B. Huglin, D. J. Pass, J. Appl. Polym. Sci., 12,473 (1968). 167. L. A. Errede, Macromolecules, 19, 1522 (1986). 168. Z. Liron, S. Cohen, J. Pharm. Sci., 72, 499 (1983). 169. C. Marco, A. Bello, J. G. Faton, J. Garza, Makromolek. Chem., 187, 177 (1986). 170. I. C. Sanchez, P. A. Rodgers, Pure Appl. Chem., 62, 2107 (1990).
171. R A. Rodgers, I. C. Sanchez, J. Polym. Sci., Part B: Polym. Phys., 31 (3), 273 (1993). 172. D. G. Peiffer, J. Appl. Polym. Sci., 25, 369 (1980). 173. J. L. Perkins, A. D. Tippit, Am. Ind. Hyg. Assoc. J., 46, 455 (1985). 174. J. L. Perkins, M. C. Ridge, A. B. Holcombe, M. K. Wang, W. E. Nonidez, Am. Ind. Hyg. Assoc. J., 47, 803 (1986). 175. R. Alamo, J. G. Fatou, A. Bello, Polym. J., 15 (7), 491 (1983). 176. M. Galin, Polymer, 24 (7), 865 (1983). 177. L. S. Huppenthal, U. Danuta, J. Nowacki, Polimery, 27(11), 427 (1982). 178. K. L. Hoy, "Tables of Solubility Parameters", Solvent and Coatings Materials Research and Development Department, Union Carbide Corporation, 1985. 179. K. L. Hoy, J. Coated Fabrics, 19, 53 (1989).
O p t i c a l l y
A c t i v e
P o l y m e r s
Katsuhiro l n o m a t a Department of Polymer Chemistry, Tokyo Institute of Technology, Tokyo, Japan Akihiro Abe Department of Industrial Chemistry, Tokyo Institute of Polytechnics, Atsugi, Japan A. Abbreviations used B. Optically Active Polymers from Chiral Monomers Table 1. Main-Chain Acyclic Carbon Polymers 1.1. Poly(alkenes) 1.2. Poly(acrylics) and Related Polymers 1.3. Poly(methacrylics) and Related Polymers 1..4. Poly(vinyl ethers), Poly(vinyl ketones), and Poly(vinyl esters) 1.5. Poly(styrenes), Poly(carbazoles) 1.6. Poly(dienes) 1.7. Poly(isonitriles) 1.8. Poly(alkynes) 1.9. Poly(maleimides) and Related Polymers 1.10. Other Compounds Table 2. Main-Chain Acyclic Heteroatom Polymers 2.1. Poly(oxides) 2.2. Poly(esters) 2.3. Poly (su If ides), Poly(thioesters) 2.4. Poly(urethanes), Poly(ureas) 2.5. Poly(amides) 2.6. Poly(isocyanates) 2.7. Poly(imines) 2.8. Poly(amino acids) Table 3. Poly(saccharides) C. Optically Active Polymers from Achiral Monomers Table 4. Main-Chain Acyclic Carbon Polymers 4.1. Poly(acrylics) and Related Polymers 4.2. Poly(methacrylics) and Related Polymers 4.3. Polytvinyl ethers)
VII-715 VII-716 VII-716 VII-716 VII-716 VII-717 VII-718 VII-719 VII-720 VII-720 VII-721 VII-722 VII-723 VII-723 VII-723 VII-724 VII-725 VII-725 VII-726 VII-728 VII-728 VII-729 VII-732 VII-733 VII-733 VII-733 VII-734 VII-735
4.4. Poly(styrenes) 4.5. Poly(dienes) 4.6. Poly(isonitriles) 4.7. Poly(maleimides) 4.8. Other Compounds Table 5. Main-Chain Acyclic Heteroatom Polymers 5.1. Poly(oxides) and Poly(sulfides) 5.2. Poly(isocyanates) D. References
VII-735 VII-735 VII-736 VII-736 VII-737 VII-737 VII-737 VII-738 VII-739
By definition the optical activity, [M] A, of polymers and their low molecular weight analogs is given by [M] A = [a\x x (mean residue weight)/100
A. ABBREVIATIONS USED AcAc Acetylacetonate AIBN Azobisisobutyronitrile BPO Benzoyl peroxide DBP Dibenzoyl peroxide DCA Dichloroacetic acid DCM Dichloromethane DDB 2,3-Dimethoxy-1,4-bis(dimethylamino)butane DMAc Dimethylacetamide DMF Dimethylformamide DMSO Dimethylsulfoxide DPEDA-Li iV^/V'-diphenylethylenediamine monolithium amide EDC Ethylene dichloride M Monomer MC Model compound NCA iV-Carboxylic anhydride P Polymer RT Room temperature TMEDA A^N,A/^JV'-tetramethylethylenediamine TCA Trichloroacetic acid TFA Trifluoroacetic acid TFEL Trifluoroethanol THF Tetrahydrofuran
B. OPTICALLY ACTIVE POLYMERS FROM CHIRAL MONOMERS TABLE 1.
MAIN-CHAIN ACYCLIC CARBON POLYMERS
Polymer Catalyst or initiator 1.1.
Polymerization system
Polymer (P) values
T(0C)
[M] D
Benzene
30-40
-20to -120 -35.3 to -144 - Ill
Isooctane
RT
Isooctane Isooctane Isooctane
Solvent
Monomer (M) or model compound (MC) values [M)0
Optical activity measured Solvent
T (0C)
Refs.
POLY(ALKENES)
Poly[(/?)(- )3,7-dimethyl-1 -octene] Al(Z-C4Hg)3ZTiCl4 Al(Z-C 4 H 9 ) 3/TiCl3 LiAlH 4/TiCl 4/monomer Poly[(S)( + )5-methyl-1 -heptene] Al(J-C4Hg)3ZTiCl3 Poly [(S)( + )4-methyl-l -hexenej Al(I-C4Hg)3ZTiCl4 Al(z-C4H9)3/TiCl3 Poly[(£)( + )6-methyl-1 -octene] Al(Z-C4Hg)3ZTiCl3 Poly[(S)( + )3-methyM-pentene] Al(Z-C4H9)3/TiCl4 Al(Z-C 4 Hg) 3 ZTiCl 3 Poly [(5)5-pheny 1-1-heptene] Al(Z-C 4 Hg) 3 ZTiCl 3 PoIy[Cff)4-phenyl-1 -hexene] Al(Z-C 4 H 9 ) 3 /TiCl 3
4,7
14.4 (MC) 14.4 (MC) 8.88 (MC)
Toluene Toluene Carbon tetrachloride
27.4-68.1
11.7 (MC)
Benzene
RT RT
205-288 149-279
21.3 (MC) 21.3(MC)
Benzene (MC); toluene (P) Benzene (P)
25 25
2-6,9
RT
16.0 20.4
13.3(MC) 13.3(MC)
Benzene
25
4 5
20-25
29.4-158
- 11.4 (MC)
Tetralin (P)
20-25
75.8-157 161
- 11.4 (MC)
Tetralin (P)
25 (P); 20 (MC) 2-6, 8,9 25 (P); 20 (MC) 5
-78.1
6.25
25 25 25
2-6
26.6
4.80 (M)
Cyclohexane (P); neat (M)
25
118
60
-61.6
- 8.99 (M)
Chloroform (P); neat (M)
25
118
Dioxane
60
-21.0
-21.0 (MC)
Dioxane
25
12
65 60 35 -70 -78
-46.1 -47.2 -47.4 -43.0 -47.2
Toluene Toluene Toluene Toluene Toluene
25 25 25 25 25
10
Benzene Toluene Toluene Toluene Dioxane
50-100 RT
23.4 17.9
55.5 (M) 42.2 (M)
Chloroform (P); neat (M) Dioxane
21 (P); 22 (M) 25
13 14
Dioxane
RT
15.3
37.4 (M)
Dioxane
30
13
Benzene
50 60
Benzene Chloroform (P); neat (M)
22 25
11 215
2,2,4-Trimethylpentane 25-60 2,2,4-Trimethylpentane
1.2. POLY(ACRYLICS) AND RELATED POLYMERS Poly(acryloyl-L-glutamic acid) AIBN Poly(L-bornyl acrylate) AIBN AIBN AIBN C 6 H 5 MgBr UV benzoin Po\y(d-sec-butyl a-chloroacrylate) BPO BPO Poly{d-sec-butyl a-bromoacrylate) BPO Poly(L-menthyl acrylate) AIBN AIBN
-79.0 -73.9
- 56.4 (M) - 56.4 (M) - 56.4 (M) - 56.4 (M) - 56.4 (M)
-99.3(M) - 88.3 (M)
PoIyU + ^-methyl-Af-a-methylbenzyl-acrylamidel AIBN Toluene n-BuLi Toluene C 6 H 5 MgBr Toluene Poly[( - W-propyl-N-a-methylbenzyl-acrylamide] Toluene AIBN Toluene /1-BuLi
(M) (M) (M) (M)
Benzene Benzene Benzene Benzene
25 25 25 25
29
- 167 -318
_ 444 (M) _ 444 (M)
Benzene Benzene
25 25
29
Toluene
20
10
-70.8
-50.1 (M) - 32.2 (M) -28.8(M)
EDC (P); ethanol (M) Benzene
25 20
23,24 25-27
- 8.6 (M)
Benzene
19
26
DCM
20
17,18
Benzene (M); methanol -0.01% CH3SO3H(P) Methanol- 0.01%CH3SO3H after 1 h Methanol-13%CH3SO3H
25
225
25
Benzene Chloroform Chloroform Benzene Benzene Chloroform
25 20 20 25 25 25
16,11
Dioxane
25
28
Water
20
119
Water
20
215
Dioxane
25
28
Water
20
222
Dioxane Dioxane Dioxane Dioxane (P); neat (M)
25 25 25 25
19-21
Chloroform (P); isooctane (M) 20 Chloroform (P); isooctane (M) 20
16,22
60 22 -50 -50
278 397 366 337
70 22
504 504 504 504
1.3. POLY(METHACRYLICS) AND RELATED POLYMERS Poly(L-bornyl methacrylate) 55 Benzene AIBN PoIy(1,2; 5,6-diisopropylidene-D-glucofuranosyl-3-methacrylate) Benzene 80 BPO 40-50 AIBN Benzene Poly(2,3 ; 4,6-diisopropylidene-L-sorbofuranosyl-1 -methacrylate) Carbon tetrachloride 60 AIBN PoIyK + M ,3-dimethylbutyl methacrylate] BPO 82-110 PoIyK + )(S)-diphenyl(l-methyl-pyrrolidin-2-yl)methyl methacrylate] DPEDA-Li/TMEDA Toluene -78
-49.0 -48.4 -84.5 18.2 780(LaJ 365 )
23.4 (MC) 30.9
43.5 (MC) -82.2(M)([aJ 365 )
-410(LaJ 365 ) 779(LaJ 365 ) Poly( 1 -menthyl methacrylate) AIBN Benzene BPO C 6 H 5 MgBr Toluene C 6 H 5 MgBr Toluene 7-Ray BuLi THF Poly(methacryloyl-D-alanine) AIBN Dioxane Poly(Af-methacryloyl-L-alanine) AIBN Dioxane Pory(N-methacryloyl-L-asparagine) AIBN Dioxane PoIy(methacryIoyl-L-glutamic acid) AIBN Dioxane Poly(s-N-methacryloyl-L-lysine] Potassium persulfate Water Poly( 1 -a-methylbenzy 1 methacrylate) UV AIBN UV benzoin /i-BuLi Toluene AIBN Dioxane Poly(2-methylbutyl methacrylate) BPO C 6 H 5 MgBr Toluene PolyL(5)4-methyl-2-M^V-dimethylaminopentyl methacrylate] AIBN Benzene
- 202 - 202 - 202 - 202 - 202
- 193 - 256.8 -158.9 - 177.0 - 194.0
55 40-85 RT -75 -75 -78
-96.9
60
42.0
48.9 (MC)
-42(La] 546 )
-41 (M) ([a]
546)
60
-24.4(La] 546 )
-36(MC)(La] 546 )
60
-23.0
- 26.0 (MC)
65
12.1
35 -65 -60 35
- 79,5 -72.5 -100
60
7(M) -151 -138 -190 -147
- 54.4 (M) - 54.4 (M) - 54.4 (M)
5.93 6.84
100 RT 2.2
(M) (M) (M) (M) (M)
- 103 (M) - 103 (M) - 103 (M) -78.8(M) 6.99 (M) 6.99 (M)
-2.1 (M)
Benzene
25
205
120
References page VII-739
TABLE 1.
cont'd
Polymer Catalyst or initiator
Polymerization system Solvent
PoIyK' + )phenyl-2-pyridyl-0-tolylmethyl methacrylate] /t-BuLi THF Diisopropyl peroxydicarbonate
Polymer (P) values
Toluene
Monomer (M) or model compound (MC) values
[M]D -78 40
395 -321 -617([aJ 365 )
[Ml0
Solvent
2T( 0 C)
Refs.
Benzene (M); THF (P) THF Chloroform(M); 90% chloroform-10% TFEL (P)
- 78 (P); 25 (M) 25 (P) 25
223
Chloroform (P); benzene (M) Chloroform (after heating at 600C) Chloroform (P); benzene (M) Chloroform (after heating at 600C)
25 25
224
25 25
224
- 47.6 (M) -47.6(M)
Chloroform Chloroform
25 25
121
- 37.7 (M) - 37.7 (M)
Chloroform Chloroform
25
121
-99.7 (M)
Chloroform
88.6 (M) 190.1 (M)(M 365 )
PoIvK + )phenYl-2-pyridyl-m-tolYlmethyl methacrylate I DPEDA-Li/(- )DDB Toluene
-78
-845(La] 365 ) 1481 (La] 365 )
14.0(M)(LaJ 3 6 5 )
DPEDA-Li/TMEDA
-78
262(LaJ 365 ) 1370(La] 365 )
14.0(M)(La] 365 )
Toluene
Optical activity measured
185
1.4. POLY(VINYL ETHERS), POLY(VINYL KETONES), POLY(VINYL ESTERS) 1.4.1. POLY(VINYL ETHERS) PoIyK- )(5)2,2/-bis(2-vinyloxyethoxy)-l,l/-binaphthyl] DCM 0 -131.6 SnCl4 Nitromethane 0 -131.9 BF 3 OEt 2 PoIyK- )(5)2,2/-bisl2-(2-vinyIoxyethoxy)ethoxy]-l ,1 '-binaphthylj -93.9 SnCl4 DCM O -95.8 BF 3 OEt 2 DCM O PoIyK-)(5)2,2 / -bisL2-(2-vinyloxyethoxy)ethoxy]-3,3 / ~dimethyl-l,r-binaphthyl] DCM O SnCl4 44.5 Poly( 1 -bornyloxyethylene) BF 3 OEt 2 PoIy(I -cholesteryloxyethylene) Poly( 1,2: 5,6-diisopropylidene-a-D-glucofuranosyl-3-oxyethylene) BF3 OEt2 n-Hexane + DCM -78 Poly( 1 -menthyloxyethylene) C 4 H 9 MgBr Toluene 80 BF 3 OEt 2 M-Hexane -78 SnCl4 Petroleum ether 25 Mn-MoO 3 -H 2 SO 4 /i-Hexane -10 Mn-MoO 3 -H 2 SO 4 Az-Hexane -30 A1(/-OC 3 H 7 ) 3 /H 2 SO 4 rc-Pentane - 15 to RT -198 BF 3 OEt 2 Toluene -78 -220 Poly( 1 -a-methy lbenzyloxyethylene) BF 3 OEt 2 Propane -78 Polyt(S)2-methylbutyloxyethylene] Al(Z-C 4 H 9 )Cl 2 Propylene + Toluene -78
25 25 (P); 29 (M) -142 -93
-122.4(M) - 131.4 (M)
5.7
-77.2
-358 -396 -373 -357 -353
- 121.9(M) -121.9(M) -121.9(M) - 118.8(M) - 118.8(M) - 72.2 (M) -61.5 (M)
68.6
-71.9 (M)
4.9
1.1 (MC) 7.6 (M) 1.1 (MC) 7.6 (M) 1.1 (MC) 7.6 (M)
A1(/-C 4 H 9 ) 3 /H 2 SO 4
Ether
15-20
-5.9
A1(/-OC 3 H 7 ) 3 /H 2 SO 4
Ethyl acetate
0-20
6.4
Benzene
245
25
31 31
EDC (P); ethanol (M)
25
36,24
Benzene (P); chloroform (M) Benzene (P) Benzene (P) Chloroform (M); benzene (P) Benzene (P) Neat (M); benzene (P) Toluene (M); benzene (P)
25 25 25 25 25 25 25 (P)
Benzene
25
35
Toluene (P); neat (M1MC)
25
34
Toluene (P)
25
Toluene (P)
25
31 33 123 124
Po Iy [(S) 1 -methylpropyloxyethylenej Al(Z-C 4 H 9 )Cl 2 Propylene -f Toluene -78 AI(Z-C 4 H 9 )SZH 2 SO 4 15-20 Diethyl ether Al(Z-OC 3 H 7 ) 3/H 2 SO 4 - 15 to RT rc-Pentane Polyl(S)2-phenylvinyl 2-methylbutyl ether] -78 BF 3 OEt 2 Toluene -78 SnCl4 Toluene Poly[(S)2-phenylvinyl 3-methylpentyl ether] BF 3 OEt 2 -78 Toluene SnCl4 Toluene -78 1.4.2. POLY(VINYL KETONES) Poly[(5)2-methylbutyl vinyl ketone] Spontaneous LiAlH 4 Toluene Poly[(S)3-methylpentyl vinyl ketone] Spontaneous Toluene LiAlH 4 Poly[(S) 1 -methylpropyl vinyl ketone] LiAlH4 Toluene Spontaneous Toluene AIBN Toluene LiAlH4 1.4.3. POLY(VINYL ESTERS) Poly(
Dioxane
246 206
13.24 (M) 13.67 (M)
285
13.8(M)
Toluene (P); neat (M) Toluene (P) Benzene (P); neat (M)
25 25 25
11.4 12.0
3(MC) 3 (MC)
DCM DCM
25 (MC) 25 (MC)
125
7.8 7.8
7.12(MC) 7.12 (MC)
DCM DCM
25 (MC) 25 (MC)
125
32 123
20-25 - 16 to 50
- 10.0 -43.0
11.5 (MC) 11.5(MC)
Chloroform (P); neat (MC) Chloroform (P)
25 25
30
20-25 0
15.6 11.7
15.2(MC) 15.2 (MC)
Chloroform (P); neat (MC) Chloroform (P)
25 25
30
0 RT 60 -15
-118 -42.5 -39.1 -139.0
33.4 (MC) 33.4 (MC)
25 25 25 25
30
44.08 (M) 44.08 (M)
Chloroform (P); neat (MC) Chloroform (P) EDC EDC
126
40
22.9
24.0 (M)
Benzene
50
40
100
-29.1
- 20.4 (M)
Dioxane
25
13
55
10.15
12.07 (M)
Dioxane
25
41
60 -78 0
-2.5 -6.2 -3.8
3.5 (M) 3.5 (M) 3.5 (M)
DCM (P); acetone (M) DCM (P) DCM (P)
25 25 25
127
-78 25 60
-13.4 -39.4 -21.4
-11.6(M) -11.6(M) - 11.6 (M)
DCM (P); heptane (M) DCM (P) DCM (P)
25 25 25
127
60 200
-14.5 -19.6 -12.2
- 7.5 (M) -7.5(M) -7.5 (M)
DCM (P); heptane (M) DCM (P) DCM (P)
25 25 25
127
76
9.57
13.97 (M)
Benzene (P); neat (M)
24.7
70
-8.5 to -11.0
2.70 (M)
Chloroform
20
1.5. POLY(STYRENES), POLY(CARBAZOLES) Poly(4-5£c-butoxymethylstyrene) BPO Dioxane Poly[(S)3-sec-butyl-9-vinylcarbazole] AIBN Benzene EtAlCl 2 Toluene C 7 H 7 SbCl 6 DCM Poly[(S)9-(2-methylbutyl)-2-vinylcarbazole] EtAlCl2 DCM n-BuLi THF AIBN Poly[(5)9-(2-methylbutyl)-3-vinylcarbazole] AIBN Benzene C 7 H 7 SbCl 6 DCM Poly[2-(2-thio-3-methylpentyl)styrene] AIBN Poly[p-(/?-tolylsulfinyl)styrene] Benzene AIBN
42 128
References page VII - 739
TABLE 1.
confd
Polymer Catalyst or initiator 1.6.
Polymerization system Solvent
T (0C)
Monomer (M) or model compound (MC) values [M]0
[M]0
Optical activity measured Solvent
:r (
0
C)
Rets.
POLY(DIENES)
Polyl 1 -(d-bornylammonium carboxylate)-1,3-butadieneJ AlBN Methanol 50 Poly[ 1 -((- ) 1 -cyclohexylethylammonium carboxylate)-1,3-butadiene] AIBN Methanol 50 Poly [(3£)(55)3,5-dimethyl-1,3-heptadieneJ K2S2O8 Aq. emulsion 55 Al(I-C 4 H 9 )SVTiCl 4 Benzene 25 Poiy[(3Z)(5S)3,5-dimethy 1-1,3-heptadiene] KaSiOg Aq. emulsion 55 AlO-C 4 H 9 J 3 ZTiCl 4 Benzene 25 PoIy[I-((- )menthy!oxycarbonyl)-1,3-pentadieneJ AlBN Benzene 50 PoIy[I -((5)(- )a-phenylethy!ammonium carboxylate)-1,3-butadiene] AlBN Methanol 50 Po\y[trans-(R)6-pheny\-1,3-heptadiene] Al(Z-C 4 Hg) 3 ZTiCl 3 rc-Heptane 25 AlEt3A^Cl3 rc-Heptane 25 w-BuLi w-Heptane 25 PolyUra/w-(/?)5-phenyl-1,3-hexadiene] A10-C 4 H 9 ) 3 /TiCl 3 n-Heptane 25 AlEt 3 ZVCl 3 /i-Heptane 25 n-BuLi rc-Heptane 25
1.7.
Polymer (P) values
14.4
6.8 (M)
Methanol
25
177
-3.6
- 3.7 (M)
Methanol
25
177
44.0 33.2
42.8 (M) 42.8 (M)
Benzene Benzene
20 (P); 25 (M) 20(P)
129
41.4 31.7
41.6(M) 41.6(M)
Benzene Benzene
20 (P); 25 (M) 20(P)
129
-71.3
- 84.5 (M)
THF (P); benzene (M)
25
190
-11.4
- 8.0 (M)
Methanol
20
178
-46.87 -45.82 -40.30
- 16.6 (M) -16.6(M) -16.6(M)
Benzene Benzene Benzene
25 (P); 15 (M) 25(P) 25 (P)
130
- 39.84 -42.86 - 37.54
- 18.74 (M) - 18.74 (M) - 18.74 (M)
Benzene Benzene Benzene
25 (P); 15 (M) 130 25(P) 25(P)
POLY(ISONITRILES)
Poly[((S)( 1 -(acetoxymethyl)ethy l)imino)methy lene] NiCI 2 -6H 2 O Methanol RT PoIyK(SX 1 -(acetoxymethyl)-2-methylpropyl)imino)methy lene J NiCl 2 6H 2 O Methanol RT Poly[((/?)(2-acetoxy-l-phenylethyl)imino)methylene] NiCl 2 6H 2 O Methanol RT Poly[(L-alanyl-(6>-acetyl)L-serine methylester)methylenej NiCl 0 -6H 2 O Chloroform
-190([M] 578 )
58.3 ([OCj 578)
74.0(M) ([MJ 57 S).
Chloroform
20-22
132
- i l l ([a].™) -172([M] 578 )
46.8 ([(X]578)
72.5 (M) [[M]5n)
Chloroform
20-22
132
-129 (M) ([M] 578 )
Chloroform
20-22
132
-58.1 (M)
Chloroform-methanol (5 :2) (P); chloroform (M)
20
231
-12.0(M)
Chloroform-methanol
20
231
40.6 (La] 578)
Chloroform
22
249
18.6 ([a]578)
Chloroform
22
249
-13.5(M)
Chloroform-methanol (5:2) (P); chloroform (M)
20
230
-82(IaJ 5 7 8 ) 205
Poly[(L-alanyl-(O-acetyl)D-serine methylester)methylenej -33 NiCl 2 -6H 2 O Chloroform Poly[(L-alanyl-(Af(Im)-tosyl)L-histidine methylester)methylenej NiCl 2 -6H 2 O Chloroform/Methanol RT 144(Ia] 578 ) Poly[(D-alanyl-(Ar(Im)-tosyl)L-histidine methylester)methylenej NiCl 2-6H 2 O Chloroform/Methanol RT -170 (N 578 ) Poly[(L-alanyl-(/V(Im)~tosyl) L-histidyl-(O-acetyl)L-serine methylester)methylenej -58.9 NiCl 2 6H 2 O Chloroform
-156([M] 5 7 8 )
-68.5
([a]578)
Poly[(L-alanyl-(A^(Im)-tosyl)L-histidyl-(O-acetyl)D-serine methylester)methylene] NiCl 2 6H2O Chloroform - 29.3 Poly[(D-alanyl-(Af(Im)4osyl)L-histidyl-(0-acetyl)L-serine methylester)methylene] NiCl 2 6H 2 O Chloroform -8.0 Poly [ ((S)( 1 -benzylethyl)imino)methylene] NiCl 2 -6H 2 O Methanol RT 15 (La] 578 ) PolyL(((5)l-(ferf-butoxycarbonyl)-2-methylpropyl)imino)methylene] NiCl 2 45 32.5 Poly[((S)( 1 -carbethoxyethyl)imino)methylene] NiCl 2 6H 2 O RT -280(La] 5 7 8 ) Poly [(((1S ,2S) 1 -carbomethoxy-2-methylbutyl)imino)methy lene] NiCl 2 45 -32.2 Poly[((S)(— )a-cyclohexylethylimirio)methylene] NiCl 2 -6H 2 O Neat 65 -295 Poly[(((S)2,2-dimethyl-13-dioxolane-4-yl)methylimino)methylene] NiCl 2 6H 2 O RT 68.5(La] 546 ) Poly [(((R) 1,2-dimethylpropyl)imino)methylene] NiCl 2 -6H 2 O Methanol RT 16.7(La] 578 ) Poly[((/?)(2-(diphenyl phosphinyl)propyl)imino)methylene] NiCl 2 -6H 2 O Methanol RT -338(La] 578 ) PoIyK(SX 1 -ethyl-2-propenyl)imino)methylene] NiCl 2 -6H 2 O Methanol RT 29(La] 578 ) PoIyK(SX 1 -ethyl-2-propynyl)imino)methylene] NiCl 2 -6H 2 O Methanol RT -HO(La] 5 7 8 ) PolyL(((S)l-(isopropyloxycarbonyl)-2-methylpropyl)imino)methylene] NiCI 2 5 -24 Poly[((-)menthylimino)methyleneJ NiCl 2 -6H 2 O Methanol 65 -207 Poly [(((S) 1 -(methoxycarbonyl)-2-methylpropyl)imino)methylene] NiCl2 RT -UO Poly[((/?)3-methyl-2-butyl)imino)methylene] NiCl 2 -6H 2 O Methanol RT -16.7 ([a]578) Poly[((i?)4-methyl-2-pentyl)imino)methylene] NiCl 2 6H2O RT 62([aJ 578 ) Poly[((/?)2-octylimino)methylene] NiCl 2 -6H 2 O Methanol RT 34 (M 578 ) Poly[(d-a-phenylethylimino)methylene] DBP-O2 Heptane 60 365 Poly[(l-a-phenylethylimino)methylene] H 2 SO 4 -O 2 Heptane 50 -382 NiCl 2 -6H 2 O 0-5 -350 (M 578 )
20
230
Chloroform-methanol (5:2) (P); chloroform (M)
20
230
Chloroform
20-22
132
Chloroform
20
236
Chloroform
20-22
132
Chloroform
20
236
THF (P); hexane (MC)
24 (P); 20 (MC) 209
38.5(M)(La] 5 4 6 )
Dioxane
25
227
-24.2 (M) (La) 578 )
Chloroform
22
236
(M)
9.2 (M)
22(LM] 5 7 8 )
48.7(LaJ 5 7 8 )
70.6(M)(LM] 5 7 8 )
29.5 (M) -355([M] 578 )
16.7 (LaJ 578 )
21.2(M)(LM] 5 7 8 )
35.0 (M) 27.4 (MC)
-910([M] 578 )
13.1 (La]578)
35.3 (M) ([M]578)
Chloroform
20-22
132
27.6(LM] 578 )
95 (La] 578 )
90.2 (M) ([M]578)
Chloroform (P); neat (M)
20
132
-102(LM] 5 7 8 ) -12.8 ([a]578)- 11.9(M)(LM] 5 7 8 )
Chloroform (P); neat (M)
20-22
132
Chloroform
20
236
Hexane
25 (P); 20 (MC) 209
Chloroform
20
236
- 16.2 (LM] 578 ) -24.2(La] 578 )- 23.5(M)(LM] 5 7 8 )
Chloroform
22
131
68.9([MJ 578 )
-61.9 (La] 578 )- 68.8(M)(LM] 578 )
Chloroform
22
131
47.3 ([M]578)
-47.6
Chloroform
22
131
Toluene
27
39
Toluene Chloroform (P); methanol (M)
27 20
39 132
n-Heptane (P); neat (MC)
25
133
-68.8(M)
Chloroform
20
197
5.90 (M)
Chloroform
20
197
32.7 (M) - 106.4 (MC) 5.5 (M)
(La] 578 )- 66.3(M)(LM] 5 7 8 )
37.2 (M)
-458([M] 578 )
- 35.8 (M) -40.9
-179.7(M) 55.0(M)(LM] 578 )
POLY(ALKYNES)
Poly[(S)3,4-dimethyl-1 -pentyne] Al(Z-C 4 H 9 ) 3/Fe(AcAc) 3 n-Heptane Poly [p-(L-( - )-menthoxycarbonyl)phenylacety lene] [Rh(norbornadiene)Cl] 2 Triethylamine Poly [/?-((-f )-2-methylbutoxy)phenylacetylene] [Rh(norbornadiene)Cl] 2 Triethylamine
20-35 RT RT
42.2 (MC)
470 -605 19.2
6££-IIA 3^d S90U3J9J9H
1.8.
Chloroform -methanol (5 :2) (P); chloroform (M)
-2.1
TABLE 1. cont'd Polymer Catalyst or initiator Poly [(S)4-methyl-1 -hexyne] Al(Z-C 4 H 9 ) 3/Fe(AcAc) 3 AlO-C 4 H 9 ) 3/Fe(AcAc) 3 Poly[(S)5-methyl-1 -heptyne] Al(I-C 4 Hg) 3 ZFe(AcAc) 3 Poly[(5)6-methyl-1 -octynej Al(i-C 4 H 9 ) 3 ZFe(AcAc)3 Poly [(S)3-methyl-1 -pentynej Al(Z-C 4 H 9) 3/Fe(AcAc) 3
Polymerization system Solvent
T(0C)
Isooctane w-Heptane
20-30 20-35
^-Heptane
Polymer (P) values WD
[M] D
Monomer (M) or model compound (MC) values MD
[M]D
Optical activity measured Solvent
T( 0 C)
Refs.
-10.6
- 3.0 (MC)
Isooctane >2-Heptane (P); neat (MC)
25 25
133
20-35
-146
12.2(MC)
n-Heptane (P); neat (MC)
25
133
n- Heptane
20-35
-34
13.7(MC)
rc-Heptane (P); neat (MC)
25
133
/7-Heptane
20-35
498
32.1 (MC)
/i-Heptane (P); neat (MC)
25
133
THF (P); ethanol (M) THF (P) THF (P)
25(P) 25(P) 25(P)
-2.97 (MC)
-22.9
1.9. POLY(MALEIMIDES) AND RELATED POLYMERS Poly(AMx>myl maleimide) BPO THF 50 AIBN THF 50 n-BuLi THF 50 Poly[A^(cholesteroxycarbonylmethyl)maleimide] AIBN THF 70 «-BuLi THF 0 Poly(/V-maleoyl-L-alanine) AIBN THF 60 Poly(/V-maleoyl-L-phenylalanine) AIBN THF 60 Poly[7V-maleoyl-L-phenylalanine ethyl esterj AIBN Dioxane 60 BuLi THF 0 Poly[Ar-((N/-((Z?)-a-methylbenzyl)aminocarbonyl)methyl)maleimideJ AIBN DCM 70 Polyt/V^./V'^^-a-methylbenzyOaminocarbonyl-fz-pentyl) maleimide] AIBN Dioxane 60 Poly[Ar-(4^/-((/?)-a-methylbenzyl)aminocarbonylphenyl)maleimideJ AIBN THF 50 rc-BuLi THF 0 Poly[A^-(4-A^'-((5)-a-methylbenzyl)aminocarbonylpheny))ma]eimideJ AIBN THF 50 Poly[W
43
8.4 10.1 -9.1
-9.6(M) -9.6(M) -9.6(M)
-25.9 -37.1
- 26.8 (MC) - 26.8 (MC)
THF THF
RT RT
203
-42.1
-49.9(MC)
THF
25
201
-144.1
-138.3(MC)
THF
25
201
- 120.0 - 222.0
-136.3(MC) -136.3 (MC)
THF THF
25 25
252
59.9
115.5 (MC)
THF
25
200
50.1
56.6 (MC)
THF
25
183
-141.4 -78.0
- 26.9 (MC) - 26.9 (MC)
THF THF
25 25
192
163.4
28.9 (MC)
THF
25
206
44.6
44.8 (MC)
THF
25
183
56.7
55.3 (MC)
THF
25
233
11.1-13.0
57.9 (M)
THF
25
137
-69.7 -65.2
-106.8(MC) -106.8 (MC)
THF THF
25 25
187
1.10.
OTHERCOMPOUNDS
Poly [(2,2/-bis(hexyloxy)-1,1 '-binaphthyl-6,6 '-ylene)-1,4-phenylenevinylene-1,4-phenylenevinylene-1,4-phenylene] Pd(PPh 3 )4 THF/K2CO3(aq.) -351 35.6 (M) Poly(bis-2-methylbutyl itaconate) 4.92 4.97 (M) RT 5.57 (M) 4.75 BPO 40-85 PoIy[A/ 3-( 1,2-diethoxycarbonylethyl)ureidoethylene] 24.3 63.1 43.5 (M) AJBN Benzene 60 31.7 82.0 43.5 (M) PoIy[N3 -(1,3-diethoxycarbonylpropyl)ureidoethyleneJ 21.6(M) AIBN Benzene 60 7.83 21.3 Poly[(/?)3,7-dimethyloctanal divinylacetal] AIBN 80 3.18 7.19 2.48 (MC) BF 3 OEt 2 -78 -6.78 -14.32 2.48 (MC) PoIy[Af3 -(1 -ethoxycarbonyl-3-methylbutyl)ureidoethylene] AIBN Benzene 60 0.5 t.l 20.3 (M) Poly(ethylidene-l-propenylidene) (from (#)2,3-pentadiene) 7i-allyl-Ni-iodide - 20 -232.10 -47.39 (M) Poly(L-menthyloxycarbonylaminoethylene) AIBN 95 AIBN Benzene 60 y-ray Benzene 22 tert-BuOOH SO2 -25 Poly[Ar-(4-Af/-((/?)-a-methylbenzyl)aminocarbonylphenyl)itaconimide] AIBN THF 60 Poly[( - )3-((3-styryloxy)menthane] BF 3 OEt 2 DCM -72 Poly[iV-(/?-(/?-tolylsulfinyl)phenyl)-2,5-dioxo-pyrrolidin-3,4-diyl] BPO THF 60 Poly(m-tolyl vinyl sulfoxide) rc-BuLi/(- )-sparteine Toluene - 78 Poly(/7-tolyl vinyl sulfoxide) rc-BuMgBr THF 30 Poly[(S) Af-vinyl-3-methyl-2-pyrrolidone] AIBN Water 95
TABLE 2.
-60.4 -60.4 -58.5 -66.2
-136.0 -136.0 -131.8
- 79.9 (M) - 79.9 (M) - 79.9 (M) - 79.9 (M)
166
THF (P); DMSO (M)
112.5 (M) 112.5 (M)
58.9 (M)
46.3 (M) -179.7 (M) - 179.7 (M) - 179.7 (M) - 179.7 (M)
15 16
Heptane
20
Dioxane Benzene
25 25
38
Benzene
25
38
Chloroform Chloroform
25 25
72
Benzene
25
38
Carbon tetrachloride (P); neat (M)
25
243
Benzene Benzene Benzene Benzene
25 25 25 25
38
52.1
-23.8(MC)
THF
25
191
- 114
- 15.9 (M)
THF
25(P)
122
-22.0
- 25.9 (M)
Chloroform
20
135
311
486 (M)
194
443 (M)
Acetone
23
134
28
69.3 (M)
Methanol (P); benzene (M)
25
136
246
MAIN-CHAIN ACYCLIC HETROATOM POLYMERS
Polymer Polymerization system Catalyst or Initiator 2.1. POLY(OXIDES) Poly[(/?)( + )citronellal] Al(i-C 4 H 9 )3 n-BuLi BF 3 OEt 2
Polymer (P) values T (0C)
Solvent
Ether rt-Hexane Ether
-78 — 78 -78
WD
[M] D
-82.7 to -90.1-127 to -139 -91.1 -140 -89.5 -138
Monomer (M) or model compound (MC) values HD
[M]D
11.2(MC) 11.2(MC) 11.2(MC)
Optical activity measured Solvent
Chloroform Chloroform Chloroform
T (0C)
25 25 25
Refs.
44
References page VII - 739
TABLE 2.
confd Polymer (P) values
Polymer Polymerization system Catalyst or Initiator Poly(D-oxy-2,3-dimethylethylene) AlO-C4H9) 3/H2O
Solvent n-Heptane
Poly[(/?)( + )oxy-5-methoxy-3-methyl-hexylidene] ZnEt 2 n-Hexane Poly[(/?)oxy-2-methylbutylidene] ZnEt2 n-Hexane Poly[( + )oxy-l-methyl-2-carbomethoxyethylene] BF3 OEt3/AlEt3 Poly[oxymethylene-(/?,/?)-dibenzo-19-crown-6] KOH DMSO Poly [oxymethylene-(S,S)-dibenzo-19-crown-6] KOH DMSO Poly(L-oxypropylene) KOH
T( 0 C)
[M] D
[M]D
58.8 (M)
-78 52.8
2.47 (M)
8.24 (MC)
Optical activity measured Solvent
T( 0 C)
Refs.
Benzene or chloroform (P); neat (M)
25
47
Chloroform
25
45
-75
36.7
-75
36.7
30.7 (M)
Chloroform
25
45
25
- 36.9
24.6 (M)
DCM (P); neat (M)
25
48
1.22 (M) ([a]435)
Chloroform
25 (P); 24 (M)
208
Chloroform
25 (P); 28 (M)
208
Benzene (P); ether (M) Chloroform (P) Benzene (P) Chloroform (P) Cyclohexane (P); neat (M) Benzene (P) Benzene (P); ethyl ether (M) Dibutyl ether (P)
20 (P); 21 (M) 20(P) 20(P) 20(P) 25 25 25 (P); 27 (M) 25(P)
46
Chloroform Chloroform
25 20
51 175
Cyclohexane Chloroform
20 (P); 25 (M)
52 140
DCM (P); chloroform (M)
20 (P); 25 (M)
140
TFEL
25
49
Benzene
25
49
TFEL
25
53
TFEL (P); chloroform (M)
25
53
TFEL (P1MC); chloroform (M)
25
53
Fuming sulfuric acid
25
237
RT RT
-6.0(M435)
-1.07 (M) ([a]435)
RT
-16±5 25±5 -20±5 25 ±5 24.9 -32.0
15(M) 15(M) 15(M) 15 (M) 11.55(M) 11.55(M) 15.0 (M) 15.0(M)
FeCl 3 -monomer
Ether
RT
ZnEt2/CH3OH
Benzene
33
Ferric acetate hydroxide
Heptane
70
2.2.
WD
Monomer (M) or model compound (MC) values
-9.50 7.36
138 139
POLY(ESTERS)
Poly[L(— )oxycarbonylethylidene] 175-195 -153.3(M 578 ) ZnCl 2 Heptane -275.8 (M) (M578) - 19.2 (M) Pyridine Pyridine 20 - 140.0 Poly(L-oxycarbonylisobutylidene) -50(MC) 180-190 ZnO -20 - 256(M) -67 180-190 ZnO Poly(L-a-oxycarbonylisopentylidene) - 226 (M) 175 -50 ZnO Poly[(/?)( -f )oxycarbonyl-3-methylhexamethylene] 0.94 (M) 215 8.55 Sb2O3/Zn(CH3COO)2 Poly [(/?)(-)oxycarbonyl-3-methylhexamethyleneJ 215 -0.96(M) 3.36 Sb2O 3/Zn(CH3COO) 2 Poly[(/?)(- )oxycarbonyl-2-methylpentamethylene] (Poly [(/?)(- )-(3-methylcaprolactone]) A10-C 4 H 9 ) 3 /H 2 O Benzene 50 32.57 (M450) 29.78 (MC) (M350) Poly[(/?)oxycarbonyl-3-rnethylpentamethylene] AlO-C 4 Hg) 3 ZH 2 O Benzene 50 26.95 (M450) 51.77 (M) Poly[(/?)oxycarbonyl-4-methylpentamethylene] A10-C4H9)3/H2O Benzene 50 8.78 (M450) - 15.91 (MC) (M350) -36.11 (M) Poly[oxycarbonyl-1,4-phenylene-oxyterephthaloyloxy-1,4-phenylene-carbonyloxy-OS1) 1 -methylethylene] EDC Reflux 42
22.3 (M)
Poly[oxycarbonyl-1,4-phenylene-oxyterephthaIoyloxy-1,4-phenylene-carbonyloxy-1,2-bis(2,2-dimethyl-1,3-dioxolane-4-yl)ethyleneJ DCM 85 228 4.0 (M) Poly(D-oxycarbonylpropylene) AIEt 3 Ether RT 19 (LaJ 300 ) Natural polymer 44 ([a] 3Oo) Poly(oxycarbonyl-1,2,3-trimethoxytetramethylene) (Poly(2,3,4-trimethyl-1 -arabonolactone)) CH3COC1/HC1 RT 39 QaJ 546 ) 203.5 (M) (LaJ 546 ) Poly[oxyisophthaloyloxy-(2-acetamide-1 -phenyl)trimethylene] Chloroform 60 - 30.8 24.9 (M) Poly foxy terephthaloyloxy-( 1 /?,3/?)-1,3-dimethyltrimethyleneJ EDC 82 -295 -136(MC) Poly[oxyterephthaloyloxy-( 1 -methyl-3-oxo)trimethylene-oxyethyleneoxy-(3-methyl-1 -oxo)trimethylene-oxycarbony IJ DCM Reflux -62 -41.8(M)
Dioxane (P); methanol (M)
25
Chloroform Chloroform
226 50
Benzene
21
54
DMF (P); methanol (M)
25
167
Chloroform
25
202
Chloroform
25
189
Benzene (P); neat (M) Benzene (P); neat (M)
25 25
142
Benzene
25
232
DMF
24 (M)
143
2.3. POLY(SULFIDES), POLY(THIOESTERS) Poly(terf~butyl thiirane) tert-BnOK DMSO RT ZnEt 2 Toluene RT Poly [thio-1 -(yV-^j^c-butyl-^-methylaminomethyOethyleneJ ZnEt2/methanol RT PolyL(5)thio(carbonyl)-l-(p-chlorobenzenesulfonamide)ethyleneJ PhCH2SH DMF 25 Poly[(/?)thio(carbonyl)-1 -methyl-1 -ethylethylenej Tetrabutylammonium versatate 100 Poly[(1S)thio(carbonyl)-l-(/?-methyloxybenzenesulfonamide)ethyleneJ PhCH2SH DMF 25 Poly[(/?)(-)thiocarbonyl-3-methylpentamethyleneJ «-BuLi RT PolyL(/?)( + )thiocarbonyl-2-methylpentamethylene] AZ-BuLi 190 PolyL(5)thio(carbonyl)-1 -(p-nitrobenzenesulfonamide)ethylenej PhCH2SH DMF 25 Poly[thio(carbonyl)-1 -tosylaminoethylenej PhCH2SH DMF 25 112 PolyL(- )thiopropylenej BF 3 OEt 2 KOH
DCM -
15
268 231-240
- 39.0 (M) - 39.0 (M)
26.1 - 85.52
- 11.08 (M)
151.7
56.9 (M)
Benzene
23 (P); 26 (M)
141
- 92.44
25.25 (M)
DMF
20(M)
143
-5.39
-3.21 (M)
Dioxane
25
57
15.66 18.62
9.03 (M)
Dioxane THF
25 25
57
-100.25
-46.01 (M)
DMF
28 (M)
-90.6 -80.6
19.87 (M) 19.87 (M)
DMF DMF
-62.8 - 126.9 -189 -159
-32.6 (M) 32.6 (M) - 35 (MC) - 35 (MC)
DCM Chloroform Chloroform Benzene (P)
143 143
22 22 18(P); 20(MC) 18(P)
55 56
2.4. POLY(URETHANES), POLY(UREAS) 2.4.1. POLY(URETHANES) Poly[oxycarbonylimino-(l-ethoxycarbonyl)pentamethyleneiminocarbonyloxyethyleneJ Neat 140-160 -12 Poly[oxycarbonylimino-(L)2-isobutylethylene-ureylene-(L)l-isobutylethylene)J Na 2 CO 3 H2O/THF <0 -48.2 Poly[oxycarbonylimino-(L)2-isobutylethyIene-ureyIene-(L)l-isopropylethylene)J Na 2 CO 3 H2O/THF <0 -27.2 PolyLoxycarbonylimino-(L)2-isobutylethylene-ureylene-(L)l-methylethylene)J Na 2 CO 3 H2O/THF <0 -19.2
174
DMSO Methanol
20
63
Methanol
20
63
Methanol
20
63
References page VII - 739
TABLE 2.
cont'd
Polymer
Catalyst or Initiator
Polymerization system
Solvent J( 0 C)
[a]D
Polymer (P) values [M]D
Monomer (M) or model compound (MC) values
MD
[M] D
Polyfoxycarbonyliminomethylene-1,3-phenylenemethy lene-urey lene-( 1 -(methoxymethyl)-2-phenyl)ethyleneJ Dibutyltin dilaurate DMSO 80 20.48 15.20 (MC) Poly[oxycarbonyliminomethylene-l,3-(I,5,5-trimethyl)cyclohexylene-iminocarbonyloxy-2,3-bornanediyl] Methyl ethyl ketone 80 - 7.4 - 11.67 (MC) Poly[oxycarbonylimino-(D)2-methylethylene-ureylene-(L)l-isobutylethylene)J Na 2 CO 3 H2O/THF <0 -54.7 Poly[oxycarbonylimino-(L)2-methylethylene-ureylene-(L)l-isobutylethylene)J Na 2 CO 3 H2O/THF <0 -47.9 Poly[oxycarbonylimino-(D)2-methylethyiene-ureylene-(L)l-isopropylethylene)] Na 2 CO 3 H2O/THF <0 -53.2 Poly[oxycarbonylimino-(L)2-methylethylene-ureylene-(L)l-isopropylethylene)j Na 2 CO 3 H2O/THF <0 -26.0 Poly[oxycarbonylimino-(D)2-methylethylene-ureylene-(L)I-methylethylene)J Na 2 CO 3 H2O/THF <0 - 16.0 Poly[oxycarbonylimino-(L)2-methylethylene-ureylene-(L)l-methylethylene)] Na 2 CO 3 H2O/THF <0 -50.0 Poly[oxycarbonylimino-1,4-phenylenemethylene-1,4-phenylene-ureylene-( l-(methoxymethyl)-2-phenyl)ethyleneJ - 8.72 (MC) Dibutyltin dilaurate DMSO 80 -14.40 Poly[oxycarbonylimino-2,4-toluyleneiminocarbonyloxy-(2-acetamide-l-phenyl)trimethylenej Chloroform 75 -20.6 -38.6 (MC) Poly[oxycarbonylimino-2,4-toluyleneiminocarbonyloxy-2,3-bornanediylJ Methyl ethyl ketone 80 - 27.6 - 14.8 (MC) 2.4.2. POLY(UREAS) Poly[((/?)5-ethyl-l,3-diazolidin-2-one-l,3-diyl)ethyleneoxyethylene] Methyl iodide Benzonitrile 150 -19.4 Poly[((/?)5-ethyl-1,3-diazolidin-2-one-1,3-diyl)methylene-1,2-phenylenemethylenej Methyl iodide Benzonitrile 150 -28.0 Poly[((/?)5-ethyl-l,3-diazolidin-2-one-l,3-diyl)tetramethyleneJ Methyl iodide Benzonitrile 150 -54.0 PoIy[((S)5-isopropyl-1,3-diazolidin-2-one-1,3-diyl)tetramethylene] Methyl iodide Benzonitrile 150 -40.5 Poly [((S)5-phenylmethyl-1,3-diazolidin-2-one-1,3-diy l)tetramethylenej Methyl iodide Benzonitrile 150 -71.4 2.5.
Optical activity measured Solvent
T( 0 C)
Refs.
DMSO
25
168
DMF
30
216
Methanol
20
63
Methanol
20
63
Methanol
20
63
Methanol
20
63
m-Cresol
20
63
m-Cresol
20
63
DMSO
25
168
DMF
25
167
DMF
30
216
39.4 (M)
Chloroform
24
250
32.1 (M)
Chloroform
24
250
38.8 (M)
Chloroform
24
250
- 34.4 (M)
Chloroform
24
250
32.0 (M)
Chloroform
24
250
POLY(AMIDES)
Poly [iminocarbonyl-l,2-(3,4-bis(2-hydroxypheny l))cy clobutylenecarbonyliminohexamethylene] DMAc 80 -241 Poly(iminocarbonyl-l,2-(3,4-bis(2-hydroxyphenyl))cyclobutyienecarbonylimino-i,4-phenyleneJ DMAc 80 - 358 Polyfiminocarbonyl-l,2-(3,4-bis(2-methoxyphenyl))cyclobutylenecarbonyliminohexamethylenej Benzyltriethylammonium chloride 1.OM NaOH/chloroform RT —70.3 Polyjiminocarbonyl-1,2-(3,4~bis(2-methoxyphenyl))cyclobutylenecarbonylirnino-1,4-phenylenej Benzyltriethylammonium chloride 1.0MNaOH/chloroform RT 5.7 Poly(/ra«$-iminocarbonyl-1,2-cyclohexyIene) Triethyiamine DMF 60 75.2-84.8
-295 (MC)
DMAc
235
- 456 (MC)
DMAc
235
-81.0 (MC)
m-Cresol
20
218
- 32.7 (MC)
DMAc
20
218
- 60.0 (MC)
DCA (P); ethanol (M)
20
144
Poly [iminocarbonyl-( 15,25) 1,2-rrans-cyc!ohexylene-carbonylirninoethylene] DMAc 56.5 Poly[iminocarbonyl-( 15,25) 1,2-fratts-cyclohexylene-carbonylimino-1,4-phenylene] DMAc 239 Poly[imino-((25,35)-2,3-dimethoxytetramethylene)-imino-(l,4-dioxotetramethylene)] Chloroform 50 -14.1 Poly [irnino-( 1,5-dioxohexamethylene)imino-( 1 R,2R) 1,2-rra«$-cyclohexylene] DMAc 65.4 PoIy[iminoethy!ideneimino-(2,3-dimethoxy-l,4-dioxo)tetramethyleneJ Chloroform RT 175.2 Poly[threo-imino-( 1 -oxo-2,3-dimethyltrimethylene)J AT-Pyrrolidone DMSO 25 -25.0 Poly[(5)imino-( 1 -oxo-3-ethyltrimethylene)] (Poly[(5)p-aminovalerate]) AT-Pyrrolidone DMSO 25 -32.7 PoIyK- )imino-(l-oxo-3-methylhexamethylene)] H2O 200 39.7 NaH 160 43.07 Poly[( 4- )imino-(l-oxo-4-methylhexamethylene)j NaH 150 19.24 Poly[( -I- )imino-(l-oxo-5-methylhexamethylene)j NaH 194 25.15 Poly[( -f )imino-( 1 -oxo-3-methyl-6-isopropylhexamethylene)] ^-C6H5COCl 150 9.5 Poly[(5)imino-( 1 -oxo-3-methyltrimethylene)] (Poly[(5)-P-aminobutyrate]) tf-Pyrrolidone DMSO 25 -9.3
DCA (P); acetone (M)
25 (P); 20 (M)
221
19.4(M)
DCA (P); acetone (M)
25 (P); 20 (M)
221
- 8.2 (M)
Formic acid (P); chloroform (M)
23
184
- 33.4 (M)
DCA (P); water (M)
25 (P); 20 (M)
221
- 38.25 (M)
Formic acid (P); chloroform (M)
23
199
-50.6(M)
TFA (P); neat (M)
25
62
- 2.4 (M)
DCA (P); neat (M)
25
62
Cresol (P); water (M) Cresol (P); water (M)
25 25
59,60
TFEL
25
TFEL
25
- 53.6 (M)
Formic acid
19
- 8.3 (M) - 8.3 (M) - 8.3 (M)
TCA (P); neat (M) DCA (P) TCA-chlorobenzene (P)
25 25 25
62
25(M)
DCA (P); neat (M)
25
62
-33.4(M)
DCA (P); water (M)
25 (P); 20 (M)
THF
21
-36.15 (M) -36.15 (M)
61 61 61 58 -26.1 -33.5
Poly t(/?)imino-( 1 -oxo-3-vinyltrimethylene)] tf-Pyrrolidone DMSO 25 -19.5 Poly [iminoterephthaloylimino-( 1 R,2R) 1,2-fra/w-cyclohexylene] DMAc Poly[(-f)iminoterephthaloylimino-2,8-naphthylene-8,2-naphthyleneJ
19.4 (M)
-211
66.6 (MC) ([a]578) -15(M 5 7 8 ) Poly[methyliminocarbonyl-l,2-(3,4-bis(2-hydroxyphenyl))cyclobutylenecarbonyl-methylimino-hexamethylene] DMAc 80 -437 Poly[A^-(phenylethylidene)iminoethylene-A^-(phenylethylidene)iminoterephthaloyl] -74 ([a]289) -294 (M 289 ) Poly[A/-(phenylethylidene)iminohexamethylene-N-(phenylethylidene)iminodipicolinoyl] -139(M 289 ) -610(M 2 8 9 ) PoIy[1,4-piperazinediylcarbonyl-1,2-(3,4-bis(2-hydroxyphenyl))cyclobutylenecarbonyl] DMAc 80 116 Poly[ 1,4-piperazinediylcarbonyl-1,2-(3,4-bis(2-methoxyphenyl))cyclobutylenecarbonyl] Benzyltriethylammonium chloride 1.0 M NaOH/chloroform RT - 40.7 - 83.0 (MC) O2N NO2
H3C CH3 (- ) R = 1,2-phenylene ( + ) R = 1,3-phenylene ( + ) R = 1,4-phenylene
- 4.94 - 0.50 6.53
- 474 (MC)
-391 (MC)
221 71 235
DMAc 20
70
20
70 235
DMAc DMAc
20
218
5% LiCl-DMF 5% LiCl-DMF 5% LiCl-DMF
20 20 20
73 73 73
References page VII-739
TABLE 2.
confd Polymerization system
Polymer Catalyst or Initiator
T (0C)
Solvent
(-) R = 1,2-pyrazolidene (- ) R = 2,5-dimethyl-l ,4-piperazinediyl Cl
Polymer (P) values
Monomer (M) or model compound (MC) values [M]D
[M]0
Optical activity measured Solvent
r(°C)
Refs.
5.4
TFEL
20
73
28.0
TFEL
20
73
5% LiCl-DMF 5% LiCl-DMF 5% LiCl-DMF TFEL TFEL TFEL
20 20 20 20 20 20
73 73 73 73 73 73
Chloroform (P); neat (M)
25
229
Chloroform(P); ethylether (M) 25
228
Chloroform
25
64
TFA
25
182
Chloroform
25
65
Cl
+COHQMQ)- CONH-R-NHi1 CH3 CH3 (-) R=l,2-phenylene (-) R=l,3-pnenylene ( ) R = 1,4-phenyiene (-) R = 1,2-piperazinediyl ( — ) R = 1,4-piperazinediyl (-) R = 2,5-dimethyl-1,4-piperazinediyl 2.6.
-19.6 -19.4 -18.2 -6.7 -10.0 -6.7
POLY(ISOCYANATES)
Poly [((R) 1 -deuterio-1 -hexyl)iminocarbonyl] NaCN DMF - 58 Poly[(((S)2,2-dimethyl-1,3-dioxolane-4-yl)methyl)iminocarbonyl] NaCN DMF - 65 Poly((5)( + )Ar-(2-methylbutyl)iminocarbonyl] NaCN DMF - 75 Poly[AH3-methyl-1 -carbomethoxybutyl)iminocarbonyl] Methyllithium DMF - 50 Poly [d- Af-(phenylpropyl )i minocarbony 1 ] NaCN DMF RT
2.7.
-367
0.65 (M)
-311 (M546)
-21.1 (M)(M 546 )
160
180.8
3.08 (M) - 6 (MC)
- 10.3 (MC)
62 -468.0
- 754.8
35(M) 114.4(MC)
44.8 (M)
POLY(IMINES)
Poly(D-conidine) BF 3 OEt 2 Ether Poly(L-conidine) BF 3 OEt 2 Ether Poly[(S)decyliminoisobutylethyIene] BF 3 OEt 2 Neat Poly[(/?)ethyliminoethylethylene] BF 3 OEt 2 Neat Polyfimino-1 -butyl-(/?)2-ethylethyleneJ BF 3 OEt 2 Poly [imino-1 -(/?)2-diethylethylene] BF 3 OEt 2 Poly[(/?)imino-2-ethylethylene] BF 3 OEt 2 -
RT
- 140.8
71.7(M)
Chloroform
69
RT
140.8
-71.0(M)
Chloroform
69
-78
-68.6
17.9 (M)
-78
155.13
-41.80(M)
98-100
137.66
2.73 (M)
Benzene (P); ethanol (M)
98-100
155.13
-20.33(M)
Dioxane (P); ethanol (M)
25
100
-127.4
17.6(M)
Benzene (P); neat (M)
23 (P); 18(M)
Benzene (P); ethanol (M)
19-21
173
Dioxane (P); methanol (M)
25
234 145 145 67
AlCl3 From (/?)-2-amino-1 -bromobutane Poly[imino-(/?)2-ethyl-1 -pentylethylene] BF 3 OEt 2 Poly(imino-N-formyl-isopropylethylene) Methyl triflate Acetonitrile BF 3 OEt 2 Acetonitrile Poly(imino-ALformyl-propyIene) Ethyl trifluoromethane-sulfonate Acetonitrile Dimethyl sulfate Poly[(S)iminoisobutyIethyIene] BF 3 OEt 2 Poly(iminoisopropylethylene) BF 3 OEt 2 Poly [imino-(S)A^-1 -methylbenzylethylene] BF 3 OEt 2 Poly(D-iminopropylene) BF 3 OEt 2 Poly(L-iminopropylene) BF 3 OEt 2 Poly[(S)methyliminoisobutylethylene] BF 3 OEt 2 Neat 2.8.
100
- 108.9 - 109.2
17.6 (M)
Benzene (P) Benzene
98-100
132.39
4.16 (M)
Benzene (P); ethanol (M)
80 80
1993 86.8
-130.5(M) - 130.5 (M)
80 120
130 107
80-100
16(P) 16 145
Chloroform (P); ethanol (M) Chloroform (P)
25 25
146
- 148 (M) 14.4 (M)
Methanol (P); ethanol (M) H 2 O (P); neat (M)
25 (P); 30 (M) 20
148 149
66.7
- 24.6 (M)
Benzene
20 (P); 32 (M)
68
80
82.8
-27.1 (M)
Ethanol
24
146
0-60
7.09 -8.15
-81.8(M) -81.8(M)
Benzene (P); neat (M) Chloroform (P)
20 20
147
80
-101.5
12.4 (M)
22
66
80
109.3
- 12.8 (M)
22
66
-78
- 163.5
33.7 (M)
Benzene (P); ethanol (M)
19-21
25 (Form I) - 175 (Form U)
90% HCOOH 90% HCOOH after 6 h
25 25
31 (W 546) 159 (M546)
DCA 10% DCA-90% EDC
25 25
173
POLY(AMINOACIDS)
Poly(6>-acetyl-L-hydroxyproline) NCA
Pyridine
Poly(O-acetyl-L-serine) NCA, triethylamine
Nitrobenzene
Poly(L-alanine) NCA, tributylamine
Benzene-dioxane
21 ([m'] D ) -90([m'] D )
99% CHCI3-1% DCA TFA
81,84
Poly(D-a-amino-n-butyric acid) NCA, benzylamine
Nitrobenzene
-19(InV] 0 ) 107([m'] D )
90% CHCl 3-10% DCA TFA
81,84
Poly(L-arginineHCl) From poly(L-nitroarginine) Poly(a-L-aspartic acid) From poly(p-benzyl-L-aspartate) (NCA, 1200C in vac.)
-21.3
Poly(p-L-aspartic acid) Active ester method
140
H2O
20
114
85
6.2
c =31 NNaOH
87
-11.2
c =51 NNaOH
88
-14(M 5 4 6 ) -23(M 5 4 6 )
0.2 M NaCl7 pH 2 0.1 M NaCl, pH 4
25 25
89
22 22
86
Poly(p-benzyl-D-aspartate) NCA, NaOMe
Chloroform
174(M 546 ) 19 (M546)
Chloroform DCA
Poly(P-benzyl-L-aspartate) NCA, NaOMe
Chloroform
-168(M 5 4 6 ) -18(M 5 4 6 )
Chloroform DCA
22 86 22 References page VII - 739
TABLE 2.
confd
Polymer Catalyst or Initiator Poly(y-benzyl-D-glutamate) NCA, NaOMe
Polymerization system Solvent
T( 0 C)
Chloroform Chloroform
NCA, NaOMe NCA, Ni-dl-2-methylbutyrate-n-Bu.^P NCA, benzylamine NCA, benzylamine Poly( 1 -benzyl-L-histidine) NCA, triethylamine Triethylamine NCA, triethylamine Poly(£-yV-carbobenzoxy-L-Jysine) NCA, NaOMe
Chloroform Chloroform Chloroform Chloroform Dioxane
30
Dioxane
30
THF
30
Dioxane Dioxane Dioxane
Poly(S-carbobenzoxymethyl-L-cysteine) NCA, NaOMe Nitrobenzene Poly(3,4-dehydro-L-proline) NCA
Pyridine
WD
[M]D
Solvent
T( 0 C)
Refs.
22 22
86
Hydrazine TFA Chloroform DCA Chloroform DCA DCA (P); ethylacetate (NCA) Chloroform (P) DCA (P); ethylacetate (NCA) Chloroform (P) DCA (P); ethylacetate (NCA)
20 20 22 22 25 25 20 20 20 20 25
96
11 (W 546 ) -208(LaJ 546 ) -21.1
Chloroform DCA-CHCl3 Acetic acid
25 25 20
101
5 (IaJ 546 ) -25(IaJ 5 4 6 )
Chloroform 50% CHCl 3 -50% DCA
25 25
84,103
-128(Ia] 546 ) -125(M 5 4 6 ) -33(M 5 4 6 )
0.2 M NaCl, pH 7 0.2 M NaCl, pH 5 0.2 M NaCl, pH 3
25 25 25
90
99% formic acid TFA
25 25
109
Dioxane-H2O, 0.2 M NaCl, pH4.7 Dioxane-H2CX 0.2 M NaCl, pH 6.5 2-Chloroethanol-HoO, 0.1 M RbCl, pH 5 2-Chloroethanol-H2O, 0.1 M RbCl, pH 7.5 0.2 M NaCL pH 4.5
22
84,92
-102
0.2 M NaCl, pH 8.0
20
23.6
H2O
23
95
-23.6
H2O
23
95
-30 -46 14(W 546 ) -15(IaJ 5 4 6 ) 15 -14 -17.0 15.3 - 17.0 16.0 -15.3
-500 -1250
-77 7 -75
Poly(y-D-glutamic acid) Active ester method PolyCy-L-glutamic acid) Active ester method
WD
Optical activity measured
Chloroform DCA
Poly(L-glutamic acid) From poly(y-benzyl-L-glutamate) (NCA, aliphatic amine, DMF)
From poly(y-benzyl-L-glutamate) (NCA, NaOMe)
[MID
Monomer (M) or model compound (MC) values
17 (M 546 )
Poly(Y-benzyl-L-glutamate) NCA NCA, NaOMe
Polymer (P) values
-6
-17.1 (NCA) -17.1 (NCA) -17.1 (NCA) - 17.1 (NCA) - 17.6 (NCA)
86,98 86 97 151
152
102
22 84,93
20
84,94
Poly(L-histidine) From poly(l-benzyl-L-histidine) (NCA, triethylamine, dioxane)
Poly(L-hydroxyproline) From poly(O-acetyl hydroxy-L-proline) Poly(L-leucine) NCA, tributylamine
0.2 M NaCl, pH 2.4 0.2 M NaCl, pH 5.85 0.2 M NaCl, pH 6.00 DCA Acetic acid
25 25 25 25 22
10.1 (LaJ 546 ) -26.5(LaJ 5 4 6 ) -31.4(La] 546 )
DMF TFEL DCA
25 25 25
83
H2O
25
no
-65(LaJ 5 4 6 )
Poly(8-hydroxy-O-acetyl-L-oc-aminovaleric acid) NCA, triethylamine Nitrobenzene
-400
Benzene -HI
Poly(L-lysine) From poly(£-/V-carbobenzoxyL-lysine)
Poly(L-lysine hydrochloride) From poly(e-/V-carbobenzoxyL-lysine) Poly(L-methionine) NCA, NaOMe
Nitrobenzene
PoIy(L- methionine-S-carboxyrnethylthetin) From poly(L-methionine) Poly(L-methionine-5-rnethylsulfonium bromide) From poly(L-methionine) Poly(/V-methyl-L-alanine) NCA, benzylamine Poly(Y-methyl-L-glutamate) NCA
Dioxane
Poly(L-nitroarginine) NCA DMF Poly(y-phthalimidomethyl-L-glutamate) NCA, triethylamine Poly(L-pipecolic acid) NCA, diethylamine Benzene or dioxane
101
-210([0Cj 546 ) -67(LaJ 5 4 6 ) 28 (LaJ 546 ) -20
([m'] D )
Benzene TFA
102
81,84 81
- 144
H 2 O, pH 7
-35 -51 -77 -108
H2O, H2O, H 2 O, H 2 O,
-78.8
6 N HCl
25
106
24.4(LaJ 546 ) 16.8 ([aj 546 ) -115.3(La] 546 ) 22(La] 546 ) -107(LaJ 5 4 6 )
90% CHCl 3-10% DCA DCA TFA Chloroform 80% TFA - 20% DCA
25 25 25
107
-44(LaJ 546 )
HCI, H 2 O (pH 1.1-2.0)
25
107
H2O 1OM LiBr
24 24
107
-3.04
TFEL
24
82
-31.3 -76.1 10
DCA TFA DMF
25 25 25
99 100
-16.6
DMF
30
85
12.5
DMF
25
91
Acetic acid Acetic acid after 2 h
25 25
109
-74.3(LaJ 5 4 6 ) -38.6(LaJ 546 )
- 325 (Form I) - 50 (Form II)
pH pH pH pH
12 10.10 9.98 9.72
105
21.4 23.2 25.6
108
References page VII - 739
TABLE 2.
confd Polymerization system
Polymer Catalyst or Initiator
T (0C)
Solvent
Polymer (P) values [a] D
[M]0
Monomer (M) or model compound (MC) values [«1D
MD
Poly(L-proline)
Poly((3-proline) Triethylamine DMF Poly(L-serine) From poIy(O-acetyl-L-serine)
Poly(6-Ar-trifluoroacetyl-L-lysine) NCA, diethylamine
DMF
Poly(L-tryptophan) NCA, diethylamine
Dioxane
Ill
25
150
H2O 1OM LiBr 8 M urea Hydrazine DCA
25 25 25 25 25
114
0 (Form i) -120 (Form U)
Acetic acid Acetic acid after 3 h
25
110
-6.8 (M 546) -36.8 ([a]546)
Methanol DCA
20 20
218 (Ia]546) 343 ([a] 546)
DMF 40% DMF - 60% DCA
20 20
184 73 150 28 8.7
DMF 20% DMF-80% DCA 0.15 MNaCl, pH 10.85 0.15MNaCl, pH 12.27 1 N NaOH
Poly(L-tyrosine) From poly(O-carbobenzoxy-L-tyrosine) (NCA, 1100C in vac.)
