Polymer handbook

2366 Pages·134.744 MB·English

by  Brandrup J., Immergut E.H., Grulke E.A. (Editors)

P O L Y M ER H A N D B O OK
F O U R TH E D I T I ON
Editors
J. B R A N D R U P, E. H. I M M E R G U T, a nd E. A. G R U L KE
Associate Editors
A . A BE
D. R. B L O CH
A WILEY-INTERSCIENCE PUBLICATION
J O HN WILEY & S O N S, I N C.
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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 98765432
Contributors
Abe, A. Elias, H.-G.
Tokyo Institute of Polytechnics, Atsugi, Japan Michigan Molecular Institute, Midland, Michigan, USA
Allegra, G. Fink, G.
Dipartimento di Chimica del Politecnico, Milano, Italy Max-Planck-Institut fur Kohlenforschung, Miilheim an der
Ruhr, FR Germany
Andreeva, L. N.
Institute of High Molecular Weight Compounds, Russian Fink, H.-P.
Academy of Sciences, St. Petersburg, Russian Federation Fraunhofer Institut fiir angewandte Polymerforschung, Teltow-
Seehof, FR Germany
Andrews, R, J.
Chemical and Materials Engineering Department, University of
Fouassier, J. P.
Kentucky, Lexington, Kentucky, USA
Laboratoire de Photochimie Generate, Ecole Nationale
Superieure de Chimie, Mulhouse, France
Bai, F.
The Maurice Morton Institute of Polymer Science, Univeristy
Fu, Q.
of Akron, Akron, USA
The Maurice Morton Institute and Department of Polymer
Bareiss, R. E. Science, University of Akron, Akron, Ohio, USA
Editorial Office, Macromolecular Chemistry and Physics,
Furuta, I.
Mainz, FR Germany
Japan Synthetic Rubber Company Ltd., Yokkaichi, Mie,
Barrales-Rienda, J. M. Japan
Instituto de Ciencia y Tecnologia de Polfmeros, Madrid, Spain
Ganster, J.
Bello, A. Fraunhofer Institute for Applied Polymer Research, Teltow-
Instituto de Ciencia y Tecnologia de Polfmeros, Madrid, Spain Seehof, Germany
Bello, P. Greenley, R. Z.
Instituto de Ciencia y Tecnologia de Polfmeros, Madrid, Spain Monsanto Corporation (retired), St. Louis, Missouri, USA
Bloch, D. R. Grulke, E. A.
Lakeshore Research, Racine, Wisconsin, USA Chemical and Materials Engineering, University of Kentucky,
Lexington, Kentucky, USA
Brandrup, J.
Wiesbaden, FR Germany Goh, S. H.
Calhoun, B. H. Department of Chemistry, National University of Singapore,
The Maurice Morton Institute of Polymers Science, University Singapore
of Akron, Akron USA
Guzman G. M.
Casassa, E. F. Instituto de Ciencia y Tecnologfa de Polfmeros, Madrid,
Department of Chemistry, Carneagfe-Mellon University, Pitts- Spain
burgh, Pennsylvania, USA
Hill, D. J. T.
Cheng, S. Z. D. Department of Chemistry, University of Queensland, St. Lucia,
The Maurice Morton Institute of Polymer Science, University Australia
of Akron, Akron, Ohio, USA
Hiltner, A.
Chiu, F.-C. Department of Macromolecular Science, School of Engineering
The Maurice Morton Institute of Polymer Science, University Case Western University, Cleveland, Ohio, USA
of Akron, Akron, Ohio, USA
Inomata, K.
Cho, J. Department of Polymer Chemistry, Tokyo Institute of Technol-
Polymer Science and Engineering Department, Dankook ogy, Ookayama, Meguro-ku, Tokyo, Japan
University, Seoul, South Korea
Iwama, M.
Collins, E. A.
Japan Synthetic Rubber Company Ltd., Yokkaichi, Mie,
Avon Lake, Ohio, USA Japan
Daniels, C. A.
Jenkins, A. D.
The Geon Company, Avon Lake, Ohio, USA
School of Chemistry, Physics and Environmental Science,
DeLassus, P. T. University of Sussex, Brighton, Sussex, UK
The Dow Chemical Company, Freeport, Texas, USA
Jenkins, J.
