polymer_handbook.pdf

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


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 .........


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


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


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


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


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


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


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) .............................................................................................


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


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 ................................................................................................


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


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.


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


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


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


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


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


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


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) ....................................................................................


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


3.2 Blends ............................................................................................... VI/312 Table 4. Poly(oxides) ............................................................................................ VI/315 4.1


4.2

Complexes ....................................................................................... VI/318

4.3

Blends ............................................................................................... VI/319


xxx

Contents Table 5. Poly(carbonates) ..................................................................................... VI/326 Table 6. Poly(esters) ............................................................................................. VI/327 6.1


6.2

Blends ............................................................................................... VI/329

6.3 Copolymers ...................................................................................... VI/331 Table 7. Poly(amides) ........................................................................................... VI/331 Table 8. Poly(siloxanes) ....................................................................................... VI/334 8.1


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 ..........................................


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) ......................................................................................


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


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) .............................................................................................


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) .........................................................


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


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


xl

Contents Table 35 Table 36 Table 37 Table 38 Table 39 Table 40 Table 41

.................................................................................................................................. .................................................................................................................................. .................................................................................................................................. .................................................................................................................................. .................................................................................................................................. .................................................................................................................................. ..................................................................................................................................


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 ..................................................................................................................................


G. Polymolecularity Correction Factors for Second Virial Coefficient Versus Molecular Weight Relationship ........................................................................................................... Table 48 .................................................................................................................................. Table 49 .................................................................................................................................. Table 50 .................................................................................................................................. Table 51 ..................................................................................................................................


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 ..................................................................................................................



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


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 ....................................................................


C. References ......................................................................................................................... VII/318


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


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 ..............................................................................


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) ...........................................................


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


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) ............................................................................................


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.


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


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 ......................................................


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 .......................................................................................................................................


IX/1

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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


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


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


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


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.



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


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



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


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


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



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


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



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


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


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


l,r-Azo-bis-l,l,l-tricyclopropylmethane


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


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



Initiator

Solvent


Cumene Ethylbenzene Octane Toluene


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


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


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



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

â(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


Initiator terf-Butyl

peroxide

Solvent Tri-n-butylamine tert-Butylbenzene


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


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



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


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



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


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


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


Table 4. cont'd Number of C atoms 4 (cont'd)


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



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



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

â(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


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



14

Initiator m-Chlorobenzoyl 2-methylbutanoyl peroxide

Solvent

Cyclobutane acetyl peroxide

2-Butanol Carbon tetrachloride Cyclohexane Carbon tetrachloride

Cyclopentane formyl peroxide


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


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




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



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


Cyclopentane acetyl peroxide


Diacetylsebacoyl diperoxide


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



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


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


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


Endo-norbornene-5-carbonylperoxide


Exo-norbornene-5-carbonylperoxide


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


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



Initiator 4-Benzylidenebutyryl peroxide

Solvent Acetophenone Benzene


Nitrobenzene Propylene carbonate

4-ter/-Butylbenzoyl peroxide cis-4-tert-Butylcyclohexane formylperoxide

Toluene Dioxane Butane Carbon tetrachloride

frarcs-4-te7t-Butylcyclohexane formylperoxide


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


Initiator

Solvent


Unknown

Lauroyl peroxide

Benzene

Chlorobenzene

Ethyl acetate

Ethyl ether Mineral oil Styrene

26 28 36 x


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


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


Previous Page


Initiator

Solvent


Unknown

Lauroyl peroxide

Benzene

Chlorobenzene

Ethyl acetate

Ethyl ether Mineral oil Styrene

26 28 36 x


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


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



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


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



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


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


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



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


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


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



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


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


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



Initiator Di(tert-butylperoxy)-oxalate

Solvent Benzene

tert-Butanol Decane Dodecane Octane n-Pentane Tetradecane Styrene

11

tert-Butyl 5-methyl-7-perthenoate


P-Methyl-P-phenyl-P-peroxypropiolactone


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


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



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


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


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


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


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



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



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


a-Methylstyrene Mineral spirits

15

4-Methoxybenzyl (tert-butylperoxy)oxalate

Benzene

1-Methyl-1-phenylethyl 2,2-dimethylperoxyporpionate

Cumene

tert-Amy\ perneodecanoate


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


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


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



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


Decane

Mineral spirits

19

Di-«-heptyl persuccinate

Styrene

tert-BxAy\ diphenylmethylperacetate terr-Butyl diphenylperglycidate (cis)


(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



20

21

22

23

Initiator ten-Butyl a-phenylpercinnamate (cw) (trans)

Cumene Cumene

Cumyl perneodecanoate


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


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


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-oôc'-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.

