seymour carraher’s polymer chemistry, seventh edition

Polymer
Chemistry
Seventh Edition
Seymour/Carraher’s
ß 2006 by Taylor & Francis Group, LLC.
ß 2006 by Taylor & Francis Group, LLC.
Polymer
Chemistry
Seventh Edition
Charles E. Carraher, Jr.
Seymour/Carraher’s
Florida Atlantic University
Boca Raton, Florida, U.S.A.
ß 2006 by Taylor & Francis Group, LLC.
CRC Press
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Library of Congress Cataloging-in-Publication Data
Carraher, Charles E.
Seymour/Carraher’s polymer chemistry. Seventh edition / by Charles E. Carraher, Jr.
p. cm.
Includes bibliographical references and index.
ISBN-13: 978-1-4200-5102-5
ISBN-10: 1-4200-5102-4
1. Polymers. 2. Polymerization. I. Seymour, Raymond Benedict, 1912- II. Title. III. Title: Polymer
chemistry.
QD381.S483 2007
547’.7 dc22 2007002479
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8
ß 2006 by Taylor & Francis Group, LLC.
Foreword
Polymer science and technology have developed tremendously over the last few decades, and
the production of polymers and plastics products has increased at a remarkable pace. By the
end of 2000, nearly 200 million tons per year of plastic materials were produced worldwide
(about 2% of the wood used, and nearly 5% of the oil harvested) to fulfill the ever-growing

needs of the plastic age; in the indust rialized world plastic materials are used at a rate of
nearly 100 kg per person per year. Plastic materials with over $250 billion per year contribute
about 4% to the gross domestic product in the United States. Plastics have no counterpart in
other materials in terms of weight, ease of fabrication, efficient utilization, and economics.
It is no wonder that the demand and the need for teaching in polymer science and
technology have increased rapidly. To teach polymer science, a readable and up-to-date
introductory textbook is required that covers the entire field of polymer science, engineering,
technology, and the commercial aspect of the field. This goal has been achieved in Carraher’s
textbook. It is eminently useful for teaching polymer science in departments of chemistry,
chemical engineering, and material science, and also for teaching polymer science and
technology in polymer science institutes, which concentrate entirely on the scienc e and
technologies of polymers.
This seventh edition addresses the important subject of polymer science and technology,
with emphasis on making it understandable to students. The book is ideally suited not only
for graduate courses but also for an undergraduate curricu lum. It has not become more
voluminous simply by the addition of information—in each edition less important subjects
have been removed and more important issues introduced.
Polymer science and technology is not only a fundamental science but also important
from the industrial and commercial point of view. The author ha s interwoven discussion of
these subjects with the basics in polymer science and technology. Testimony to the high
acceptance of this book is that early demand required reprinting and updating of each of the
previous editions. We see the result in this new significantly changed and improved edition.
Otto Vogl
Herman F. Mark Professor Emeritus
Department of Polymer Science and Engineering
University of Massachusetts
Amherst, Massachusetts
ß 2006 by Taylor & Francis Group, LLC.
ß 2006 by Taylor & Francis Group, LLC.
Preface

As with most science, and chemistry in particular, there is an explosive broadening and
importance of the application of foundational principles of polymers. This broadening is
seen in ever-increasing vistas allowing the promotion of our increasingly technologically
dependent society and solutions to society’s most important problems in areas such as the
environment and medicine. Some of this broadening is the result of extended understanding
and application of already known principles but also includes the development of basic
principles and mate rials known to us hardly a decade ago. Most of the advancements in
communication, computers, medicine, air and water purity are linked to macromolecules and
a fundamental understanding of the principles that govern their behavior. Much of this
revolution is of a fundamental nature and is explored in this seventh edition. The text contains
these basic principles and also touches on their application to real-life situations. Technology
is the application of scientific principles. In polymers there is little if any division between
science and technology.
Polymers are found in the organic natural world as the building blocks for life itself. They
are also found as inorganic building blocks that allow construction of homes, skyscrapers,
and roads. Synthetic polymers serve as basic building blocks of society now and in the future.
This text includes all three of these critical segments of polymeric materials.
A basic understanding of polymers is essential to the training of today’s science, biomed-
ical, and engineering students. Polymer Chemistry complies with the American Chemical
Society’s Committee on Professional Training old and revised guidelines as an advanced or
in-depth course. It naturally integrates and interweaves the important core areas since
polymers are critical to all of the core areas, which in turn contribute to the growth of
polymer science. Most of the fundamental principles of polymers extend and enhance similar
principles found throughout the undergraduate and graduate training of students. This allows
students to integrate their chemical knowledge illustrating the connection between funda-
mental and applied chemical information. Thus, along with the theoretical information,
application is integrated as an essential part of the information. As in other areas such as
business and medicine, short case studies are integrated as historical material.
While this text is primarily written as an introductory graduate-level text, it can also be
used as an undergraduate text, or as an introductory undergraduate–graduate text. The topics

