Applied Polymer Science

1301 Pages·1985·22.404 MB·English

by  Roy W. Tess and Gary W. Poehlein (Eds.)

ACS SYMPOSIUM SERIES 285
Applied Polymer Science
Second Edition
Roy W. Tess, EDITOR
Gary W. Poehlein, EDITOR
American Chemical Society, Washington, D.C. 1985
In Applied Polymer Science; Tess, R., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1985.
Library of Congress Cataloging in Publication Data
Applied polymer science.
(ACS symposium series, ISSN 0097-6156; 285)
Includes bibliographies and indexes.
1. Polymers and polymerization.
I. Tess, Roy W. (Roy William), 1915-
II. Poehlein, Gary W. III. Series.
QD381.A66 1985 547.7
ISBN 0-8412-0891-3
Copyright © 1985
American Chemical Society
All Rights Reserved. The appearance of the code at the bottom of the first page of each
chapter in this volume indicates the copyright owner's consent that reprographic copies of the
chapter may be made for personal or internal use or for the personal or internal use of specific
clients. This consent is given on the condition, however, that the copier pay the stated per
copy fee through the Copyright Clearance Center, Inc., 27 Congress Street, Salem, MA 01970,
for copying beyond that permitted by Sections 107 or 108 of the U.S. Copyright Law. This
consent does not extend to copying or transmission by any means—graphic or electronic—for
any other purpose, such as for general distribution, for advertising or promotional purposes,
for creating a new collective work, for resale, or for information storage and retrieval systems.
The copying fee for each chapter is indicated in the code at the bottom of the first page of the
chapter.
The citation of trade names and/or names of manufacturers in this publication is not to be
construed as an endorsement or as approval by ACS of the commercial products or services
referenced herein; nor should the mere reference herein to any drawing, specification, chemical
process, or other data be regarded as a license or as a conveyance of any right or permission,
to the holder, reader, or any other person or corporation, to manufacture, reproduce, use, or
sell any patented invention or copyrighted work that may in any way be related thereto.
Registered names, trademarks, etc., used in this publication, even without specific indication
thereof, are not to be considered unprotected by law.
PRINTED IN THE UNITED STATES OF AMERICA

In Applied Polymer Science; Tess, R., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1985.
ACS Symposium Series
M. Joan Comstock, Series Editor
Advisory Board
Robert Baker Rober Or
U.S. Geological Survey
Martin L. Gorbaty
Geoffrey D. Parfitt
Exxon Research and Engineering Co.
Carnegie-Mellon University
Roland F. Hirsch
James C. Randall
U.S. Department of Energy
Phillips Petroleum Company
Herbert D. Kaesz Charles N. Satterfield
University of California—Los Angeles Massachusetts Institute of Technology
Rudolph J. Marcus W. D. Shults
Office of Naval Research Oak Ridge National Laboratory
Charles S. Tuesday
Vincent D. McGinniss
General Motors Research Laboratory
Battelle Columbus Laboratories
Douglas B. Walters
Donald E. Moreland National Institute of
USDA, Agricultural Research Service Environmental Health
W. H. Norton C. Grant Willson
J. T. Baker Chemical Company IBM Research Department
In Applied Polymer Science; Tess, R., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1985.
FOREWORD
The ACS SYMPOSIUM SERIES was founded in 1974 to provide a
medium for publishing symposia quickly in book form. The
format of the Series parallels that of the continuing ADVANCES
IN CHEMISTRY SERIES except that, in order to save time, the
papers are not typeset but are reproduced as they are submitted
by the authors in camera-ready form. Papers are reviewed under
the supervision of th
Advisory Board and
symposia; however, verbatim reproductions of previously pub
lished papers are not accepted. Both reviews and reports of
research are acceptable, because symposia may embrace both
types of presentation.
In Applied Polymer Science; Tess, R., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1985.
