Textbook of Polymer Science

597 Pages·2016·23.73 MB·English

by  Fred W. Billmeyer

TEXTBOOK
OF POLYMER SC
THIRD EDITION
FRED W. BILLMEYER, JR.
Professor oj Analytzcal Chemzshy
Rensselaer Polytechnic Instztute, Troy, New York
A Wiley-lnterscience Publication
John Wiley & Sons
New York Chichester Brisbane Toronto Singapore
Copyright Q 1984 by John Wiley & Sons, Inc
All rights reserved Published simultaneously in Canada
Reproduction or translation of any part of this work
beyond that permitted by Section 107 or 108 of the
1976 United States Copyright Act without the permission
of the copyright owner is unlawful Requests for
permission or further information should be addressed to
the Permissions Department, John Wiley & Sons, Inc
Library of Congress Cataloging in Publication Data:
Billmeyer , F~edW
Textbook of polymer science
Includes bibliographies and indexes
1 Polymers and polymerization I Title
QD381 B52 1984 668 9 83-19870
ISBN 0-471-03196-8
Printed in the United States of' America
PREFACE
''I am incllned to think that the development ojpolymer~zationI S,p erhaps, the blggest thrng
chemistry has done, where ~th as had the brggest effect on everyday life The world would
be a totally d~rerenpt lace w~thouta rtijiclal fibers, plastrcs, elastomers, etc Even in the
field of electronics, what would you do wlthout msulatron? And there you come back to
polymers agaln " f
And indeed one does From the lowly thmwaway candy wrapper to the artificial
heart, polymers touch our lives as does no other class of' materials, with no end to
new uses and improved products in sight. Yet, many instances of' the need fbr better
education in the polymer field, both in our universities and for the public, remain
unchanged. Some of these were discussed at length in the Preface to the second
edition of'this book, which fbllows, and I shall not repeat them
The present revision has two major directions. The first is to improve its value
as a textbook. To this end I have rearranged the text to consider polymerization
before describing the properties of'polymers, a change that several of my colleagues
feel has pedagogical advantages I have also drawn on my files from 2.5 yeas of'
teaching polymer science, at the University of' Delaware, the Massachusetts Institute
of' Technology, and Rensselaer Polytechnic Institute, to provide material for a
section on Discussion Questions and Problems at the end of' each chapter
The second objective of' the revision is the more common one, to bring the
contents up-to-date by judicious addition, deletion, and revision, and in this I hope
I have been successful. Many sections have been changed little, reflecting the
maturity of certain aspects of' polymer science, but the reader will find new material
inserted in every chapter. A few additions of' particular note axe a section on
polymerization reaction engineering in Chapter 6, a discussion of scaling concepts
in Chapter 7, and expansion of' the sections on polymer processing in Chapter 17
i Lord Todd, president of the Royal Soclety of London, quoted in Chem Eng News 58(40), 29 (1980),
m answer to the question, What do you think has been chemistry's biggest contribution to science, to
Society?
