Macromolecules: Volume 1 · Structure and Properties

1228 Pages·1977·115.785 MB·English

by  Hans-Georg Elias (auth.)

Macromolecules ·1
Structure and Properties
Macromolecules
VOLUME 1 • Structure and Properties
VOLUME 2 • Synthesis and Materials
Macromolecules ./
Structure and Properties
Hans-Georg Elias
Midland Macromolecular Institute
Midland, Michigan
Translated from German by John W. Stafford
SPRINGER SCIENCE+BUSINESS MEDIA, LLC
Library of Congress Cataloging in Publication Data
Elias, Hans-Georg, 1928-
Macromolecules.
Translation of Makromolekiile.
Includes bibliographical references and indexes.
CONTENTS: v. 1. Structure and properties. - v. 2. Synthesis and materials.
1. Macromolecules. I. Title. [DNLM: 1. Macromolecular systems. QD381
E42m]
QD381.E4413 574.1'924 76-46499
ISBN 978-1-4615-7366-1 ISBN 978-1-4615-7364-7
DOl 10.1007/978-1-4615-7364-7
© 1977 Springer Science+Business Media New York
Originally published by Plenum Press, New York in 1977
Softcover reprint of the hardcover 1st edition 1977
All rights reserved
No part of this book may be reproduced, stored in a retrieval system, or transmitted,
in any form or by any means, electronic, mechanical, photocopying, microfilming,
recording, or otherwise, without written permission from the Publisher
Acknowledgments
The permlSSlOn of the following publishers to reproduce tables and figures is gratefully acknowl
edged:
Part I
Academic Press, London: D. Lang, H. Bujard, B. Wolff, and D. Russell, I. Mol. Bioi. 13, 163
(1967) (Fig. 4-10).
Akademie Verlag, Berlin: H. Dautzenberg, Faser/orsch. Textiltech. 11, 117 (1970) (Fig. 4-18).
American Chemical Society, Washington, D.C.: P. Doty and J. T. Yang, J. Am. Chem. Soc. 78,
498 (1956) (Fig. 4-24); M. Goodman and E. E. Schmitt, I. Am. Chem. Soc. 81, 5507 (1959)
(Fig. 4-20); S. I. Mizushima and T. Shimanouchi, I. Am. Chem. Soc. 86, 3521 (1964)
(Table 4-4).
American Institute of Physics, New York: W. D. Niegisch and P. R. Swan, I. Appl. Phys. 31,
1906 (1960) (Fig. 5-15).
Butterworths, London: A. Nakajima and F. Hameda, Macromolecular Chemistr}' 8 and 9, Pro
ceedings, lUPAC (1972), p. 1 (Fig. 5-21).
W. H. Freeman and Company, Publishers, San Francisco: M. F. Perutz, Sci. Am. 1964 (Nov.), 71
(Fig. 4-19).
Gazzetta Chimica ltaliana, Rome: G. Natta, P. Corradini, and I. W, Bassi, Gazz. . Chim. Ital. 89,
784 (1959) (Fig. 4-5). . . . .
Interscience Publishers, New York: T. M. Birshtein and O. B, Ptitsyn, Con/ormation of Macro
molecules, p. 34 (Fig. 4-2); P. H. Lindenmeyer, V. F: Holland, and F. R. Anderson,
I. Polym. Sci. C 1, 5 (1963) (Figs. 5-16, 5-17, and 5-19); P. J. Flory, Statistical Mechanics 0/
Chain Molecules (1969), Chapter V, Fig. 9 (Fig. 4-14); J. Berry and E. F. Casassa, I. Polym.
Sci. D 4, 33 (1972) (Fig. 4-15); P. Pino, F. Ciardelli, G MontagnoIi, and O. Pieroni, Polym.
Lett. 5, 307 (1967) (Fig. 4-21); A. Jeziorny and S. Kepka, J. Pol),m. Sci. B 10, 257 (1972)
(Fig. 5-4); H. D. Keith, F. J. Padden and R. G. Vadimsky, I. Polym. Sci. A 2 (4), 267 (1966)
(Fig. 5-22).
Kogyo Chosakai Pub. Co., Tokyo, Japan: M. Matsuo, Japan Plastics, 1968 (July), 6 (Fig. 5-31).
Pergamon Press, New York: J. T. Yang, Tetrahedron 13, 143 (1961) (Fig. 4-23).
Societa Italiana di Fisica, Bologna: G. Natta and P. Corradini, Nuol'O Cimento Suppl. 15, 111 (1960)
(Fig 5-9).
D. Steinkopff Verlag, Darmstadt: A. J. Pennings, J. M. M. A. van der Mark, and A. M. Ken,
Kol/oid-Z., 237, 336 (1970) (Fig. 5-28).