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tn ti2 ti3 114 ui u2 u3 U4 U5

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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)

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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


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



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



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


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


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



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


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



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

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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


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


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


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


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


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


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


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


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.



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



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



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


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



T( 0 C)

Methyl methacrylate (cont'd) Carbon tetrabromide (cont'd)


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


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


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


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


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



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


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


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


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)


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


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.


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


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


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


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



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


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


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


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



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


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


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, AÂf'-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


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, ô'-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(Aêthyl-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


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

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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


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


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


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


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.


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, AÂf-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


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


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


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


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


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


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


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


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


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, /?-AÂîmethyl-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


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


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


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


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


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


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


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


0.48

1.21

678

Styrene

0.2

0.23

678

Styrene

0.58

0.15

678


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


0.4

1.03

678

Styrene

0.4

0.38

678

Methacrylate, methyl Styrene

0.28 0.19

1.11 0.54

678 678


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


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


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


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


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


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.


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, 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


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


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


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



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


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


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



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


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


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


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


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.


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


0.82

0.53

596

Styrene

0.68

0.55

596

Acrylate, methyl

0.11

0.29

596


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


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


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


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


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


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


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



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


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


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-ôbutyl 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


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


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


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


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



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


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


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



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


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


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


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


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-cyanoacetate 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


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


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


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


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


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


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


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


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


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.


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 fmaxf THEN fmin = f IF fmax

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

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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


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



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


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
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



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, AÂf-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


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


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


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



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



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


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).


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.


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


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


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.


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


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



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


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


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


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



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


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 2DEÊDCBAABCDE, etc III. AB and CDÂBCD then ABCD and EFÂBCDEF, 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


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


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


Varies

Uniform

Polymer

6.2.15


Polymer

6.2.16


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


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


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


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


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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


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





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


- , 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



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


- , 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


-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


TABLE 1. cont'd Monomer - , phenyl ester - , rc-propyl ester Methacrylonitrile


-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



-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


TABLE 1.

cont'd

Monomer


= 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)


-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


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


-, 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-


- 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


TABLE 2. cont'd Monomer Oxepane


—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


343 343 343

ss ss ss

10.5 -2 2.9 -2 0 — 2

4a 4a 4a


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


-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


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


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



-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


—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).


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


-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


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



- , 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


TABLE 4. cont'd

Monomer


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


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


-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.


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



Hexanal

Octanal 4-Oxapentanal Pentanal oPhthalaldehyde Propanal

-, 2-chloro 2-methyl-, 2,2-dichloro-, 2-methyl-


"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


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


-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


-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.


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


Tc [ 0 C]


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


Monomer 8.1.

Tc [ 0 C]


Notes

Refs.


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


TABLE 8.

cont'd


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]


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.


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


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


3.

Equilibria Involving Monomers in Solution

TABLE 9. MONOMERS GIVING POLYMERS CONTAINING MAIN CHAIN CARBON ONLY Monomer


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-methoxyAWAÂf'-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


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.


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


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.


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


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.


Previous Page

TABLE 11. COPOLYMERS Monomer A

Monomer B


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.


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


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


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


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


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

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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


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



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



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


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


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



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

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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)


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


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


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.


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


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


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


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


TABLE 1. cont'd Copolymerization parameters Monomer 1

Monomer 2

Methyl methacrylate

Acenaphthylene

Styrene

Solvent


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


TABLE 3. cont'd Activation volume (cm3/mol) Monomer 1

Monomer 2

Methyl methylacrylate Styrene

Methyl acrylate

TABLE 4.

Solvent


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).

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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

287-400 Ambient to 500 Ambient to 500

49

1.2. POLY(ALKENES) Poly(ethylene) - , low density


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


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





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,



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


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



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




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


- , 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



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


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



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


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.


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


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


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


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


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


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),



-, -, -, -,

(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-AÂf-dimethylamino-



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-AÂf-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-AÂf-dimethylaminostyrene and closely related compounds



- , /?-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
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


Refs.

iV,iV-dimethylaniline (0.2% of original polymer weight), AÂf-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


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


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


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


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




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


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



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)


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,





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



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


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





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.