are arranged so that the order and inclusion or exclusion of chapters or parts of cha pters will
still allow students an adequate understanding of the science of polymers. Most of the
chapters begin with the theory followed by application. The most important topics are
generally at the beginning of the chapter followed by important, but less critical, sections.
Some may choose to study the synthesis-intense chapters first, others the analytical=
analysis=properties chapters, and yet others to simply read the chapters as they appear in
the book. All of the elements of an introductory text with synthesis, property, application and
characterization are present, allowing this to be the only polymer course taken by an
individual or the first in a series of polymer-related courses taken by the student.
This edition continues in the ‘‘user-friendly’’ mode with special sections in each chapter
containing de finitions, learning objectives, questions, and further reading. Applicati on and
theory are integrated so that they reinforce one another. There is a continued emphasis on
pictorializing, reinforcing, interweaving, and integrating basic concepts. The initial chapter is
short, allowing students to become acclimated. Other chapters can be covered in about a
ß 2006 by Taylor & Francis Group, LLC.
week’s time or less. Where possible, difficult topics are distributed and reinforced over several
topics.
The basic principles that apply to synthetic polymers apply equally to inorganic and
biological polymers and are present in each of the chapters covering these important polymer
groupings.
The updating of analytical, physical, and special characterization techniques continues.
The chapter on biological polymers has been expanded so that it is now two chapters. The
chapter on organometallic and inorganic polymers has likewise been greatly upgraded. An
additional chapter covering the important area of composites has been added. Topics such as
blends, multiviscosity oils, cross-linking, microfibers, protein folding, protein site identifica-
tion, aerogels, carbon nanotubes, breakage of polymer chains, permeability and diffusion,
mass spectroscopy, polyethers and epoxies, synthetic rubbers, poly(methyl methacrylate),
polyacrylonitrile, and polyurethanes have been added or greatly enhanced. A number of
new selected topics have been added including nonlinear optical behavior, photo phy sics,
drug design and activity, flame retardants, textiles, water-soluble polymers, hydrogels, and

anaerobic adhesives. The emphasis on the molecular behavior of materials has been expanded
as has been the emphasis on nanotechnology and nanomaterials. The practice of including a
number of appendices has continued, including an enlargement of the trade names appendix.
ß 2006 by Taylor & Francis Group, LLC.
Acknowledgments
The author gratefully acknowledges the contributions and assistance of the following in
preparing this text: John Droske, Charles Pittman, Edward Kresge, Gerry Kir shenbaum,
Sukumar Maiti, Alan MacDiarmid, Les Sperling, Eckhard Hellmuth, Mike Jaffe, Otto Vogl,
Thomas Miranda, Murry Morello, and Graham Allan; and a number of our children who
assisted in giving suggestions for the text: Charles Carraher III, Shawn Carraher, Colleen
Carraher-Schwarz, Erin Carraher, and Cara Carraher—to Erin for discussions on materials,
Cara for her help with the biomedical material, and Shawn for his help in relating the business
and industrial aspects. Special thanks to Gerry Kirshenbaum for his kind permission to utilize
portions of my articles that appeared in Polymer News. This book could not have been written
except for those who have gone before us, especially Raymond Seymour, Herman Mark,
Charles Gebelein, Paul Flory, and Linus Pauling; all of these friends shepherded and helped
me. My thanks to them.
I thank Girish Barot, Amitabh Battin, and Randy Doucette, for their assistance in
proofing. I also thank my wife Mary Carraher for her help in proofing and allowing this
edition to be written.
ß 2006 by Taylor & Francis Group, LLC.
ß 2006 by Taylor & Francis Group, LLC.
Table of Contents
Chap ter 1
Introduc tion to Polym ers
1.1 History of Pol ymers
1.2 Why Polymer s?
1.3 Today ’s Market place
1.4 Summar y
Glos sary