TABLE 3.
Refs.
Chloroform
7.6 (MC)
-22 [a] 546 -7.3 [aj 546 -25.2 M546 -9.3 [a] 546 -9.7 [a] 546
Poly(O-/?~tolylsulfonyloxy-L-proline) NCA Pyridine
T(0C)
25 25
-10 to -11
30
Solvent Acetic acid Acetic acid 10% Pyridine 90% H 2 O 10% Pyridine after 5Oh H2O 0.1 M KCl
50 (Form I) - 540 (Form 11) 48 (Form I) - 420 (Form II) 33 (Form I) - 540 (Form II)
NCA, pyridine
Optical activity measured
112 113
115
116
20
117
POLY(SACCHARIDES)
Polymer (P) values
Polymer Polymerization system Catalyst or initiator
Solvent
PoIyK 1 ->6)-2,5-anhydro-3,4-di-0-decyl-D-glucitol J BFvOEt 9 DCM 0 tert-BuOK THF 60 PoIyK l->6)-2,5-anhydro-3,4-di-<9-ethy]-D-gluritol] BF 3 OEt 2 DCM -30
T (0C)
MD
16.0 23.7 32.7
[M] D
MD
Monomer (M) or model compound (MC) values [M] D 6.8 (M) 6.8 (M)
54.1 (MC); -5.2(M)
Optical activity measured Solvent
T (0C)
Refs.
Chloroform Chloroform
22 22
211
Chloroform
22
210
Poly[( 1 -^6)-2,5-anhydro-3,4-di-O-methyl-D-glucitol] tert-BuOK Toluene 60 KOH Toluene 60 BF 3 OEt2 (from D-rnannitol) DCM 0 BF3 OEt2 (from L-iditol) DCM 0 Poly(2,5-anhydro-3,4-di-O-methyl-r>mannitol) BF 3 OEt 2 DCM 0 Poly[(l-»6)-2,5-anhydro-3,4-di-O-pentyl-D-glucitol] BF 3 OEt 2 DCM 0 tert-BuOK THF 60 Poly [a-( 1 —>6 ')-anhydro-D-galactopyranose] From 2,3,4-tri-O-benzyl derivative Poly( 1,6-anhydro- p-D-glucopyranose) Chloroacetic acid 21 -127 Poly(a-1,6-anhydro-D-mannopyranose) From 2,3,4-tri-O-benzyl derivative PoIy(Ot-1,6-anhydro-2,3,4-tri-(9-acetyl-p-D-mannopyranose) PF5 DCM 0 Poly[a(l —>6 O-anhydro^^^-tri-O-benzyl-p-D-galactopyranose] PF5 DCM -78 Polyfoc-1,6-anhydro-2,3,4-tri-<9-benzyl-p-D-mannopyranose] PF5 DCM -78 Poly[l,6-anhydro-2,3,4-tri-O-methyl-p-D-glycopyranose] BF 3 OEt 2 Toluene RT BF 3 OEt 2 Toluene RT Poly(D-galactose) HCl DMSO 40 Poly(D-glucose) HCl DMSO 40 Polyphosphate formamide 50-60 Poly(D-mannose) HCl DMSO 40 PoIy(2,3,6-tri-(9-methyl-D~glucose) HBr-HCl-P2O5 DMSO RT Poly(D-xylose) HCl DMSO 40
-12.3(M)(M 546 ) -9.8(M)(W 546 )
Chloroform Chloroform Chloroform Chloroform
23 23 22 22
50.2(M 546 )
-9.6 (M) (M546); 44.1 (MC)
Chloroform
22 (P, M); 23 (MC) 214
25.8 32.8
9.3 (M) 9.3 (M)
Chloroform Chloroform
22 22
211
10% LiOH - 0.5% borate
25
75
H2O
22
77
1%DMSO
30
80
DMSO
30
80
84.5 (M546) 75.5 (M 546) 41.3(M 546 ) 43.1 (M546)
207.1 91 122.8 96
212 213
105.1
-46.1 (M)
Chloroform
25
75
57.5
-32(M)
Chloroform
30 (P); 25 (M)
80
199 204
-63.7(M) -63.7(M)
Chloroform Chloroform
25 (P); 20 (M) 25 (P); 20 (M)
78
79.1
H2O
20
74
90.3 16
H2O
20
74 76
102.9
H2O
20
74
136.6
Chloroform
20
79
96.1
H2O
20
74
C. OPTICALLY ACTIVE POLYMERS FROM ACHIRAL MONOMERS TABLE 4.
MAIN-CHAIN ACYCLIC CARBON POLYMERS
Polymer Polymerization system Catalyst or initiator
Solvent
Optical activity measured
Polymer (P) Values T (0C)
WD
[M] D
Origin of optical activity
Solvent
T (0C)
Refs.
4.1. POLY(ACRYLICS) AND RELATED POLYMERS Poly(JV-acryloylcarbazole) Fluorenyllithium/(- )-sparteine Poly(Ar-acryloyliminodibenzyl) Fluorenyllithium/(— )-sparteine
Toluene Toluene
- 97 — 97
57.4
Helix-sense asymmetry
Chloroform
25
188
-0.5
Helix-sense asymmetry
Chloroform
25
188
References page VII - 739
TABLE 4.
confd
Polymer Catalyst or initiator
Polymerization system Solvent
Poly(iV-acryloylphenothiazine) Fluorenyllithium/(- )-sparteine Toluene Poly(iV,JV-diphenylacrylamide) BuLi/(- )-sparteine Toluene Fluorenyllithium/(- )-sparteine Toluene Poly(W,iV-di(2-pyridyl)-acrylamide] Fluorenyllithium/(- )-sparteine Toluene Poly[A^-methyl-N-triphenylmethyl-acrylamide] «-BuLi/(— )-sparteine Toluene Poly( 1 -phenyldibenzosuberyl aery late) DPEDA-Li/( + )-DBB Toluene Poly(N-phenyl-iV-1 -naphthylacrylamide) BuLi/(- )-sparteine Toluene Poly(Af-phenyl-Af-2-naphthyIacrylamide) BuLi/(- )-sparteine Toluene Poly [Af-phenyl-AK 1 -phenylethyl)-acrylamide] Fluorenyllithium/(— )-sparteine Toluene Poly(triphenylmethyl acrylate) DPEDA-Li/( + )l-(2-pyrroliToluene dinylmethyl)pyrrolidine 4.2.
T(0C)
Polymer (P) Values WD
[M] D
Optical activity measured Origin of optical activity
Solvent
T (0C)
Refs.
-97
8.2
Helix-sense asymmetry
Chloroform
25
188
-96 -97
-44.2 to-50.9 -101
Helix-sense asymmetry
THF Chloroform
25 25
153 188
-97
-23.7
Helix-sense asymmetry
Chloroform/DC A (22/1)
25
188
-78
-2.4
Helix-sense asymmetry
THF
25
188
-40
-129
Helix-sense asymmetry
Chloroform
25
219
-78
8.7
Helix-sense asymmetry
Toluene
25
153,188
-78
81.7
Helix-sense asymmetry
Toluene
25
153,188
-97
-0.3
Helix-sense asymmetry
THF
25
188
-78
102(M365)
Helix-sense asymmetry
Chloroform
25
186
Miscellaneous
THF
25
164
Miscellaneous
THF
25
164
Helix-sense asymmetry
THF
25
220
Helix-sense asymmetry
Chloroform
25
240
Chloroform Chloroform after 1 h
60 60
Helix-sense asymmetry
Chloroform
25
240
Helix-sense asymmetry
THF
25
220
Helix-sense asymmetry
90% Chloroform - 10% TFEL 25
155
Helix-sense asymmetry
90% Chloroform - 10% TFEL 25
154
Induced asymmetry
Benzene
162
POLY(METHACRYLICS) AND RELATED POLYMERS
Poly(benzyl methacrylate) (5)2,3:4,5-bis[ 1,2-(3-methylnaphtho)]-1,6,9,12,15,18-hexaoxacycloeicosa-2,4-diene-A:0-terr-Bu 95% Toluene-5% THF- 78 350 ([a] 578) Poly(rerr-butyl methacrylate) (5)2,3:4,5-bis[ 1,2-(3-methylnaphtho)]-1,6,9,12,15,18-hexaoxacycloeicosa-2,4-diene-#0-terr-Bu 95% Toluene-5% THF- 78 117 ([a] 578) Poly(m-chlorophenyldiphenylmethyl methacrylate) DPEDA-Li/(-h)-DDB Toluene -78 314 Poly(cyclohexyldiphenylmethyl methacrylate) DPEDA-Li/( + )1 -(2-pyrroToluene - 78 758 ([a] 365) lidinylmethyl)pyrrolidine 770(Ia]365) -480(M 365 ) Poly(cyclopropyldiphenylmethyl methacrylate) DPEDA-Li/( + )-DDB Toluene -78 -44 (M365) Poly(diphenyl-m-fluorophenylmethyl methacrylate) DPEDA-Li/( + )-DDB Toluene -78 297 Poly(diphenyl-2-pyridylmethyl methacrylate) DPEDA-Li/(- )-DDB " Toluene - 78 -1403 ([a] 365) Poly(diphenyl-4-pyridylmethyl methacrylate) BuLi/(- )-sparteine Toluene - 78 - 40 ([a] 546) Poly(methyl methacrylate) From poly(methacrylic acid) (potassium persulfate/dextrin, water, 00C) 6.4(M 350 )
25
From poly(methacrylic acid) (potassium persulfate/chitosan, water, 300C) 16.6 (5)2,3:4,5-bis[ 1,2-(3-methylnaphtho)]-1,6,9,12,15,18-hexaoxacycloeicosa-2,4-diene-/ft>-ter/-Bu 95% Toluene-5% THF -78 250 (M57S) From poly(2,3-O-isopropylidene-l,4-di-O-methacryloyl-L-threitol) (AIBN, toluene, 600C) -4.3(W 405 ) PoIy(I -phenyldibenzosuberyl methacrylate) Diisopropyl peroxydicarbonate (4- )Menthol/toluene 50 - 200 (W 365) Diisopropyl peroxydicarbonate (-)Menthol/toluene 50 180 (W 365) Diisopropyl peroxydicarbonate/ Toluene 40 ~140([a] 36 5) (-f- )neomenthanethiol (-)Dimethyl peroxydicarbonate Toluene 50 40 ([aJ365) DPEDA-Li/(-)-sparteine Toluene -78 1670 (W 365 ) Poly[ 1 -(2-pyridyl)dibenzosuberyl methacrylate] DPEDA-Li/(- )-sparteine Toluene - 78 1290 ([a] 365) Poly(triphenylmethyl methacrylate) Li(R)-AK 1 -phenylethyl)anilide THF - 78 -104 BuLi/(- )-sparteine Toluene -78 363 (S)-6-(2-dimethylaminoethyl)-1,11 -dimethyl-6?7-dihydro-5H-dibenz[c,e]azepine Toluene - 78 373 Poly[tris(m-chlorophenyl)methyl methacrylate] DPEDA-Li/(-)-DDB Toluene -78 -251 Poly[tris(m-tolyl)methyl methacrylate] DPEDA-Li/(- )-DDB Toluene - 78 - 234 (W 546) 4.3.
Chloroform
21
163
Miscellaneous
THF
25
164
Induced asymmetry
Chloroform
20
244
Helix-sense asymmetry
THF THF THF
25 25 25
196 196 253
THF Chloroform
25 25
253 196
Helix-sense asymmetry
Chloroform
25
251
Helix-sense asymmetry
Toluene Toluene
20 20
156
THF
25
157
Helix-sense asymmetry
THF
25
220
Helix-sense asymmetry
Chloroform
25
220
Induced asymmetry
Benzene Benzene
18
169 242
Induced asymmetry
Chloroform
20
170
Induced asymmetry
Chloroform
20
170
Induced asymmetry
Chloroform
20
198
Chloroform
20
198
THF
30
179,180
THF
30
179,180
Methanol
25
177
POLY(VINYLETHERS)
Poly(benzofuran) AlCl3/phenylalanine Toluene -75 24-56.7 AlCl3/Et3SnCl/(-)menthoxyToluene -75 73.8 triethyltin Poly(a-naphthofuran) 2A1C13/(- )-p-phenylalanine Toluene - 75 41 Poly(p-naphthofuran) 2A1C13/(- )-(3-phenylalanine Toluene - 75 - 145 Poly(2-phenyl-l,3-dioxane-4,6-diyl) (Poly(benzaldehyde divinyl acetal)) ZnCl 2 OEt 2 /(-h)-10Toluene 0 ~17.1 (W435) camphor-sulfonic acid ZnCl2OEt2/(-)-10Toluene 0 13.7 (W435) camphor-sulfonic acid 4.4.
Induced asymmetry
POLY(STYRENES)
Poly(4-iodostyrene) From copolymer of 3,4-O-cyclohexylidene-D-mannitol-l,2:5,6-bis~O-[(4-vinylphenyl)boronate] and styrene (AIBN, toluene, 60-700C) 0 to —4.5 (W 436) Induced asymmetry Polystyrene From copolymer of 3,4-O-cyclohexylidene-D-mannitol-l,2:5,6-bis-O-[(4-vinylphenyl)boronate] and styrene (AIBN, toluene, 60-700C) -0.5 to -3.5 (W365) Induced asymmetry 4.5.
POLY(DIENES)
Poly (3-carboxy-1 -butenylene) From poly[l-(d-bomylammonium carboxylate)-l,3-butadiene] (AEBN, methanol, 500C. See Section B. Table 1, 1.6) 0.2 Induced asymmetry
References page VII-739
TABLE 4.
confd
Catalyst or initiator
Solvent
Optical activity measured
Polymer (P) Values
Polymer Polymerization system T (0C)
WD
[M]0
Solvent
Origin of optical activity
From poly[l-(S(-)a-phenylethylammonium carboxylate)-1,3-butadiene] (AlBN, methanol, 500C. See Section B. Table 1, 1.6) -4.8 -4.7 Poly(3-carboxy-4-methyI-l-butenylene) (Poly(sorbic acid)) Potassium persulfate/chitosan Water 50 2.32 Induced asymmetry From polyl1-((-)menthyloxycarbonyl)-l,3-pentadiene] (AlBN, benzene, 500C. See Section B. Table 1, 1.6) -58.3 Polyl3-(ethoxycarbonyl)-1 -butenylene] Induced asymmetry - 14.0 -78 /2-BuLi/sodium 1-menthoxide Toluene 6.0 -78 n-BuLi/sodium d-bornoxide Toluene Poly [3-(methoxycarbonyl)-1 -butenylene] Induced asymmetry -2.4 -78 rt-BuLi/sodium 1-menthoxide Toluene 2.7 -78 /2-BuLi/sodium d-bornoxide Toluene Poly(/r
Refs.
Methanol
20
178
Methanol
20
161
THF
25
190
Benzene Benzene
RT RT
176
Benzene Benzene
RT RT
176
Carbon tetrachloride Carbon tetrachloride
20 20
159 160
Carbon tetrachloride Carbon tetrachloride
20 20
159 160
Hexane
18
171
Carbon tetrachloride Chloroform
20 26
159 158
Chloroform Carbon tetrachloride Chloroform
25 20 26
172 159 158
Chloroform
20
207
POLY(ISONITRILES)
Poly[(terf-butylimino)methylene] tris(terf-butyl isocyanide)[(S)(- )-(1 -phenylethyl)amino(te^butylamino)carbene]-nickel(ll) perchlorate Neat RT - 28.7 Helix-sense asymmetry Poly[5,8-dimethyl-6,7-bis(propoxymethyl)-quinoxaline-2,3-diyl] (PoIy[1,2-diisocyano-3,6-dimethyl-4,5-bis(propoxymethyl)benzeneJ) (+ )oligo(5,8-di-/?-tolylquinoxaline-2,3-diyl)/Pd(II) THF RT - 171 Helix-sense asymmetry 4.7.
T( 0 C)
204
POLY(MALEIMIDES)
Poly(yV-benzyl maleimide) n-BuLi/(— )-sparteine Poly(/V~/7-butyl maleimide) /i-BuLi/(— )-sparteine Poly(Af~sec-butyl maleimide) n-BuLi/(- )-sparteine
Toluene
0
11.3
Induced asymmetry
Chloroform or THF
181
Toluene
0
-7.1
Induced asymmetry
Chloroform or THF
181
Toluene
6
-21.0
Induced asymmetry
Chloroform or THF
181
Poly(/V-terf-butyl maleimide) A7-BuLi/(— )-sparteine Poly(/V-cyclohexyl maleimide) n-BuLi/(— )-sparteine PoIy(ZV-2-fluorenyl maleimide) n-BuLi/(— )-sparteine Poly(yV-isobutyl maleimide) /i-BuLi/(—)-sparteine Poly(N-isopropyl maleimide) n-BuLi/(— )-sparteine PoIy(N-1 -naphthyl maleimide) /7-BuLi/(— )-sparteine Poly(iV-phenyl maleimide) fl-BuLi/(-)-sparteine n-BuLi/(— )-sparteine/CuI Poly^-n-propyl maleimide) /?-BuLi/(— )-sparteine
Toluene
0
2.8
Induced asymmetry
Chloroform or THF
181
Toluene
0
-39.5
Induced asymmetry
Chloroform or THF
181
Toluene
0
-0.4
Induced asymmetry
Chloroform or THF
181
Toluene
0
- 13.4
Induced asymmetry
Chloroform or THF
181
Toluene
0
-18.7
Induced asymmetry
Chloroform or THF
181
Toluene
0
0.9
Induced asymmetry
Chloroform or THF
181
Toluene Toluene
0 0
- 15.4
Induced asymmetry
Chloroform or THF Chloroform
Toluene
0
-23.7
(IaJ 435 )
181 241 181
Induced asymmetry
-4.9
4.8. OTHER COMPOUNDS
Chloroform or THF
Poly(methylene-l,3-cyclopentylene) (from 1,5-hexadiene) (H-)(5,5)ethylene-l,2-bis(?75-4,5,6,7-tetrahydro-l-indenyl)zirconium-l,l '-bi-2-naphtholate/methylaluminoxane Toluene RT 51.0([M] 4 Os) Induced asymmetry Poly[ 1 -(m-tolylsulfonyl)ethylenej From poly(m-tolyl vinyl sulfoxide) («-BuLi/(- )-sparteine, toluene, -78°C. See Section B, Table 1, 1.10) 42 Miscellaneous
TABLE 5.
25
28 Chloroform
239 246
MAIN-CHAIN ACYCLIC HETROATOM POLYMERS
Polymer Catalyst or initiator
Polymerization system Solvent
7( 0 C)
Optical activity measured
Polymer (P) values WD
[M]0
Origin of optical activity
Solvent
T (0C)
Refs.
5.1. POLY(OXIDES) AND POLY(SULFIDES) Poly(chloral) Tetramethylammonium ( — ) acetyl mandelate Lithium coprostan-3(3-oxide Hexane Poly(oxy-1,2-cyclohexylidene) ZnEt 2/( 1S,2/?)-ephedrine Poly(oxy-1,2-dimethylethylene) ZnEt 2/( 15,2/?)-ephedrine Poly(thio-1,2-cyclohexylidene) ZnEt 2/(R,R)-1,2-diphenyl-1,2-ethandiol Toluene Poly(thio-1,2-dimethylethylene) ZnEt2KRM)-1,2-diphenyl-1,2-ethandiol
0-75 <58 80
242-668 2970 -9.1 to 12.3
Helix-sense asymmetry
Film (soaked in diphenyl ether) 25 Film (soaked in diphenyl ether) RT
Induced asymmetry
Benzene
25 25
80
15
Induced asymmetry
Benzene
RT
59
Induced asymmetry
Trichlorobenzene
25
RT
154
Induced asymmetry
Chloroform
25
165 247 194 238 238
238 References page VII - 739
TABLE 5.
confd
Polymer Catalyst or initiator Solvent 5.2.
Polymerization system T( 0 C)
[a]D [M] D
Polymer (P) values Origin of optical activity
Optical activity measured Solvent
T( 0 C)
Refs.
POLY(ISOCYANATES)
Poly [(butyl )iminocarbony IJ (/?)iV-benzyl-l-phenylethylamine lithium amide Toluene Poly [iV-(p-chiorophenyl )iminocar bony 1] ^rr-BuLi/(5)(-)-(2-methyoxymethyl)pyrrolidine THF Poly[AH3,4-dimethylphenyl)iminocarbony!J tert-Buhi/(S)(- )-(2-methyoxymethyl)pyrrolidine THF Poly[A^(/>methoxyphenyl)iminocarbonylJ r^r/-BuLi/(5)(-H2-methyoxymethyl)pyrrolidine THF Poly[A/-(m-methylphenyl)iminocarbonyl] tert-BuL\/{S)( — )-(2-methyoxymethyl)pyrrolidine THF Poly[A^-(y?-methylphenyl)iminocarbonylJ /^rr-BuLi/(5)(-)-(2-methyoxymethyl)pyrrolidine THF PoIy[N-(I-naphthyl)iminocarbonylj tert-BuLi/(S){ — )-(2-methy oxymethy l)pyrrolidine THF Poly[(4-phenylbutyl)irninocarbonyl] (/?)/V-benzyH-phenylethylamine lithium amide Toluene
- 78
-40 (La] 365)
Helix-sense asymmetry
- 98
377 ([a] 365)
Helix-sense asymmetry
- 98
569([aJ 365 )
Helix-sense asymmetry
- 98
588 ([aj365)
Helix-sense asymmetry
- 98
819([a] 36 5)
Helix-sense asymmetry
- 98
748([0Cj 365 )
Helix-sense asymmetry
- 98
529 ([a]365)
Helix-sense asymmetry
- 78
- 17 (IaJ 365)
Helix-sense asymmetry
Chloroform
THF
25
25
DCM
193
25
Chloroform
THF
193
25
25
Chloroform
DCM
193
193
25
25
Chloroform
248
193
193
25
248
D.
REFERENCES
1. F. Ciardelli, E. Benedetti, O. Pieroni, Makromol. Chem., 103, 1 (1967). 2. P. Pino, G. P. Lorenzi, L. Lardicci, Chim. lnd. (Milan), 42, 712(1960). 3. P. Pino, G. P. Lorenzi, J. Am. Chem. Soc, 82, 4745 (1960). 4. P. Pino, F. Ciardelli, G. P. Lorenzi, G. Montagnoli, Makromol. Chem., 61, 207 (1963). 5. P. Pino, P. Salvadori, E. Chiellini, P. L. Luisi, Pure Appi. Chem., 16,469 (1968). 6. P. Pino, G. P Lorenzi, L. Lardicci, F. Ciardelli, Vysokomol. Soedin., 3, 1567 (1961). 7. M. Goodman, K. J. Clark, M. A. Stake, A. Abe, Makromol. Chem., 72, 131 (1964). 8. W. J. Bailey, E. T. Yates, J. Org. Chem., 25, 1800 (1960). 9. S. Nozakura, S. Takeuchi, H. Yuki, S. Murahashi, Bull. Chem. Soc. (Japan), 34, 1673 (1961). 10. R. C. Schulz, H. Hilpert, Makromol. Chem., 55, 132 (1962). 11. R. C. Schulz, Z. Naturforsch 19b, 387 (1964). 12. R. K. Kulkarni, H. Morawetz, J. Polym. ScL, 54,491 (1961). 13. C. S. Marvel, J. Dec, H. G. Cooke, Jr., J. Am. Chem. Soc, 62, 3499 (1940). 14. J. W. C. Crawford, D. Plant, J. Chem. Soc, 4492 (1952). 15. P. Walden, Z. Phys. Chem., 20, 383 (1896). 16. E. I. Klabunovskii, I. I. Petrov, M. I. Schvartmen, Vysokomol. Soedin., 6, 1487 (1964). 17. C. L. Arcus, D. W. West, Chem. lnd. (London), 230 (1958). 18. C. L. Arcus, D. W. West, J. Chem. Soc, 2699 (1959). 19. K. J. Liu, J. S. Lignowski, R. Ullrnan, Makromol. Chem., 105,8(1967). 20. N. Beredjick, C. Schuerch, J. Am. Chem. Soc, 78, 2646 (1956). 21. N. Beredjick, C. Schuerch, J. Am. Chem. Soc. 80, 1933 (1958). 22. E. I. Klabunovskii, M. I. Schvartmen, I. I. Petrov, Vysokomol. Soedin., 6, 1579 (1964). 23. T. P. Bird, W. A. P. Black, E. T. Dewar, D. Rutherford, Chem. lnd. (London), 1331 (1960). 24. W. A. P. Black, E. T. Dewar, D. Rutherford, J. Chem. Soc, 4433 (1963). 25. S. Kimura, M. Imoto, Makromol. Chem., 50, 155 (1961). 26. S. Kimura, K. Hirano, M. Imoto, Kogyo Kagaku Zasshi (Japan), 65, 688 (1962). 27. M. Imoto, S. Kimura, Makromol. Chem., 53, 210 (1962). 28. R. K. Kulkarni, H. Morawetz, J. Polym. Sci., 54,491 (1961). 29. V E. Kaiser, R. C. Schulz, Makromol. Chem., 81, 273 (1965). 30. O. Pieroni, F. Ciardelli, C. Botteghi, L. Lardidi, P. Salvadori, P. Pino, J. Polym. Sci. C, 22, 993 (1967). 31. G. Anzuino, V. Crescenzi, M. D'Alagni, A. M. Liquori, F. Quadrifoglio, F. Ascoli, Communication at the IX, Natl. Meeting of Italian Chem. Soc, Naples, 1962. 32. G. P. Lorenzi, E. Benedetti, E. Chiellini, Chim. lnd. (Milan), 46, 1474 (1964). 33. D. Basagni, A. M. Liquori, B. Pispesa, J. Polym. Sci. B, 2, 241 (1964).
34. P. Pino, G. P. Lorenzi, Makromol. Chem., 47, 242 (1961). 35. G. J. Schmitt, C. Schuerch, J. Polym. Sci., 45, 313 (1960). 36. W. A. P. Black, E. T. Dewar, D. Rutherford, Chem. lnd. (London) 1624 (1962). 37. R. C. Schulz, R. H. Jung, Makromol. Chem., 96, 295 (1966). 38. R. C, Schulz, H. Hartman, Makromol. Chem., 65, 106 (1963). 39. F. Millich, G. K. Baker, Macromolecules 2, 122 (1969). 40. C. S. Marvel, C. G. Overberger, J. Am. Chem. Soc, 68, 2106 (1946). 41. C S . Marvel, C. G. Overberger, J. Am. Chem. Soc, 66, 475 (1944). 42. C. G. Overberger, L. C. Palmer, J. Am. Chem. Soc, 78, 666 (1956). 43. H. Yamaguchi, Y. Minoura, J. Polym. Sci. A-I, 8, 929 (1970). 44. A. Abe, M. Goodman, J. Polym. Sci. A, 1, 2193 (1963). 45. A. Abe, M. Goodman, J. Polym. Sci., 59, S37 (1962). 46. C. C. Price, M. Osgan, R. E. Hughes, C. Shambelan, J. Am. Chem. Soc, 78, 690 (1956); 4787 (1956). 47. E. J. Vandenberg, J. Am. Chem. Soc, 83, 3538 (1961). 48. H. Shimazaki, J. Chem. Soc (Japan), 87, 462 (1966). 49. C G . Overberger, S. Ozaki, D. M. Braunstein, Makromol. Chem., 93, 13 (1966). 50. J. R. Shelton, J. B. Lando, D. E. Agostini, Polym. Lett. 9,173 (1971). 51. R. C Schulz, J. Schwaab, Makromol. Chem., 87, 90 (1965). 52. Y. Iwakura, K. Iwata, S. Matsuo, A. Tohara, Makromol. Chem., 122, 275 (1969). 53. C. G. Overberger, H. Kaye, J. Am. Chem. Soc, 89, 5649 (1967). 54. H. D. K. Drew, W. N. Haworth, J. Chem. Soc, 775 (1927). 55. N. Spassky, P. Sigwalt, Bull. Chim. Soc France, 4617 (1967). 56. T. Tsunetsugu, J. Furukawa, T. Fueno, J. Polym. Sci. A-I, 9, 3541 (1971). 57. C. G. Overberger, J. K. Weise, J. Am. Chem. Soc, 90, 3538 (1968). 58. M. Imoto, H. Sakurai, T. Kono, J. Polym. Sci., 50, 467 (1961). 59. C. G. Overberger. H. Jabloner, J. Polym. Sci., 55, 32 (1961). 60. C. G. Overberger, H. Jabloner, J. Am. Chem. Soc, 85, 3431 (1963). 61. C G . Overberger, G. M. Parker, J. Polym. Sci. C, 22, 387 (1968). 62. E. Schmidt, Angew. Makromol. Chem., 14, 185 (1970). 63. Y Iwakura, K. Hayashi, K. Inagaki, Makromol. Chem., 110, 84 (1967). 64. M. Goodman, S. Chen, Macromolecules, 4, 625 (1971). 65. M. Goodman, S. Chen, Macromolecules, 3, 398 (1970). 66. Y. Minoura, S. Takebayashi, C. C Price, J. Am. Chem. Soc, 81,4689 (1959). 67. K. Tsuboyama, S. Tsuboyama, M. Yanagita, Bull. Chem. Soc (Japan), 40, 2954 (1967).
68. S. Tsuboyama, Bull. Chem. Soc. (Japan), 35, 1004 (1962). 69. M. S. Toy, C. C. Price, J. Am. Chem. Soc, 82, 2613 (1960). 70. A. P. Terentev, V. V. Dunina, E. G. Rukhadze, Vysokomol. Soedin. A, 9, 599 (1967). 71. R. C. Schulz, R. H. Jung, Makromol. Chem., 116, 190 (1968). 72. A. Abe, M. Goodman, J. Polym. Sci. A, 2, 3491 (1964). 73. C. G. Overberger, T. Yoshimura, A. Ohnishi, A. S. Gomes, J. Polym. Sci. A-I, 8, 2275 (1970). 74. R Micheel, A. Bockmann, W. Meckstroth, Makromol. Chem., 48, 1 (1961). 75. T. Uryu, H. Libert, J. Zachoval, C. Schuerch, Macromolecules, 3, 345 (1970). 76. G. Schramm, H. Grotsch, W. Pollman, Angew. Chem., 74, 53 (1962). 77. J. Das. Carvalho, W. Trins, C. Schuerch, J. Am. Chem. Soc, 81, 4054 (1959). 78. C. C. Tu. C. Schuerch, J. Polym. Sci. B, 1, 163 (1963). 79. F. Micheel, A. Bockmann, Makromol. Chem., 51, 97, (1962). 80. F. Frechet, C. Schuerch, J. Am. Chem. Soc, 91, 1161 (1969). 81. A. R. Downie, A. Elliot, W. E. Hanby, B. R. Malcolm, Proc. Roy. Soc A, 242, 325 (1957). 82. M. Goodman, Fu Chen, F. R. Prince, Biopolymers, 12, 2549 (1973). 83. M. Goodman, A. M. Felix, Biochemistry, 3, 1529 (1964). 84. P. Urnes, P. Doty, Advan. Protein Chem., 16, 401 (1961). 85. T. Hayakawa, Y. Fujiwara, J. Noguchi, Bull. Chem. Soc. (Japan), 40, 1205 (1967). 86. E. R. Blout, R. H. Karlson, J. Am. Chem. Soc, 80, 1259 (1958). 87. M. Frankel, A. Berger, J. Org. Chem., 16, 1513 (1951). 88. A. Berger, E. Katchalski, J. Am. Chem. Soc, 73, 4084 (1951). 89. J. Kovacs, R. Ballina, R. L. Rodin, D. Balasurkamanium, H. Applequist, J. Am. Chem. Soc, 87, 119 (1965). 90. S. Ikeda, Biopolymers, 5, 359 (1967). 91. M. Wilchek, A. Fransdorff, M. SeIa, Arch. Biochem. Biophys., 113, 742 (1966). 92. W. Moffitt, J. T. Young, Pro. Nat. Acad. Sci. USA, 42, 596 (1956). 93. L. Goldstein, E. Katchalski, Bull. Research Council Israel, A9, 138 (1960). 94. A. Wada, MoL Phys., 3, 409 (1960). 95. J. Kovacs, G. H. Schmit, E. J. Jonson, Can. J. Chem., 47, 3690 (1960). 96. J. T. Yang, P. Doty, J. Am. Chem. Soc, 79, 761 (1957). 97. E. R. Blout, R. H. Karlson, J. Am. Chem. Soc, 78, 941 (1958). 98. W. E. Hanby, S. G. Ealey, J. Eatson, J. Chem. Soc, 3239, (1950). 99. M. Goodman, E. Schmitt, I. Listowoky, F. Boardman, I. G. Rosen, M. Stake, in M. A. Stahmann (Ed.), "Polyamino Acids, Polypeptides and Proteins", Univ. Wisconsin Press, Madison, 1962. 100. M. Goodman, E. E. Schmitt, J. Am. Chem. Soc, 81, 5507 (1959).
101. K. S. Norland, G. D. Fasman, E. Katchalski, E. R. Blout, Biopolymers, I1 277 (1961). 102. A. Patchornik, A. Berger, E. Katchalski, J. Am. Chem. Soc, 79, 5227 (1957). 103. G, D. Fasman, M. Idelson, E. R. Blout, J. Am. Chem. Soc, 83, 709 (1961). 104. M. SeIa, R. Arnon, I. Jacobson, Biopolymers, 1, 517 (1963). 105. J. Applequist, P. Doty, in: M. A. Stahmann (Ed.), "Polyamino Acids, Polypeptides and Proteins", Univ. Wisconsin Press, Madison, 1962. 106. H. Devoe, I. Tinoco, J. MoI. BioL, 4, 518 (1962). 107. G. E. Perlmann, E. Katchalski, J. Am. Chem. Soc, 84, 452 (1962). 108. G. D. Fasman, in: M. A. Stahmann (Ed.) "Polyamino Acids, Polypeptides and Proteins", Univ. Wisconsin Press, Madison, 1962. 109. E. Katchalski, A. Berger, J. Kurtz, in: G. N. Ramachandran (Ed.) ,"Aspects of Protein Structure", Academic Press, New York, 1963, p.205. 110. J. Kurtz, G. D. Fasman, A. Berger, E. Katchalski, J. Am. Chem. Soc, 80, 393 (1958). 111. E. Katchalski, I. Z. Steinberg, Ann. Rev. Phys. Chem., 12, 433 (1961). 112. J. Kurtz, A. Berger, E. Katchalski, Nature, 178, 1066 (1956). 113. W. F. Harrington, M. SeIa, Biochem. Biophys. Acta, 27, 24 (1958). 114. G. D. Fasman, E. R. Blout, J. Am. Chem. Soc, 82, 2262 (1960). 115. M. SeIa, I. Z. Steinberg, E. Daniel, Biochem. Biophys. Acta, 46, 433 (1961). 116. J. D. Coombes, E. Katchalski, P. Doty, Nature, 185, 534 (1960). 117. E. Katchalski, M. SeIa, J. Am. Chem. Soc, 75, 5284 (1953). 118. C. Carlini, F. Ciardelli, D. Pino, Makromol. Chem., 174, 15 (1974). 119. J. M. Sauvage, M. Morcellet, C. Loucheux, Macromolecules 16, 1564 (1983). 120. T. Sato, T. Kadowaki, H. Takeda, T Otsu, J. Macromol. Sci., Chem. A, 12, 1225 (1978). 121. T. Kakuchi, K. Yokota, Makromol. Chem., Rapid Commun., 6, 551 (1985). 122. H. Yamaguchi, K. Sekioka, M. Kurokawa, T. Doiuchi, Makromol. Chem., 184, 455 (1983). 123. E. Chiellini, Macromolecules 3, 527 (1970). 124. M. Kurokawa, H. Yamaguchi, Y Minoura, J. Polym. Sci., Polym. Chem. Ed., 17, 485 (1979). 125. R. Vukovic, D. Fles, J. Polym. Sci., Polym. Chem. Ed., 13, 49 (1975). 126. N. Thien, U. W. Suter, P. Pino, Makromol. Chem., 184, 2335 (1983). 127. E. Chiellini, R. Solaro, A. Ledwith, Makromol. Chem., 179, 1929 (1978). 128. N. Kunieda, J. Shibatani, Y Fijiwara, M. Kinoshita, Makromol. Chem., 175, 2509 (1974). 129. Z. Janovic, D. Fles, J. Polym. Sci. A-I, 9, 1103 (1971). 130. R. R. Kiprijanova, D. Fles, J. Polym. Sci., Polym. Chem. Ed., 13, 1141 (1975).
131. A. J. M. Beijnen, R. J. M. Nolte, W. Drenth, A. M. F. Hezemans, P. J. F. M. Coolwijk, Macromolecules, 13, 1386 (1980). 132. A. J. M. Beijnen, R. J. M. Nolte, A. J. Naaktgeboren, J. W. Zwikker, W. Drenth, A. M. F. Hezemans, Macromolecules, 16, 1679 (1983). 133. F. Ciardelii, S. Lanzillo, O. Pieroni, Macromolecules 7, 174 (1974). 134. N. Kunieda, M. Kinoshita, M. Imoto, J. Polym. Sci. B, 9,241 (1971). 135. N. Kunieda, H. Wada, J. Shibatani, M. Kinoshita, Makromol. Chem., 172, 237 (1973). 136. J. Huguet, M. Vert, Polym. Bull., 5, 505 (1981). 137. T. Oishi, M. Fujimoto, J. Polym. Sci., Polym. Chem. Ed., 22, 2789 (1984). 138. T. Hirano, A. Sato, T. Tsuruta, W. C. Johnson, J. Polym. Sci., Polym. Phys. Ed., 17, 1601 (1979). 139. E. Chiellini, P. Salvadori, M. Osgan, P. Pino, J. Polym. Sci. A-I, 8, 1589 (1970). 140. Y. Iwakura, K. Iwata, S. Matsuo, A. Tohara, Makromol. Chem., 146,21 (1971). 141. B. Jerman, D. Fles, J. Polym. Sci., Polym. Chem. Ed., 14, 1117(1976). 142. P. Dumas, N. Spassky, P. Sigwalt, Makromol. Chem., 156,55 (1972). 143. D. Fles, V. Tomasic, M. Samsa, D. Ahmetovic, B. Jerman, M. Fles, J. Polym. Sci., Symposium Ed., 42, 321 (1973). 144. K. Ehara, T. Miura, W. Urahashi, H. Kitahara, H. Nohira, Kobunshi Ronbunshu (Japan), 37, 463 (1980). 145. N. Yahiro, K. Asakawa, Kobunshi Ronbunshu (Japan), 39, 507 (1982). 146. Y. Kawakami, T. Sugiura, Y. Mizutani, Y. Yamashita, J. Polym. Sci., Polym. Chem. Ed., 18, 3009 (1980). 147. A. D. Aliev, E. P. Tiurina, A. Y. Koschevnik, S. L. Aliev, B. A. Krentsel, Eur. Poiym. J., 16, 679 (1980). 148. T. Saegusa, S. Kobayashi, M. Ishiguro, Macromolecules 7, 958 (1974). 149. J. G. Hamilton, K. J. Ivin, L. C. K. Essig, P. Watt, Macromolecules, 9, 67 (1976). 150. H. Yuki, Y. Okamoto, Y. Kobayashi, J. Polym. Sci., Polym. Chem. Ed., 17, 3867 (1979). 151. S. Yamashita, K. Waki, N. Yamawaki, H. Tani, Macromolecules, 7, 410 (1974). 152. N. Oguni, H. Kuboyama, A. Nakamura, J. Polym. Sci., Polym. Chem. Ed., 21, 1559 (1983). 153. Y. Okamoto, M. Adachi, H. Shohi, H. Yuki, Poiym. J., 13, 175 (1981). 154. Y. Okamoto, M. Ishikura, K. Hatada, H. Yuki, Polym. J., 15, 851 (1983). 155. Y. Okamoto, H. Mohri, M. Ishikura, K. Hatada, H. Yuki, J. Polym. Sci., Polym. Symposium Ed., 74, 125 (1986). 156. Y. Okamoto, K. Suzuki, H. Yuki, J. Polym. Sci., Polym. Chem. Ed., 18, 3043 (1980). 157. S. Kanoh, H. Suda, N. Kawaguchi, M. Motoi, Makromol. Chem., 187,53 (1986). 158. G. Audisio, A. Silvani, J. Chem. Soc, Chem. Commun., 481, (1976).
159. M. Miyata, Y. Kitahara, K. Takemoto, Polym. Bull., 2, 671 (1980). 160. M. Miyata, Y. Kitahara, K. Takemoto, Polym. J., 13, 111 (1981). 161. S. Kataoka, T. Ando, Kobunshi Ronbunshu (Japan), 37, 375 (1980). 162. K. Nozaki, Y. Matsubara, M. Yoshihara, T. Maeshima, Makromol. Chem., Rapid Commun., 5, 723 (1984). 163. S. Kataoka, T. Ando, Kobunshi Ronbunshu (Japan), 37, 185 (1980). 164. D. J. Cram, D. Y. Sogah, J. Am. Chem. Soc, 107, 8301 (1985). 165. W. J. Harris, O. Vogl, Polym. Prepr., Am. Chem. Soc, Div. Polym. Chem., 22 (2), 309 (1981). 166. Q.-S. Hu, D. Vitharana, G.-Y. Liu, V. Jain, M. W. Waganam, L. Zhang, T. R. Lee, L. Pu, Macromolecules, 29, 1082 (1996). 167. Y. Chen, J.-J. Tsay, Polym. J., 24, 263 (1992). 168. Y. Chen, H.-H. Tseng, J. Polym. Sci., Polym. Chem. Ed., 31, 1719 (1993). 169. M. Farina, G. Bressan, Makromol. Chem., 61, 79 (1963). 170. G. Bressan, M. Farina, G. Natta, Makromol. Chem., 93, 283 (1966). 171. G. Natta, L. Porri, S. Valenti, Makromol. Chem., 67, 225 (1963). 172. M. Farina, G. Audisio, G. Natta, J. Am. Chem. Soc, 89, 5071 (1967). 173. N. Yahiro, S. Ito, Kobunshi Ronbunshu, 42, 427 (1985). 174. R. D. Katsarava, T. M. Kartvelishvili, M. M. Zaalishvili, Dokl. Chem., 281, 99 (1985). 175. 175 H. R. Kricheldorf, J. M. Jonte, Polym. Bull., 9, 276 (1983). 176. T. Tsunetsugu, T. Fueno, J. Furukawa, Makromol. Chem., 112, 220 (1968). 177. H. Yamaguchi, T. Iwama, T. Hayashi, Makromol. Chem., 191, 1243 (1990). 178. Y. Bando, H. Yamaguchi, Y. Minoura, Eur. Polym. J., 15,497 (1979). 179. G. Wulff, P. K. Dhal, Angew. Chem. Int. Ed. Engl., 28, 196 (1989). 180. G. Wulff, P. Kemmerer, B. Vogt, J. Am. Chem. Soc, 109, 7449 (1987). 181. T. Oishi, H. Yamasaki, M. Fujimoto, Polym. J., 23, 795 (1991). 182. F. Sanda, T. Tanaka, T. Endo, J. Polym. Sci., Polym. Chem. Ed., 33, 2353 (1995). 183. T. Oishi, K. Kagawa, M. Fujimoto, J. Polym. Sci., Polym. Chem. Ed., 33, 1341 (1995). 184. J. J. Bou, I. Iribarren, S. M.-Guerra, Macromolecules, 27, 5263 (1994). 185. Y. Okamoto, M. Nishikawa, T. Nakano, E. Yashima, K. Hatada, Macromolecules, 28, 5135 (1995). 186. S. Habaue, T. Tanaka, Y. Okamoto, Macromolecules, 28, 5973 (1995). 187. K. Kagawa, T. Oishi, Polym. J., 27, 579 (1995). 188. Y. Okamoto, H. Hayashida, K. Hatada, Polym. J., 21, 543 (1989).
189. T. Kobayashi, M. Kakimoto, Y. Imai, Polym. J., 26, 758 (1994). 190. T. Doiuchi, T. Dodoh, H. Yamaguchi, Makromol. Chem., 191, 1253 (1990). 191. T. Oishi, T. Kawamoto, Polym. J., 26, 920 (1994). 192. T. Oishi, M. Fujimoto, J. Polym. Sci., Polym. Chem. Ed., 30, 1821 (1992). 193. Y. Okamoto, M. Matsuda, T. Nakano, E. Yashima, J. Polym. Sci., Polym. Chem. Ed., 32, 309 (1994). 194. M. Sepulchre, A. Kassamaly, N. Spassky, Makromol. Chem., Macromol. Symp., 42/43, 489 (1991). 195. L. Angiolini, C. Carlini, M. Tramontini, Macromol. Chem., 191, 2083 (1990). 196. Y. Okamoto, T. Nakano, Y. Shikisai, M. Mori, Macromol. Symp., 89, 479 (1995). 197. T. Aoki, M. Kokai, K. Shinohara, E. Oikawa, Chem. Lett., 2009, (1993). 198. O. Haba, T. Kakuchi, K. Yokota, Macromolecules. 26, 1782 (1993). 199. J. J. Bou, A. Rodriquez-Galan, S. Munoz-Guerra, Macromolecules, 26, 5664 (1993). 200. T. Oishi, K. Kagawa, M. Fujimoto, Macromolecules, 26, 24 (1993). 201. T. Oishi, K. Matsusaki, M. Fujimoto, Polym. J., 24, 1281 (1992). 202. T. Kobayashi, M. Kakimoto, Y. Imai, Polym. J., 25, 741 (1993). 203. T. Oishi, Y. Otsubo, M. Fujimoto, Polym. J., 24, 527 (1992). 204. Y. Ito, E. Ihara, M. Murakami, Angew. Chem. Int. Ed. Engl., 31, 1509 (1992). 205. A. Altomare, F. Ciardelli, R. Lima, R. Solaro, Chirality 3, 292 (1991). 206. T. Oishi, M. Fujimoto, J. Macromol. Chem., Pure Appl. Chem. A, 29, 1187 (1992). 207. P. C. Kamer, R. J. M. Nolle, W. Drenth, J. Am. Chem. Soc, 110, 6818 (1988). 208. H. Hashimoto, T. Kakuchi, O. Haba, K. Yokota, Macromolecules, 25, 1828 (1992). 209. D. Pini, A. Iuliano, P. Salvadori, Macromolecules, 25, 6059 (1992). 210. H. Hashimoto, T. Kakuchi, K. Yokota, J. Org. Chem., 56, 6470 (1991). 211. T. Kakuchi, T. Satoh, J. Muta, S. Umeda, H. Hashimoto, K. Yokota, J. Macromol. Sci., Pure Appl. Chem. A, 33, 352 (1996). 212. T. Satoh, T. Hatakeyama, S. Umeda, H. Hashimoto, K. Yokota, T. Kakuchi, Macromolecules, 29, 3447 (1996). 213. T. Kakuchi, T. Satoh, S. Umeda, H. Hashimoto, K. Yokota, Macromolecules, 28, 5643 (1995). 214. T. Satoh, T. Hatakeyama, S. Umeda, K. Yokota, T. Kakuchi, Polym. J., 28, 520 (1996). 215. A. Lekchiri, J. Morcellet, M. Morcellet, Macromolecules 20, 49 (1987). 216. J.-H. Liu, F-R. Tsai, Y-C. Lai, Angew. Makromol. Chem., 231, 35 (1995). 217. A. Lekchiri, J. Morcellet, M. Morcellet, Macromolecules 20, 49 (1987).
218. Y. Chen, K. Saigo, N. Yonezawa, M. Hasegawa, Bull. Chem. Soc. Japan, 60, 1895 (1987). 219. T. Tanaka, S. Habaue, Y Okamoto, Polym. J.. 27, 1202 (1995). 220. Y. Okamoto, E. Yashima, M. Ishikura, K. Hatada, Polym. J., 19, 1183 (1987). 221. Y. Okamoto, N. Nagamura, T. Fukumoto, K. Hatada, Polym. J., 23, 1197 (1991). 222. A. Castellano, A. Lekchiri, J. Morcellet, M. Morcellet, J. Polym. Sci., Polym. Chem., 25, 1419 (1987). 223. Y Okamoto, E. Yashima, K. Hatada, J. Polym. Sci., Polym. Lett., 25, 297 (1987). 224. Y. Okamoto, T. Nakano, T. Asakura, H. Mohri, K. Hatada, J. Polym. Sci., Polym. Chem., 29, 287 (1991). 225. Y. Okamoto, T. Nakano, E. Ono, K. Hatada, Chem. Lett., 525, (1991). 226. E. Chiellini, G. GaIH, R. Po, Polym. Bull., 23, 397 (1990). 227. M. M. Green, R. A. Gross, F. C. Schilling, K. Zero, C. Crosby III, Macromolecules, 21, 1839 (1988). 228. M. M. Green, R. A. Gross, C. Crosby III, F. C. Schilling, Macromolecules, 20, 992 (1987). 229. S. Lifson, C. Andreola, N. C. Peterson, M. M. Green, J. Am. Chem. Soc, 111, 8850 (1989). 230. H. G. J. Visser, R. J. M. Nolte, J. W. Zwikker, W. Drenth, J. Org. Chem., 50, 3133 (1985). 231. H. G. J. Visser, R. J. M. Nolte, J. W. Zwikker, W. Drenth, J. Org. Chem., 50, 3138 (1985). 232. J. Huguet, D. Vallin, M. Vert, Polym. J., 14, 335 (1982). 233. T. Oishi, M. Fujimoto, J. Macromol. Sci., Chem. A, 23, 619 (1986). 234. N. Yahiro, Kobunshi Ronbunshu, 40, 371 (1983). 235. K. Saigo, Y. Chen, N. Yonezawa, T. Kanoe, K. Tachibana, M. Hasegawa, Macromolecules, 19, 1552 (1986). 236. P. C. Kamer, M. C. Cleij, R. J. M. Nolte, T. Harada, A. M. F. Hezemans, W. Drenth, J. Am. Chem. Soc, 110, 1581 (1988). 237. E. Chiellini, R. Po, S. Carrozzino, G. GaIIi1 and B. Gallot, MoI. Cryst. Liq. Cryst., 179, 405 (1990). 238. N. Spassky, A. Momtaz, A. Kassamaly, M. Sepulchre, Chirality, 4, 295 (1992). 239. G. W. Coates, R. M. Waymouth, J. Am. Chem. Soc, 115, 90 (1993). 240. Y Okamoto, T. Nakano, T. Fukuoka, K. Hatada, Polym. Bull, 26, 259 (1991). 241. Y Okamoto, T. Nakano, H. Kobayashi, K. Hatada, Polym. Bull., 25, 5 (1991). 242. Y. Takeda, Y Hayakawa, T. Fueno, J. Furukawa, Makromol. Chem., 83, 234 (1965). 243. L. Porri, R. Rossi, G. Ingrosso, Tetrahedron Lett., 1083, (1971). 244. T. Kakuchi, H. Kawai, S. Katoh, O. Haba, K. Yokota, Macromolecules, 25, 5545 (1992). 245. K. Yokota, T. Kakuchi, H. Sasaki, H. Ohmori, Makromol. Chem., 190, 1269 (1989). 246. F. Toda, K. Mori, J. Chem. Soc, Chem. Commun., 1059, (1986). 247. G. D. Jaycox, O. Vogl, Makromol. Chem., Rapid Commun., 11, 61 (1990).
248. Y. Okamoto, M. Matsuda, T. Nakano, E. Yashima, Polym. J., 25, 391 (1993). 249. J. M. van der Eijk, R. J. M. Nolte, W. Drenth, A. M. F. Hezemans, Macromolecules, 13, 1391 (1980). 250. M. Miyamoto, T. Umezawa, Polym. J., 28, 432 (1996).
251. T. Nakano, A. Matsuda, M. Mori, Y. Okamoto, Polym. J., 28, 330 (1996). 252. K. Kagawa and T. Oishi, Polym. J., 28, 1 (1996). 253. T. Nakano, Y. Shikisai, Y. Okamoto, Polym. J., 28, 51 (1996).
A n i s o t r o p y
o f
S e g m e n t s
U n i t s
o f
P o l y m e r
a n d
M o n o m e r
M o l e c u l e s
V . N . T s v e t k o v , L. N . A n d r e e v a , N . V . T s v e t k o v Institute of High Molecular Weight Compounds, Russian Academy of Sciences, St. Petersburg, Russian Federation
A. Introduction B. Tables of Anisotropy of Segments and Monomer Units of Polymer Molecules Table 1. Main-Chain Acyclic Carbon Polymers 1.1. Poly(dienes) 1.2. Poly(alkenes) 1.3. Poly(acrylic acid) and Derivatives 1.4. Poly(methacrylic acid) and Derivatives 1.5. Poly(acrylic acid) Derivatives with Mesogenic Side Groups 1.6. Poly(methacrylic acid) Derivatives with Mesogenic Side Groups 1.7. Vinyl Polymers 1.8. Poly(vinyl) Derivatives with Mesogenic Side Groups 1.9. Copolymers, Graft and Block Copolymers Table 2. Main-Chain Carbocyclic Polymers Table 3. Main-Chain Heteroatom Polymers 3.1. Poly(oxides) 3.2. Poly(esters) 3.3. Poly(amides) 3.4. Poly(peptides) and Nucleic Acids 3.5. Poly(phosphazenes) 3.6. Poly(siloxanes) Table 4. Main-Chain Heterocyclic Polymers 4.1. Poly(imides) 4.2. Poly(pyrromellitimides) 4.3. Poly(quinoxalines) 4.4. Poly(benzimidazoles), Poly(benzoxazoles) 4.5. Poly(saccharides) C. References
VII-745 Vli-746 VII-746 VII-746 VII-747 VII-747
A.
INTRODUCTION
Segmental anisotropy (a i — a2) of a chain molecule may be determined experimentally from measurements of flow birefringence in the solution of a polymer with a sufficiently high molecular weight, so that the conformation of its molecules would correspond to that of a Gaussian coil. For calculating (^ 1 — OL1) , Kuhn's equation was used (Ref. 1):
VII-748 VII-748 (Al) VII-749 VII-750 VII-751 VII-751 VII-752 VII-752 VII-752 VII-752 VII-755 VII-755 VII-755 VII-756 VII-756 VII-756 VII-756 VII-757 VII-757 VII-758 VII-760
where A r is the tangential flow stress (shearing stress), An is the observed flow birefringence of the solution, g is the velocity gradient, c and 77 are the concentration and the viscosity of the solution, respectively, [77] and [n] are intrinsic values of viscosity and flow birefringence of the solution, and 770 and n are the viscosity and the refractive index of the solvent. The value A n / A r = [n]/[rj\ may be called the shear optical coefficient. Another method of determining segmental anisotropy (which is seldom used) is through the measurement of stress birefringence in swollen polymers (74). The stress optical coefficient e = An/Ap (where Ap is the normal stress in the sample) determined experimentally is equal to AnjlAr (2), where An/Ar is also related to (a 1 - a2) * according to Eq. (Al). Data obtained by this method are marked in the table with the symbol sw. p. (swollen polymer). If the refractive indices of the polymer and the solvent are not equal, the experimental value of (OLi-Oi1) includes not only the intrinsic segmental (a\ -OL1), but also a part produced by the form effect (3,4). In this case the value a ] -OL1 may be calculated using (a 1 -OL1) and the theoretical equation for macro- and micro-form effects (3,4).
For determining a\ — Ot2, it is preferable to use the "matching" solvent in which the increment of index of the polymer, dn/dc, is equal to zero The tables give the intrinsic segmental anisotropy, a i — a 2 , obtained directly from measurements in the "matching" solvent, as well as the (a\-a2)* values including the form effect. The corresponding figures are marked with the symbol *. In some of the reviewed works in which measurements were carried out in "nonmatching" solvents, the segmental anisotropy was calculated on the basis of the theory of the form effect (3,4). In these cases the figures are marked with the symbol **. Intrinsic segmental anisotropy of the polymer chain in various solvents, even in the absence of the form effect, may differ owing to a "specific" effect of the solvent (see, e.g., poly(vinyl acetate)) (5-11). "Specific" effect may probably includes phenomena such as a change in the type of rotation of the side groups (5,6,8,12), a change in the polarizability of its bonds, and the short-range ordering of the solvent molecules (11). Principal values which effect the intrinsic segmental anisotropy of the chain are the anisotropy of the monomer unit and the equilibrium rigidity of the chain. The Kuhn segment with the length A is the measure of the equilibrium rigidity of the chain. If the chain adopts the conformation of the Gaussian coil, then we have A = (r2)/L, where L is the complete length of the extended chain and (r 2 ) is the mean square end-to-end distance. Also, a\\—a± is the difference between the polarizabilities of the monomer unit in the parallel and perpendicular directions of the chain. Values of a ^ —a^ presented in the table were calculated from
Many rigid-chain polymers have been investigated in the molecular-weight range in which their molecules exhibit a conformation intermediate between the rodlike conformation and the Gaussian coil. The best model for these polymers is the wormlike chain. Under these conditions the shear optical coefficient An/Ar varies with the molecular weight M of the polymer and is given by the equation (100) (A3) where B = (4n/45kT)(n2 4- I)1Jn, (71 - 72) is the mean value of the wormlike chain optical anisotropy, (h2) and (Zi4) are the mean square and fourth degree end-to-end distance of the wormlike chain. For the wormlike chain, the value of (71 - 7 2 ) as a function of the reduced chain length x = 2L/A is given by the equations
(A4)
According to Eqs. (A3) and (A4) the limit values of An/Ar for wormlike chains are as follows: at x —* 0, (An/Ar)0 = B(^i — 7I)JC —> 0 as for a thin rod, and at x —> 00, (An/Ar)^ x = B(a\ — Ct2) as for a kinetically flexible Gaussian coil. The dependence of An/Ar on M for the wormlike chains given by the Eqs. (A3) and (A4) may be approximated (100,101) by a linear relationship (A5) between the inverse values {An/Ar)" and M~[\
(A2) where A is the length of the monomer unit in the chain direction. For cellulose esters, a\\ —a\_ and correspondingly, a i — a 2 depend on the degrees of substitution (DS), which are also given in the table. For heterocyclic polycondensation polymers, the term "monomer unit" means the repeat unit of the polymer chain.
(A5) where MQ is the molecular weight of the repeat unit of the chain. If the experimental dependence of {An/Ar) ~ on \/M is plotted, the slope of the straight line obtained makes it possible to calculate Aa = a^ —a±, and its intercept with the ordinate gives ct\ -Qt2.
B. TABLES OF ANISOTROPY OF SEGMENTS AND MONOMER UNITS OF POLYMER MOLECULES TABLE 1. MAIN-CHAIN ACYCLIC CARBON POLYMERS Polymer
(a Il - a ;)
(fljj - a )
Solvent
xl02scm3
xl025cm3
Benzene, sw. p. Carbon tetrachloride, sw. p. sw. p. Cyclohexane, sw. p. Toluene, sw. p. /;-Xylene, sw. p.
61.3-63 53.5* 55.2* 57.3 72 86.9
Refs.
1.1. POLY(DIENES) Poly (butadiene) \A-cis
30.8 31.7* 33.9 42.6 51.4
52-54 53 54 53 53 53
TABLE 1. cont'd Polymer
Solvent
Poly(butadiene) \A-trans
Benzene sw. p. Carbon tetrachloride, sw. p. sw. p. Cyclohexane, sw. p. Toluene, sw. p. />Xylene, sw. p. a-Bromonaphthalene Carbon tetrachloride Chlorobenzene Dichloroethane cx-Methylnaphthalene Tetrachloroethylene Toluene p-Xylene Benzene Squalene, sw. p. Benzene
Poly(chloroprene)
Poly(isoprene) cis trans
1.2.
(«||
x 10 2S cm 3
71 70.4 58.1* 61.1* 57.3 81.6 101 110* 33 64 39 99 * 46 67 88 48 53.1 49
~«±)
37.4
36.3* 33.1* 48.6 60.2
30.5 31
Refs. 52 53 55 53 53 53 53 11 11 11 11 11 11 11 11 52 56 52
POLY(ALKENES)
PoIy(I-butene) atactic isotactic PoIy(I-decene) isotactic PoIy(I -dodecene) Polyethylene) PoIy(I-heptene) isotactic PoIy(I-hexadecene) isotactic Poly(l-hexene) atactic isotactic Poly(isobutene)
Poly( 1-octadecene) isotactic PoIy(I-octene) isotactic PoIy(I-pentene) isotactic Poly(diphenylpropylene) Polypropylene) atactic
isotactic Poly(l-tetradecene) isotactic
1.3.
(«-I - « i )
x 10 2 5 c m 3
Toluene Toluene Toluene Toluene Tetralin, xylene Decalin Toluene Toluene Toluene Toluene Benzene, chlorobenzene, tetrachloroethylene, m-xylene Carbon tetrachloride Decalin /7-Xylene Toluene Toluene Toluene Bromoform Benzene, xylene Carbon tetrachloride Decalin Toluene Carbon tetrachloride Toluene
33.4 25.2 -82.5 - 120 60 30 -24.5 -205 to-213 12.1 -6.5 45-59 35 30 69 -257 -39 8.0 9.3 80 45 30 30 55 30 -176 -171
13 13 13 13 14 14 13 13 13 13 11,14,15
3.5
3.5
11 14 11 13 13 13 13 16 14 17 14 13 17 13 13
POLY(ACRYLIC ACID) AND DERIVATIVES
Poly(acrylic acid) - , sodium salt Poly(H-butyl acrylate)
Poly(cetyl acrylate) Poly(cholesteryl acrylate)
Dioxane 0.0012MNacl, pH 7 Water, pH 6.1 Benzene Decalin Toluene Decalin Toluene Benzene
~-0.5** 20** -4**to-flO** - Ii -17.8 -10.1 -6.5 -141 -164 - 360
^-0.1**
18
- 1-5 -1.9 -1.1 -0.9 -6.5 -7.5 - 16
19 20 21 21 20 22 21 23
References page VII/760
TABLE 1. cont'd Polymer
Solvent
Poly(decyl acrylate)
Decalin Toluene Benzene, sw. p. Bromobenzene, sw. p. Bromoform, sw. p. Dibromoethane, sw. p. Dimethylformamide, sw. p. Benzene Toluene
Poly (ethyl acrylate)
Poly(methyl acrylate) Poly(octadecyl acrylate) Poly(octyl acrylate)
1.4.
(aH - « ± ) x 10 2S cm 3
Decalin Toluene Decalin Toluene
-74 -95 3.0 10** -37** - 1 4 ** -11** 17 16 26 - 190 -232 - 57.4 -47.9
Benzene Benzene Benzene Benzene Bromobenzene o-Toluidine Dioxane 0.1 M NaCl Benzene 0-Toluidine Dimethylformamide Ethyl alcohol Water Benzene Carbon tetrachloride Methanol 0.002 M HCl 0.012M NaCl, pH 7 0.0012 M NaCl, pH 7 Water Dibromoethane Benzene Benzene Tetrabromoethane Benzene Carbon tetrachloride o-Toluidine Bromobenzene
-14 -2.0 2.1 19.3 - 90 -230 180 * 370* - 160 — 160 1.0 - 6.0 ** -6.0** -40 - 9.7 50 * 150* 150 * 400 56 *-300 * — 77 2.0 25 -60 -47 -12.5 - 103 -10.5
(a\\ ~ « i ) x 10 2S cm 3 -3.7 -4.7 0.36 1.2** 4.5** ~ 1.7** -1.7** 2.5 1.9 3.6 - 6.6 -8.0 - 4.3 -3.6
Refs. 21 21 24 24 24 24 24 20 21 20 21 21 21 21
P O L Y ( M E T H A C R Y L I C ACID) AND DERIVATIVES
Poly(«-butyl methacrylate) atactic isotactic Poly(terf-butyl methacrylate) atactic isotactic Poly(p-te/t-butylphenyl methacrylate) Poly(p-carbethoxy-Af-phenylmethacrylamide) Poly(p-carboxyphenyl methacrylate) Poly(cetyl methacrylate) Poly(p-chloro-/V-phenylmethacrylamide) Poly(glycol methacrylate) Poly(hexyl methacrylate) Poly(methacrylic acid) -, sodium salt Poly(p-methylcarboxy-phenyl methacrylate) Poly(methyl methacrylate) atactic isotactic Poly(P-naphthyl methacrylate) Poly(octyl methacrylate) Poly(Af-phenylmethacrylamide) Poly(phenyl methacrylate)
—2.1 -0.3 0.3 3.0 - 7.5 -23 8.0* - 8.9 — 20 0.18 -1.1** -1.1** -4.6 -1.1
- 7 0.3 3.5 -8.5 -5.9 - 1.6 - 13 -1.5
25 26 20 20 22,28 40 35 35 29 40 30 30 30 31 31 32 32 33 33 34 35 38 38 4 31 31 40 4
1.5. POLY(ACRYLIC ACID) DERIVATIVES WITH MESOGENIC SIDE GROUPS
Tetrachloroethane
- 520 *
100
Tetrachloroethane
-520*
100
TABLE 1. cont'd C« H — « JL) Polymer
Solvent
x 10 2S cm 3
(flu-aj x 10 2S cm 3
Refs.
Tetrachloroethane
-630*
100
Tetrachloroethane
- 810 *
100
Tetrachloroethane
-800*
100
Tetrachloroethane
-450*
-19*
100,102
Tetrachloroethane
-510*
-21
100,102
Benzene
- 300 *
- 15 *
100,103
1.6. POLY(METHACRYLIC ACID) DERIVATIVES WITH MESOGENIC SIDE GROUPS
Carbon tetrachloride
- 445 *
- 18 *
100,105
Dimethylformamide
- 240 *
100,106
Tetrachloroethane
-500*
100
-320*
36,100
Benzene
-370*
100,107
Dioxane
- 1200*
100,106
Dimethylformamide/ toluene (1/1)
Carbon tetrachloride
- 600 *
- 40 *
100,108
Carbon tetrachloride
- 2700 *
- 110 *
100,109
Carbon tetrachloride
- 2350 *
100
References page VII/760
TABLE 1. cont'd Polymer
Copolymer with cetylmethacrylate mol% 70/30 50/50
Solvent
(«i| ~ a L) 10 2 5 cm 3
Refs.
Benzene Bromoform Chloroform Carbon tetrachloride Tetrahydrofuran Benzene/heptene (52/48), (66/34)
- 1600* -1000* - 1400* - 2700* -890* -4200*
Carbon tetrachloride Carbon tetrachloride
-1050* - 680 *
-44* - 28 *
100,93 100,93
Benzene
-3000*
-150*
100,111
Chloroform
- 4900 *
- 100 *
100,111
Carbon tetrachloride
Dioxane
Tetrachloromethane
1.7.