Dixon, K. W. School of Chemistry, Physics and Environmental Science,
Akzo Nobel Chemicals, Inc., Dobbs Ferry, New York, USA University of Sussex, Brighton, Sussex, UK
Johnson, M. Muck, K.-F.
Chemistry/Physics Library, University of Kentucky, Lexington, Ticona GmbH, Kelsterbach, FR Germany
Kentucky, USA
Nagai, S.
Kamachi, M. Plastics Technical Association, Osaka, Japan
Department of Applied Physics and Chemistry, Fukui Uni-
Nordmeier, E.
versity of Technology, Gakuen, Fukui, Japan
Physikalische Chemie, Universitat Osnabriick, Osnabriick
Kerbow, D. L. FR Germany
DuPont Fluoroproducts, Wilmington, Delaware, USA
Ogo, Y.
Kimura, S.-L Research Institute for Solvothermal Technology, Hayashi,
Japan Synthetic Rubber Company Ltd., Yokkaichi, Mie, Takamatsu, Kagawa, Japan
Japan
Orwoll, R. A.
Korte, S. College of William and Mary, Williamsburg, Virginia, USA
Zentrale Ferschung, Bayer AG, Leverkunsen, FR Germany
Pauly, S.
Krause, S. Fachlaboratorium fur Permeationspriifung, Wiesbaden,
Department of Chemistry, Rensselaer Polytechnic Institute, FR Germany
Troy, New York, USA
Peebles, L. H., Jr.
Kurata, M. Chemistry Division, Naval Research Laboratory, Washington,
Institute for Chemical Research, Kyoto University, Uji, Kyoto, DC, USA
Japan
Perera, M. C. S.
Lechner, M. D. Magnetic Resonance Facility, School of Science, Griffith
Physikalische Chemie, Universitat Osnabriick, Osnabriick, FR University, Nathan, Australia
Germany
Porzio, W.
Leonard, J. Instituto di Chimica delle Macromolecole del C.N.R., Milano,
Department de Chimie and CERSIM, Universite Laval, Italy
Quebec, Canada
Pyda, M.
Li, F.
Department of Chemistry, University of Tennessee, Knoxville,
The Maurice Morton Institute of Polymer Science, University
Tennessee, USA
of Akron, Akron, Ohio, USA
Quirk, R. P.
Liggat, J.
The Maurice Morton Institute of Polymer Science, University
Department of Pure and Applied Chemistry, University of
of Akron, Akron, Ohio, USA
Strathclyde, Glasgow, Scotland
Riande, E.
Lindemann, M.
Instituto de Ciencia y Tecnologia de Polimeros, Madrid,
Greenville, South Carolina, USA
Spain
Luft, G.
Institut fur Chemische Technologie, Technische Hochschule, Richter, W. J.
Darmstadt, FR Germany Max-Planck-Institut fur Kohlenforschung, Miilheim an der
Ruhr, FR Germany
Magill, J. H.
School of Engineering, University of Pittsburgh, Pittsburgh, Rothe, M.
Pennsylvania, USA University of UIm, UIm, FR Germany
McKenna, T. F. Rule, M.
Centre Nationale de Ia Recherche Scientifique, Laboratoire de Coca Cola Company, Atlanta, Georgia, USA
Chimie et Procedes de Polymerisation/Departement Genie des
Salort, J. F.
Procedes, Villeurbanne, France
Madrid, Spain
Mehta, R. H.
Salom, C.
Dupont Nylon, Chattanooga, Tennessee, USA
Escuela Tecnica Superior de Ingenieros Aeronauticos, Uni-
Mettle, S. V. versidad Politecnica, Madrid, Spain
Dipartimento di Chimica del Politecnico, Milano, Italy
Sanchez, I. C.
Metanomski, W. V. Chemical Engineering Department, University of Texas at
Chemical Abstracts Service, Columbus, Ohio, USA Austin, Austin, Texas, USA
Michielsen, S. Santos, A. M.
School of Textile and Fiber Engineering, Georgia Institute of Faculdade de Engenharia Quimica de Lorena - FAENQUIL,
Technology, Atlanta, Georgia, USA Lorena, Sao Paulo, Brazil
Miller, R. L. Schoff, C. K.
Michigan Molecular Institute, Midland, Michigan, USA PPG Industries, Allison Park, Pennsylvania, USA
Morita, Y. Schuld, N.