Exercis es
Further Readi ng
Genera l Ency clopedia s and Dictionar ies
Chap ter 2
Polym er Struct ure (Morp hology)
2.1 Stereoc hemis try of Pol ymers
2.2 Molecul ar In teractions
2.3 Polymer Crystals
2.4 Amorp hous Bulk State
2.5 Polymer Structure–P ropert y Rel ationsh ips
2.6 Cross-Li nking
2.7 Crystal line and Amor phous Com bination s
2.8 Summar y
Glos sary
Exercis es
Addition al Readi ng
Chap ter 3
Molecu lar W eight of Polym ers
3.1 Introduc tion
3.2 Solubil ity
3.3 Averag e Mo lecular Weight Values
3.4 Fractio nation of Polyd isperse Systems
3.5 Chrom atograp hy
3.6 Collig ative Molecul ar Weights
3.6.1 Osm ometry
3.6.2 End- Group Anal ysis
3.6.3 Ebul liometry and Cryomet ry
3.7 Light-S cattering Photomet ry
3.8 Other Tech niques
3.8.1 Ult racentrif ugatio n

3.8.2 M ass Spectrom etry
3.9 Viscomet ry
3.10 Summar y
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Glos sary
Exe rcises
Fur ther Readi ng
Chap ter 4
Polycond ensat ion Polymers (Step-R eaction Polym eriza tion)
4.1 Com pariso n be tween Polymer Type and Kinet ics of Polymer ization
4.2 Introduc tion
4.3 Stepw ise Kinetics
4.4 Polyco ndensatio n Mechanis ms
4.5 Polyest ers
4.6 Polycarbo nates
4.7 Synthet ic Polyamid es
4.8 Polyim ides
4.9 Polyb enzimidazo les and Related Polymer s
4.10 Polyu rethane s and Pol yureas
4.11 Polysul fides
4.12 Polyether s and Epoxy s
4.13 Polysul fones
4.14 Poly(et her ketone) an d Pol yketones

4.15 Phenol ic and Ami no Plastics
4.16 Furan Resi ns
4.17 Synthet ic Routes
4.18 Liquid Cry stals
4.19 Microf ibers
4.20 Genera l Step wise Pol ymerizati on
4.21 Summar y
Glos sary
Exe rcises
Fur ther Readi ng
Chap ter 5
Ionic Chain-React ion and Comp lex Coor dination
Polym eriza tion (Addition Polym erizatio n)
5.1 Chain -Growt h Polymer ization—G eneral
5.2 Cationi c Polymer ization
5.3 Anioni c Pol ymerizati on
5.4 Stereor egular ity and Stereog eomet ry
5.5 Polymer izat ion wi th Com plex Coordinati on Catalys ts
5.6 Solub le Stereor egulat ing Catalys is
5.7 Polyethy lenes
5.8 Polyp ropylene
5.9 Polymer s from 1,4-Die nes
5.10 Polyis obutyle ne
5.11 Metat hesis React ions
5.12 Zwitter ionic Pol ymerizati on
5.13 Isome rization Polymer ization
5.14 Precipi tation Polymer izat ion
5.15 Summar y
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Exercis es
Further Readi ng
Chap ter 6
Free Radical Chain Polym erizatio n (A ddition Polymeriza tion )
6.1 Initiat ors for Free Radical Chain Pol ymerizatio n
6.2 Mechan ism for Free Radi cal Chai n Polymer ization
6.3 Chain Tran sfer
6.4 Polymer ization Tec hniques
6.4.1 Bul k Pol ymerizati on
6.4.2 Sus pension Polymer ization
6.4.3 Solu tion Polymer izat ion
6.4.4 Em ulsion Polymer izat ion
6.5 Fluorine- Containi ng Polymer s
6.6 Polyst yrene
6.7 Poly(vi nyl chlori de)
6.8 Poly(m ethyl metha cryla te)