(«U ~ « i ) xl025cm3
-40* - 1 K)*
36 36 36 37,100 36 36
-117*
100,109
-90*
100,109
- 180* -250*
153 153
VINYL POLYMERS
Poly(acrylonitrile) PoIyO?-chlorostyrene) Poly(2,5-dichlorostyrene) Poly(3,4-dichlorostyrene) Poly(a-methylstyrene) Poly(/>methylstyrene) atactic isotactic Poly(2,5-dimethylstyrene) Poly(2-methyl-5-vinyl-/V-butylpyridinium bromide) Poly(2-methyl-5-vinyl-pyridine) Poly(2-methyl-5-vinyl-pyridinium chloride) Poly(styrene) atactic isotactic Poly(vinyl acetate)
Dimethylformamide Bromoform Bromoform Tetrabromoethane Tetrabromoethane Bromoform Bromoform Bromoform 0.01 M NaCl 0.1 M NaCl Bromoform 0.1 M HCl Bromoform Bromoform Acetone sw. p. Benzene sw. p. Bromobenzene. sw. p. Bromoform sw. p. Carbon tetrachloride sw. p. Chlorobenzene Chloroform sw. p. Cyclohexanone Dichloroethane
- 23 -230 -265 -300 -133 — ) 47 - 140 -180 - 900 * -270* - 260 - 300 * - 145 - 224 -20** _37** 4.0-5.9 5.1** 9.4** - 20 ** -18.7** - 16 -26 -25.2 14** -34.9** -24 - 17.9 -23 -36 - 39
-1.8 -35 -30 -25 -17 — 20 - 19 -25
- 29 - 18 — 23 -5.3** -5.3** 0.5 to 0.8 0.75** 1.3** -2.7** - 2.0 -3.6 1.75** -2.6** -3.0 -2.9 -4.5 - 4.9
4 41 41 15 128 42 42 41 43 43 44 45 46,41 46 7 10 6,8,9,11 10 10 7 10 9,11 6 10 11 6 9,11 10 9,11 11 11
TABLE 1.
cont'd
Polymer
Solvent Tetrabromoethane sw. p. Toluene
Poly(vinyl butyral) Poly(vinyl butyrate) Poly(vinyl chloride) Poly(vinyl cinnamate) Poly(p-vinylnaphthalene) Poly (vinyl propionate)
Poly(4-vinylpyridine) Poly(4-vinylpyridiniurn chloride) Poly(vinylpyrrolidone) Poly(vinyl stearate)
sw. p. o-Xylene sw. p. Chloroform Toluene/phenol (79/21) Benzene Carbon tetrachloride Chloroform Tetrahydrofuran Bromoform Tetrabromoethane Bromoform Benzene Carbon tetrachloride Chloroform Toluene Bromoform 0.1 M HCl 0.05 M HCl Benzyl alcohol Carbon tetrachloride
(«0-ax) xl02Scm3 -25** -33** -46.4** 10 13.5 19 9.4** 2.0 9.8** 81 173 - 8.0 - 36 -48 40 - 420 — 430 - 440 —4.4 —31 -40 1.3 -240 - 260 * -440* — 75 —130
(a\\~aL) 25 cm3
fxl0
-3.1** -6.6** 1.25 2.0 1.3** 0.25 1.4**
- 35 — 30 - 20 to - 30
-22 - 10 —4.7
Refs. 11 7 10 9,11 8 6 10 9,11 10 11,47 11,47 11,47 11,47 11,47 48 49 4 39 11,47 11,47 11,47 11,47 50 50 50 4 51
1.8. POLY(VINYL) DERIVATIVES WITH MESOGENIC SIDE GROUPS Poly[4-(4-nonyloxy-benzamido)styrene]
Benzene
-2500*
-100*
100,104
1.9. COPOLYMERS, GRAFT AND BLOCK COPOLYMERS Poly(acryl amide-comethacrylic acid ether)
R = -C 2 H 5 ;X- = - C r nmol%= 0 6 30 69 80 100 Poly(p-(4-cetoxybenzoxy)-phenyl methacrylate-co-cetyl methacrylate)
mol% 81/19 60/40 59/41 22/78 15/85 8/92 4/96
0.001 M NaCl
Water
2.5* 15 35 * 90 * 80 * 40 *
Carbon tetrachloride
157
93
-2000* -920* 540* -400* -277* -180* -16* References page VII/760
TABLE 1. cont'd Polymer
Solvent
Poly(methyl methacrylate-a>/?-r
TABLE 2.
Chlorobenzene
Carbon tetrachloride Bromoform
Bromoform Bromobenzene Chlorobenzene Chlorobenzene Bromoform Bromoform Bromoform
Chlorobenzene Benzene
(a!I - « ± ) x 10 2 S c m 3
1.5 -7.4 - 30.4 - 44 12 * -165 - 172 -198 - 202 -226 — 26 - 34 ~ 88 - 68 - 34 - 8 1190 540 700-7000 30 100-1100 22 330 180 155 110
(*||-«±) xl025cm3
Solvent
Poly(acenaphthylene) helix 4! trans PoIy(1,2,3-trimethyl-2,3-dihydro-1,6-indendiyl) Poly( 1,2,3-trimethyl-2,3-dihydro-1,6indendiyl-l,4-phenylene-ethylene)
Bromoform Bromoform Bromoform
- 300 ** - 300 ** 78
Bromoform
142
60 95
63 96
97 98 98 98,99 98 16 93 48
(«|| -«±) xl025cm3 - 13.6** - 20 **
Refs. 39 39 92 92
Solvent
((XH-(X 1 )
(aH - f l j . )
xl025cm3
xl025cm3
Refs.
POLY(OXIDES)
Poly(oxypropylene) 3.2.
94
MAIN-CHAIN HETEROATOM POLYMERS
Polymer 3.1.
Refs.
MAINCHAIN CARBOCYCLIC POLYMERS
Polymer
TABLE 3.
(«-:| ~~«±) x 10 2 5 c m 3
Cyclohexanone
18
6
57
-114
-76
58
POLY(ESTERS)
Poly(oxycarbonyloxy-1,4-phenylenecyclohexylidene-1,4-phenylene)
Bromoform Poly(oxyethyleneoxyterephthaloyl)
Dichloroethane/phenol (1/1) Dichloroacetic acid
70 48.7*
33.7*
59 89
TABLE 3. cont'd Polymer
Solvent
(«||-a±)
(fl||-«i)
x 10 2 S cm 3
x 10 2 S cm 3
Refs.
Poly(oxy-tt-methyleneoxycarbonyl-1,4-phenyleneoxyterephthaloyloxy-1,4-phenylene-carbonyl)
n=4 n=5 n=\0
Dichloroacetic acid Dichloroacetic acid Dichloroacetic acid
280 * 250 * 200 *
Dichloroacetic acid Tetrachloroethane
1800 * 1800 *
158 158
Dichloroacetic acid
3000 *
159
Dichloroacetic acid Dioxane
1600 * 1600 *
160 160
Dichloroacetic acid
600 *
161
132 * -165 *
89 89 89
Poly[ 1,4-phenylene (phenylterephthalate)]
Poly[(phenyl( 1,4-phenylene)-terephthalate]
Dichloroacetic acid
18.2*
162
Dioxane
375*
163
Dioxane
185*
163
Tetrachloroethane
153*
315 *
164
Tetrachloroethane
150*
136 *
165
Tetrachloroethane
200*
365
166
References page VII/760
TABLE 3. cont'd («l|-«±)
Polymer
(«||
-«i)
Solvent
x 1025 cm 3
x 1025 cm 3
Dioxane
260*
Tetrachloroethane Chloroform Dioxane Tetrachloroethane
186* 270* 254* 256*
168 168 168 168
Dichloroacetic acid Trifluoroacetic acid Tetrachloroethane Trifluoroacetic acid Tetrachloroethane Tetrachloroethane Tetrachloroethane Tetrachloroethane Tetrachloroethane
268* 594* 221* 396* 249* 187* 179* 188* 196*
169
Tetrachloroethane
380*
170
Tetrachloroethane
228*
170
513*
Refs. 167
Tetrachloroethane 57.5*
170
Tetrachloroethane 259*
144*
171
139*
146*
171
353*
196*
171
Tetrachloroethane
Tetrachloroethane
Dichloroacetic acid
2120*
172
TABLE 3. cont'cl Polymer
N N : T: D (moWc) =
3.3.
Solvent
T 0:1:1 0.1:1:0.9 0.2:1:0.8 0.3:1:0.7 0.4:1:0.6 0.5:1:0.5 0.6:1:0.4 0.7:1:0.3
Refs.
Tetrachloroethane
229 * 250* 335* 410* 510* 630* 740* UOO*
91
280*
91
POLY(AMIDES)
Poly(chlorohexyliminocarbonyl) Poly(hydrazocarbonyl-1,4-phenylene iminoterephthaloyl) Poly(iminocarbonyl-cyclohexylene) Poly(iminocarbonyl-1.4-phenylene) Poly[imino-(4,6-dicarboxyisophthaloyl -imino) biphenyl-4,4'-diyl] Polylimino (l-oxohexamethylene)J (PoIy(E-caprolactam)) Poly[imino-1.4-phenyleneimino-(4,6dicarboxyisophthaloylimino)-1,4phenyleneimino-terephthaloyl] Poly(imino-1.3-phenyleneiminoisophthaloyl.) Poly (imino- 1,4-phenyleneiminoterephthaloyl) Poly( imino-1,4-phenyleneimino-terephthaloyl), copolymer with poly(iminocarbonyl-l,4-phenylene) (ratio 1/9) Poly(iminio-terephthaloylimino-l,4phenylenediphenylmethyl-1,4-phenylene) Poly(/Molyliminocarbonyl)
Carbon tetrachloride Carbon tetrachloride/ pentafluorophenol (0.9/0.1) Carbon tetrachloride Dimethylsulfoxide Sulfuric acid Sulfuric acid Dimethylacetamide
4100
11
60,100
800 3000
1)
100 60
3630* 390* 10500* 75*
85* 103*
100,123 100,115 100.117,118 100
Sulfuric acid
63*
100.115
Dimethylacetamide
88*
100
Sulfuric acid Sulfuric acid Sulfuric acid
360* 5250* 4380*
Sulfuric acid
130*
Bromoform
-39
100* 206*
100,121,122 100,119,120 110,119
100.127 -5
60,100
POLY(PEPTIDES) AND NUCLEIC ACIDS
Poly("-benzyl-L-glutamate) helix coil Poly(S-carbobenzoxyniethyl-i.-cystein) Poly(s,/V-carbobenzoxy-L-lysine) helix coil Poly(L-glutamic acid) helix coil DNA
3.5.
x 10 2 5 c m 3
D
Poly(/i-butyliminocarbonyl) (Poly(butylisocyanate))
3.4.
x 10 2 5 c m 3
Dichloroethane Dichloroacetic acid Dichloroacetic acid Dimethylformamide Dichloroacetic acid Phosphate buffer 0.1 M, pH 4.2 0.1 M, pH 12.5 aqueous 0.2 M NaCl < 2MNaCl >3MNaCl
25000* 230* 22* 3600* <-f 1900* 136* - 30000 * -33000* -41000*
25* 25* 12*
- 67 *
86,87,100 88,100 86 86 86 86 86 100 154,157 154,157
POLY(PHOSPHAZENES)
PoIy(Muoroalkoxy phosphazene) -PR 2 - NR^-OCH 2 -CF., -OCHn-(CFOv-H -OCHr-(CF2)^-H
Ethyl acetate Ethyl acetate Ethyl acetate
160 145 106
155 156 156
References page VII/760
TABLE 3. cont'd Polymer 3.6.
Solvent
(«l|-ai)
(fly-fli)
x 10 25 cm 3
x 10 25 cm 3
Refs.
POLY(SILOXANES)
Poly(oxydimethylsilylene) Poly(oxyethylphenylsilylene) 14:86 Poly(oxymethylphenylsilylene) 90:10 87.5:12.5 75:25 62.5:37.5 50:50 atactic isotactic Poly(oxyphenylsilylene)
Petroleum ether Benzene Petroleum ether Decalin Benzene Decalin Decalin Benzene Decalin, tetralin Decalin, tetralin Benzene
4.7 - 230 * - 2.3 -10 -13.6 -21 - 36 ** - 25.5 - 52 ** -82** -85
0.96 77 - 29.5 173 - 0.47 77 -2.0 78 -2.7 79 -4.0 78 - 7.2 ** 78 - 5.1 79 - 10 ** 78 - 1 6 * * 78 -17 79
LADDER POLYMERS Poly(isobutylphenyl-silsesquioxane) ( 1 : 1) Poly(isohexylphenyl-silsesquioxane) ( 1 : 1) Poly(m-chlorophenyl-silsesquioxane) Poly(dichloropheny 1-silsesquioxane) Poly(3-methyl-l-butene-silsesquioxane) Poly(phenyl-silsesquioxane)
Benzene Benzene Carbon tetrachloride Bromoform Tetrabromoethane Benzene Butylacetate Bromoform
-840 -980 -4700 * - 4450 -4700 -570* -400* - 1060 to - 1800
-22 80,100 - 1 9 . 5 80,100 - 40 * 100,80 - 50 100,112 -53 100,112 - 6 . 5 * 81,100 - 4 . 2 * 81,82,100 - 23 to - 31 83-85, 100
TABLE 4. MAIN-CHAJN HETEROCYCLIC POLYMERS Ca 1 J-ax)
Polymer 4.1.
Solvent
«J|-«JL
x 10 25 cm 3
Refs.
POLY(IMIDES)
Poly(/V-2,4-dimethylphenylmaleimide) Poly(iV-isobutylmaleimide) Poly(Af-methylcitraconimide) Poly(Af,A^piperazindiyl-2,5-diketo-l,3-pyrrolidindiylhexamethylene-2,5-diketo-l,3-pyrrolidindiyl) Poly(/?-tolylmaleimide)
Bromoform Chlorobenzene Bromoform Benzyl alcohol Bromoform/cyclohexanol (60:40) Bromoform
H 2 SO 4 , 101%
4.2.
x 102S cm 3
-200 160 150 56 30 - 160
500 *
-12.5 10 16.7 31 - 10
50 *
61,100 62,100 63 64 64 65
110
POLY(PYRROMELLITIMIDES)
Poly[l,3,5,7-tetraoxo-2,3,6,7-tetrahydro-lH,5H-benzo-[l,2-c,4,5-c' dipyrrol-2,6-diyl)-1,4-phenylene] Poly[(l,3,5,7-tetraoxo-2,3,6,7-tetrahydro-lH,5H-benzo [l,2-c,4,5-c' dipyrrol-2,6-diyl)1,4-phenyleneimino-terephthaloyl-imino-1,4-phenylene]
H 2 SO 4
2500 * -4400 *
100
H 2 SO 4
3400 *
100
TABLE 4. cont'd («U-«i)
Polymer 4.3.
Solvent
xlD 2 5 cm 3
(«||
-fli)
xl025cm3
Refs.
POLY(QUINOXALINES)
Rl = nought, R2 -
Tetrachloroethane, chloroform
1750 *
100,116
Rl = nought, R2 =
Tetrachloroethane, chloroform
1060 *
100,116
Rl =
Tetrachloroethane, chloroform
650 *
100,116
4.4.
- O - , R2 =
POLY(BENZIMIDAZOLES), POLY(BENZOXAZOLES)
Poly(benzimidazole-2,6-diyl-iminoterephthaloylimino-l,4-phenylene)
5080*
360*
100,124
4900*
100
3625*
150
1250*
150
1250*
150
750*
150
Poly(benzoxazole-2,6-diyl-iminoterephthaloyliminio-l,4-phenylene)
Poly(benzoxazole-2,6-diyl-iminoterephthaloylimino1,4-(3-hydroxyphenylene))
Poly(benzoxazole-2,4-diyl-iminoterephtaloylimino1,3-(4-hydroxyphenylene)) Poly(benzoxazole-2,6-diyl-iminocarboxy-1,4-phenyleneiminoterephthaloy limino-1,4-phenylene-carboxyimino-1,4-phenylene)
5940*
360*
100,125
5940*
320*
100,126
2340*
300*
100,126
4100*
152
Poly(oxadiazole-2,5-diyl~ 1,4-phenylene) 1750*
80*
100,114
References page VII/760
TABLE 4.
cont'd
Polymer 4.5.
Solvent
(a j - a _) x K)2S cm 3
Dioxane Cadoxene 2MNaOH 0.5MNaOH Aniline Dioxane Pyridine Trichloromethane Tetrachloroethane Dioxane Dioxane Dioxane Dioxane Dioxane Dioxane Dioxane Dioxane Dioxane Dioxane Dioxane Dioxane Benzene oDichlorobenzene Dichloromethane Trichloromethane Tetrachloromethane Pentachloroethane /;«ra-Chlorotoluene a-Bromonapthaline Tetrachloromethane Tetrachloromethane Tetrachloromethane Dioxane Tetrachloroethane Tetrachloroethane Tetrachloroethane Tetrachloroethane Dioxane Dioxane Dioxane Dioxane Dioxane Dioxane Dioxane Dioxane Dioxane Dioxane Dimethylformamide Chloroform Bromobenzene Dimethylphthalate Dioxane Dioxane Tetrachloroethane Bromoform Dioxane Methyl ethyl ketone Dioxane Trichloromethane Tetrachloroethane
294* 310 * 450* 560* 260* 39* 0 - 8.4* - 57 * - 1330 * - 870 * -575* -350* -1900* -1300* -450* 1280* 1200* 1345* 1020* 405* - 110* -164* -190* -210* -223* -194* -171* 142* -228* -217* -240* -72* -150* -100* -66* -25* 365* 250* 90* 50* 65* 70 * 70* 55* - 115 * 1100* -617* -763* -914* -830* - 447 * -1350* - 34 35* 61* 144* 90* < 111 * -47.3*
(a | — r/ L) x 102? cm 3
Refs.
POLY(SACCHARIDES)
CELLULOSE ESTERS Benzyl cellulose, DS = 2.5 Carboxymethyl cellulose, DS = 0.9 Cellulose acetate, D S - 2 . 4
Cellulose acetate benzoate, D S = 55/245 Cellulose acetate benzhydroxamate, DS = 15/285 60/240 90/170 Cellulose acetate cinnamate, DS = 60/200 160/140 250/50 Cellulose acetate diphenylacetate, DS = 10/290 40/150 20/130 130/115 270/30 Cellulose acetate myristate, D S = 10/290
D S = 25/275 50/250 100/200 150/150
Cellulose
Cellulose Cellulose Cellulose Cellulose
200/100 245/55 290/10 acetate monophenylacetate, DS = 40/260 100/150 200/70 246/32 285/5 acetate a-naphthylacetate, DS = 250/50 275/25 290/10 acetate nitrobenzoate, DS = 275/25 acetate triphenylmethylate, DS = 110/145 benzoate, DS = 3.0
2.16 Cellulose butyrate, DS = 3.0
2.75
5*
5.3* 0.78* 0 - 0.21 * - 1.6 * - 26.6* - - 17.4 * -11.5* -7* -38* -26* -9* 25.6* 24.0* 26.9* 20.4* 8.1* - 2.2* -3.1* -3.8* -4.2* -4.5* -4.5* - 3.6 * 3.6* -4.6* -4.3* -4.8* -1.4* -4.3* -3.0* -1.8* -0.6* 7.3* 5.0* 1.8* 1.0* 1.3* 1.4* 1.4* 1.1* - 2.3 * 22 * -10.4* -16.4* -19.6* -17.8* 67 -27* - 26 2.7* 1.0* 5.6* 1.8* < |0.03| -1.6*
67,100 147 147 147 136 136 100 136 136 137 137 137 137 137,138 137,138 137,138 137,138 137,138 137,138 137,138 137,138 137 136 136 136 136 136 136 136 136 136 136 136 136 136 136 136 137 137 137 137 137 137 137 137 137 137 66,100 66,100 66.100 66,100 137 72,100 72,100 67 72,100 136 136 136
TABLE 4. cont'd Polymer
Solvent
Cellulose dimethylphosphonocarbamate DS = 2.0 Cellulose diphenylacetate
0.Oi M NaCl 0.2 M NaCl Acetophenone Dioxane Dioxane Dioxane Tetrachloroethane Tetrachloroethane Tetrachloroethane Tetrachloroethane Tetrachloroethane Bromobenzene Bromoform Cyclohexanone Cyclohexanone Amyl acetate Acetone Butyl acetate Ethyl acetate Cyclohexanone Cyclohexanone Dioxane Acetophenone Benzophenone 55° 80° Dioxane 21° 65° Ethyl acetate Dioxane Dioxane Ethyl acetate/dioxane (0.017/1) (0.034/1) (0.063/1) (0.091/1) (0.224/1) (0.469/1) Dioxane Ethyl acetate Cyclohexanone Dimethylacetamide Tetrachloroethane Cyclohexanone Cyclohexanone Cyclohexanone Cyclohexanone, sw. p. Acetone Dimethylformamide Cyclohexanone Cyclohexanone Cyclohexanone, sw. p. Cyclohexanone Cyclohexanone Cyclohexanone Cyclohexanone Cyclohexanone Cyclohexanone Cyclohexanone Cyclohexanone Carbon tetrachloride Dioxane Dimethylacetamide Tetrachloroethane Water
DS = 2.9 Cellulose diphenylphosphonocarbamate DS = 2.2 Cellulose hydroxypropylacetate, DS = 3.3, 2.3 Cellulose hydroxypropylbutyrate, DS = 3.3, 2.2 DS = 3.3, 0.6 Cellulose hydroxypropylcaprinate, DS = 3.3, 2.0 Cellulose hydroxypropylstearate, DS = 3.3, 0.9 Cellulose monophenylacetate DS = 2.8 Cellulose nitrate, DS = 2.8 2.7
2.3 1.9 Cellulose phenylcarbamate DS = 3.0
2.2 2.3
2.7
Cellulose stearate DS = 2.0 Cyanoethyl cellulose DS = 2.6 2.66 2.37 Cyanoethylacetyl cellulose Cyanoethyl hydroxyethyi cellulose DS= 1.8 Cyanoethyl hydroxypropyl cellulose DS = 2.4 Cyanoethyltrityl cellulose Cyanoethyl nitrate cellulose DS = 248/26 233/52 181/79 100/117 62/192 36/213 34/226 19/242 Ethyl cellulose DS = 2.5 Hydroxypropyl cellulose, DS = 2.5-3.8
(«H~«i)
(«||-«±)
x 10 25 cm 3
x 10 2S cm 3
710 * 640 * 1360 1030 * 1760* 626 *-640 400 270 490 230 230 600 478 -820 -540 - 320 * -115* - 300 * - 140 * -330 -62 149 -1100 -742 -572 - 1830 * -872* -560* -1880* - 1700 * - 1440 * -1664* -1440 * -1360* -1260* -962* -2030* -1216 * - 1254 * - 1280 * - 500 900 970 * 715 * -1-15 390 * 90 900 660 220 855 * 890 * 470 * 165 * 35 * - 190 * -115 * -190* 430 512 450 * 505
Refs.
16 * 16 * 22 22 * 35.2* 10*-13.7* 12 8.3 12
68 68 69 67 137,138 100,129 144,145 145,146 145,146 145 145 13 100,129 10.3 100,129 -14 70,100 - 9 . 0 100,130 - 5.4* 100,130 - 1 . 9 * 100,130 - 5.0 * 100,130 - 2.3* 100,130 - 8 . 4 100,131 - 2 . 0 100,132 4.8 100,132 ~ 18 69 71 71 -45.8* 100,134 100,134 -15.2* 100,134 -47.0* 100,133 - 34 * 140 - 45 * 140 -52* 140 -45 * 140 -40* 140 - 3 5 * 140 -26* 140 -40* 141 - 32 * 141 - 38 * 141 -40 * 141 72 17.8 100,135 139 139 0.4 73,74 17.0* 73,100 3.9 73,100 148 148 74 139,151 139,151 139,151 139,151 139,151 139,151 139,151 139,151 11 75 4.6 100,129 9.9* 142,143 11.3 142,143 12.4* 143
References page VII/760
TABLE 4. cont'd x 10 2S cm 3
Polymer
Solvent
Polymaltotriose
Dimethylsulfoxide Water Aqueous NaCl 0.2 M 0.15M 0.10M 0.01 M 0.005 M 0.001 M
33 to 39 109* 634* 645* 680* 980* 1300* 1750*
Acetic acid 4- NaCl, IS = 0.1 to 0.5
670*
Sulfate cellulose, sodium salt DS = 0.4
CHITINS Chitozane
x 10 25 cm 3
7 16 * 17* 16 * 16* 16* 16*
Refs.
149 149 76, 100 76,100 76,100 76,100 76,100 76,100 174
C. REFERENCES 1. W. Kuhn, H. Kuhn, HeIv. Chim. Acta, 20, 1394 (1943). 2. A. Lodge, Trans. Faraday Soc, 42, 273 (1946). 3. V. N. Tsvetkov, Chapter XIV in Bacon Ke (Ed.) "Newer Methods of Polymer Characterization", Interscience, New York, 1964. 4. V. N. Tsvetkov, V. E. Eskin, S. Ya. Frenkel, "Structure of Macromolecules in Solutions", National Lending Library for Science and Technology, Boston Spa, Yorkshire, England, 1971. 5. V. N. Tsvetkov, J. Polym. SdL, 57, 727 (1962). 6. E. V. Frisman, V. A. Andreichenko, Vysokomol. Soedin., 4, 1559 (1962). 7. E. V. Frisman, A. B. Chzu, Vysokomol. Soedin., 4, 1564 (1962). 8. V. N. Tsvetkov, N. N. Boitsova, M. G. Vitovskaja, Vysokomol. Soedin., 6, 267 (1964). 9. E. V. Frisman, G. A. Dyuzev, A. K. Dadivanyan, Vysokomol. Soedin., 6, 341 (1964). 10. V. N. Tsvetkov, A. E. Grishchenko, L. E. De-Millo, E. N. Rostovskii, Vysokomol. Soedin., 6, 384 (1964). 11. E. V. Frisman, A. K. Dadivanyan, J. Polym. Sci. C, 16, 1001 (1967). 12. V. N. Tsvetkov, Leningrad. Univ. Vestnik, Ser. Fiz. Khim, N22, 39 (1961). 13. W. Philippoff, E. G. M. Tornqist, J. Polym. Sci. C, N23, 881 (1968). 14. T. I. Garmonova, Leningrad. Univ. Vestnik, Ser. Fiz. Khim, N22, 72 (1961). 15. V N . Tsvetkov, V. E. Bychkova, S. M. Savvon, I. K. Nekrasov, Vysokomol. Soedin., 1, 1407 (1959). 16. P. Gramain, J. Leray, H. Benoit, J. Polym. Sci. C, 16, 3983 (1968). 17. V N. Tsvetkov, O. V. Kallistov, E. V. Korneeva, I. K. Nekrasov, Vysokomol. Soedin., 5, 1538 (1963). 18. V N. Tsvetkov, S. Ya. Ljubina, T. V Barskaya, Vysokomol. Soedin., 6, 1806 (1964). 19. W. Kuhn, H. Oswald, H. Kuhn, HeIv. Chim. Acta, 36, 1209 (1953).
20. V. N. Tsvetkov, N. N. Boitsova, M. G. Vitovskaja, Vysokomol. Soedin., 6, 297 (1964). 21. V. N. Tsvetkov, L. N. Andreeva, E. V. Korneeva, P. N. Lavrenko, Dokl. Akad. Nauk SSSR, 205, 895 (1972). 22. V. N. Tsvetkov, L. N. Andreeva, E. V. Korneeva, P. N. Lavrenko, N. A. Plate, V. P. Shibaev, B. S. Petrukhin, Vysokomol. Soedin., 13A, 2226 (1971). 23. V. N. Tsvetkov, E. V Korneeva, I. N. Shtennikova, P. N. Lavrenko, G. F. Kolbina, D. Hardi, K. Nitrai, Vysokomol. Soedin., 14A, 427 (1972). 24. A. E. Grishchenko, E. P. Vorobjeva, Vysokomol. Soedin., 15A, 895 (1973). 25. V. N. Tsvetkov, S. Ya. Ljubina, Vysokomol. Soedin., 1, 577 (1959). 26. V. N. Tsvetkov, M. G. Vitovskaja, S. Ya. Ljubina, Vysokomol. Soedin., 4, 577 (1962). 27. V. N. Tsvetkov, S. Ya. Magarik, Doki. Akad. Nauk SSSR, 115,911 (1957). 28. V N. Tsvetkov, I. N. Shtennikova, Zh. Tekh. Fiz., 29, 885 (1959). 29. V N. Tsvetkov, D. Hardi, I. N. Shtennikova, E. V Korneeva, G. F. Pirogova, K. Nitrai, Vysokomol. Soedin., HA, 349 (1969). 30. A. E. Grishchenko, R. I. Esrielev, Vysokomoi. Soedin., 14A, 521 (1972). 31. A. E. Grishchenko, M. G. Vitovskaja, V. N. Tsvetkov, L. N. Andreeva, Vysokomol. Soedin., 8A, 800 (1972). 32. V N. Tsvetkov, S. Ya. Ljubina, K. L. Bolevskii, Vysokomol. Soedin. Sb. Karbotsepnie Soedin., 4, 26 (1959). 33. V N. Tsvetkov, S. Ya. Ljubina, K. L. Bolevskii, Vysokomol. Soedin. Sb. Karbotsepnie Soedin., 4, 33 (1959). 34. W. Kuhn, O. Kuenzle, A. Katchalsky, HeIv. Chim. Acta, 31, 1994 (1948). 35. E. N. Zakharova, P. N. Lavrenko, G. A. Fomin, I. I. Konstantinov, Vysokomol. Soedin., 13A, 1870 (1971). 36. V. N. Tsvetkov, I. N. Shtennikova, E. I. Rjumtsev, G. F. Kolbina, I. I. Konstantinov, Ju. B. Amerik, B. A. Krentsel, Vysokomol. Soedin., HA, 2528 (1969).
37. V. N. Tsvetkov, I. N. Shtennikova, E. I. Rjumtsev, G. F. Kolbina, I. I. Konstantinov, Ju. B. Amerik, B. A. Krentsel, Vysokomol. Soedin., 15A, 2158 (1973). 38. V. N. Tsvetkov, N. N. Boitsova, Vysokomol. Soedin., 2, 1176(1960). 39. V. N. Tsvetkov, M. G. Vitovskaja, R N. Lavrenko, E. N. Zakharova. Vysokomol. Soedin., 13A, 2532 (1971). 40. V. N. Tsvetkov, V. E. Bychkova Vysokomol. Soedin., 6, 600 (1964). 41. E. V. Frisman, A. M. Maztsinivsky, N. A. Domnicheva, Vysokomol. Soedin., 2, 1148 (1960). 42. V. N. Tsvetkov, N. N. Boitsova, Vysokomol. Soedin., 5, L263 (1963). 43. V. N. Tsvetkov, S. Ya. Ljubina, V. E. Bychkova, I. A. Strelina, Vysokomol. Soedin., 8, 846 (1966). 44. I. N. Shtennikova, E. V. Korneeva, V. E. Bychkova, G. M. Pavlov, G. S. Sogomonyants, Vysokomol. Soedin., 14B, 118 (1972). 45. S. Ya. Ljubina, I. A. Strelina, G. S. Sogomonyants, S. I. Dmitrieva, O. Z. Korotkina, G. V. Tarasova, V. S. Skazka, V M. Jamschchikov, Vysokomol. Soedin., 12A, 1560 (1970). 46. V. N. Tsvetkov, S. Ja. Magarik, Dokl. Akad. Nauk SSSR, 127, 840 (1959). 47. E. V. Frisman, A. K. Dadivanyan, G. A. Dyuzhev, Dokl. Akad. Nauk SSSR, 153, 1062 (1963). 48. S. P. Micengendler, K. I. Sokolova, G. A. Andreeva, A. A. Korotkov, T. Kadirov, S. I. Klenin, S. Ja. Magarik, Vysokomol. Soedin., 9A, 1133 (1967). 49. V. N. Tsvetkov, E. N. Zakharova, G. A. Fomin, P. N. Lavrenko, Vysokomol. Soedin., 14A, 1956 (1972). 50. S. Ya. Ljubina, I. A. Strelina, G. V. Tarasova, V. S. Skazka, V. M. Jamschchikov, Vysokomol. Soedin., 14A, 1371 (1972). 51. V S . Skazka, G. A. Fomin, G. V Tarasova, I. G. Kirillova, V. M. Jamschchikov, A. E. Grishchenko, I. A. Shefer, I. S. Alekseeva, Vysokomol. Soedin., 15A, 2561 (1973). 52. I. Ja. Poddubnyi, E. G. Erenburg, M. A. Eruomina, Vysokomol. Soedin., 10A, 1381 (1968). 53. M. Fukuda, G. L. Wilkes, R. S. Stein, J. Polym. Sci. A-2, 1417 (1971). 54. T. Ishikava, K. Nagai, J. Polym. Sci. A-2, 1123 (1969). 55. T. Ishikava, K. Nagai, Polym. J. (Japan), 1, 116 (1970). 56. L. R. G. Treloar, Trans. Faraday Soc, 43, 234 (1947). 57. V. N. Tsvetkov, T. I. Garmonova, R. P. Stankevitch, Vysokomol. Soedin., 8, 980 (1966). 58. T. I. Garmonova, M. G. Vitovskaja, P. N. Lavrenko, V N. Tsvetkov, E. V. Korovina, Vysokomol. Soedin., 13, 884 (1971). 59. S. M. Savvon, K. K. Turoverov, Vysokomol. Soedin., 6, 205 (1964). 60. V. N. Tsvetkov, I. N. Shtennikova, E. I. Rjumtsev, Ju. P. Getmanchuk, Eur. Polym. J., 1, 767 (1971). 61. V N . Tsvetkov, G. V. Tarasova, E. L. Vinogradov, N. N. Kuprijanova, V. M. Jamshchikov, V. S. Skazka, V. S. Ivanov, V. K. Smirnova, I. I. Migunova, Vysokomol. Soedin., 10A, 620 (1968). 62. V. N. Tsvetkov, G. A. Fomin, P. N. Lavrenko, I. N. Shtennikova, T. V. Sheremeteva, Vysokomol. Soedin., 10A, 903 (1968).
63. M. G. Vitovskaja, V. N. Tsvetkov, L. I. Godunova, T. V. Sheremeteva, Vysokomol. Soedin., 9A, 1682 (1967). 64. T. I. Garmonova, M. G. Vitovskaja, S. V. Bushin, T. V Sheremeteva, Vysokomol. Soedin., 16A, 265 (1974). 65. V N. Tsvetkov, N. N. Kuprijanova, G. V. Tarasova, P. N. Lavrenko, I. I. Migunova, Vysokomol. Soedin., 12A, 1974 (1970). 66. V. N. Tsvetkov, I. N. Shtennikova, Vysokomol. Soedin., 6, 1041 (1964). 67. V. N. Tsvetkov, E. I. Rjumtsev, I. N. Shtennikova, T. V. Peker, N. V. Pogodina, Dokl. Akad. Nauk SSSR, 207, 1173 (1972). 68. E. N. Zakharova, L. I. Kutsenko, V N. Tsvetkov, V. S. Skazka, G. V. Tarasova, V. M. Jamschikov, Leningrad. Univ. Vestnik, Ser. Fiz. Khim., N16, 55 (1970). 69. G. I. Okhrimenko, Thesis, Inst. Macromolecular Compounds Ac. Sci. SSSR, Leningrad, 1969. 70. V. N. Tsvetkov, I. N. Shtennikova, N. A. Megeritskaya, L. S. Bolotnikova, Vysokomol. Soedin., 5, 74 (1963). 71. H. Janeschitz-Kriegl, W. Burhard, Adv. Polym. Sci., 6, 170 (1969). 72. V N. Tsvetkov, S. Ya. Ljubina, I. A. Strelina, S. I. Klenin, V. I. Kurljankina, Vysokomol. Soedin., 15A, 691 (1973). 73. V. N. Tsvetkov, A. E. Grischchenko, P. A. Slavetskaja, Vysokomol. Soedin., 6, 856 (1964). 74. V. N. Tsvetkov, A. E. Grischchenko, J. Polym. Sci. C, 16, 3195 (1968). 75. V. N. Tsvetkov, I. N. Shtennikova, Vysokomol. Soedin., 2, 808 (1960). 76. V. N. Tsvetkov, E. N. Zakharova, M. M. Krunchak, Vysokomol. Soedin., 10A, 685 (1960). 77. V. N. Tsvetkov, E. V. Frisman, N. N. Boitsova, Vysokomol. Soedin., 2, 1001 (1960). 78. V. N. Tsvetkov, K. A. Andrianov, E. L. Vinogradov, S. E. Yakushkina, Ts. V. Vardasanidze, Vysokomol. Soedin., 9B, 893 (967). 79. V. N. Tsvetkov, K. A. Andrianov, E. L. Vinogradov, V. I. Pakhomov. S. E. Yakushkina, Vysokomol. Soedin., 9A, 3 (1967). 80. V N. Tsvetkov, Makromol. Chem., 160, 1 (1972). 81. V N . Tsvetkov, K. A. Andrianov, M. G. Vitovskaja, N. N. Makarova, E. N. Zakharova, S. V. Bushin, P. N. Lavrenko, Vysokomol. Soedin., 14A, 369 (1972). 82. V. N. Tsvetkov, K. A. Andrianov, M. G. Vitovskaja, N. N. Makarova, S. V. Bushin, E. N. Zakharova, P. N. Lavrenko, A. A. Gorbunov, Vysokomol. Soedin., 15A, 872 (1973). 83. V. N. Tsvetkov, K. A. Andrianov, E. L. Vinogradov, I. N. Shtennikova, S. E. Yakushkina, V I. Pakhomov, J. Polym. Sci. C, 23, 385 (1968). 84. V. N. Tsvetkov, K. A. Andrianov, I. N. Shtennikova, G. I. Okhrimenko, L. N. Andreeva, G. A. Fomin, V. I. Pakhomov, Vysokomol. Soedin., 10A, 547 (1968). 85. V. N. Tsvetkov, K. A. Andrianov, G. I. Okhrimenko, I. N. Shtennikova, G. A. Fomin, M. G. Vitovskaja, V. I. Pakhomov, A. A. Jarosh, D. N. Andreev, Vysokomol. Soedin., 12A, 1892(1970). 86. V N. Tsvetkov, I. N. Shtennikova, V. S. Skazka, E. I. Rjumtsev, J. Polym. Sci. C, 16, 3205 (1968).
87. V. N. Tsvetkov, E. I. Rjumtsev, I. N. Shtennikova, G. I. Okhrimenko, Vysokomol. Soedin., 8, 1466 (1966). 88. V. N. Tsvetkov, I. N. Shtennikova, E. I. Rjumtsev, G. F. Pirogova, Vysokomol. Soedin., 9A, 1575 (1967). 89. V. N. Tsvetkov, L. N. Andreeva, P. N. Lavrenko, E. V. Beliaeva, O. V. Okatova, A. Yu. Bilibin, S. S. Skorokhodov, Eur. Polym. J., 20, 817 (1984). 90. V. N. Tsvetkov, L. N. Andreeva, R N. Lavrenko, O. V. Okatova, E. V. Beliaeva, A. Yu. Bilibin, S. S. Skorokhodov, Eur. Polym. J., 21, 933 (1985). 91. V. N. Tsvetkov, L. N. Andreeva, S. V. Bushin, A. I. Mashoshin, V. A. Cherkasov, Z. Edlinski, D. Sek, Eur. Polym. J., 20, 371 (1984). 92. V. N. Tsvetkov, S. Ya. Magarik, Dokl. Acad. Nauk SSSR, 115,911 (1957). 93. V. N. Tsvetkov, E. I. Rjumtsev, I. N. Shtennikova, E. V. Korneeva, G. 1. Okhrimenko, N. A. Mikhailova, A. A. Baturin, Ju. A. Amerik, B. A. Krentsel, Vysokomol. Soedin., 15A, 2570 (1973). 94. S. Ja. Magarik, Zh. Fiz. Khim., 33, 835 (1959). 95. T. M. Birshtein, V. P. Budtov, E. V. Frisman, N. K. Janovskaja, Vysokomol. Soedin., 4, 455 (1962). 96. E. V. Frisman, N. N. Boitsova, Leningrad. Univ. Vestnik, N4, 26 (1959). 97. A. Romanov, S. Ja. Magarik, M. Lazar, Vysokomol. Soedin., 9B, 292 (1967). 98. V. N. Tsvetkov, G. A. Andreeva, I. A. Baranovskaja, V. E. Eskin, S. I. Klenin, S. Ja. Magarik, J. Polym. Sci. C, 16, 239 (1967). 99. V. N. Tsvetkov, S. Ja. Magarik, T. Kadirov, G. A. Andreeva, Vysokomol. Soedin., 1OA, 943 (1968). 100. V. N. Tsvetkov, "Rigid-Chain Polymers", Consultants Bureau, Plenum, New York, 1989. 101. V. N. Tsvetkov, Vysokomol. Soedin., 25A, 1571 (1983). 102. G. M. Pavlov, E. V. Korneeva, T. I. Garmonova, D. Hardi, K. Nitrai, Vysokomol. Soedin., 2OA, 1634 (1978). 103. V. N. Tsvetkov, E. V. Korneeva, I. N. Shtennikova, P. N. Lavrenko, G. F. Kolbina, D. Hardi, K. Nitrai, Vysokomol. Soedin., 14A, 427 (1972). 104. E. I. Rjumtsev, I. N. Shtennikova, N. V. Pogodina, G. F. Kolbina, I. I. Konstantinov, Ju. B. Amerik, Vysokomol. Soedin., 18A, 439 (1976). 105. V. N. Tsvetkov, I. N. Shtennikova, E. I. Rjumtsev, N. V. Pogodina, G. F. Kolbina, E. V Korneeva, P. N. Lavrenko, O. V. Okatova, Ju. B. Amerik, A. A. Baturin, Vysokomol. Soedin., 18A, 2016 (1976). 106. G. F. Kolbina, Theses, Inst. MacromolecuJar Compounds Ac. Sci. SSSR, Leningrad, 1981. 107. V. N. Tsvetkov, E. I. Rjumtsev, I. I. Konstantinov, Ju. B. Amerik, B. A. Krentsel, Vysokomol. Soedin., 14A, 67 (1972). 108. V N. Tsvetkov, I. N. Shtennikova, E. 1. Rjumtsev, G. F. Kolbina, E. V. Korneeva, B. A. Krentsel, Ju. B. Amerik, 1.1. Konstantinov, Vysokomol. Soedin., 15A, 2158 (1973). 109. I. N. Shtennikova, T. V. Peker, G. F. Kolbina, V R. Petrov, V. S. Grebneva, I. I. Konstantinov, Ju. B. Amerik, Vysokomol. Soedin., 24A, 2047 (1982). 110. T. I. Garmonova, V N. Artem'eva, Ye. M. Nekrasova, Vysokomol. Soedin., 32A, 2062 (1990).
111. V N . Tsvetkov, I. N. Shtennikova. G. F. Kolbina, A. 1. Mashoshin, P. N. Lavrenko, S. V Bushin, A. A. Baturin, Ju. A. Amerik, Vysokomol. Soedin., 27A, 319 (1985). 112. L. N. Andreeva, E. V. Beliaeva, A. A. Boikov, A. M. Muzafarov, V. N. Emelianov, K. A. Andrianov. V. N. Tsvetkov, Vysokomol. Soedin., 21A, 362 (1979). 113. V N. Tsvetkov, K. A. Andrianov, N. N. Makarova, Wl. G. Vitovskaja, Vysokomol. Soedin., 15A, 400 (1973). 114. V N. Tsvetkov, N. A. Mikhailova, V. B. Novakovsky, A. V. Volokhina, A. B. Raskina, Vysokomol. Soedin., 22A, 1028 (1980). 115. N. V. Pogodina, L. V Starchenko, V. N. Tsvetkov. Eur. Polym. J., 16, 387 (1980). 116. V. N. Tsvetkov, V V. Korshak, I. N. Shtennikova. Kh. Raubakh, E. S. Krongauz, G. M. Pavlov, G. F. Kolbina, S. O. Tsepelevich, Vysokomol. Soedin., 21A. 83 (1979); Macromolecules, 12, 645 (1979). 117. V. N. Tsvetkov, G. I. Kudryavtsev, I. N. Shtennikova. T. V. Peker, E. N. Zakharova, V. D. Kalmykova. A. V. Volokhina, Eur. Polym. J., 12, 517 (1976). 118. V N. Tsvetkov, N. V. Pogodina. I. N. Bogatova, L. V. Starchenko, Vysokomol. Soedin., 26A, 122 (1984). 119. N. V. Pogodina, L. V. Starchenko, K. S. Pozhivilko, V. D. Kalmykova, T. A. Kulichikhina, A. V. Volokhina, G. I. Kudryavtsev, V. N. Tsvetkov, Vysokomol. Soedin., 23A, 2185 (1981). 120. V. N. Tsvetkov, I. N. Shtennikova, T. V. Peker. Eur. Polym. J., 13, 455 (1977). 121. V N . Tsvetkov, E. N. Zakharova, N. A. Mikhailova. Dokl. Akad. Nauk SSSR, 224, 1365 (1975). 122. N. A. Mikhailova, Theses, University of Leningrad. 1982. 123. V. N. Tsvetkov, N. V. Pogodina, L. V. Starchenko. Eur Polym. J., 19, 837 (1983). 124. I. N. Shtennikova, T. V Peker, T. I. Garmonova. G. F Kolbina, L. V Avrorova, A. B. Tokareva. G. I. Kudryavtsev, V. N. Tsvetkov, Vysokomol. Soedin., 23A. 2510 (1981). 125. N. A. Mikhailova, V. N. Tsvetkov, V. B. Novakovsky, Vysokomol. Soedin., 24B, 770 (1982). 126. N. V. Pogodina, L. V. Starchenko. V. N. Tsvetkov. Eur. Polym. J., 19, 841 (1983). 127. P. D. Sybert, W. H. Beever. J. K. Stille, Macromolecules, 14, 493 (1981). 128. L. N. Andreeva, E. V. Beliaeva, A. A. Boikov, P. N. Lavrenko, V. N. Tsvetkov. Vysokomol. Soedin.. 25A, 1631 (1983). 129. L. N. Andreeva, T. I. Garmonova, I. N. Shtennikova, V. N. Tsvetkov, The Fifth Meeting on Cellulose, Vladimir 1976. 130. N. V. Pogodina, K. S. Pozhivilko, A. B. Melnikov, S. A. Didenko, G. N. Marchenko, V N. Tsvetkov. Vysokomol. Soedin., 23A, 2454 (1981). 131. N. V. Pogodina, P N. Lavrenko, K. S. Pozhivilko, A. B. Melnikov, T. A. Kolobova, G. N. Marchenko, V. N. Tsvetkov, Vysokomol. Soedin., 24A, 332 (1982). 132. N. V. Pogodina, Y. B. Tarabukina, L. V. Starchenko. G. N. Marchenko, V. N. Tsvetkov, Vysokomol. Soedin., 22A, 2219 (1980). 133. L. N. Andreeva, V. Yu. Elohovski, Vysokomol. Soedin.. 19B, 111 (1977).
134. P. N. Lavrenko, E. U. Urinov, L. N. Andreeva, K. J. Linow, H. Dautzenberg, B. Philipp, Vysokomol. Soedin., 18A, 2579 (1976). 135. V. N. Tsvetkov, P. N. Lavrenko, L. N. Andreeva, A. I. Mashoshin, V. Okatova, O. I. Mikriukova, L. I. Kutsenko, Eur. Polym. J., 20, 823 (1984). 136. N. V. Tsvetkov, A. K. Khripunov, E. P. Astapenko, S. A. Didenko, Vysokomol. Soedin. 37A, 1306 (1995). 137. V. N. Tsvetkov, N. V. Tsvetkov, Russian Chem. Rev., 62, 851 (1994). 138. N. V. Tsvetkov, G. N. Marchenko, M. A. Bezrukova, S. A. Didenko, V. M. Denisov, A. K. Khripunov, A. V. Lezov, V. N. Tsvetkov, Polym. Sci. (Russ.), 35, 345 (1993). 139. N. V. Tsvetkov, L. I. Kutsenko, S. A. Didenko, Vysokomol. Soedin., 37A, 1300(1995). 140. N. V. Tsvetkov, S. A. Didenko, Vysokomol. Soedin., 35A, 1640(1993). 141. V. N. Tsvetkov, A. V. Lezov, N. V. Tsvetkov, L. N. Andreeva, Eur. Polym. J., 26, 1103 (1990). 142. I. N. Stennikova, G. F. Kolbina, V. P. Shibaev, I. V. Ekaeva, Eur. Polym. J., 26, 787 (1990). 143. I. N. Stennikova, G. F. Kolbina, Vysokomol. Soedin., 37A, 1314 (1995). 144. 1. N. Stennikova. E. V. Korneeva, G. F. Kolbina, I. A. Strelina, P. N. Lavrenko V. P. Shibaev, I. V. Ekaeva, Eur. Polym. J., 28, 353 (1992). 145. G. F. Kolbina. E. V. Korneeva, I. N. Stennikova, MoI. Mat., 5, 79 (1995). 146. I. N. Stennikova, G. F. Kolbina, E. V. Korneeva, I. A. Strelina, V. P. Shibaev. I. V. Ekaeva, Polym. Sci., 34, 1022 (1992). 147. I. N. Stennikova, T. V. Filippova, H. Dautzenberg, Vysokomol. Soedin., 35, 1459 (1993). 148. P. N. Lavrenko, I. A. Strelina, S. Ya. Magarik, L. I. Kutsenko, Vysokomol. Soedin., 37, 2007 (1995). 149. G. M. Pavlov, N. P. Evlampieva, Biophisica, 40 (6), 1220 (1995). 150. G. M. Pavlov, A. N. Kozlov, S. M. Yakopson, S. V. Usova, L. S. Efros. Vysokomol. Soedin., 27A, 30 (1985). 151. N. V. Tsvetkov, S. A. Didenko, V. N. Tsvetko, Dokl. A Nauk. SSSR, 337, 483 (1994). 152. P. N. Lavrenko. T. I. Garmonova, M. M. Gel'mont, L. S. Efros, I. M. Kralina, Vysokomol. Soedin., 34B, 45 (1992). 153. I. P. Kolomiets, P. N. Lavrenko, A. V. Lezov, A. M. Ovsipyan, H. Finkelmann, Vysokomol. Soedin., 35A, 1620 (1993). 154. E. V. Frisman. N. A. Kas'yanenko, MoI. Biol., 24 (2), 318 (1990). 155. E. 1. Rumtsev, I. N. Shtennikova, D. R. Tur, G. F. Kolbina, E. V. Korneeva. V G. Kulichikhin, Vysokomol. Soed., 31B, 648 (1990). 156. E. 1. Rumtsev, I. P. Kolomiets, I. N. Shtennikova, G. F. Kolbina, D. R. Tur, V. G. Kulichikhin, Polym. Sci., 34, 541 (1992).
157. N. A. Kas'yanenko, E. V. Frisman, S. I. Klenin, Ye. N. Bykova, I. S. Kochetkova, Vysokomol. Soedin., 29A, 1129 (1987). 158. V. N. Tsvetkov, S. V. Bushin, L. N. Andreeva, K. P. Smirnov, E. V. Belyaeva, A. Yu Bilibin, and A. R. Stepanova, Polym. Sci., 34, 229, (1992). 159. V. N. Tsvetkov, L. N. Andreeva, S. V. Bushin, E. V. Belyaeva, V. A. Cherkasov, A. I. Mashoshin, A. Yu. Bilibin, S. S. Skorokhodov, Vysokomol. Soedin., 3OA, 713 (1988). 160. V. N. Tsvetkov, L. N. Andreeva, A. P. Filippov, E. V. Belyaeva, A. Yu. Bilibin, and A. R. Stepanova, Eur. Polym. J., 27, 319(1991). 161. V. N. Tsvetkov, L. N. Andreeva, P. N. lavrenko, O. V. Okatova, E. V. Beliaeva, A. Yu. Bilibin, and S. S. Skorokhodov, Eur. Polym. J., 21, 933 (1985). 162. V. N. Tsvetkov, L. N. Andreeva, P. N. Lavrenko, O. V. Okatova, E. V. Beliaeva, A. Yu. Bilibin, and S. S. Skorokhodov, Vysokomol. Soedin. A, XXX, 1263 (1933). 163. V. N. Tsvetkov, S. V. Bushin, L. N. Andreeva, K. P. Smirnov, E. V. Belyaeva, E. P. Astapenko, A. Yu. Bilibin, A. V. Ten'kovtsev, A. R. Stepanova, Polym. Sci., 34, 536 (1992). 164. S. V. Bushin, N. V. Tsvetkov, E. P. Astapenko, V. N. Tsvetkov, E. V. Belyaeva, V. V. Zuev, S. S. Skorokhodov, Vysokomol. Soedin., 38A, 1308 (1996). 165. N. V. Tsvetkov, V. N. Tsvetkov, S. S. Skorokhodov, Vysokomol. Soedin., 38A, 1032 (1996). 166. V. N. Tsvetkov, S. V. Bushin, E. P. Astapenko, N. V. Tsvetkov, S. S. Skorokhodov, V. V. Zuev, R. Zentel, H. Potsch, Polym. Sci., 36A, 813 (1994). 167. N. V. Tsvetkov, V. N. Tevetkov, V. V. Zuev, S. S. Skorokhodov, R. Zentel, Vysokomol. Soedin., 38A, 1831 (1996). 168. N. V. Tsvetkov, N. V. Pogodina, V. V. Zuev, Vysokomol. Soedin., 38A, 1133 (1996). 169. N. V. Tsvetkov, V. V. Zuev, 1. V. Ksenofontov, S. A. Didenko, Vysokomol. Soedin. 38A, 1840 (1996). 170. V. N. Tsvetkov, L. N. Andreeva, S. V. Bushin, A. I. Mashoshin, A. Yu. Bilibin, S. S. Skorokhodov, Vysokomol. Soedin., 3OA, 2128 (1988). 171. S. V. Bushin, V. N. Tsvetkov, L. N. Andreeva, E. P. Astapenko, E. V. Belyaeva, D. N. Asinovskaya, S. S. Skorokhodov, Polym. Sci., 39, 943 (1997). 172. L. N. Andreeva, S. V. Bushin, A. I. Mashoshin, M. A. Bezrukova, V. N. Tsvetkov, A. Yu. Bilibin, S. S. Skorokhodov, Vysokomol. Soedin., 32A, 1754 (1990). 173. I. N. Stennikova, G. F. Kolbina, S. V. Bozhko, N. N. Makarova, Vysokomol. Soedin., 37B, 1585 (1995). 174. S. Ya. Lyubina, I. A. Strelina, L. A. Nud'ga, Ye. A. Plisko, I. N. Bogatova, Vysokomol. Soedin., 25A, 1467 (1983).
G e l a t i o n
P r o p e r t i e s
A.
o f
P o l y m e r
S o l u t i o n s
Hiltner
Department of Macromolecular Science, School of Engineering, Case Western Reserve University, Cleveland, O H , USA
Some polymer solutions show the phenomenon of gelation. The polymeric chains form association complexes at widely separated points at a certain reduced solvent power of the medium. This leads to the formation of a continuous physical network structure extending throughout the volume of the system. The association producing quasi-crosslinkages is a reversible process, so that the gel may be liquified and reset many times. The nature of the linkages is rather imperfectly understood, but the phenomenon is usually encountered with more or less crystalline polymers. Sometimes, sharp X-ray diffraction patterns are observed which disappear at the melting point of the gel. The table contains data for a selected number of synthetic polymers which are capable of forming physical, thermoreversible gels with various solvents. Since no standard definition or standard measurement methods have been established for physical polymer gels, the gelation properties are taken from the references cited.
EXPLANATION OF ABBREVIATIONS USED Mw
A 5 Polymer
The molecular weight of polymer refers to the weight average molecular weight unless otherwise stated. The branch density of branched polymer. The syndiotacticity diad content in %. Solvent
Poly(ethylene), low density A = 2.9 Decalin A = 6.8 Decalin A = 5.6 Decalin A = 8.9 Decalin A = 6.8 Toluene A = 6.8 o-Xylene A = 6.8 A = 6.8 Tetralin A = 3.1 Cyclohexane-CS A =4.7 (1/1, v/v) A= 12.2 A = 7.18 Cyclohexane-CS2 A=O (1/1, v/v) A = 4.07
Mw 74000 161000 137000 175000 161000 161000 161000 161000 30000 65000 222000 30000 10100 15100
Cone, (g/1) 50-140 40-140 50-140 50-140 60-150 50-140 50-150 60-140 40-75 40-75 30-75 65-95 30-65 50-95
TgQ\
Tm A//m
The temperature (in degrees centigrade) at which the gel forms when the solution is cooled; the solgel transition temperature. The melting temperature (in degrees centigrade); the gel-sol transition temperature. When DSC was used, this is the enthalpy associated with the endotherm. When other methods are used, AH is obtained from the van't Hoff plot.
Methods Used for the Measurement of Melting Temperature of the Gel 1. Flow: A U-tube in which the two limbs are joined by a capillary section is used. The gel is allowed to set with different heights in the two links and the melting point is the temperature at which flow starts from one limb to the other. 2. Ball drop: A steel ball with a known diameter or weight is placed on the gel and the gel warmed at a certain heating rate. The ball drops at the gel melting temperature. 3. DSC: Differential scanning calorimetry. 4. Tilting: The gel is warmed in the test tube and the melting point is observed when the gel begins to flow under its own weight when the upright test tube is tilted. Tgel (0C)
Tm (0C) 54-72 58-72 60-74 50-67 68-76 67-76 68-75 72-78 30-41 36-43 34-44 40-55 73-75 55-65
AH m (kj/mol)
Method
Refs.
Ball drop
6
Ball drop
8
Polymer
Solvent
Mw
Cone, (g/1)
Tgel ( C)
T 111 ( 0 C)
A / / m (kj/mol)
Method
Poly(ethylene), high density -Dichlorobenzene Poly(ethylene-co-butene-1) Decalin
Poly(ethy]ene-c<94-methylpentene-i) Poly(ethylene-ro-octene-1)
Poly(propylene) Poly(4-methylpentene-1) Poly(acrylonitrile) Poly(acrylonitrile-a?vinyl acetate)
Poly(cetyl acrylate)
Decahydronaphthalene Cyclopentane Cyclohexane Dimethyl sulfoxide DimethyJacetarnide Dimethyl sulfoxide Dimethylformamide Ethylene carbonate y-Butyrolactone n-Aliphatic alcohols C= 7 C= 8 C= 9 C=IO C=12 Hydrocarbons C=IO C=12 C =14 C = 16 /7-Decane
Cetane
Alcohols
Poly(docosyl acrylate)
Poly(octadecyl acrylate)
/7-Aliphatic alcohols C= 7 C= 8 C=IO C=12 /?-Aliphatic alcohols C= 7 C= 8 C=IO C = 12 Hydrocarbons C= 6 C= 8 C=12
220000 113000 104000 71000 55000 80000 84000 87000 83000 119000 80000 90000
200000 200000 200000 200000 200000
120 50-140 60-140 50-140 60-140 60-140 50-120 60-120 50-120 50-100 60-120 50-115 50 100 5-100 72 240-280 270-320 290-310 230-300 250-270
Tilting
26 23
Visual observation
10 22
Flow
15 18
DSC
24
DSC
24
57 57 56 56
DSC
24
38 38 37 37
DSC
24
89
10
129 86-91 87-90.5 83-88 82-89 88.5-92.5 89.5-93 89-93 91-94.5 92-95 91-94 90.5-94 97.7 80 45 35 42-75 34-46 56-66 41-72 66-73 28 28 27 26 25
100 200 400 500 700 800 900 300 500 700 900 100 200 300 400 500 600 700 800 900
Refs.
12 15 24 26 17 18 18 20 25 26 30 30 31 32 34 29 29 28 27 27 27 27 28 29
18 20 28
35 (J/g) 79 96 8 12 21 29 38 46 50 59
Polymer
Solvent
Poly(methyl methacrylate) Dimethylformamide Poly(vinyl acetate)
Poly(vinyl alcohol)
highly syndiotactic 5 = 65%
Glycerin/water (40/60)
Mw
Cone, (g/1)
Tm (0C)
AHm (kj/mol)
(60/40)
60000
(80/20)
60000
20 50 100 200 20 50 100 200 100 151 200 250
82 94 99 106 96 101 112 123 35 58 73 78
Af-Methylpyrrolidone
60000
50 100 200
87.5 101 120
54
Formamide
60000
20 50 100 200
62 68 98 106
48
90 140 200 300 0.6 0.8 1 2 3 5 0.4 0.8 1 2 3 4 5
Phenol/water
4
Bromobenzene
Dichloroethane Dimethyl phthalate
Dioxane
34000 59000 145000 235000 98000 145000 154000 34000 62000 145000 135000 154000 200000 154000 56000 103000 114200 133000 62000 145000 235000
19 5 6.5 10 12.5 100 100 100 100 100 100 80-120 100 100 100 100 10-100 100 (w/w) 50-120 50-140 40-100 30-100 20-80 100 100 100
19
15
7 20 47 58 75 82 86 102 105 118 42 59 60 72 79 88 93 28 20 29 37 42 27.3 48.0 88.3 116 44 73 42-72 85.5 99.0 116 133 52.0-104.0 50-67* 42.0-84.0 45-70 50-75 50-80 60-85 43.5 79.8 96.9
14
71
60000
Water
Refs.
54
Methanol/water (40/60)
45%
Method
A very special case of gelation is observed in cosolutions of isotactic and syndiotactic PMMA. 60000 50 77 55 100 89 200 101
57%
Poly(vinyl chloride)
7gei (0C)
58
Tilting
27
DSC
20
51
Ball drop
2
2 13.0 2
50.6 50.6 36 35 37 45
3,4 2 1
Ball drop
2
References page VII - 768
Polymer
Solvent Bromobenzene 1,2-Dichlorobenzene Nitrobenzene Butanone Tritolyl phosphate Di-isopropyl ketone Dimethyl phthalate Nitrochlorobenzene Dibutyl phthalate
Poly(styrene), atactic
Dipentyl phthalate Dihexyl phthalate Diheptyl phthalate Dinonyl phthalate Pentan-3-one Dimethylformamide Tetrachloroethane Chlorobenzene Methoxybenzene Carbon disulfide
Poly(styrene), isotactic
w-Amyl acetate Isoamyl acetate n-Butyl acetate fl-Propyl acetate 1-Chloropentane 1-Chlorobutane 1-Chloropropane Decalin
1-Chlorodecane Nitrobenzene Aniline Benzaldehyde Poly(oxy-2,6-dimethyl1-Bromonaphthalene phenylene) 1-Chloronaphthalene Carbon disulfide Poly(y-benzyl L-glutamate) Benzyl alcohol
a b
Mw
Cone, (g/1)
40-120 100 (w/w) 92 100 (w/w) 100 (w/w) 200000 100 (w/w) 56000 92 200000 100 (w/w) 56000 92 200000 100 (w/w) 200000 100 (w/w) 200000 100 (w/w) 100 (w/w) 148000 40-70 56000 92 148000 40-70 148000 40-70 148000 40-70 148000 50 56000 92 56000 92 56000 92 56000 92 56000 92 2000000 5-135 670000 10-140 410000 17-170 200000 20-150 30000 70-190 20000 90-170 4000 120-180 670000 166 670000 166 670000 166 670000 166 670000 166 670000 166 670000 166 190000 50 670000 10 670000 10 670000 10 670000 10 670000 10 25000 (Mv) 25000 (Mv) 25000 (Mv) 50000 (Mv) 30 80000 30 150000 30 300000 30 150000 50 150000 100 150000 200 150000 300 150000 400 150000 500
Tgel (0C)
154000 200000 56000 200000
12 25 -2 -20 -35 25 25
Tm (0C) 38.0-82.5 40-63° 76.2 44-68° 55-90 a 40-55° 32.7 56-76° 51.0 58-87° 54-89° 54-74° 43-75° 90-105 93.7 97-112 101-119 107-123 126 46.7 20.0 69.1 78.4 85.1 -53-7 -63-0 - 56 to - 1 0 - 70 to - 20 - 76 to - 1 2 - 72 to - 22 -55 to-23 -52 -56 -65 -68 -76 -79 -86 670 63 88 52 5 20 110 86 0 50 55 58 58 55 56 58 58.5 59 60
AHm (kj/mol) 21.0 90-110* 34.0 87-103* 90-137* 57-75* 23.1 98-102* 17.2 96-142* 89-120* 100-150* 116-139* 22.3
Method DSC
Flow Flow
10.9 35.7 61.7 43.1 31 27 26 24 10 6 5 11.7 11.4 10.6 10.6 12.2 8.0 5.8 62
Refs. 2 3,4 1 3,4 3,4 3,4 1 3,4 1 3,4 3,4 3,4 3,4 25 1 25
Tilting
1 1 1 1 1 13
DSC Tilting
11 12
Tilting
12
Ball drop
21
Ti endotherm. Ti endotherm.
REFERENCES
1. M. A. Harrison, P. H. Morgan, G. S. Park, Eur. Polym. J., 8, 1361 (1972). 2. Y. C. Yang, P. H. Geil, J. Macromol. Sci. B: Phys., 22, 463 (1983).
3. S. J. Guerrero, A. Keller, J. Macromol. Sci. B: Phys., 20 (2), 167 (1981). 4. S. J. Guerrero, A. Keller, P. L. Soni, P. H. Geil, J. Polym. Sci., Polym. Phys. Ed., 18, 1533 (1980).
5. S. J. Guerrero, A. Keller, P. L. Soni, P. H. Geil, J. Macromol. Sci. B: Phys., 20(2), 161 (1981). 6. H. Matsuda, M. Imaizumi, H. Fujimatsu, S. Kuroiwa, M. Okabe, Polym. J., 16 (2), 151 (1984). 7. H. Matsuda, K. Araki, H. Fujimatsu, S. Kuroiwa, Poiym. J., 13 (6), 587 (1981). 8. A. Takahashi, M. Sakai, T. Kato, Polym. J., 12 (5), 335 (1980). 9. P. J. Barham, Polymer, 23 (8), 1112 (1982). 10. JP 57,180,635 [82,180,635] (1982)). 11. M. Giroiamo, A. Keller, K. Miyasaka, N. Overberg, J. Polym. Sci., Polym. Phys. Ed., 14, 39 (1976). 12. S. Wellinghoff, J. Shaw, E. Baer, Macromol., 12 (5), 932 (1979). 13. H. -M. Tan, A. Moet, A. Hiltner, E. Baer, Macromol., 16 (1), 28 (1983). 14. C. F. Ryan. P. C. Fleischer, Jr., J. Phys. Chem., 69, 3384 (1965). 15. S. Vladimir, Czech. Patent 178, 638 (1979). 16. J. Bisschops. J. Polym. Sci., 17, 89 (1955).
17. J. Bisschops, J. Polym. Sci., 12, 583 (1954). 18. D. R. Paul, J. Appl. Polym. Sci., 11, 439 (1967). 19. L. Z. Rogovina, G. L. Slonimskii, L. S. Gembitskii, Ye. A. Serova, V. A. Grigor'eva, Ye. N. Gubenkova, Vysokomol Soyed. A, 15 (6), 1256(1973). 20. S. Matsuzawa, K. Yamaura, H. Kobayashi, Colloid Polym. Sci., 259, 1147 (1981). 21. S. Sasaki, M. Hikata, C. Shiraki, I. Uematsu, Polym. J., 14, 205 (1982). 22. G. Charlet, H. Phuong-Nguyen, G. Delmas, Macromol., 17, 1200(1984). 23. H.-M. Tan, B. H. Chang, E. Baer, A. Hiltner, Eur. Polym. J., 19, 1021 (1983). 24. R. V. Tal'roze, V. P. Shibaev, N. A. Plate, J. Polym. Sci. Symp., 44, 35 (1974). 25. S. A. Leharne, G. S. Park, Eur. Polym. J., 21, 383 (1985). 26. M. Okabe, M. Isayama, H. Matsuda, Polym. J., 17, 369 (1985). 27. M. Komatsu, T. Inoue, K. Miyasaka, J. Polym. Sci., Polym. Phys. Ed., 24, 303 (1986).
S E C T I O N
A
B
B
R
E
V
P
O
L
Y
M
I
A E
T R
I
V I I I
O N
N A
S M
O E
S
F
A b b r e v i a t i o n s F i b e r s ,
f o r
T h e r m o p l a s t i c s ,
E l a s t o m e r s ,
a n d
T h e r m o s e t s ,
A d d i t i v e s
H a n s - G . Elias Michigan Molecular Institute, 1910 West St. Andrews Rd., Midland, Ml 48640, USA
A. Introduction B. Abbreviations in Alphabetical Order C. Abbreviations and Acronyms Based on Poly(monomer) Names D. Abbreviations for Polymers Named After a Characteristic Polymer Croup E. Abbreviations for Polymers Produced by Chemical Transformation of Other Polymers F. Abbreviations for Blends, Reinforced Polymers, etc. G. ISO Codes for Thermoplastic Materials 1. Codes for ISO Data Blocks 1-5 1.1. ISO and DlN Codes for Data Block 1 1.2. ISO Codes for Items in Data Block 2 1.3. ISO Codes for Items in Data Block 3 1.4. ISO Codes for Extending and Reinforcing Fillers (Data Block 4) 1.5. ISO Codes for Data Block 5 H. SPI Codes for the Recycling of Plastics I. Recommended Abbreviations and Acronyms for Names of Elastomers J. Abbreviations for Textile Fibers A.
VIII-1 VIII-2 VIII-15 VIII-17
The following tables report abbreviations either found in the scientific or technical literature or recommended or proposed by the organizations listed below. Note that * and ** are part of the recommended ASTM abbreviations and acronyms and not symbols for footnotes. ANSI/ASTM
VIII-18 VIII-19 VIII-19 VIII-19 VIII-19 VHI-20 VHI-20 VIII-20 VIII-21 VIII-21 VIII-21 VIII-22
INTRODUCTION
Abbreviations and acronyms for the names of thermoplastics, thermosets, fibers, elastomers, and additives have been proposed by many national and international organizations. Some of these abbreviations were introduced by law, others are trademarks in certain countries. As a result, the same abbreviation is often used for different polymers. The same polymer may also have different abbreviations or acronyms. Furthermore, some abbreviations refer to chemical compounds (IUPAC) whereas abbreviations recommended by ASTM, BS, DIN, and ISO usually refer to plastics, fibers, elastomers, etc., that are based on the corresponding polymers, i.e., polymers plus additives, modifiers, fillers, etc.