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)


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


TABLE 3.

cont'd

Polymer


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


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


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)


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





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

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TABLE 5. CELLULOSE AND ITS DERIVATIVES Polymer


Cellulose


- , a form

330-440

Cellulose (oxidized)

180-331

Cellulose triacetate

250-310 250-900

Ethyl cellulose

C.

230-320 306


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).

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TABLE 5. CELLULOSE AND ITS DERIVATIVES Polymer


Cellulose


- , a form

330-440

Cellulose (oxidized)

180-331


250-310 250-900

Ethyl cellulose

C.

230-320 306


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

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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)


TABLE 1. cont'd Polymer Poly (methyl bromoacrylate) Poly(methyl a-chloroacrylate)

G(R)

G(X)

G(products)

6.98 5.1


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


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



G(R)

G(X) 0.077

G(S)

G(products)


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


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)


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



G(R)

G(X)

G(S)

G(products)


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)


G(R)

G(X)

G(S)

G(products)


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


TABLE 2. COPOLYMERS Copolymers 2.1.

G(R)

G(X)

G(S)


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.


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


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)


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)


Refs.

Glass-DGEBA-DDM Color-DGEBA-DDM

H 2 , CO, CO2 H 2 , CO, CO2

77 K, RT 77 K, RT

227 227

C

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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


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


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


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)


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)


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


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


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.


CAS Registry Number

CAS Registry Number

MoI. wt.


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)


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


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.


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.


-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)


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



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


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,



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


Melting point (0C)

1,2-BUTADIENES

1,2-Butadiene - , 4-Bromo- , 4-Chloro- , 4-Hydroxy- , 4-Iodo- , 3-Methyl10.2.


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.


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)


Flash point (0C)

RTECS Number

WN0875000 TI3350000 TI3450000 GW5775000 1.005

1.4790

>110

WN1300000

DB9300000 162

QK3695000

Density (at 2O0C)


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


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


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


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)


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 CioHÔ 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.


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)


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)


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)


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


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 )Ô-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


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)


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


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)


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


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)


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


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


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


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


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


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


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


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


/-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%
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


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%
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


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


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


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% ) 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


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
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

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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

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]Î 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

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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).

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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


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.


8.1.4.2. 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

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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. Â = 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. Â = 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. Â = 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. Â = 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.

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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)


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)


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)


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)


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


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


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.


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.


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.


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


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.


b

III. -, tetrafluoro(112.03)

Amorph.a


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



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


8.76 8.76

PoIy(I-dodecene) 1.(168.32)

Poly(ethylene) 1.(28.05)


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



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


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


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



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.


0.726 0.908

Cl-I

(3 = 90

Amorph.a


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


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


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


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


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



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."



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)


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



0.97 (1.06) 1.118


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




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


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


C3-2

C2h-2

Hex Ortho Mono

Amorph.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



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


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.*


z

2.55 2.56 2.56 2.57 9.23 2.58 9.18 9.20

Angles


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)


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



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




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



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


/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



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."




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




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



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



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


7.18

1.114

syndiotactic a

Amorph.a


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


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




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*


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


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."


Heat of fusion kj/molfl


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.


TABLE 4. POLY(DIENES) AND POLY(DIYNES) Density (g/cm3)


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


4.72

D2h-ll

10.98

D3d-6

17.3

C2h-5

6.60 17.3

Phex Hex


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)


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



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




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



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."


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



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




— 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



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."



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


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




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



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




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




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."


Crystal.

D4-4

b


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


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."


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




Cryst syst.

Space group

a

b

c

Angles

z

Crystal.

Amorph.a




- , 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.



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




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.*




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


TABLE 6. POLY(AMIDES) (-NH-X-NH-CO-Y-CO- or -NH-X-CO-) see also POLY(PEPTIDES) Density (g/cm3)


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."


Heat of fusion kj/mol*

550/735


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


TABLE 6.



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


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


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


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



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


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


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


TABLE 6.



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."


26.3

9.10

59,90,106

azelamide) [7.9] Phex pimelamide) [7.7] Phex Cs-I

z


18.95*

7=120

1

1.337

312


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



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



232/244 235/291 241/1202


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




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




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



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




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


Next Page



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



> 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


TABLE 7.

POLY(ESTERS) ( - O - X - O - C O - Y - C O - or - O - X - C O - ) Density (g/cm3)


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



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 ^ ô{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



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
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
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


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.


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

-



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


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


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.