PREFACE
SURFACE COATINGS, PLASTICS, POLYMER CHEMISTRY, AND RELATED
TOPICS were covered in the 1975 edition of Applied Polymer Science. The
favorable reception of the original edition, as well as specific requests for a
new edition because of the many new developments in the field, has
encouraged us to undertake the preparation of this new volume. Some
entirely new chapters on new topics include the following: Transport
Properties of Polymers, Fractur
Polymers, Foamed Plastics
Insulation, Medical Applications of Polymers, Resins for Aerospace,
Polymer Processing, Corrosion Control by Organic Coatings, Appliance
Coatings, Polymer Coatings for Optical Fibers, and Paint Manufacture. A
chapter entitled Introduction to Polymer Science and Technology has been
included for the first time to provide some definitions of polymer terms, to
cover certain omissions in the original and current editions, and to ease the
way for the general reader or student. In this chapter, certain topics pertinent
to an introduction have been covered only briefly or occasionally not at all
because the topics are covered thoroughly in subsequent chapters. On the
other hand, limited repetition has been tolerated among different chapters
when it seemed desirable to provide continuity of thought within a chapter.
Several chapters in the original edition have been deleted in this volume
for the following reasons: in two cases because of their strictly historical
nature; the lack of substantive new developments in the topic; and the
nonavailability of the original authors. Quite a few new authors were
recruited to prepare entirely new or revised versions of former chapters.
Unfortunately, some promised chapters never were forthcoming and had to
be abandoned. Although all topics of potential interest simply could not be
included in the present volume, nevertheless a very broad range of topics has
been covered. The original edition should continue to be useful because it
contains some chapters, including those of historical importance, that are not
repeated in this new edition.
The subject matter of this book represents a major segment of chemical
industry and a growing segment of the chemical curriculum in academia.
Reflecting the interest of both industry and academia in the topics, the
authors and editors of this volume are affiliated with industry, academia, or
both. It is hoped that this book will find use by students and teachers in
ix
In Applied Polymer Science; Tess, R., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1985.
coursework and research as well as by scientific and technical personnel in
industrial and governmental work.
Acknowledgments
We are indebted to the capable and conscientious contributing authors
who are among the foremost authorities in their fields. We also thank the
Executive Committee of the Division of Polymeric Materials: Science and
Engineering for its endorsement of this book, and the staff of the American
Chemical Society Books Department for their help and advice. Useful
comments were made by an advisory committee consisting of J. K. Craver,
R. R. Myers, J. L. Gardon, D. R. Paul, R. D. Deanin, R. B. Seymour, J. K.
Gillham, C. E. Carraher, J. C. Weaver, K. L. DeVries, and L. F. Thompson.
Many experts have been helpful in providing outside reviews of
chapters. We express our appreciation to the following: D R Paul Aldo
DeBenedictis, F. M. McMillan
Klein, J. W. Gooch, Charles Aloisio, John Muzzy, Alan Berens, F. J.
Schork, A. P. Yoganathan, Albin Turbak, Miroslav Marek, T E. Futern,
Robert Samuels, Wayne Tincher, J. D. Willons, George Fowies, S. S.
Labana, T. J. Miranda, J. E. Carey, J. P. McGuigan, A. L. Rocklin, J. K.
Gillham, G. D. Edwards, J. M. Klarquist, G. G. Velten, G. A. Short, T K.
Rehfeldt, E. W. Starke, Jr., D. C. Rich, A. G. Rook, and S. L. Davidson.
The generosity of several publishers in permitting reproduction of text and
figures is gratefully acknowledged and mentioned specifically at various
places in the text.
ROY W. TESS
Consultant
P.O. Box 577
Fallbrook, CA 92028
GARY W. POEHLEIN
School of Chemical Engineering
Georgia Institute of Technology
Atlanta, GA 30332-0100
April 1985
x
In Applied Polymer Science; Tess, R., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1985.
1
A Century of Polymer Science and Technology
HERMAN F. MARK
Polytechnic Institute of New York, Brooklyn, NY 11201
Since the beginning of history, natural polymers such as fur, wood,
hide, wool, horn, cotton, flax, resins, and gum, together with
stone and a few metals, were the backbone of all civilization and
art.
We would have no Bible,
Roman history without
paintings of Leonardo, Raphael, and Rembrandt without canvas and
polymerizing oils. And were would be no music of Corelli,
Beethoven, and Tchaikovsky without string instruments, all of which
consist entirely of natural organic polymers such as wood, resins,
and lacquers.
All naval battles until 100 years ago were fought with wooden
ships that were kept afloat and moving by rosin, ropes, and sails.
Hardened wood and strongly tanned leather were the first offensive
and defensive weapons, and later, catapults and artillery were
placed in position on wooden carriages drawn by horses or men using
cellulosic ropes. Even today, the common propellants for all
firearms are based on cellulose nitrate or on equivalent organic
polymers.