Japan Atomic Energy Research Institute, Takasaki, Institut fur Physikalische Chemie, Universitat Mainz, Mainz,
Gunma-ken, Japan FR Germany
Seferis, J. C. Wagener, K. B.
Chemical Engineering Department, University of Washington, Department of Chemistry and Center for Macromolecular
Seattle, Washington, USA Science and Engineering, University of Florida, Gainesville,
Florida, USA
Seguchi, T.
Japan Atomic Energy Research Institute, Takasaki, Gunma-ken, Whiteman, N. F.
Japan The Dow Chemical Company, Freeport, Texas, USA
Schrader, D. Witenhafer, D. E.
The Dow Chemical Company, Midland, Michigan, USA Dublin, Ohio, USA
Sperati, C. A. Wolf, B. A.
Chemical Engineering Department, Ohio University, Athens, Institut fur Physikalische Chemie, Universitat Mainz, Mainz,
Ohio, USA FR Germany
Steinmeier, D. G.
Wu, S.
Physikalische Chemie, Universitat Osnabriick, Osnabruck,
E. I. DuPont de Nemours, Central Research and Development
FR Germany
Department, Experimental Station, Wilmington, Delaware
Tsunashima, Y.
Wunderlich, B.
Institute for Chemical Research, Kyoto University, Uji, Kyoto,
Department of Chemistry, University of Tennessee, Knoxville,
Japan
Tennessee, USA
Tsvetkov, N. V.
Wunderlich, W.
Institute of High Molecular Weight Compounds, Russian
Academy of Science, St. Petersburg, Russian Federation ROHM GmbH, Darmstadt, FR Germany
Tsvetkov, V. N. Yamada, B.
Institute of High Molecular Weight Compounds, Russian Department of Applied Chemistry, Faculty of Technology,
Academy of Science, St. Petersburg, Russian Federation Osaka City University, Sumiyoshi, Osaka, Japan
Ueda, A. Zhu, L.
Osaka Municipal Technical Research Institute, Morinomiya, The Maurice Morton Institute of Polymer Science, University
Joto-ku, Osaka, Japan of Akron, Akron, Ohio, USA
Preface
The purpose of the Polymer Handbook is to bring together A critical evaluation of the values published in the
the data and constants needed in theoretical and experi- literature was not attempted, since such a task would have
mental polymer research. All polymer researchers have required an inordinate amount of time and a sizable staff.
experienced the frustration of searching for data in the ever- Therefore, the users of this Handbook should consult the
expanding polymer literature and know the difficulties original literature for details when in doubt about the
involved in trying to locate a particular constant that is validity of any data. (The authors of the individual tables
buried in a long journal article. The contributors to this were nevertheless requested to eliminate obviously erro-
Handbook have taken on the arduous task of searching the neous data from otherwise complete compilations.)
literature and compiling the data and constants that polymer The Fourth Edition revisions have focused on data
chemists, polymer physicists, and polymer engineers are generated in the ten years since the publication of the Third
likely to need. Edition. Therefore, a completely revised Polymer Hand-
The 520 and odd tables in this Handbook are divided into book has been prepared. We have added new tables and
eight sections. The first lists the IUPAC nomenclature rules incorporated a large amount of new data into existing
for polymers and the International System of Units. tables. As a result, the Fourth Edition contains approxi-
Although several naming conventions exist in the technical mately twenty-five percent more data, and the number of
literature, IUPAC names permit a consistent listing of all pages has increased from about 1850 in the Third Edition to
polymers. Section II contains data and constants needed for about 2250.
polymer synthesis, kinetic mechanisms, and thermody- We hope that this new edition will be as useful to the
namic studies of polymerization and depolymerization polymer research community as the three earlier editions
reactions. Sections III and IV contain physical constants and that many of the Polymer Handbook's previous users
of monomers, solvents, and oligomers. Section V lists the will also obtain the Fourth Edition for their laboratory and
physical constants of many important commercial poly- library.
mers. Section VI and VII cover the solid state properties of The publisher plans a CD-ROM for the Polymer
polymers and the properties of polymer solutions. Section Handbook in the near future. We would be grateful if our
VIII of the Handbook lists the commonly used abbrevia- contributors and users send us any new data they
tions or acronyms for polymers and Chemical Abstract accumulate in the course of their research, and any errors,
Registry Numbers, and gives suggestions for electronic data misprints, omissions and other flaws. We will pass on such
searching for polymer information. This section should also data to the publisher, for the polymer database, and for
be consulted in the few cases where contributors have not future editions of this Handbook.