vi PREFACE
I have tried to include brief descriptions of the new polymer materials in the
marketplace in Chapters 13-16 and in a section on composite materials in Chapter
17 Unfortunately, some discussion of less timely topics had to be eliminated to
prevent undue expansion of the text
My approach to referencing the literature had to remain essentially the same as
that adopted in the second edition, despite some dissenting opinions The explosion
of the literature in polymer science makes it totally impossible to provide full
coverage of original articles, as was possible 20 or 25 years ago I have therefore
cited many new books, and many articles from the Encyclopedza ojPolymer Science
and Technology, the Kirk-Othmer Encyclopedza oj Chemzcal Technology, third
edition, and the Modern Plastics Encyclopedia Each of these sources (save the
last, which provides information on curlent commercial products and processes)
was selected to provide detailed citation of the original literatwe, as well as more
complete coverage of the topic for which it was cited
With retirement imminent, I look back with pleasure on the preparation of this
volume and its predecessors They have brought me much pleasure, more in the
"
friendship of many readers and colleagues than in the accomplishment I hope that
the usefulness of this last revision will surpass that of those before it
Troy, New York
January 1984
ACKNOWLEDGMENTS
I wish to thank many colleagues, both in the Polymer Science and Engineering
Program at Rensselaer and elsewhere, for valuable suggestions that have been
incorporated into this revision Seventy-five Rensselaer students who used a first
draft of about two-thirds of the text in the course Introduction to Polymer Chemistry
also provided helpful ideas and corrections
The text was capably typed and retyped by Peggy Ruggeri To her, to my g~aduate
students, and especially to my patient wife Annette, I owe many thanks

PREFACE TO THE SECOND EDITION
"Dear Colleague, Leave the concept of large molecules well alone there can be no
such thrng as a macromolecule "
It is said7 that this advice was given to Hermann Staudinger just 45 years ago,
after a major lecture devoted to his evidence in favor of the macromolecular concept
Today it seems almost impossible that this violent opposition to the idea of the
existence of polyme~m olecules could have existed in relatively recent times NOW
we take f o ~gr anted not only the existence of macromolecules, but their value to
us in food, clothing, shelter, transportation, communication, most other aspects of
modern technology, and, last but far from least, the muscles, sinews, genes, and
chromosomes that constitute our bodies and intellect
Even within the years since the first edition of Textbook OJ Polymer Science
(1962) was written, the use of synthetic polymers has proIiferated, as discussed in
Chapte~7 E Not only has the annual production of plastics (for example) increased
some 250% in the last eight years, but on a volume basis it has already exceeded
that of copper and aluminum, and is expected to surpass the production of steel by
the mid-1980's. One consequence of this widening use of polymeric materials is
that a substantial if not major fraction of all chemists and chemical engineers, to
say nothing of those in other disciplines, is employed in industry related in some
way to polymers Estimates vary, but this fraction appears to be one-third to one-
half or higher
Education in polymer science has not kept pace By far the majority of colleges
and universities in the United States have no courses in polymer science, no staff
member conducting research in this area, and only cursory mention of polymers in
other courses. There are, needless to say, many exceptions, ranging from the isolated
effort of a single staff member to such major centers for polymer research as those
iR obert Olby, "The Macromolecula~C oncept and the Origins of Molecuia~B iology," J Chem Educ
47, 168-174 (1970)
x PREFACE 'TO THE SECOND EDITION
at Case-Western Reserve, the Universities of' Akson and Massachusetts, and Rens-
selaer, where 10 or more staff members constitute a fbrrnal or infbrmal polymer
research center
Fortunately, this scascity of education in polymer science is slowly diminishing,
but it is still evident in many areas.. What is most unfbr.tunate is that it appears to
exist, not because of'a lack of awareness but, rather, a lack of' interest..F or example,
on several occasions a graduating W.D. student in my own institution has dropped
by to say that he was trained in another area of chemistry and was vaguely awase
of' our polymer science program, but he had now accepted employment with a lasge
company where he was told that he would be working in the polymer field, and
please, was there any way he could learn all about polymers in the short time
remaining before he started the job?
Perhaps we could overlook a few individual instances of'this sort, but it is more
disturbing to note that, while polymeric materials are widely used as previously
indicated, most "materials" cur.r.icula ase merely renamed metallurgy departments
'
giving only lip service to major families of materials other than metals, such as
ceramics and polymers. Again, there are many exceptions, and I do not wish to
leave the impression that this is always the case I have, however, yet to see an
introductory materials course or textbook that treats polymers hirly in accord with
their wide usage throughout the world.