ASTM BS DIN EDV EC ISO IUPAC WTR
American National Standards Institute (ASTM D 1600-75; D 1600-86a; D 1418-77) American Society for Testing of Materials (ASTM D 1600-64; D 1600-86a; D 1418-67; D 4020-81) British Standards (Standard 3502-1862) German Industrial Standard (DIN 7723, 7728, 16913, 55950, 60001) Data processing key of the European Textile Characterization Law European Community International Organization for Standardization (ISO 1043-1980, 1629-1980) International Union for Pure and Applied Chemistry [Pure Appl Chem., 18, 583 (1969); 40, 473 (1974); 59, 691 (1987)] Working Group Toxicology of Rubber Auxiliaries
Section B lists, in alphabetical order, the abbreviations and acronyms for thermoplastics, thermosets, fibers, elastomers, and additives. Sections C and D list the abbreviations for polymers, based on their monomeric units and characteristic groups, respectively. Section E contains abbreviations and acronyms for polymers obtained by chemical transformation of base polymers. Section F contains special abbreviations for blends, reinforced polymers, etc., and Section G the ISO and DIN codes for plastics. Section H lists the special abbreviations connected with the recycling of plastics. Recommended abbreviations and acronyms for elastomers and fibers are given in Sections I and J, respectively. The material presented has been reproduced (with small corrections and additions) with the permission of the following publishers:
Hiithig Verlag, Heidelberg (H.-G. Elias, Makromolektile, vol. II, 5th ed. 1992; Tables 2 - 5 and 8-10); VCH Verlag, Weinheim (H.-G. Elias, An Introduction to Plastics, 1993; Table 6 (incl. text)). B. ABBREVIATIONS IN ALPHABETICAL ORDER AB ABR
ABS
AC ACM
ACS
ACSP ADA ADC ADCK ADEC ADPA AE AES
AF AFK AFMU
AG Ag AI AIBN Ak AL AMMA
A/MMA
Manila hemp fibers (Abaca) (EDV); see also Ma Acrylate-butadiene rubber; elastomeric copolymer from an acrylic ester and butadiene (ANSI/ASTM, IUPAC); see also AR Acrylonitrile-butadiene-styrene; a thermoplastic from acrylonitrile, butadiene and styrene (ASTM, DIN, ISO, IUPAC) Fiber from deacetylated cellulose acetate (EDV) Elastic copolymer from an acrylic ester and a small proportion of a vulcanizable monomer, e.g., 2-chlorovinyl ether (ANSI, ASTM) Thermoplastic blend of a copolymer from acrylonitrile and styrene with chlorinated poly(ethylene) Acetyl cyclohexylsulfonyl peroxide Adipic acid Azodicarbonamide (WTR), see also ADEC Activated azodicarbonamide (WTR) Ammonium diethyl dithiocarbamate (WTR); see also ADC Condensation product from acetone and diphenylamine (WTR) Aminoethyl (with cellulosics) Thermoplastic quaterpolymer from acrylonitrile, ethylene, propylene, and styrene Other fibers (i.e., those not specified by the EDV system) Asbestos fiber reinforced plastic Elastomeric terpolymer from tetrafluoroethylene, trifluoronitrosomethane, and a small amount of nitrosoperfluorobutyric acid; nitroso rubber (ANSI/ASTM); see also CNR Alginate fiber (EDV) 1. Silver (IUPAC) 2. Esparto grass fiber (DIN) Amide-imide polymers A^/V-Azobisisobutyronitrile Angora wool (DIN) 1. Alfalfa fibers (EDV) 2. Alginate fibers (DIN); see also AG Thermoplastic copolymer from acrylonitrile and methyl methacrylate (ASTM); see also A/MMA See AMMA
An AN An-AE ANM AO Ap AP
APH APR APT
APTK
Aq AR
As AS ASA
AJS/A
ASE ASR ATE ATH ATO AU
AU-I AU-P BA BAA BBP BD BDMA BDP BDSH BFE
Calatropis fiber (DIN) Acrylonitrile Elastomeric copolymer from acrylonitrile and acrylic ester; see also ANM See AN-AE Antioxidant Alpaca wool (DIN) Elastic copolymer from ethylene and propylene; see also APR, E/P, EPM, and EPR (older German literature) Alkylated phenol See AP Elastomeric copolymer from ethylene, propylene, and an unsaturated termonomer; see also APTK, EPD, EPDM, EPT, EPTR Elastomeric copolymer from ethylene, propylene, and an unsaturated termonomer; see also APT, EPD, EPDM, EPT, EPTR Anthraquinone 1. Elastomeric copolymer from acrylic esters and olefins; see also ABR 2. Ardein fibers (DIN) 1. Arsenic (IUPAC). 2. Asbestos (DIN); see also AS Asbestos fiber (EDV); see also As Thermoplastic copolymer from acrylonitrile, styrene, and acrylic esters (ASTM); see also A/S/A Thermoplastic copolymer from acrylonitrile, styrene, and acrylic esters (DIN, ISO); see also ASA Alkylsulfonic acid ester (ISO) Alkylene sulfide rubber Aluminium triethyl Alumina trihydrate Antimony trioxide 1. Elastomeric polyurethane with polyester segments (ANSI/ASTM, ISO) 2. Polyester rubbers with carbon, oxygen, and nitrogen in the chain. Both classifications probably refer to the same type of elastomer AU, cross-linkable with isocyanates AU, cross-linkable with peroxides Condensation product of butyraldehyde and aniline (WTR) Condensation product of butyraldehyde and aniline Benzylbutyl phthalate (DIN, ISO) 1. 1,4-Butanediol 2. Derivative of benzofuran Butanediol 1,4-dimethacrylate (WTR) Butyldecyl phthalate (WTR) Benzene-1,3-disulfonyI hydrazide (WTR) Bromotrifluoroethylene polymers
BFK BHA BHET BHT BiDMC BIIR
BMC BMDC BOA BOP BOPP BP BPH BPO BR
BSH BT BTDA BTX Buna
Butyl
BVE Bw
Boron fiber reinforced plastic (German technical literature) Butylated hydroxyanisole; /-butyl-4-methoxyphenol Bis(2-hydroxyethyl) terephthalate Butylated hydroxytoluene; 2,6-di(r-butyl)p-cresol Bismuth dimethyl dithiocarbamate (WTR); see also BMDC Brominated elastomer from isobutene and isoprene; bromobutyl rubber (ANSI/ ASTM) Bulk molding compound Bismuth dimethyl dithiocarbamate (WTR) Benzyl octyl adipate ( = benzyl 2-ethylhexyl adipate) (ISO) Benzyl octyl phthalate ( = benzyl 2-ethylhexyl phthalate) Biaxially oriented polypropylene) film; balanced oriented poly(propylene) film Poly(butadiene) rubber; see also BR and CBR 2,2 '-Methylene-bis(4-methyl-6-f-butylphenol) (WTR) Dibenzoyl peroxide Elastomeric poly(butadiene); butadiene rubber (ANSI/ASTM, IUPAC); see also BP and CBR Benzene sulfonyl hydrazide (WTR) Thermoplastic poly(l-butene); see also Pb, PBT 3,3 ',4,4 '-Benzophenonetetracarboxylic dianhydride Benzene, toluene, and xylenes Butadiene elastomers (old German literature). The first types were synthesized by sodium ('Wtftrium") initiated totadiene polymerizations, hence the name "Buna"; the various grades were differentiated by numbers (hence "number Buna"). Later Buna types were copolymers from the free-radical copolymerization of butadiene with various comonomers. These types were called ''letter Buna" (Buna S = copolymer of butadiene and styrene, Buna N = copolymer of butadiene and acrylonitrile, etc.). Elastomeric copolymer from isobutene and isoprene; butyl rubber (BS); see also GR-I, IIR, PIBI Butyl vinyl ether (WTR) Cotton ("Baumwolle") (DIN); see also CO
C CA
CAB CAP CAR CBA CBR CBS CC
CDB CdDEC CDP CdPDC CE CEM CF
CFK
CFM
CFRP CHC
CHDM CHR CUR
CL CM CMBT
C
1. Carbon (IUPAC) 2. Channel black 3. Cellophane (ASTM); "Cellophan " " is a registered trademark in Germany
CMC
Saran coated cellophane (ASTM) 1. Cellulose acetate (ASTM, DIN, ISO, IUPAC); see also AC 2. Hemp fibers (EDV) Cellulose acetate-butyrate (ASTM, DIN, ISO, IUPAC) Cellulose acetate-propionate (ASTM, DIN, ISO, IUPAC) Carbon fiber Chemical blowing agent Butadiene rubber; l,4-c/.s-poly(butadiene); see also BP and BR /V-Cyclohexyl-2-benzothiazolesulfene amide 1. Cocos fiber (EDV) 2. Cupro (regenerated cellulose fibers via the copper/ammonia process (DIN); see also CU Conjugated diene butyl elastomer Cadmium diethyl dithiocarbamate (WTR); also Cd-DEDC Cresyl diphenyl phosphate Cadmium pentamethylene dithiocarbamate (WTR) Cellulose plastics in general (ASTM) Poly(chlorotrifluoroethylene) (ASTM); see also CFM, CTFE, PCTFE Thermoset from cresol and formaldehyde; cresol-formaldehyde resin (ASTM, DIN, ISO, IUPAC) 1. Man-made fiber reinforced plastic (German technical literature: "Chemie/aserverstarkter Xiinststoff") 2. Carbon fiber reinforced plastic (German technical literature); see also CRP I. Poly(chlorotrifluoroethylene) (ANSI/ ASTM); see also CEM, CTFE, PCTFE 2. Copolymer from chlorotrifluoroethylene and vinylidene fluoride Carbon fiber reinforced plastics Elastomeric copolymer from epichlorohydrin and ethylene oxide; see also ECO 1,4-Cyclohexanedimethylol Elastomeric poly(epichlorohydrin) (ISO); see also CO Postchlorinated elastomeric copolymer from isobutene and isoprene (ANSI/ ASTM) Poly(vinyl chloride) fiber (EWG; EDV); see also PVC Postchlorinated poly(ethylene) (ANSI/ ASTM); see also CPE Copper mercaptobenzothiazole, see also CuMBT 1. Carboxymethylcellulose (ASTM, DIN, ISO, IUPAC) 2. Critical micelle concentration
CMHEC CMF CN C/N CNR
CO
COX CP CP. CP2 CP4 CPE CPET
CPI CPP
CPVC
CR CRP CS CSM CSPR CSR CT
CTA CTFE CTP CTS CU
(Carboxymethyl/hydroxyethyl) cellulose Classified mineral filler Cellulose nitrate (ASTM, DIN, ISO, IUPAC); see also NC, C/N Cellulose nitrate, see also CN, NC Elastomeric terpolymer from tetrafluoroethylene, trifluoronitrosomethane, and a small amount of an unsaturated termonomer, e.g., nitrosoperfluorobutyric acid; nitroso rubber, carboxynitroso rubber; see also AFMU 1. Elastomeric poly(chloromethyl)oxirane; poly(epichlorohydrin) (ANSI/ASTM; ISO); see also CHR 2. Cotton (EDV); see also Bw Carboxylic rubber Cellulose propionate (ASTM, DIN, ISO, IUPAC) Chemically pure Alternating copolymer from vinyl ether and maleic acid Copolymer from acrylic acid and maleic acid Chlorinated poly(ethylene) (ASTM); see also CM Crystallizable poly(ethylene terephthalate) (i.e., a PET with fast-acting nucleating agents) (trade journals) cw-Poly(isoprene); see also IR, PIP Spinning paper (small cut strips from sodium cellulose or sulfite cellulose paper) or cellulon (wet strips from cellulose pulp) (DIN) 1. Postchlorinated poly(vinyl chloride) (ASTM); see also PC, PeCe, PVCC 2. Critical pigment concentration Poly(chloroprene) (ANSI/ASTM, BS, IUPAC) Carbon fiber reinforced plastics; see also CFK Casein (ASTM, DIN, ISO, IUPAC) Chlorosulfonated poly(ethylene) (ANSI/ ASTM); see also CSPR, CSR Chlorosulfonated poly(ethylene) (BS); see also CSM, CSR Chlorosulfonated poly(ethylene); see also CM, CSPR 1. Cellulose triacetate (DIN); see also CTA, TA 2. Continuous thread Cellulose triacetate (ASTM); see also CT, TA Poly(chlorotrifluoroethylene) (ASTM); see also CEM, CFM, PCTFE N-Cyclohexylthiophthalimide (WTR) Compact tension specimen Copper silk ("cupro silk" = regenerated cellulose fibers) (EDV); see also CC
CuDEC CuDMC CuMBT Culhp CV DABCOll DAC
DADI DAF DAIP DAM DAP DATBP DBDPO DBEEA DBEP DBF DBNPG DBP DBPPD DBS DBTDL DBTU DCBS DCHP DCP DDP DE DEA DEAE DEG DEHP DEP DETA DETU DGEBA DHA DHBP DHP DHS DHXP DIBA DIBP DIDA
Copper diethyl dithiocarbamate (WTR); also CDC, CuDC Copper dimethyl dithiocarbamate (WTR); see also CuDMDC Copper mercaptobenzothiazole; see also CMBT Copper laminated hard paper (German technical literature) Viscose (rayon) (DIN); see also VI Triethylenediamine = Diazabicyclo [2.2.2] octane Diallyl chlorendate; diallyl 1,4,5,6,7,7hexachlorobicyclo[2.2.2]hept-5 ene-2,3dicarboxylate (ASTM) Dianisidine diisocyanate (WTR) Diallyl fumarate (ASTM) Diallyl isophthalate resin (ASTM) Diallyl isophthalate resin (ASTM) Diallyl phthalate resin (ASTM, DIN); see also FDAP Diallyl tetrabromophthalate Decabromodiphenyl oxide Dibutoxyethoxyethyl adipate (WTR) Bis(2-butoxyethyl) phthalate Dibutyl fumarate Dibromoneopentyl glycol Dibutyl phthalate (ASTM, DIN, ISO, IUPAC) A^r,A^/-Di(5-butyl)-/7-phenylenediamine (WTR) Dibutyl sebacate Dibutyltin dilaurate Dibutyl urea (WTR) Benzothiazyl-2-dicyclohexylsuIfene amide (WTR) Dicyclohexyl phthalate Dicapryl phthalate (ASTM, DIN, ISO, IUPAC) Didecyl phthalate Diatomaceous earth A^iV-Diethylaniline (Diethylamino)ethyl- (with cellulose) Diethylene glycol Bis(2-ethylhexyl) phthalate; see also DOP Diethyl phthalate (ISO) Diethylenetriamine (WTR) Diethyl thiourea (WTR) Diglycidyl ethers of bisphenol A Dehydroacetic acid, acetic anhydride 2,4-Dihydroxy benzophenone (WTR) Diheptyl phthalate (ISO) Dihexyl sebacate (WTR) Dihexyl phthalate (ISO) Diisobutyl adipate Diisobutyl phthalate (DIN, ISO) Diisodecyl adipate (ASTM, DIN, ISO, IUPAC)
DIDG DIDP DINA DINP DIOA DIOF DIOM DIOP DIOS DIOZ DIPP DITDP DITP DLTDP DMA DMAA DMAC DMBPPD DMBS DMC DME DMEP DMF DMG DMHPPD DMP DMPTD DMSO DMT DMTD DMTDP DMTDS DNA DNHZ DNODA DNPDP DNP DNPT DNS
DOA DODP
Diisodecyl glutarate Diisodecyl phthalate (ASTM, DIN, ISO, IUPAC) Diisononyl adipate (ISO) Diisononyl phthalate (DIN, ISO) Diisooctyl adipate (ASTM, DIN, ISO, IUPAC) Diisooctyl fumarate Diisooctyl maleate (WTR) Diisooctyl phthalate (ASTM, DIN, ISO, IUPAC) Diisooctyl sebacate Diisooctyl azelate Diisopentyl phthalate Diisotridecyl phthalate (DIN, ISO); see also DITP Diisotridecyl phthalate (DIN); see also DITDP Dilauryl 3,3 '-thiodipropionate A^Af-Dimethylacetamide /V,/V-Dimethylacetoacetamide /V,/V-Dimethylacetamide AH1,3~Dimethylbutyl)-N '-phenyl-/?-phenylenediamine (WTR) Dimethylbenzothiazylsulfeneamide (WTR) Dough molding compound (UP resin) (DIN) 1. Dimethylethanolamine, 2-(dimethyla~ mino)ethanol Bis(2-methoxyethyl) phthalate 1. /V,AT-Dimethyl phthalate (ISO); 2. NJVdimethyl formamide Dimethyl glutarate Ar,A^r/-Di(3-methylheptyl)-/?-phenylenediamine (WTR) Dimethyl phthalate (ISO) Dimethylphenyl thiuram disulfide (WTR) Dimethyl sulfoxide Dimethyl terephthalate 2,5-Dimercapto-l,3,4-thiadiazole (WTR) Dimyristyl-3,3 '-thiodipropionate 2,5-Dimercapto-1,3,4-thiadiazole disulfide (WTR) 1. Deoxyribonucleic acid 2. Dinonyl adipate Di(w-hexyl) azelate Di(fi-octadecyl) adipate Di(w-octadecyl) phthalate (ASTM) Dinonyl phthalate (ASTM, ISO, IUPAC) AyV~Dinitrosopentamethylene tetramine 1. Di(3,5,5-trimethylhexyl) sebacate (WTR) 2. Deoxyribonucleic acid (German: Des oxyribonukleinsaure) Dioctyl adipate, bis(2-ethylhexyl)adipate (ASTM, DIN, ISO, IUPAC) Di(octadecyl) phthalate (ISO)
DOF DOIP DOM DOP DOS DOTG DOTP DOZ DPA DPCF DPCP DPG DPOF DPOP DPP DPPD DPQD DPTD DPTH DPDM DPTT DPTU DR DRC DS DSTDP DTBP DTDC DTDM DTDP DTPD
DUP DVB
EA EAA EAM EBM
Dioctyl fumarate Dioctyl isophthalate, bis(2-ethylhexyl) isophthalate (DIN, ISO) Dioctyl maleate, bis(2-ethylhexyl) maleate (WTR) Dioctyl phthalate, bis(2-ethylhexyl) phthalate (ASTM, DIN, ISO, IUPAC) Dioctyl sebacate, bis(2-ethylhexyl) sebacate (ASTM, DIN, ISO, IUPAC) M/V'-DKo-tolyOguanidine (WTR) Dioctyl terephthalate, bis(2-ethylhexyl) terephthalate (DIN, ISO) Dioctyl azelate, bis(2-ethylhexyl) azelate (ASTM, DIN, ISO, IUPAC) Diphenylamine Diphenyl cresyl phosphate (ASTM, ISO); see also DPCP Diphenyl cresyl phosphate (ASTM, ISO); see also DPCF AW'-Diphenylguanidine (WTR) Diphenyl 2-ethylhexyl phosphate (ASTM, ISO); see also EHDPP Diphenyl octyl phosphate 1. Diphenyl phthalate 2. Dipropyl phthalate Af5Af'-Diphenyl-/?-phenylene diamine (WTR) Dibenzoyl-/?-quinone dioxime Di(pentamethylene)thiuram hexasulfide, see also DPTH Di(pentamethylene)thiuram hexasulfide (WTR), see also DPTD Di(pentamethylene)thiuram monosulfide (WTR) Di(pentamethylene)thiuram tetrasulfide (WTR) Diphenyl thiourea (WTR) Degree of reaction Dry rubber content Degree of substitution Distearyl 3,3 '-dithiopropionate Di(r-butyl) peroxide (WTR) Dithiodicaprolactam (WTR) 4,4-Dithiodimorpholine (WTR) Di(tridecyl) phthalate 1. Di(tridecyl) phthalate 2. N,N '-Ditolyl-p-phenylenediamine (WTR) Di(undecyl) phthalate Divinyl benzene
Segmented polyurethane fiber (Elasthan fiber) (EDV); see also PUE Ethylene acrylic acid copolymers Elastomeric copolymer of ethylene and vinyl acetate (ANSI/ASTM) Extrusion blow molding
EC ECB ECO
ECTFE E-CTFE EDA EDC EDMA EDTA EEA E/EA EG EHDPP EHEC EL ELO EMA
EOT EP E/P EPC EPD
EPDM
EPE EP-G-G EP-K-L EPM
EPR
EPS EPT
Ethyl cellulose (ASTM, DIN, ISO, IUPAC) Blends from ethylene copolymers with bitumen Elastomeric copolymer from ethylene oxide and epichlorohydrin, chloromethyloxirane (ANSI/ASTM); see also CHC Poly(ethylene-co-chlorotrifluoroethylene); see also E-CTFE Poly(ethylene-cr>chlorotrifluoroethylene); see also ECTFE Ethylene diamine (WTR) Ethylene dichloride, 1,2-dichloroethane Ethylene glycol dimethacrylate Ethylenediaminetetraacetic acid Elastomeric copolymer from ethylene and ethyl acrylate (ASTM); see also E/EA Elastomeric copolymer from ethylene and ethyl acrylate (ISO); see also EEA Ethylene glycol 2-Ethylhexyldiphenyl phosphate; see also DPOF Hydroxyethylcellulose Elastodiene fiber (EDV); see also EU, LA Epoxidized linseed oil (DIN, ISO) 1. Copolymer from ethylene and methacrylic acid (ASTM) 2. Alternating copolymer from ethylene and maleic anhydride Ethylene oxide polysulfide Epoxy resin (ASTM, DIN, ISO, IUPAC) Copolymer from ethylene and propylene (ISO); see also AP, APR, EPM, EPR Easy processing channel black Elastomeric terpolymer from ethylene, propylene, and a nonconjugated diene (ASTM); see also APT, EPDM, EPT, EPTR Elastomeric terpolymer from ethylene, propylene, and a nonconjugated diene (ASTM); see also, APT, APTK, EPD, EPT, EPTR Ester of an epoxy resin (DIN) Prepreg from an epoxy resin and a textile glass fabric (German technical literature) Prepreg from an epoxy resin and a carbon fiber fabric (German technical literature) Elastomeric copolymer of ethylene and propylene (ANSI/ASTM, ISO); see also AP, APR, E/P, EPM, EPR Elastomeric copolymer of ethylene and propylene (BS); see also AP, APR, E/P, EPM Expanded poly(styrene) [poly(styrene) foam] Elastomeric terpolymer from ethylene, propylene and a diene; see also APT, APTK, EPD, EPDM, EPTR
EPTD EPTM EPTR
E-PVC ERM E-SBR ESC ESCR ESO ET ETCH ETFE E/TFE ETG ETMQ EU
EVA
E/VAC EVAL K E/VAL EVE EVOH H EVM
F FC FDAP FE FEF FEP
FF
Diethyl diphenyl thiuram disulfide (WTR) Diethyl diphenyl thiuram monosulfide (WTR) Elastomeric terpolymer from ethylene, propylene and a diene (BS); see also APT, APTK, EPD, EPDM, EPT Emulsion-polymerized poly(vinyl chloride) Elastin reservoir molding Copolymer from styrene and butadiene, polymerized in emulsion Environmental stress cracking Environmental stress cracking resistance Epoxidized soy bean oil (DlN, ISO) Ethylene polysulfide Ethylene chlorohydrine; 2-chloroethanol Copolymer of ethylene and tetrafluoroethylene (ASTM) Copolymer of ethylene and tetrafluoroethylene Ethylene triglycol 2,2,4-Trimethyl-1,2-dihydro-6-ethoxy quinoline (WTR) 1. Elastomeric polyurethane with polyether segments (ANSI/ASTM) 2. Polyether rubber with carbon, oxygen, and nitrogen in the polymer chain (ISO) 3. Elastodiene fibers (ASTM); see also EL, LA Classifications 1 and 2 probably refer to the same polymer Copolymer from ethylene and vinyl acetate (ASTM, DIN, ISO); see also E/VAC, EVM, VAE Copolymer from ethylene and vinyl acetate (ASTM, DIN); see also E/VAC, EVM, VAE Copolymer of ethylene and vinyl alcohol Copolymer of ethylene and vinyl alcohol Ethylene vinyl ether Copolymer with ethylene and vinyl alcohol units Elastomer from ethylene and vinyl acetate; see also EVA, E/VAC, VAE 1. Fluorine (IUPAC) 2. Furnace black Fluorocarbon Diallyl phthalate or resins therefrom, see also DAP Fluorine containing elastomer Fast extruding furnace black Copolymer from tetrafluoroethylene and hexafluoropropyiene (ASTM, DIN, ISO, IUPAC); see also PFEP 1. Resin from furan and formaldehyde (ASTM) 2. Fine furnace black
Fi FK FKM
FL Fl FMQ FPM
FPVC FQ FR FRP FSI FT FVMQ FVSI GC GEP GF GF-EP GFK GF-PF GF-UP GI GL GP GPF GPO
GR
GR-A GRAS GR-I GR-N GRP GR-P
Fique (DIN) Fiber reinforced plastic ("faserverstarkter Kunststoff"; German technical literature) Elastomer with saturated main chain and fluoro, perfluoroalkyl, or perfluoroalkoxy substituents (ANSI/ASTM); see also FPM Fluorofiber (EDV); probably fibers from poly(tetrafluoroethylene) Flax (DIN) Methyl fluorosilicone rubber; see also MFQ 1. Elastomeric copolymer from vinylidene fluoride and hexafluoropropylene (ASTM) 2. Fluoroelastomers in general 3. Rubbers having fluoro and fluoroalkyl or fluoroalkoxy substituent groups at the polymer chain (ISO) Flexible PVC film Elastomeric silicone with fluorine containing substituents (ASTM); see also FSI Flame retardant Glass fiber reinforced polyester Fluorinated silicone (ASTM); see also FQ Fine thermal black Silicone rubber with fluorine, vinyl, and methyl substituents (ANSI/ASTM) Fluorosilicone Glass coupled Glass fiber reinforced epoxy resin Glass fiber reinforced plastic; see also GFK Glass fiber reinforced epoxy resin Glass fiber reinforced plastic (German technical literature) Glass fiber reinforced phenolic resin Glass fiber reinforced unsaturated polyester (German technical literature) Broom (fibers from) (EDV) Glass fiber (DIN, EDV) 1. Gutta percha 2. General purpose (ASTM) General purpose furnace black Elastomeric copolymer from propylene oxide and allyl glycidyl ether (ANSI/ ASTM) 1. Glass fiber reinforced 2. Former US symbol for "government rubber" Former US symbol for nitrile rubber; see also GR-N Generally recognized as safe Former US symbol for butyl rubber Former US symbol for nitrile rubber; see also GR-A Glass fiber reinforced plastic Glass fiber reinforced plastic
GR-S Gu GU GUP GUR GV HA HAF HBPA HDI HDPE
He HE HEC HEMA HEXA HF HFIP HFP Hgw HIPS Hm HM HMC HMDAC HMDI HMF HMPT HMT HMWPE H-NBR HP HPA HPC HPMC HPT
Former US symbol for styrene-butadiene rubber Guanaco wool (DIN) Fibers from diene rubbers (old German technical literature) Glass fiber reinforced unsaturated polyester resins (German technical literature) Ultrahigh molecular weight polyethylene); see also UHMPE Glass fiber reinforced thermoplastics Human hair (EDV) High abrasion furnace black 2,2-bis(4-hydroxycyclohexyl)propane Hexamethylene-1,6-diisocyanate (WTR) High-density poly(ethylene) (ASTM); in the older German technical literature, HDPE was sometimes used for polyethylene) from high pressure polymerizations ("Hochdruck"), i.e., for poly(ethylene)s with mostly low densities; see also PEH 1. Helium 2. Henequen (DIN); see also HE Henequen (EDV); see also He Hydroxyethylcellulose 2-Hydroxyethyl methacrylate Hexamethylene tetramine (WTR); see also HMT Half linen (EDV) Hexafluoroisopropanol; 1,1,1,3,3,3-hexafluoro-2-propanol; see also HFP 1. Hexafluoroisopropanol; see also HFIP 2. Hexafluoropropene Hard fabric ('' Hartgewebe'', German technical literature) High impact poly(styrene) Hard mat (German technical literature) Hot melt adhesive Sheet molding compound with high glass fiber content (UP resin) (DIN) Hexamethylene diamine carbamate (WTR) Hydrogenated diphenylmethane diisocyanate High-modulus furnace black Hexamethylphosphoric acid triamide; see also HPT Hexamethylene tetramine Poly(ethylene) with very high molar mass (molecular weight) Hydrogenated nitrile rubber Hard paper (German technical literature) Hydroxypropyl acrylate 1. Hydroxypropyl cellulose 2. Hard processing channel black (Hydroxypropyl)methyl cellulose Hexamethyl phosphorotriamide; see also HMPT
HR Hs HS HTBA HTE HTST Hz ICR IEN IFR IHPN HR
IM IMW IPA IPDI IPN IPO IPP IPPD IR IRT IS IT IVE
High resiliency foam Hare hair (DIN) 1. Heat stabilized 2. High percent solids High temperature blowing agent Hydroxyl terminated polyether High-temperature, short-term processing Goat hair ("Haar von der Ziege"; DIN) Initial concentration rubber (from undiluted natural rubber latex) Interpenetrating elastomeric network Intumescent flame retardant Interpenetrating homopolymer network Elastomeric copolymer from isobutene and isoprene (ANSI/ASTM, IUPAC); see also Butyl, GR-I, PIBI Poly(isobutylene); see also PIB Intermediate molecular weight Isophthalic acid 3-Isophorone diisocyanate (WTR) Interpenetrating polymer network Isopropyl oleate Isopropyl percarbonate; diisopropyl peroxydicarbonate iV-Isopropyl-N '-phenyl-p-phenylenediamine (WTR) Synthetic ds-i,4-poly(isoprene) (ANSI/ ASTM, BS, IUPAC); see also CPI, PIP Insect resistant treated Insoluble sulfur (WTR) Interrupted or split thread Isobutyl vinyl ether
Ju JU
Jute (DIN); see also JU Jute (EDV); see also Ju
KA KE KEK Kf KFA Km Kn Ko Kp KP Kz
Casein fibers (DIN) Kenaf (EDV); see also Kf Carbon fiber reinforced plastic (DIN) Kenaf (DIN); see also KE Potassium fatty acid soap Camel hair (DIN) Rabbit hair (DIN) Coir (DIN) Kapok (DIN); see also KP Kapok (EDV); see also Kp Cashmere goat wool (DIN)
LA
Fibers from diene rubbers (DIN); see also EL, EU Low-density poly(ethylene) (ASTM); in the older German technical literature, LDPE was sometimes used for polyethylene) from low pressure polymerizations, i.e., for poly(ethylene)s with mostly high densities; see also NDPE
LDPE
LI LIM LIPN LLDPE Lm LRM LRMR L-SBR M Ma MA MABS MAN MBI MBS
MBSS MBT MBTS MC MCB MD MDA MDAC MDI MDPE ME MEK MEKP MF MFK MFQ
MG MMA Mo MOCA MOD MP MPE
Linen, flax (EDV) Liquid impingement molding (now RIM) Latex interpenetrating polymer network Linear low-density poly(ethylene) (ASTM) Llama wool (DIN) Liquid reaction molding (now RIM) Reinforced liquid reaction molding Solution polymerized SBR Medium thermal carbon black Manila hemp fibers (Abaca) (DIN) 1. Modacrylic fiber (EDV); see also PAM 2. Maleic anhydride Copolymer from methyl methacrylate, acrylonitrile, butadiene, and styrene Methacry lonitri Ie Mercaptobenzimidazole; 2-benzimidazolethiol 1. Copolymer from methyl methacrylate, butadiene, and styrene 2. Benzthiazyl-2-sulfene morpholide (WTR) 2-(4-Morpholinyldithio)benzothiazole (WTR) Mercaptobenzothiazole; 2-benzthiazolethiol 2-Benzthiazolyl disulfide Methyl cellulose Monochlorobenzene Modal fiber (EDV) 1. Methylenediamine 2. 4,4 '-Diaminodiphenylmethane 4-Methyl-7-(diethylarnino)coumarine 4,4 '-Diphenylmethane diisocyanate; methylene di-/>phenylene diisocyanate Poly(ethylene) with medium density ( « 0.93-0.94 g/cm3) (ASTM) Metal fiber (EDV) Methyl ethyl ketone; 2-butanone Methyl ethyl ketone peroxide Melamine-formaldehyde resin (ASTM, DIN, ISO, IUPAC) Metal fiber reinforced plastic (German technical literature) Silicone rubber having both methyl and fluorine substituent groups on the polymer chain (ISO); see also FMQ Maguey (EDV) Methyl methacrylate (ASTM) 1. Molybdenum (IUPAC) 2. Mohair wool (DIN) 4,4/-Methylenebis(2-chloroaniline); 3,3 'dichloro-4,4'-diaminodiphenylmethane Modacryl fiber (EWG) Melamine-phenol -formaldehyde resin; see also MPF Metallized polyester film
MPF MPPPD MPQ
MPTD M-PVC MPVQ
MQ MR Ms MSA MT MTI MTM MVQ
MWR
NBR
NC NCR NDBC NDGA NDI NDOP NDPA NDPE NEM Nf NHDP NIR NK NMP NODA NODP NPG NPP NR
Melamine-phenol-formaldehyde resin (ISO); see also MP ^MethyI-2-pentyl-N'-phenyl-/?-phenylene diamine (WTR) Silicone rubbers having both methyl and phenyl substituent groups on the polymer chain (ISO); see also PMQ Dimethyl diphenyl thiuram disulfide (WTR) PVC, polymerized in bulk (mass) (German technical literature) Silicone rubbers having methyl, phenyl, and vinyl substituent groups on the polymer chain (ISO); see also PVMQ Elastomeric silicones with methyl substituents (ANSI/ASTM) Mold resistant Silk from the silkworm (mulberry spinner; Bombyx inori L) (DIN) Maleic anhydride (German technical literature) Metal fibers (DIN); see also ME Methylene tri(/?-phenylene isocyanate) Mixed tertiary mercaptans Silicone rubbers having both methyl and vinyl substituent groups on the polymer chain (ISO); see also VMQ Molding with rotation
Elastomeric copolymer from butadiene and acrylonitrile; nitrile rubber (ANSI/ ASTM, BS, IUPAC); see also GR-N, PBAN Cellulose nitrate; see also SN Elastomeric copolymer from acrylonitrile and chloroprene (ANSI/ASTM, IUPAC) Nickel dibutyl dithiocarbamate (WTR) Nordihydroguaiaretic acid 1,5-Diisocyanatonaphthalene (WTR) n-Decyl-w-octyl phthalate; see also ODP Af-Nitrosodiphenylamine (WTR) Low-density poly(ethylene); see also LDPE iV-Ethylmorpholine Phormium (DIN) /?-Hexyl-f7-decyl phthalate Elastomeric copolymer from acrylonitrile and isoprene (ANSI/ASTM) Natural rubber; see also NR /V-Methylpyrrolidone 7?-Octyl-7?-decyl adipate /7-Octyl-«-decyl phthalate; see also ODP Neopentyl glycol /?-Propyl percarbonate; dipropyl peroxydicarbonate Natural rubber (ANSI/ASTM, IUPAC); see also NK
OBSH ODP ODPA ODPP OER OPET OPP OPR OPS OPVC OT OTBG OTOS
P3FE PA
PA* PA** PAA PAB PABM PAC PAE PAI PAM PAMS PAN
PAPA PAPDC PAPI
^,p'-Oxybisfaenzenesulfonyl hydrazide) Octadecyl phthalate (ISO); see also NODP Octylated diphenylamine (WTR) Octyldiphenyl phthalate Oil-extended rubber Oriented poly(ethylene terephthalate) Oriented poly(propylene) film or bottles; see also PP Elastomeric polymer from propylene oxide Oriented poly(styrene) film Oriented poly(vinyl chloride) Polysulfide rubber o-Tolyl biguanide (WTR) /V-Oxydiethylenedithiocarbamyl-N '-oxydiethylenesulfamide (WTR) Poly(trifluoroethylene) (IUPAC) 1. Polyamide (ASTM, DIN, ISO, IUPAC); the acronym PA is normally followed by a number, a combination of numbers, a letter, or a combination of letters and numbers. A single number / refers to a polyamide from an oc,co-amino acid or its lactam with / carbon atoms in the aliphatic chain of the monomeric unit. A combination of two numbers indicates polyamides from the polycondensation of a diamine and a dicarboxylic acid; the first number gives the number of methylene groups of aliphatic diamines, the second number the number of carbon atoms of straight-chain aliphatic dicarboxylic acids. Both numbers are sometimes separated by a period. 44 I" stands for isphthalic acid, " T " for terephthalic acid. 2. Phthalic anhydride Saran coated polyamide (ASTM) Metal coated polyamide (ASTM) Poly(acrylic acid) (ASTM) p-Aminobiphenyl Polyaminobismaleimide Poly(acrylonitrile) fiber (DIN, IUPAC); see also PAN, PC Phthalate ester plasticizer Polyamide-imide (ASTM) Modacryl fiber (DIN); see also MA Poly(cx-methyl styrene) 1. Poly(acrylonitrile) fiber (ASTM, IUPAC, EDV); see also PAC, PC. PAN K is also a German trademark. 2. Phenyl-a-naphthylamine (WTR) Polyazelaic polyanhydride Pentamethylene ammonium /V-pentamethylene dithiocarbamate (WTR) Polymethylenepolyphenylene isocyanate; see also PMPPI
PARA PAS
PAT PB
PBA PBAN PBB PB I PBMA PBNA PBR PBS PBT
PBTP PC
PCB PCD PCDT PCF PCO PCTFE
PCU PDAP PDMS PE
PEA PEC PeCe
Polyarylamide (ASTM) 1. Polyaryl sulfone 2. Poly(acrylic acid) (German technical literature) Polyaminotriazole 1. PoIy(I-butene) (ASTM, DIN, ISO); see also BT, PBT 2. Polyurea fiber (EDV); see also PUA 3. Elastic polydiene fiber (German technical literature) Physical blowing agent Copolymer from butadiene and acrylonitrile (ASTM); see also GR-N, NBR Polybrominated biphenyl Poly benzimidazole Poly(rc-butyl methacrylate) Phenyl-p-naphthylamine; N-phenyl-2naphthylamine Copolymer from butadiene and vinylpyridine (ANSI/ASTM, IUPAC) Copolymer from butadiene and styrene (ASTM); see also SB, GR-S, SBR 1. Poly(butylene terephthalate) (ASTM); see also PBTP, PTMT 2. PoIy(I-butene), see also BT, PB 3. Poly(p-phenylenebenzobisthiazole) Poly(butylene terephthalate) (DIN, ISO); see also PTMT 1. Polycarbonate (ASTM, DIN, ISO, IUPAC); see also PCO 2. Poly(acrylonitrile) fiber (EWG, EDV); see also PAC, PAN 3. Formerly: chlorinated PVC; see also CPVC, PeCe, PVCC Polychlorinated biphenyl Polycarbodiimide Poly (1,4-cyclohexylenedimethylene terephthalate) Poly(chlorotrifluoroethylene) fiber (DIN) Polycarbonate; see also PC Poly(chlorotrifluoroethylene) (ASTM, DIN, ISO, IUPAC); see also CEM. CFM, CTFE Unchlorinated poly(vinyl chloride) (old German technical literature) Poly(diallyl phthalate) (ASTM, DIN, ISO, IUPAC); see also DAP, FDAP Poly(dimethyl siloxane) 1. Polyethylene) (ASTM, DIN, ISO, IUPAC); see also PL 2. Polyester fiber (EWG) 3. Pentaerythritol Poly(ethyl acrylate) Chlorinated poly(ethylene) (DIN, ISO); see also CPE Chlorinated PVC; see also CPVC, PC, PVCC
PEE PEEK
PEEKK PEG PEH PEHA PE-HD PEK PEKEKK PEKK PEL PEM PEO PEOX PEP PES
PESU PET PET* PETP PETS PF PFA
PFEP PF-P-B PG PHAS PHA PHB
PHEMA PHP PI
PIB
Polyester ether fibers (containing diol and /7-hydroxybenzoate units) (DlN) Polyether ether ketone = Poly(oxy-1,4phenylene~oxy~ 1,4-phenylene-carbonyl-1, 4~phenylene) Polyether ether ketone ketone Polyethylene glycol) Poly(ethylene) with high density; see also HDPE Pentaethylenehexamine (WTR) Poly(ethylene) with high density (DIN, ISO); see also HDPE, PEH Polyether ketone Polyether ketone ether ketone ketone Polyether ketone ketone Poly(ethylene) with low density; see also LDPE, PE-LD Poly(ethylene) with medium density; see also MDPE Polyethylene oxide) (ASTM, IUPAC); see also PEOX Polyethylene oxide) (DIN, ISO); see also PEO Thermoplastic copolymer from ethylene and propylene 1. Polyester fiber (DIN); see also PET, PL 2. Polyether sulfone (ASTM); see also PSU Polyether sulfone (ASTM); see also PES Poly(ethylene terephthalate) (ASTM); see also PETP, PE, PES Saran coated PET (ASTM) Polyethylene terephthalate) (ASTM, DIN, ISO, IUPAC); see also PET, PE, PES Pentaerythryl tetrastearate (WTR) Phenol-formaldehyde resin (ASTM, DIN, ISO, IUPAC) Perfluoroalkoxy resins, copolymers of tetrafluoroethylene and perfluorinated alkyl vinyl ethers Copolymer from tetrafluoroethylene and hexafluoropropylene; see also FEP Phenolic resin-paper prepreg Propylene glycol Poly(a-hydroxy acrylic acid) Poly(hydroxyalkanoate) 1. Poly(/?-hydroxybenzoate); see also POB 2. Poly(oc-hydroxybutyrate) Poly(2-hydroxyethyl methacrylate) Physiological hydrophilic polymers 1. fra/u?-l,4-Poly(isoprene), gutta percha (BS) 2. Polyimide (ASTM) 3. Paper (EDV) Poly(isobutene) (ASTM, BS, DlN, ISO, IUPAC)
PlBl
PIBO PIP PIR PIS PL
PMA
PMAC PMCA PMF PMI PMMA PMMI PMP PMPPI PMQ PMTT PNA PNAH PNF PNR PO
POB POM POP POR PP PP* PPA PPC PPI PPO l{ PPOX PPP PPS
Elastomeric copolymer from isobutene and isoprene (butyl rubber); see also Butyl, GR-I, HR Poly(isobutylene oxide) Synthetic m-l,4-poly(isoprene); see also CPI, IR Poly(isocyanurate) (DIN) Poly(isobutylene) 1. Poly(ethylene) (EWG); see also PE 2. Polyester fiber (EDV); see also PES, PET 1. Pyromellitic acid 2. Pyromellitic dianhydride 3. Poly(methyl acrylate) Polymethoxy acetal Poly(methyl a-chloromethacrylate) (ASTM) Processed mineral fiber Poly(methacrylimide) (Poly(methyl methacrylate) (ASTM, DIN, ISO, IUPAC) Poly(pyromellitimide) Poly(4-methyM-pentene) (ASTM, DIN, ISO); see also TPX Polymethylenepolyphenylene isocyanate; see also PAPI Silicon rubbers with methyl and phenyl substituents (ANSI/ASTM) 3-Phenyl-5-mercapto-1,3,4-thiadiazole-2thione (WTR) Poly nuclear aromatics Polynuclear aromatic hydrocarbons Phosphorus nitrile fluoroelastomer Poly(norbornene) rubber 1. Elastomeric poly(propylene oxide) (ASTM) 2. Poly(olefin) 3. Phenoxy resin Poly(p-hydroxybenzoate); see also PHB Poly(oxymethylene), poly (formaldehyde) (ASTM, DIN, ISO, IUPAC) PoIy(1,4-phenylene oxide) (ASTM); see also PPO Elastomeric copolymer from propylene oxide and allyl glycidyl ether Poly(propylene) (ASTM, DIN, EDV, ISO, IUPAC) Metallized poly(propylene) (ASTM) 1. Poly(parabanic acid) 2. Poly(propylene adipate) Chlorinated poly(propylene) (DIN) Polymeric polyisocyanate Poly(oxy-1,4-phenylene) = "poly(phenylene oxide)"; see also POP Polypropylene oxide) (ASTM, DIN, ISO) Poly(p-phenylene) Poly(p-phenylene sulfide) (ASTM)
PPSU PPT PQ PQD PR PS P-S PSA PSAB
PSAN PSBR
PSF PSI PSO PST PS-TSG
PSU PSUL PTA PTF PTFE PTMA PTMEG PTMG PTMT PU PUA PUE PUR PVA
PVAC PVAL
Poly(phenylene sulfone) (ASTM, DIN, ISO); see also PSU Poly(propylene terephth^Uite) Elastomeric silicone with phenyl substituents (ASTM) p-Quinone dioxime (WTR) Regenerated protein fiber (EDV) Poly(styrene) (ASTM, DIN, ISO, IUPAC) Pressure-sensitive adhesive Pressure-sensitive adhesive Thermoplastic copolymer from styrene, acrylic ester and butadiene (DIN); see also SBV, S/B Thermoplastic copolymer from styrene and acrylonitrile (DIN), see also SAN Elastomeric terpolymer from vinylpyridine, styrene, and butadiene (ANSI/ ASTM) Polysulfone; see also PSO Poly(methyl phenyl siloxane) (ASTM) Polysulfone; see also PSF Poly (styrene) fiber with at least 85% styrene units (DIN) Poly(styrene) foam, processed by thermoplastic injection (German technical literature) Poly(phenylene sulfone); see also PPSU Polysulfone (ASTM) 1. Purified terephthalic acid 2. Phthalic anhydride Pole(tetrafluoroethylene) fiber Poly(tetrafluoroethylene) (ASTM, DIN, ISO, IUPAC) Polyftetramethylene adipate) Poly(tetramethylene ether glycol) Poly(oxytetramethylene glycol) Poly(tetramethylene terephthalate) = poly(butylene terephthalate) see also PBTP 1. Polyurethane elastomer (BS) 2. Polyurethane fiber (EDV) Polyurea fiber (DIN); see also PB Segmented polyurethane fiber (DIN); see also EA Polyurethane (ASTM, DIN, ISO, IUPAC); see also PU 1. Poly(vinyl acetate); see also PVAC 2. Poly(vinyl alcohol) (ASTM); see also PVAL, PVOH 3. Poly(vinyl alcohol) fiber with at least 85% vinyl alcohol units (DIN); see also VY 4. Poly (vinyl ether) (old German technical literature); see also PVOM, PVME Poly(vinyl acetate) (ASTM, DIN, ISO, IUPAC); see also PVA Poly(vinyl alcohol) (ASTM, DIN. ISO, IUPAC)
PVC
PY
1. Poly(vinyl chloride) (ASTM., DIN, ISO, IUPAC); see also CL 2. Poly(vinyl chloride) fiber with at least 50 wt.% vinyl chloride units (DIN) 3. Pigment volume concentration Copolymer from vinyl chloride and vinyl acetate (ASTM, DIN1 IUPAC); see also PVCAC Copolymer from vinyl chloride and vinyl acetate (ASTM); see also PVCA Chlorinated PVC (DIN, ISO); see also CPVC, PC, PeCe Poly(vinylidene chloride) fiber with at least 50 wt.% vinylidene chloride units (DIN); see also PVDC Poly(vinylidene chloride) (ASTM5 DIN, ISO, IUPAC); see also PVD Poly(vinylidene fluoride) (ASTM, DIN, ISO, IUPAC); see also PVF 1. Poly(vinyl fluoride) (ASTM, DIN, ISO, IUPAC) 2. Poly(vinylidene fluoride); see also PVDF Poly(vinyl formal) (ASTM, DIN, ISO, IUPAC); see also PVFO Poly(vinyl formal) (DIN); see also PVFM Poly(vinyl isobutyl ether) Poly(vinylidene cyanide) Poly(Af-vinylcarbazole) (ASTM, DIN, ISO) 1. Copolymer from vinyl chloride and vinyl methyl ether 2. Fiber from the copolymer of vinyl and/ or vinylidene compounds with a main component of at least 85 wt.% (DIN) Poly(vinyl methyl ether) Silicone rubber with methyl, phenyl. and vinyl substituents (ANSI/ASTM) Poly(vinyl alcohol); see also PVA, PVAL Poly(iV-vinylpyrrolidone) (ASTM, DIN, ISO) Poly(dimethyl siloxane) with phenyl and vinyl substituents (ASTM) Unsaturated polyester resins (BS)
QMC
Quick molding change
Ra RA RAM RAN
Ramie (DIN) Ramie (EDV) Restricted area molding Residual acrylonitrile (monomer in polymer) Resorcine- formaldehyde resin 1. Rhenium (IUPAC) 2. Horse hair ("Rosshaar") (DIN) Reheat blow molding Rubber hydrocarbon content Cow hair ("Rind") (DIN)
PVCA
PVCAC PVCC PVD
PVDC PVDF PVF
PVFM PVFO PVI PVID PVK PVM
PVME PVMQ PVOH PVP PVSI
RF Rh RHB RHC Ri
RIM Ro RP RP/C RP/M RPVC RRIM RTP RTV RVCM RUC
Reaction injection molding Rosella (DIN) Reinforced plastics Reinforced plastics (composite) Reinforced polyester (mortar) Rigid PVC film Reinforced reaction injection molding Reinforced thermoplastic Room temperature vulcanization Residual vinyl chloride monomer Chlorinated isoprene rubber (DIN)
S SAF SAF-HS SAF-LS SAIB SAL SAN
Styrene Super abrasion furnace black High structure SAF Low-structure SAF Sucrose acetate isobutyrate Salicylic acid Thermoplastic copolymer from styrene and acrylonitrile (ASTM, DIN, ISO, IUPAC); see also PSAN Thermoplastic copolymer from styrene and butadiene (ASTM); see also S/B Thermoplastic copolymer from styrene and butadiene (ANSI/ASTM, ISO, IUPAC); see also SB 1. s-Butyl percarbonate; di~,? -butyl peroxydicarbonate 2. Styrene- butadiene resin Elastomeric copolymer from styrene and butadiene (ASTM, BS, IUPAC); see also GR-S 1. Solid bleached sulfate 2. Styrene-butadiene-styrene triblock copolymer Elastomeric copolymer from styrene and chloroprene (ANSI/ASTM, IUPAC) Sodium dimethyldithiocarbamate Aralkylated diphenylamines (WTR) 1. Sulfoethyl- (with cellulose) 2. Silk ("Seide") (EDV) Styrene-ethylene/butylene-styrene triblock copolymer ( = hydrogenated styrene-isoprene-styrene triblock copolymer) Selenium diethyl dithiocarbamate (WTR) Sulfonated ethylene-propylene-diene ter~ polymer Structural foam Synthetic fiber reinforced plastic (German technical literature) Scrapless forming process Super-high impact poly(styrene) 1. Silicon (IUPAC) 2. Sisal (DIN); see also SI 1. Silicones in general (ASTM, DIN, ISO) 2. Poly(dimethyl siloxane) (ASTM) 3. Thermoplastic silicone (IUPAC) 4. Sisal (EDV); see also S3
SB S/B
SBP
SBR
SBS
SCR SDD SDPA SE SEBS
SEDC S-EPDM SF SFK SFP SHIPS Si SI
SIN SIPN SIR
SIS SL SM SMA SMC SMR SMS S/MS Sn SN SP SPF SPH SPPF SPSF S-PVC SR SRF SRF-HM SRF-HM-NS SRF-LM SRF-LM-NS SRP SS
ST SWP
T TA TAC TATM TBBS TBC TBP TBPA TBPB TBS TBT
1. Simultaneous interpenetrating network 2. Semi-interpenetrating network Sequential interpenetrating poJymer network 1. Elastomeric copolymer from styrene and isoprene (ANSI/ASTM, IUPAC) 2. Standardized Indonesian rubber Siyrene-isoprene-styrene triblock copolymer Slag wool (DIN) Styrene monomer Copolymer from styrene and maleic anhydride (ASTM) Sheet molding compound (UP resin) Standardized Malaysian rubber Copolymer from styrene and a-methylstyrene (ASTM, DIN); see also S/MS Copolymer from styrene and a-methylstyrene (DIN, ISO); see also SMS 1. Tin (IUPAC) 2. Sunn hemp fibers (DIN); see also SN Sunn hemp fibers (EDV) Superior processing rubber (a grade of natural rubber) Superior processing furnace black Styrenated phenol (WTR) Solid-phase pressure forming Solid-phase stretch forming Poly(vinyl chloride), polymerized in suspension Synthetic rubber Semi-reinforcing furnace black High-modulus SRF Nonstaining high-modulus SRF Low-modulus SRF Nonstaining low-modulus SRF Rubber reinforced poly(styrene) (ASTM) 1. Single stage (ASTM) 2. Steam-stripped (to remove residual monomer) Stone wool (DIN) 1. Sol vent-welded plastics pipe 2. Synthetic wood pulp 1. Polysulfide rubber; see also OT, TR 2. Thermal black Cellulose triacetate (EDV); see also CT, CTA Triallyl cyanurate (ASTM) Triallyl trimellitate (WTR) Benzothiazyl-2-r-butyl sulfenamide (WTR) Total Broadhurst Lee process f-Butyl perbenzoate; see also TBPB Tetrabromophthalic anhydride f-Butyl perbenzoate; see also TBP r-Butylstyrene Tetrabutyl titanate
TBTD TBTU TBUT TC TCE TCEF TCF
TCM TCP
TDEC TDI
TDID TDM TEAE TEDMA TEGDA TEP TEPA TETA TETD TFE THBP THF THT TIOTM TKP Tl TM TMA TMC TMETD TMP TMPT TMQ TMS TMTD TMTS TMTT TMTU TMU TNPP TOF
Tetrabutyl thiuram disulfide (WTR); see also TBUT Tributyl thiourea (WTR) Tetrabutyl thiuram disulfide (WTR) Technically classified natural rubber Trichloroethylene Trichloroethyl phosphate (ASTM, ISO); see also TCEP Tricresyl phosphate, tritolyl phosphate (ASTM, DIN, ISO); see also TCP, TKP, TTP Trichloromelamine (WTR) Tricresyl phosphate (IUPAC); TCP 5 is a registered trademark in the United Kingdom; see also TCF, TKP, TTP Tellurium diethyl dithiocarbamate (WTR) Tolylene diisocyanate; tolylene isocyanate; methylphenylene diisocyanate; usually an 80:20 mixture of the 2,4- and 2,6-isomers Dimeric tolylene diisocyanate r-Dodecyl mercaptan (WTR) Triethylaminoethyl- (with cellulose) Triethylene glycol dimethacrylate (WTR) Triethylene glycol diacetate (WTR) Triethyl phosphate Tetraethylene pentamine (WTR) Triethylene tetramine Tetraethyl thiuram disulfide (WTR) Tetrafluoroethylene (ASTM) 2,4,5-Trihydroxybutyrophenone Tetrahydrofuran Tetrahydrothiophene (WTR) Triisooctyl trimellitate (DIN, ISO) Tricresyl phosphate; see also TCE, TCP, TTP 1. Thallium (IUPAC) 2. American moss (DIN) Thioplastics Trimellitic anhydride Thick molding compound Tetramethyl tetraethyl thiuram disulfide (WTR) 1. Thermal mechanical pulp 2. Trimethylol propane (WTR) Trimethylol propane trimethacrylate (WTR) 2,2,4-Trimethyl-1,2-dihydroquinone (WTR) Tetramethylsilane Tetramethyl thiuram disulfide (WTR) Tetramethyl thiuram monosulfide (WTR) Tetramethyl thiuram tetrasulfide (WTR) Tetramethyl urea (WTR); see also TMU Tetramethyl urea; see also TMTU Trinonyl phenyl phosphate (WTR) Trioctyl phosphate = tris(2-ethylhexyl) phosphate (ASTM, DIN, ISO); see also TOP
TOP
TOPM TOR TOTM TPA
TPE TPEL TPES TPF TPI TPO TPP TPR
TPS TPTD TPU TPUR TPX TR
TRIM Ts TSH TSUR TTP TTT TU TV Tz UE UF UFS UHMPE UHMW-PE
UP
Trioctyl phosphate = tris(2-ethylhexyl) phosphate (ASTM, DIN, ISO); see also TOF Tetraoctyl pyromellitate, i.e., tetrakis(2ethylhexyl) pyromellitate (DIN, ISO) /ra;?j-Poly(octenamer) Trioctyl mellitate = tris(2-ethylhexyl) pyromellitate (DIN, ISO) 1. l,4-frans-Poly(pentenamer); see also TPR 2. Terephthalic acid Thermoplastic elastomer Thermoplastic rubber or elastomer (ASTM) Thermoplastic polyester in general (ASTM) Triphenyl phosphate (DIN, ISO); see also TPP Thermoplastoid (WTR) Thermoplastic olefin elastomer Triphenyl phosphate (ASTM, IUPAC); see also TPF 1. l,5-fra/?s-Poly(pentenamer); see also TPA 2. Thermoplastic elastomer; see also TR, TPE Toughened poly(styrene) (in the UK for HIPS) Tetraisopropyl thiuram disulfide (WTR) Thermoplastic polyurethanes Thermoplastic urethane (ASTM) Poly(4-methyl-l-pentene); see also PMP 1. Thermoplastic elastomer 2. Thio rubber (in the UK for polysulfide) 3. Textile residues or fiber or fabric of unknown composition (EDV) Trimethylolpropane trimethacrylate Tussah silk (DIN) Toluene sulfonyl hydrazide (WTR) Thermoset polyurethane (ASTM) Tricresyl phosphate, tritolyl phosphate (ISO); see also TCE, TCP, TKP Triethyltrimethylenetnamine (WTR) Thiourea Trivinyl fiber (EDV) Tibet goat hair (goat = "Ziege") (DIN) Polyurethane elastomer (ASTM); see also UR Urea-formaldehyde resin (ASTM, DIN, ISO, IUPAC) Urea-formaldehyde foam Poly(ethylene) with ultrahigh molar mass Poly(ethylene) with ultrahigh molar mass (molar mass over 3 100 000 g/mol) (ASTM) Unsaturated polyester (ASTM, DIN, ISO, IUPAC)
UP-G-G UP-G-M UP-G-R Ur UR VA VAC VAE VC VC/E VC/E/MA VC/E/VAC VCI VCM VC/MA VC/MMA VC/OA VC/VAC VC/VDC VDC Vf VF/HFP Vi VI VMQ VPE VQ VRI VSI VT VVO VY
WA WB WFK WG
Prepreg from unsaturated polyesters and textile glass fibers Prepreg from unsaturated polyesters and textile glass mats Prepreg from unsaturated polyesters and textile glass rovings Urena (DIN) Poiyurethane elastomers (BS); see also UP Vinyl acetate Vinyl acetate Vinyl acetate-ethylene copolymers; see also EVA, E/VAC Vinyl chloride Copolymer from ethylene and vinyl chloride (ISO) Copolymer from ethylene, vinyl chloride, and maleic anhydride (ISO) Copolymer from ethylene, vinyl chloride, and vinyl acetate (ISO) Volatile corrosion inhibitor Vinyl chloride (monomer); see also VC Copolymer from vinyl chloride and methyl acrylate (ISO) Copolymer from vinyl chloride and methyl rnethacrylate (ISO) Copolymer from vinyl chloride and octyl acrylate (ISO) Copolymer from vinyl chloride and vinyl acetate (ISO) Copolymer from vinyl chloride and vinylidene chloride (ISO) Vinylidene chloride 1. Vulcan fiber 2. Vinyl fluoride Copolymer from vinylidene fluoride and hexafl uoropropy lene Vicuna wool (DIN) Viscose (rayon) (EDV); see also CV Silicone rubber with methyl and phenyl substituents (ANSI/ASTM) Cross-linked poly(ethylene) (DIN) Elastomeric silicone with vinyl substituents (ASTM) Volatile rust inhibitor Poly(dimethyl siloxane) with vinyl groups (ASTM) Vinyl toluene Vulcanized vegetable oil = factice (WTR) Vinal (— poly(vinyl alcohol) fiber) (ASTM, EDV) Angora (rabbit) wool (EDV) Beaver wool (EDV) Whisker reinforced plastic (German technical literature) Vicuna wool (EDV)
WK WL WM
Wo WO WP WS WT WU WV WY XABS
XLPE XNBR
XPS XSBR
YSBR
YXSBR
Z5MC
Camel wool (EDV) Llama wool (EDV) 1. Plasticizer (German technical literature: "Weichmacher") 2. Mohair wool (EDV) 1. Tungsten (IUPAC) 2. Sheep's wool (DIN); see also WO Sheep's wool (EDV); see also Wo Alpaca wool (EDV) Cashmere goat wool (EDV) Otter wool (EDV) Guanaco wool (EDV) Virgin sheep wool (EDV) Yak wool (EDV) Elastomeric copolymer from acrylonitrile, butadiene, styrene, and a carboxylic group containing monomer (ASTM) Crosslinked poly(ethylene) Elastomeric copolymer from acrylonitrile, butadiene, and a carboxylic group containing monomer (ANSI/ASTM) Expandable (or expanded) poly(styrene) Elastomeric copolymer from butadiene, styrene, and a carboxylic group containing monomer (ANSI/ASTM)
ZBDC ZBPD ZBX ZDBC ZDEC ZDMC ZE ZEH ZEPC ZIX ZMBI ZMBT
Zinc dibenzyl dithiocarbamate (WTR) Zinc dibutyl dithiophosphate (WTR) Zinc dibutyl xanthate (WTR) Zinc dibutyl dithiocarbamate (WTR) Zinc diethyl dithiocarbamate (WTR) Zinc dimethyl dithiocarbamate (WTR) Zein fibers (DIN) Zinc ethylhexanoate (WTR) Zinc ethylphenyl dithiocarbamate (WTR) Zinc isopropyl xanthate (WTR) Zinc 2-mercaptobenzimidazole Zinc-2-mercaptobenzthiazole
C. ABBREVIATIONS AND ACRONYMS BASED ON POLY(MONOMER) NAMES
Thermoplastic triblock copolymer from styrene and butadiene (ANSI/ASTM); see also SBS Thermoplastic block copolymer from styrene and butadiene containing carboxylic groups (ANSI/ASTM)
The following table contains the abbreviations and acronyms of names of polymeric materials whose base polymers were obtained by chain polymerization (addition polymerization), copolymerization, polycondensation (condensation polymerization), and polyaddition. Note that these abbreviations and acronyms do not apply in industry to polymers per se but to polymeric materials, i.e. polymers with or without additives, fillers, plasticizers, etc. Abbreviations and acronyms are in part based on the poly(monomer) nomenclature, i.e., on the names of the monomers used in the manufacture of polymers, sometimes however, without a prefix " P " for "poly". The names of monomers for copolymers are given in alphabetical order without regard to their prevalence.
Zinc pentamethylene (WTR)
Registered trademarks: a) SAN in Japan and the USA; b) PAN in Europe.
dithiocarbamate
Polymers of
ASTM
DIN
ISO
Acrylic ester 4- acrylonitrile 4- butadiene Acrylic ester + acrylonitrile + styrene Acrylic ester -f ethylene Acrylic acid Acrylonitrile Acrylonitrile -I- butadiene Acrylonitrile -f- butadiene + methyl methacrylate 4- styrene Acrylonitrile-K butadiene 4-styrene Acrylonitrile 4- chlorinated poly(ethylene) 4- styrene Acrylonitrile 4-ethylene-propylene-diene 4-styrene Acrylonitrile 4 methyl methacrylate Acrylonitrile 4-styrene Adipic acid 4- hexamethylenediamine Adipic acid 4- hexamethylenediamine 4-sebacic acid Adipic acid 4-tetramethylene glycol Allyl diglycol carbonate /7-Aminobenzoic acid
ABA ASA EEA PAA PAN PBAN
A/B/A A/S/A
A/B/A A/S/A E/EA
ABS
ABS
ABS
A/PE-C/S
A/CPE/S
A/EPDM/S A/MM A SAN PA 66
A/EPDM/S A/MMA SAN PA 66
IUPAC
Other
PAS PAC
PAN
MABS
AMMA SAN PA 6.6
ABS ACS
SAN PA 6.6
AS
PA 66/610 PTMA ADC PAB
Polymers of Aminotriazol Aminoundecanoic acid, 11Azelaic acid anhydride Bisphenol A + phosgene Bitumen + ethylene Butadiene + methyl methacrylate -f styrene Butadiene -f styrene (thermoplastic) Butene-1 Butyl acrylate Butylene glycol + terephthalic acid Butyl methacrylate 8-Caprolactam s-Caprolactam + co-dodecanolactam Chlorotrifluoroethylene Chlorotrifluoroethylene + ethylene Cresol + formaldehyde 1,4-CycIohexanedimethylol + terephthalic acid Diallyl chloroendate ( = diallyl ester of 4,5,6,7,7-hexachlorobicyclo-[2,2,1]5-heptane-2,3-dicarbonic acid) Diallyl fumarate Diallyl isophthalate Diallyl maleate Diallyl phthalate 1,4-Dichlorobenzene + disodium sulflde 2,6-Dimethylphenol -I- oxygen co-Dodecanolactam (laurolactam) Ethyl acrylate Ethyl acrylate + ethylene Ethylene -, chlorinated polymer -, cross-linked polymer -, high-density polymer -, high impact polymer ~, linear low-density polymer -, low density polymer -, medium density polymer -, very low density linear polymer -, ultra-high molar mass polymer Ethylene + methacrylic acid Ethylene 4- maleic anhydride + vinyl chloride Ethylene + methyl methacrylate Ethylene + propylene Ethylene + propylene (4- diene) Ethylene + tetrafluoroethylene Ethylene+ vinyl acetate Ethylene + vinyl acetate + vinyl chloride Ethylene + vinyl chloride Ethylene glycol Ethylene glycol + maleic anhydride Ethylene glycol + terephthalic acid(ester) - , with glycol comonomer -, fast crystallizing polymer - , oriented polymer Ethylene oxide Formaldehyde (or trioxane) Formaldehyde + furan Formaldehyde + melamine Formaldehyde + melamine + phenol Formaldehyde + phenol Formaldehyde + urea Furfural + phenol Hexafluoropropylene + tetrafluoroethylene Hexamethylenediamine + sebacic acid
ASTM
DIN
ISO
IUPAC
PA 11
PA 11
PC
PC
PBT
MBS S/B PB PBA PBTP
MBS S/B PB PBA PBTP
PA 6
PA 6
PA 6
PCTFE
PCTFE
PA 6 PA 6/12 PCTFE
CF
CF
CF
CF
Other PAT PAPA
PC PBS PB
PC ECB S/B
SB BT
PBA PTMT PBMA PCTFE ECTFE PCDT
PDAC PDAF PDAIP PDAM PDAP PPS POP PA 12
PDAP PPS
PDAP
PDAP
PA 12
PA 12
PA 12
EEA PE CPE
E/EA PE PE-C
HDPE
PE-HD
LLDPE LDPE MDPE
PE-LD
E/EA PE PE-C PE-X PE-HD PE-HI PE-LLD PE-LD PE-MD
DAP PPO ™ PEA
PE
PL VPE
VLDPE UHMW-PE EMA
EPDM ETFE EVA
PE-UHMW VC/E/MA E/MMA E/P EPDM E/TFE E/VA VC/E/VAC VC/E
VC/E/MA E/MMA E/P EPDM E/TFE E/VAC
UP PET
UP PET
PEP EVAC VC/E/VAC
VC/E PEG
UP PET PETG
UP PETP
PETE CPET OPET
PEO POM FF MF PF UF PFF FEP PA 6.10
PEOX POM MF MPF PF UF FEP PA 610
PEOX POM FF MF
PEO POM
PF UF
PF UF
FEP PA 610
MF
PA 6.10
Polymers of
ASTM
p-Hydroxybenzoic acid 3-Hydroxybutyric acid 2-Hydroxyethylmethacrylate Isobutene (isobutylene) Isocyanurates Laurolactam (dodecanolactam) Linseed oil, epoxidized Maleic anhydride 4- styrene Methacrylimide Methyl acrylate Methyl acrylate 4-vinyl chloride Methyl a-chloromethacrylate Methyl methacrylate Methyl methacrylate 4- vinyl chloride 4-Methylpentene-1 a-Methylstyrene oc-Methylstyrene 4- styrene Octyl acrylate+ vinyl chloride Perfluoro alkoxy alkane Phosphoric acid (polymer) Propylene - , oriented polymer - , biaxially oriented polymer Propylene 4- tetrafluoroethylene (alt.) Propylene oxide Soybean oil, epoxidized Styrene - , expanded (foamed) polymer - , high-impact polymer - , impact resistant polymer - , oriented polymer - , biaxially oriented polymer Tetrafluoroethylene Tetrahydrofuran - , polymer with hydroxy endgroups Trially] cyanurate Trifluoroethylene Trioxane (4-Co-monomers) Vinyl acetate Vinyl acetate 4 vinyl chloride W-Vinylcarbazole Vinyl chloride - , polymerized in bulk - , polymerized in emulsion - , polymerized in suspension - , polymer as flexible - , polymer as oriented - , polymer as rigid Vinyl chloride 4 vinylidene chloride Vinyl fluoride Vinylidene chloride Vinylidene fluoride Vinyl methyl ether N-Vinylpyrrolidone
POB
D.
