Structure—Property Relationships in Polymers

233 Pages·1984·3.413 MB·English

by  Raymond B. Seymour, Charles E. Carraher Jr. (auth.)

Structure - Property
Relationships
in Polymers
Structure - Property
Relationships
in Polymers
Raymond B. Seymour
College of Science and Technology
University of Southern Mississippi
Hattiesburg, Mississippi
and
Charles E. Carraher, Jr.
College of Science and Engineering
Wright State University
Dayton, Ohio
Plenum Press • New York and London
Library of Congress Cataloging in Publication Data
Seymour, Raymond Benedict, 1912-
Structure-property relationships in polymers.
Bibliography: p.
Includes index.
1. Polymers and polymerization. I. Carraher, Charles E. II. Title.
TA455.P58S48 1984 620.1'92 84-13475
ISBN-13: 978-1-4684-4750-7 e-ISBN-13: 978-1-4684-4748-4
DOl: 10.1007/978-1-4684-4748-4
© 1984 Plenum Press, New York
A Division of Plenum Publishing Corporation
233 Spring Street, New York, N.Y. 10013
Softcover reprint of the hardcover 1s t edition 1984
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
*
Preface
The first concern of scientists who are interested in synthetic polymers has
always been, and still is: How are they synthesized? But right after this comes
the question: What have I made, and for what is it good? This leads to the
important topic of the structure-property relations to which this book is
devoted.
Polymers are very large and very complicated systems; their character
ization has to begin with the chemical composition, configuration, and con
formation of the individual molecule. The first chapter is devoted to this
broad objective. The immediate physical consequences, discussed in the second
chapter, form the basis for the physical nature of polymers: the supermolecular
interactions and arrangements of the individual macromolecules.
The third chapter deals with the important question: How are these
chemical and physical structures experimentally determined? The existing
methods for polymer characterization are enumerated and discussed in this
chapter.
The following chapters go into more detail.
For most applications-textiles, films, molded or extruded objects of all
kinds-the mechanical and the thermal behaviors of polymers are of pre
ponderant importance, followed by optical and electric properties. Chapters
4 through 9 describe how such properties are rooted in and dependent on
the chemical structure.
More-detailed considerations are given to certain particularly important
and critical properties such as the solubility and permeability of polymeric
systems.
Macromolecules are not always the final goal of the chemist-they may
act as intermediates, reactants, or catalysts. This topic is presented in Chapters
10 and 11.
v
vi Preface
The last five chapters go somewhat deeper into particularly interesting
and important groups of macromolecules such as polyolefins, vinyls, styrenics,
and aromatic polymers.
Special chapters are devoted to the important role which certain addi
tives-stabilizers, plasticizers, flame retardants, and others-play in the ul
timate behavior of polymeric systems and to the class of high-performance
polymers, the study of which is a new but rapidly growing branch of polymer
science, which will playa growing role in the construction of space vehicles,
airplanes, ships, and all vehicles of ground transportation.
H. Mark
*
Acknowledgments
The authors are extremely appreciative of the advice provided by Drs. Herman
F. Mark, Rudolph Deanin, and Roger Porter who reviewed the manuscript.
These scientists are recognized internationally for their contributions to poly
mer science education at the Polytechnic Institute of New York and the
Universities of Lowell and Massachusetts respectively. Appreciation is also
given to Charles E. Carraher III and Shawn Carraher for their assistance in
the proofing and indexing of the text.
R.B.S.
C.E.C.
vii
*
Contents
1. Chemical Structure of Polymers
1.1 Introduction ......................................... .
1.2 Shapes and Energy Considerations .................... . 2
1.3 Copolymers .......................................... . 10
1.4 Heteroatomic Polymers ............................... . 11
1.5 References ........................................... . 16
2. Physical Structure of Polymers
2.1 Introduction ......................................... . 19
2.2 Melt Viscosity ........................................ . 19
2.3 Interchain and Intrachain Forces ...................... . 20
2.4 Glass Transition Temperature ......................... . 23
2.5 Crystallinity .......................................... . 26
2.6 Elastomers ........................................... . 29
2.7 Fibers ................................................ . 30
2.8 Plastics .............................................. . 30
2.9 References ........................................... . 30
3. Tests for Properties of Polymers
3.1 Introduction .................. . . . . . . . . . . . . . . . . . . . . . . . . 31
3.2 Thermal Tests. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
3.3 Solubility Tests. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
3.4 Tests for Diffusion and Permeability. . . . . . . . . . . . . . . . . . . 36
3.5 Tests for Mechanical Properties. . . . . . . . . . .. . . . . . . . . . . . . 37
3.6 Tests for Optical Properties. . . . .. . . . . . . . . .. . . . . . . . . . . . . 44
3.7 Flammability Tests................... ............. .... 44
3.8 Tests for Electric Properties. . . . . . . . . . . .. . . . . . . . . . . . . . . . 44
ix
x Contents
3.9 Tests for Chemical Resistance .................. " . . .. . . 45
3.10 Weatherability. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
3.11 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
4. Optical Properties of Polymers
4.1 General .............................................. . 47
4.2 Refractive Index ...................................... . 48
4.3 Optical Clarity ....................................... . 50
4.4 Absorption and Reflectance ........................... . 52
4.5 References ........................................... . 55
5. Mechanical Properties of Polymers
5.1 Introduction ...... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
5.2 Molecular Weight. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
5.3 Crystallinity........ ............................. . ..... 59
5.4 Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
5.5 Polar Substituents. . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