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


TABLE 1. cont'd

Polymer Poly(cyclohexyl methacrylate)

Solvent Benzene Butanol

Butanone Cyclohexane

(ml/g)



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


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


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



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


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


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


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


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


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)


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)


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


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.



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.


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


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



Solvent

Fr.

W.P.


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


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


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.


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


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
591 B

592 772 772



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/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.


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


Solvent

Temp. (0C)

K(XlO 3 ) (ml/g)

a

Poly(p-diethylphosphonomethylstyrene-c
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


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


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 ôM 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


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.


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


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.


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
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


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
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


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


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


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


Solvent

Chlorobenzene Cyclohexane

Cyclohexanone ds-Decalin trans-Decalin n-Decane Di(«-propyl)ether
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.


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
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

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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



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


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


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



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


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


25 30


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



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


Solvent

T (0C)

Remarks

M

Precooled to form clusters Precooled to form clusters Water Water

25 30 30(?)

100 132


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



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


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



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


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


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


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



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


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


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


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

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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 Â3/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 ô 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 (î8), 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


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


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



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


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


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



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


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


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


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
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



-, urethanized

4.9% 8.1% 11.5%

Poly(vinyl benzoate) Poly(4-vinyl biphenyl) Poly(vinyl bromide) Poly(vinyl carbanilate)

PoIy(TV-vinyl carbazole)


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


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



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


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



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


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



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)


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


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)


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
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
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)


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



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

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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

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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
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
Hexane, methanol

25 26

27,247 28 7



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
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


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


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



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
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


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


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


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


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


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
TABLE 4.

Nonsolvents

Refs.

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



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


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


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



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
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


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),


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


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
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

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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


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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


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



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


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


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


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 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


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


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


D.

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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.

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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


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


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


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



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.


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


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


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



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


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


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(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


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



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



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


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



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



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


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


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


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



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
wt.% tert-butyloxy carbonyloxy styrene) wt.% terf-butyloxy carbonyloxy styrene) wt.% tert-butyloxy carbonyloxy styrene) wt.% terf-butyloxy carbonyloxy styrene)


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


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


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



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


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



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


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


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



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


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.


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
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


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


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


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


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.


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 Cô) 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.


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.



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


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



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.


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

ô = 1.93D /x0 = 2.08D ô = 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.


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

ô = 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

ô = 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
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.



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

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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


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


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


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


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.


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


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


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.


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


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


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


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


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


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
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

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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


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 rrû PONH -LAJINH^ ^N^ C" ^ O ^\ ^ ^ C N H HCONH-NHCOO-NHCONHIl îsrC^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


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


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


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


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


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


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


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


#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


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


^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.


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


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


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



dd

dp

6h

Poly(vinyl chloride-co-vinyl acetate) (87/13) VYHH Poly(vinyl chloride-o?-vinyl acetate-comaleic acid) Poly(vinyl chloride-c
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


TABLE 10. confd Solubility parameters (MPa) 1 / 2 Polymer


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


<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


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)


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.



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.

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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)


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


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)


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


TABLE 1.

confd

Polymer Catalyst or initiator 1.6.


T (0C)

Monomer (M) or model compound (MC) values [M]0

[M]0


: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)


25 (P); 15 (M) 25(P) 25 (P)

130

- 39.84 -42.86 - 37.54

- 18.74 (M) - 18.74 (M) - 18.74 (M)


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)


20

132

-102(LM] 5 7 8 ) -12.8 ([a]578)- 11.9(M)(LM] 5 7 8 )


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


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


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


25 25

72

Benzene

25

38

Carbon tetrachloride (P); neat (M)

25

243


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)


Chloroform Chloroform Chloroform

T (0C)

25 25 25

Refs.

44


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)


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


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


-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


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


TABLE 2.

cont'd

Polymer

Catalyst or Initiator

Polymerization system

Solvent J( 0 C)

[a]D

Polymer (P) values [M]D


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.


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


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


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


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)


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)


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)


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


T( 0 C)


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


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


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


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


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)


T (0C)

Refs.