PlB
DIN
ISO
IUPAC
Other
PIB
PHB PHB PHEMA IM
PIB PIR PA 12 ELO S/MA PMI
PIB PIR PA 12 ELO SMA PMI
VC/MA
VC/MA
PMMA
PMMA
PFA
PMP PMS S/MS VC/OA PFA
PMMA VC/MMA PMP PMS S/MS VC/OA PFA
PP
PP
PP
PP
PA 12 SMA
PA 12
PMA PMCA PMMA PMP SMS
TPX PAMS
PPA OPP BOPP TFE-P PPOX
PPOX ESO PS
PS
PPOX ESO PS
PS EPS HIPS
PS-HI SRP
IPS OPS BPS
PTFE
PTFE
PTFE
PTFE PTHF PTMEG
PTAC POM PVAC PVCA PVK PVC
P3FE POM PVAC
POM PVAC VC/VAC PVK PVC
POM PVAC VC/VAC PVK PVC
PVC
PVF PVDC PVDF
VC/VDC PVF PVDC PVDF
VC/VDC PVF PVDC PVDF
PVF PVDC PVDF
PVP
PVP
PVP
film film film
PVA
PCU;V M-PVC E-PVC S-PVC FPVC OPVC RPVC
PVME
ABBREVIATIONS FOR POLYMERS N A M E D AFTER A CHARACTERISTIC POLYMER G R O U P
Characteristic polymer group
ASTM
DIN
ISO
Amide Amide, aromatic (aryl amide) - , metal coated - , saran coated Amide-imide
PA PARA PA*! PA: PAI
PA
PA
films films
IUPAC
Other
PAR
PAI
PAI
Characteristic polymer group Arylene sulfone Benzimidazole Bisphenol A-sulfone Carbodiimide Carbonate, aromatic Epoxide (epoxy) - , glass fiber reinforced Ester, saturated (polyester) - , thermoplastic - , - , metallized polymer film Ester, unsaturated (polyester) - , - , glass fiber reinforced Ester-alkyd Ester-ether (thermoplastic elastomer) Ester-imide Ester-urethane Ether-fc/odfc-amide Ether ether ketone Ether-imide Ether-sulfone Imide Parabanic acid Phenylene ether Phenylene sulfide Phenylene sulfone Silicone (plastics) Sulfone Urethane - , thermoplastic - , thermoset
ASTM
DIN
ISO
IUPAC
Other PAS PBl PSF PCD
PC EP
PC EP
PC EP
SP
SP
UP
UP
PC EP GEP
TPES MPE UP
UP FRP
PAK TEEE PEi PEBA PEEK PES PESU PI PPE PPS PPSU SI PSU PUR TPUR TSUR
PEBA
PEI PEUR PEBA PEEK
PEI PES
PES
PI
PI
PPE
PPE PPS PPSU Sl PSU PUR
PPSU SI PSU PUR
PES
PPA PPO ™ PSU PSU PUR TPU
E. ABBREVIATIONS FOR POLYMERS PRODUCED BY CHEMICAL TRANSFORMATION OF OTHER POLYMERS Resulting polymer
ASTM
DIN
ISO
IUPAC
Carboxymethyl cellulose Carboxymethyl hydroxyethyl cellulose Casein, crosslinked with formaldehyde Cellulose, as Cellophan " - , coated with Saran Cellulose acetate Cellulose acetobutyrate Cellulose acetopropionate Cellulose nitrate Cellulose plastics, unspecified Cellulose propionate Cellulose triacetate Ethyl cellulose Hydroxyethyl cellulose Hydroxypropyl cellulose Hydroxypropyl methyl cellulose Methyl cellulose Poly(ethylene), chlorinated - , chlorosulfonated Po]y(ethylene-co-vinyl alcohol)
CMC
CMC
CMC
CMC
CS C C* CA CAB CAP CN CE CP CTA EC
CS
CS
CS
CA CAB CAP CN
CA CAB CAP CN
CA CAB CAP CN
CP CTA EC
CP CTA EC
CP
Other
CMHEC
NC
TA EC HEC HPC HPMC
CPE CSM
MC PE-C
MC PE-C
E/VAL
EJVAL
CSR
EVAL™ EVOH Poly(propylene), chlorinated Poly(vinyl alcohol) Poly(vinyl butyral) Poly(vinyl chloride), chlorinated Poly(vinyl formal)
PVAL PVB CPVC PVFM
PPC PVAL PVB PVC-C PVFM
PVAL PVB PVC-C PVFM
PVAL
PVOH PC. PeCe
PVFM
F. ABBREVIATIONS FOR BLENDS, REINFORCED POLYMERS, ETC.
For mixtures of polymers, ISO recommends that the symbols for the parent polymers be put in parentheses, Resulting polymer Bulk molding compound Elastomers, thermoplastic - , - , containing ester and ether groups - , - , olefin-based - , - , styrene-based Epoxide, glass fiber reinforced Plastic, carbon fiber reinforced - , glass fiber reinforced - , man-made fiber reinforced ~, metal fiber reinforced Poly(acrylonitrile-co-styrene) -f chlorinated polyethylene) Poly(styrene), rubber-modified Sheet molding compound - , with high glass fiber content
G.
separated by a plus sign; for example, (PMMA -f ABS) for a physical blend of poly(methyl methacrylate) and ABS. ASTM recommends GP for "general purpose" and SS for "single stage".
ASTM
DIN
ISO
IUPAC
Other BMC
TEEE TEO TES EP-G
GEP CFP GFK CFK MFK
KEK
SRP
ISO CODES FOR THERMOPLASTIC MATERIALS
The standard designation of a thermoplastic material consists of - a description block (giving the type of material), - a standard number block (consisting of the number of the ISO standard or a national standard such as DIN), followed by a hyphen, and - an individual item block (with five data blocks). An example is Molding material DIN 7744-PA 12, XF, 22-030, GF 30 The code letters are arranged after the symbol for the base polymer according to ISO and DIN; in the technical literature, however, they are commonly placed in front of the base symbol, following ASTM, which uses similar code letters and asterisks. A designation system similar to the above ISO/DIN system has been recommended by ASTM. A typical ASTM designation, for example, would read Molding material ASTM D-4000 PI000G42360 This molding material is a polyimide (PI), whose properties have been specified via cell table G of the ASTM standard D-4000. This particular cell table identifies five different properties by designating cell limits to the five digits following the letter G. According to cell table G, the " 4 " indicates a tensile strength of at least 85MPa. The measured flexural modulus is characterized by " 2 " , the Izod impact strength of 50J/m by " 3 " , and the heat deflection temperature of 3000C by " 6 " . The fifth digit is undetermined; the t c 0" indicates an unspecified property.
ACS u HIPS SMC
IPS HMC
1.
Codes for ISO Data Blocks 1 - 5
T. /. ISO and DIN Codes for Data Block 1 Data block 1 of the individual item block contains the abbreviation of the chemical name of the material, e.g., PA 12 (see example). This abbreviation may be followed by analytical data with respect to the composition of the material; an example is the content of vinyl acetate units in ethylenevinyl acetate copolymers. Such chemical structure data may be composition, such as content of vinyl acetate (VAC) or acrylonitrile units (AN), configuration as measured by isotacticity ("isotaxy") (IT), branching as revealed by density (D). These analytical data are, however, not the exact analytical data but rather code numbers for the range (called "cell") which will permit this material to substitute for a similar one. Separated by a hyphen, other supplementary may be given too, e.g., H — homopolymer, P = plasticized, E — polymerized in emulsion, Q = mixture of different polymers, etc. (see ISO and DIN codes for data block 1). Furthermore, ASTM uses * for saran coated polymer films and ** for metallized polymer films. The technical literature indicates biaxially oriented films by BO and oriented films by O (see Abbreviations in alphabetical order). Code
ISO data block 1
A B C D E F
-
G H
-
Block copolymer Chlorinated Polymerization in emulsion -
Homopolymer
DIN data block 1
Chlorinated Density Expanded or expandable Flexible or fluid (liquid state) High
Code 1 J K L M N O P Q R
ISO data block 1
DIN data block 1
-
Impact resistant
Bulk polymerization -
Linear or low Medium or molecular Normal or novolac
Plasticized Mixtures of different polymers Random copolymer
Plasticized Resol; formerly also: raised (enhanced)
-
-
S T U V W X
Polymerization in suspension Unplasticized No indication
Y Z
Ultra or unplasticized Very Weight (mass) Crosslinked or crosslinkable —
—
1.2. ISO Codes for Items in Data Block 2 Data block 2 may comprise up to four letters which give qualitative information. The first letter denotes the intended application, e.g., B = blow molding, G = general purpose, X = no indication (see example). The following letters 2, 3, and 4 can code up to three essential additives or supplementary information, for example, D = powder (dry blend), F = special burning characteristics (see example), L = light and weather stabilizer, etc.
Code Position 1
Code
Positions 2-4
A B C D E
A B C D E
Antioxidant for processing Antiblocking agent Colored Powder (dry blend) Additive for expansion
F
Adhesives Blow molding Calendering Disc manufacture Extrusion (pipes, profiles, sheets) Extrusion (films, foils)
F
G H K L
General purpose Coating Cable and wire insulation Extrusion (monofilament)
G H K L
Special burning characteristics Granules (pellets) Heat aging stabilizer
Injection molding
M N P Q R S T W
M N P Q R S T W X Y Z
Paste resin Compression molding Rotational molding Powder spray sintering Tape manufacture No indication Textile yarn -
X Y Z
Light and weather stabilizer Natural (not colored) Polymer modifier Mold release agent Slip agent, lubricant Improved transparency Stabilized against hydrolysis Antistatic agent
1.3. ISO Codes for Items in Data Block 3 Data block 3 contains quantitative information about the designated properties. Such properties include Molar mass indicators Intrinsic viscosity ("viscosity number") Fikentscher's K value (viscosity-based quantity for PVC) Macrostructure data Bulk density Rheological data Melt flow rate (melt flow index) Thermal data Vicat temperature Torsional stiffness temperature Mechanical properties Modulus of elasticity Tensile stress at 100% strain Shore hardness Impact strength (notched)
IV FK BD MFR VST TST E TS SH ISN
Each material is characterized by one or more than one property. The following leading criteria are used for the various polymers: Poly(ethylene) Poly(propylene) Poly(styrene) and acrylonitrilestyrene copolymer Styrene-acrylonitrile copolymer Styrene-butadiene copolymer Acrylonitrile-butadiene-styrene, and acrylonitrile-styreneacrylic acid copolymers Ethylene- vinyl acetate copolymer Poly(vinyl chloride) Poly(vinyl chloride), unplasticized Poly(vinyl chloride), plasticized Polyamide Polycarbonate Poly(methyl methacrylate) Polyethylene terephthalate)
D, MFR I, MFR VST, MFR VST, MFR, AN VST, MFR, ISN VST, MFR, ISN, AN VAC, MFR IV, (FK), BD VST, E, ISN TS, SH, TST IV, E IV, MFR, E IV, VST IV
In the example for a polyamide 12, the code "22-030" of data block 3 indicates a polymer with an intrinsic viscosity of 210ml/g ("cell 22"), and a modulus of elasticity of 280MPa ("cell 030"). On the other hand, "20-D050" in data block 3 for a poly(ethylene) tested according to DIN 16776 means a material with a density within cell "020" (e.g., 0.918 g/cm3) and a melt flow rate within the cell "050" (e.g., 4.2g/min), measured under condition D (a temperature of 1900C under a load of 2.16 kg). The definition of cells for each material and testing procedure can be found in special tables. 1.4. ISO Codes for Extending and Reinforcing Fillers (Data Block 4) Data block 4 gives information about the type and content of fillers or reinforcing materials. The first
letter gives the type of filler: C = carbon, G = glass, etc. The second letter indicates the shape of the filler: F —fiber, S = spheres, etc. The third position is a code for the weight content of the filler, e.g., "30" for the "cell" (range) 27.532.5 wt.%.
1.5. ISO Codes for Data Block 5 Data block 5 is reserved for specifications based on individual agreements between supplier and customer. It may code additional requirements, restrictions, or supplemental information. H. SPI CODES FOR THE RECYCLING OF PLASTICS
Code Position 1 (material)
Code
B Boron C Carbon D E Clay F G Glass H K Calcium carbonate L Cellulose M Mineral, metal N P Mica Q Silicon R Aramid S Synthetic, organic T Talcum V W Wood X Not specified Z Others
B C D E F G H K L M N P Q R S T V W X Z
Position 2 (form or structure) Balls, beads, spheres Chips, cuttings Powder (dry blend) Fiber Ground, grinding stock Whisker Knitted fabric Layer Mat (thick) Non-woven (fabric, thin) Paper Roving Scale, flake (spheres: now B) Cord Veneer Woven fabric Not specified Others
Number code
Letter code
Polymer
1 2 3 4 5 6 7
PETE HDPE V LDPE PP PS -
Polyethylene terephthalate) High-density poly(ethylene) Vinyl chloride polymers Low-density poly(ethylene) Poly(propylene) Poly(styrene) All other plastics, including multilayered materials
I. RECOMMENDED ABBREVIATIONS A N D ACRONYMS FOR NAMES OF ELASTOMERS
Names of elastomers are listed in alphabetical order of the names of their monomers, regardless of their proportions. A "PM" indicates an after-treatment of the polymer; "Other" refers to old or often used "unofficial" abbreviations; # indicates that the abbreviation is recommended by IUPAC.
Monomers (incl. after-treatment of PM)
ASTM
Acrylic ester 4- acrylonitrile Acrylic ester 4- butadiene Acrylester (4- saturated vulcanizable comonomer) Acrylonitrile -f butadiene -, PM contains carboxylic groups -, PM is hydrogenated Acrylonitrile 4- butadiene -f styrene, PM contains COOH groups Butadiene Butadiene 4- styrene Butadiene -I- styrene, PM contains COOH groups Butadiene 4- styrene, elastomeric triblock copolymers Butadiene -I- styrene, elastomeric block copolymers with COOH groups Butadiene 4- 2-vinylpyridine Butadiene 4- 2-vinylpyridine 4- styrene Chloroprene Chloroprene 4- acrylonitrile Chloroprene 4- styrene Cyclooctene (trans polymer) Cyclopentene (trans polymer) Epichlorohydrine Epichlorohydrine 4- ethylene oxide Ethylene (PM postchlorinated) Ethylene (PM perchlorosulfonated) Ethylene 4- acrylic ester Ethylene 4- ethyl acrylate Ethylene 4-propylene Ethylene 4- propylene f non-conjugated diene Ethylene 4- vinyl acetate Ethylene 4- tetrafluoroethylene Fiuorinated carbon chains (substituents: fluoroperfluoroalkyl-, perfluoroalkoxy-) Hexafluoropropylene 4- tetrafluoroethylene Hexafluoropropylene + vinylidenefluoride Isobutylene
ANM ABR# ACM NBR# XNBR
BS
ISO
Other AR GR-N H-NBR
XABS BR# SBR# XSBR YSBR YXSBR PBR# PSBR CR# NCR# SCR# CO# ECO CM CSM EAM EEA EPM EPDM EVM
BP, CBR GR-S
SBR
SBS
CR
CO CSPR EPR EPTR
TOR TPA, TPR CHR CHC CSR
E/EA EPM
AP APT, EPT ETFE
FKM
FPM FEP
FPM PIB#
PIB
PIB
PIS
Monomers (incl. after-treatment of PM)
ASTM
BS
Isobutylene + isoprene Isobutylene 4- isoprene (postbrominated PM) Isobutylene -f isoprene (postchlorinated PM) Isoprene (natural rubber) Isoprene (natural rubber, easy-processing) Isoprene (natural rubber, standardized Indonesian) Isoprene (natural rubber, standardized Malaysian) Isoprene (natural rubber, technical classification) Isoprene (synthetic rubbers) Isoprene (chlorinated PM) Isoprene + acrylonitrile Isoprene -h styrene Isoprene -f styrene (triblock copolymer) Isoprene 4- styrene (hydrogenated triblock copolymer) Norbornene Phosphonitrile dichloride, with fluorine-containing substituents Propylene oxide Propylene oxide + allylglycidyl ether Silicone with fluoro substituents Silicone with fluoro + methyl substituents Silicone with fluoro 4- methyl 4- vinyl substituents Silicone with methyl substituents Silicone with phenyl substituents Silicone with phenyl 4- methyl substituents Silicone with phenyl 4- vinyl 4- methyl substituents Silicone with vinyl substituents Silicone with vinyl 4- methyl substituents Sulfides (thioplastics) Tetrafluoroethylene 4- trifluoronitrosomethane 4- nitrosoperfluorobutyric acid (nitroso rubber) Urethane elastomers Urethane elastomers with polyester segments Urethane elastomers with polyether segments Urethane-polyester elastomers, crosslinkable by isocyanates Urethane-polyester elastomers, crosslinkable by peroxides Vinylidenefluoride 4- hexafluoropropylene Tetrafluoroethylene 4- perfluoralkylvinyl ether Thermoplastic elastomers, in general Thermoplastic olefin elastomers Thermoplastic elastomers on basis styrene-diene Thermoplastic elastomers on basis ester Thermoplastic elastomers on basis ether-amide
IIR# BIIR CIIR NR#
Butyl
IR#
IR
ISO
Other GR-I, PIBI NK SP SIR SMR TC CPI, PIP RUC
NIR SIR# SIS SEBS PNR PNF OPR POR
PO GPO FQ FMQ FVMQ MQ PQ PMQ PVMQ VQ VMQ
MFQ
MPQ MPVQ MVQ T, TR, OT
AFMU UE AU EU AU-I AU-P FPM
CNR UR AU EU FPM PFA TPE, TPR TPE-O, TPO TPE-S TPE-E TPE-A
TPEL
The following abbreviations are also used. ICR: rubber from undiluted latex of natural rubber (initial concentration rubber); OER: oil-extended rubber; RTV: room temperature vulcanization.
J.
ABBREVIATIONS FOR TEXTILE FIBERS*
Short Name Name NATURAL PROTEIN FIBERS (SILK) Mulberry spinner (Bombyx mori L) Tussah NATURAL PROTEIN HBERS (WOOL) Alpaca (Llama pacos) Angora rabbit ("Angorakaninchen") Beaver
ISO
FTC
Abbreviation DIN
ASTM
ETG
Ms
SE Ts
Ap Ak
WP WA "rB
* ISO: International Standardization Organization; FTC: US Federal Trade Commission; DIN: German Standards (Deutsches Institut fur Normung), DIN 60001; '*..." indicates the German word from which the abbreviation or acronym was derived; ASTM: American Society for Testing and Materials; ETG: European Textile Characterization Law.
Short Name Name
ISO
FTC
Cashmere goat ("Kaschmir-Ziege") Guanaco Llama Mohair Otter Sheep - , virgin wool Vicuna Yak
DIN
ASTM
Kz
ETG WS WU WL WM WT WO WV WG WY
Lm Mo Wo Vi
NATURAL PROTEIN FIBERS (HAIRS) Camel ( " K a m e D Cow ("Rind") Goat ("Haar der Ziege") Hare ("Hase") Horse ("Rosshaar") Human ("Haar") Rabbit ("Kaninchen") Tibetan goat ("Tibetziege")
Km Ri
WK Hz Hs
Rh HA Kn Tz
NATURAL CELLULOSE FIBERS (TEXTILE FIBERS) Cotton ("Baumwolle") Flax - , linen - , half-linen Ramie
Bw Fl
CO LI LI HF RA
Ra
NATURAL CELLULOSE FIBERS (HARD FIBERS AND OTHERS) Alfalfa Broom ("Ginster") Calatropis CoirrKokos") Esparto grass [alfa) Hemp (Cannabis) - , Bombay (Sunn hemp) --, Manila (Abaca) Henequen (Agave) Jute Kapok Kenaf Maguey Mauritius fiber (Fique) Moss, American Phormium (New Zealand flax) Rosella Sisal Urena
AL Gl An Ko Ag
CC CA SN AB
Sn Ma He Ju Kp Kf
JU KP KE MG
Fi Tl Nf Ro Si Ur
REGENERATED POLYSACCHARIDE FIBERS Alginate Cellulose
Cupro
Cellulose 2 1/2 acetate Cellulose triacetate
Viscose Modal Deacetylated Acetate Acetate triacetate
REGENERATED PROTEIN FIBERS Ardein fibers Casein fibers Regenerated protein fibers, in general Zein fibers
Abbreviation
Cupra (rayon) Rayon Rayon Rayon
AL CC
AG CU
CV
VI MD
Acetate triacetate
CA CT
AR KR Protein
SI
Azlon
CA CTA
AC TA
CS PR
ZE
Short Name Name SYNTHETIC FIBERS Elastodiene Fluoro Poly(acrylonitrile) Poly(acrylonitrile), copolymeric Polyamide, aliphatic Polyamide, aromatic Polyester [poly(ethylene terephthalate] - , [from ethylene glycol, terephthalic acid and p-hydrooxybenzoic acid] Poly(ethylene) Polypropylene) Poly(styrene) (>88% sty) Polyurea Polyurethane - , segmented Poly(vinyl alcohol) Poly(vinyl chloride) (>85% VC) Poly(vinyl chloride), copolymeric Poly(vinylidene chloride), copolymeric Trivinyl
ISO
fibers
DIN
ASTM
ETG
LA
EU
PAC PAM
PAN
EL FL PAN MA
PA
PA
PA
PES
PET
PL
PE PP
PE PP
fiber Acrylic Modacrylic Nylon, Polyamide Aramide
Acrylic Modacrylic Nylon, Polyamide Aramide
Polyester
Polyester
Elastan Vinylal Chlorofiber Chlorofiber
Vinyon
PEE PE PP PST PUA PUR PUE PVA PVC PVM
Chlorofiber
Saran
PVD
Polyethylene Olefin Polypropylene Olefin
Spandex Vinal
fiber
INORGANIC FIBERS Asbestos Glass Metal Mineral (rock wool) Slag wool OTHER FIBERS Unspecified Unknown
FTC
Abbreviation
PB PU EA VY
TV
Glass
fibers fibers
PUR
Glass
As GL MT ST SL
AS GL ME
AF TR
C h e m i c a l a n d
A b s t r a c t
O n l i n e f o r
R e g i s t r y
D a t a b a s e
P o l y m e r
N u m b e r s
S e a r c h i n g
L i t e r a t u r e
M . J o h n s o n , E. A . G r u l k e University of Kentucky, Lexington, KY 40506, USA A. Nomenclature B. CAS Registry Numbers C. Indexing and CAS Registry Number Assignment D. Example Searches 1. Example of a Search Using the Polymer CAS Registry Number 2. Example of a Search Using the Monomer CAS Registry Number 3. Example of a Combined Search 4. Example of a Copolymer Search 5. Example of an Engineering Database Search 6. Example of a Search with Punctuation in the Polymer Name 7. Example of an Engineering Materials Abstracts Search 8. Example of a Polymer Trademark Search E. List of CAS Regisry Numbers of Common Polymers
VIII-25 VIII-25 VIH-26 VIH-26 VIH-26 VIH-26 VIH-26 VIII-28 VIII-29 VIII-29 VIII-29 VIII-29 VIII-32
The advent of computerized database searching for polymer literature has made locating technical information both easier and harder. While computers greatly increase the speed and completeness of a search, the algorithms and conventions used are often quite different from those used for hardcopy (paper) indexes. The following discussion and tables give basic information needed to start identifying and searching the most common polymers in the most used databases and paper indexes. A.
NOMENCLATURE
The Common Name is the name used by many scientists and engineers, and is used for listing polymers in catalogs such as Aldrich, and engineering indexes such as Engineering Index. Various other common Synonyms or Trade Names are also listed in the table and used in the literature. The Chemical Abstracts (CA) Index Name is the most recent name used by Chemical Abstracts Service (CAS). In general, Chemical Abstracts follows IUPAC
guidelines when naming polymers. The CAS Registry Number (CAS Reg. No.) is a unique identifying number given to each of the 18 million chemical compounds CAS has indexed. The Molecular Formula is the formula for the smallest repeating unit of the polymer. In some cases, such as cellulose, the exact molecular formula is not known. B. CAS REGISTRY NUMBERS CAS Registry Numbers provide a consistent method of identifying and searching for polymers in literature databases, and have been used to develop the table in this section. CAS indexes the chemical and chemical engineering literature from about 80000 worldwide journals, conference papers, books, and patent literature. The way that CAS (or IUPAC) names a compound is often very different from that used in scientific journals or the popular press. Polyethylene provides an excellent example of this problem. The name in CA is currently Ethene, homopolymer. CAS used to index it under Ethylene, polymers. Over 2000 synonyms or trade names are listed for polyethylene compounds, ranging from Alathon (registered trademark of the Lyondell Petrochemical Company) to Suzulon (a tradename used by Aicello Chemical Corporation, but not trademarked). As CAS understates in its publication, "Polymer Searching", "Unfortunately, naming conventions for polymers have not achieved widespread understanding, and molecular formulas are not unique search terms." CAS Registry Numbers are used not only by CAS in their database indexing but by the US Federal Government in their Toxic Substances Inventory, by the US Department of Transportation for regulating transport of chemicals, and by other indexes such as Merck and Aldrich. They are the most precise and unique compound identification. Authors of polymer literature may not always be able to report the precise structure of their materials. However, they usually do report the monomers used in the polymerization. Thus, while polymers are represented in two ways, as monomers and by final structure (Structural Repeating Unit or SRU), the primary registration of a polymer is by its component monomers. The Registry Number for most
polymers in the table can be used to find the component Registry Numbers for their corresponding monomers. Similarly, the Registry Number for copolymers will lead to the monomer registry numbers. Searching just by the SRU, the homopolymer, or the copolymer number will not retrieve a complete citation list. C. INDEXING AND CAS REGISTRY NUMBER ASSIGNMENT Chemical Abstracts assigns Registry Numbers to polymers based on both their monomers and their final structure. The table here usually lists the Registry Number for the homopolymer or copolymer. However, searches that use only one Registry Number for a polymer are often incomplete. Polymers based on more than one monomer should be searched using all the component monomers. All the copolymer references of a specific monomer can be found by searching the monomer's Registry Number. The polymers having the same final structure can be found by searching the final structure's Registry Number. Some compounds are so well characterized that they do not follow the rules and are indexed only under their structural repeating unit (SRU). These are marked (R) in the table and include common polymers such as Nylon 6 or PET Some polymers are not indexed by registry numbers at all but only by subject. These include tung oil, cellulose, and linseed oil, which are marked (S) in the table. These materials are exceptions and, in most searching, registry numbers must be used in the CAS online files. Some registry numbers in the Registry File are marked with an asterisk (*). STN gives the message on-line that these "represent substances of unknown or variable composition, complex reaction products, or biological substances that do not meet the criteria for Chemical Abstracts indexing". These substances generally have been registered for regulatory agencies and receive a CA Index Name. Searching these substances in STN files can be done by using the Registry Number(s) from the record, terms derived from the name, terms that are more or less specific than those in the name (which may include other CAS Registry Numbers), or associated trade names. Every likely term should be tried, and additional help should be sought if other references seem likely. Section E gives the common names and CA Registry Numbers for a number of important polymers. A list of Registry Numbers in numerical order with their corresponding names is available from the authors. Additional synonyms and trade names are provided, as are the CA Index names. Molecular formulae are provided, and can be helpful in searching with structural-related databases. The Search Guide indices have the following meanings: S search by CA Index names as a subject in the citation file * search using every likely term - Registry Numbers, name, synonyms, etc. R search by Registry Numbers for components, copolymers, SRU's U search using the single Registry Number provided.
The CAS database system is available commercially, most commonly through STN (1-800-848-6538) and Dialog (1-800-334-2564). Most academic and industrial libraries have ready access to these systems and may be consulted for assistance. For illustrative purposes, searches from each system are demonstrated here. The logic of searching each system is the same, but commands and features can vary. For more information about online searching, consult a librarian or the database vendors. The Chemical Abstracts Service book, "Searching for Polymer Information in CAS Online", American Chemical Society, Chemical Abstracts Service, 1990, p. 173, is the best starting source for polymer information within Chemical Abstracts. It may be ordered by calling the STN toll-free number or using the web page. D.
EXAMPLE SEARCHES
1. Example of a Search Using the Polymer CAS Registry Number The first step in a CA search is to identify the registry numbers. Section E lists registry numbers for many common polymers. The Registry Number for poly-(acrylamide) is 9003-05-8. Leading zeros should be disregarded when searching online, for example, search 009003-05-8 as 9003-05-8. Using the CA Registry Number to search the chemical compound registry file would return the following information (Fig. 1) from the Dialog database. The Dialog File number at the beginning of each output refers to a specific work session for the user. This particular database provides the molecular formula, related CAS Registry Numbers, the CA name, a list of synonyms including tradenames, the CA Registry Number for the monomer, and the number of literature references over the specified time interval. 2. Example of a Search Using the Monomer CAS Registry Number The CAS Registry Number for the monomer from the previous example, acrylamide, is 79-06-1. Searching by the component Registry Number in the Registry File gives the following record (Fig. 2). 3. Example of a Combined Search The results of both searches (polymer and monomer CAS Registry Numbers) would be combined to generate a more complete listing of the literature. The following answers (Fig. 3) are found by searching the abstracts file for CA (399 on Dialog) with the monomer and polymer Registry Numbers. Searching by the homopolymer Registry Number (RN), 9003-05-8, produced most citations. However, over 6000 additional articles containing information about the monomer would have been missed if the monomer Registry Number, 79-06-1, had not been used. Some of these may contain needed information about the polymer. Only 539 articles were indexed using both Registry Numbers.
(Dialog File 398) CAS REGISTRY NUMBER: 9003-05-8 (POLYMER) MOLECULAR FORMULA: (C3H5NO)x REPLACED CAS REGISTRY NUMBER(S): 9082-06-8 12624-24-7 25038-45-3 27754-57-0 33338-03-3 39355-07-2 39387-77-4 51312-40-4 57679-11-5 68247-81-4 72270-86-1 79079-15-5 104981-89-7 114265-35-9 143180-09-0 143180-13-6 143180-22-7 CA NAME(S): HP = 2-Propenamide (9CI) NM = homopolymer HP = Acrylamide (8CI) NM — polymers SYNONYMS: Acrylarmde homopolymer; Acrylamide polymer; Alcoflood 1175; Alcoflood 935; American Cyanamid KPAM; American Cyanamid P 250; AMF; Aminogen PA; AP 273; Aron F 40; BanDrift; Boze Floe N 46BT; Calgon 470; Calgon 800; Cogum 2OP; Cogum 25H; Cyanamer N 300LMW; Cyanamer P 250; Cyanamer P 35; Cytame 5; Diaclear MA 3000H; Diaclear MN 3000H; DK Dry Capsule ESP; Dow ET 597; Dow J 100; Dow 164; DP 1916; DP 9-6193; Drew Floe 41; E 936; ET 597; Flygtol GB; Formula 358; Gelamide 250; Get-Down ; GPA-u; Himoloc OK 507; Himoloc SS 200; Hiset P 700; Hyset P 700SN; Instar NS; J 100; J lOO(polymer); K 4; K 4(acrylic polymer); K-PAM; KAL 13; KW 677; Magnifloc 900N; Maquat 100; Migunon NS; Mirbane 301; Nalco Lp 3033; Nalco 7871; Nalco 8871; NL; P 250; P 250(polymer); P 300; P 300(polyacrylamide); PAA 1; PAA 7OL; PAM; PAM 50; PAM(homopolymer); Pamid; PC 305; Percol 333; Plex 4847D; Polias 320; Polyacron KR 143; Polyacrylamide; Polyacrylamide resin; Polyhall 2J; Polyhall 5J; Polymerset C 305; Polysic; Polystron 117; Polystron 145; Polystron 191; Polystron 194-7; Pomosist 117; Praestol 2800; Praestol 2810/73; Praestol 6000; Sanpoly A 520; Santac SP 66; Santac SP 67; Seabetter AD; Sedipur TF; Sedipur TF 514; Sepaflux CE 5174; Solidokoll K; Solvitose 433; Stargum AD-S; Stokopol D 2624; Sumifloc FN 10H; Sumirez A 17; Sumirez A 27: Sursolan P 5; Texapret AM; Tulsepar PNS 1; TY 007; Versicol W I l : Versicol W 17; Versicol W 25; Versicol WN 15; Viterra II ; X-Coat P 130C; X-Coat P 180S; Zonen A; 2J; 3330s; 38F COMPONENT CAS REGISTRY NUMBER(S): (79-06-1) Component RN
Component Molecular Formula
1) 79-06-1 C3H5NO SUBFILE: CHEMNAME LASTUPDATE: 199611
13873 LITERATURE REFERENCES) IN FILE 399.
Figure 1. Dialog database output from searching CAS Registry No. 9003-05-8.
CAS REGISTRY NUMBER: 79-06-1 MOLECULAR FORMULA: C3H5NO CA NAME(S): HP = 2-Propenamide (9CI) HP = Acrylamide (8CI) SYNONYMS: Acrylic amide; Ethylenecarboxamide; Propenamide; Vinyl amide SUBFILE. CHEMNAME 6574 LITERATURE REFERENCES) IN FILE 399. LAST UPDATE: 199608 Figure 2.
Dialog database output from searching CAS Registry No. 79-06-1.
Set Items Description ?srn-9003-05-8
51 14051 R N = 9003-05-8 ?srn = 79-06-1 52 6622 R N = 79.06-1 ?s si or s2 14051 Sl 6622 S2 53 20134 Sl O R S2 ?s si and s2 14051 Sl 6622 S2 54 539 Sl A N D S2 Figure 3. Dialog database output from combining the polymer and monomer searches.
4. Example of a Copolymer Search Poly(acrylonitrile-co-butadiene) is a common commercial product. The STN database was searched for this copolymer, using its CAS Registry Number along with those of the monomers. The search method is similar to that for homopolymers; the copolymer and the two monomers are searched separately, and the results are combined. Some records have been edited for clarity and conciseness. In Fig. 4, component 1 is acrylonitrile and component 2 is butadiene.
(STN Registry File) Ll ANSWER 1 OF 1 REGISTRY COPYRIGHT 1997 ACS RN ***9003-18-3*** REGISTRY CN 2-Propenenitrile, polymer with 1,3-butadiene (9CI) (CA INDEX NAME) OTHER CA INDEX NAMES: CN 1,3-Butadiene, polymer with 2-propenenitrile (9CI) CN 1,3-Butadiene, polymer with acrylonitrile (8CI) CN Acrylonitrile, polymer with 1,3-butadiene (8CI) OTHER NAMES: CN 1,3-Butadiene-acrylonitrile copolymer CN 1,3-Butadiene-acrylonitrile polymer CN Acrylonitrile-1,3-butadiene copolymer (30 other chemical names or synonyms or trade names are listed) MF (C4 H6 . C3 H3 N)x CM 1 (Component One) CRN 107-13-1 (Component Registry Number) CMF C3 H3 N (Component Molecular Formula) CM 2 (Component Two) CRN 106-99-0 (Component Registry Number) CMF C4 H6 (Component Molecular Formula) Figure 4.
STN database output from a copolymer search.
Searching by the two component Registry Numbers given above, (107-13-1, acrylonitrile; 106-99-0, butadiene), gives the following records in the Registry File (Fig. 5). Figure 6 shows the output when all the separate searches (Figs. 4 and 5) are combined. Search strings for each command are shown. In this case, there are fewer articles for the copolymer (9003-18-3) than for either of the component monomers individually. On the other hand, 550 citations have the two components together, with very little overlap between that set and the copolymer. This once again illustrates the importance of including the monomers to get a complete search in CA files online. A similar search in the paper version of CA could be done by finding the latest CA name for the homopolymer or copolymer and all related monomers in the Chemical Substance Index, and then referring to the abstracts. The Chemical Substance Index also lists the Registry !Numbers for all compounds indexed, and should be checked prior to online work. Additional search methods include using the trade name, chemical name, and molecular formula in the Registry File to start the search for a polymer Registry Number. The table gives a starting point for common polymers, but with over 700000 polymeric entries, it is impossible to list them all.
L2 ANSWER 1 OF 2 REGISTRY COPYRIGHT 1997 ACS RN ***i07-13-l*** REGISTRY CN 2-Propenenitrile (9CI) (CA INDEX NAME) OTHER CA INDEX NAMES: CN Acrylonitrile (8CI) OTHER NAMES: CN Acrylon CN Carbacryl CN Cyanoethene CN Cyanoethylene CN Fumigrain CN Propenenitrile CN VCN CN Ventox CN Vinyl cyanide L2 ANSWER 2 OF 2 REGISTRY COPYRIGHT 1997 ACS RN **• 106-99-0*** REGISTRY CN 1,3-Butadiene (8CI, 9CI) (CA INDEX NAME) OTHER NAMES: CN .alpha.,.gamma.-Butadiene CN Biethylene CN Bivinyl CN Butadiene CN Butadiene-1,3 CN Divinyl CN Erythrene CN Vinylethylene MF C4 H6 Figure 5. STN database output of comonomer searches.
(File CA on STN) = > s 9003-18-3 L3 7648 9003-18-3 = > s 107-13-1 L4 16353 107-13-1 = > s 106-99-0 L5 12917 106-99-0 = > s 14 and 15 L6 550L4ANDL5 = > s 13 and 16 L7 19 L3 AND L6 Figure 6. STN database output from a combined search for a coplymer and its monomers. 5. Example of an Engineering Database Search
Searching the engineering databases is a less formidable task. In most cases, the searches for polymers are started using the common names of the compound. The indexing of the answer set is then evaluated for other terms to use. The following search is from the Engineering Index (file 8) on Dialog (Fig. 7). Set Items Description ?s polyoxymethylene (compound entered as one word) 51 396 POLYOXYMETHYLENE ?s poly()oxymethylene (compound entered as two words) 39391 POLY 155 OXYMETHYLENE 52 87 POLYQOXYMETHYLENE ?s si or s2 396Sl 87 S2 53 459 Sl OR S2 ?t 1/8/1 1/8/1 DIALOG(R)FiIe 8:(c) 1997 Engineering Info. Inc. All rts. reserv. 04628455 Title: Hybrid effects on mechanical properties of polyoxymethylene Descriptors: *Polymers; Fracture toughness; Strain rate; Tensile strength; Bending strength; Impact resistance; Elastic moduli Identifiers: Polyoxymethylene; Hybrid strength; Impact strength; Flexural modulus 2/8/2 DIALOG(R)FiIe 8:(c) 1997 Engineering Info. Inc. All rts. reserv. 04572617 Title: Spatially resolved in situ analysis of polymer additives by two-step laser mass spectrometry Descriptors: *Additives; Polyvinyl chlorides; Polypropylenes; Polyethylene terephthalates; Composition effects; Desorption; Stabilizers (agents); Carbon dioxide lasers; Laser ablation; Antioxidants Identifiers: Polyoxymethylene; Hydroxyphenylbenzotriazole; Polymer additives Figure 7.
Engineering Index output for poly(oxymethylene).
In this case, poly(oxymethylene) is indexed as one word so the search term was appropriate to this database. The two-word search (S2 and S3) was taken from the authors' abstracts, which are searched automatically in this database (unlike in CAS files). 6. Example of a Search with Punctuation in the Polymer Name Poly(L-proline) is a more difficult search because most databases do not index punctuation. In this case, the compound is entered as if it were three words. In the first search, each word is specified to bedn that specific order (adjacent to each other). This search yielded 26 hits (Fig. 8), but the specific records show that the term was found just in the abstract, not in the indexing. Searching by the broader term "polypeptides" would get a larger, less specific, answer set since any polypeptide could be included. The database also shows that "polypeptides" has been an index term since 1977. Searching poly(L-proline) as three separate words would pull the terms from anywhere in the database record. This method gives more answers than the first search strategy (Fig. 9) but less than the broad polypeptide search. 7. Example of an Engineering Materials Abstracts Search Similar strategies of searching chemical names and checking indexing should be used for other engineering databases such as Engineering Materials Abstracts. A search of the word, nylon, retrieves a larger answer set than the search of the sequence, nylon 6 (Fig. 10). A check of the indexing determines that nylon 6 is a valid term and would be a more specific, focused search on the topic. Chemical Abstracts, Engineered Materials, Engineering Index, and other indexes such as Current Contents or the National Technical Information Service are available online through many vendors, on CDROM, at libraries, and over the Internet, via accounts with security and passwords. They are still available in paper copy at many libraries. Before doing any kind of literature search, the researcher must first decide how much information is needed, for what time period, what limits such as language or type of material are to be applied, and how much time is to be devoted to the search. Then each resource can be evaluated for what is covered and how it is indexed so that the proper tools will be used. Finding information is a lot like doing an experiment. Many paths can be explored and different techniques are tried until the researcher is satisfied. 8. Example of a Polymer Trademark Search A trademark is either a word, phrase, symbol or design, or combination of words, phrases, symbols or designs, which identifies and distinguishes the source of the goods or services of one party from those of others. US trademark rights arise from either (a) actual use of the mark, or (b) the filing of a proper application to register a mark in the Patent
?s poly()l()proline 39391 POLY 71166 L 259 PROLINE Sl
26 P O L Y ( ) L ( ) P R O L I N E
?t 7/5 7/5/1 DIALOG(R)FiIe 8:Ei Compendex(R) (c) 1997 Engineering Info. Inc. All rts. reserv.
03979891 E.I. No: EIP94112411957 Title: Optical activity measurements in solids 7. Polylactides and poly ( beta -hydroxybutyrates) Author: Bartus, Jan; Weng, Dexi; Vogl, Otto Corporate Source: Polytechnic Univ, Brooklyn, NY, USA Source: Polymer International v 34 n 4 Aug 1994. p 433-442 Publication Year: 1994 CODEN: PLYIEI ISSN: 0959-8103 Language: English Document Type: JA; (Journal Article) Treatment: X; (Experimental) Journal Announcement: 9412W4 Abstract: The optical activities of poly-(R)-lactide, poly-(S)-lactide, poly (beta -hydroxybutyrate) and two beta -hydroxyvalerate copolymers were measured in solution, as solid powders in suspension, and where possible, as films. Poly-(plus)-3-methyl-l-pentene was also reinvestigated. In some cases the specific rotation values of powder samples showed significant differences from the values of the solution measurements. The discrepancies of the data observed seem to reflect the local environment of the polymer chains in supermolecular assemblies and consequently the solid state structure (morphology) of the polymers. The circular dichroism (CD) spectra of the polymers were also measured in solution and in the form of their films. For comparison, the CD spectra of the naturally occurring protein casein and of the synthetic polypeptide poly-(L)-proline were also measured. (Author abstract) 21 Refs. Descriptors: *Polymers; Optical variables measurement; Powders; Plastic films; Molecular structure; Morphology; Proteins; Casein; Polypeptides; Sodium compounds Identifiers: Polylactides; Polyhydroxybutyrates; Circular dichroism ?s polypeptides Sl 1783 POLYPEPTIDES (January 1977) Figure 8.
Engineering Index output for an adjacent word search.
?s poly and 1 and proline 39391 POLY 71166 L 259 PROLINE S8 39 POLY AND L AND PROLINE Title: Synthesis of crosslinked poiy(vinyl alcohol) with L- proline pendant as the chiral stationary phase for resolution of ammo acid enantiomers Abstract: The porous crosslinked poly (vinyl alcohol) beads with the L -proline pendant was synthesized as the chiral stationary phase (CSP) for ligand-exchange chromatography of amino... ...and triallyl isocyanurate as a crosslinker, methanolysis of the copolymer, glycidylation of the formed crosslinked poly (vinyl alcohol), and final functionalization with L-proline. After the polymer with the chiral ligand was complexed with copper(II) cations, it was... Figure 9.
Engineering Index output for a general word search.
?s nylon 57 3241 NYLON ?s nylon()6 3241 NYLON 18621 6 58 1615NYLON()6 t 8/8/1 Engineering composites with nylon 6 matrix. Descriptors: Conference Paper; Nylon 6 - Composite materials; Styrene butadiene resins- Composite materials; Thermoplastic elastomersMechanical properties; Tensile strength; Impact strength Section Headings: D2 Materials Development Subfile: P Polymers Figure 10. Engineering Materials Abstracts output.
ALATHON
Stylized Letters INTL CLASS: 1 (Chemicals) U.S. CLASS: 6 (Chemicals and Chemical Compositions) STATUS. Renewed SERlALNO.: 71-569,356 REG. NO.: 543,580 REGISTERED: June 12, 1951 PUBLISHED: March 13, 1951 ORIGINAL REGISTRANT: E.I. DU PONT DE NEMOURS AND COMPANY (Delaware Corporation), J007 MARKET STREET. WILMINGTON, DE (Delaware). USA (United States of America) 3RD NEW OWNER ENTERED AFTER REGISTRATION: OCCIDENTAL CHEMICAL 2400, HOUSTON, TX (Texas), 77046. USA (United States of America) RENEWAL OWNER: (New Samek Corporation), 5 GREENWAY PLAZA, SUITE Renewed: June 12, 1971ARENEWAL OWNER: OCCIDENTAL CHEMICAL CORPORATION (New York Corporation), 5 GREENWAY PLAZA, SUITE 2400, HOUSTON, TX (Texas), 77046, USA (United States of America) Renewed: June !2, 1991 ASSIGNEE(S). CHASE MANHATTAN BANK. THE (NATIONAL ASSOCIATION)
AS AGENT FOR THE BANKS Assignor(s): CAIN CHEMICAL INC. (Delaware Corporation) Reel/Frame: 0564/0786 Recorded: June 8, 1987 Brief: SECURITY INTEREST ASSIGNEE(S): CAIN CHEMICAL INC. (Delaware Corporation), ELEVEN GREENWAY PLAZA. SUITE 2700, HOUSTON. TX (Texas). USA (United States of America) Assignor(s): E. I. DU PONT DE MEMOURS AND COMPANY (Delaware Corporation), 1007 MARKET ST., WILMINGTON, DE (Delaware). USA (United States of America) Reel/Frame: 0574/0432 Acknowledged: June 9. 1987 Recorded: August 24. 1987 Brief: ASSIGNS THE ENTIRE INTEREST AND GOOD WILL ASSIGNEE(S): CAIN CHEMICAL INC. (Delaware Corporation) Assignor(s): CHASE MANHATTAN BANK, THE (NATIONAL ASSOCIATION), AS AGENT Reel/Frame: 0648/0279 Recorded: December 19, 1988 Brief: RELEASE BY SECURED PARTY OF THE SECURITY AGREEMENT RECORDED ON JUNE 8, 1987, AT REEL 0564, FRAME 786. ASSIGNEE(S): OXY PETROCHEMICALS INC. Assignor(s): CAIN CHEMICAL INC. (Delaware Corporation) Reel/Frame: 0738/0721 Recorded June 14, 1990 Brief. CHANGE OF NAME EFFECTIVE SEP. 21, 1989 ASSIGNEE(S): OCCIDENTAL CHEMICAL CORPORATION (New York Corporation), FIVE GREENWAY PLAZA, SUITE 2400, HOUSTON, TX (Texas), USA (United States of America) Assignor(s): OXY PETROCHEMICALS INC. (Delaware Corporation), FIVE GREENWAY PLAZA, SUITE 2500, HOUSTON. TX (Texas). USA (United States of America) Reel/Frame: 0738/0728 Recorded: June 14, 1990 Brief: ASSIGNS THE ENTIRE INTEREST AND GOOD WILL ASSIGNEES): LYONDELL PETROCHEMICAL COMPANY (New York Corporation), 1221 MCKINNEY ST., SUITE 1600. HOUSTON. TX (Texas). 77010, USA (United States of America) Assignor(s): OCCIDENTAL CHEMICAL CORPORATION (New York Corporation) Reel/Frame: 1434/0830 Recorded: February 13. 1996 Brief: ASSIGNS THE ENTIRE INTEREST AND GOOD WILL Figure 11. Trademark database search for Alathon.
and Trademark Office (PTO) stating that the applicant has a bonafide intention to use the mark in commerce regulated by the US Congress. Federal registration is not required to establish rights in a mark, nor is it required to begin use of a mark. However, federal registration can secure benefits beyond the rights acquired by merely using a mark. For example, the owner of a federal registration is presumed to be the owner of the mark for the goods and services specified in the registration, and to be entitled to use the mark nationwide. There are two related but distinct types of rights in a mark: the right to register and the right to use. Generally, the first party who either uses a mark in commerce or files an application in the PTO has the ultimate right to register that mark. The PTO's authority is limited to determining the right to register. The right to use a mark can be more complicated to determine.
Information on polymer trademarks can be found by searching in trademark databases on Dialog. The search is complicated because a name may be trademarked in one country, and yet not in another. Trademarks may be sold, or they may be assigned by one business to another. A search for Alathon, a registered trademark for polyethylene, is given as an example (Fig. 11). Dialog's trademark scan software provides a description of the goods or services the trademark describes, gives the trademark status, the application number, the registration number and type, and the dates of the action. Previous owners or assignees of the trademark can be identified. Usually, the trademark database of each country of interest must be checked to determine whether the name is registered.
E. LIST OF CAS REGISTRY NUMBERS OF COMMON POLYMERS
Common name Alginic acid Alginic acid, sodium salt Bayberry wax Beeswax, refined, yellow Boron nitride Candelilla wax, natural Carboxymethyi cellulose Carboxymethyi cellulose, sodium salt Carnauba wax, refined, No. 1, yellow Carrageenan, type I (tt-carrageenan) Carrageenan, type II (t-carrageenan) Cellulose Cellulose acetate Cellulose acetate butyrate
Synonyms
CAS Registry No.
Myrtle wax
Carboxymethylated cellulose sodium salt; cellulose glycolate Ambergum, carboxymethyicellulose; sodium carboxylmethyl cellulose
9005-32-7 9005-38-3 8038-77-5 8012-89-3 10043-11-5 8006-44-8 9004-32-4 9004-32-4
CA name
Alginic acid Alginic acid, sodium salt Fats and Glyceridic oils, bayberry Beeswax Boron nitride Beeswax Cellulose, carboxymethyl ether, sodium salt Cellulose, carboxymethyi ether, sodium salt
8015-86-9
Acetic acid, cellulose ester Acetobutyrate cellulose; cellulose acetobutyrate
Cellulose acetate butyrate, acrylamidomethyl
Search method R R S* S* R S* R R
Unk
9000-07-1
Carrageenan
R
Unk
9062-07-1
i-Carrageenan
R
Unk
9004-34-6 9004-35-7 9004-36-8
Cellulose Cellulose, acetate Cellulose, acetate butanoate
R R R
Cellulose, acetate butanoate, ((1 -oxo-2-propenyl)amino)methyl ether
R
Unk (C2H4O2)*; Unk (C 4HsO2)* (C2H 4O2 ) x; Unk (C 4 H 8 O 2 )* (C4H 7 NO 2)x (C 2 H 4 O 2 ) X ; Unk (C 8 H 6 O 4 )* (C 2 H 4 O 2 )*; Unk (C 3 H 6 O 2 )* (C 2 H 4 O 2 )*; Unk (C 4 H 7 NO 2 )* (C 3 H 6 O 2 )* (C 2 H 4 O 2 )*; Unk (C 9 H 6 O 6 )* (C 2 H 4 O 2 )*; Unk (C 2 H 4 O 2 ) 1/2; Unk
91313-01-8
Acetyl phthalyl cellulose; cellulose acetate phthalate
9004-38-0
Cellulose, acetate hydrogen 1,2-benzene dicarboxylate
R
Cellulose acetate propionate
Acetylpropionyl cellulose
9004-39-1
Cellulose, acetate propanoate
R
Cellulose acetate propionate, acrylamidomethyl
97635-64-8
Cellulose, acetate propanoate, ((l-oxo-2-propenyl)amino)methyl ether
R
Cellulose acetate trimellitate
52907-01-4
Cellulose, acetate 1,2,4-benzenetricarboxylate
R
Cellulose, diacetate
R
Diacetyl cellulose
* Indicates that the precise molecular formula is unknown.
Unk* Unk Unk Unk BN Unk (CiHUO3)* Nax; Unk (C2H4O3)* Nax; Unk
S*
Cellulose acetate hydrogen phthalate
Cellulose diacetate
Molecular formula
9035-69-2
Common name
Synonyms
CAS Registry No.
Cellulose nitrate Cellulose propionate Cellulose sulfate
Collodion; soluble gun cotton Sodium cellulose sulfate
9004-70-0 9004-48-2 9005-22-5
Cellulose triacetate
Poroplastic; triacetyicellulose
9012-09-3
Cellulose tributyrate
Cellulose xanthate Cellulose, cyanoethylated
Cellulose carbonodithioate; cellulose hydrogen dithiocarbonate Cellulose cyanoethyl ether; cellulose ethylcyanide
Cellulose, tributanoate
R
9047-07-8
Cellulose, tris (phenylcarbamate)
R
9032-37-5
Cellulose, hydrogen carbonodithioate
R
(HNO3).,; Unk (C3H6O2)A; Unk (H2O4S).V Na.t; Unk (C 2 H 4 O 2 ) 1/3; Unk (C 4 H 8 O 2 ) 1/3; Unk (C 7 H 7 NO 2 ) 1/3; Unk (CH2OS2).,; Unk
9004-41-5
Cellulose, 2-cyanoethyl ether
R
(C3H5NO)x; Unk
Cellulose, mixt. with cellulose carboxymethyl ether sodium salt Chitin Chitosan Ethene, chloro-, homopolymer, chlorinated Rubber, synthetic, chlorinated polyethylene Coconut oil Cellulose, ethyl ether
R
(C 2 H 4 O 3 )* Nav; Unk
S* R *
Unk Unk Unk
S
Unk
S* R
Unk (C2H6O)A; Unk
R R
Unk Unk
R
9004-62-0
Carbon fluoride Guar gum, carboxymethyl 2-hydroxypropyl ether, sodium salt Cellulose, hydroxybutyi methyl ether Cellulose, 2-hydroxyethyl ether
R
(C4Hi0O2).v (CH4O)x; Unk (C 2 H 6 O 2 ),; Unk
9004-64-2
Cellulose, 2-hydroxypropyl ether
R
(C 3 H 8 O 2 ).,; Unk
9004-65-3
Cellulose, 2-hydroxypropyl methyl ether Cellulose, hydrogen 1,2-benzenedicarboxylate, 2-hydroxypropyl methyl ether Lignin, alkali Lignin, alkali, 2-hydroxypropyl ether Lignin, alkali, carboxymethyl ether
R
R R
(C3H8O2)A (CH4O)x; Unk (C 8 H 6 O 4 )* (C3H8O2)., (CH4O).V; Unk Unk (C 3 H 8 O 2 )/, Unk
R
(C2H4O3Xx; Unk
Lignin, hydrolytic Lignin, organosolv Lignin, organosolv, 2-hydroxyethyl ether Lignosulfonic acid, sodium salt Linseed oil Maltodextrin Benzene, (chloromethyl)ethenyl-, polymer with diethenylbenzene and ethenylbenzene
R R R
Unk Unk (C 2 H 6 O 2 ).,; Unk
R S* R R
Unk Unk Unk (C10H10C9H9 Cl-C 8 H 8 ).,
R
(C2H6O2),(CH4O).,-; Unk (CH4O),-; Unk
51395-75-6
Chitin, crab shells Chitosan Chlorinated poly(vinyl chloride) Chlorinated polyethylene
1398-61-4 9012-76-4 68648-82-8
Graphite, fluorinated, polymer Guar gum carboxymethyl 2-hydroxypropyl ether, sodium salt Hydroxybutyl methyl cellulose
63231 66-3 Fats and glyceridic oils Cellulose ethyl ether; cellulose ethylate; ethocel, ethyl cellulose ether Sodium carboxymethyl hydroxypropyl guar
Cellosize; cellulose hydroxyethyl ether; cellulose hydroxyethyl ate; glycol cellulose Hydroxypropyl cellulose Cellulose hydroxypropyl ether; hydropropyl cellulose; hydroxypropyl cellulose Hydroxypropyl methyl cellulose Cellulose hydroxypropyl methyl ether Hydroxypropyl methyl Cellulose phthalate hydroxypropyl cellulose phthalate methyl ether
Lignin, alkali Lignin, alkali, 2-hydroxypropyl ether Lignin, alkali, carboxymethyl ether Lignin, hydrolytic Lignin, organosolv Lignin, organosolv, 2-hydroxyethyl ether Lignosulfonic acid, sodium salt Linseed oil Maltodextrin Merrifield's peptide resin, cross-linked
lnduHn A Kraft lignin carboxymethyl ether Dioxane lignin
Fats and glyceridic oils
Chloromethylstyrene/;-divinylbenzene-styrene copolymer; A221481; chloromethylstyrene-styrene divinylbenzene copolymer Methyl 2-hydroxyethyl cellulose Hydroxyethyl methyl cellulose
Methyl cellulose
8001-31-8 9004-57-3 51311-17-2 68130-15-4 9041-56-9
Hydroxyethyl cellulose (2-hydroxyethyl cellulose)
Methyl ether cellulose
Molecular formula
R R R
Cellulose, microcrystalline, colloidal
Coconut oil Ethyl cellulose
Search method
Cellulose, nitrate Cellulose, propanoate Cellulose, hydrogen sulfate, sodium salt Cellulose, triacetate
39320-16-6
Cellulose tricarbanilate
CA name
9050-31-1 8068-05-1 88402-77-1 102962-28-7 8072-93-3 8068-03-9 90881-34-8 8061-51-6 8001-26-1 9050-36-6 55844-94-5
9032-42-2 9004-67-5
Cellulose, 2-hydroxyethyl methyl ether Cellulose, methyl ether
R
R
R
Common name
Synonyms
CAS Registry No.
Net-Poly (acrylic acid)-internet-poly(siloxane)
143106-82-5
CA name
Search method
2-Propenoic acid, 2-methyl-. 3-(dimethoxymethylsilyl)propyl ester, polymer with butyl 2-propenoate, decamethylcy-
R
clopentasiloxane, etc.
Nylon 6 Nylon 9 Nylon Il Nylon 12
Nylon 46
Polyamide 6 Polynonanamide; poly(imino1 -oxononamethylene) Poly(imino-l-oxoundecamethylene) Polydodecanamide; poly(iminocarbonylundecamethylene); poly(imino-1 -oxododecamethylene) Adipic acid-l,4-butanediamine copolymer, SRU; poly(tetramethylene adipamide)
Nylon 46, monomer-based Nylon 6, 6
Nylon 6, 9 Nylon 6/66
Nylon 610
Adipic acid-1, 6-hexanediamine copolymer; adipoyl dichloridehexamethylenediamine polymer, SRU; polyamides, nylon 66; poly(hexamethylene adipamide); poly(iminoadipoyl iminohexamethylene) Azelaic acid-1,6-hexanediamine salt polymer, SRU Adipic acid-£-caprolactam1,6-hexanediamine copolymer; nylon 6-nylon 66 copolyamide; nylon 6-nylon 66 copolymer; poly(hexamethyleneadipamide) Poly(iminohexamethylene iminosebacoyl); poly(hexamethylenesebacamide)
Nylon 612
25038-54-4 25748-72-5 25035-04-5 24937-16-4
(C 1n H 30 O 3 SiS Ci0H2OO4Si • CsHi 4 O 4 Si 4 • C 7 Hi 2 O 2 C7H KIOI •
U R
C 6 H 18 O 3 Si 3 QsH8O2)V (C6HMNO)1, (Ct)Hi 7 NO),
R
(C M H 2 |NO)
R
(Ci 2 H 23 NO),,
50327-22-5
Poly(imino-1,4butartediylimino (1.6-dioxo-1,6-hexanediyi))
R
(C I0H I 8 N 2 O 2 ),,
50327-77-0
Hexanedioic acid, polymer with 1,4-butanediamine Poly(imino(l,6-dioxol,6-hexanediyl)imino1,6-hexanediyl)
R U
(C 6 H I0O4 • C4Hi2N2)v (C I 2 H 22 N 2 O 2 ),,
Poly(imino-l,6-hexanediylimino (1,9-dioxo-1,9-nonanediyl)) Hexanedioic acid, polymer with hexahydro-2H-azepin-2-one and 1,6-hexanediamine
R
(Ci 5 H 2 8 N 2 O 2 ),,
R
(C 6 Hi 6 N 2 C 6 HnNOC 6 H I 0 O 4 ),
Poly(imino-l,6-hexanediyliminol,10-dioxo-l,10-decanediyl))
R
(C I 6 H 30 N 2 O 2 ),,
32131-17-2
28757-63-3 24993-04-2
9008-66-6
24936-74-!
(Ci 8 H 3 4 N 2 O 2 ),,
30525-89-4
Poly(imino-l,6-hexanediylimino R (1,12-dioxo- 1,12-dodecanediyl)) 1,4-Benzenedicarboxylic acid, R polymer with 1,6-hexanediamine Paraffin waxes and hydrocarbon S* waxes Paraformaldehyde R
9003-35-4
Phenol, polymer with formaldehyde R
(C 6 H 6 OCH 2 O), (C 3 H 7 NO 2 ), (C 3 H 7 NO 2 ), (C 3 H 7 NO 2 ), (C 4 Hc)NO 2 ),
Nylon 6/T, poly(hexamethylene terephthalamide) Paraffin wax, chunks
Hexamethylenediamine-terephthalic acid polymer
24938-03-2
Paraformaldehyde
Paraform
Phenol-formaldehyde resin
Formaldehyde-phenol polymer
Poly(D-alanine) Poly(L-alanine) Poly(D,L-alanine) Poly(Y-aminobutyric acid)
Poly-D-alanine Polyalanine Poly(4-aminobutyric acid)
26701-36-0 25191-17-7 25281-63-4 53504-43-1
Poly(L-aspartic acid), sodium salt Poly(acenaphthylene) Poly(aerylamide) Poly(acrylamide-co-acrylic acid)
Poly(aspartic acid) sodium salt
34345-47-6
8002-74-2
Oligoacenaphthylene Acrylamide polymer Acrylamide-acrylate polymer; acrylamide-acrylic acid polymer; poly(acrylic acid-acrylamide) Poly(acrylamide-cc-diallyl Acrylamide-diallyldimethyldimethyl ammonium chloride) ammonium chloride polymer
Poly(imino(l-oxo-l,6-hexanediyl)) Nonanoic acid, 9-amino-, homopolymer Poly(imino(l-oxo1,11-undecanediyl)) Poly(imino(l-oxo1,12-dodecanediyl.))
Molecular formula
25036-01-5 9003-05-8 9003-06-9
26590-05-6
D-Alanine, homopolymer L-Alanine, homopolymer DL-Alanine, homopolymer Butanoic acid, 4-amino-, homopolymer L-Aspartic acid, homopolymer, sodium salt Acenaphthylene, homopolymer 2-Propenamide, homopolymer 2-Propenoic acid, polymer with 2-propenamide
R R R R
2-Propen-l-aminium, N,Ndimethyl-./V-2-propenyl-, chloride, polymer with 2-propenamide
R
R R R R
(C 8 H 6 O 4 C 6 H 1 6 N 2 ), link (CH 2 O),
(C 4 H 7 NO 4 ), vNa (Ci 2 H 8 ), (C3H5NOXv (C 3 H 5 NOC3H4O2), (C 8 Hi 6 N C 3 H 5 NO-Cl) v
Common name
Synonyms
CAS Registry No.
Poly(2-acrylamido. 2-methyl, 1-propane suJfonic acidco-acrylonitrile) Poly(2-acrylamido-2-methyl1-propane sulfonic acid) Poly(2-acryiamido-2-methyl1-propane sulfone acid-costyrene) Poly(acrylic acid) Poly(acrylic acid), ammonium salt Poly(acrylic acid), potassium salt, crosslinked Poly(acrylic acid), sodium salt Poly(acrylic acid-co trimethylolpropane), sodium salt
54640-82-3
27119-07-9
51121-85-8
Acrylic acid polymer Ammonium polyacrylate; ammonium polyacrylic acid Potassium polyacrylate Acrylic acid polymer, sodium salt Acrylic acid-sodium aery latetrimethylolpropane triacrylate copolymer
9003-01-4 9003-03-6 25608-12-2 9003-04-7 76774-25-9
Poly(acrylic acid, sodium Acrylic acid-vinyl alcohol polymer, 27599-56-0 salt-gra//-poly(ethyiene oxide)), sodium salt crosslinked Poly(acrylic acid-cr;-acrylamide), Acrylamide-potassium acrylate 31212-13-2 potassium salt, crosslinked copolymer Poly(acrylic acid-cu-maleic acid) 29132-58-9 Poly(acrylic acid-comaleic acid), sodium salt Poly(acrylonitnle) Poly(acrylonitrile-cY;-butadiene)
Acrylic acid-maleic anhydride copolymer, sodium salt
52255-49-9
Acrylonitrile polymer; poly( 1 -cyanoethylene) Acrylonitrile-butadiene polymer
25014-41-9 9003-18-3
Poly(acrylonitrile-cY;-butadiene), amine terminated
68683-29-4
Poly(acrylonitrile-a;-butadiene), hydrogenated Poly(acrylonitrile-£Y>butadieneco-acrylic acid), dicarboxy terminated
88254-10-8
Poly(acrylonitrile-c<7butadiene-cc?-styrene) Poly(acrylonitrile-(Y;-vinylidene chloride-tw-methyl methacrylate)
68891-50-9
Acrylonitrile-butadiene-styrene polymer; cycolac; styreneacrylonitrile-butadiene polymer Acrylonitrile-methyl methacrylatevinylidene chloride polymer
9003-56-9
25214-39-5
Poly(allyl amine hydrochloride)
Allylamine hydrochloride
71550-12-4
Poly(p-aminobenzaldehyde)
Poly(4-aminobenzaldehyde)
28107-09-7
Poly(anethole sulfonic acid). sodium salt
Polyanethole sulfonate; sodium polyanetholesulfonate
52993-95-0
Poly((oc,(3)-D,L-aspartic acid), sodium salt Poly(azelaic anhydride) PoIy(1,4-benzene dicarboxyfl/f-bis(4-phenoxyphenyl) methanone)
94525-01-6 Azelaic acid polymer
26776-28-3 55088-54-5
CA name
Search method
1 -Propanesulfonic acid, 2-methyl2-((l-oxo-2-propenyl)amino)-, polymer with 2-propenenitrile 1-Propanesulfonic acid, 2-methyl2-((l-oxo-2-propenyl)amino)-, homopolymer 1-Propanesulfonic acid, 2-methyl2-((l-oxo-2-propenyl)amino)-, polymer with ethenylbenzene 2-Propenoic acid, homopolymer 2-Propenoic acid, homopolymer, ammonium salt 2-Propenoic acid, homopolymer. potassium salt 2-Propenoic acid, homopolymer, sodium salt 2-Propenoic acid, polymer with 2-ethyl-2-(((l-oxo-2-propenyl)oxy)methyl)-l,3-propanediyl di-2-propenoate and sodium 2-propenoate 2-Propenoic acid, polymer with ethenol, sodium salt 2-Propenoic acid, potassium salt, polymer with 2-propenamide 2-Butenedioic acid (Z)-, polymer with 2-propenoic acid 2-Propenoic acid, polymer with 2,5-furandione, sodium salt 2-Propenenitrile, homopolymer
R
(C 7 HI 3 NO 4 SC3H3N)X
R
(C 7 Hi 3 NO 4 S)V
R
(C 8 H 8 C 7 Hi 3 NO 4 S) x
R R R
(C 3 H 4 O 2 ) x (C 3 H 4 O 2 ), • A-H3N (C 3 H 4 O 2 J x A-K
R
(C 3 H 4 O 2 ) x A-Na
R
(Ci 5 H 2 OO 6 C3H4O2 C 3 H 4 O 2 Na)x
R
(C3H4O2 • C 2 H 4 O) vA"Na
R
(C 3 H 5 NO C 3 H 4 O? K)v (C 4 H 4 O 4 • C3H4O2Xx (C 4 H 2 O 3 • C^HtOi)x • A-Na (C 3 H 3 N).,
R R
R
2-Propenenitrile, polymer with R 1,3-butadiene 2-Propenenitrile, polymer with R 1,3-butadiene, 1-cyano-l-methyl4-oxo-4-((2-(l-piperazinyl)ethyl)amino)butyl-terminated 2-Propenenitrile, polymer with * 1,3-butadiene, hydrogenated 2-Propenoic acid, polymer with * 1,3-butadiene and 2-propenenitrile, 3-carboxy-l-cyano-l-methylpropylterminated 2-Propenenitrile, polymer with R L3-butadiene and ethenylbenzene 2-Propenoic acid, 2-methyl-, methyl ester, polymer with l.l-dichloroethene and 2-propenenitrile 2-Propen-1 -amine, hydrochloride, homopolymer Benzaldehyde, 4-amino-, homopolymer Benzene, l-methoxy-4(1-propenyl)-, (E)-, homopolymer, sulfonated, sodium salt DL-Aspartic acid, homopolymer, sodium salt Nonanedioic acid, homopolymer 1,4-Benzenedicarbonyl dichloride, polymer with bis(4-phenoxyphenyDmethanone
Molecular formula
(C 4 H 6 C 3 H 3 N) x (C 4 H 6 C 3 H 3 N) x
(C 4 H 6 • C 3 H 3 N) x (C 4 H 6 • C3H4O2 • C 3 H 3 N)., (C 8 H 8 C 4 H 6 C 3 H 3 N) x
R
(CsH 8 O 2 C 3 H 3 NC 2 H 2 C 2 )V
R
(C 3 H 7 N ClH)x
R
(C 7 H 7 NO),
R
Unk
R
(C 4 H 7 NO 4 ). X A-Na (C9H J6O4)x (C 2 5 Hi 8 O 3 C 8 H 4 C1 2 O 2 ) V
R R
Common name Poly(benzimidazole)
Synonyms
CAS Registry No.