5.6 Additives. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
5.7 Pressure...... ... .......................... ............ 66
5.8 Physical Models. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
5.9 Viscoelasticity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
5.10 References............................................ 72
6. Electric Properties of Polymers
6.1 Dielectric Properties-Contributions. .................. . 73
6.2 Delocalization ........................................ . 76
6.3 Direct Current Measurements ......................... . 77
6.4 Dielectric Constant. .................................. . 78
6.5 Alternating Current .................................. . 78
6.6 General .............................................. . 80
6.7 References ........................................... . 81
7. Thermal Properties of Polymers
7.1 Glass Transition and Melting Range .................. . 83
7.2 Copolymers .......................................... . 86
7.3 Additives ............................................ . 87
7.4 Thermal Conductivity ................................ . 88
7.5 Heat Capacity ........................................ . 89
7.6 Thermal Linear Expansivity ........................... . 89
7.7 Thermal Stability ..................................... . 90
7.8 References ........................................... . 92
Contents xi
8. Solubility
8.1 Solubility Parameter. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
8.2 Polymer Compatibility................................. 97
8.3 Viscosity.. . . . . . . . . . . . . . . . . . . . . .. . . . . . . . .. . . . . . . . . . . . .. 101
8.4 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
9. Diffusion and Permeation of Gas and Vapors
in Polymers
9.1 Introduction. . . . . . . . . .. . . . . . . . .. . . . . . . . . . . . . . . . . . . . . .. 107
9.2 References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . III
10. Chemical Resistance of Polymers
10.1 Rate of Attack ....................................... . 113
10.2 Chemical Oxidation .................................. . 114
10.3 Stress Cracking and Crazing .......................... . 116
10.4 Combustion .......................................... . 116
10.5 Polyolefins ........................................... . 118
10.6 Halogenated Aliphatic Polymers ...................... . 119
10.7 Hydroxyl-Containing Polymers ........................ . 119
10.8 Condensation Polymers ............................... . 119
10.9 Aromatic Polymers ................................... . 120
10.10 References ........................................... . 120
11. Effect of Additives on Polymers
11.1 Introduction ......................................... . 121
11.2 Fillers ............................................... . 122
11.3 Reinforcements ....................................... . 125
11.4 Coupling Agents ..................................... . 125
11.5 Antioxidants ......................................... . 126
11.6 Ultraviolet Light Stabilizers .......................... .. 127
11.7 Flame Retardants .................................... . 128
11.8 Plasticizers ........................................... . 129
11.9 Heat Stabilizers ...................................... . 130
11.10 Impact Modifiers ..................................... . 131
11.11 Other Additives ...................................... . 131
11.12 References ........................................... . 132
12. Properties of Polyolefins
12.1 Introduction.......................................... 133
12.2 High-Density Polyethylene ............ , .. . . . .. . .. . .. . .. 133
xii Contents
12.3 Low-Density Polyethylene ............................ . 135
12.4 Copolymers of Ethylene .............................. . 136
12.5 Crosslinked Polyethylene ............................. . 137
12.6 Polypropylene ........................................ . 138
12.7 Copolymers of Propylene ............................. . 139
12.8 Polyisobutylene ...................................... . 140
12.9 Poly-I-butene ........................................ . 140
12.10 Poly-4-methylpentene-1 ............................... . 141
12.11 Polyalkadienes ....................................... . 142
12.12 References ........................................... . 145
13. Polymeric Hydrocarbons with Pendant
Groups
13.1 Polystyrene........................................... 147
13.2 Styrene Copolymers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
13.3 Substituted Styrene Polymers.. ......... .. ...... ....... 150
13.4 Polyvinyl Chloride and Chlorinated Polyvinyl Chloride. 151
13.5 Copolymers of Vinyl Chloride and of Vinylidene
Chloride.................. ........................... . 153
13.6 Fluorine-Containing Polymers and Copolymers. ..... ... 154
13. 7 Polymers and Copolymers of Acrylonitrile. . . . . . . . . . . . . . 155
13.8 Polymers and Copolymers of Acrylamide and
Methacrylamide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
13. 9 Polymers and Copolymers of Acrylic Acid and
Methacrylic Acid. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
13.10 Polymers and Copolymers of Alkyl Acrylates. . . . . . . . . . . 158
13.11 Polyalkyl-2-cyanoacrylates............... . . . . . . . . . . . . . . 158
13.12 Polymers and Copolymers of Alkyl Methacrylates . . . . . . 158
13.13 Polyvinyl Acetate ...... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160
13.14 Polyvinyl Alcohol and Polyvinyl Acetals............... 160
13.15 Polyvinyl Methyl Ether. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
13.16 Polyvinyl-2-pyrrolidone................................ 161
13.l7 Poly-N-vinylcarbazole.................................. 162
13.18 Polycbloroprene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
13.19 References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
14. Aliphatic Polymers with Heteroatom Chains
14.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . .. . . . . . . . . 165
14.2 Polyetbers. . . . . . . . .. . . .. . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . 165
14.3 Polyolefin Polysulfictes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
14.4 Aliphatic Polyesters.. . . . . . .. .. . . . . . . . . . . . . .. .. . . . . . . . . 167
14.5 Nylons. . . . . . . .. . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
14.6 Polyurethanes and Polyureas. . . . . . . . . . . . . . . . . . . . . . . . . . . 172