6.9 Poly(vi nyl alcoho l) and Poly(vin yl acetal s)
6.10 Poly(ac ryloni trile)
6.11 Solid State Irradiati on Polymer ization
6.12 Plasm a Pol ymerizati ons
6.13 Summar y
Glos sary
Exercis es
Further Readi ng
Chap ter 7
Copo lymeriza tion
7.1 Kinetics of Copol ymeri zation
7.2 The Q –e Scheme
7.3 Commerci al Copo lymers
7.4 Block Copol ymers
7.5 Graft Copol ymers
7.6 Elasto mers
7.7 Thermop lastic Elast omers
7.8 Blends
7.8.1 Imm iscible Blends
7.8.2 M iscible Bl ends
7.9 Networks —Gener al
7.10 Polymer Mixtures
7.11 Dendri tes
7.12 Ionomers
7.13 Viscosi ty Mo difiers
7.14 Summar y
Glos sary
Exercis es
Further Readi ng
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Chap ter 8
Compo sites and Fill ers
8.1 Fillers
8.2 Type s of Comp osites
8.3 Long Fiber Com posit es—Theo ry
8.4 Fibers and Resins
8.5 Long Fiber Com posit es—Ap plications
8.6 Nanoco mposites
8.7 Fabricat ion
8.7.1 Processin g of Fiber- Reinforced Com posit es
8.7.2 Structural Comp osites
8.7.3 Laminating
8.7.4 Particulat e
8.8 Metal –Matr ix Com posites
8.9 Summar y
Glos sary

Exe rcises
Fur ther Readi ng
Chap ter 9
Nat urally Occurring Polym ers: Plants
9.1 Polysaccha rides
9.2 Cellul ose
9.2.1 Paper
9.3 Cellul ose-Regen erating Processes
9.4 Esters an d Ethers of Cellul ose
9.4.1 Inorgani c Es ters
9.4.2 Organic Esters
9.4.3 Organic Ethers
9.5 Starch
9.6 Homopo lysaccha rides
9.6.1 Fructans
9.6.2 Chitin and Chi tosan
9.6.3 Others
9.7 Hete ropolys acchari des
9.8 Synthet ic Rubbers
9.9 Natur ally Occur ring Polyis opren es
9.10 Resin s
9.11 Balloons
9.12 Lign in
9.13 Melani ns
9.14 Summar y
Glos sary
Exe rcises
Fur ther Readi ng
Chap ter 10
Nat urally Occurring Polym ers: Animal s

10.1 Protei ns
10.2 Levels of Pr otein Struct ure
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10.2.1 Pr imary Struct ure
10.2.2 Se condary Struct ure
10.2. 2.1 Keratins
10.2. 2.2 Silk
10.2. 2.3 Wool
10.2. 2.4 Collagen
10.2. 2.5 Elastin
10.2.3 Ter tiary Structu re
10.2. 3.1 Globul ar Pro teins
10.2.4 Quat ernary Structu re
10.3 Nucle ic Aci ds
10.4 Flow of Biologi cal Inform ation