Diphenyl isophthalate3,3',4,4/-tetraaminodiphenyl polymer
25928-81-8
Poly(benzoguanamine-coformaldehyde), methylated/ ethylated
68037-08-1
PolyCbenzophenone tetraBenzophenonetetracarboxylic carboxylic dianhydride-codianhydride-4,4'-oxydianilinephenylene diamine) ra-phenylenediamine copolymer
31942-21-9
Poly(2-(4-benzoyl-3-hydroxyphenoxy) ethyl acrylate)
2-Hydroxy-4-acryloxyethoxybenzophenone polymer
29963-76-6
Poly(benzyl methacrylate)
Benzyl methacrylate polymer
25085-83-0
Poly((3-cydodextrin-c
25655-42-9 68555-36-2 93975-09-8
Poly(bis(ethyl thio)acetylene)
93975-08-7
Poly(bis(methyl thio)acetylene)
93975-07-6
Poly(bisphenol A-co-4-nitrophthalic anhydrideC0-l,3-phenylene diamine)
2,2-Bis(4-(3,4-dicarboxyphenoxy)phenyl)propane dianhydridem-phenylenediamine copolymer
Poly(bisphenol A-coepichlorohydrin)
61128-46-9
25036-25-3
Poly(bisphenol A-coepichlorohydrin)
Bisphenol A epoxy resin; phenoxy resin
25068-38-6
Poly(bisphenyl tetracarboxylic dianhydride-co-phenylene diamine) Poly(4-bromostyrene)
Biphenyl dianhydride-p-phenylenediamine copolymer
29319-22-0
/?-Bromostyrene polymer
24936-50-3
Poly(butadiene) Poly(butadiene); cis and trans Poly(butadiene), cis Poly(butadiene), dicarboxy terminated
PoIy(I-butenylene); butadiene homopolymer PoIy(I-butenylene)
9003-17-2 25038-44-2 40022-03-5 68891-79-2
Poly(butadiene), hydroxyl functionalized Poly( 1,4-butanediol bis(4-aminobenzoate))
69102-90-5
PoIy(1,4-butanediol/neopentyl glycol-a/f-adipic acid)
36609-31-1
Poly(butene) PoIy(I-butene)
54667-43-5
Polybutene; polybutylene Polybutene
9003-29-6 9003-28-5
CA name
Search method
1,3-Benzenedicarboxylic acid, R diphenyl ester, polymer with (1,1 '-biphenyl)3,3',4,4/-tetramine Formaldehyde, polymer with * 6-phenyl-l,3,5-triazine2,4-diamine, ethylated/ methylated 1,3-Isobenzofurandione, R 5,5'-carbonylbis-, polymer with 1,3-benzenediamine and 4,4' -oxybis(benzenamine) 2-Propenoic acid, 2-(4-benzoylR 3-hydroxyphenoxy)ethyl ester, homopolymer 2-Propenoic acid, 2-methyl-, R phenylmethyl ester, homopolymer (3-Cyclodextrin, polymer with R (chloromethyl)oxirane Urea, ^N'-bis(3~(dimethylammo)- R propyl)-, polymer with l,l'-oxybis(2-chloroethane) Benzene, l,r-(l,2-ethynediylbisR (thiomethylene) )bis-, homopolymer Ethyne, bis(ethylthio)-, R homopolymer Ethyne, bis(methylthio)-, R homopolymer 1,3-Isobenzofurandione, R 5,5/-((l-methylethylidene) bis(4,l-phenyleneoxy)) bis- polymer with 1,3-benzenediamine Phenol, 4,4/-(l-methylethylidene)- R bis-, polymer with 2,2/-((l-ethylethylidene) bis(4,1 -phenyleneoxymethylene))bis(oxirane) Phenol, 4,4/~(l-methylethylidene)- R bis-, polymer with (chloromethyl)oxirane (5,5'Biisobenzofuran)R l,l',3,3'-tetrone, polymer with 1,4-benzenediamine Benzene, l-bromo-4-ethenyl-, R homopolymer 1,3-Butadiene, homopolymer R PoIy(I-butene-l,4-diyl) Poly(l-butene-l,4-diyl), 1,3-Butadiene, homopolymer, 3-carboxy-1 -cyano-1 -methy lpropyl-terminated 1,3-Butadiene, homopolymer, hydroxy-terminated Poly(oxy-1,4-butanediyl), oc-(4-aminobenzoyl)co-((4-aminobenzoyl)oxy)Hexanedioic acid, polymer with 1,4-butanediol and 2,2-dimethyl-l,3-propanediol Butene, homopolymer 1-Butene, homopolymer
Molecular formula (C 20 H 14 O 4 CI2HHN4)V Unk
(Ci 7 H 6 O 7 CJ2HJ2N2O C 6 H 8 N 2 ), (Ci8H I6O5)A (CnHi 2 O 2 ) v (C 42 H 70 O 35 • C3H5ClO)V (C J1H26N4OC 4 H 8 Cl 2 O), (Ci 6 H u S 2 ) v (C 6 HI 0 S 2 XV (C4H6S2)., (C3JH20Og C 6 HgN 2 ),
(C 2 iH 24 O 4 Ci 5 Hi 6 O 2 ),
(C I 6 H 6 O 6 C 6 HgN 2 ), (CgH7Br), (C 4 H 6 ),
R R *
(C4H6),, (C4H6),, Unk
*
Unk
R
(C4H 8O) „ Ci 4 Hi 2 N 2 O 3
R
(C 6 H 10 O 4 • C 5 Hj 2 O 2 C 4 Hi 0 O 2 )., (C 4 H 8 ), (C4H8).,
R R
Common name
Synonyms
CAS Registry No.
Po)y(butenes), hydrogenated
68937-10-0
Poly(butenes), monoepoxide
119275-53-5
Poly(butyl acrylate)
Butyl acrylate polymer
Poly(4-ter/-butylcyclohexyi methacrylate)
9003-49-0 34903-89-4
Poly(butyl methacrylate)
Butyl methacrylate polymer
9003-63-8
Poly(butyl methacrylate-rtfisobutyl methacrylate)
Butyl methacrylate - isobutyl methacrylate polymer
9011-53-4
Po!y(butyl methacrylate-cr;methyl methacrylate)
Methyl methacrylate - butyl methacrylate polymer
25608-33-7
Poly(4-terf-butylphenyl methacrylate)
p-tert-Butylphenyl methacrylate polymer
29696-27-3
Poly(4-terf-butylstyrene)
p-terf-Butylstyrene polymer
26009-55-2
Poly(l,4-butylene adipate)
Adipic acid-butylene glycol 25103-87-1 copolymer; adipic acidbutylene glycol polymer; PBAG; poly(butylene adipate); poly(tetramethylene adipate) Adipic acid-l,4-butanediol-HMDI- 119553-67-2 succinic acid copolymer
Poiy(l,4-butylene adipateco-i,4-butylene succinate) PoIy(1,2-butylene glycol)
1,2-Epoxybutane-propylene glycol polymer
PoIy(1,2-butylene glycol), monobutyl ether PoIy(1,4-butylene glutarate), hydroxy terminated PoIy(1,4-butylene succinate) Poly(1,4-butylene succinate-ct? HMDI) Poly( 1,4-butylene terephthalate)
Poly(caprolactone diol) Poly(caprolactone triol)
144437-84-3 1,4-Butanediol-glutaric acid copolymer Butylene glycol-succinic acid copolymer; poly(tetramethylene succinate) 1,4-Butanediol-HMDI-succinic acid copolymer
52256-54-9 25777-14-4 143606-53-5
Butanediol-terephthalic acid 24968-12-5 copolymer; poly(oxytetramethyleneoxyterephthalic acid-terephthaloyl); tetramethylene glycol polymer, SRU Caprolactone - diethylene glycol 36890-68-3 polymer e-Caprolactone - trimethylolpropane 37625-56-2 polymer
Poly(caprolactone triol)
Poly(caprolactone) Poly(chloroprene)
31923-86-1
54735-63-6
Chlorobutadiene polymer
24980-41-4 9010-98-4
CA name
Search method
Butene, homopolymer, hydrogenated 1-Butene, polymer with 2-butene and 2-methyl1-propene, epoxidized 2-Propenoic acid, butyl ester, homopolymer 2-Propenoic acid, 2-methyl-, 4-( 1,1 -dimethylethyl)cyclohexyl ester, homopolymer 2-Propenoic acid, 2-methyl, butyl ester, homopolymer 2-Propenoic acid, 2-methyl, butyl ester, polymer with 2-methylpropyl 2-methyl2-propenoate 2-Propenoic acid, 2-methyl-, butyl ester, polymer with methyl 2-methyl-2-propenoate 2-Propenoic acid, 2-methyl-, 4-(l,l-dimethylethyl)phenyl ester, homopolymer Benzene, l-(l,l-dimethylethyi)4-ethenyl-, homopolymer Hexanedioic acid, polymer with 1,4-butanediol
Molecular formula
*
Unk
*
(C 4 H 8 • C 4 H 8 • C4H8)*
R
(C7Hi2O2Xv
R
(Ci4H24O2Xv
R
(C8Hi4O2Xv
R
(C 8 HI 4 O 2 C8H]4O2Xv
R
(C 8 Hi 4 O 2 • C5H8O2)x
R
(Ci 4 Hi 8 O 2 )*
R
(C I2Hi6)A-
R
(C 6 Hi 0 O 4 C4Hi0O2Xy
Hexanedioic acid, polymer with butanedioic acid, 1,4-butanediol and 1,6-diisocyanatohexane
R
1,2-Propanediol, polymer with ethyloxirane Oxirane, ethyl-, homopolymer, mono(2-butoxy-l-methylethyl) ether Pentanedioic acid, polymer with 1,4-butanediol Butanedioic acid, polymer with 1,4-butanediol
R
(C 8 Hi 2 N 2 O 2 • C 6 H 10 O 4 C 4 Hi 0 O 2 C4H6O4) (C 4 H 8 O CiH8O2).*(C 7 Hi 6 O 2 • C 4 H 8 O) x
Butanedioic acid, polymer with 1,4-butanediol and 1,6-diisocyanatohexane Poly(oxy-l,4-butanediyloxycarbonyl-l,4-phenylenecarbonyl)
R
2-Oxepanone, polymer with 2,2'-oxybis(ethanol) 2-Oxepanone, polymer with 2-ethyl-2-(hydroxymethyl)1,3-propanediol Poly(oxy(l-oxo-l,6-hexanediyl)), a-hydro-co-hydroxy-, ester with 2-ethyl-2-(hydroxymethyl)1,3-propanediol (3:1) 2-Oxepanone, homopolymer 1,3-Butadiene, 2-chloro-, homopolymer
R
R R R
R
R R
R R
(C 5 H 8 O 4 C 4 Hi 0 O 2 ) A (C 4 Hi 0 O 2 • C4H6O4Xx (C 8 Hi 2 N 2 O 2 C 4 Hi 0 O 2 C 4 H 6 O 4 )* (Ci 2 Hi 2 O 4 ),,
(C 6 Hi 0 O 2 C4Hi0O3)A (C 6 Hj 4 03C 6 Hi 0 O 2 ) A (C 6 Hi 0 O 2 ),, (C 6 Hi 0 O 2 ),, (C6H I0O2),, C 6 Hi 4 O3 (C6H I0O2) A (C4H5Cl).,-
Common name
Synonyms
Poly(chlorostyrene)
Chlorostyrene polymer
Poly(4-chlorostyrene)
/;-Chlorostyrene polymer 4-Chlorostyrene polymer
Poly(chlorotrifluoroethylene)
Halocarbon oil
Poly(chlorotrifluoioethyleneco-vinylidene fluoride)
CAS Registry No.
CA name
9022-52-0
Benzene, chloroethenyl-, homopolymer Benzene, l-chloro~4-ethenyl-, homopolymer
Chlorotrifiuoroethylene-vinylidene fluoride polymer; trifluorochloroethylene-vinylidene fluoride polymer
24991-47-7
9002-83-9 9010-75-7
Poly(coumarone-cr;-indene)
35343-70-5
Poly(o-cresol glycidyl ether-coformaldehyde)
29690-82-2
Poly(-cresyl glycidyl etherco-formaldehyde)
Cresol-epichlorohydrinformaldehyde polymer
37382-79-9
Poly(2-cyanobutyl acrylate)
Butyl 2-cyanoacrylate polymer; poly (butyl cyanoacrylate) Poly(ethyl cyanoacrylate);
25154-80-7
Poly(2-cyanoethyl acrylate) Poly(2-cyanoheptyl acrylate)
25067-30-5 26936-29-8
Poly(2~cyanohexyl acrylate)
Poly(hexyl cyanoacrylate)
26877-39-4
Poly(2-cyanoisobutyl acrylate) Poly(2-cyanoisopropyl acrylate)
Isobutyl 2-cyanoacrylate polymer Poly(isopropyl cyanoacrylate)
26809-38-1 25931-02-6
Poly(cyclododecyl acrylate) PoIy(1,4-cyclohexane dimethylene terephthalateco-ethylene terephthalate)
56710-66-8 Dimethyl terephthalate-ethylene glycol-l,4-bis(hydroxymethyl)cyclohexane copolymer
Poly(cyclohexyl methacrylate)
25640-14-6
25768-50-7
Poly(di(ethylene glycol) glycerol-a/r-adipic acid)
Diethylene glycol-glycerol-adipic acid copolymer
26760-54-3
Poly(diallyl dimethyl ammonium chloride)
Diallyldimethylammonium chloride polymer
26062-79-3
Poly(diallyl isophthalate)
Diallyl isophthalate polymer
25035-78-3
Poly(diallyl phthalate)
Diallyl phthalate polymer
25053-15-0
Poly(diaminobenzophenoneco-benzophenone tetracarboxylic dianhydride)
Benzophenone tetracarboxylic acid dianhydridem,m'*diaminobenzophenone polymer, SRU
51518-44-6
Poly((dibenzo-18-crown-6)co-formaldehyde)
53660-42-7
Poly(dibromostyrene)
62354-98-7
Poly(dichlorophosphazene)
Dichlorophosphazine polymer; Poly(nitrile(dichlorophosphoranylidyne))
26085-02-9
Search method
Molecular formula
R
(CsH7CDv
R
(C 8 H 7 Cl) 1
Ethene, chlorotrifluoro-, homopolymer Ethene, chlorotrifluoro-, polymer with 1,1 -difluoroethene
R
(C2ClF3)V
R
(C 2 H 2 F 2 C2ClF-Ov
Benzofuran, polymer with 1 H-indene Formaldehyde, polymer with (chloromethyi)oxirane and 2-methylphenol Formaldehyde, polymer with (chloromethyl)oxirane and methylphenol 2-Propenoic acid, 2-cyano-, butyl ester, homopolymer 2-Propenoic acid, 2-cyano-, ethyl ester, homopolymer 2-Propenoic acid, 2-cyano-, heptyl ester, homopolymer 2-Propenoic acid, 2-cyano-, hexyl ester, homopolymer 2-Propenoic acid, 2-cyano2-Propenoic acid, 2-cyano-, 1 -methylethyl ester, homopolymer 2-Propenoic acid, cyclododecyl ester, homopolymer 1,4-Benzenedicarboxylic acid, dimethyl ester, polymer with 1,4-cyclohexanedimethanol and 2-ethanediol 2-Propenoic acid, 2-methyl-, cyclohexyl ester, homopolymer Hexanedioic acid, polymer with 2,2/-oxybis(ethanol) and 1,2,3-propanetriol 2-Propen-l-aminium, N,Ndimethyl-N-2-propenyl-, chloride, homopolymer 1,3-Benzenedicarboxylic acid, di-2-propenyl ester, homopolymer 1,2-Benzenedicarboxylic acid, di-2-propenyl ester, homopolymer Poly((l,3-dihydro-l,3-dioxo2H-isoindole-2,5-diyl)carbonyl(l,3-dihydro-l,3-dioxo-2Hisoindole-5,2-diyl)-l,3-phenylenecarbonyl-1,3-phenylene) Formaldehyde, polymer with 6,7,9,10,17,18,20,21 -octahydrodibenzo(b,k)( 1,4,7,10,13,16) hexaoxacyclooctadecin Benzene, dibromoethenyl-, homopolymer Poly(nitrilo(dichlorophosphoranylidyne))
R
(CgH8 C 8 H 6 O) 1
R
R
(C 7 H 8 O C3H5CIO CH 2O) v (C 7 H 8 O C 3 HsClO CH 2 O) 1 ( C 8 H N NO 2 ) v
R
(C 6 H 7 NO 1 J) 1
R
(CNHI7NO2)v
R
(C K)Hi5NO2) v
R R
( C 8 H N NO 2 ).v (C 7 HyNO?) v
R
(Ci 3 H 26 O 2 ).,
R
(C K)HK)O 4 C 8 Hi 6 O 2 • C2H6O2)
R
(CK)HI6O2)V
R
R
(C6Hi0O4' C 4 Hi 0 O 3 C3H8O3) (C 8 H) 6 N Cl) 1
R
(C i4H I 4 O 4 ).,
R
(C I 4 H| 4 O 4 ) V
R
(C 3 OHi 4 N 2 O 6 ),,
R
(C 2 0 H 2 4 O 6 CH 2O) v
R
(C8H6Br2)A
R
(Cl2NP),,
R
Common name
Synonyms
Poly(diethyl fumarate) Poly(diethylene glycol adipate) Poly(diethylene glycol/trimethylol propanetf/f-adipic acid), polyol
2698-06-6 Adipic acid-diethylene glycol polymer Adipic acid-diethylene glycoltrimethylolpropane polymer
PoIy(1,2-dihydro-2,2,4-trimethyl quinoline) Polyfdimer acid--ethylene glycol), hydrogenated
Antioxidant HS; trimethyldihydroquinoline polymer
Poly(AW-dimethylacrylamide)
/V./V-Dimethylacrylamide polymer
Poly(dimethyl siloxane), distearate terminated
Poly(dimethyl siloxaneo?-( 3-hydroxypropyl )-methyl siloxane). ethoxylated/ propoxylated Poly(dimethyl siloxane-romethyl(3-OH-propyl) siloxane)-y-PEG 3-aminopropyl ether) Poly(dimethyl siloxane), hydroxy terminated Poly(dimethylamine-£Y;epichlorohydrin) Poly(dimethylamine-tY;epichlorohydriiwflethylene diamine) Poly(dimethylsiloxane) Poly(dimethylstloxane), vinyl terminated Poly(dimethylsiloxane-C0methylphenyl siloxane) Poly(dipropylene glycol). phenyl phosphite
9010-89-3 28183-09-7
26780-96-1 68855-78-7
PoIy(Kl-dimethyl 3,5-dimethylene piperidinium chloride) Poly(2,6-dimethyl-l, Poly(2,6-xylenol) 4-phenylene oxide) Poly(2,2-dimethyl-l,3-propylene) Polyneopentyl glycol succinate
Poly(dimethyl siloxane), hydride terminated Poly(dimethyl siloxane), methoxy terminated Poly(dimethyl siloxane), vinyl terminated
CAS Registry No.
26793-34-0 32168-43-7
25134-01-4 28776-65-0
130169-63-0
Hydrogen-terminated di-Me silicones
70900-21-9 68951-97-3 68951-99-5
68937-55-3
133779-15-4
Silanol-terminated di-Me siloxanes
70131-67-8
Epichlorohydrin-dimethylamine copolymer
25988-97-0 42751-79-1
Dimethyl silicone; dimethylsilanediol polymer Dimethylsiloxanes, dimethylvinylsilyl-terminated Methylphenylsiloxane polymer
9016-00-6 68083-19-2 9005-12-3 116265-68-0
Poly(3-dodecyl thiophene), regioregular Poly(epichlorohydrin)
3-Dodecylthiophene homopolymer
104934-53-4
Poly(chloromethyl)ethylene oxide
24969-06-0
Polylethyl acrylate)
Ethyl acrylate polymer
9003-32-1
Poly(ethyl methacrylate)
Ethyl methacrylate polymer
9003-42-3
CA name
Search method
2-Butenedioic acid (E)-, diethyl ester, homopolymer Hexanedioic acid, polymer with 2,2'-oxybis(ethanol) Hexanedioic acid, polymer with 2-ethyl-2-(hydroxymethyl)1,3-propanediol and 2,2'-oxybis(ethanol) Quinoline, l,2-dihydro-2,2,4trimethyl-, homopolymer Fatty acids, C18-unsatd., dimers, hydrogenated, polymers with ethylene glycol 2-Propenamide,/V,N-dimethyl-, homopolymer PoIy(0,1-dimethylpiperidinium3,5-diyl)methylene chloride)
Molecular formula
R
(C 8 Hi 2 O 4 )V
R R
(Cr 1 Hi 0 O 4 C 4 Hi 0 O 3 )V (C6Hj 4 O 3 • CGHI0O4 C4Hi0O3),
R
(C 1 2 Hi 5 N),
S
Unk
R
(C5H9NO)V
R
(C 8 Hi 6 N),, -Cl
Phenol, 2,6-dimethyk homopolymer Poly(oxy(2,2-dimethyl1,3-propanediyl)oxy( 1,4-dioxo1,4-butanediyl)) Siloxanes and silicones, di-Me, ((l-oxooctadecyl)oxy)terminated Siloxanes and silicones, di-Me, hydrogen-terminated Siloxanes and silicones, di-Me, methoxy-terminated Siloxanes and silicones, di-Me, Me vinyl, mono(vinyl group)terminated Siloxanes and silicones, di-Me, 3-hydroxypropyl Me, ethoxylated propoxylated
R
(C 8 H] 0 O),.
R
(C 9 Hj 4 O 4 ),,
S
Unk
S
Unk
S
Unk
S
Unk
S
Unk
Siloxanes and silicones, di-Me, 3-hydroxypropyl Me, ethers with polyethylene glycol mono(3-aminopropyl) ether Siloxanes and silicones, di-Me, hydroxy-terminated Methanamine, ./V-methyl-, polymer with (chloromethyl)oxirane 1,2-Ethanediamine, polymer with (chloromethyl)oxirane and A^-methylmethanamine Poly(oxy(dimethylsilylene))
S
Unk
S
Unk
R
R
(C 3 H 5 ClO C 2 HyN) 1 (C 3 H 5 ClO C 2 HgN 2 C 2 HyN) x (C2HeOSi),,
*
Unk
R
(C7HgOSi),,
R
C IgHj 5 O 3 P • CgHi 4 O 3
R
(Ci6H2gS)v
R
(C3H5C1O)V
R
(C 5 H 8 O 2 ),
R
(C6HI0O2),
Siloxanes and Silicones, di-Me, vinyl group-terminated Poly(oxy(methylphenylsilylene)) Phosphorous acid, triphenyl ester, reaction products with dipropylene glycol Thiophene, 3-dodecyl-. homopolymer Oxirane, (chloromethyl)-, homopolymer 2-Propenoic acid, ethyl ester, homopolymer 2-Propenoic acid, 2-methyl-, ethyl ester, homopolymer
R
Common name Poly(ethyl methacrylate-comethyl acrylate) Poly(ethylene adipate)
Polyethylene adipate), tolylene 2,4-diisocyanate terminated Poly(ethylene azelate) Poly(ethylene glycol methyl ether methacrylate) Poly(ethylene glycol)
Synonyms
CAS Registry No.
Molecular formula (C6H I0O2 • C 4 H 6 O 2 )* (C6H ((,O4 • C2H6O2Jv
26572-20-3
2-Propenoic acid, 2-methyl-
R
24938-37-2
Hexanedioic acid, polymer with 1,2-ethanediol
R
R
Carbowax; oxirane polymer; PEG, poly(ethylene oxide), poly(oxyethylene); poly(vinyl oxide)
25322-68-3
Hexanedioic acid, polymer with 1,3-diisocyanatomethyibenzene and 1,2-ethanediol Nonanedioic acid, polymer with 1,2-ethanediol HP = Poly(oxy-l,2-ethanediyl)t a-(2-methyl-l-oxo-2-propenyl)co-methoxyPoly(oxy-l,2-ethanediyl), a-hydroco-hydroxy-
U
(C2H4O),,H2O
Poly(oxy-l,2-ethanediyl), a-methyl(jo-(2~propenyloxy)Poly(oxy-l,2-ethanediyl), oc-(2ethyl-l-oxohexyi)-co-((2-ethyll-oxohexyl)oxy)Poly(oxy-l,2-ethanediyl), a-butylco-hydroxyPoly(oxy-l,2-ethanediyl), a-O-oxo-2-propenyl)©-(( 1 -oxo-2-propenyl)oxy )Poly(oxy-l,2-ethanediyl), a-benzoyl-co-(benzoyloxy)Poly(oxy-l,2-ethanediyl), a-(2-methyl- l-oxo-2-propenyl)o-((2-methyl- 1-oxo2-propenyl)oxy)Poly(oxy-l,2-ethanediyl), a-methyi-co-methoxyPoly(oxy-l,2-ethanediyl), a-( 1 -oxooctadecyl)co-((l-oxooctadecyl)oxy)Poly(oxy-l,2-ethanediyl), ot-methyl-oo-hydroxy-
R
(C2H4O),, C 4 HsO (C2H4O),, C I6HwO3
9019-92-5 26760-99-6 26915-72-0
27252-80-8 9004-93-7
Poly(ethylene glycol), butyl Polyoxyethylene butyl alcohol ether 9004-77-7 ether Poly(ethylene glycol), diacrylate 26570-48-9 Polyoxyethylene dibenzoate
9004-86-8
Polyethylene glycol methacrylate
25852-47-5
Poly(ethylene glycol), dimethyl ether Poly(ethylene glycol), distearate
Polyoxyethylene dimethyl ether
24991-55-7
Polyethylene oxide distearate
9005-08-7
Polyethylene glycol), methyl ether
9004-74-4
Polyethylene glycol), methyl ether acrylate
Carbowax; methoxypoly(ethylene glycol); methyl polyglycol; monomethoxy poly(ethylene oxide) Acrylic acid-methoxy(polyethylene glycol) ester
Poly(ethylene glycol), 4-nonylphenyl ether acrylate
Tetraethylene glycol nonyiphenyl ether acrylate
87079-63-8
Polyethylene glycol), bis carboxymethyl ether
Carboxymethylpolyethylene glycol
39927-08-7
32171-39-4
Poly(ethylene glycol), bis(3-aminopropyl) terminated Poly(ethylene glycol), divinyl ether Polyethylene glycol), ethyl ether methacrylate
34901-14-9
Polyethylene glycol), methyl glutarate
79934-70-6
Poly(ethylene glycol), phenyl ether acrylate
Search method
Acrylic acid methyl ester, polymer with ethyl methacrylate Adipic acid-ethylene glycol polymer; PEGA; polyethylene glycol adipate) Adipic acid-ethylene glycoltoluene diisocyanate copolymer Azelaic acid-ethylene glycol polymer Methoxypolyethylene gtycol monomethacrylate
Polyethylene glycol), allyl methyl ether Poly(ethylene glycol), bis-2-ethyl-hexanoate
Poly(ethylene glycol), dibenzoate Poly(ethylene glycol), dimethacrylate
CA name
50856-26-3 35625-93-5
Phenol ethoxylate acrylate, polyethylene glycol monophenyl ether acrylate
56641-05-5
Poly(oxy~l,2-ethanediyl), *-(l-oxo-2-propenyl)co-methoxy2-Propenoic acid, 2-(2-(2-(2(nonylphenoxy)ethoxy)ethoxy)ethoxy)ethyl ester Poly(oxy-l,2-ethanediyl), 7.-(carboxymethyl)co-(carboxymethoxy)Poly(oxy-l,2-ethanediyl), a-(3-aminopropyl)©-(3-aminopropoxy)Poly(oxy-l,2-ethanediyl), a-ethenyl-Q)-(ethenyloxy)Poly(oxy-l,2-ethanediyl), a-(2-methyl-l-oxo-2-propenyl)co-ethoxyPoly(oxy-l,2-ethanediyl), a-(4-carboxy-l-oxobutyl)co-methoxyPoly(oxy-l,2-ethanediyl), oc-(l-oxo-2-propenyl)co-phenoxy-
R R
R R R R R
R
(C 9 H 6 N 2 O 2 C6HK)O4C2H6O2Jv (C 9 Hi 6 O 4 C2H6O2) v (C2H4O),, C5H8O2
(C2H4O),, C4Hu)O (C2H4O)/? C6H6O3 (C2H4O),, Ci4HiOO3 (C^H4O),, C«H I0O3
R
(C2H4O),, C2H6O (C2H4O),, C36H 70O ^
R
(C^H4O),,CH4O
R
(CiH4O)1, C4H6O2
R
C26H4^O6
R
(C2H4O),, C4H6O5
R
(C2H4O),, C 6 HI 6 N 2 O
R
(C2H4O),, C4H6O (C2H4O),, C6H U ) 0 2
R R
(C2H4O),, C 6 H 10 O 4
R
(C2H4O),, C9H8O2
Common name
Synonyms
CAS Registry No.
Polyethylene glycol), reacted with bisphenol A diglycidyl ether
Bisphenol A diglycidyl etherpolyethylene glycol polymer
37225-26-6
Polyethylene glycol), tetrahydrofurfuryl ether
Glycofurol; tetrahydrofurfuryl alcohol polyethylene glycol
31692-85-0
Poly(ethylene glycol), methacrylate
25736-86-1
Poly(ethylene glycol-c<9propylene glycol)
Polyethylene-polypropylene glycol monobutyl ether
Poly(ethylene imine) Poly(ethylene imine)
Polyaziridine, polyethenimide 9002-98-6 Ethylenediamine-ethylenimine 25987-06-8 polymer Aziridine-ethylene oxide copolymer 26658-46-8
Poly(ethylene imine), ethoxylated Poly(ethylene monoalcohol) Poly(ethylene succinate) Poly(ethylene terephthalate) Poly(ethylene) Poly(ethylene), chlorinated
Ethylene glycol-succinic acid polymer Dimethyl terephthalate-ethylene glycol polymer; PET; poly(oxyethylene oxyterephthaloyl) Poly(methylene)
Poly(ethylene), chlorosulfonated Polyethylene), oxidized Poly(ethylene-c//rchlorotrifluoroethylene) Poly(ethylene-a//-maleic anhydride) Poly(ethylene block-po\y (ethylene glycol)) Poly (ethylene-cY>-1-butene) Poly(ethylene-a>- 1-butenecr;-l-hexene) Poly(ethylene-co-l-octene) Poly(ethylene-cY?-acrylic acid) Poly(ethylene-cc;-acrylic acid), sodium salt Poly(ethylene-c-c;-acrylic acid), zinc salt Polyethylene-r^-butyl acrylate)
25038-59-9 9002-88-4 63231-66-3
68441-17-8 Chlorotrifluoroethene-ethene 25101-45-5 copolymer; ethylene-trifluorochloroethylene copolymer Maleic anhydride-ethyiene polymer 9006-26-2 97953-22-5 Butene-ethylene polymer; 25087-34-7 ethylene-1-butene copolymer; 1-butene-ethene polymer Butene-ethene~hexene-l copolymer 60785-11-7 Ethylene-1-octene polymer Acrylic acid-ethylene polymer; ethylene-acrylic acid polymers; primacor Ethylene-acrylic acid polymer, sodium salt
26221-73-8 9010-77-9 25750-82-7 28208-80-2
Butyl acrylate-ethylene copolymer
25750-84-9 64652-60-4
Carbon monoxide-ethylene copolymer Ethyl acrylate-ethylene polymer
Poly(ethylene-cr;-ethyl acrylatectf-maleic anhydride) Poly(ethylene-a>-glycidyl methacrylate)
71750-71-5 25569-53-3
68037-39-8
Poly(ethylene-™-butyl acrylateo?-maleic anhydride) Poly(ethylene-cY;-Ccirbon monoxide) Poly(ethylene-cr;-ethyl acrylate)
9038-95-3
25052-62-4 9010-86-0 41171-14-6
2,3-Epoxypropyl methacrylateethylene copolymer
26061-90-5
CA name
Search method
Oxirane, 2,2'-((l-methylethylidene) bis(4,l-phenyleneoxymethylene))bis-polymer with oc-hydro-co-hydroxypoly (oxy-l,2-ethanediyl) Poly(oxy-l,2-ethanediyl), a-((tetrahydro-2-furanyl)methyl)co-hydroxyPoly(oxy-l,2-ethanediyl), ot-(2-methyl-l-oxo-2-propenyl)co-hydroxyOxirane, methyl-, polymer with oxirane, monobutyl ether Aziridine, homopolymer 1,2-Ethanediamine, polymer with aziridine Aziridine, polymer with oxirane
R
(C21H24O4 • (C2H4O),, H 2 O),
R
(C2H4O),, C5H10O2
R
(C2H4O),, C4H6O2
R
C4H10O • (C 3 H 6 O C 2 H 4 O) 1 (C 2 H 5 N) 1 (C 2 H 8 N 2 C 2 H 5 N) x (C2H5NC 2 H 4 O), Unk (C 4 H 6 O 4 C 2 H 6 O 2 ), (CiOH8O4),,
R R R
Alcohols, c> 14 S Butanedioic acid, polymer with R 1,2-ethanediol Poly(oxy-l,2-ethanediyloxyU carbonyl-l,4-phenylenecarbonyl) Ethene, homopolymer Rubber, synthetic, chlorinated polyethylene Ethene, homopolymer, chlorinated, chlorosulfonated Ethene, homopolymer, oxidized Ethene, chlorotrifluoro-, polymer with ethene
Molecular formula
R S
(C2H4),Unk
*
Unk
* R
Unk (C 2 H 4 C 2 ClF 3 ),
2,5-Furandione, polymer with ethene Alcohols, C>30, ethoxylated
R S
(C 4 H 2 O 3 C 2 H 4 ), Unk
i-Butene, polymer with ethene
R
(C 4 H 8 C 2 H 4 ) v
1-Hexene, polymer with 1-butene and ethene 1-Octene, polymer with ethene 2-Propenoic acid, polymer with ethene
R
(C 6 Hi 2 C4H8C2H4), (C 8 H 16 C 2 H 4 ) v (C 3 H 4 O 2 C 2 H 4 ),
2-Propenoic acid, polymer with ethene, sodium salt 2-Propenoic acid, polymer with ethene, zinc salt 2-Propenoic acid, butyl ester, polymer with ethene 2-Propenoic acid, butyl ester, polymer with ethene and 2,5-furandione Ethene, polymer with carbon monoxide 2-Propenoic acid, ethyl ester, polymer with ethene 2-Propenoic acid, ethyl ester, polymer with ethene and 2,5-furandione 2-Propenoic acid, 2-methyl-, oxiranylmethyl ester, polymer with ethene
R R R R R R R R R R
(C 3 H 4 O 2 • C 2 H 4 ), -xNa (C 3 H 4 O 2 • C2H4),--.xZn (C 7 Hi 2 O 2 C 2 H 4 ), (C 7 Hi 2 O 2 • C4H2O3 • C 2 H 4 ), (C 2 H 4 CO), (C 5 H 8 O 2 • C 2 H 4 ), (C 5 H 8 O 2 • C4H2O3 • C 2 H 4 ), (CvHio0 3 C 2 H 4 ),
Common name Poly(ethylene-cc>-methacrylic acid) Poly(ethylene-c-methacrylic acid), sodium salt Poly(ethylene-co-methacrylic acid), zinc salt Poly(ethylene-c-methyl acrylate) Poly(ethylene-c<2-methyl acrylate-co-acrylic acid)
Synonyms
Ethylene-methacrylic acid 25053-53-6 copolymers; Poly(ethylenemethacrylic acid) Ethylene-methacrylic acid polymer. 25608-26-8 sodium salt 28516-43-0 Ethylene-methyl aery late polymer
Poly(ethylene-c<9-propylene-a?5-methylene-2-norbornene)
Poly(ethylene-c
51541-08-3
Ethylene-propene copolymer; 9010-79-1 poly(ethylene-propylene); polypro, polypropylene-polyethylene copolymer Ethylene-ethylidenebicycloheptene- 25038-36-2 propene copolymer; ethyleneethylidenenorbornene-propylene polymer Ethylene copolymer with 25038-71-5 tetrafluoroethylene Vinyl acetate-ethylene polymer 24937-78-8 Carbon monoxide-ethylene-vinyl acetate polymer
Poly(4-ethylstyrenec'o-divinylbenzene) Poly(furfuryl alcohol) Poly(D-glutamic acid), sodium salt Poly(L~glutamic acid), sodium salt Poly(glycine) Poly(glycolide)
26337-35-9 106343-08-2 68954-09-6
2-Ethylhexyl acrylate polymer
Poly(2~ethylhexyl methacrylate) Poly(2-ethyl-2-oxazoline)
25103-74-6 41525-41-1
Poly(ethylene-o?-methyl acrylate-co-glycidyl methacrylate) Poly(ethylene-c-propylene)
CAS Registry No.
9003-77-4 25719-51-1
2-Ethyl-2-oxazoline polymer; 2-ethyloxazoline homopolymer Divinylbenzene-ethylstyrene polymer
25805-17-8 9043-77-0 25212-86-6 30811-79-1
Poly(glutamic acid) sodium salt
26247-79-0
Poly(hexadecyl methacrylate)
Nylon 2, poly(imino(l-oxoethylene)) 25718-94-9 Hydroxyacetic acid polymer; 26124-68-5 poly(glycolic acid) Poly(cetyl methacrylate) 25986-80-5
Poly(hexafluoroisopropylidene diphthalic anhydride-cooxydianiline)
Hexafluoroisopropylidenebis032240-73-6 (phthalic anhydride)-oxydianiline copolymer
PoIy(1,6-hexamethylene adipate) Adipic acid-hexanediol polymer
25212-06-0
Poly(l,6-hexanediol/neopentyl glycol/di(ethylene glycol)fl/f-adipic acid) diol
68492-71-7
CA name
Search method
Molecular formula
2-Propenoic acid, 2-rnethyl-, polymer with ethene
R
(C4H6O2 • C2H4),
2-Propenoic acid, 2-methyl, polymer with ethene, sodium salt 2-Propenoic acid, 2-methyl-, polymer with ethene, zinc salt 2-Propenoic acid, methyl ester, polymer with ethene 2-Propenoic acid, polymer with ethene and methyl 2-propenoate
R
(C4H6O2 C 2 H 4 ) v -.vNa
R
(C4H6O2 C 2 H 4 ) v vZn (C4H6O2 C2H4) v (C4H6O2 C3H4O2 C2H4), (C7HK)OV C4H6O2 C 2 H 4 )v
2-Propenoic acid, 2-methyl-, oxiranylmethyl ester, polymer with ethene and methyl 2-propenoate 1-Propene, polymer with ethene
R R
R
R
(C3H6-C2H4) v
Bicyclo(2.2.1)hept-2-ene, 5-ethylidene-, polymer with ethene and 1-propene
R
(C 9 Hi 2 - C 3 H 6 C2H4) v
Ethene, tetrafluoro-, polymer with ethene Acetic acid ethenyl ester, polymer with ethene Acetic acid ethenyl ester, polymer with carbon monoxide and ethene 2,5-Furandione, polymer with ethene, graft 1,3-Butadiene, homopolymer, hydrogenated 2-Propenoic acid, 2-ethylhexyl ester, homopolymer 2-Propenoic acid, 2-methyl-. 2-ethylhexyl ester, homopolymer Oxazole, 2-ethyl-4,5-dihydro-. homopolymer Benzene, diethenyl-polymer with ethenylethylbenzene 2-Furanmethanol, homopolymer D-Glutamic acid, homopolymer, sodium salt L-Glutamic acid, homopolymer. sodium salt Glycine, homopolymer Acetic acid, hydroxy-, homopolymer 2-Propenoic acid, 2-methyl-, hexadecyl ester, homopolymer 1,3-Isobenzofurandione, 5,5'-(2,2, 2-trifluoro-l-(trirluoromethyl)ethylidene)bis-, polymer with 4,4 '-oxybisCbenzenamine) Hexanedioic acid, polymer with 1,6-hexanediol Hexanedioic acid, polymer with 2,2-dimethyl-l,3-propanediol, 2-ethyl-2-(hydroxymethyl)1,3-propanediol, 1,6-hexanediol and 2,2'-OXyMsIe^aIiOl)
R
(C 2 H 4 C 2 F 4 ) v
R
*
(C4H6O2 C2H4) v (C4H6O2 C 2 H 4 C0)A (C4H2O3 C2H4), Unk
R
(C M H 2 0 O 2 ) v
R
(CI2H22O2),
R
(C 5 H q NO) v
R
R R
(C u,H )2 • C|oH| O ) v (C 5 H 6 O 2 ) V (C.sH 9 NO 4 ) v • vNa (C 3 H 9 NO 4 )V vNa (C 2 H 5 NO 2 ) V (C 2 H 4 O V ) V
R
(C 2 ( ) H 3 8 O 2 ) V
R
(C I 9 H 6 F 6 O 6 • C ) 2 H 1 2 N 2 O) V
R
(C6Hi4O2 C6 HinO 4 ) v (C 6 H U O 3 • C6HI4O2 • C6H | 0 O 4 • CsHi2O2 C 4 Hi 0 O 3 )V
R R
R R R
R
Common name
Synonyms
CAS Registry No.
Poly( 1.6-hexanediol/neopentyl glycol-*///-adipic acid)
Adipic acid-hexamethylene glycol- 25214-14-6 neopentyl glycol polymer
PoJy(hexamethylene diisocyanate) Poly(hexyl methacrylate)
HMDI homopolymer
28182-81-2
Hexyl methacrylate polymer
25087-17-6
PoIy(I-hexene) Poly(3-hexyl thiophene), regioregular Poly(L-histidine) Poly(L-histidine hydrochloride)
25067-06-5 140934-50-1 Polyhistidine Polyhirtidine hydrochloride
26062-48-6 61857-39-4
Poly(4-hydroxybenzoate) Poly(4-hydroxy benzoic acid-cv>6-hydroxy2-naphthoic acid) Poly(3-hydroxybutyric acid)
Poly(p-acetoxybenzoic acid) /?-Acetoxybenzoic acid-6-acetoxy2-naphthoic acid polymer
26099-71-8 70679-92-4
Poly(p-hydroxybutyric acid)
26063-00-3
Poly(3-hydroxybutyric acidcY>-3-hydroxy valeric acid)
Bipol PHBV; 3-hydroxy butanoic acid-3-hydroxy valeric acid copolymer Ethylene glycol monomethacrylate polymer
80181-31-3
Search method
Molecular formula
R
R
(C6Hi4O2 C6HK)O4 C 5 Hi 2 O 2 )., (C 8 Hi 2 N 2 O 2 )V
R
(CI0HI8O2).,
R R
(C 6 H 12 )V (Ci 0 Hi 6 S) A
R R
(C6H7N3Ov (C6HyN3O2),-
R R
(C 7 H 4 O 2 ),, (C I 3 Hi 0 O 4 • CgH8O4),
R
(C 4 H 8 O 3 )V
R
(C5Hi0O3 • C 4 H 8 O 3 Jv
R
(C 6 Hi 0 O 3 )V
R
(C7Hi2O3),
R
(C|4H|4 Cl 4 N 2 O 2 ),,
R
(C| 4 H 2 2 O 2 ) V
R
(C8H|4O2)V
R
(C 4 H 8 )*
2,5-Furandione, polymer with 2-methyl- 1-propene 1,3-Butadiene, 2-methyl, polymer with 2-methyl-1 -propene 1,3-Butadiene, 2-methyl-, polymer with 2-methyl-1-propene, chlorinated 1,3-Butadiene, 2-methyl-, polymer with 2-methyl-1-propene, brominated 2-Propenoic acid, 2-methyl-. isodecyl ester, homopolymer Cyclohexane, 5-isocyanato1 -(isocyanatomethyl )1,3,3-trimethyl-, homopolymer Poly(oxy(methyl-l,2-ethanediyl)). 2-hydro-co-hydroxy-, polymer with
R R
(C4H8C4H2O3) v (C^H8-C4H8) v
*
(C 5 H 8 C 4 H 8 ) ,
*
(C 5 H 8 C 4 H 8 ) ,
R
(C I 4 H 2 6 O 2 ) v
R
(C !2 H I 8 N 2 O 2 ) v
R
(Ci2Hi8N2O2 (C 3 H 6 O),, H 2 O).,
1.3-Butadiene, 2-methyl-. homopolymer Poly( 1 -methyl-l-butene-1,4-diyl). (E)-
R
(C5H8),
CA name Hexanedioic acid, polymer with 2,2-dimethyl-l,3-propanediol and 1,6-hexanediol Hexane, 1,6-diisocyanato-. homopolymer 2-Propenoic acid, 2-methyl-, hexyl ester, homopolymer 1-Hexene, homopolymer Thiophene, 3-hexyl-, homopolymer L-Histidine, homopolymer L-Histidine, homopolymer. hydrochloride
Poly(2-hydroxyethyl methacrylate) Poly(2-hydroxypropyl methacrylate)
25249-16-5
25703-79-1
Poly(imino(tetrachloroterephthaloyl)-iminohexamethylene) Polydsobornyl methacrylate)
Hexamethylenediamine-perchlorolerephthaloyl dichloride copolymer, SRU Methacrylic acid, isobornyl ester, polymers
Poly(isobutyl methacrylate)
lsobutyl methacrylate polymer
9011-15-8
Poly(isobutylene)
PoIy(1,1-dimethylethylene); isobutene polymer; isobutylene polymer; polyisobutene
9003-27-4
Poly(isobutylene-c///-maleic anhydride) Poly(isobutylene-rr;-isoprene)
071164-49-3
64114-51-8
26426-80-2 Isobutylene-isoprene polymer
9010-85-9
Poly(isobutylene-(Y>-isoprene)
68081-82-3
Poly(isobutylene-<7J-isoprene), brominated
68441-J4-5
Polydsodecyl methacrylate)
27300-12-7
Polydsophorone diisocyanate)
53880-05-0
Poly(isophorone diisocyanaten?-poly(propylene glycol))
lsophorone diisocyanate039323-37-0 polypropylene ether glycol polymer; polypropylene glycoltsophorone diisocyanate copolymer PoIy(I-methyl-1-butenylene) 9003-31-0
Poly(isoprene), c/.v Poly(isoprene), trans
104389-32-4
Poly(oxy-l,4-phenylenecarbonyl) 2-Naphthalenecarboxylic acid, 6-(acetyloxy)-, polymer with 4-(acetyloxy)benzoic acid Butanoic acid, 3-hydroxy-, homopolymer Pentanoic acid. 3-hydroxy-, polymer with 3-hydroxybutanoic acid 2-Propenoic acid, 2-methyl-, 2-hydroxyethyl ester, homopolymer 2-Propenoic acid, 2-methyl, 2-hydroxypropyl ester, homopolymer Poly(iminocarbonyl(2,3,5,6tetrachloro-1.4-phenylene)carbonylimino-1.6-hexanediyl) 2-Propenoic acid. 2-methyl-. 1.7,7-trimethylbicyclo(2.2.1) hept-2-yl ester, exo-, homopolymer 2~Propenoic acid, 2-methyl-, 2-methylpropylester, homopolymer 1-Propene, 2-methyl. homopolymer
YCIH
R
(C 5 H 8 )//
Common name Poly(isoprene)-b/oc/cpoly(butadiene)
Synonyms
CAS Registry No.
Butadiene-isoprene polymer; 1,3-Butadiene-isoprene polymer
25102-52-7
Poly(isoprene-£ra/r-maleic acid monomethyl ester)
128000-08-8
Poly(2>isopropenyl-2-oxazolineco-methyl methacrylate) Poly(isopropyl methacrylate)
27341-60-2 26655-94-7
Poly(isopropyl vinyl ether)
Isopropyl vinyl ether polymer
25585-49-3
Poly(itaconic acid)
Poly(2-methylenesuccinic acid)
25119-64-6
Poly(lactide)
Lactide polymer; poly(DL-lactide)
26680-10-4
Poly(D,L-lactide-co-glycolide)
Glycolide-DL-lactide polymer; polyglactin
26780-50-7
Poly(laury 1 lactam)-blockpoly(tetrahydrofuran) Poly(lauryl methacrylate)
Maleic anhydride-1-tetradecene polymer Poly(dodecyl methacrylate)
31473-53-7
Poly (laury 1 methacrylate-Coethylene glycol dimethacrylate)
Ethylene glycol dimethacrylatelauryl methacrylate copolymer
Poly(D,L-lysine hydrobromide) Poly(L-leucine) Poly(L~leucine hydrobromide)
25719-52-2 61181-29-1
73565-55-6 Polyleucine Poly-L-lysine hydrogen bromide; polyIysine hydrobromide
Poly(D-lysine hydrobromide)
25248-98-0 25988-63-0 27964-99-4
CA name
Search method
1,3-Butadiene, 2-methyl-, polymer with 1,3-butadiene
R
(CsHg -C4H6Xv
1,3-Butadiene, 2-methyl-, homopolymer, maleated, mono-methyl esters 2-Propenoic acid, 2-methyl-, methyl ester, polymer 2-Propenoic acid, 2-methyl-, 1-methylethyl ester, homopolymer Propane, 2-(ethenyloxy)-, homopolymer Butanedioic acid, methylene, homopolymer l,4-Dioxane-2,5-dione, 3,6-dimethyl-homopolymer l,4-Dioxane-2,5-dione, 3,6-dimethy !polymer with 1,4-dioxane- 2,5-dione 2,5-Furandione, polymer with 1-tetradecene 2-Propenoic acid, 2-methyl-, dodecyl ester, homopolymer 2-Propenoic acid, 2-methyl-, 1,2-ethanediyl ester, polymer with dodecyl 2-methyl2-propenoate DL-Lysine, homopolymer, hydrobromide L-Leucine, homopolymer L-Lysine, homopolymer, hydrobromide D-Lysine, homopolymer,
*
link
R R
(C6H9NO CsH8O2)V (C7H12O2)V
R
(CsHioO)v
R
(CsH6O4)V
R
(C6H8O4)V
R
(C 6 H 8 O 4 • C4H4O4K
R
(C I4H28C4H2O3) v (C I6H30O2).,
R R
(Ci6H3OO2 C I 0 Hi 4 O 4 ) v
R
R
(C 6 H 14 N 2 O 2 ) V • vBrH (C6H I3NO2)v (C6H I4N2O2) v • ABIH (C6H I 4 N 2 O 2 ), •
R
(C 6 H l4 N 2 O 2 ) v •
R R
(C 6 Hi 4 N 2 O 2 ) v (Ci8H36 C 4 H 2 O 3 ), (C 3 H 6 N 6 CH2O)V
R R
hydrobromide
Poly(L~lysine hydrochloride)
Lysine homopolymer hydrochloride
28826-16-6
Poly(L-lysine) Poly(maleic anhydride-a/r1-octadecene) Poly(maleic anhydride-a/fa-olefin)
Lysine homopolymer 1-Octadecene-maleic anhydride polymer
25104-18-1 25266-02-8
L-Lysine, homopolymer,
ABIH
hydrochloride
68036-97-5
Poly(melamine-co-formaldehyde), butyiated
68002-25-5
Poly(melamine-co-formaldehyde), butylated Poly(melamine-co-formaldehyde), butylated/methylated Poly(melamine-coLaurolactam-polytetramethylene formaldehyde), methylated glycol copolymer
68459-79-0
Poly(melamine-coformaldehyde), isobutylated Poly(methacrylic acid), sodium salt Poly(L-methionine) Poly(4-methoxystyrene) Polymethylene polyphenylene isocyanate
70750-53-7 84732-38-7 68002-21-1 54193-36-1
Methionine homopolymer Poly(p-methoxystyrene); poly(4-vinylanisole) Poly(phenyl isocyanate-coformaldehyde), poly(methylene poly(phenyl isocyanate))
26242-79-0 24936-44-5 9016-87-9
Molecular formula
L-Lysine, homopolymer 2,5-Furandione, polymer with 1-octadecene l,3,5-Triazine-2,4,6-triamine, polymer with formaldehyde, butylated methylated l,3,5-Triazine-2,4,6-triamme, polymer with formaldehyde, butylated Alkenes, C24-28 a-, polymers with maleic anhydride Teipenes and terpenoids, limonene fraction, polymd. Azacyclotridecan-2-one, polymer with a-hydro-co-hydroxypoly(oxy- 1,4-butanediyl) l,3,5-Triazine-2,4,6-triamine, polymer with formaldehyde, isobutylated 2-Propenoic acid, 2-methyl-, homopolymer, sodium salt L-Methionine, homopolymer Benzene, l-ethenyl-4-methoxy-, homopolymer Isocyanic acid, polymethylenepoiyphenylene ester
ACIH
* *
(C 3 H 6 N 6 CH2O)x
S
Unk
S
Unk
R
(Ci2H23NO(C4H8O)7, H2O)v (C 3 H 6 N 6 CH 2 O) 1
!|:
R
(C 4 H 6 O 2 ) v xNa
R R
(C5H nNO2S).v (C9Hi()O)v
R
link
Common name PolyCmethyl acrylate)
Synonyms
CAS Registry No.
Methyl acrylate polymer
Poly(4,4'-methylene bis(phenyl isocyanateH///-butanediol/ di-PG/polycaprolactone))
9003-21-8 68084-39-9
Poly(4,4'-methylene bisphenyl isocyanate)
1,4-Butanediol-methylenedi-/;phenylene isocyanate-polytetramethylene-ether glycol copolymer
9018-04-6
Poly(methyl methacrylate)
9011-14-7
Poly(methyl methacrylate-cobutadiene-costyrene)
Methacrylic acid methyl ester; methyl methacrylate polymer Butadiene-methyl methacrylatestyrene polymer
Polydnethyl methacrylate-a;ethyl acrylate)
Methyl methacrylate-ethyl acrylate polymer
Poly(3-methyl 1,5-pentanediol adipate) Poly(4-methyl-l-pentene)
Adipic acid-3-methyl1,5-pentanediol copolymer Methylpentene polymer; 4-methylpentene homopolymer
Polydnethyl sorbate) Poly(4~methyl styrene) Poly(a-methyl styrene) Poly(methyl styrene-cY?indene), hydrogenated Polydnethyl vinyl eiher-altmaleic acid monoethyl ester)
Polydnethyl vinyl ether-altmaleic acid monoisopropyl ester) Polydnethyl vinyl ether-altmaleic acid) Polydnethyl vinyl ether-altmaleic anhydride) Polydnethyl vinyl ether-altmaleic anhydride) Poly(methylhydrosiloxane) Poly(neopentyl glycol adipate)
25053-09-2 9010-88-2 39751-34-3 25068-26-2 30813-48-0
/;-Methylstyrene polymer; 4-methylstyrene homopolymer 2-Methylstyrene polymer
24936-41-2 25014-31-7 69430-35-9
Ethyl maleate-methyl vinyl ether 25087-06-3 polymer; maleic acid monoethyl ester-methyl vinyl ether polymer; monoethyl maleate-methyl vinyl ether polymer 31307-95-6 Maleic acid-methyl vinyl ether copolymer; maleic acid-methyl vinyl ether polymer Maleic anhydride-methyl vinyl ether polymer 1,9-Decadiene-maleic anhydridemethyl vinyl ether copolymer Methyl hydrogen siloxane Adipic acid-neopentyl glycol copolymer
25153-40-6 9011-16-9 136392-67-1 9004-73-3 27925-07-J
Polylneopentyl glycol sebacate)
28759-54-8
Polydieopentyl methacrylate)
34903-87-2
Poly(norbornene)
25038-76-0
Poly(octadecyl methacrylate)
Poly(2-norbornene); polynorbornenylene Stearyl methacrylate homopolymer
Poly(octadecyl vinyl eiher-comaleic anhydride) PolyCoctyl acrylate)
Maleic anhydride-octadecyl vinyl ether polymer Octyl acrylate polymer
28214-64-4
25639-21-8
25266-13-1
CA name
Search method
Molecular formula
2-Propenoic acid, methyl ester, homopolymer 2-Oxepanone, polymer with 1,4-butanediol, 1,1'-methylenebis(isocyanatobenzene) and oxybis(propanol) 1,4-Butanediol, polymer with a-hydro-ohydroxypoly(oxy-l,4-butanediyl) and 1,1'-methylenebis(4-isocyanatobenzene) 2-Propenoic acid, 2-methyl, methyl ester, homopolymer 2-Propenoic acid,2-methyl-, methyl ester, polymer with 1,3butadiene and ethenylbenzene 2-Propenoic acid, 2-methyl-, methyl ester, polymer with ethyl 2-propenoate Hexanedioic acid, polymer with 3-methyl-1,5-pentanediol 1-Pentene, 4-methyl-, homopolymer 2,4-Hexadienoic acid, methyl ester, (EJB)-, homopolymer Benzene, l-ethenyl-4-methyl-, homopolymer Benzene, (1-methylethenyl)-, homopolymer Hydrocarbons, C6-C20, polymers, hydrogenated 2-Butenedioic acid (Z)-, monoethyl ester, polymer with methoxyethene
R
(C 4 H 6 O 2 ) V
R
(Ci 5 Hi 0 N 2 O 2 • C 6 Hi 4 O 3 C6HI0O2C 4 H I0O2) v (C 15Hi0N2O2 • C4HI 0 O 2 (C4HgO)7, H 2 O) 1
R
R
(C 5 H 8 O 2 ) v
R
(C 8 H 8 C5H8O2 C4H6Xx(C 5 H 8 O 2 • C5H8O2) v
R R R
(C 6 H) 4 O 2 C6Hi0O4Xx (C6Hi2)Jc
R
(C 7 Hi 0 O 2 K
R
(CgHi0)V
R
(CQHJOXV
S
Unk
R
(C 6 H 8 O 4 C3H6O)x
2-Butenedioic acid (Z)-, mono(l-methylethyl) ester, polymer with methoxyethene 2-Butenedioic acid (Z)-, polymer with methoxyethene
R
(C 7 Hi 0 O 4 • CaH6O)x
R
(04H 4 O 4 C 3 H 6 O),
2,5-Furandione, polymer with methoxyethene 2,5-Furandione, polymer with 1,9-decadiene and methoxyethene Poly(oxy(methylsiiylene)) Hexanedioic acid, polymer with 2,2-dimethyl-l,3-propanediol Poly(oxy(2,2-dimethyl-l,3propanediyl)oxy(l,10-dioxo1,10-decanediyl)) 2-Propenoic acid, 2-methyl-, 2,2-dimethylpropyl ester, homopolymer Bicyclo(2.2.1)hept-2-ene, homopolymer 2-Propenoic acid, 2-methyl-, octadecyl ester, homopolymer 2,5-Furandione, polymer with l-(ethenyloxy)octadecane 2-Propenoic acid, octyl ester, homopolymer
R
R
(C4H2O3 • C3H6O)., (Ci 0 H, 8 C4H2O3C 3 H 6 O) x (CH4OSi),, (C 6 Hi 0 O 4 . C 5 HI 2 OT) X (Ci 5 H 26 O 4 ),,
R
(CgHi6O2)V
R
(C7Hl0).v
R
(C22H42O2).,
R
(C20H40OC4H2O3).X (Ci1H20O2)V
R R R
R
Common name Poly(3-octyl thiophene), regioregular Poly(L-ornithine) Poly(L-ornithine hydrobromide)
Synonyms
CAS Registry No. 104934-51-2
Polyornithine Polyorthine hydrobromide
Poly(D,L-ornithine hydrobromide)
25104-12-5 27378-49-0 82682-33-5
Poly(L-ornithine hydrochloride)
Poly-L-ornithine-hydrochloride
26982-21-8
Poly[oxy(2,6-dimethyl1,4-phenylene)]
Poly(2.6-dimethyl-/;-phenylene ether); poly(2,6-dimethyl1,4-phenylene oxide). SRU 4.4'-Difluorobenzophenonehydroquinone copolymer, SRU; PEEK Bisphenol A polycarbonate; poly (4,4'-isopropylidenediphenyl carbonate) Poly(formaldehyde); formaldehyde polymer Poly(oxymethylene) diacetate
24938-67-8
Butanediol formal-trioxane copolymer; formaldehyde tetramethylene acetal-trioxane copolymer; 1,3-dioxepanetrioxane polymer Starburst 2nd generation
25214-85-1
PoIy(OXy-1,4-phenylene oxy1,4-phenylene carbonyl 1,4-phenylene) Poly(oxycarbonyloxy1,4-phenylene.isopropylidene1,4-phenylene) Poly(oxymethylene) Poly(oxymethylene), acetate end-capped Poly(oxymethylene-c1,3-dioxepane)
PoIy(PAMAM), starburst dendrimer
31694-16-3
24936-68-3
9002-81-7 25231-38-3
93376-66-0
Poly(perfluoropropylene oxideco-perfluoro formaldehyde) Poly(/?,/?'-l,4-phenylene-3,3/, 4,4/-benzophenone tetracarboxylic imid/amic acid
69991-67-9 Benzophenonetetracarboxylic dianhydride-/.?-phenylenediamine polymer, SRU
26023-21-2
Poly(/7,/7'-l,3-phenylene isophthalamide)
Isophthaloyl chloride1.3-phenylenediamine polymer
25765-47-3
Poly(/?,/?-1,4-phenylene terephthalamide)
/;-Phenylenediamine-terephthaloyl chloride copolymer
26125-61-1
Poly((phenyl glycidyl ether)ro-dicyclopentadiene) PolyCphenyl glycidyl etherco-formaldehyde) Poly(phenyl vinyl ketone)
119345-05-0
28064-14-4 Poly(acrylophenone)
26742-84-7
Poly( 1,4-phenylene diisocyanatea?-poly(l,4-butanediol))
89339-41-3
Poly( 1,4-phenylene ether ether sulfone)
28212-68-2
Poly( 1,4-phenylene ether sulfone) Poly(phenylene oxide) Poly( 1,4-phenylene sulfide)
25667-42-9
Poly(/;-phenylene terephthalamide)
Poly(phenylene ether) /?-Dichlorobenzene-sodium sulfide polymer; poly(/;-phenylene sulfide) PPTA
9041-80-9 25212-74-2
24938-64-5
CA name
Search method
!Molecular formula
Thiophene, 3-octyl-, homopolymer
R
(C|2H2oS).v
L-Omithine, homopolymer L-Ornithine, homopolymer. hydrobromide DL-Ornithine, homopolymer, hydrobromide L-Ornithine, homopolymer, hydrochloride Poly(oxy(2,6-dimethyl1,4-phenylene))
R R
(C^H^NiO])., (C 5 H 12N2O2)V • vBrH (C 5 H I 2 N 2 O 2 ). v • \BiH (C 5 Hi 2 N 2 O 2 )A \C1H
Poly(oxy-l,4-phenyleneoxy1,4-phenylenecarbonyl1,4-phenylene) Poly(oxycarbonyloxy-l,4phenylene(l-methylethylidene)1,4-phenylene) Poly(oxymethylene)
R R R
R
(C[C)Hi2O;,),,
R
(CI6HI4OI),,
R
(CH2O),,
Poly(oxymethylene), ot-acetylco-(acetyloxy)1,3-Dioxepane, polymer with 1,3.5-trioxane
R
(CH2O),, C 4Hc1O 3 (C5H 10O2 • C3H6O3) v
4,7.11,14.18,21,25,28,32,35Decaazaoctatriacontanediamide. etc 1-Propene, 1,1,2,3,3,3-hexafluoro-, oxidized, polymd. PoIy(O 3-dihydro-l,3-dioxo2H-isoindole-2,5-diyl)carbonyl(l,3-dihydro-l,3-dioxo-2Hisoindole-5,2-diyl)1,4-phenylene) 1,3-Benzenedicarbonyl dichloride, polymer with 1,3-benzenediamine 1,4-Benzenedicarbonyl dichloride, polymer with 1.4-benzenediamine Phenol, polymer with 3a,4,7,7atetrahydro-4,7-methanoIH-indene, glycidyl ether Phenol, polymer with formaldehyde. glycidyl ether 2-Propen-i-one, 1-phenyl-, homopolymer Poly(oxy-l,4-butanediyl),c/.-hydroa)-hydroxy-. polymer with 1,4-diisocyanatobenzene Poly(oxy-l,4-phenyleneoxy1,4-phenylenesulfonyl1,4-phenylene) Poly(oxy-l,4-phenylenesulfonyl1,4-phenylene) Poly(oxyphenylene) Poly(thio- 1,4-phenylene)
R
C142H288N58O28
*
Link
U
(C23H 10N2O5),,
R
(C 8 H 4 Cl 2 O 2 C6H8N2) v
R
(C 8 H 4 Cl 2 O 2 C6H8N2)v
Poly(imino-l,4-phenyleneiminocarbonyl-1,4-phenylenecarbonyl)
R
*
(C m H !2 C 6 H 6 O),
R
(C 6 H 6 O CH2O).V (C 9 H 8 O),
R R
R
(C 8 H 4 N 2 O 2 • (C 4 H 8 O),, H 2 O) v (CI8HI2O4S),,
U
(Ci 2 H 8 O 3 S),,
R U
(C 6 H 4 O),, (C 6 H 4 S),,
U
(C 14H K)N2O2),,
Common name
Synonyms
CAS Registry No.