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)


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)


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


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


Chloroform

25

188


TABLE 4.

confd



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


Chloroform

25

188

-96 -97

-44.2 to-50.9 -101


THF Chloroform

25 25

153 188

-97

-23.7


Chloroform/DC A (22/1)

25

188

-78

-2.4


THF

25

188

-40

-129


Chloroform

25

219

-78

8.7


Toluene

25

153,188

-78

81.7


Toluene

25

153,188

-97

-0.3


THF

25

188

-78

102(M365)


Chloroform

25

186

Miscellaneous

THF

25

164

Miscellaneous

THF

25

164


THF

25

220


Chloroform

25

240

Chloroform Chloroform after 1 h

60 60


Chloroform

25

240


THF

25

220


90% Chloroform - 10% TFEL 25

155


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


THF THF THF

25 25 25

196 196 253

THF Chloroform

25 25

253 196


Chloroform

25

251


Toluene Toluene

20 20

156

THF

25

157


THF

25

220


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


TABLE 4.

confd

Catalyst or initiator

Solvent


Polymer (P) Values

Polymer Polymerization system T (0C)

WD

[M]0

Solvent


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


20 20

159 160


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



7( 0 C)


Polymer (P) values WD

[M]0


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


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


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)


- 98

377 ([a] 365)


- 98

569([aJ 365 )


- 98

588 ([aj365)


- 98

819([a] 36 5)


- 98

748([0Cj 365 )


- 98

529 ([a]365)


- 78

- 17 (IaJ 365)


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

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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(î — 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


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


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


- 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)


- 600 *

- 40 *

100,108


- 2700 *

- 110 *

100,109


- 2350 *

100



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*


-1050* - 680 *

-44* - 28 *

100,93 100,93

Benzene

-3000*

-150*

100,111

Chloroform

- 4900 *

- 100 *

100,111


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 *


157

93

-2000* -920* 540* -400* -277* -180* -16* References page VII/760


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


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


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



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 =


1060 *

100,116

Rl =


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


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


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


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

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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
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%


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


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


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 AîV-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 AÂf-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 terephthÛite) 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


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


/;-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(
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


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

C26H4Ô6

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
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
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'-OXyMsIeâIiOl)

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


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-c
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(/
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)-
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 OîC 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


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


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


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


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


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


I/10

II/490

segmental anisotropy

VII/751


VII/58

VII/65


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


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/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


VIII/20


VIII/20 This page has been reformatted by Knovel to provide easier navigation.

IX/10

Index terms

Links


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


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


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


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


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


II/449

IX/15

Index terms

Links

Flory-Orwoll-Vrij equation of state

VI/594


VI/599

Flow-induced crystallization

VI/289

Fluorocarbon surfaces

VI/524

Fluoropolymers: diffusion coefficients

VI/552

VI/562


VI/552

VI/562

physical constants

V/31


II/488


VI/552

VI/562

Force: conversion factors

I/15

SI units

I/13

Formaldehyde resins: fractionation systems

VII/397


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


VII/333

main-chain carbocyclic polymers

VII/397

main-chain heteroatom polymers

VII/398

poly(acrylic acids)


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


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


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)


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


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


VI/219


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/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


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


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


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


VI/597

Heat: conversion factors

I/16

SI units

I/13


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


VII/662

common polymers

VII/671


VII/659


VII/650


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/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


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


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


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


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


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


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


VI/244

Logarithmic normal molecular weight distribution Lorentz-Lorentz equation

II/353 VI/571

Low density poly(ethylene)

V/160

Lyotropic phases

VI/280


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


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


II/382

fractionation systems

VII/333


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


VII/746


VII/702


VII/499


VII/551


II/398

IX/26

Index terms

Links

Main-chain acyclic carbon polymers: (Continued) thermal degradation

II/451


VII/47


VII/5

Main-chain acyclic heteroatom polymers: ceiling temperatures

II/395


II/387


VII/398


VI/219


VII/659

heat of polymerization

II/373


IV/33

optically active polymers from achiral monomers

VII/737

optically active polymers from chiral monomers

VII/723


VII/752


VII/708


VII/511


VII/594

thermal degradation

II/465


VII/60


VII/32

Main-chain carbocyclic polymers: fractionation systems

VII/397


VI/218


IV/90


VII/752


VII/509


VII/594

thermal degradation

II/464


VII/47


VII/31

Main-chain carbonyl polymers, solvent-nonsolvent tables

VII/510

Main-chain heterocyclic polymers: glass transition temperature

VI/243


IV/99

polymerizability

II/401


VII/756


VII/523


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


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


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


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


II/415

Q values

II/310

reactivity pattern parameters

II/323


II/98

N National Technical Information Service

VIII/29

Natural cellulose fibers

VIII/23

Natural polymers: glass transition temperature

VI/244


VII/528

Natural protein fibers

VIII/22

Natural rubber: physical constants

V/5


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


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


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/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/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