Textile Research Institute, Princeton, N. J.: H. M. Morgan, Textile Res. J., 32, 866 (1962)
(Fig. 5-33).
Verlag Chemie, Weinheim/Bergstrasse: L. Pauling, Die Natur der chemischen Bindung, p. 80
(Table 2-2); H. Staudinger and E. Husemann, Liebigs Ann. Chem. 527 (1937) 195 (Table 1-3).
Part II
Akademie-Verlag, Berlin: K. Edelmann, Faserforsch. Textiltech. 3, 344 (1952) (Fig. 7-6).
American Chemical Society, Washington, D.C.: K. G. Siow, G. Delmas, and D. Patterson, Macro
molecules 5, 29 (1972) (Fig. 6-10).
The Biochemical Journal, London: P. Andrews, Biochem. J. 91, 222 (1964) (Fig. 9-18).
Butterworths, London: H. P. Schreiber, E. B. Bagley, and D. C. West, Polymer 4, 355 (1963)
(Fig. 7-7).
The Faraday Society, London: R. M. Barrer, Trans. Faraday Soc. 35,·628 (1939) (Table 7-2);
R. B. Richards, Trans. Faraday Soc. 41, 10 (1946) (Fig. 6-19).
General Electric Co., Schenectady: A. R. Schultz, General Electric Report 67-C-072 (Fig. 6-15).
Carl Hanser Zeitschriften Verlag, Munchen: G. Rehage, Kunststoffe 53, 605 (1963) (Fig. 6-11).
Institution of the Rubber Industry, London: G. Gee, Trans. Inst. Rubber Ind. 18, 266 (1943)
(Fig. 6-1).
Interscience Publishers, New York: T. G. Fox, I. Polym. Sci. C 9, 35 (1965) (Fig. 7-8); G. Rehage
and D. Moller, I. Polym. Sci. C 16, 1787 (1967) (Fig. 6-14); Z. Grubisic, P. Rempp, and
H. Benoit, J. Polym. Sci. B S, 753 (1967) (Fig. 9-19).
Journal of the Royal Netherlands Chemical Society, 's-Gravenhage: D. T. F. Paals and J. J.
Hermans, Rec. Trav. 71, 433 (1952) (Fig. 9-25).
Pergamon Press, New York: H. Hadjichristidis, M. Devaleriola, and V. Desreux Eur. Polym. I.
8, 1193 (1972) (Fig. 9-27).
Springer Verlag, New York: H.-G. Elias, R. Bareiss, and J. G. Watterson, Adv. Polym. Sci. 11,
111 (1973) (Fig. 8-6).
Verlag Chemie, Weinheim/Bergstrasse: H. Benoit, Ber. Bunsenges 70, 286 (\966) (Fig. 9-5);
G. V. Schulz, Ber. Dtsch. Chem. Ges. 80, 232 (1947) (Fig. 9-1).
Part III
American Institute of Physics, New York: H. D. Keith and F. J. Padden, Jr., J. Appl. Phys. 30,
1479 (1959) (Fig. 11-15); R. S. Spencer and R. F. Boyer, J. Appl. Phys. 16, 594 (1945) (Fig.
11-17).
Badische Anilin- & Soda-Fabrik AG, Ludwigshafen: Kunststofl-Physik im Gespriich, pp. 103, 107
(Figs. 11-1 and 11-2).
Butterworths, London: A. Sharples, Polymer 3, 250 (1962) (Fig. 10-7); A. Gandica and J. H.
Magill, Polymer 13, 595 (1972) (Fig. 10-9).
Engineering, Chemical & Marine Press, Ltd., London: R. A. Hudson, Brit. Plast. 26, 6 (1953)
(Fig. 11-12).
The Faraday Society, London: L. R. G Treloar, Trans. Faraday Soc. 40, 59 (1944) (Fig. 11-5).
General Electric Co., Schenectady: F. E Karasz, H. E. Bair, and J. M. O'Reilly, General Electric
Report 68-C-OOI (Fig. 10-4).
Interscience Publishers, New York: N. Berendjick, in: Newer Methods of Polymer Characteriza
tion (B. Ke, ed.) (1964) (Fig. 13-1); J. P. Berry, J. Polym. Sci. 50, 313 (1961) (Fig. 11-14); O. B.