Poly(2-pinene)
70750-57-1
Poly(poly(tetrahydrofuran) carbonate), diol
92538-66-4
CA name
Search method
Terpenes and terpenoids, turpentine-oil, oc-pinene fraction, polymd. Carbonic acid, diethyl ester, polymer with a-hydro-oo-
S
Unk
R
(C5Hi0O3 • (C 4 HgO),,
L-Proline, homopolymer 2-Propenoic acid, 2-methyl-, oxiranylmethyl ester, polymer with ethene and ethyl 2-propenoate Oxirane, methyl-, polymer with carbon dioxide Pentanedioic acid, polymer with 1,3-propanediol Poly(oxy(methyl-l,2-ethanediyl)), a-(2-arninornethylethyl)o)-(2-aminomethylethoxy)Poly(oxy(methyl-l,2-ethanediyl)), a-hydro-co-hydroxy-
R R
(C5HgNOi) 1 (C7Hi0O3C^HgO 2 C 2 H 4 ). V
R
(C 3 HeO C 0 2 ) v
R
(C^HgO 4 C 3 HgOz)V (C 3 H 6 O),, C6Hi6N2O
U
(C 3 H 6 O),,H 2 O
Poly(oxy(methyl-l,2-ethanediyl)), ot-( 1 -oxo-2-propenyl)(O-(nonylphenoxy)Poly(oxy(methyl-l,2-ethanediyl)), oc-(l -oxo-2-propenyl)co-(( I -oxo-2-propenyl )oxy)Poly(oxy(methyl-l,2-ethanediyl)), ot~(2-methyl-l -oxo-2-propenyl)to-((2-methyl-1-oxo2-propenyl)oxy)Poly(oxy(methyl-l,2-ethanediyl)), oc-(2-methyl-l -oxo-2-propenyl)co-hydroxyPoly(oxy(methyl-l,2-ethanediyl)), a-benzoyl-co-(benzoyloxy)Poly(oxy(methyl-l,2-ethanediyl)), a-(oxiranylmethyl)oo-(oxiranylmethoxy)Poly(oxy(methyl-l,2-ethanediyl)), a-butyl-co-hydroxyOxirane methyl, polymer with oxirane
R
(C 3 H 6 O),, CIgH 2 6 O 2
R
(C 3 H 6 O),, C6H6O3
R
(C 3 H 6 O),, CgHmO 3
R
(C 3 H 6 O),, C 4H 6 O 2
R
(C 3 H 6 O),, CuHiOO 3 (C 3 H 6 O),, C6Hi0O3
hydroxypoly(oxy-l,4-butaned ; )l)
Poly(L-proline) PoIy(1,3-propylene adipate)
Polyproline; proline homopolymer Ethyl acrylate-ethyleneglycidyl methacrylate polymer
25191-13-3 35830-43-4
Poly(propylene carbonate)
Carbon dioxide-propylene oxide polymer Poly(trimethylene glutarate)
25511-85-7
Poly(propylene glycol bis(2-aminopropyl ether))
Poly(oxypropylene)diamine
9046-10-0
Poly(propylene glycol)
Oxirane, methyl-, homopolymer; poly(propylene oxide); PPG: propylene glycol -propylene oxide polymer
Poly( 1,3-propylene glutarate)
52256-48-1
25322-69-4
Poly (propylene glycol), 4-nonyl phenol ether acrylate
71926-19-7
Poly(propylene glycol), diacrylate
52496-08-9
Poly(propylene glycol), dimethacrylate
25852-49-7
Poly(propylene glycol), methacrylate
39420-45-6
PoIy(propylene glycol), dibenzoate Polypropylene glycol), diglycidyl ether
72245-46-6
PoIy(propylene glycol), monobutyl ether Poly(propylene glycol )-copoly(ethylene glycol)
Polypropylene glycoi-blockPEG-block-PPG bis (2-aminopropyl ether)) Poly( 1,3-propylene succinate)
26142-30-3
Butoxypolypropylene glycoi; 9003-13-8 polyoxypropylene monobutyl ether Ethylene glycol-propylene glycol 9003-11-6 copolymer; ethylene glycolpropylene oxide copolymer; ethylene oxide-propylene oxide copolymer ethylene glycol ether; methyloxirane-oxirane copolymer Ethylene oxide-propylene oxide 65605-36-9 copolymer bis(2-aminopropyl)ether Poly(trimethylene succinate) 28158-21-6
Poly (propylene) Poly(propylene), chlorinated
Poly(propene); propene polymer
Poly(propylene). isotactic Poly(propylene-<7//-ethylene, multiarm
lsotactic propylene polymer; polypro 25085-53-4 127883-08-3
Poly(propylene-cY;-l-butene) Poly(propylene-cY;tetrafliioroethy lene)
Propene-tetrafluoroethene polymer
9003-07-0 68442-33-1
29160-13-2 27029-05-6
Molecular formula
Oxirane, methyl-, polymer with oxirane, bis(2-aminopropyl) ether Butanedioic acid, polymer with 1,3-propanediol 1-Propene, homopolymer 1-Propene, homopolymer, chlorinated 1-Propene, homopolymer isotactic Benzene, diethenyl-. polymer with 2-methyl- 1,3-butadiene, hydrogenated 1-Butene, polymer with 1-propene 1-Propene, polymer with tetrafluoroethene
HTO)X
R
R
R R
R
(C 3 H 6 O),, C4H10O (C 3 H 6 O C2H4O)x
R *
(C 3 HgNO) | / 2 (C3H6OC2H4O)1 (C 4 H 6 O4C 3 HgO 2 ) v (C 3 H 6 K Unk
R *
(C 3 H 6 ) v (C| 0 H| 0 -C.^Hg),
R R
(C 4 H 8 C 3 H 6 ). V (C3H6-C2F4)v
R
Common name Poly(propylene-gra/f-maleic anhydride) PolyCpyromellitic dianhydridecfl-4,4'-oxydianiline) Poly(sebacic anhydride) Poly(L-serine) Poly(sodium 4-styrene sulfonate) Poly(styrene) Poly(styrene-a//-maleic acid), sodium salt Poly(styrene-fr-butadiene)
Poly(styrene-£-poly(ethyleneran-butylene)-bpoly(styrene)) Poly(styrene-6/0cA:-poly(oxyethylene)) Pory(styrene-£>/ock-polyisoprene-b/-allyl alcohol) Poly(styrene-cc?-a-methylstyrene) Poly(styrene-cc?-divinyl benzene)
Synonyms
CAS Registry No.
Molecular formula
2,5-Furandione, polymer with 1-propene, graft IH, 3H-Benzo(l,2-c:4,5-c')difuran-l,3,5,7-tetrone, polymer with 4,4/-oxybis(benzenamine)
R
Decanedioic acid, homopolymer L-Serine, homopolymer Benzenesulfonic acid, 4-ethenyl-, sodium salt, homopolymer
R R R
(C I0Hi8O4)V (C 3 H 7 NO 3 ), (C 8 H 8 O 3 S • Na),-
Benzene, ethenyk homopolymer
R
(C8H8)V
2,5-Furandione, polymer with ethenylbenzene, sodium salt
R
(C 8 H 8 C 4 H 2 O 3 ),
Benzene, ethenyl-, polymer with 1,3-butadiene
R
(C8Hs C4H6)A
Benzene, ethenyl-, polymer with 1,3-butadiene, hydrogenated
*
Unk
Ethylene oxide-styrene polymer
25267-79-2
R
(C 8 H 8 C 2 H 4 O),
Isoprene-styrene polymer
25038-32-8
Oxirane, polymer with ethenylbenzene Benzene, ethenyl-, polymer with 2-methyl-l,3-butadiene 2-Propenenitrile, polymer with ethenylbenzene
R
(C 8 H 8 C 5 H 8 ),
R
(C 8 H 8 C 3 H 3 N) 1
2-Propen-l-ol, polymer with R ethenylbenzene Benzene, ethenyl-, polymer R with (l-methylethenyl)benzene Benzene, diethenyi-, polymer * with ethenylbenzene and ethenylethylbenzene, chloromethylated Methanamine, TV-methyl-, reaction * products with chloromethylated divinylbenzene-ethenylethylbenzene-styrene polymer 2-Butenedioic acid (Z)-, R monomethyl ester, polymer with ethenylbenzene, 2,5furandione and (Z)-2-methylpropyl hydrogen 2-butenedioate 2,5-Furandione, polymer with R ethenylbenzene, 2-butoxyethyl ester 2,5-Furandione, telomer with R ethenylbenzene and (1-methylethyl)benzene, 2-butoxyethyl ester 2,5-Furandione, telomer with R ethenylbenzene and (1-methyl ethyl)benzene, cyclohexyl 1-methylethyl ester 2,5-Furandione, polymer with R ethenylbenzene, cyclohexyl 1-methylethyl ester 2-Butenedioic acid (Z)-, mono R (2-methylpropyl) ester, polymer with ethenylbenzene 2,5-Furandione, polymer with R ethenylbenzene, isooctyl ester
(C 8 H 8 C 3 H 6 O) x
Acrylonitrile-styrene polymer; poly styrene-aery lonitrile; styrene-acrylonitrile polymer AHyI alcohol-styrene polymer Styrene-a-methylstyrene polymer
9003-54-7 25119-62-4 9011-11-4 69011-14-9
69011-17-2
Poly(styrene-co-maleic acid), isobutyl/methyl mixed ester
63528-92-7
Poly(styrene-comaleic acid), partial 2-butoxyethyl ester Poly(styrene-a?-maleic acid), partial 2-butoxyethyl ester, cumene terminated Poly(styrene-co-maleic acid), partial cyclohexyl/1-PR ester, cumene terminated
68890-84-6
Poly(styrene~a?-maleic acid), partial isooctyl ester
Search method
Maleic anhydride-PN 240 graft 107001-49-0 copolymer Diaminodiphenyl ether-pyromellitic 25038-81-7 dianhydride polymer; oxydianiline-pyromeliitic dianhydride polymer Sebacic acid polyanhydride 26776-29-4 Polyserine 25821-52-7 Poly (sodium /?-styrenesulfonate); 25704-18-1 poly(sodium /?-vinylbenzenesulfonate) PoIy(I-phenylethylene); poly9003-53-6 (vinylbenzene) Maleic acid anhydride-styrene 25736-61-2 polymer, sodium salt; 2,5-furandione-styrene copolymer, sodium salt Butadiene-styrene polymer, 9003-55-8 poly butadiene- polystyrene copolymer, styrene-butadiene polymer 66070-58-4
Poly(styrene-a?-divinyl benzene), amine functionalized
Poly(styrene-c«9-maleic acid), partial cyclohexyl/ isopropyl ester Poly(styrene-co-maleic acid), partial isobutyl ester
CA name
160611-50-7 160611-51-8
68890-82-4 Hydrogen isobutyl maleatestyrene copolymer
28571-95-1 68441-87-2
(C 4 H 2 Ov C 3 H 6 ), (Ci 2 Hi 2 N 2 O CK)H 2 O 6 )V
R
A Na
(C9H10 C8H8)A (Ci0H12 C | 0 H )0 • C 8 H 8 ), (C 10H [2 • C] 0 Hi 0 C8H8 • C 2 H 7 N) x (C 8 Hi 2 O 4 • C8H8 C5H6O4 • C 4 H 2 O 3 ), Unk C9H l2 (C 8 H 8 C 4 H 2 O 3 ), • AC 6 H i4 O 2 C 9 Hi 2 • (C 8 H 8 C 4 H 2 O 3 ), AC 6 H t 2 O AC3H8O Unk (C 8 Hi 2 O 4 • C 8 H 8 ), Unk
Common name
Synonyms
CAS Registry No.
Poly(styrene-cc>-maleic acid), partial propyl ester Poly(styrene-(Y;-maleic acid), partial propyl ester, cumene terminated Poly(styrene-co-maleic acid), ^c-butyl/methyl mixed ester
Maleic anhydride-styrene polymer, propyl ester
Poly(styrene-co-maleic anhydride) Polystyrene-co-maleic anhydride), cumene terminated Poly(styrene sulfonic acid-o?maleic acid), sodium salt
Maleic anhydride-styrene polymers
Poly(sulfone)
Bisphenol A-bis(chlorophenyJ) sulfone copolymer, SRU
160611-48-3
65652-36-0
9011-13-6 26762-29-8
68037-40-1
Poly(//7-but.yl methacrylate)
25135-51-7
25189-00-8
Poly(tetrafluoroethylene)
Poly(difluoromethylene); fluoropolymers; perfluoroethylene polymer Poly (tetrahy drof man) Poly(butylene oxide); tetrahydrofuran homopolymer, SRU; THF polymer, SRU Poly( tetrahy drofuran), Polytetramethylene glycol bis(3-aminopropyl) terminated bis(3-aminopropyl) ether Poly(tetrahydrofuran), linear
68890-81-3
9002-84-0
R
CgH l2 • ( C 8 H 8 C4HiOi)V • ACiH 8 O (C8Hj2O4C8H8C5H6O4 • C4H2O^v) v
R
R R
(C 8 H 8 C 4 H 2 O - Ov CqH )2 • (C 8 H 8 • C4H2O-O
*
(C8H8C 4 H 2 O ^ Na) v
U
(C 2 7 H 2 2 O 4 S),,
R
(C 8 H| 4 O 2 ). V
R
(C2F 4 ) v
72088-96-1
Poly(oxy-l,4-butanediyl), 7.-(3-aminopropyl)co-( 3-aminopropoxy )Furan, tetrahydro-, polymer with oxirane
R
(C 4 H 8 O) 1 , C6Hi6N2O
R
(C4H8OC2H4O)1
R
(C 4 H 8 S),
U R
(C 6 H 4 S) v (C?H9NO 2 SCH 2 O) v (CyH^N 2 O 2 ) V
9016-75-5 25035-71-6
Poly(tolylene 2,4-diisocyanatecY>-poly(l,4-butanediol))
Poly(tetramethylene ether glycol)TDI copolymer; polytetramethylene glycol-tolylene isocyanate polymer Potyoxypropylene glycol-tolylene diisocyanate polymer; polypropylene glycol-TDI polymer
9069-50-5
Poly(urea-rr;-formaldehyde), butylated Poly(urea-t^-formaldehyde), methylated
Unk
(C 4 H 8 O),,H 2 O
Poly(phenylene sulfide) Formaldehyde-/;-toluenesulfonamide polymer 2.4-Toluene diisocyanate polymer
27637-03-2
26373-01-3
26006-20-2
9057-91-4
68133-07-3
Polytyrosine
R
R
PolyCthio^henylene) Poly(p-toluene sulfonamideco-formaldehyde) Poly(tolylene 2,4-diisocyanate)
Poly(L-tyrosine) Poly(L-tyrosine hydrobromide)
2,5-Furandione, polymer with ethenylbenzene, propyl ester 2,5-Furandione, telomer with ethenylbenzene and (1-methyl ethylJbenzene, propyl ester 2-Butenedioic acid (Z)-, monomethyl ester, polymer with ethenylbenzene, 2,5furandione and (Z)-I-methylpropyl hydrogen 2-butenedioate 2.5-Furandione, polymer with ethenylbenzene 2,5-Furandione, telomer with ethenylbenzene and (l-methylethyl Jbenzene 2,5-Furandione, polymer with ethenylbenzene, sulfonated, sodium salt Poly(oxy-l,4-phenylenesulfonyll,4-phenyleneoxy-l,4phenylene( 1 -methylethylidene)1,4-phenylene) 2-Propenoic acid, 2-methyl-, 1,1-dimethylethyl ester, homopolymer Ethene, tetrafluoro-homopolymer
Molecular formula
Poiy(oxy-l,4-butanediyl), a-hydro-co-hydroxy-
Poly(thioisobutylene)
Poly(trimethylolpropane/ di(propylene glycol)-/radipic acid/phthalic anhydride))
Search method
25190-06-1
Oxirane-THF copolymer; polyethylene-poly(tetramethylene) glycol lsobutylene sulfide polymer
Poly(tolylene 2,4-diisocyanatectf-poly(propylene glycol))
CA name
25619-78-7 27378-49-0 68002-19-7 68071-45-4
Thirane. 2,2-dimethyl-, homopolymer Poly(thiophenylene) Benzenesulfonamide. 4-methyl-, polymer with formaldehyde Benzene, 2,4-diisocyanatol-methyl- homopolymer Poly(oxy-l,4-butanediyl), 7.-hydro-co-hydroxy-, polymer with 1,3-diisocyanatomethylbenzene Poly(oxy(methyl-l,2-ethanediyl)), a-hydro-co-hydroxy-, polymer with 1,3-diisocyanatomethylbenzene Hexanedioic acid, polymer with 2-ethyl-2-(hydroxymethyl)1,3-propanediol, 1,3-isobenzofurandione and 1,1'-oxybis(2-propanol) L-Tyrosine, homopolymer i.-Tyrosine, homopolymer. hydrobromide Urea, polymer with formaldehyde. butylated Uiea. polymer with formaldehyde, methylated
R R
(C9H6N2O2 (C 4 H 8 O),, H 2 O) V
R
(CgH6N2O2(C^H 6 O),, H 2 O) v
R
(C 8 H 4 O^C6H|4O3C 6 Hi 4 O^iC 6 H 10O4)v
R R
(CqHnNOi); (C5H I 2 N 2 O 2 ) v • vBrH Unk
:;:
*
(CH 4 N 2 OCH 2 O) x
Common name PolyCvinyl acetate)
Synonyms
CAS Registry No.
PoIy(I-acetoxyethylene): PVAC
9003-20-7
Poly(vinyl acetate-cobutyl maleate-cY?isobornyl acrylate)
136392-68-2
Poly(vinyl acetate-cocrotonic acid) Poly(vinyl alcohol)
Crotonic acid-vinyl acetate polymer 25609-89-6
Poly(vinyl alcohol-co-ethylene) Poly(vinyl alcohol -covinyl acetate) Poly(4-vinyl biphenyl) Poly (vinyl bromide) Poly(vinyl butyral) PolyCvinyl butyral-co-vinyl alcohol-co-vinyl acetate)
Poly( l-hydroxyethylene): gohsenal; 9002-89-5 lemol; polyvinol; polyviol Ethylene-vinyl alcohol polymer 25067-34-9 Vinyl alcohol-vinyl acetate polymer 25213-24-5 25232-08-0 Bromoethylene polymer
Poly(vinyl butyrate) Poly(vinyl chloride) PolyCvinyl chloride-co-vinyl acetate) PolyCvinyl chloride-co-vinyl acetate-etf-2-hydroxypropyl acrylate) PolyCvinyl chloride-a;-vinyl acetate-co-maleic acid) PolyCvinyl chloride-co-vinyl acetate-vinyl alcohol)
25951-54-6 63148-65-2 27360-07-2
24991-31-9 PoIy(I-chloroethylene) Vinyl chloride-vinyl acetate polymer
9002-86*2 9003-22-9 41618-91-1
Maleic acid-vinyl acetate-vinyl: vinyl acetate-vinyl chloridemaleic acid polymer Vinyl acetate-vinyl alcohol-vinyl chloride polymer; vinyl chloridevinyl acetate-vinyl alcohol copolymer
PolyCvinyl cinnamate)
9005-09-8
(C 4 H 6 O 2 Jv
R
(Ci3H2nO2 C I2H2nO4 • C 4 H 6 O.? ).v
R
(C 4 Hf 1 O 2 C4H6O2), (C2H4O),
R R R R R S R
R R R R
R
(C 2 H 4 O C 2 H 4 ),v (C4H6O2 C 2 H 4 O) x (C 14H l 2 ),. (C 2 H 21 Br) x Unk (CsHi 4 O 2 C4H6O2 C 2 H 4 O) x (C 6 H 1( )O 2 ) V (C 2 H 3 Cl) x (C4H6O2 C 2 H^Cl) x (C 6 H mOj • C4H6O2 C 2 H 3 Cl) x (C4H6O2 C4H4O4 C 2 H3Cl) 1 (C4H6O2 C2H4O C 2 H 3 Cl) x
24968-99-8
2-Propenoic acid,3-phenyl-. ethenyl ester, homopolymer Ethene. ethoxy-, homopolymer Ethene, fluoro-, homopolymer l.r-(methylenebis(oxy))bis-, homopolymer Acetamide, N-ethenyl-/V~methyl-, homopolymer Ethene methoxy, homopolymer 3-Buten-2-one, homopolymer Naphthalene. 2-ethenyl-, homopolymer Carbamic acid, octadecyl-, ethenyl ester, homopolymer Phenol. 4-ethenyl-. homopolymer
R
(C N H 1,,O2),.
R R R
(C4HNO), (C 2 H 3 F) x (C 5 HsO 2 )V
R
(C5HMNO)X
R R R
(C 3 H 6 O) x (C 4 H 6 O) x (Ci 2 Hm) x
R
(C2|H4|NO2)V
R
(CsH
Propanoic acid, ethenyl ester, homopolymer Pyridine, 2-ethenyl-. homopolymer Pyridine, 2-ethenyl-. polymer with styrene 2-Pyrrolidinone. 1-ethenyl-, homopolymer
R
(C 5 HsO 2 ) v
R
(C 7 H 7 N) x
R R
(CsHs C7H7NXv (C 6 I-UNO),
2-Pyrrolidinone, 1-ethenyl-, homopolymer, compd. with iodine
R
(C6H1)NO) x -vl 2
PolyC/V-vinyl-methylacetamide)
Poly(A^methyl-/V-vinylacetamide)
26616-03-5
PolyCvinyl methyl ether) PolyCvinyl methyl ketone) Poly(2-vinyl naphthalene)
Methyl vinyl ether homopolymer Methyl vinyl ketone polymer
9003-09-2 25038-87-3 28406-56-6 36671-85-9
Poly(vinyl propionate)
/?-Vinylphenol polymer; /?-vinylphenol polymer Vinyl propionate polymer
25035-84-1
Poly(2-vinyl pyridine)
2-Vinylpyridine polymer
25014-15-7
Poly(2-vinyl pyridine-c"6>styrene) PolyCvinyl pyrrolidone)
2-Vinylpyridine-styrene polymer
24980-54-9
PolyCvinyl pyiTolidone), iodine complex
Ethenol, polymer with ethene Acetic acid ethenyl ester, polymer with ethenol 1,1 '-Biphenyl, 4-ethenylhomopolymer Ethene, bromo-, homopolymer Vinyl acetal polymers, butyrals Acetic acid ethenyl ester, polymer with l.l-bis(ethenyloxy)butane and ethenol Butanoic acid, ethenyl ester, homopolymer Ethane, chloro-homopolymer Acetic acid ethenyl ester, polymer with chloroethene 2-Propenoic acid. 2-hydroxypropyl ester, polymer with chloroethene and ethenyl acetate 2-Butenedioic acid (Z)-, 2-Butenedioic acid (Z)-
R
R
25104-37-4 24981-14-4 9003-33-2
Poly(/?-pyrrolidinylethylene): poly(vinylpyrrolidone); vinylpyrrolidone polymer
Acetic acid ethenyl ester, homopolymer 2-Butenedioic acid (Z)-, dibutyl ester, polymer with ethenyl acetate and exo-1.7,7-trimethylbicyclo(2.2.1)hept-2-yl 2-propenoate 2-Butenoic acid, polymer with ethenyl acetate Ethenol, homopolymer
Molecular formula
Acetic acid ethenyl ester, polymer with chloroethene and ethenol
Poly(ethyl vinyl ether) Monofluoroethylene polymer Poly(divinyl formal)
Poly(4-vinyl phenol)
Search method
25086-48-0
Poly(vinyl ethyl ether) PolyCvinyl fluoride) PolyCvinyl formal)
PolyCvinyl /?-octodecylcarbamate)
CA name
24979-70-2
9003-39-8
25655-41-8
Common name
Search method
Molecular formula
Synonyms
CAS Registry No.
CA name
Poly( 1-vinyl pyrrolidoneco-acrylic acid) Poly(l-vinyl pyrrolidoneco-2-dimethylamino-ethyl methacrylate)
Acrylic acid-vinylpyrrolidone polymer
28062-44-4
R
PoIy(I-vinyl pyrrolidoneco-styrene)
Styrene-Af-vinylpyrrolidone polymer; 25086-29-7 vinylpyrrolidinone-styrene polymer N-Vinyl-2-pyrrolidone-vinyl acetate 25086-89-9 copolymer; poly(vinyl acetatevinylpyrrolidinone); vinyl acetate-vinylpyrrolidone copolymer 136445-69-7
2-Propenoic acid, polymer with l-ethenyl-2-pyrrolidinone 2-Propenoic acid, 2-methyl-, 2-(dimethylamino)ethyl ester, polymer with l-ethenyl2-pyrrolidinone 2-Pyrrolidinone, 1-ethenyl-, polymer with ethenylbenzene
R
(C 8 H 8 C 6 HQNO) X
Acetic acid ethenyl ester, polymer with l-ethenyl-2-pyrrolidinone
R
(C6H9NOC4H6O2)x
Alkenes, C> 10 a-, polymers with vinylpyrrolidone 2-Pyrrolidinone, 1-ethenylhexadecyl-, homopolymer Octadecanoic acid, ethenyl ester, homopolymer Sulfuric acid, monoethenyl ester, potassium salt, homopolymer Ethenesulfonic acid, homopolymer, sodium salt
S
Unk
R
(C22H4iNO)x
R
(C 20H38O 2)*
R
(C 2 H 4 O 4 S • K)x
R
(C 2 H 4 O 3 S) x *Na
R
(C9H 10)*
R
(C 9 Hi 0 -C9H10) x
PoIy(I-vinyl pyrrolidoneCo-vinyl acetate)
PoIy(I-vinyl pyrrolidoney-(l-triacontene)) Poly(l-vinyl pyrrolidoney-1-hexadecene) Poly(vinyl stearate)
30581-59-0
63231-81-2 Vinyl stearate polymer
Poly(vinyl sulfate), potassium salt Poly (vinyl sulfonic acid), sodium salt Poly(vinyl toluene) Poly (vinyl toluene-co-alphamethylstyrene) Poly(vinylcarbazole); Poly(9-vinyl carbazole) Poly(vinylcyclohexane) Poly(vinylferrocene) Poly(vinylidene chloride) Poly(vinylidene chloride-coacrylonitrile) Poly(vinylidene chloride-comethyl acrylate)
9003-95-6 26182-60-5
Ethenesulfonic acid polymer sodium salt; ethenesulfonic acid polymer sodium salt Poly(methylstyrene); vinyltoluene polymer a-Methylstyrene-vinyltoluene polymer Poly(n-carbazolylethylene); poly(Af-vinylcarbazole)
25053-27-4 9017-21-4 9017-27-0 25067-59-8 25498-06-0
Poly(l,l-dichloroethylene) Acrylonitrile-vinylidene chloride polymer Methyl acrylate-vinylidene chloride polymer
34801-99-5 9002-85-1 9010-76-8 25038-72-6
Poly(vinylidene chloride-coVinyl chloride-vinylidene chloride 9011-06-7 vinyl chloride) polymer Poly(vinylidene fluoride) Poly(l,l-difluoroethylene); PVDF 24937-79-9 Poly(vinylidene fluoride-coHexafluoropropene-vinylidene 9011-17-0 hexafluoropropylene) fluoride polymer Poly(vinylidene fluoride-coHexafluoropropene-tetrafluoro25190-89-0 hexafluoropropylene-coethylene-vinylidene fluoride tetrafluoroethylene) polymer; vinylidene fluoridetetrafluoroethylene-perfluoropropylene copolymer Poly (vinylidene fluoride-Co- Propene- tetrafluoroethylene54675-89-7 tetrafluoroethylene-covinylidene fluoride copolymer propylene) Poly(vinylisobutyl ether) Isobutyl vinyl ether polymer 9003-44-5 Poly(4-vinyl pyridine) Poly(4-vinyl pyridine-co-butyl methacrylate) Poly(4-vinyl pyrideneCo-styrene) Poly(4-vinyl pyridine hydrochloride), crosslinked Poly(4-vinyl pyridine), crosslinked
4-Vinylpyridine homopolymer Butyl methacrylate-4-vinylpyridine polymer
25232-41-1 53761-76-5 26222-40-2 29323-87-3
Divinylbenzene-4-vinylpyridine polymer
9017-40-7
Benzene, ethenylmethylhomopolymer Benzene, ethenylmethyl-, polymer with (l-methylethenyl)benzene 9H-Carbazole, 9-ethenyl-, homopolymer Cyclohexane, ethenyl-, homopolymer Ferrocene, ethenyl-, homopolymer Ethene,l,l-dichloro-, homopolymer 2-Propenenitrile, polymer with 1,1-dichloroethene 2-Propenoic acid, methyl ester, polymer with 1,1-dichloro ethene Ethene, 1,1-dichloro-, polymer with chloroethylene Ethene, 1,1-difluoro-, homopolymer 1-Propene, 1,1,2,3,3,3-hexafluoro-, polymer with 1,1-difluoroethene 1-Propene, 1,1,2,3,3,3-hexafluoro-, polymer with 1,1-difluoroethene and tetrafluoroethene 1-Propene, polymer with 1,1-difluoroethene and tetrafluoroethene Propane, l-(ethenyloxy)2-methyl-, homopolymer Pyridine, 4-ethenyl-, homopolymer 2-Propenoic acid, 2-methyl-, butyl ester, polymer with 4-ethenylpyridine Pyridine, 4-ethenyl-, polymer with ethenylbenzene Pyridine, 4-ethenyl-, hydrochloride, homopolymer Pyridine, 4-ethenyl-, polymer with dietheny!benzene
R
R
(C6H9NOC 3 H 4 Oi) x (C 8 Hi 5 NO 2 • C6HgNO)x
(Ci 4 HnN) x
R
(C 8 Hi 4 ),
R R R
(Ci 2 Hi 2 Fe) x (C 2 H 2 Cl 2 )* (C 3 H 3 NC2H2C12)X (C 4 H 6 O 2 • C2H2Cl 2 ) x
R R R R R
R R
(C2H3Cl C 2 H 2 Ch) x (C 2 H 2 F 2 ) X (C 3 F 6 C2H2F2)X (C 3 F 6 C 2 H 2 F 2 • C2F4)X
(C 3 H 6 C2H2F2C2F4)X (C 6 Hi 2 O) x
R R
(C 7 H 7 N) x (C 8 Hi 4 O 2 . C 7 H 7 N) x
R
(C 8 H 8 -C 7 H 7 N) x
R
(C 7 H 7 NClH) x
R
(CioHioC 7 H 7 N) x
Common name
Synonyms
CAS Registry No.
Poly(4-vinyl pyridinium dichromate)
82246-45-5
Poly(4-vinyl pyridinium tribromide)
91650-35-0
Poly(/?-xylylene)
25951-90-0
Rosin, ester with glycerol
8050-31-5
Rosin, ester with pentaerythritol
8050-26-8
Rubber, chlorinated Safflower seed oil Silicone oil Soybean oil Starch Starch, soluble Starch-gra/3f-poly(acrylic acid), sodium salt Tri-o-benzyl cellulose Tung oil Zein
Methyl phenyl silicones Fats and glyceridic oils Arrowroot starch; potato starch; rice starch; tapioca starch Acrylic acid-starch polymer sodium salt Fats and glyceridic oils
9006-03-5 8001-23-8 63148-58-3 8001-22-7 9005-25-8 9005-84-9 60323-79-7 91104-69-7 8001-20-5 9010-66-6
CA name
Search method
Chromic acid (H 2 Cr 2 O 7 ), salt with diethenylbenzene polymer with 4-ethenylpyridine Hydrogen tribromide, compd. with 4-ethenylpyridine (1:1), homopolymer Benzene, 1,4-dimethyl-, homopolymer Resin acids and rosin acids, esters with glycerol Resin acids and rosin acids, esters with pentaerythritol Rubber, chlorinated Safflower oil Siloxanes and Silicones, Me Ph Soybean oil Starch Amylodextrin Starch, polymer with 2-propenoic acid, sodium salt Cellulose, tris(phenylmethyl) ether Tung oil Zeins
R
Molecular formula
R
(Ci 0 H 10 . C7H7N)* • ^Cr 2 H 2 O 7 (C7H7N Br 3 H) x '
R
(C8H iO)x
S*
Unk
S*
Unk
R S* S S* R
Unk Unk Unk Unk Unk
R R
Unk (C 3 H 4 O 2 • Unk) ^xNa (C7H8O) }/3 ; Unk Unk Unk
R S* S*
Index
This index lists only physical constants of polymer classes and a few selected specific polymers. Information on specific polymers can be found under the polymer class name. Specific polymers in the index, mostly from Section V, do not necessarily represent the only place of reference of that polymer. Additional references may be found under the respective polymer class name.
Index terms
Links
A Abbreviations and acronyms: alphabetical order
VIII/2
blends, reinforced polymers, etc.
VIII/19
chemical transformation of other polymers
VIII/18
elastomers
VIII/21
ISO codes for thermoplastics
VIII/19
polymer characteristic group based
VIII/17
poly(monomer) based
VIII/15
SPI codes for plastics recycling
VIII/21
textile fibers
VIII/22
Acetylene monomers, physical constants Acetylene oligomers
III/4 IV/19
Acid anhydrides, solubility parameter Acid dichloride monomers, physical constants
VII/700 III/4
Acid halides, solubility parameter
VII/700
Acids, solubility parameter
VII/701
Acoustic properties, and glass transition temperature Acrolein monomers, physical constants
VI/194 III/4
Acronyms, see Abbreviations and acronyms Acrylamide monomers, physical constants
III/4
Acrylate monomers, acids/esters, physical properties
III/8
Acrylic fibers
V/61
Acrylic monomers: oligomers
IV/22
propagation/termination activation energies
II/417
propagation/termination constants
II/80
Acrylic polymers, see Poly(acrylic acid) and derivatives Activation energy, free radical initiator decomposition Activation energy, of propagation and termination
II/1 II/415
acrylic derivatives
II/417
dienes
II/416
methacrylic derivatives
II/418 This page has been reformatted by Knovel to provide easier navigation.
IX/1
IX/2
Index terms
Links
Activation energy, of propagation and termination (Continued) miscellaneous compounds
II/423
olefins
II/416
styrene derivatives
II/421
vinyl esters
II/421
vinyl ethers
II/421
vinyl halogens
II/420
vinyl heteroaromatics
II/422
Activation enthalpies, of stereocontrol
II/445
Activation entropies, of stereocontrol
II/445
Activation volume
II/429
chain propagation
II/435
chain termination
II/436
chain transfer
II/436
copolymerization
II/439
initiator decomposition
II/435
selected polymerization reactions
II/432
Acyl peroxide initiators, decomposition rates
II/29
Addition polymerization: living polymers with partial deactivation
II/344
with termination
II/341
Additives: ISO codes for
VIII/20
transfer constants to
II/110
Adhesive hard spheres
VI/594
characteristic parameters
VI/600
Adhesives, surface properties
VI/534
Adsorption chromatography
VII/330
Alcohol monomers, physical properties Alcohols, solubility parameter
III/16 VII/700
Aldehydes: propagation/termination constants
II/90
solubility parameter
VII/699
Alfrey-Price equation
II/309
Alkane-diol monomers: physical properties
III/16
surface properties
VI/534
Alkanes, permeability through Santoprene TM Alkyl peroxide initiators, decomposition rates
VI/566 II/23
Allene oligomers
IV/17
Allyl functional monomers, physical properties
III/18
This page has been reformatted by Knovel to provide easier navigation.
II/321
IX/3
Index terms
Links
Alternating copolymers, fractionation systems American Chemical Society Nomenclature Committee Amine monomers, difunctional, physical properties Ammo sugar oligomers
VII/366
VII/425
I/1 III/20 IV/103
Amorphous fluoropolymers, physical constants Amorphous polymers
V/52 VI/194
heat capacity
VI/484
Anhydride monomers, physical properties
III/20
Anisotropy of segments, see Segmental anisotropy Annealing
VI/195
Area: conversion factors
I/14
SI units
I/13
Aromatic hydrocarbons, solubility parameter
VII/698
Aromatic polymers, see Poly(aromatics) ATHAS Data Bank, of heat capacities
VI/484
Avrami constants, see Bulk crystallization rates Avrami equation
VI/282
Azo derivative initiators, decomposition rates
II/9
Azonitrile initiators, decomposition rates
II/2
B Baker-Williams method
VII/330
Barrier polymers
V/160
physical constants
V/164
Baumann-Kurata-Stockmayer procedure
VII/222
Baumann-Stockmayer-Fixman procedure
VII/242
VII/243
Blends: abbreviations and acronyms
VIII/19
crystallization
VI/280
VI/287
poly(alkenes)
VI/312
VI/353
poly(dienes)
VI/312
VI/353
poly(esters)
VI/329
VI/377
poly(oxides)
VI/319
VI/371
poly(urethanes)
VI/383
poly(vinyls)
VI/312
VI/353
VII/395
VII/438
crystallization rates
fractionation systems radiation chemical yield
II/493
Block copolymers: fractionation systems
VII/382 This page has been reformatted by Knovel to provide easier navigation.
VII/427
IX/4
Index terms
Links
Block copolymers: (Continued) segmental anisotropy
VII/751
solvent-nonsolvent tables
VII/533
Boiling point: monomers, see Monomer physical constants oligomers, see Oligomer physical constants polymer solvents
III/59
Branched phenol-formaldehyde oligomers Brownian motion fractionation
IV/94 VII/333
Bulk crystallization rates: composites
VI/389
miscellaneous polymers
VI/385
poly(alkenes)
VI/341
poly(amides)
VI/379
poly(carbonates)
VI/372
poly(dienes)
VI/341
poly(esters)
VI/373
poly(oxides)
VI/365
poly(phosphazenes)
VI/384
poly(siloxanes)
VI/384
poly(urethanes)
VI/383
poly(vinyls)
VI/341
Burchard-Stockmayer-Fixman procedure
VII/240
Butadiene monomers, physical properties
III/24
1,3-Butadiene oligomers
IV/14
Butene monomers, physical properties
III/26
Butyl rubber, physical constants
IV/16
V/4
C CA Index polymer names
I/1 VI/113
Carbon-sulfur chains, theta solvents CAS Registry Numbers
VII/317 I/8
common polymers
VIII/32
example searches
VIII/26
indexing and assignment
VIII/25
Catalysts, transfer constants to
II/106
Ceiling temperature: copolymers
II/401
defined
II/393
gaseous monomer
II/397
monomers in solution
II/398 This page has been reformatted by Knovel to provide easier navigation.
I/8 VIII/25 VIII/25
IX/5
Index terms
Links
Ceiling temperature: (Continued) pure liquid monomer
II/394
Cell models
VI/592
Cellulose and derivatives: diffusion coefficients
VI/561
heat, entropy, and volume change of solution
VII/662
Huggins constant
VII/282
permeability coefficients
VI/561
physical constants
V/135
radiation chemical yield
II/487
solubility coefficients
VI/561
solution properties
V/147
solvent-nonsolvent tables
VII/529
specific refractive index increments
VII/609
surface properties
VI/533
thermal degradation
II/475
unperturbed dimensions of linear chains
VII/66
viscosity-molecular weight relationship
VII/43
Cellulose esters, solvent-nonsolvent tables
VII/530
Cellulose ethers, solvent-nonsolvent tables
VII/529
Cellulose nitrate, solvent-nonsolvent tables
VII/531
Cellulose sulfate, solvent-nonsolvent tables
VII/531
Chain conformation: isomorphous polymer pairs
VI/399
poly(amides)
VI/33
poly(aromatics)
VI/15
poly(dienes)
VI/22
poly(diynes)
VI/22
poly(esters)
VI/40
poly(ethers)
VI/51
poly(imides)
VI/15
poly(olefins)
VI/6
poly(oxides)
VI/52
poly(peptides)
VI/26
poly(saccharides)
VI/59
poly(sulfides)
VI/57
poly(sulfones)
VI/57
poly(ureas)
VI/49
poly(urethanes)
VI/49
poly(vinylidenes)
VI/13
poly(vinyls)
VI/13
Chain propagation activation energy, see Propagation activation energy This page has been reformatted by Knovel to provide easier navigation.
VI/593
IX/6
Index terms
Links
Chain propagation activation volumes
II/435
Chain propagation constants, see Propagation constants Chain termination activation energy, see Termination activation energy Chain termination activation volumes
II/436
Chain termination constants, see Termination constants Chain transfer activation volumes Chemical Abstracts
II/436 VIII/29
Chemical Abstract Service Registry Numbers, see CAS Registry Numbers Chemical Abstracts Index polymer names Chlorinated poly(ethylene)
I/1 VI/113
I/8 VIII/25
V/161
Chlorocarbon surfaces
VI/524
Chromatographic fractionation
VII/330
Classical cross fractionation
VII/332
Cleavage rate constants, photopolymerization
II/170
Cloud point titration
VII/294
Cloud temperature titration
VII/294
Coacervate extraction
VII/329
Cocrystallization
VI/280
Cohesion parameter, see Solubility parameter Cohesive energy density
VII/676
group contributions
VII/684
polar systems
VII/677
Colligative properties
VII/163
Column chromatography
VII/330
Column extraction
VII/329
Common names
I/8
Compendium of Macromolecular Nomenclature
I/1
Competitive selective adsorption
VII/330
Composites: abbreviations and acronyms
VIII/19
bulk crystallization rates
VI/389
radiation chemical yield
II/493
radiation resistance
VI/588
Compressibility equations, Isothermal Concentration dependence, polymer-solvent interaction parameter Condensation polymerization
VI/592 VII/249 II/346
molecular weight distribution
II/354
Constitutional base units
VI/113
Constitutional repeating units
I/3
This page has been reformatted by Knovel to provide easier navigation.
VIII/25
IX/7
Index terms
Links
Continuous film extraction
VII/329
Continuous polymer fractionation
VII/329
Continuum equations of state
VI/594
Conversion factors
I/14
English-American units
I/17
Copolymer abbreviations, see Abbreviations and acronyms Copolymers, see also Free radical copolymerization CAS Registry Number search example ceiling temperatures
VIII/28 II/401
crystallization rates poly(alkenes)
VI/353
poly(dienes)
VI/353
poly(esters)
VI/331
poly(siloxanes)
VI/334
poly(vinyls)
VI/353
entropy of polymerization
II/392
glass transition temperature
VI/196
heat of polymerization
VI/377
VI/252
II/380
isomorphous polymer pairs
VI/401
metallocene-catalyzed
II/329
nomenclature
I/2
radiation chemical yield
I/10
II/490
segmental anisotropy
VII/751
unperturbed dimensions of linear chains
VII/58
VII/65
viscosity-molecular weight relationship
VII/27
VII/42
Cowie-Bywater procedure
VII/241
Critical pressure, and cohesive energy density
VII/680
Cross fractionation
VII/332
Crosslinking: and glass transition temperature
VI/196
with thermal degradation
II/350
Crystal growth rates: poly(alkenes)
VI/291
poly(dienes)
VI/291
poly(oxides)
VI/300
poly(vinyls)
VI/291
Crystal habit
VI/194
Crystallinity, and glass transition temperature
VI/196
Crystallization
VI/280
blends
VI/280
cocrystallization
VI/280
composites
VI/389 This page has been reformatted by Knovel to provide easier navigation.
VI/287
IX/8
Index terms
Links
Crystallization (Continued) computer simulation
VI/290
epitaxial
VI/289
flow-induced
VI/289
kinetics
VI/282
lamellar structure growth kinetics
VI/284
mesophases
VI/282
nonisothermal
VI/286
orientational
VI/289
pressure-induced
VI/288
solvent-induced
VI/288
thermodynamics
VI/284
Crystallization analysis fractionation
VII/330
Crystallization rates: bulk crystallization rates composites
VI/389
miscellaneous polymers
VI/385
poly(alkenes)
VI/341
poly(amides)
VI/379
poly(carbonates)
VI/372
poly(dienes)
VI/341
poly(esters)
VI/373
poly(oxides)
VI/365
poly(phosphazenes)
VI/384
poly(siloxanes)
VI/384
poly(urethanes)
VI/383
poly(vinyls)
VI/341
crystal growth rates poly(alkenes)
VI/291
poly(dienes)
VI/291
poly(oxides)
VI/300
poly(vinyls)
VI/291
radial spherulite growth rates miscellaneous polymers
VI/336
poly(alkenes)
VI/304
poly(amides)
VI/331
poly(carbonates)
VI/326
poly(dienes)
VI/304
poly(esters)
VI/327
poly(oxides)
VI/315
poly(siloxanes)
VI/334
poly(vinyls)
VI/304 This page has been reformatted by Knovel to provide easier navigation.
VI/288
IX/9
Index terms
Links
Crystallization rates: (Continued) study principles/techniques
VI/282
Crystallographic data: miscellaneous polymers
VI/64
poly(amides)
VI/33
poly(aromatics)
VI/15
poly(dienes)
VI/22
poly(diynes)
VI/22
poly(esters)
VI/40
poly(ethers)
VI/51
poly(imides)
VI/15
poly(olefins)
VI/6
poly(oxides)
VI/52
poly(peptides)
VI/26
poly(saccharides)
VI/59
poly(sulfides)
VI/57
poly(sulfones)
VI/57
poly(ureas)
VI/49
poly(urethanes)
VI/49
poly(vinylidenes)
VI/13
poly(vinyls)
VI/13
Cumulative volume of precipitate
VII/328
Current Contents
VIII/29
Cyclic formaldehyde-thioformaldehyde oligomers
IV/62
Cyclic oligo(alkynes)
IV/20
Cyclic oligo(ethersulfides)
IV/63
Cyclic oligo(heterocyclics)
IV/99
Cyclic oligo(selenomethylenes)
IV/62
Cyclic oligo(thioalkylenes)
IV/62
Cyclic oligo(thioethylenes), substituted
IV/62
Cyclic oligo(thiomethylenes)
IV/62
Cyclic oligo(xylylenes)
IV/90
Cyclic phenol-formaldehyde oligomers
IV/94
1,3-Cyclohexadiene oligomers
IV/17
Cyclopentadiene oligomers
IV/17
D Data block 1, ISO codes for
VIII/19
Data block 2, ISO codes for
VIII/20
Data block 3, ISO codes for
VIII/20
Data block 4, ISO codes for
VIII/20 This page has been reformatted by Knovel to provide easier navigation.
IX/10
Index terms
Links
Data block 5, ISO codes for
VIII/21
Decomposition rates, free radical initiators
II/1
acyl peroxides
II/29
alkyl peroxides
II/23
azo derivatives
II/9
azonitriles
II/2
hydroperoxides
II/43
ketone peroxides
II/43
miscellaneous initiators
II/67
peresters
II/48
peroxy carbonates
II/48
Demixing solvents
VII/329
Dendrimers, solvent-nonsolvent tables
VII/534
Density: conversion factors
I/14
and glass transition temperature
VI/194
isorefractive and isopycnic solvent pairs
III/43
monomers, see Monomer physical constants oligomers, see Oligomer physical constants poly(amides)
VI/33
poly(aromatics)
VI/15
poly(dienes)
VI/22
poly(diynes)
VI/22
poly(esters)
VI/40
poly(ethers)
VI/51
poly(imides)
VI/15
polymer solvents
III/59
poly(olefins)
VI/6
poly(oxides)
VI/52
poly(peptides)
VI/26
poly(saccharides)
VI/59
poly(sulfides)
VI/57
poly(sulfones)
VI/57
poly(ureas)
VI/49
poly(urethanes)
VI/49
poly(vinylidenes)
VI/13
poly(vinyls)
VI/13
SI units
I/13
Density gradient technique
VII/333
Description block, ISO codes
VIII/19
Dianhydride monomers, physical properties Dielectric coefficients, and glass transition temperature This page has been reformatted by Knovel to provide easier navigation.
III/24 VI/194
II/415
IX/11
Index terms
Links
Dielectric thermal analysis, for glass transition temperature measurement
VI/196
Diene monomers: propagation/termination activation energies propagation/termination constants
II/416 II/79
Diene oligomers
IV/14
Diepoxide monomers, physical properties
III/26
Differential heat of dilution
VII/650
Differential heat of solution
VII/650
Diffusion, and glass transition temperature
VI/194
Diffusion coefficient: alkanes through Santoprene TM
VI/566
cellulose and derivatives
VI/561
esters through poly(epichlorohydrin)
VI/567
fluorinated polymers
VI/552
inorganic polymers
VII/141
molar mass averages determined from
VII/89
poly(acrylics)
VII/96
poly(alkanes)
VI/545
poly(alkenes)
VII/92
poly(amides)
VI/559
poly(aryl ether ether ketone)
VI/561
poly(carbonates)
VI/555
VII/134
poly(dienes)
VI/553
VII/165
poly(esters)
VI/555
VII/134
poly(ethers)
VII/134
poly(imides)
VI/559
poly(methacrylates)
VI/548
poly(nitriles)
VI/549
poly(nucleotides)
VII/137
VII/157
poly(oxides)
VI/555
poly(saccharides)
VII/144
poly(siloxanes)
VI/558
poly(styrenes)
VI/547
poly(sulfones)
VI/560
poly(ureas)
VII/109
VII/137
poly(urethanes)
VI/560
VII/137
poly(vinyls)
VI/549
VII/105
poly(xylylenes)
VI/555
proteins
VII/157
theory
VII/87
various compounds through high-density poly(ethylene)
VI/564
various compounds through high-density poly(propylene)
VI/564
This page has been reformatted by Knovel to provide easier navigation.
IX/12
Index terms
Links
Diffusion coefficient-molecular weight relationship, polymolecularity correction factors
VII/229
Diffusion fractionation
VII/333
Dilatometry, for glass transition temperature determination
VI/194
Diluents, and glass transition temperature
VI/197
DIN codes
VIII/19
Diphenyliodonium salts, electron transfer reaction of radicals with Dipole moments in solution
VI/195
II/176 VII/637
and cohesive energy density
VII/680
poly(acrylics)
VII/643
poly(carbonates)
VII/641
poly(dienes)
VII/644
poly(esters)
VII/640
poly(ethers)
VII/638
poly(itaconates)
VII/644
poly(methacrylics)
VII/644
poly(oxides)
VII/638
poly(sulfides)
VII/639
poly(thioethers)
VII/639
poly(vinyls)
VII/642
silicon polymers
VII/645
styrene copolymers
VII/645
Direct extraction
VII/329
Dosimetry
VI/584
Double-strand organic polymer nomenclature
I/6
E Elastomers
V/161
abbreviations and acronyms
VIII/21
permeability of gases through
VI/566
physical constants
V/168
radiation resistance
VI/586
Electrical conductivity, SI units
I/13
Electrical resistance, SI units
I/13
Electron microscope counting method
VII/333
Electron transfer rate constants, photopolymerization
II/170
Electron transfer reaction, radicals with diphenyliodonium salts
II/176
Empirical 3-parameter equations of state
VI/593
Energy: conversion factors
I/16
SI units
I/13
Engineered Materials
VIII/29 This page has been reformatted by Knovel to provide easier navigation.
II/177
IX/13
Index terms
Links
Engineering Index
VIII/29
VIII/30
Engineering Materials Abstract search
VIII/29
VIII/30
Engineering thermoplastics
V/166
English-American unit conversions
I/17
Entropy, SI units
I/13
Entropy of polymerization: copolymers
II/392
monomers giving main-chain carbon polymers
II/382
monomers giving main-chain heteroatom polymers
II/387
Entropy of solution
VII/649
cellulose and derivatives
VII/662
main-chain acyclic heteroatom polymers
VII/659
main-chain acyclic polymers
VII/650
poly(acrylics)
VII/654
poly(alkenes)
VII/651
poly(amides)
VII/661
poly(dienes)
VII/650
poly(esters)
VII/659
poly(oxides
VII/659
poly(siloxanes)
VII/661
poly(styrenes)
VII/655
poly(vinyls)
VII/655
Epitaxial crystallization
VI/289
Epoxide monomers, physical properties
III/26
Epoxy resins: interfacial tension with other polymers
VI/539
surface properties
VI/530
Equations of state
VI/591
characteristic parameters AHS + vdW equation of state
VI/600
Flory-Orwell-Vrij equation of state
VI/59
Hartmann-Haque equation of state
VI/597
Sanchez-Cho equation of state
VI/597
Sanchez-Lacombe equation of state
VI/600
Simha-Somcynsky equation of state
VI/599
simple cell model equation of state
VI/598
continuum models
VI/594
isothermal compressibility equations
VI/592
lattice models
VI/593
3-parameter equations
VI/593
Equilibrium monomer concentration: copolymers
II/401 This page has been reformatted by Knovel to provide easier navigation.
IX/14
Index terms
Links
Equilibrium monomer concentration: (Continued) gaseous monomer
II/397
monomers in solution
II/398
pure liquid monomer
II/394
Equilibrium polymerization
II/347
Esters: permeability though poly(epichlorohydrin) solubility parameter
VI/567 VII/699
Ether diol monomers, physical properties Ethers, solubility parameter
III/18 VII/699
Ethylene-acrylic acid copolymers
V/160
Ethylene copolymers, radiation chemical yield
II/490
Ethylene halide monomers, physical properties
III/28
Ethylene-methacrylic acid copolymers
V/159
Ethylene-propylene-diene terpolymers
V/161
physical constants
V/6
Ethylene-styrene interpolymers
V/160
Ethylene-vinyl acetate copolymers
V/160
Ethylene-vinyl alcohol copolymers
V/160
e values: monomers
II/310
monomers by e values
II/317
pressure effects
II/440
telogens
II/314
Excitation transfer rate constants, thioxanthones and photoinitiators
II/178
Extending fillers, ISO codes for
VIII/20
Extraction
VII/329
F Field How fractionation
VII/331
Fillers, ISO codes for
VIII/20
Film extraction
VII/329
First-order Markov mechanism
II/445
metallocene-catalyzed copolymerization
II/330
Flash point: monomers, see Monomer physical constants polymer solvents, most common Flexible poly(vinyl chloride)
III/59 V/159
Flory-Huggins interaction parameter, see Polymer-solvent interaction parameter Flory-Huggins lattice theory
VI/288
This page has been reformatted by Knovel to provide easier navigation.
II/449
IX/15
Index terms
Links
Flory-Orwoll-Vrij equation of state
VI/594
characteristic parameters
VI/599
Flow-induced crystallization
VI/289
Fluorocarbon surfaces
VI/524
Fluoropolymers: diffusion coefficients
VI/552
VI/562
permeability coefficients
VI/552
VI/562
physical constants
V/31
radiation chemical yield
II/488
solubility coefficients
VI/552
VI/562
Force: conversion factors
I/15
SI units
I/13
Formaldehyde resins: fractionation systems
VII/397
solvent-nonsolvent tables
VII/523
Formaldehyde-thioformaldehyde cyclic co-oligomers Formula index table
IV/62 VI/113
Formula weight, see Molecular weight Fox-Flory relationship
VII/235
Fractional crystallization
VII/329
Fractional precipitation
VII/328
Fractionation
VII/327
by chromatography
VII/330
cross fractionation
VII/332
by diffusion
VII/333
electron microscope counting method
VII/333
by sedimentation
VII/333
by solubility
VII/328
by ultrafiltration
VII/333
by zone melting
VII/333
Fractionation systems: blends
VII/395
VII/438
copolymers, block
VII/382
VII/427
copolymers, graft
VII/389
VII/430
VII/438 copolymers, random and alternating
VII/366
formaldehyde resins
VII/397
main-chain acyclic polymers
VII/333
main-chain carbocyclic polymers
VII/397
main-chain heteroatom polymers
VII/398
poly(acrylic acids)
VII/344 This page has been reformatted by Knovel to provide easier navigation.
VII/425
VII/351
IX/16
Index terms
Links
Fractionation systems: (Continued) poly(alkenes)
VII/336
poly(amides)
VII/411
poly(amino acids)
VII/414
poly(carbonates)
VII/404
poly(dienes)
VII/333
poly(esters)
VII/405
poly(imines)
VII/411
poly(methacrylic acids)
VII/346
poly(oxides)
VII/398
poly(phenylenes)
VII/397
poly(phosphazenes)
VII/422
poly(saccharides)
VII/431
poly(silanes)
VII/418
poly(siloxanes)
VII/418
poly(styrenes)
VII/356
poly(sulfides)
VII/416
poly(sulfonamides)
VII/416
poly(sulfones)
VII/416
poly(ureas)
VII/410
poly(urethanes)
VII/410
poly(vinyl alcohol)
VII/353
poly(vinyl esters)
VII/355
poly(vinyl ethers)
VII/353
poly(vinyl ketones)
VII/353
poly(vinyl nitriles)
VII/353
Free radical copolymerization
II/181
activation volumes
II/439
e values monomers
II/310
monomers by e values
II/317
pressure effects
II/440
telogens
II/314
pressure effects
II/437
Q values monomers
II/310
monomers by Q values
II/314
pressure effects
II/440
telogens
II/314
reactivity pattern scheme
II/321
monomer parameters
II/323
transfer agent parameters
II/326 This page has been reformatted by Knovel to provide easier navigation.
IX/17
Index terms
Links
Free radical copolymerization (Continued) transfer constant prediction
II/322
reactivity ratios
II/182
Quick Basic program for calculating
II/288
terpolymerization
II/438
Free radical initiators: active volumes
II/435
decomposition rates, see Decomposition rates, free radical initiators half life
II/2
photoinitiators
II/169
transfer constants to
II/106
Free radical polymerization
II/77
See also Free radical copolymerization activation energies, Initiator decomposition activation volumes
II/1 II/429
initiator decomposition rates
II/1
photopolymerization
II/169
propagation constants
II/79
stereocontrol activation enthalpies/entropies
II/445
temperature dependence
II/415
termination constants
II/79
transfer constants to catalysts and initiators
II/106
to monomers
II/98
to polymers
II/103
to solvents and additives
II/110
to sulfur compounds
II/150
transfer reaction
II/97
Frequency, SI units
I/13
Frequency function
II/352
Frictional ratio: inorganic polymers
VII/141
poly(acrylics)
VII/96
poly(alkenes)
VII/92
poly(amides)
VII/137
poly(carbonates)
VII/134
poly(dienes)
VII/165
poly(esters)
VII/134
poly(ethers)
VII/134
poly(nucleotides)
VII/157
poly(saccharides)
VII/144
poly(styrenes)
VII/109 This page has been reformatted by Knovel to provide easier navigation.
IX/18
Index terms
Links
Frictional ratio: (Continued) poly(ureas)
VII/137
poly(urethanes)
VII/137
poly(vinyls)
VII/105
proteins
VII/157
theory
VII/89
Fumaric monomers: physical properties of acids/esters
III/30
propagation/termination constants
II/87
G G, see Crystal growth rates; Spherulite growth rates Gamma function values
VII/223
Gaussian molecular weight distribution
II/352
Gelation
VII/765
Gelation properties, selected polymers
VII/765
Gel permeation chromatography
VII/330
Generalized exponential molecular weight distribution Generalized Flory model
II/354 VI/595
General purpose poly(styrene)
V/160
Gladstone-Dale equation
VI/571
Glass transition temperature: carbohydrates
VI/243
copolymers
VI/196
defined
VI/194
estimation methods
VI/197
factors affecting
VI/196
liquid crystals
VI/244
main-chain acyclic carbon polymers
VI/198
main-chain acyclic heteroatom polymers
VI/219
main-chain carbocyclic polymers
VI/218
main-chain heterocyclic polymers
VI/243
measurement methods
VI/195
natural polymers
VI/244
nitroso-polymers
VI/231
as nonequilibrium transition
VI/194
poly(acetals)
VI/244
poly(acrylamides)
VI/201
poly(acrylic acid esters)
VI/198
poly(acrylic acids)
VI/198
poly(acrylics)
VI/198
poly(alkenes)
VI/205 This page has been reformatted by Knovel to provide easier navigation.
VI/252
IX/19
Index terms
Links
Glass transition temperature: (Continued) poly(amides)
VI/235
poly(anilines)
VI/241
poly(benzimidazoles)
VI/245
poly(benzothiazinophenothiazines)
VI/245
poly(benzothiazoles)
VI/245
poly(benzoxazines)
VI/245
poly(benzoxazoles)
VI/245
poly(carbonates)
VI/219
poly(carboranes)
VI/245
poly(dibenzofurans)
VI/246
poly(dienes)
VI/207
poly(dioxoisoindolines)
VI/246
poly(esters)
VI/221
poly(ether ketones)
VI/226
poly(fluoresceins)
VI/247
poly(furan tetracarboxylic acid diimides)
VI/247
poly(imides)
VI/241
poly(imines)
VI/241
poly(methacrylamides)
VI/205
poly(methacrylic acid esters)
VI/201
poly(methacrylic acids)
VI/201
poly(methacrylics)
VI/198
poly(oxabicyclononanes)
VI/247
poly(oxadiazoles)
VI/248
poly(oxides)
VI/226
poly(oxindoles)
VI/248
poly(oxoisoindolines)
VI/248
poly(phenylenes)
VI/218
poly(phosphazenes)
VI/242
poly(phthalazines)
VI/248
poly(phthalides)
VI/248
poly(piperazines)
VI/248
poly(piperidines)
VI/249
poly(pyrazinoquinoxalines)
VI/249
poly(pyrazoles)
VI/249
poly(pyridazines)
VI/249
poly(pyridines)
VI/249
poly(pyromellitimides)
VI/249
poly(pyrrolidines)
VI/250
poly(quinones)
VI/250
poly(quinoxalines)
VI/250
This page has been reformatted by Knovel to provide easier navigation.
IX/20
Index terms
Links
Glass transition temperature: (Continued) poly(silanes)
VI/243
poly(silazanes)
VI/243
poly(siloxanes)
VI/231
poly(styrenes)
VI/209
poly(sulfides)
VI/233
poly(sulfonamides)
VI/234
poly(sulfonates)
VI/233
poly(sulfones)
VI/234
poly(thioesters)
VI/235
poly(triazines)
VI/252
poly(triazoles)
VI/252
poly(ureas)
VI/242
poly(urethanes)
VI/229
poly(vinyl alcohols)
VI/212
poly(vinyl esters)
VI/213
poly(vinyl ethers)
VI/214
poly(vinyl halides)
VI/215
poly(vinyl ketones)
VI/212
poly(vinyl nitriles)
VI/215
poly(vinyl thioethers)
VI/214
and surface tension
VI/522
Glassy polymers
VI/194
Graft copolymers: fractionation systems
VII/389
VII/430
VII/438 segmental anisotropy
VII/751
Gutta percha, solvent-nonsolvent tables
VII/529
G values, see Radiation chemical yield
H Halogenated hydrocarbons: solubility parameter
VII/698
surface properties of polymers
VI/525
Hansen parameter
VII/677
Hard sphere chain models
VI/592
Hartmann-Haque equation of state
VI/592
characteristic parameters
VI/597
Heat: conversion factors
I/16
SI units
I/13
This page has been reformatted by Knovel to provide easier navigation.
VI/593
IX/21
Index terms
Links
Heat capacity: conversion factors
I/16
data tables for specific polymers
VI/486
defined
VI/483
experimental curves
VI/485
SI units
I/13
Heat of fusion: poly(amides)
VI/33
poly(aromatics)
VI/15
poly(dienes)
VI/22
poly(diynes)
VI/22
poly(esters)
VI/40
poly(ethers)
VI/51
poly(imides)
VI/15
poly(olefins)
VI/6
poly(oxides)
VI/52
poly(peptides)
VI/26
poly(saccharides)
VI/59
poly(sulfides)
VI/57
poly(sulfones)
VI/57
poly(ureas)
VI/49
poly(urethanes)
VI/49
poly(vinylidenes)
VI/13
poly(vinyls)
VI/13
Heat of polymerization: copolymers
II/380
monomers giving main-chain carbon polymers
II/365
monomers giving main-chain heteroatom polymers
II/373
Heat of solution
VII/649
cellulose and derivatives
VII/662
common polymers
VII/671
main-chain acyclic heteroatom polymers
VII/659
main-chain acyclic polymers
VII/650
miscellaneous polymers
VII/659
poly(acrylics)
VII/654
poly(alkenes)
VII/651
poly(amides)
VII/661
poly(dienes)
VII/650
poly(esters)
VII/659
poly(oxides)
VII/659
poly(siloxanes)
VII/661
poly(styrenes)
VII/655 This page has been reformatted by Knovel to provide easier navigation.
VII/663
IX/22
Index terms
Links
Heat of solution (Continued) poly(vinyls)
VII/655
Heterocyclic oligomers
IV/99
Hexose oligomers
IV/102
High density poly(ethylene)
V/160
High impact poly(styrene)
V/160
Hildebrand parameter, see Solubility parameter Hoffman-Lauritzen spherulite growth equation
VI/285
Hole models
VI/592
Homologous oligomers
VI/594
IV/2
Homopolymer nomenclature
I/2
Hoy’s system
VII/687
Huggins constant: cellulose and derivatives
VII/282
defined
VII/265
poly(acrylic acids)
VII/268
poly(alkenes)
VII/266
poly(amides)
VII/279
poly(dienes)
VII/266
poly(esters)
VII/278
poly(methacrylic acids)
VII/268
poly(oxides)
VII/277
poly(saccharides)
VII/282
poly(vinyls)
VII/272
Hydrocarbon polymers: interfacial tension with other polymers
VI/535
surface properties
VI/524
Hydrocarbon surfaces
VI/524
Hydrodynamic chromatography
VII/332
Hydroperoxide initiators, decomposition rates Hydroquinone oligomers
II/43 IV/95
I Immiscible solvent partitioning
VII/329
Indexing, CAS Registry Numbers
VIII/25
Index of refraction, see Refractive index Individual item block, ISO codes
VIII/19
Initiators, free radical, see Free radical initiators Inorganic fibers
VIII/24
Inorganic polymers: diffusion coefficients
VII/137 This page has been reformatted by Knovel to provide easier navigation.
VI/533
IX/23
Index terms
Links
Inorganic polymers: (Continued) frictional ratios
VII/137
partial specific volumes
VII/137
second virial coefficients
VII/192
sedimentation coefficients
VII/137
solvent-nonsolvent tables
VII/532
Integral heat of dilution
VII/650
Integral heat of solution
VII/649
Interchange energy density
VII/678
Interfacial tension
VI/521
VI/523
See also Surface tension epoxy resins vs. others
VI/539
hydrocarbon polymers vs. others
VI/535
miscellaneous polymers
VI/540
poly(acrylics) vs. others
VI/538
poly(amides) vs. others
VI/539
poly(esters) vs. others
VI/539
poly(ethers) vs. others
VI/539
poly(methacrylics) vs. others
VI/538
poly(siloxanes) vs. others
VI/539
poly(styrenes) vs. others
VI/537
poly(vinyls) vs. others
VI/537
International System of Units (SI) International Union of Pure and Applied Chemistry (IUPAC) nomenclature Intrinsic birefringence
I/13 I/1 VI/573
Intrinsic viscosity
VII/2
Ion-exchange chromatography
VII/332
Irregular polymer nomenclature
I/7
ISO codes
VIII/19
Isocyanate monomers, physical properties
III/30
Isomorphism
VI/287
Isomorphous polymer pairs
VI/399
Isoprene oligomers
IV/15
Isopycnic solvent pairs
III/43
Isopycnic solvents
III/43
Isorefractive solvent pairs
III/43
Isorefractive solvents
III/43
Isotactic polymers
VI/6
Isothermal compressibility equations
VI/592
Isothermal crystallization
VI/281
This page has been reformatted by Knovel to provide easier navigation.
VI/399
IX/24
Index terms
Links
Itaconic derivatives: dipole moments in solution
VII/644
propagation/termination constants IUPAC (International Union of Pure and Applied Chemistry) nomenclature
II/85 I/1
K Kauri butanol values, and cohesive energy density
VII/680
kD see Decomposition rates, free radical initiators Kelen-Tudos method
II/181
Quick Basic program for implementing Ketone peroxide initiators, decomposition rates
II/288 II/43
Ketones: light stabilizer interactions
II/179
solubility parameter
VII/699
kP, see Propagation constants kT, see Termination constants
L Lactam monomers, physical properties
III/32
Lactone monomers, physical properties
III/32
Lamellae
VI/281
growth kinetics
VI/284
Lattice fluid model
VI/594
Lattice models
VI/593
Length: conversion factors
I/14
SI units
I/13
Light stabilizers
II/169
ketone interactions
II/179
Linear acetylene oligomers
IV/19
Linear low density poly(ethylene)
V/160
Linear oligo(xylylenes)
IV/90
Linear phenol-formaldehyde oligomers
IV/92
Liquid crystals
VI/280
glass transition temperature
VI/244
Logarithmic normal molecular weight distribution Lorentz-Lorentz equation
II/353 VI/571
Low density poly(ethylene)
V/160
Lyotropic phases
VI/280
This page has been reformatted by Knovel to provide easier navigation.
VII/678
IX/25
Index terms
Links
M Macleod exponent: cellulose and derivatives
VI/533
epoxy resins
VI/530
halogenated hydrocarbon polymers
VI/525
hydrocarbon polymers
VI/524
methacrylic hydrogels
VI/527
miscellaneous polymers
VI/533
organosilanes
VI/532
phenoxy resins
VI/530
poly(acrylics)
VI/526
poly(amides)
VI/530
poly(carbonates)
VI/530
poly(esters)
VI/529
poly(ethers)
VI/528
poly(imides)
VI/531
poly(imines)
VI/531
poly(methacrylics)
VI/527
poly(peptides)
VI/533
poly(siloxanes)
VI/531
poly(styrenes)
VI/525
poly(sulfones)
VI/530
poly(urethanes)
VI/531
poly(vinyl esters)
VI/526
poly(vinyls)
VI/526
Macleod’s relation
VI/522
Macromolecular assembly nomenclature Macromolecular isomorphism
I/3 VI/405
Main-chain acyclic carbon polymers: ceiling temperatures
II/394
entropy of polymerization
II/382
fractionation systems
VII/333
glass transition temperature
VI/198
heat, entropy, and volume change of solution heat of polymerization
VII/650 II/365
oligomer physical constants
IV/3
optically active polymers from achiral monomers
VII/733
optically active polymers from chiral monomers
VII/716
segmental anisotropy
VII/746
solubility parameter
VII/702
solvent-nonsolvent tables
VII/499
specific refractive index increments
VII/551
This page has been reformatted by Knovel to provide easier navigation.
II/398
IX/26
Index terms
Links
Main-chain acyclic carbon polymers: (Continued) thermal degradation
II/451
unperturbed dimensions of linear chains
VII/47
viscosity-molecular weight relationship
VII/5
Main-chain acyclic heteroatom polymers: ceiling temperatures
II/395
entropy of polymerization
II/387
fractionation systems
VII/398
glass transition temperature
VI/219
heat, entropy, and volume change of solution
VII/659
heat of polymerization
II/373
oligomer physical constants
IV/33
optically active polymers from achiral monomers
VII/737
optically active polymers from chiral monomers
VII/723
segmental anisotropy
VII/752
solubility parameter
VII/708
solvent-nonsolvent tables
VII/511
specific refractive index increments
VII/594
thermal degradation
II/465
unperturbed dimensions of linear chains
VII/60
viscosity-molecular weight relationship
VII/32
Main-chain carbocyclic polymers: fractionation systems
VII/397
glass transition temperature
VI/218
oligomer physical constants
IV/90
segmental anisotropy
VII/752
solvent-nonsolvent tables
VII/509
specific refractive index increments
VII/594
thermal degradation
II/464
unperturbed dimensions of linear chains
VII/47
viscosity-molecular weight relationship
VII/31
Main-chain carbonyl polymers, solvent-nonsolvent tables
VII/510
Main-chain heterocyclic polymers: glass transition temperature
VI/243
oligomer physical constants
IV/99
polymerizability
II/401
segmental anisotropy
VII/756
solvent-nonsolvent tables
VII/523
specific refractive index increments
VII/608
thermal degradation
II/473
Maleic anhydride copolymers: unperturbed dimensions of linear chains This page has been reformatted by Knovel to provide easier navigation.