10.5 RNA Inter ference
10.6 Polymer Structu re
10.7 Protei n Folding
10.8 Genet ic Engin eering
10.9 DNA Profil ing
10.10 The Human Genome: Genera l
10.11 Chrom osomes
10.12 Proteomi cs
10.13 Protei n Site Activi ty Iden tification
10.14 Summar y
Glos sary
Exercis es
Further Readi ng
Chap ter 11
O rganometa llic and Inorga nic–Organi c Polym ers
11.1 Introduc tion
11.2 Inorgani c Reaction Mecha nisms
11.3 Condens ation Organo metallic Polymer s
11.3.1 Pol ysiloxanes
11.3.2 Orga notin and Related Condens ation Polymer s
11.4 Coordi nation Pol ymers
11.4.1 Plati num-Co ntaining Polymer s
11.5 Addition Polymer s
11.5.1 Fer rocene- Containi ng and Rel ated Polymer s
11.5.2 Pol yphosph azenes a nd Related Polymer s
11.5.3 Bor on-Co ntaining Polymer s
11.6 Ion-Exchan ge Resi ns
11.7 Summar y
Glos sary
Exercis es

Further Readi ng
Chap ter 12
Inorga nic Polym ers
12.1 Introduc tion
12.2 Portla nd Cemen t
12.3 Other Cem ents
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12.4 Silicates
12.4.1 Network
12.4.2 Layer
12.4.3 Chain
12.5 Silico n Dioxi de (Amorph ous)
12.6 Kinds of Amor phous Glas s
12.7 Safet y Glas s

12.8 Lens es
12.9 Sol–Ge l
12.9.1 Aerogels
12.10 Silico n Dioxi de (Cryst alline Forms) —Quartz Forms
12.11 Silico n Dioxi de in Electron ic Chip s
12.12 Silico n Dioxi de in Optical Fib ers
12.13 Asbes tos
12.14 Polymer ic Carbon —Diamon d
12.15 Polymer ic Carbon —Grap hite
12.16 Inter nal Cycl ization—C arbon Fibers and Related Mater ials
12.17 Carb on Nanotubes
12.17. 1 Structu res
12.18 Bitum ens
12.19 Carb on Black
12.20 Polysul fur
12.21 Cera mics
12.22 High- Temperat ure Supe rcond uctors
12.22. 1 Discovery of the 123-C ompound
12.22. 2 Structu re of the 123-C ompoun d
12.23 Zeolit es
12.24 Summar y
Glos sary
Exe rcises
Fur ther Readi ng
Chap ter 13
T esting and Spe ctromet ric Char acterizat ion of Polym ers
13.1 Spec tronic Char acterizat ion of Polymer s
13.1.1 Infrared Spec troscop y
13.1.2 Raman Spe ctrosco py
13.1.3 Nuclear Magn etic Resona nce Spectros copy

13.1.4 Nuclear Magn etic Resona nce Applicati ons
13.1.5 Electron Par amagnet ic Resona nce Spec troscop y
13.1.6 X-Ray Spectros copy
13.2 Surface Chara cterizat ion
13.2.1 Auger Electr on Spectros copy and X-R ay
Photoelect ron Spectros copy
13.2.2 Near-Fiel d Scanning Optical Micros copy
13.2.3 Electron M icrosco py
13.2.4 Scanning Prob e M icroscop y
13.2.5 Seconda ry Ion Mass Spectros copy
13.3 Amor phous Regi on Determi nations
13.4 Mass Spectrom etry
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13.5 Thermal Analysis
13.6 Thermal Property Tests
13.6.1 Sof tening Range
13.6.2 Heat Deflecti on Temperat ure
13.6.3 Glas s Tr ansition Tempe ratures
13.6.4 Ther mal Condu ctivity
13.6.5 Ther mal Expa nsion
13.7 Flamm ability
13.8 Electr ical Properti es: Theor y
13.9 Electr ic Measurem ents
13.9.1 Diel ectric Constant
13.9.2 Ele ctrical Resi stance
13.9.3 Dis sipation Factor and Power Loss
13.9.4 Ele ctrical Condu ctivity and Diel ectric Strength
13.10 Optical Properti es Tests
13.10.1 Ind ex of Ref raction
13.10.2 Opti cal Clarit y
13.10.3 Absor ption and Ref lectance
13.11 Weather ability
13.12 Chem ical Resist ance
13.13 Measurem ent of Par ticle Size
13.14 Measurement of Adhesi on
13.15 Permeabi lity and Diffusi on
13.16 Summar y
Glos sary
Exercis es
Further Readi ng
Chap ter 14
Rheo logy and Physica l Tes ts
14.1 Rheol ogy