Edgar and R. Hill, J. Polym. Sci. 8, 1 (1952) (Fig. 10-17); K. V. Fulcher, D. S. Brown, and
R. E. Wetton, J. Polym. Sci. C 38, 315 (1972) (Fig. 10-10); H. W. McCormick, F. M. Brower,
and L. Kin, J. Poly",. Sci. 39, 87 (1959) (Fig. 11-16); N. Overbergh, H. Bergmans, and
G. Smets, J. Polym. Sci. C 38, 237 (1972) (Fig. 10-12); G. Rehage and W. Borchard, in:
The Physics of the Glassy State (R. N. Haward, ed.), p. 54 (Fig. 10-2); P. I. Vincent,
Encyclopedia of Polymer Science Technology, Vol. VII, p. 292 (Fig. 11-10); A. Ziabicki, in:
Man-Made Fibers (H. Mark, S. M. Atlas, and E. Cernia, eds.), Vol. I (1967), pp. 17, 21
(Figs. 12-4 and 12-5).
Japan Synthetic Rubber Co., Tokyo: anon., Japan Synthetic Rubber News 10 (I) (1972) (Fig. 10-18).
Verlag B. M. Leitner, Wien: F. Patat, AUg. Prakt. Chem. 18, 96 (1967) (Fig. 13-5).
McGraw-Hili Book Co., New York: A. X. Schmidt and C. A. MarJies, Principles of High Polymer
Theory and Practice (1948), p. 66 (Fig. 10-6).
Research Group of Polymer Physics in Japan, Tokyo: H. Tadokoro, Y. Chatani, M. Kobayashi,
T. Yoshihara, S. Murahashi, and K. lmada, Rep. Prog. Polym. Phys. Jpn 6, 305 (1963)
(Fig. 10-15).
Society of Plastics Engineers, Greenwich, Conn.: J. D. Hoffman, SPE Trans. 4, 315 (1964)
(Fig. 10-11).
Springer-Verlag, Berlin: H. Mark, in: Die Physik der Hochpolymeren (H. A. Stuart, ed.), Vol. IV
(1956), p. 630 (Table 12-5).
Dr. Dietrich Steinkopff Verlag, Darmstadt: G. Kanig, Ko/loid-Z. 190, I (1963) (Fig. 10-22).
Van Nostrand Reinhold Company, New York: R. C. Bowers and W. A. Zisman, in: Engineering
Design for Plastics (E. Baer, ed.), p. 696 (Fig. 13-4).
Verlag Chemie, Weinheim/Bergstrasse: K.-H. IIIers, Ber. Bunsenges. 70, 353 (1966) (Fig. 10-20);
G. Rehage, Ber. Bunsenges. 74, 796 (1970) (Fig. 10-3).
Part IV
Akademische Verlagsgesellschaft, Leipzig: G. V. Schulz, A. Dinglinger, and E. Husemann,
Z. Phys. Chem. B43, 385 (1939) (Fig. 20-7).
American Chemical Society, Washington: P. J. Flory, J. Am. Chem. Soc. 63, 3083 (1941) (Fig.
17-5); H. P. Gregor, L. B. Luttinger, and E. M. Loebl, J. Phys. Chern. 59, 34 (1955) (Fig.
23-4); G. V. Schulz, Cherntech., 1973 (April), 224 (Fig. 18-3), 221 (Fig. 20-3).
Butterworths, London: C. E. H. Bawn and M. B. Huglin, Polymer 3, 257 (1962) (Fig. 17-6);
D. R. Burfield and P. J. T. Tait, Polymer 13, 307 (1972) (Figs. 19-1 and 19-2); I. D. McKenzie,
P. J. Tait, and D. R. Burfield, Polymer 13, 307 (1972) (Fig. 19-3).
The Chemical Society, London: W. C. Higginson and N. S. Wooding, J. Chern. Soc. 1952, 774
(Table 18-1).
Chemie-Verlag Vogt-Schild AG, Solothurn: G. Henrici-Olive and S. Olive, Kunstst.-Plast. 5,
315 (1958) (Figs. 20-4 and 20-5).
The Faraday Society, London: F. S. Dainton and K. J. Ivin, Trans. Faraday Soc. 46, 331 (1950)
(Table 16-9).
Interscience Publishers, New York: E. J. Lawton, W. T. Grubb, and J. S. Balwit, J. Polym. Sci.
19, 455 (1956) (Fig. 21-1).
The Royal Society, London: N. Grassie and H. W. Melville, Proc. R. Soc. (London) A 199, 14
(1949) (Fig. 23-6).
Verlag Chemie, Weinheim/Bergstrasse: F. Patat and Hj. Sinn, Angew. Chem. 70, 496 (1958)
(Eq. 19-11); G. V. Schulz, Ber. Dtsch. Chern. Ges. 80, 232 (1947) (Fig. 20-6); J. Smid, Angew.
Chern. 84, 127 (1972) (Fig. 18-1); K. J. Ivin, Angew. Chem. 85, 533 (1973) (Fig. 16-3).