Another dichotomy that deserves mention, and which I wish I had the ability to
overcome, is exemplified by the communications gap between the polymer scientist
as now trained in the university or in industry and the biologist or biomedical
scientist, whose concepts of' macromolecules ase vastly different. Many of' my
colleagues seem to share my feeling that major advances can be made in the next
few years by the application of' polymer physics and physical chemistry to biological
materials
The foregoing commentary emphasizes my feeling that the need for education
in polymer science exists more than ever today, and that it must be filled by teaching
at several levels in several disciplines. Clearly, no single book can serve all needs
in this field, but I hope that in its new edition Te,xtbook oj'Polymer Science will
continue to be valuable in many ways. In the revision I have attempted to keep in
mind its use as supplemental reading material in such undergraduate chemistry
courses as physical chemistry, organic chemistry, and instsumental analysis, where
an effort is made to introduce polymer science into the chemistrly cur~iculuma t
appropriate places; as supplemental reading in other curricula such as biology and
its interdisciplinary offshoots, materials in the broad sense, and the environmental
sciences growing in popularity today; as the textbook in polymer science and
engineering courses at the undergraduate and first-year graduate levels; as supple-
mentary reading to broaden the background of the student in advanced polymer
courses using appropriate specialized texts; in continuing education at the post,-
graduate level, in universities but particularly in industry; and as a reference and
guide to the literature for the practicing polymer scientist and engineer.
Just as the use of' polymers has proliferated in the past decade, so has its literature
The leading journal in the field, Journal ofpolymer Science, has subdivided into
several largely independent parts. New journals have appe&ed, some with national
~REFAC.'ET O THE SEC.OND EDITION xi
society sponsorship, such as Macromolecules, sponsored by the American Chemical
Society, others as commercial ventures Polymer articles, and even polymer sec-
tions, appear in other journals, new and old. POST-J, described below, abstracts
approximately 500 journals for articles on polymers
Abstract journals devoted solely to polymers have appeared POST--J, acronym
for Polymer Science and Technology-Journals, and its companion POST-P (Pat-
ents) are published biweekly, at a rate of 500-700 abstracts per issue in mid-1970,
by the Chemical Abstracts Service of the American Chemical Society i Other such
services exist, sponsored by universities and as commercial ventures
Not only has the number of general and specialized books on polymers increased
at a tremendous rate in recent years, but a number of valuable compilations has
appeared. Outstanding among these are the Encyclopedza of Polymer Sclence and
Technology and the Modern Plastrcs Encyclopedza, both referenced in this book
One result of the appearance of many specialized books and encyclopedias is
that it is no longer necessary for a textbook to cite the original literature in detall;
indeed, it would be impossible to do so today Therefore I have limited references
to specialized books and compilations where possible, on the assumption that most
of them will be as readlly available as the original literature and can in their turn
cover the subject more completely than is possible in the present volume The
exceptions, aside from some key references of historical value, lie in the areas
where adequate specialized coverage has not yet appeared The reader will recognize
these areas by the extent and content of the bibliography at the end of each chapter
In revising the Textbook of Polymer Science, I have reached the conclusion that
many of the basic principles of polymer science are now well established Examples
are the kinetics of condensation and free-radlcal addition polymerization In areas
such as these, the reader will find only minor changes from the 1962 edition
Elsewhere the revision has been more extensive Much new material has been
added, particularly in areas still under rapid development This has had to be
counterbalanced by the omission of an equivalent amount of material that no longer
represents the current state of our knowledge, or was of lesser or only historical
interest, in order to keep the length (and price) of the volume in hand.
The actual arnngement of material has undergone little change Chapters 1--4
now comprise Part I, dealing with introductory concepts and the characterization
of macromolecules Important additions in this section include discussion of sol-
ubility parameters, free-volume theories of polymer solution thermodynamics, gel
permeation chromatography, vapor-phase osmometry, and scanning electron mi-
croscopy, with extensive revision of many other sections
Part I1 (Chapters 5-7) deals with the structure and properties of bulk polymers
and includes considerable revision of parts of Chapter 5, where a few of the concepts
of crystallinity in polymers, new in 1962, have had to be modified as our knowledge
in this area has grown Chapter 7 has been revised in order of presentation, with
considerable new material added
The format and content of Part 111, concerned with polymerization kinetics, have
?Post-J and Post-P ale now combined and issued as part of the Mac~omolecularS ections of Chemical
Abstracts (footnote added in 1983)