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


VI/561

conversion factors for

VI/545


VI/567


VI/552

gases through elastomers

VI/566

poly(alkanes)

VI/545

poly(amides)

VI/559


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


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


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


VI/525


VI/524


VI/527


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


VII/504

theta solvents

VII/313

Poly(acetylenes): solvent-nonsolvent tables

VII/499


VII/48

Poly(acrylamides): glass transition temperature

VI/201


II/486


VII/503

Poly(acrylic acid) and derivatives: diffusion coefficients

VII/96

dipole moments in solution

VII/643


VII/344

frictional ratios


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


VII/96


II/483


VII/170


VII/96


VII/747


VII/501


VII/557

surface properties

VI/526

thermal degradation

II/454

theta solvents

VII/307


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


VII/336

frictional ratios

VII/92


VI/205


VII/651

Huggins constant

VII/266

optically active

VII/716


VII/92


VII/165


VII/92


VII/747


VII/500


VII/553

spherulite growth rates

VI/304

thermal degradation


VII/733

VII/748 VII/573

IX/38

Index terms

Links

Poly(alkenes): (Continued) theta solvents

VII/299


VII/48

Poly(alkynes): optically active

VII/721


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


VI/559


VII/411

frictional ratios

VII/137


VII/137

VI/235


VII/661

Huggins constant

VII/279


VI/539 VI/2

optically active

VII/726


VII/137


VI/559

physical constants

V/121


VII/191


VII/137


VII/755


VI/559


VII/518


VII/600


VI/331

surface properties

VI/530

thermal degradation

II/470

theta solvents

VII/316


VII/63


VII/36


VI/4

IX/39

Index terms

Links

Poly(amines), nomenclature

VI/4

Poly(amino acids): crystallographic data

VI/26


VII/414

optically active

VII/729


II/487


VII/755


VII/604

surface properties

VI/533


VII/63


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


VI/587

Poly(aryl ether ether ketone), permeability, diffusion, and solubility coefficients

VI/561

Poly(benzimidazoles): glass transition temperature

VI/245


VII/757


VII/526

Poly(benzimides), solvent-nonsolvent tables Poly(benzothiazinophenothiazines), glass transition temperature

VII/524 VI/245

Poly(benzothiazoles): glass transition temperature

VI/245


VII/524

Poly(benzoxazines), glass transition temperature

VI/245

Poly(benzoxazoles): glass transition temperature

VI/245


VII/757


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


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


VI/555


VII/641


VII/404

frictional ratios

VII/134


VII/134

VI/219


VII/134


VI/555


VII/188


VII/134


VI/555


VII/513


VI/326

surface properties

VI/530

thermal degradation

II/468

unperturbed dimensions of lienar chains

VII/61


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


VI/291


VI/22


VI/553


VII/644


VII/333

frictional ratios

VII/94


VI/207


VII/650

Huggins constant

VII/266

optically active

VII/720


VII/94



VII/94

VII/735

IX/41

Index terms

Links

Poly(dienes): (Continued) radiation chemical yield

II/482


VII/168


VII/94


VII/746


VI/553


VII/499


VII/551


VI/304


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


VI/40


VI/555


VII/640


VII/405

frictional ratios

VII/134


VII/134

VI/221


VII/659

Huggins constant

VII/278


VI/539 VI/2

optically active

VII/724


VII/134


VI/555


II/488


VII/188


VII/134


VII/752


VI/555


VII/513


VII/594


VI/327

surface properties


VI/4

IX/42

Index terms

Links

Poly(esters): (Continued) thermal degradation

II/466

theta solvents

VII/315


VII/61


VII/34

Poly(ether ketones), glass transition temperature

VI/226

Poly(ethers): crystallographic data

VI/51


VII/134


VII/638

frictional ratios

VII/134

interfacial tension with other polymers

VI/539


VII/134


VII/188


VII/134

surface properties

VI/528

theta solvents

VII/313


VII/60


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


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


VI/488

IX/43

Index terms

Links

Poly(imides): crystallographic data

VI/15


VI/559


VI/241


VI/559


VII/756


VI/559


VII/524

surface properties

VI/531

Poly(imines): fractionation systems

VII/411


VI/241

optically active

VII/728

surface properties

VI/531


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


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


VII/503

Poly(methacrylic acid) and derivatives: diffusion coefficients

VI/548


VII/644


VII/346


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


VII/734

VI/548

propagation/termination constants radiation chemical yield

II/82 II/484


VII/748


VI/548


VII/501


VII/561

surface propertis


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


VI/549


II/486


VI/549

Poly(nucleotides): diffusion coefficients

VII/157

frictional ratios

VII/157


VII/157


VII/196


VII/157


VII/755

Polyolefin elastomers

V/161

Polyolefin plastomer

V/160

Poly(olefins)