used IUPAC nomenclature. We would like to thank all of the contributors to the
As in the previous editions, the Polymer Handbook Polymer Handbook for their help and continued patience.
concentrates on synthetic polymers, poly(saccharides) and The staff at John Wiley, especially Carla Fjerstad, Shirley
derivatives, and oligomers. Few data on biopolymers are Thomas, and Jacqueline Kroschwitz, have provided excel-
included. Spectroscopic data as well as data needed by lent help and support in getting all the work done. We hope
engineers and designers, such as mechanical and rheologi- that the outstanding efforts of all these people will find due
cal data, are minimized, since many excellent compilations appreciation among the users of this Handbook.
exist elsewhere. Only fundamental constants and para-
meters that refer to the polymer molecule, that describe the July, 1998 J. Brandrup
solid state of polymer molecules, or that describe polymer E. H. Immergut
solutions, were compiled. Constants that depend on E. A. Grulke
processing conditions or on sample history were not A. Abe
emphasized, as they can be found in existing plastics D. R. Bloch
handbooks and encyclopedias.
Contents
Contributors ............................................................................................................................. v
Preface .................................................................................................................................... ix
I. Nomenclature Rules – Units
Nomenclature ............................................................................................................................................... I/1
A. Introduction ........................................................................................................................ I/1
B. IUPAC Recommendations .................................................................................................. I/1
1. Source-based Nomenclature .................................................................................. I/2
1.1 Homopolymers ........................................................................................ I/2
1.2 Copolymers ............................................................................................. I/2
1.3 Nonlinear Macromolecules and Macromolecular Assemblies ................ I/3
2. Structure-based Nomenclature ............................................................................... I/3
2.1 Regular Single-strand Organic Polymers ............................................... I/3
2.2 Regular Double-strand Organic Polymers .............................................. I/6
2.3 Regular Single-strand Inorganic and Coordination Polymers ................. I/6
2.4 Regular Quasi-single-strand Coordination Polymers .............................. I/7
2.5 Irregular Single-strand Organic Polymers ............................................... 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 ..................................... II/2
Table 1. Azonitriles ............................................................................................................... II/2
Table 2. Miscellaneous Azo-derivatives ................................................................................ II/9

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xii Contents
Table 3. Alkyl Peroxides ....................................................................................................... II/23
Table 4. Acyl Peroxides ........................................................................................................ II/29
Table 5. Hydroperoxides and Ketone Peroxides .................................................................. II/43
Table 6. Peresters and Peroxycarbonates ............................................................................ II/48
Table 7. Miscellaneous Initiators ........................................................................................... 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 Propagation and Termination Constants ............................................................. II/79
Table 1. Dienes ..................................................................................................................... II/79
Table 2. Olefins ..................................................................................................................... II/79
Table 3. Acrylic Derivatives ................................................................................................... II/80
Table 4. Methacrylic Derivatives ........................................................................................... II/82
Table 5. Itaconic Derivatives ................................................................................................. II/85
Table 6. Fumaric Derivatives ................................................................................................ II/87
Table 7. Vinyl Halides ........................................................................................................... II/87
Table 8. Vinyl Esters ............................................................................................................. II/87
Table 9. Vinyl Ethers ............................................................................................................. II/88
Table 10. Styrene Derivatives ................................................................................................. II/88
Table 11. Vinyl Heteroaromatics ............................................................................................. II/90
Table 12. Aldehydes ............................................................................................................... II/90
Table 13. Others ..................................................................................................................... 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 ............................................................................................. II/98
Table 1. Transfer Constants to Monomers ........................................................................... II/98
Table 2. Transfer Constants to Polymers ............................................................................. II/103
Table 3. Transfer Constants to Catalysts and Initiators ........................................................ II/106
Table 4. Transfer Constants to Solvents and Additives ........................................................ II/110
Table 5. Transfer Constants to Sulfur Compounds ............................................................... II/150
C. Remarks ............................................................................................................................. II/157
D. References ......................................................................................................................... II/159
Photopolymerization Reactions ................................................................................................................... II/169
A. Introduction ........................................................................................................................ II/169