14.1.1 Rheo logy and Phys ical Tests
14.1.2 Respon se Time
14.2 Typical Stress–Str ain Behavior
14.3 Stress–S train Relati onships
14.4 Specif ic Phys ical Tests
14.4.1 Tens ile Strengt h
14.4.2 Tens ile Strengt h of Ino rganic and Me tallic Fibers and Whisker s
14.4.3 Com pressi ve Strengt h
14.4.4 Impact Strengt h
14.4.5 Hardn ess
14.4.6 Br inell Hardnes s
14.4.7 Rock well Hardnes s
14.4.8 She ar Strengt h
14.4.9 Abras ion Resist ance
14.4.10 Fai lure
14.5 Summar y
Glos sary
Exercis es
Further Readi ng
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Chap ter 15
Additi ves
15.1 Plast icizers
15.2 Antio xidants
15.3 Heat Stab ilizers
15.4 Ultravi olet Stabil izers
15.5 Flame Retardan ts
15.6 Colo rants
15.7 Curin g Agent s
15.8 Antist atic Agent s—An tistats
15.9 Chem ical Blowin g Agent s
15.10 Com patibili zers
15.11 Impact M odifiers
15.12 Proc essing Aids
15.13 Lubr icants
15.14 Microor ganism Inhibitors
15.15 Summar y
Glos sary
Exe rcises
Fur ther Readi ng
Chap ter 16
Reac tions on Polymers

16.1 React ions with Polyo lefines a nd Polyenes
16.2 React ions of Arom atic and Aliphati c Penda nt Groups
16.3 Degra dation
16.4 Cros s-Linking
16.5 React ivities of End Groups
16.6 Supr amolecu les and Self-As sembl y
16.7 Tran sfer and Reten tion of Oxygen
16.8 Natur e’s Macromol ecular Catalys ts
16.9 Mech anisms of Ener gy Absor ption
16.10 Break age of Polymer ic M aterials
16.11 Summar y
Glos sary
Exe rcises
Fur ther Readi ng
Chap ter 17
Syn thesis o f Reac tants and Inter mediates for Polym ers
17.1 Mon omer Sy nthesis from Bas ic Feed stocks
17.2 React ants for Step-React ion Polymer ization
17.3 Synthesi s of Vin yl Mon omers
17.4 Synthesi s of Free Radi cal Init iators
17.5 Summar y
Glos sary
Exe rcises
Fur ther Readi ng
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Chap ter 18
Polym er Tec hnolog y
18.1 Fibers
18.1.1 Pol ymer Pro cessing—S pinning and Fiber Production
18.1. 1.1 Melt Spinn ing
18.1. 1.2 Dry Spin ning
18.1. 1.3 Wet Spin ning
18.1. 1.4 Other Spinning Pro cesses
18.1.2 Non spinni ng Fi ber Pr oduction
18.1. 2.1 Natural Fibers
18.2 Elasto mers
18.2.1 Elast omer Processi ng
18.3 Films and She ets
18.3.1 Cal endering
18.4 Polymer ic Foam s
18.5 Reinforced Plast ics (Co mposites) an d Laminat es
18.5.1 Com posit es
18.5.2 Par ticle-Reinf orced Comp osites—Larg e-Pa rticle Com posit es
18.5.3 Fib er-Reinf orced Compo sites
18.5. 3.1 Processi ng of Fiber- Rein forced Com posit es
18.5.4 Struct ural Compo sites
18.5. 4.1 Laminat ing