V/160


VI/6

nomenclature

VI/2

physical constants

V/164


II/482

Poly(organosiloxanes)

V/161

See also Poly(siloxanes) Poly(oxabicyclononanes), glass transition temperature


VI/247

IX/46

Index terms

Links

Poly(oxadiazoles): glass transition temperature

VI/248


VII/523

Poly(oxadiazolidines), solvent-nonsolvent tables

VII/523

Poly(oxides): bulk crystallization rates

VI/365


VI/300


VI/52


VI/555


VII/638


VII/398


VI/226


VII/659

Huggins constant

VII/277

nomenclature optically active permeability coefficients

VI/2

VI/4

VII/723

VII/737

VI/555


VII/752


VI/555


VII/511


VII/594


VI/315

thermal degradation

II/465


VII/60


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


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


VI/218


VII/509

Poly(phosphates): unperturbed dimensions of linear chains

VII/64


VII/39

Poly(phosphazenes): bulk crystallization rates

VI/384


VII/422


VI/242


VII/755


VII/522

Poly(phthalazines), glass transition temperature

VI/248

Poly(phthalides), glass transition temperature

VI/248

Poly(piperazines): glass transition temperature

VI/248


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


VII/756


VII/525

Poly(pyrrolidines), glass transition temperature

VI/250

Poly(quinones), glass transition temperature

VI/250


IX/48

Index terms

Links

Poly(quinoxalines): glass transition temperature

VI/250


VII/757


VII/526

Poly(saccharides): crystallographic data

VI/59


VII/144


VII/431

frictional ratios

VII/144


VI/243

Huggins constant

VII/282


VII/144


VII/194


VII/144


VII/758


VII/531


VII/611

theta solvents

VII/316


VII/66


VII/43

Poly(silanes): fractionation systems

VII/418


VI/243


VII/522


VII/606

Poly(silazanes): glass transition temperature

VI/243


VII/522


VII/606

Poly(silmethylenes), unperturbed dimensions of linear chains

VII/64

Poly(siloxanes): bulk crystallization rates

VI/384


VI/558


VII/418


VI/231


VII/661


VI/539


VI/558


II/487


VII/756


VI/558



IX/49

Index terms

Links

Poly(siloxanes): (Continued) spherulite growth rates

VI/334

surface properties

VI/531

thermal degradation

II/471


VII/64


VII/40

Poly(silsesquioxanes): unperturbed dimensions of linear chains

VII/64


VII/40

Poly(styrene)