Most of all, in daily life, shelter, clothing, food, education,
and recreation depended, and still depend, essentially on the use
of natural polymers--wood, cotton, fur, wool, silk, starch,
leather, paper, rubber, and a variety of resins, glues, and
coatings. Around each of these materials a highly sophisticated
art developed--entirely empirical and without any basic knowledge
and, in fact, in most cases, without any concern about the
material's composition and structure.
No wonder then that leading philosophers and scientists always
have been strongly attracted by the exceptional properties and the
outstanding capabilities of these materials and have studied them
with whatever methods they had available. Such fascinating pheno
mena as the spinning of strong, tough, glossy, and extremely
durable threads by spiders and silkworms are said to have caused
early speculation in China about making artificial silk long before
Robert Hooke suggested it in his "Micrographia" in 1664.
0097 6156/85/0285-0003S06.00/0
© 1985 American Chemical Society
In Applied Polymer Science; Tess, R., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1985.
4 APPLIED POLYMER SCIENCE
Evidently, the idea was there but the material was lacking then to
perform successfully the process of fiber spinning. But when Henri
Braconnot in 1832 and Christian Friedrich Schoenbein in 1846
discovered how to make cellulose nitrate, the time for the "spark11
had arrived. British Patent 283, issued in 1855, disclosed the
treating of bast fibers from mulberry twigs with nitric acid,
dissolving the product in a mixture of alcohol and ether together
with rubber, and from this viscous mass drawing fibers with a steel
needle; after these fibers solidified in air, they were wound on a
spool.
The first man-made fiber was prepared by the manipulation of a
natural polymer, cellulose, which was made soluble through nitra
tion. These fibers, which were highly flammable, represented an
impractical but pioneering step in a promising direction.
However, after Ozanam in 1862 constructed the first spinning
jets, and Joseph W. Swa
filaments and convert the
for Count Hilaire de Chardonnet to obtain a patent in 1885 and to
bridge the gap from the laboratory to the plant by simplifying and
coordinating the four essential steps: nitration, dissolution,
spinning, and regeneration. His invention and enterprise initiated
a new era in the textile business, which now—only 90 years later—
has grown into a multifaceted industry whose output has a value of
several billion dollars per year. Chardonnet's procedure made it
clear that to form fibers the cellulose (or some other natural
polymer) must first be made soluble, then the solution must be
extruded, and finally the cellulose (or the original polymer) must
be regenerated in the form of a fine fiber.
Soon after 1890, additional methods were found to solubilize
cellulose by acetylation, xanthation, and cuproxyammoniation; to
spin the resulting solutions by coagulating them into the form of a
filament; and to use the resulting fiber as it is or to regenerate
it into cellulose. These artificial products were started with an
already existing natural polymer, generally cellulose, and modified
chemically and brought into fiber form by coagulation, stretching,
and drying. The resulting rayons dominated the field of man-made
fibers until the mid-1930s.
Rubber was another natural polymer whose exceptionally useful
properties aroused the interest of many prominent scientists. In
1826, iMichael Faraday performed elemental analysis of rubber and
established its correct empirical formula as C^Hg. This formula
was confirmed by Jean Baptiste Andre Dumas in 1838. Destructive
distillation then was used to explore the structure of complex
materials because this procedure has capacity to decompose large
molecules into simpler structural units. Justus von Liebig, John
Dalton, and others used this method and obtained several low-
boiling liquids from rubber. In 1860, C. Greville Williams
isolated the most preponderant species, which had the formula C^Hg,
and called it isoprene. In the best tradition of classical organic
chemistry, he proceeded from analysis to synthesis and found that a
white spongy elastic mass could be obtained from isoprene through
the action of oxygen. But it remained for Gustave Bouchardat in
1879 to take isoprene obtained from natural rubber by dry distilla
tion and convert it by treatment with hydrochloric acid into an
elastic, rubberlike solid.
In Applied Polymer Science; Tess, R., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1985.
1. MARK A Century of Polymer Science and Technology 5
That same year the first laboratory sample of synthetic rubber
was developed. Otto Wallach in 1887 and William A. Tilden in 1892
confirmed this synthesis and showed that this synthetic elastomer
reacted with sulfur in the same way as ordinary rubber to form a
tough, elastic, insoluble product.