18.6 Molding
18.6.1 Inject ion Molding
18.6.2 Blo w Molding
18.6.3 Rota tional Mo lding
18.6.4 Com pressi on and Transfe r M olding
18.6.5 Ther mofor ming
18.7 Casting
18.8 Extrusi on
18.9 Coatings
18.9.1 Pr ocessing
18.10 Adhesi ves
18.11 Summar y
Glos sary
Exercis es
Further Readi ng
Chap ter 19
Select ed Topics
19.1 Conduct ive Pol ymeric Mater ials
19.1.1 Phot ocond uctive and Phot onic Polymer s
19.1.2 Elec trically Conduct ive Pol ymers
19.1.3 Nan owires
19.2 Nonli near Opti cal Beha vior
19.3 Photo physics
19.4 Drug Design and Act ivity
19.5 Synthet ic Bio medical Polymer s
19.5.1 Den tistry
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19.6 Sutures
19.7 Geote xtiles
19.8 Smart M aterials
19.9 High-P erforman ce Ther moplas tics
19.10 Const ruction and Bui lding
19.11 Flame- Resist ant Tex tiles
19.12 Water -Solubl e Polymer s
19.13 Anaer obic Adhesive s
19.14 Hydroge ls
19.15 Emergi ng Polymer s
19.16 Summar y
Glos sary
Exe rcises
Fur ther Readi ng
Soluti ons
Appe ndices
A. Symbols

B. Tr ade Names
C. Sylla bus
D. Polymer Core Cours e Com mittees
E. Struct ures of Com mon Polymer s
F. Mathem atic al Values and Unit s
G. Com ments on Health
H. ISO 9000 and 14000
I. Electr onic Educa tion Web Sites
J. Stereog eomet ry of Polymer s
K. Statist ical Treatm ent of Measurem ents
L. Com binator ial Chemist ry
M. Polymer izat ion React ors
N. Material Selection Char ts
ß 2006 by Taylor & Francis Group, LLC.
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Polymer Nomenclature
As with most areas, the language of the area is important. Here we will focus on naming
polymers with the emphasis on synthetic polymers. Short presentations on how to name
proteins and nucleic acids are given in Chapter 10 and for nylons in Chapter 5.
The fact that synthetic polymer science grew in many venues before nomenclature groups
were present to assist in standardization of the naming approach resulted in many popular
polymers having several names including common names. Many polymer scientists have not
yet accepted the guidelines given by the official naming committee of the International Union
of Pure and Applied Chemistry (IUPAC), because the common names have gained such
widespread acceptance. Although there is a wide diversity in the practice of naming polymers,
we will concentra te on the most utilized systems.
COMMON NAMES
Little rhyme or reason is associated with many of the common names of polymers. Some
names are derived from the place of origin of the material, such as Hevea brasilliensis—
literally ‘‘ru bber from Brazil’’—for natural rubber. Other polymers are named after their
discoverer, as is Bakelite, the three-dimensional polymer produced by condensation of phenol
and formaldehyde, which was commercialized by Leo Baekeland in 1905.

For some important groups of polymers, special names and systems of nomenclature were
developed. For instance, the nylons were named according to the number of carbons in the
diamine and dicarboxylic acid reactants used in their synthesis. The nylon produced by the
condensation of 1,6-hexamethylenediamine (6 carbons) and adipic acid (6 carbons) is called
nylon-6,6. Even here, there is no set standard as to how nylon-6,6 is to be written with
alternatives including nylon-66 and nylon-6,6.
H
2
N
NH
2
OH
OH
OH
OH
O
O
R
NH
NH
R
n
+
Nylon-6,6
SOURCE-BASED NAMES
Most common names are source-based, i.e., they are based on the common name of the
reactant monomer, preceded by the prefix ‘‘poly.’’ For example, polystyrene is the most
ß 2006 by Taylor & Francis Group, LLC.
frequently used name for the polymer derived from the mono mer 1-phenylethene, which has
the common name styrene.