B. Tables ................................................................................................................................ II/170
Table 1. Rate Constants of Cleavage, Electron Transfer and Monomer Quenching in
Radical Photoinitiators ............................................................................................ II/170
Annex to Table 1. Photoinitiator Compound Chemistries ...................................... II/173

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Contents xiii
Table 2. Bimolecular Rate Constants for the Reaction of Phosphonyl Radicals with
Various Monomers in Cyclohexane at Room Temperature .................................... II/176
Table 3. Bimolecular Rate Constants for the Reaction of Various Radicals with
Various Olefinic Monomers at Room Temperature ................................................. II/176
Table 4. Bimolecular Rate Constants for the Reaction of Ph P = O and Ph P = S with
2 2
Various Monomers .................................................................................................. II/176
Table 5. Electron Transfer Reaction of Radicals with Diphenyliodonium Salts .................... II/176
Table 6. Electron Transfer Rate Constants (k ) between Photosensitizers and
e
Cationic Photoinitiators and Quenching Rate Constants (k ) for Cyclohexene
q
Oxide in Methanol (M) and Acetonitrile (AN) .......................................................... II/177
Table 7. Excitation Transfer Rate Constants (k ) for Thioxanthones and
T
Photoinitiators ......................................................................................................... II/178
Annex to Table 7. Compound Chemistries ............................................................ II/178
Table 8. Triplet State Lifetimes (τ ) of the Sensitizer (TXI) in Different Media, and
T
Rate Constant (k ) of the Interaction between TXI and TPMK ............................... II/179
T
Table 9. Some Values of the Triplet State Energy Levels of Photoinitiators and
Monomers ............................................................................................................... II/179
Table 10. Values of τ0 , τ , and kb in Solution ........................................................................ II/179
T T a
Table 11. Rate Constant of Interaction of Ketones and Light Stabilizers in Solution .............. II/179
Annex to Table 11 ................................................................................................... II/179
C. References ......................................................................................................................... II/180
Free Radical Copolymerization Reactivity Ratios ....................................................................................... II/181
A. Introduction ........................................................................................................................ II/181
B. Tables ................................................................................................................................ II/182
Table 1. Copolymer Reactivity Ratios ................................................................................... II/182
Acenaphthalene to Fumarate, bis(3-chloro-2-butyl) ................................................ II/182
Fumarate, di-(2-chloroethyl) to N-N-divinylaniline ................................................... II/212
N-vinylimidazole to Styrene, p-2-(2-hydroxypropyl)- ............................................... II/241
Styrene, p-4-methoxyphenyl ketone to Vinylbenzoate, p-, sodium ......................... II/268
Vinylbenzoic acid, p- to Xanthate, S-methacryloyl O-ethyl ..................................... II/285
Table 2. Listing of Quick Basic (Microsoft) Program for Calculating Reactivity Ratios ......... II/288
C. References ......................................................................................................................... II/290
Q and e Values for Free Radical Copolymerizations of Vinyl Monomers and Telogens ........................... II/309
A. Introduction ........................................................................................................................ II/309
B. Q and e Values for Free Radical Copolymerizations .......................................................... II/310
Table 1. Monomers ............................................................................................................... II/310
Table 2. Telogens ................................................................................................................. II/314
Table 3. Monomers Arranged by Q Values ........................................................................... II/314
Table 4. Monomers Arranged by e Values ........................................................................... 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

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xiv Contents
B. Example ............................................................................................................................. II/322
C. Transfer Constants ............................................................................................................. II/322
D. Tables of Parameters ......................................................................................................... II/323
Table 1. Monomers ............................................................................................................... II/323
Table 2. Transfer Agent ........................................................................................................ 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 ................................................. II/329
1. First-order Markov Model ........................................................................................ II/330
2. Second-order Markov Model ................................................................................... II/330
C. Calculation of the Copolymerization Parameters ................................................................ II/331
1. First-order Markov Model ........................................................................................ II/331
1.1. Copolymerization Parameters Deduced from the Mayo-lewis
Equation .................................................................................................. II/331
1.2. Determination of Copolymerization Parameters from the
Sequence Distribution (Triad Distribution) .............................................. II/331
2. Second-order Markov Model ................................................................................... II/332
3. Example .................................................................................................................. II/332
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 .................................................................................................................... II/340
Table 1. Addition Polymerization with Termination ............................................................... II/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

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