VII/65
II/399
IX/27
Index terms
Links
Maleic anhydride copolymers: (Continued) viscosity-molecular weight relationship
VII/42
Maleic monomers, acids/esters, physical properties
III/32
Mark-Houwink-Sakurada equation
VII/2
Markov first-order mechanism, see First-order Markov mechanism Markov second-order mechanism, see Second-order Markov mechanism Mass: conversion factors
I/14
SI units
I/13
Mayo-Lewis equation
II/329
Mean-square end-to-end distance, Interconversion of different averages
VII/236
Mean-square radius of gyration, Interconversion of different averages
VII/236
Mean-square radius of gyration-molecular weight relationship
VII/232
Mechanical properties, and glass transition temperature
II/331
VI/194
Melting point: monomers, see Monomer physical constants oligomers, see Oligomer physical constants poly(amides)
VI/33
poly(aromatics)
VI/15
poly(dienes)
VI/22
poly(diynes)
VI/22
poly(esters)
VI/40
poly(ethers)
VI/51
poly(imides)
VI/15
polymers
VI/71
polymer solvents
III/59
poly(olefins)
VI/6
poly(oxides)
VI/52
poly(peptides)
VI/26
poly(saccharides)
VI/59
poly(sulfides)
VI/57
poly(sulfones)
VI/57
poly(ureas)
VI/49
poly(urethanes)
VI/49
poly(vinylidenes)
VI/13
poly(vinyls)
VI/13
Melting temperature
VI/194
See also Glass transition temperature Memory
VI/195
Mesophases: crystallization
VI/282
This page has been reformatted by Knovel to provide easier navigation.
VI/288
IX/28
Index terms
Links
Mesophases: (Continued) polydisperse high-molecular-weight polymeric Metallocene-catalyzed copolymerization Methacrylamide monomers, physical constants Methacrylate monomers, physical properties Methacrylic hydrogels, surface properties Methacrylic monomers, propagation/termination activation energies
VI/280 II/329 III/6 III/12 VI/527 II/418
Methacrylic polymers, see Poly(methacrylic acid) and derivatives Methyl methacrylate copolymers, radiation chemical yield Miscibility
II/490 VII/676
polymer-polymer guidelines
VII/679
polymer-solvent guidelines
VII/678
Miscible polymers
VI/409
polymer pairs chemically dissimilar
VI/411
having both lower and upper critical solution temperatures
VI/458
having lower critical solution temperature above room temperature
VI/454
high temperature miscible
VI/450
molecular weight dependence
VI/450
with one monomer in common
VI/411
polymer triads/tetrads, chemically dissimilar
VI/448
Molar refraction
VI/571
Molecular formula
VIII/25
Molecular Nucleation model
VI/286
Molecular weight, see also Viscosity-molecular weight relationship crystallizable polymers
VI/71
dispersion, and scattering
VII/631
and glass transition temperature
VI/197
monomers, see Monomer physical constants oligomers, see Oligomer physical constants and polymer miscibility
VI/450
and polymer-solvent interaction parameter polymer solvents
VII/250 III/59
and surface tension
VI/522
Molecular weight distribution: condensation polymers
II/354
generalized exponential distribution
II/354
logarithmic normal distribution
II/353
normal (Gaussian) distribution
II/353
Poisson distribution
II/354
and reactor conditions/design
II/352
This page has been reformatted by Knovel to provide easier navigation.
IX/29
Index terms
Links
Molecular weight distribution: (Continued) Stockmayer distribution
II/354
and viscosity constant
VII/5
Monoanhydride monomers, physical properties Monodisperse oligomers
III/20 IV/2
Monoepoxide monomers, physical properties
III/26
Monomer physical constants: acetylene monomers
III/4
acid dichloride monomers
III/4
acrolein monomers
III/4
acrylamide monomers
III/4
acrylate monomers, acids/esters
III/8
alcohol monomers
III/16
alkanediol monomers
III/16
allyl functional monomers
III/18
amine monomers, difunctional
III/20
anhydride monomers
III/20
1,2-butadiene monomers
III/24
1,3-butadiene monomers
III/24
butene monomers
III/26
dianhydride monomers
III/24
diepoxide monomers
III/26
epoxide monomers
III/26
ether diol monomers
III/18
ethylene halide monomers
III/28
fumaric monomers, acids/esters
III/30
isocyanate monomers
III/30
lactam monomers
III/32
lactone monomers
III/32
maleic monomers, acids/esters
III/32
methacrylamide monomers
III/6
methacrylate monomers, acids/esters
III/12
monoanhydride monomers
III/20
monoepoxide monomers
III/26
propene monomers
III/32
styrene monomers
III/34
vinyl monomers
III/36
Monomer quenching rate constants, photopolymerization
II/170
Monomer reactivity ratios, free radical copolymerization
II/182
Quick Basic program for calculating Monomers
II/288 III/1
See also Monomer physical constants; specific Monomers This page has been reformatted by Knovel to provide easier navigation.
II/177
IX/30
Index terms
Links
Monomers (Continued) bimolecular rate constants, photopolymerization
II/176
CAS Registry Number search example
VIII/26
compensation temperatures/enthalpies
II/449
e values
II/310
isomorphous polymer pairs
II/317
VI/399
propagation/termination activation energies
II/415
Q values
II/310
reactivity pattern parameters
II/323
transfer constants to
II/98
N National Technical Information Service
VIII/29
Natural cellulose fibers
VIII/23
Natural polymers: glass transition temperature
VI/244
solvent-nonsolvent tables
VII/528
Natural protein fibers
VIII/22
Natural rubber: physical constants
V/5
solvent-nonsolvent tables
VII/528
Nitrogen-containing compounds, solubility parameter
VII/700
Nitroso-polymers, glass transition temperature
VI/231
Nomenclature
VIII/25
See also CAS Registry Numbers Chemical Abstracts index names
I/8
common and systematic names
I/8
crystallizable polymers
VI/2
polymer classes
I/111
source-based
I/2
VI/2
structure-based
I/3
VI/3
Non-classical cross fractionation
VII/332
Nonisothermal crystallization
VI/286
Nonlinear macromolecule nomenclature Nonlinear polymerization
I/3 II/348
Nonsolvents, see Solvent-nonsolvent tables Normal molecular weight distribution
II/353
Normal-phase liquid chromatography
VII/330
Nucleation
VI/281
Nylon 6: heat capacity
VI/511 This page has been reformatted by Knovel to provide easier navigation.
IX/31
Index terms
Links
Nylon 6: (Continued) physical constants
V/121
Nylon 12, physical constants
V/121
Nylon 66
V/161
heat capacity
VI/512
physical constants
V/121
Nylon 610, physical constants
V/121
Nylon 612, heat capacity
VI/512
Nylons
V/161
heat capacity
VI/486
physical constants
V/121
O Olefin monomers: propagation/termination activation energies propagation/termination constants Olefin oligomers
II/416 II/79 IV/3
Oligo(acetals)
IV/33
Oligo(acteylenes)
IV/19
1,4-Oligo(alkadienes)
IV/16
Oligo(1-alkenylenes)
IV/9
Oligo(alkynes)
IV/20
Oligo(amides)
IV/64
Oligo(benzyls)
IV/91
Oligo(carbonates)
IV/47
Oligo(cyclopentylenes)
IV/90
Oligo(dienes)
IV/14
Oligo(diphenylmethanes)
IV/91
Oligo(esters)
IV/48
Oligo(ethers)
IV/33
Oligo(ethylenes)
IV/3
Oligo(furans)
IV/99
Oligo(imines)
IV/88
Oligo(isobutenes)
IV/8
Oligomeric α-ω-diynes
IV/20
Oligomer physical constants: with aliphatic side chains with heteroatoms with main-chain acyclic carbon only
IV/22 IV/3
with main-chain cyclic units
IV/90
with main-chain heteroatoms
IV/33
with main-chain heterocyclic rings
IV/99
This page has been reformatted by Knovel to provide easier navigation.
IX/32
Index terms
Links
Oligomers
IV/2
Oligo(methylenes)
IV/3
Oligo(olefins)
IV/3
Oligo(peptides)
IV/72
Oligo(perfluoroethylenes)
IV/6
Oligo(perfluoromethylenes)
IV/6
Oligo(p-phenoxy phenylmethanes)
IV/91
Oligo(p-phenylene oxides)
IV/91
Oligo(phenylenes)
IV/96
Oligo(p-phenylene sulfides)
IV/91
Oligo(pyridines)
IV/99
Oligo(pyrroles)
IV/99
Oligo(p-quinones)
IV/98
Oligo(saccharides)
IV/101
Oligo(selenides)
IV/62
Oligo(spiranes)
IV/90
Oligo(stilbenes)
IV/91
Oligo(styrenes)
IV/30
Oligo(sulfides)
IV/62
Oligo(thiophenes)
IV/99
Oligo(ureas)
IV/89
Oligo(urethanes)
IV/58
Oligo(vinyl) derivatives
IV/26
Oligo(xylylenes)
IV/90
Optical anisotropy
IV/27
VI/572
Optically active polymers: achiral monomers
VII/733
chiral monomers
VII/716
main-chain acyclic heteroatom polymers achiral monomers
VII/737
chiral monomers
VII/723
main-chain acyclic polymers achiral monomers
VII/733
chiral monomers
VII/716
poly(acrylics)
VII/716
poly(alkenes)
VII/716
poly(alkynes)
VII/721
poly(amides)
VII/726
poly(amino acids)
VII/729
poly(carbazoles)
VII/719
poly(dienes)
VII/720 This page has been reformatted by Knovel to provide easier navigation.
VII/733
VII/735
IX/33
Index terms
Links
Optically active polymers: (Continued) poly(esters)
VII/724
poly(imines)
VII/728
poly(isocyanates)
VII/728
VII/738
poly(isonitriles)
VII/720
VII/736
poly(maleimides)
VII/722
VII/736
poly(methacrylics)
VII/717
VII/734
poly(oxides)
VII/723
VII/737
poly(saccharides)
VII/732
poly(styrenes)
VII/719
VII/735
poly(sulfides)
VII/725
VII/737
poly(thioesters)
VII/725
poly(ureas)
VII/725
poly(urethanes)
VII/725
poly(vinyl esters)
VII/718
poly(vinyl ethers)
VII/718
poly(vinyl ketones)
VII/718
Organic free radical initiators, see Free radical initiators Organic pigments, surface properties
VI/534
Organosilanes, surface properties
VI/532
Orientational crystallization
VI/289
Orthogonal chromatography
VII/332
Oscillating load methods, of glass transition temperature measurement
VI/196
P Paraffinic hydrocarbons, solubility parameter
VII/698
Partial heat of dilution
VII/650
Partial heat of solution
VII/650
Partial specific volume: inorganic polymers
VII/141
poly(acrylics)
VII/96
poly(alkenes)
VII/92
poly(amides)
VII/137
poly(carbonates)
VII/134
poly(dienes)
VII/165
poly(esters)
VII/134
poly(ethers)
VII/134
poly(nucleotides)
VII/157
poly(saccharides)
VII/144
poly(styrenes)
VII/109
poly(ureas)
VII/137
poly(urethanes)
VII/137 This page has been reformatted by Knovel to provide easier navigation.
VII/735
IX/34
Index terms
Links
Partial specific volume: (Continued) poly(vinyls)
VII/105
proteins
VII/157
theory
VII/89
Particle scattering factors
VII/629
Partition chromatography
VII/331
Partition function
VI/591
Patterns A,S scheme
II/322
Patterns of reactivity scheme
II/321
monomer parameters
II/323
transfer agent parameters
II/326
transfer constant prediction
II/322
Patterns U,V scheme
II/322
Pentose oligomers
IV/102
Perester initiators, decomposition rates
II/48
Pericyclynes
IV/21
Permeability
VI/543
Permeability coefficient
VI/543
alkanes through Santoprene TM
VI/566
cellulose and derivatives
VI/561
conversion factors for
VI/545
esters through poly(epichlorohydrin)
VI/567
fluorinated polymers
VI/552
gases through elastomers
VI/566
poly(alkanes)
VI/545
poly(amides)
VI/559
poly(aryl ether ether ketone)
VI/561
poly(carbonates)
VI/555
poly(dienes)
VI/553
poly(esters)
VI/555
poly(imides)
VI/559
poly(methacrylates)
VI/548
poly(nitriles)
VI/549
poly(oxides)
VI/555
poly(siloxanes)
VI/558
poly(styrenes)
VI/547
poly(sulfones)
VI/560
poly(urethanes)
VI/560
poly(vinyls)
VI/549
poly(xylylenes)
VI/555
various compounds through chemically crosslinked poly(oxypropylene)
VI/565
various compounds through high-density poly(ethylene)
VI/564
This page has been reformatted by Knovel to provide easier navigation.
VI/562
IX/35
Index terms
Links
Permeability coefficient (Continued) various compounds through high-density poly(propylene)
VI/564
various compounds through low-density poly(ethylene)
VI/562
various compounds through low-density poly(ethylene), Irradiation crosslinked
VI/564
Peroxy carbonate initiators, decomposition rates
II/48
Phase distribution chromatography
VII/331
Phase equilibrium, and theta solvent determination
VII/293
Phenol alcohol oligomers
IV/93
Phenol formaldehyde oligomers
IV/92
Phenols, solubility parameter
VII/701
Phenoxy resins, surface properties
VI/530
Phosphonyl radicals
II/176
Phosphorus-containing polymers, thermal degradation
II/472
Phosphorus-oxygen chains, theta solvents
VII/318
Photo-induced polymerization
II/169
Photoinitiators
II/169
compound chemistries
II/173
Photopolymerization
II/169
Photosensitizes
II/169
Physical constants, see also specific Physical constants cellulose and derivatives
V/135
fluoropolymers
V/31
monomers, see Monomer physical constants oligomers, see Oligomer physical constants poly(acrylonitrile)
V/59
poly(amides)
V/121
poly(ethylenes)
V/9
polyethylene terephthalate)
V/113
polymer solvents
III/59
poly(methyl methacrylate)
V/87
poly(oxyethylene-oxyterephthaloyl) poly(oxymethylene)
V/113 V/97
poly(oxytetramethylene-oxyterephthaloyl)
V/119
poly(propylenes)
V/21
poly(styrenes)
V/91
poly(vinyl acetate)
V/77
poly(vinyl chloride)
V/67
rubbery polymers
V/1
selected important polymers
V/159
Pigments, surface properties
VI/534
Plasticizers, surface properties
VI/534 This page has been reformatted by Knovel to provide easier navigation.
IX/36
Index terms
Links
Plastics recycling, SPI codes
VIII/21
Poisson molecular weight distribution
II/354
Polarity: cellulose and derivatives
VI/533
epoxy resins
VI/530
halogenated hydrocarbon polymers
VI/525
hydrocarbon polymers
VI/524
methacrylic hydrogels
VI/527
miscellaneous polymers
VI/533
organosilanes
VI/532
phenoxy resins
VI/530
poly(acrylics)
VI/526
poly(amides)
VI/530
poly(carbonates)
VI/530
poly(esters)
VI/529
poly(ethers)
VI/528
poly(imides)
VI/531
poly(imines)
VI/531
poly(methacrylics)
VI/527
poly(peptides)
VI/533
poly(siloxanes)
VI/531
poly(styrenes)
VI/525
poly(sulfones)
VI/530
poly(urethanes)
VI/531
poly(vinyl esters)
VI/526
poly(vinyls)
VI/526
Poly(acetals): glass transition temperature
VI/244
solvent-nonsolvent tables
VII/504
theta solvents
VII/313
Poly(acetylenes): solvent-nonsolvent tables
VII/499
unperturbed dimensions of linear chains
VII/48
Poly(acrylamides): glass transition temperature
VI/201
radiation chemical yield
II/486
solvent-nonsolvent tables
VII/503
Poly(acrylic acid) and derivatives: diffusion coefficients
VII/96
dipole moments in solution
VII/643
fractionation systems
VII/344
frictional ratios
VII/96 This page has been reformatted by Knovel to provide easier navigation.
VII/351
IX/37
Index terms
Links
Poly(acrylic acid) and derivatives: (Continued) glass transition temperature
VI/198
heat entropy, and volume change of solution
VII/654
Huggins constant
VII/268
interfacial tension with other polymers nomenclature
VI/198
VI/538 VI/2
optically active
VII/716
partial specific volumes
VII/96
radiation chemical yield
II/483
second virial coefficients
VII/170
sedimentation coefficients
VII/96
segmental anisotropy
VII/747
solvent-nonsolvent tables
VII/501
specific refractive index increments
VII/557
surface properties
VI/526
thermal degradation
II/454
theta solvents
VII/307
unperturbed dimensions of linear chains
VII/49
Poly(acrylonitrile): heat capacity
VI/508
physical constants
V/59
Poly(alkanes): permeability, diffusion, and solubility coefficients theta solvents
VI/545 VII/295
Poly(alkenes): bulk crystallization rates
VI/341
crystal growth rates
VI/291
diffusion coefficients
VII/92
fractionation systems
VII/336
frictional ratios
VII/92
glass transition temperature
VI/205
heat, entropy, and volume change of solution
VII/651
Huggins constant
VII/266
optically active
VII/716
partial specific volumes
VII/92
second virial coefficients
VII/165
sedimentation coefficients
VII/92
segmental anisotropy
VII/747
solvent-nonsolvent tables
VII/500
specific refractive index increments
VII/553
spherulite growth rates
VI/304
thermal degradation
II/452 This page has been reformatted by Knovel to provide easier navigation.
VII/733
VII/748 VII/573
IX/38
Index terms
Links
Poly(alkenes): (Continued) theta solvents
VII/299
unperturbed dimensions of linear chains
VII/48
Poly(alkynes): optically active
VII/721
second virial coefficients
VII/165
Polyamide 6: heat capacity
VI/511
physical constants
V/121
Polyamide 12, physical constants
V/121
Polyamide 66: heat capacity
VI/512
physical constants
V/121
Polyamide 610, physical constants Polyamide 612, heat capacity
V/121 VI/512
Poly(amides): bulk crystallization rates
VI/379
crystallographic data
VI/33
diffusion coefficients
VI/559
fractionation systems
VII/411
frictional ratios
VII/137
glass transition temperature
VII/137
VI/235
heat, entropy, and volume change of solution
VII/661
Huggins constant
VII/279
interfacial tension with other polymers nomenclature
VI/539 VI/2
optically active
VII/726
partial specific volumes
VII/137
permeability coefficients
VI/559
physical constants
V/121
second virial coefficients
VII/191
sedimentation coefficients
VII/137
segmental anisotropy
VII/755
solubility coefficients
VI/559
solvent-nonsolvent tables
VII/518
specific refractive index increments
VII/600
spherulite growth rates
VI/331
surface properties
VI/530
thermal degradation
II/470
theta solvents
VII/316
unperturbed dimensions of linear chains
VII/63
viscosity-molecular weight relationship
VII/36
This page has been reformatted by Knovel to provide easier navigation.
VI/4
IX/39
Index terms
Links
Poly(amines), nomenclature
VI/4
Poly(amino acids): crystallographic data
VI/26
fractionation systems
VII/414
optically active
VII/729
radiation chemical yield
II/487
segmental anisotropy
VII/755
specific refractive index increments
VII/604
surface properties
VI/533
unperturbed dimensions of linear chains
VII/63
viscosity-molecular weight relationship
VII/38
Poly(anhydrides): glass transition temperature solvent-nonsolvent tables thermal degradation
VI/219
VI/244
VII/515
VII/527
II/468
Poly(anilines), glass transition temperature
VI/241
Poly(aromatics): crystallographic data
VI/15
radiation resistance
VI/587
Poly(aryl ether ether ketone), permeability, diffusion, and solubility coefficients
VI/561
Poly(benzimidazoles): glass transition temperature
VI/245
segmental anisotropy
VII/757
solvent-nonsolvent tables
VII/526
Poly(benzimides), solvent-nonsolvent tables Poly(benzothiazinophenothiazines), glass transition temperature
VII/524 VI/245
Poly(benzothiazoles): glass transition temperature
VI/245
solvent-nonsolvent tables
VII/524
Poly(benzoxazines), glass transition temperature
VI/245
Poly(benzoxazoles): glass transition temperature
VI/245
segmental anisotropy
VII/757
solvent-nonsolvent tables
VII/523
cis-1,4-Poly(butadiene), heat capacity
VI/486
trans-1,4-Poly(butadiene), heat capacity
VI/487
1,4-cis(96-98%)Poly(butadiene), physical constants
V/1
Poly(butadiene-co-acrylonitrile), physical constants
V/2
Poly(butadiene-co-styrene), physical constants
V/3
Poly(1-butene), heat capacity
VI/490
Poly(n-butyl acrylate), heat capacity
VI/502
This page has been reformatted by Knovel to provide easier navigation.
IX/40
Index terms
Links
Poly(n-butyl methacrylate), heat capacity
VI/506
Poly(carbazoles), optically active
VII/719
Poly(carbodiimides), solvent-nonsolvent tables
VII/521
Poly(carbonate)
V/161
Poly(carbonates): bulk crystallization rates
VI/372
diffusion coefficients
VI/555
dipole moments in solution
VII/641
fractionation systems
VII/404
frictional ratios
VII/134
glass transition temperature
VII/134
VI/219
partial specific volumes
VII/134
permeability coefficients
VI/555
second virial coefficients
VII/188
sedimentation coefficients
VII/134
solubility coefficients
VI/555
solvent-nonsolvent tables
VII/513
spherulite growth rates
VI/326
surface properties
VI/530
thermal degradation
II/468
unperturbed dimensions of lienar chains
VII/61
viscosity-molecular weight relationship
VII/34
Poly(carboranes), glass transition temperature Poly(chloroprene), physical constants
VI/245 V/3
Poly(chlorotrifluoroethylene): heat capacity
VI/497
physical constants
V/55
Poly(dibenzofurans), glass transition temperature
VI/246
Poly(dienes): bulk crystallization rates
VI/341
crystal growth rates
VI/291
crystallographic data
VI/22
diffusion coefficients
VI/553
dipole moments in solution
VII/644
fractionation systems
VII/333
frictional ratios
VII/94
glass transition temperature
VI/207
heat, entropy, and volume change of solution
VII/650
Huggins constant
VII/266
optically active
VII/720
partial specific volumes
VII/94
permeability coefficients
VI/553 This page has been reformatted by Knovel to provide easier navigation.
VII/94
VII/735
IX/41
Index terms
Links
Poly(dienes): (Continued) radiation chemical yield
II/482
second virial coefficients
VII/168
sedimentation coefficients
VII/94
segmental anisotropy
VII/746
solubility coefficients
VI/553
solvent-nonsolvent tables
VII/499
specific refractive index increments
VII/551
spherulite growth rates
VI/304
unperturbed dimensions of linear chains
VII/47
Poly(dioxoisoindolines), glass transition temperature
VI/246
Polydisperse high-molecular-weight polymeric mesophases
VI/280
Poly(disubstituted esters), solvent-nonsolvent tables
VII/502
Poly(dithiazoles), solvent-nonsolvent tables
VII/524
Poly(diynes), crystallographic data Poly(electrolytes), solvent-nonsolvent tables Polyenyne oligomers
VI/22 VII/533 IV/20
Poly(epichlorohydrin), permeability of esters through
VI/567
Poly(esters): bulk crystallization rates
VI/373
crystallographic data
VI/40
diffusion coefficients
VI/555
dipole moments in solution
VII/640
fractionation systems
VII/405
frictional ratios
VII/134
glass transition temperature
VII/134
VI/221
heat, entropy, and volume change of solution
VII/659
Huggins constant
VII/278
interfacial tension with other polymers nomenclature
VI/539 VI/2
optically active
VII/724
partial specific volumes
VII/134
permeability coefficients
VI/555
radiation chemical yield
II/488
second virial coefficients
VII/188
sedimentation coefficients
VII/134
segmental anisotropy
VII/752
solubility coefficients
VI/555
solvent-nonsolvent tables
VII/513
specific refractive index increments
VII/594
spherulite growth rates
VI/327
surface properties
VI/529 This page has been reformatted by Knovel to provide easier navigation.
VI/4
IX/42
Index terms
Links
Poly(esters): (Continued) thermal degradation
II/466
theta solvents
VII/315
unperturbed dimensions of linear chains
VII/61
viscosity-molecular weight relationship
VII/34
Poly(ether ketones), glass transition temperature
VI/226
Poly(ethers): crystallographic data
VI/51
diffusion coefficients
VII/134
dipole moments in solution
VII/638
frictional ratios
VII/134
interfacial tension with other polymers
VI/539
partial specific volumes
VII/134
second virial coefficients
VII/188
sedimentation coefficients
VII/134
surface properties
VI/528
theta solvents
VII/313
unperturbed dimensions of linear chains
VII/60
viscosity-molecular weight relationship
VII/32
Poly(ethyl acrylate), heat capacity
VI/502
Poly(ethylenes)
V/160
heat capacity
VI/486
permeability of various compounds through high-density
VI/564
permeability of various compounds through low-density
VI/562
permeability of various compounds through low-density, Irradiation crosslinked
VI/564
physical constants
V/9
Polyethylene terephthalate)
V/159
physical constants
V/113
Poly(ethylene terephthalate, 1,4-cyclohexane dimethanol)
V/159
Poly(ethylene-co-tetrafluoroethylene), physical constants
V/45
Poly(ethyl methacrylate), heat capacity
VI/505
Poly(fluoresceins), glass transition temperature
VI/247
Poly(furan tetracarboxylic acid diimides), glass transition temperature
VI/247
Poly(heterocyclics): unperturbed dimensions of linear chains
VII/64
viscosity-molecular weight relationship
VII/41
Poly(1-hexene), heat capacity
VI/491
Poly(hexyl methacrylate), heat capacity
VI/507
Poly(hydrazides), solvent-nonsolvent tables
VII/520
Polyhydric alcohols, solubility parameter
VII/701
This page has been reformatted by Knovel to provide easier navigation.
VI/488
IX/43
Index terms
Links
Poly(imides): crystallographic data
VI/15
diffusion coefficients
VI/559
glass transition temperature
VI/241
permeability coefficients
VI/559
segmental anisotropy
VII/756
solubility coefficients
VI/559
solvent-nonsolvent tables
VII/524
surface properties
VI/531
Poly(imines): fractionation systems
VII/411
glass transition temperature
VI/241
optically active
VII/728
surface properties
VI/531
viscosity-molecular weight relationship
VII/39
Poly(iminoadipoyl-iminododecamethylene) (Polyamide 612), heat capacity
VI/512
Poly(iminoadipoyl-iminohexamethylene) (Polyamide 66): heat capacity
VI/512
physical constants
V/121
Poly[imino(1-oxododecamethylene)] (Polyamide 12), heat capacity
VI/512
Poly[imino(1-oxohexamethylene)] (Polyamide 6): heat capacity
VI/511
physical constants
V/121
Poly(isobutene), heat capacity
VI/492
Poly(isobutene-co-isoprene), physical constants
V/4
Poly(isobutyl acrylate), heat capacity
VI/503
Poly(isobutyl methacrylate), heat capacity
VI/506
Poly(isocyanates): optically active
VII/728
specific refractive index increments
VII/600
Poly(isonitriles), optically active
VII/720
Poly(isoprene), physical constants
VII/738 VII/736
V/5
Poly(ketones): radiation chemical yield
II/488
thermal degradation
II/465
Poly(lacticacid)
V/160
Poly(maleimides), optically active
VII/722
Polymer abbreviations, see Abbreviations and acronyms Polymer characteristic groups, abbreviations and acronyms based on Polymer classes
VIII/17 I/111
Polymer degradation, see Thermal degradation This page has been reformatted by Knovel to provide easier navigation.
VII/736
IX/44
Index terms
Links
Polymerizability, heterocyclic ring compounds: 5-membered ring compounds
II/402
6-membered ring compounds
II/403
7-membered ring compounds
II/404
unsubstituted 5-, 6-, and 7-membered ring compounds
II/405
Polymerization, see also Addition polymerization; Condensation polymerization; Free radical copolymerization; Free radical polymerization equilibrium
II/347
nonlinear
II/348
photopolymerization
II/169
Polymer liquids, experimental T-P range
VI/596
Polymer miscibility, see Miscible polymers Polymer-solvent interaction parameter
VII/678
concentration dependence
VII/249
determination methods
VII/248
equations
VII/247
molecular weight dependence
V1I/250
selected polymer solutions
VII/250
temperature dependence
VII/249
Polymer trademark search
VIII/29
Poly(methacrylamides): glass transition temperature
VI/205
heat capacity
VI/508
solvent-nonsolvent tables
VII/503
Poly(methacrylic acid) and derivatives: diffusion coefficients
VI/548
dipole moments in solution
VII/644
fractionation systems
VII/346
glass transition temperature
VI/198
VI/201
heat capacity
VI/501
VI/504
Huggins constant
VII/268
interfacial tension with other polymers oligomers
VI/538 IV/24
optically active
VII/717
permeability coefficients
VII/734
VI/548
propagation/termination constants radiation chemical yield
II/82 II/484
segmental anisotropy
VII/748
solubility coefficients
VI/548
solvent-nonsolvent tables
VII/501
specific refractive index increments
VII/561
surface propertis
VI/527 This page has been reformatted by Knovel to provide easier navigation.
VII/749
IX/45
Index terms
Links
Poly(methacrylic acid) and derivatives: (Continued) thermal degradation
II/454
theta solvents
VII/308
cis-1,4-Poly(2-methylbutadiene), heat capacity Poly(methyl methacrylate)
VI/488 V/161
heat capacity
VI/504
physical constants
V/87
Poly(4-methyl-1-pentene), heat capacity
VI/492
Poly(a-methylstyrene), heat capacity
VI/500
Polymolecularity correction factors: defined
VII/217
diffusion coefficient-molecular weight relationship
VII/229
intrinsic viscosity-molecular weight relationship
VII/223
macromolecular dimension determination
VII/235
mean square radius of gyration-molecular weight relationship
VII/232
second virial coefficient-molecular weight relationship
VII/234
sedimentation coefficient-molecular weight relationship
VII/227
unperturbed macromolecule dimension determination
VII/240
Polymorphism
VI/287
Poly(nitriles): diffusion coefficients
VI/549
permeability coefficients
VI/549
radiation chemical yield
II/486
solubility coefficients
VI/549
Poly(nucleotides): diffusion coefficients
VII/157
frictional ratios
VII/157
partial specific volumes
VII/157
second virial coefficients
VII/196
sedimentation coefficients
VII/157
segmental anisotropy
VII/755
Polyolefin elastomers
V/161
Polyolefin plastomer
V/160
Poly(olefins)
V/160
crystallographic data
VI/6
nomenclature
VI/2
physical constants
V/164
radiation chemical yield
II/482
Poly(organosiloxanes)
V/161
See also Poly(siloxanes) Poly(oxabicyclononanes), glass transition temperature
This page has been reformatted by Knovel to provide easier navigation.
VI/247
IX/46
Index terms
Links
Poly(oxadiazoles): glass transition temperature
VI/248
solvent-nonsolvent tables
VII/523
Poly(oxadiazolidines), solvent-nonsolvent tables
VII/523
Poly(oxides): bulk crystallization rates
VI/365
crystal growth rates
VI/300
crystallographic data
VI/52
diffusion coefficients
VI/555
dipole moments in solution
VII/638
fractionation systems
VII/398
glass transition temperature
VI/226
heat, entropy, and volume change of solution
VII/659
Huggins constant
VII/277
nomenclature optically active permeability coefficients
VI/2
VI/4
VII/723
VII/737
VI/555
segmental anisotropy
VII/752
solubility coefficients
VI/555
solvent-nonsolvent tables
VII/511
specific refractive index increments
VII/594
spherulite growth rates
VI/315
thermal degradation
II/465
unperturbed dimensions of linear chains
VII/60
viscosity-molecular weight relationship
VII/32
Poly(oxindoles), glass transition temperature
VI/248
Poly(oxoisoindolines), glass transition temperature
VI/248
Poly(oxycarbonyloxy-1,4-phenylene-isopropylidine-1,4-phenylene), heat capacity
VI/518
Poly(oxy-2,6-dimethyl-1,4-phenylene), heat capacity
VI/517
Poly(oxy-2,6-diphenyl-1,4-phenylene), heat capacity
VI/517
Poly(oxyethylene), heat capacity
VI/514
Poly(oxyethylene-oxyterephthaloyl): heat capacity
VI/485
physical constants
V/113
Poly(oxymethylene)
V/161
heat capacity
VI/486
physical constants
V/97
Poly(oxymethylene-carbonyloxyethylene), heat capacity
VI/485
Poly(oxy-1-oxoethylene), heat capacity
VI/509
Poly(oxy-1-oxohexamethylene), heat capacity
VI/510
Poly(oxy-1,4-phenylene), heat capacity
VI/516
This page has been reformatted by Knovel to provide easier navigation.
VI/510
VI/513
IX/47
Index terms
Links
Poly(oxypropylene): heat capacity
VI/515
permeability of various compounds through chemically crosslinked
VI/565
Poly(oxyetramethylene), heat capacity
VI/515
Poly(oxytrimethylene), heat capacity
VI/514
Poly(1-pentene), heat capacity
VI/490
Polypeptides, see Poly(amino acids) Poly(phenylenes): fractionation systems
VII/397
glass transition temperature
VI/218
solvent-nonsolvent tables
VII/509
Poly(phosphates): unperturbed dimensions of linear chains
VII/64
viscosity-molecular weight relationship
VII/39
Poly(phosphazenes): bulk crystallization rates
VI/384
fractionation systems
VII/422
glass transition temperature
VI/242
segmental anisotropy
VII/755
solvent-nonsolvent tables
VII/522
Poly(phthalazines), glass transition temperature
VI/248
Poly(phthalides), glass transition temperature
VI/248
Poly(piperazines): glass transition temperature
VI/248
solvent-nonsolvent tables
VII/526
Poly(piperidines), glass transition temperature Poly(propylene)
VI/249 V/160
diffusion of various compounds through high-density
VI/564
heat capacity
VI/489
physical constants
V/21
Poly(pyrazinoquinoxalines), glass transition temperature
VI/249
Poly(pyrazoles), glass transition temperature
VI/249
Poly(pyridazines), glass transition temperature
VI/249
Poly(pyridines), glass transition temperature
VI/249
Poly(pyromellitimides): glass transition temperature
VI/249
segmental anisotropy
VII/756
solvent-nonsolvent tables
VII/525
Poly(pyrrolidines), glass transition temperature
VI/250
Poly(quinones), glass transition temperature
VI/250
This page has been reformatted by Knovel to provide easier navigation.
IX/48
Index terms
Links
Poly(quinoxalines): glass transition temperature
VI/250
segmental anisotropy
VII/757
solvent-nonsolvent tables
VII/526
Poly(saccharides): crystallographic data
VI/59
diffusion coefficients
VII/144
fractionation systems
VII/431
frictional ratios
VII/144
glass transition temperature
VI/243
Huggins constant
VII/282
partial specific volumes
VII/144
second virial coefficients
VII/194
sedimentation coefficients
VII/144
segmental anisotropy
VII/758
solvent-nonsolvent tables
VII/531
specific refractive index increments
VII/611
theta solvents
VII/316
unperturbed dimensions of linear chains
VII/66
viscosity-molecular weight relationship
VII/43
Poly(silanes): fractionation systems
VII/418
glass transition temperature
VI/243
solvent-nonsolvent tables
VII/522
specific refractive index increments
VII/606
Poly(silazanes): glass transition temperature
VI/243
solvent-nonsolvent tables
VII/522
specific refractive index increments
VII/606
Poly(silmethylenes), unperturbed dimensions of linear chains
VII/64
Poly(siloxanes): bulk crystallization rates
VI/384
diffusion coefficients
VI/558
fractionation systems
VII/418
glass transition temperature
VI/231
heat, entropy, and volume change of solution
VII/661
interfacial tension with other polymers
VI/539
permeability coefficients
VI/558
radiation chemical yield
II/487
segmental anisotropy
VII/756
solubility coefficients
VI/558
solvent-nonsolvent tables
VII/515 This page has been reformatted by Knovel to provide easier navigation.
IX/49
Index terms
Links
Poly(siloxanes): (Continued) spherulite growth rates
VI/334
surface properties
VI/531
thermal degradation
II/471
unperturbed dimensions of linear chains
VII/64
viscosity-molecular weight relationship
VII/40
Poly(silsesquioxanes): unperturbed dimensions of linear chains
VII/64
viscosity-molecular weight relationship
VII/40
Poly(styrene)
V/160
diffusion coefficients
VI/547
fractionation systems
VII/356
frictional ratios
VII/109
glass transition temperature
VII/109
VI/209
heat, entropy, and volume change of solution
VII/655
heat capacity
VI/485
interfacial tension with other polymers
VI/537
optically active
VII/719
partial specific volumes
VII/109
permeability coefficients
VI/547
physical constants
V/91
propagation/termination constants
II/88
radiation chemical yield
VI/499 VII/735
V/166
II/485
second virial coefficients
VII/179
sedimentation coefficients
VII/109
solubility coefficients
VI/547
solvent-nonsolvent tables
VII/507
specific refractive index increments
VII/574
surface properties
VI/525
thermal degradation
II/461
theta solvents
VII/300
unperturbed dimensions of linear chains
VII/54
Poly(sulfides): crystallographic data
VI/57
dipole moments in solution
VII/639
fractionation systems
VII/416
glass transition temperature
VI/233
nomenclature
VI/4
optically active
VII/725
solvent-nonsolvent tables
VII/516
thermal degradation
II/468
unperturbed dimensions of linear chains
VII/63
This page has been reformatted by Knovel to provide easier navigation.
VII/737
IX/50
Index terms
Links
Poly(sulfides): (Continued) viscosity-molecular weight relationship
VII/39
Poly(sulfonamides): fractionation systems
VII/416
glass transition temperature
VI/234
Poly(sulfonates): glass transition temperature
VI/233
solvent-nonsolvent tables
VII/515
Poly(sulfones): crystallographic data
VI/57
diffusion coefficients
VI/560
fractionation systems
VII/416
glass transition temperature
VI/234
permeability coefficients
VI/560
radiation chemical yield
II/488
solubility coefficients
VI/560
solvent-nonsolvent tables
VII/517
specific refractive index increments
VII/599
surface properties
VI/530
thermal degradation
II/468
Poly(tetrafluoroethylene)
V/160
heat capacity
VI/493
physical constants
V/31
Poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP), physical constants
V/41
Poly[tetrafluoroethylene-co-perfluoro(alkoxy vinyl ether)] (PFA), physical constants
V/41
Poly(thioesters): glass transition temperature
VI/235
optically active
VII/725
Poly(thioethers), dipole moments in solution
VII/639
Poly(thiophenes), solvent-nonsolvent tables
VII/527
Poly(triazines), glass transition temperature
VI/252
Poly(triazoles), glass transition temperature
VI/252
Poly(trifluoroethylene), heat capacity
VI/495
Poly(ureas): crystallographic data
VI/49
diffusion coefficients
VII/137
fractionation systems
VII/410
frictional ratios
VII/137
glass transition temperature
VI/242
optically active
VII/725
partial specific volumes
VII/137
second virial coefficients
VII/191 This page has been reformatted by Knovel to provide easier navigation.
IX/51
Index terms
Links
Poly(ureas): (Continued) sedimentation coefficients
VII/137
solvent-nonsolvent tables
VII/521
theta solvents
VII/316
viscosity-molecular weight relationship Poly(urethane) elastomers
VII/39 V/161
Poly(urethanes): bulk crystallization rates
VI/383
crystallographic data
VI/49
diffusion coefficients
Vl/560
fractionation systems
VII/410
frictional ratios
VII/137
glass transition temperature
VI/229
nomenclature
VI/4
optically active
VII/725
partial specific volumes
VII/137
permeability coefficients
VI/560
second virial coefficients
VII/191
sedimentation coefficients
VII/137
solubility coefficients
VI/560
solvent-nonsolvent tables
VII/515
specific refractive index increments
VII/600
surface properties
VI/531
thermal degradation
II/471
theta solvents
VII/316
unperturbed dimensions of linear chains
VII/63
viscosity-molecular weight relationship
VII/39
Poly(vinyl acetate): heat capacity
VI/498
physical constants
V/77
Poly(vinyl alcohol): fractionation systems
VII/353
glass transition temperature
VI/212
heat capacity
VI/498
solvent-nonsolvent tables
VII/504
unperturbed dimensions of linear chains Poly(vinyl benzoate), heat capacity Poly(vinyl chloride)
VII/53 VI/500 V/159
heat capacity
VI/496
physical constants
V/67
Poly(vinyl esters): fractionation systems
VII/355 This page has been reformatted by Knovel to provide easier navigation.
VII/137
IX/52
Index terms
Links
Poly(vinyl esters): (Continued) glass transition temperature
VI/213
optically active
VII/718
solvent-nonsolvent tables
VII/506
surface properties
VI/526
unperturbed dimensions of linear chains
VII/53
Poly(vinyl ethers): fractionation systems
VII/353
glass transition temperature
VI/214
optically active
VII/718
solvent-nonsolvent tables
VII/503
thermal degradation
II/461
unperturbed dimensions of linear chains
VII/53
Poly(vinyl fluoride), heat capacity
VII/735
VI/494
Poly(vinyl halides): glass transition temperature
VI/215
solvent-nonsolvent tables
VII/505
unperturbed dimensions of linear chains Poly(vinylidene chloride), heat capacity
VII/53 VI/496
Poly(vinylidene fluoride): heat capacity
VI/494
physical constants
V/48
Poly(vinylidenes): crystallographic data
VI/13
heat capacity
VI/494
physical constants
VI/496
V/48
Poly(vinyl ketones): fractionation systems
VII/353
glass transition temperature
VI/212
optically active
VII/718
solvent-nonsolvent tables
VII/504
thermal degradation
II/461
Poly(vinyl nitriles): fractionation systems
VII/353
glass transition temperature
VI/215
solvent-nonsolvent tables
VII/506
Poly(vinyls): bulk crystallization rates
VI/341
crystal growth rates
VI/291
crystallographic data
VI/13
diffusion coefficients
VI/549
dipole moments in solution
VII/642 This page has been reformatted by Knovel to provide easier navigation.
VII/105
IX/53
Index terms
Links
Poly(vinyls): (Continued) frictional ratios
VII/105
heat, entropy, and volume change of solution
VII/655
Huggins constant
VII/272
interfacial tension with other polymers nomenclature
VI/37 VI/2
partial specific volumes
VII/105
permeability coefficients
VI/549
radiation chemical yield
II/486
second virial coefficients
VII/177
sedimentation coefficients
VII/105
segmental anisotrophy
VII/750
solubility coefficients
VI/549
spherulite growth rates
VI/304
surface properties
VI/526
thermal degradation
II/459
theta solvents
VII/305
Poly(vinyl thioethers), glass transition temperature
VI/214
Poly(xylylenes), permeability, diffusion, and solubility coefficients
VI/555
Power: conversion factors
I/16
SI units
I/13
Precipitation chromatography
VII/330
Pressure: conversion factors
I/15
and glass transition temperature
VI/197
SI units
I/13
Pressure-induced crystallization
VI/288
Propagation activation energy
II/415
acrylic derivatives
II/417
dienes
II/416
methacrylic derivatives
II/418
miscellaneous compounds
II/423
olefins
II/416
styrene derivatives
II/421
vinyl esters
II/421
vinyl ethers
II/421
vinyl halogens
II/420
vinyl heteroaromatics
II/422
Propagation constants
II/77
acrylic derivatives
II/80
aldehydes
II/90 This page has been reformatted by Knovel to provide easier navigation.
IX/54
Index terms
Links
Propagation constants (Continued) dienes
II/79
fumaric derivatives
II/87
itaconic derivatives
II/85
methacrylic derivatives
II/82
miscellaneous compounds
II/90
olefins
II/79
styrene derivatives
II/88
vinyl esters
II/87
vinyl ethers
II/88
vinyl halides
II/87
vinyl heteroaromatics
II/90
Propene monomers, physical properties
III/32
Proteins: diffusion coefficients
VII/157
fibers
VIII/22
frictional ratios
VII/157
partial specific volumes
VII/157
second virial coefficients
VII/196
sedimentation coefficients
VII/157
Pulse laser polymerization (PLP) method PVT relationship
II/78 VI/591
See also Equations of state miscellaneous polymers
VI/597
polymer liquids
VI/596
and second virial coefficients
VII/164
zero pressure volume and bulk modulus
VI/593
VI/595
II/309
II/321
Q Q-e scheme Quasi-lattice models
VI/593
Quasi-single-strand coordination polymer nomenclature Quenching rate constants, photopolymerization
I/7 II/170
Q values: monomers
II/310
monomers by Q values
II/314
pressure effects
II/440
telogens
II/314
R Radial spherulite growth rates: miscellaneous polymers
VI/336 This page has been reformatted by Knovel to provide easier navigation.
II/177
IX/55
Index terms
Links
Radial spherulite growth rates: (Continued) poly(alkenes)
VI/304
poly(amides)
VI/331
poly(carbonates)
VI/326
poly(dienes)
VI/304
poly(esters)
VI/327
poly(oxides)
VI/315
poly(siloxanes)
VI/334
poly(vinyls)
VI/304
Radiation chemical yield
II/481
blends
II/493
cellulose and derivatives
II/487
composites
II/493
copolymers
II/490
fluoropolymers
II/488
poly(acrylamides)
II/486
poly(acrylates)
II/483
poly(amino acids)
II/487
poly(dienes)
II/482
poly(esters)
II/488
poly(ketones)
II/488
poly(methacrylates)
II/484
poly(nitriles)
II/486
poly(olefins)
II/482
poly(siloxanes)
II/487
poly(styrenes)
II/485
poly(sulfones)
II/488
poly(vinyls)
II/486
vinyl monomers
II/486
Radiation resistance
VI/583
composites
VI/588
elastomers
VI/586
poly(aromatics)
VI/587
thermoplastics
VI/585
Random copolymers, fractionation systems
VII/366
Rayleigh scattering
VII/629
Reactivity pattern scheme
II/321
monomer parameters
II/323
transfer agent parameters
II/326
transfer constant prediction
II/322
Reactivity ratios
II/182
Quick Basic program for calculating This page has been reformatted by Knovel to provide easier navigation.
II/288
VII/425
IX/56
Index terms
Links
Reactivity ratios (Continued) terpolymerization
II/438
Refractive index
VI/571
See also Specific refractive index increments and cohesive energy density
VII/680
heterogeneous polymers
VI/572
isorefractive and isopycnic solvent pairs molar refraction
III/43 VI/571
monomers, see Monomer physical constants optical anisotropy
VI/572
polymers in alphabetical order
VI/578
polymers in order of increasing index
VI/574
polymer solvents
III/55
Refractometric calibration data
VII/550
Regenerated polysaccharide fibers
VIII/23
Regenerated protein fibers
VIII/23
Regular polymer nomenclature
I/3
Reinforced polymers, see Composites Reinforcing fillers, ISO codes for
VIII/20
Reptation
VI/286
Reverse-phase liquid chromatography
VII/330
Rigid poly(vinyl chloride)
V/159
Rubber-modified styrene-acrylonitrile copolymers
V/160
Rubbery polymers
VI/194
physical constants
V/1
S Sanchez-Cho equation of state
VI/592
characteristic parameters
VI/597
Sanchez-Lacombe equation of state, characteristic parameters
VI/600
Santoprene TM, permeability of alkanes through
VI/566
Scattering factors
VII/629
Scattering methods, solutions
VII/163
Schulz-Blaschke constant: defined
VII/265
selected polymers
VII/284
Screw dislocations
VI/281
Second-order Markov mechanism metallocene-catalyzed copolymerization Second virial coefficient-molecular weight relationship
This page has been reformatted by Knovel to provide easier navigation.
II/445 II/330 VII/234
VI/593
IX/57
Index terms
Links
Second virial coefficients: averages
VII/164
factors affecting
VII/164
inorganic polymers
VII/192
poly(acrylics)
VII/170
poly(alkenes)
VII/165
poly(alkynes)
VII/165
poly(amides)
VII/191
poly(carbonates)
VII/188
poly(dienes)
VII/168
poly(esters)
VII/188
poly(ethers)
VII/188
poly(nucleotides)
VII/196
poly(saccharides)
VII/194
poly(styrenes)
VII/179
poly(ureas)
VII/191
poly(urethanes)
VII/191
poly(vinyls)
VII/177
proteins
VII/196
theory
VII/163
for theta solvent determination
VII/293
Sedimentation coefficient: inorganic polymers
VII/141
molar mass averages determined from
VII/89
poly(acrylics)
VII/96
poly(alkenes)
VII/92
poly(amides)
VII/137
poly(carbonates)
VII/134
poly(dienes)
VII/165
poly(esters)
VII/134
poly(ethers)
VII/134
poly(nucleotides)
VII/157
poly(saccharides)
VII/144
poly(styrenes)
VII/109
poly(ureas)
VII/137
poly(urethanes)
VII/137
poly(vinyls)
VII/105
proteins
VII/157
theory
VII/86
Sedimentation coefficient-molecular weight relationship
VII/227
Sedimentation equilibrium
VII/164
fractionation application
VII/333 This page has been reformatted by Knovel to provide easier navigation.
IX/58
Index terms
Links
Sedimentation fractionation
VII/333
Sedimentation velocity
VII/163
fractionation application
VII/333
Segmental anisotropy: copolymers
VII/751
defined
VII/745
main-chain acyclic heteroatom polymers
VII/752
main-chain acyclic polymers
VII/746
main-chain carbocyclic polymers
VII/752
main-chain heterocyclic polymers
VII/756
poly(acrylic acids)
VII/747
poly(alkenes)
VII/747
poly(amides)
VII/755
poly(benzimidazoles)
VII/757
poly(benzoxazoles)
VII/757
poly(dienes)
VII/746
poly(esters)
VII/752
poly(imides)
VII/756
poly(methacrylic acids)
VII/748
poly(nucleotides)
VII/755
poly(oxides)
VII/752
poly(peptides)
VII/755
poly(phosphazenes)
VII/755
poly(pyromellitimides)
VII/756
poly(quinoxalines)
VII/757
poly(saccharides)
VII/758
poly(siloxanes)
VII/756
poly(vinyls)
VII/750
Semiempirical 3-parameter equations of state
VI/593
Silicone polymers
V/161
Silicone surfaces
VI/524
Silicon-oxygen chains, theta solvents
VII/317
Silicon polymers, dipole moments in solution
VII/645
Siloxane copolymers, unperturbed dimensions of linear chains
VII/65
Simha-Somcynsky equation of state
VI/594
characteristic parameters
VI/599
Simple cell model equation of state characteristic parameters
VI/593 VI/598
Single-strand inorganic and coordination polymer nomenclature
I/6
Single-strand organic polymer nomenclature
I/3
SI units
I/13
prefixes
I/14 This page has been reformatted by Knovel to provide easier navigation.
VII/748
VII/749
IX/59
Index terms
Links
Solid-state multiphase systems
VI/280
Solubility coefficient: alkanes through Santoprene TM
VI/566
cellulose and derivatives
VI/561
esters through poly(epichlorohydrin)
VI/567
fluorinated polymers
VI/552
poly(alkanes)
VI/545
poly(amides)
VI/559
poly(aryl ether ether ketone)
VI/561
poly(carbonates)
VI/555
poly(dienes)
VI/553
poly(esters)
VI/555
poly(imides)
VI/559
poly(methacrylates)
VI/548
poly(nitriles)
VI/549
poly(oxides)
VI/555
poly(siloxanes)
VI/558
poly(styrenes)
VI/547
poly(sulfones)
VI/560
poly(urethanes)
VI/560
poly(vinyls)
VI/549
poly(xylylenes)
VI/555
Solubility fractionation
VII/328
Solubility parameter: acid anhydrides
VII/700
acid halides
VII/700
acids
VII/701
alcohols
VII/700
aldehydes
VII/699
aromatic hydrocarbons
VII/698
esters
VII/699
ethers
VII/699
group contributions
VII/686
halohydrocarbons
VII/698
ketones
VII/699
main-chain C-N polymers
VII/709
main-chain C-O polymers
VII/708
main-chain polymers
VII/702
nitrogen-containing compounds
VII/700
paraffinic hydrocarbons
VII/698
phenols
VII/701
polyhydric alcohols
VII/701 This page has been reformatted by Knovel to provide easier navigation.
IX/60
Index terms
Links
Solubility parameter: (Continued) solvents in alphabetical order
VII/688
solvents in increasing order
VII/694
sulfur-containing compounds
VII/700
water
VII/701
Solvent-induced crystallization
VI/288
Solvent-nonsolvent tables
VII/498
block copolymers
VII/533
cellulose and derivatives
VII/529
cellulose esters
VII/530
cellulose ethers
VII/529
cellulose nitrate
VII/531
cellulose sulfate
VII/531
dendrimers
VII/534
formaldehyde resins
VII/523
gutta percha
VII/529
inorganic polymers
VII/532
main-chain acyclic heteroatom polymers
VII/511
main-chain acyclic polymers
VII/499
main-chain carbocyclic polymers
VII/509
main-chain carbonyl polymers
VII/510
main-chain heterocyclic polymers
VII/523
natural polymers
VII/528
natural resins
VII/532
natural rubber
VII/528
poly(acetals)
VII/504
poly(acetylenes)
VII/499
poly(acrylamides)
VII/503
poly(acrylates)
VII/501
poly(acrylic acids)
VII/501
poly(acrylics)
VII/501
poly(alkenes)
VII/500
poly(amides)
VII/518
poly(anhydrides)
VII/515
poly(benzimidazoles)
VII/526
poly(benzimides)
VII/524
poly(benzothiazoles)
VII/524
polybenzoxazoles)
VII/523
poly(carbodiimides)
VII/521
poly(carbonates)
VII/513
poly(dienes)
VII/499
poly(disubstituted esters)
VII/502 This page has been reformatted by Knovel to provide easier navigation.
VII/527
IX/61
Index terms
Links
Solvent-nonsolvent tables (Continued) poly(dithiazoles)
VII/524
poly(electrolytes)
VII/533
poly(esters)
VII/513
poly(hydrazides)
VII/520
poly(imides)
VII/524
poly(methacrylamides)
VII/503
poly(methacrylates)
VII/501
poly(methacrylics)
VII/501
poly(oxadiazoles)
VII/523
poly(oxadiazolidines)
VII/523
poly(oxides)
VII/511
poly(phenylenes)
VII/509
poly(phosphazenes)
VII/522
poly(piperazines)
VII/526
poly(pyromellitimides)
VII/525
poly(quinoxalines)
VII/526
poly(saccharides)
VII/531
poly(silanes)
VII/522
poly(silazanes)
VII/522
poly(siloxanes)
VII/515
poly(styrenes)
VII/507
poly(sulfides)
VII/516
poly(sulfonates)
VII/515
poly(sulfones)
VII/517
poly(thiophenes)
VII/527
poly(ureas)
VII/521
poly(urethanes)
VII/515
poly(vinyl alcohol)
VII/504
poly(vinyl esters)
VII/506
poly(vinyl ethers)
VII/503
poly(vinyl halides)
VII/505
poly(vinyl ketones)
VII/504
poly(vinyl nitriles)
VII/506
starches
VII/531
Solvent pairs, Isorefractive and isopycnic
III/43
Solvents, see also Miscibility; Solubility parameter and free radical initiator decomposition
II/1
isorefractive and isopycnic solvent pairs
III/43
physical constants of most common for polymers
III/59
refractive index of common
III/55
transfer constants to
II/110 This page has been reformatted by Knovel to provide easier navigation.
IX/62
Index terms
Links
Source-based nomenclature
I/2
VI/2
Space groups: poly(amides)
VI/33
poly(aromatics)
VI/15
poly(dienes)
VI/22
poly(diynes)
VI/22
poly(esters)
VI/40
poly(ethers)
VI/51
poly(imides)
VI/15
poly(olefins)
VI/6
poly(oxides)
VI/52
poly(peptides)
VI/26
poly(saccharides)
VI/59
poly(sulfides)
VI/57
poly(sulfones)
VI/57
poly(ureas)
VI/49
poly(urethanes)
VI/49
poly(vinylidenes)
VI/13
poly(vinyls)
VI/13
Specific heat: conversion factors
I/16
and glass transition temperature
VI/194
SI units
I/13
Specific refractive index increments
VII/547
cellulose and derivatives
VII/609
main-chain acyclic heteroatom polymers
VII/594
main-chain acyclic polymers
VII/551
main-chain carbocyclic polymers
VII/594
main-chain heterocyclic polymers
VII/608
poly(acrylic acids)
VII/557
poly(alkenes)
VII/553
poly(amides)
VII/600
poly(amino acids)
VII/604
poly(dienes)
VII/551
poly(esters)
VII/594
poly(isocyanates)
VII/600
poly(methacrylic acids)
VII/561
poly(oxides)
VII/594
poly(saccharides)
VII/611
poly(silanes)
VII/606
poly(silazanes)
VII/606
poly(styrenes)
VII/574 This page has been reformatted by Knovel to provide easier navigation.
VII/573
IX/63
Index terms
Links
Specific refractive index increments (Continued) poly(sulfones)
VII/599
poly(urethanes)
VII/600
Specific volume-temperature curves
VI/194
Spherulite growth rates
VI/284
miscellaneous polymers
VI/336
poly(alkenes)
VI/304
poly(amides)
VI/331
poly(carbonates)
VI/326
poly(dienes)
VI/304
poly(esters)
VI/327
poly(oxides)
VI/315
poly(siloxanes)
VI/334
poly(vinyls)
VI/304
Spherulites
VI/280
SPI codes, for plastics recycling
VIII/21
Standard number block, ISO codes
VIII/19
Starches, solvent-nonsolvent tables
VII/531
Statistically associated fluid theory
VI/595
Stockmayer molecular weight distribution
II/354
Stress: conversion factors
I/15
SI units
I/13
Structural repeating units
I/10
CAS Registry Number indexing by Structure-based nomenclature
VIII/25 I/3
Styrene-acrylonitrile copolymers
V/160
rubber-modified
V/160
Styrene copolymers: dipole moments in solution
VII/645
radiation chemical yield
II/490
Styrene monomers: physical properties
III/34
propagation/termination activation energy
II/421
Styrene oligomers
IV/30
Styrene polymers, see Poly(styrene) Sugars, see Poly(saccharides) Sulfone copolymers: unperturbed dimensions of linear chains
VII/65
viscosity-molecular weight relationship
VII/42
Sulfur, surface properties
VI/534 This page has been reformatted by Knovel to provide easier navigation.
VI/3
IX/64
Index terms
Links
Sulfur compounds: solubility parameter
VII/700
transfer constants to
II/150
Sulfur dioxide copolymers, radiation chemical yield
II/490
Summative precipitation
VII/328
Surface exclusion chromatography
VII/331
Surface tension
VI/521
See also Interfacial tension cellulose and derivatives
VI/533
and cohesive energy density
VII/680
conversion factors
I/16
epoxy resins
VI/530
halogenated hydrocarbon polymers
VI/525
hydrocarbon polymers
VI/524
methacrylic hydrogels
VI/527
miscellaneous polymers
VI/533
organosilanes
VI/532
phenoxy resins
VI/530
poly(acrylics)
VI/526
poly(amides)
VI/530
poly(carbonates)
VI/530
poly(esters)
VI/529
poly(ethers)
VI/528
poly(imides)
VI/531
poly(imines)
VI/531
poly(methacrylics)
VI/527
poly(peptides)
VI/533
poly(siloxanes)
VI/531
poly(styrenes)
VI/525
poly(sulfones)
VI/530
poly(urethanes)
VI/531
poly(vinyl esters)
VI/526
poly(vinyls)
VI/526
SI units
I/13
and surface chemical constitution Syndiotactic polymers
VI/524 VI/6
Syndiotactic poly(styrene)
V/160
Synonyms
VIII/25
common polymers
VIII/32
Synthetic fibers
VIII/24
Systematic polymer names
I/8
This page has been reformatted by Knovel to provide easier navigation.
IX/65
Index terms
Links
T Tacticity
II/445
Tait equation
VI/593
Telogens, Q and e values
II/314
Temperature: and polymer-solvent interaction parameter and radiation resistance
VII/249 VI/584
SI units
I/13
and solubility parameter
VII/677
and surface tension
VI/522
Temperature-rising elution fractionation Termination activation energy
VII/329 II/415
acrylic derivatives
II/417
dienes
II/416
methacrylic derivatives
II/418
miscellaneous compounds
II/423
olefins
II/416
styrene derivatives
II/421
vinyl esters
II/421
vinyl ethers
II/421
vinyl halogens
II/420
vinyl heteroaromatics
II/422
Termination constants
II/77
acrylic derivatives
II/80
aldehydes
II/90
dienes
II/79
fumaric derivatives
II/87
itaconic derivatives
II/85
methacrylic derivatives
II/82
olefins
II/79
styrene derivatives
II/88
vinyl esters
II/87
vinyl ethers
II/88
vinyl halides
II/87
vinyl heteroaromatics
II/90
Terpolymerization reactivity ratios
II/438
Textile fibers: abbreviations and acronyms
VIII/22
acrylic fibers
V/61
Tg, see Glass transition temperature Thermal conductivity: conversion factors
I/16 This page has been reformatted by Knovel to provide easier navigation.
IX/66
Index terms
Links
Thermal conductivity: (Continued) SI units
I/13
Thermal degradation
II/451
cellulose and derivatives
II/475
with crosslinking
II/350
main-chain acyclic carbon polymers
II/451
main-chain carbocyclic polymers
II/464
main-chain heteroatom polymers
II/464
main-chain heterocyclic polymers
II/473
Thermal diffusion fractionation
VII/333
Thermal history, and glass transition temperature
VI/197
Thermodynamic perturbation theory
VI/595
Thermodynamics: and cohesive energy density
VII/679
crystallization
VI/284
glass transition temperature
VI/195
theta solvents
VII/291
Thermoplastics
V/159
ISO codes for
VIII/19
physical constants
V/162
radiation resistance
VI/585
Thermotropic phases
VI/280
Theta solvents: carbon-sulfur chains
VII/317
defined
VII/291
determination methods
VII/293
phosphorus-oxygen chains
VII/318
poly(acetals)
VII/313
poly(acrylics)
VII/307
poly(alkanes)
VII/295
poly(alkenes)
VII/299
poly(amides)
VII/316
poly(esters)
VII/315
poly(ethers)
VII/313
poly(methacrylics)
VII/308
poly(saccharides)
VII/316
poly(styrenes)
VII/300
poly(ureas)
VII/316
poly(urethanes)
VII/316
poly(vinyls)
VII/305
silicon-oxygen chains
VII/317
unperturbed dimensions of linear chains
VII/292
This page has been reformatted by Knovel to provide easier navigation.
VII/294
IX/67
Index terms
Links
Theta state
VII/291
Thiacyclophanes
IV/63
Thin layer chromatography
VII/330
Thioxanthones, excitation transfer rate constants 3-Parameter equations of state
II/178 VI/593
Time, SI units
I/13
Tm, see Melting point; Melting temperature Trademark search
VIII/29
Trade names
VIII/25
Transfer agents
II/97
reactivity pattern parameters
II/326
Transfer constants: to catalysts and initiators
II/106
to monomers
II/98
to polymers
II/103
prediction by reactivity patterns
II/322
to solvents and additives
II/110
to sulfur compounds
II/150
Trigonal selenium, heat capacity
VI/519
Triplet state lifetimes, of photosensitizers Turbidimetric titration
II/170 VII/328
U Ultrafiltration fractionation
VII/333
Ultra-low density poly(ethylene)
V/160
Unit cell parameters: poly(amides)
VI/33
poly(aromatics)
VI/15
poly(dienes)
VI/22
poly(diynes)
VI/22
poly(esters)
VI/40
poly(ethers)
VI/51
poly(imides)
VI/15
poly(olefins)
VI/6
poly(oxides)
VI/52
poly(peptides)
VI/26
poly(saccharides)
VI/59
poly(sulfides)
VI/57
poly(sulfones)
VI/57
poly(ureas)
VI/49
poly(urethanes)
VI/49
This page has been reformatted by Knovel to provide easier navigation.
II/179
IX/68
Index terms
Links
Unit cell parameters: (Continued) poly(vinylidenes)
VI/13
poly(vinyls)
VI/13
Units
I/13
English-American unit conversions Unperturbed dimensions, linear chain molecules
I/17 VII/4
cellulose and derivatives
VII/66
copolymers
VII/58
poly(acetylenes)
VII/48
poly(acrylic acids)
VII/49
poly(alkenes)
VII/48
poly(amides)
VII/63
poly(amino acids)
VII/63
poly(carbonates)
VII/61
poly(dienes)
VII/47
poly(esters)
VII/61
poly(ethers)
VII/60
poly(heterocyclics)
VII/64
polymolecularity correction factors
VII/240
poly(oxides)
VII/60
poly(phosphates)
VII/64
poly(saccharides)
VII/66
poly(silmethylenes)
VII/64
poly(siloxanes)
VII/64
poly(silsesquioxanes)
VII/64
poly(styrenes)
VII/54
poly(sulfides)
VII/63
poly(urethanes)
VII/63
poly(vinyl alcohol)
VII/53
poly(vinyl esters)
VII/53
poly(vinyl ethers)
VII/53
poly(vinyl halides)
VII/53
theta solvents
VII/292
UV curing technologies
II/169
V Very low density poly(ethylene)
V/160
Vinyl ester monomers: propagation/termination activation energy propagation/termination constants
II/421 II/87
Vinyl ether monomers: propagation/termination activation energy This page has been reformatted by Knovel to provide easier navigation.
VII/65
II/421
VII/294
IX/69
Index terms
Links
Vinyl ether monomers: (Continued) propagation/termination constants
II/88
Vinyl halide monomers: propagation activation energy
II/420
propagation/termination constants
II/87
Vinyl heteroaromatic monomers: propagation/termination activation energy propagation/termination constants Vinylidene chloride copolymers
II/422 II/90 V/160
Vinyl monomers: copolymerization
II/181
copolymerization reactivity ratios
II/181
pattern of reactivity parameters
II/32
physical properties aryl monomers
III/36
ester monomers
III/36
ether monomers
III/38
N-substituted monomers
III/38
sulfonate monomers
III/40
propagation/termination activation energies
II/420
propagation/termination constants
II/87
Q and e values
II/309
radiation chemical yield
II/486
Vinyl oligomers
IV/27
β-alkyl substituted
IV/26
Vinyl polymers, see Poly(vinyls) Viscosity: conversion factors
I/15
dilute solutions, Huggins and Schulz-Blaschke constants and glass transition temperature
VII/265 VI/194
polymer solvents
III/59
SI units
I/13
Viscosity-molecular weight relationship
VII/2
cellulose and derivatives
VII/43
copolymers
VII/27
main-chain acyclic carbon polymers
VII/5
main-chain carbocyclic polymers
VII/31
main-chain heteroatom polymers
VII/32
molecular weight distribution and viscosity constant
VII/5
poly(acetylenes)
VII/7
poly(acrylic acids)
VII/10 This page has been reformatted by Knovel to provide easier navigation.
VII/42
IX/70
Index terms
Links
Viscosity-molecular weight relationship (Continued) poly(alkenes)
VII/7
poly(amides)
VII/36
poly(amino acids)
VII/38
poly(carbonates)
VII/34
poly(dienes)
VII/5
poly(esters)
VII/34
poly(ethers)
VII/32
poly(heterocyclics)
VII/41
poly(imines)
VII/39
polymolecularity correction factors
VII/223
poly(oxides)
VII/32
poly(phosphates)
VII/39
poly(saccharides)
VII/43
poly(siloxanes)
VII/40
poly(silsesquixanes)
VII/40
poly(styrenes)
VII/17
poly(sulfides)
VII/39
poly(ureas)
VII/39
poly(urethanes)
VII/39
poly(vinyl alcohol)
VII/17
poly(vinyl esters)
VII/17
poly(vinyl ethers)
VII/17
poly(vinyl halides)
VII/17
Volume: conversion factors
I/14
SI units
I/13
Volume change of solution
VII/650
cellulose and derivatives
VII/662
main-chain acyclic heteroatom polymers
VII/659
main-chain acyclic polymers
VII/650
poly(acrylics)
VII/654
poly(alkenes)
VII/651
poly(amides)
VII/661
poly(dienes)
VII/650
poly(esters)
VII/659
poly(oxides)
VII/659
poly(siloxanes)
VII/661
poly(styrenes)
VII/655
poly(vinyls)
VII/655
Volumetric thermal expansion coefficient
This page has been reformatted by Knovel to provide easier navigation.
VI/194
IX/71
Index terms
Links
W Water, solubility parameter
VII/701
Work, SI units
I/13
Z Zero pressure bulk modulus
VI/593
VI/595
Zero pressure volume
VI/593
VI/595
Ziegler-Natta catalysis
II/329
Zone melting fractionation
VII/333
This page has been reformatted by Knovel to provide easier navigation.