At the end of the 19th century, rubber, with gutta-percha, was
used mainly as an electrical insulator on wires and cables. Demand
was limited, and the supply of natural rubber at a reasonable price
(about $1.00/lb in 1900) was ensured. Some work was done during
these years on practical syntheses of isoprene and on the replace
ment of isoprene by its simpler homolog, butadiene, which had been
known since 1863. However, advent of the automobile and
accelerated use of electric power rapidly increased the demand for
rubber, thus raising its price to about $3.00/lb in 1911. These
circumstances focused new attention on the production of a synthe
tic rubber. S. B. Lebede polymerized butadien i 1910 d Carl
Dietrich Harries, betwee
the structure of rubbe 1,4-polyisopren synthesize
larger quantities of rubberlike materials from isoprene and other
dienes.
Little was known, however, about the exact configuration of the
rubber molecule or the molecular mechanism of rubber elasticity.
Two world wars and the mushrooming development of the automobile
and the airplane raised the demand for elastomeric materials to a
level that, by the 1950s, dozens of large industrial organizations
produced some 2 million tons of synthetic rubber per year. Most of
the production steps are now fundamentally well known, and most of
the basic properties of raw and cured elastomers are now reasonably
well understood.
1900-1910
At the beginning of this century the first fully synthetic polymer
was made, that is, a material that was prepared by the interaction
of small, ordinary organic molecules and represented a system of
very high molecular weight. This synthesis was not only step of
scientific importance but also the beginning of a new technology.
The development of Bakelite by Leo H. Baekeland was actually an
outgrowth of his search for a synthetic substitute for shellac.
Such a material, he believed, might offer properties superior to
those of natural shellac.
Baekeland decided to make the synthetic material by reacting
phenol with formaldehyde to form a hard resin and then dissolving
the resin in a suitable solvent. He had no difficult forming
various resins, but to his dismay he could find no satisfactory
solvent. However, he realized that some of the hard, solvent-
resistant resins he had produced in the laboratory might have great
commercial value in themselves. One advantage they had was an
outstanding ability to maintain their shape. In addition, they
were good electrical insulators, could be machined easily, and were
resistant to heat and many chemicals.
In 1909, at a meeting of the New York Section of the American
Chemical Society, Baekeland announced his development of Bakelite.
In Applied Polymer Science; Tess, R., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1985.
6 APPLIED POLYMER SCIENCE
The thermosetting plastic was first made commercially in 1910 by
General Bakelite Company (later called Bakelite Corporation), which
Union Carbide acquired in 1939.
During the first decade extensive descriptive studies were
carried out on natural polymers of all kinds: proteins (wool,
silk, and leather), carbohydrates (cellulose, starch, and gums),
and other resinous products (shellac, rubber, and gutta-percha).
Three large domains of scientific and technical interest came into
being:
1. The field of proteinic materials with special institutes for
research on leather, wool, silk, with corresponding textbooks,
journals, and societies serving and advancing large industries:
shoe, luggage, textiles, and others.
2. The discipline of cellulosics having its own special textbooks,
for example, "Wood
for example, Pape
example, the Paper and Textile Society.
3. The domain of rubber and resin science and industry with its
own largely empirical know-how and its own highly sophisticated
technologies.
Rubber chemists, fiber chemists, and resin chemists pursued
their eminently practical goals with admirable empirical skill and
success without being too much concerned about basic structural
problems. For them, in general, these three disciplines were
different worlds as were Jupiter and Saturn before Copernicus.
During this period, two events clearly foreshadowed the exis
tence of very large chainlike molecules.
In 1900, E. Bamberger and F. Tschirner reacted diazomethane
with 6-arylhydroxylamines to methylate the hydroxy1 groups of the
substituted hydroxylamine. Instead they obtained a product in
which two phenylhydroxylamines were connected by the methylene
bridge:
CH=-=N=N
2
They concluded that diazomethane dissociates into N and CH2» which
2
in turn can either react with the amine or polymerize to form
polymethylene. This material (CHo) was found to be a white,
x
chalklike, fluffy powder, apparently amorphous, with a melting
point of 128 °C.
This work was the first correct formulation and description of
a polyhydrocarbon, linear polymethylene, which in its structure and
properties is identical with linear 1,2-polyethylene. However,
because interest in the amorphous byproducts of organic chemical
syntheses was lacking, and evidently also because diazomethane was
limited in availability, no impression was made on the chemists of
1900.
In 1906, Hermann Leuchs, one of Emil Fischer's most distin
guished associates, made an ingenious step in the direction of
In Applied Polymer Science; Tess, R., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1985.