Part V
Academic Press, New York: R. S. Baer, Adv. Protein Chern. 7, 69 (1952) (Fig. 30-3).
W. H. Freeman and Company Publishers, 'San Francisco: Hans Neurath, "Protein-digesting
enzymes," Sci. Am. 1964 (December), 69 (Fig. 30-1).
Interscience Publishers, New York: J. F. Brown, Jr., J. Polyrn. Sci. C 1, 83 (1963) (Fig. 33-3).
Verlag Chemie, Weinheim/Bergstrasse: E. Thilo, Angew. Chern. 77, 1057 (1965) (Fig. 33-4).
Didici in mathematicis ingenio, in natura
experimentis, in /egibus divinis humanisque
auctoritate, in historia testimoniis nitendum esse,
G. W. Leibniz
{I learned that in mathematics one depends on inspiration,
in science on experimental evidence, in the study of divine
and human law on authority, and in historical research on
authentic sources.}
Preface
Like so many of its kind, this textbook originated from the requirements
of teaching. While lecturing on macromolecular science as a required
subject for chemists and materials scientists on the undergraduate, graduate,
and postgraduate levels at Swiss Federal Institute of Technology at Zurich
(1960-1971), I needed a one-volume textbook which treated the whole
field of macromolecular science, from its chemistry and physics to its
applications, in a not too elementary manner. This textbook thus intends to
bridge the gap between the often oversimplified introductory books and
the highly specialized texts and monographs that cover only parts of
macromolecular science. This first English edition is based on the third
German edition (1975), which is about 40% different from the first German
edition (1971), a result of rapid progress in macromolecular science and
the less rapid education of the writer.
This text intends to survey the whole field of macromolecular science.
Its organization results from the following considerations.
The chemical structure of macromolecular compounds should be
independent of the method of synthesis, at least in the ideal case. Part I
is thus concerned with the chemical and physical structure of macro
molecules.
Properties depend on structure. Solution properties are thus discussed
in Part II, solid state properties in Part III. There are other reasons for
discussing properties before syntheses: For example, it is difficult to under
stand equilibrium polymerization without knowledge of solution thermody
namics, the gel effect without knowledge of the glass temperature, etc.
Part IV treats the principles of macromolecular syntheses and reactions.
The emphasis is on general considerations, not on special mechanisms,
ix
x Preface
which are treated in Part V. Part V is a surveylike description of important
polymers, especially the industrially important ones. It also contains
information about industrial monomer syntheses and selected biopolymers.
Undergraduate-level knowledge of inorganic, organic, and physical
chemistry is assumed for the study of certain chapters. Whenever possible,
all treatments and derivations were developed step-by-step from basic
phenomena and concepts. In certain cases, I found it necessary to replace
rigorous and mathematically complex derivations by simpler ones. I
very much hope that this makes the book suitable for self-study.
Physical quantities are expressed in SI units. In many cases, the
gram and not the kilogram was chosen as the more convenient unit and
commas to group numbers have been retained, in addition to decimal points.
Most symbols for physical quantities correspond to those recommended by
the International Union of Pure and Applied Chemistry, although sometimes
others had to be chosen for the sake of clarity.
A textbook must, of necessity, rely heavily on secondary literature
available as review articles and monographs. Although I have consulted
more than 5000 original papers before, during, and after the compilation
of the individual chapters, I have (with the exception of one area) not
cited the original literature. The exception is in the historical development
of the subject, and this exception has been made because I was unable
to find an accessible, balanced account treating macromolecular science
in terms of the development of its ideas and concepts. I believe also that
reading these old original works rewards the student with an insight on
how a better understanding of the observed phenomena developed from the
difficulties, prejudices, and ill-defined concepts of the times. However,
because of the width and diversity of the field, a fully comprehensive and
historically sound treatment of the development of its ideas and discoveries
is beyond the scope of this work. Thus, since I have not been able to give
due recognition to the work of individual chemists and physicists, I have
only used names in the text when they have become termini technici in
relation to methodology, phenomena, and reactions (for example: Ziegler
catalysis, Flory-Huggins constant, Smith-Harkins theory, etc.). The
occasional use of trade names cannot be taken to mean that these are
free for general use.
In writing this book, I have tried to follow the practice of Dr. Andreas
Libavius, * who had
principally taken, from the most far-flung sources, individual data from the best authors,
old and new, and also from some general texts, and these were then, according to
theoretical considerations and the widest possible experience, carefully interpreted
and painstakingly molded into a homogeneous treatise.
The reader may judge how much of this is true of this book.
* Alchemia, chemistry textbook from the year 1597; new edition in German, Gmelin Institute,
1964.