V/160


VI/547


VII/356

frictional ratios

VII/109


VII/109

VI/209


VII/655

heat capacity

VI/485


VI/537

optically active

VII/719


VII/109


VI/547

physical constants

V/91


II/88


VI/499 VII/735

V/166

II/485


VII/179


VII/109


VI/547


VII/507


VII/574

surface properties

VI/525

thermal degradation

II/461

theta solvents

VII/300


VII/54

Poly(sulfides): crystallographic data

VI/57


VII/639


VII/416


VI/233

nomenclature

VI/4

optically active

VII/725


VII/516

thermal degradation

II/468


VII/63


VII/737

IX/50

Index terms

Links

Poly(sulfides): (Continued) viscosity-molecular weight relationship

VII/39

Poly(sulfonamides): fractionation systems

VII/416


VI/234

Poly(sulfonates): glass transition temperature

VI/233


VII/515

Poly(sulfones): crystallographic data

VI/57


VI/560


VII/416


VI/234


VI/560


II/488


VI/560


VII/517


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


VII/137


VII/410

frictional ratios

VII/137


VI/242

optically active

VII/725


VII/137



IX/51

Index terms

Links

Poly(ureas): (Continued) sedimentation coefficients

VII/137


VII/521

theta solvents

VII/316

viscosity-molecular weight relationship Poly(urethane) elastomers

VII/39 V/161

Poly(urethanes): bulk crystallization rates

VI/383


VI/49


Vl/560


VII/410

frictional ratios

VII/137


VI/229

nomenclature

VI/4

optically active

VII/725


VII/137


VI/560


VII/191


VII/137


VI/560


VII/515


VII/600

surface properties

VI/531

thermal degradation

II/471

theta solvents

VII/316


VII/63


VII/39

Poly(vinyl acetate): heat capacity

VI/498

physical constants

V/77

Poly(vinyl alcohol): fractionation systems

VII/353


VI/212

heat capacity

VI/498


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/137

IX/52

Index terms

Links

Poly(vinyl esters): (Continued) glass transition temperature

VI/213

optically active

VII/718


VII/506

surface properties

VI/526


VII/53

Poly(vinyl ethers): fractionation systems

VII/353


VI/214

optically active

VII/718


VII/503

thermal degradation

II/461


VII/53

Poly(vinyl fluoride), heat capacity

VII/735

VI/494

Poly(vinyl halides): glass transition temperature

VI/215


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


VI/212

optically active

VII/718


VII/504

thermal degradation

II/461

Poly(vinyl nitriles): fractionation systems

VII/353


VI/215


VII/506

Poly(vinyls): bulk crystallization rates

VI/341


VI/291


VI/13


VI/549



VII/105

IX/53

Index terms

Links

Poly(vinyls): (Continued) frictional ratios

VII/105


VII/655

Huggins constant

VII/272


VI/37 VI/2


VII/105


VI/549


II/486


VII/177


VII/105

segmental anisotrophy

VII/750


VI/549


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


VI/197

SI units

I/13

Pressure-induced crystallization

VI/288

Propagation activation energy

II/415

acrylic derivatives

II/417

dienes

II/416


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


II/422

Propagation constants

II/77

acrylic derivatives

II/80

aldehydes


IX/54

Index terms

Links

Propagation constants (Continued) dienes

II/79

fumaric derivatives

II/87

itaconic derivatives

II/85


II/82


II/90

olefins

II/79

styrene derivatives

II/88

vinyl esters

II/87

vinyl ethers

II/88

vinyl halides

II/87


II/90

Propene monomers, physical properties

III/32

Proteins: diffusion coefficients

VII/157

fibers

VIII/22

frictional ratios

VII/157


VII/157


VII/196


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


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


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


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


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


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


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


VII/752


VII/746


VII/752


VII/756

poly(acrylic acids)

VII/747

poly(alkenes)

VII/747

poly(amides)

VII/755


VII/757

poly(benzoxazoles)

VII/757

poly(dienes)

VII/746

poly(esters)

VII/752

poly(imides)

VII/756


VII/748

poly(nucleotides)

VII/755

poly(oxides)

VII/752

poly(peptides)

VII/755

poly(phosphazenes)

VII/755


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


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


VI/561


VI/567


VI/552

poly(alkanes)

VI/545

poly(amides)

VI/559


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


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


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


VII/511


VII/499


VII/509

main-chain carbonyl polymers

VII/510


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


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/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


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


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



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


VI/194

SI units

I/13

Specific refractive index increments

VII/547


VII/609


VII/594


VII/551


VII/594


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


VII/561

poly(oxides)

VII/594

poly(saccharides)

VII/611

poly(silanes)

VII/606

poly(silazanes)

VII/606

poly(styrenes)


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


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


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


VII/42

Sulfur, surface properties


VI/3

IX/64

Index terms

Links

Sulfur compounds: solubility parameter

VII/700


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


VI/525


VI/524


VI/527


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


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


II/418


II/423

olefins

II/416

styrene derivatives

II/421

vinyl esters

II/421

vinyl ethers

II/421

vinyl halogens

II/420


II/422

Termination constants

II/77

acrylic derivatives

II/80

aldehydes

II/90

dienes

II/79

fumaric derivatives

II/87

itaconic derivatives

II/85


II/82

olefins

II/79

styrene derivatives

II/88

vinyl esters

II/87

vinyl ethers

II/88

vinyl halides

II/87


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


II/475

with crosslinking

II/350


II/451


II/464


II/464


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


VI/195

theta solvents

VII/291

Thermoplastics

V/159

ISO codes for

VIII/19

physical constants

V/162


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


VII/292


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


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


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


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


II/420


II/87

Q and e values

II/309


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


VII/43

copolymers

VII/27


VII/5


VII/31


VII/32

molecular weight distribution and viscosity constant

VII/5

poly(acetylenes)

VII/7

poly(acrylic acids)


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


VII/662


VII/659


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


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


polymer_handbook.pdf

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