H
2
C
Styrene Polystyrene
R
R
n
The vast majority of commercial polymers based on the vinyl group (H
2
C¼CHX) or the
vinylidene group (H
2
C¼CX
2
) as the repeat unit are known by their source-based names.
Thus, polyethylene is the name of the polymer synthesized from the monomer ethylene;
poly(vinyl chloride) from the monomer vinyl chloride, and poly(methyl metha crylate) from
methyl methacrylate.
Many condensation polymers are also named in this manner. In the case of poly(ethylene
terephthalate), the glycol portion of the name of the monomer, ethylene glycol, is used in
constructing the polymer name, so that the name is actually a hybrid of a source-based and a
structure-based name.
OH
HO
O
HO
ϩ
OH
Poly(ethylene terephthalate)
O

R
O
O
O
R
n
O
This polymer is well known by a number of trade names, such as Dacron, its common
grouping, polyester, and by an abbreviation, PET.
Although it is often suggested that parentheses be used in naming polymers of more than
one word [like poly(vinyl chloride)], but not for single-word polymers (like polyethylene),
some authors entirely omit the use of parentheses for either case (like polyvinyl chloride), so
even here there exist a variety of practices. We will employ parenthe ses for naming polymers
of more than one word.
Copolymers are composed of two or more mon omers. Source-based names are conveni-
ently employed to describe copolymers using an appropriate term between the names of the
monomers. Any of half a dozen or so connecting terms may be used depending on what is
known about the structure of the copolymer. When no information is known or intended to
be conveyed, the connective term ‘‘co’’ is employed in the general format poly(A-co-B), where
A and B are the names of the two monomers. An unspecified copolymer of styrene and
methyl methacrylate would be called poly[styrene-co-(methyl methacrylate)].
Kraton, the yellow rubber-like material often found on the bottom of running shoes, is a
copolymer whose structural information is known. It is formed from a group of styrene
units, i.e., a ‘‘block’’ of polystyrene, attached to a group of butadiene units, or a block of
ß 2006 by Taylor & Francis Group, LLC.
polybutadiene, which is attached to another block of polystyrene forming a triblock copoly-
mer. The general representation of such a block might be –AAAAAAAABBBBBBB-
AAAAAAAA–, where each A and B represents an individual monomer unit. The proper
source-based name for Kraton is polystyrene-block-polybutadiene-block-polystyr ene, or
poly-block-styrene-block-polybutadiene-block-polystyrene, with the prefix ‘‘poly’’ being

retained for each block. Again, some authors will omit the ‘‘poly,’’ giving polystyrene-
block-butadiene-block-styrene.
STRUCTURE-BASED NAMES
Although source-based names are generally employed for simple polymers, IUPAC has
published a number of reports for naming polymers. These reports are being widely accepted
for the naming of complex polymers. A listing of such reports is given in the references
section. A listing of source- and structure-based names for some common polymers is given in
Table 1.
LINKAGE-BASED NAMES
Many polymer ‘‘families’’ are referred to by the name of the particular linkage that connects
the polymers (Table 2). The family name is ‘‘poly’’ followed by the linkage name. Thus, those
polymers that contain an ester linkage are known as polyesters; those with an ether linkage
are called polyethers, etc.
TRADE NAMES, BRAND NAMES, AND ABBREVIATIONS
Trade (and=or brand) names and abbreviations are often used to describe a particular
material or a group of materials. They may be used to identify the product of a manufacturer,
processor, or fabri cator, and may be associated with a particular product or with a material
or modified material, or a material grouping. Trade names are used to describe specific
groups of materials that are produced by a specific company or under license of that
company. Bakelite is the trade name given for the phenol–formaldehyde condensation devel-
oped by Baekeland. A sweater whose material is described as containing Orlon contains
polyacrylonitrile fibers that are ‘‘protected’’ under the Orlon trademark and prod uced or
licensed to be produced by the holder of the Orlon trademark. Carina, Cobex, Dacovin,
TABLE 1
Source- and Structure-Based Names
Source-Based Names Structure-Based Names
Polyacrylonitrile Poly(1-cyanoethylene)
Poly(ethylene oxide) Polyoxyethylene
Poly(ethylene terephthalate) Polyoxyethyleneoxyterephthaloyl
Polyisobutylene Poly(1,1-dimethylethylene)

Poly(methyl methacrylate) Poly[(1-methoxycarbonyl)-1-metylethylene]
Polypropylene Poly(1-methylethylene)
Polystyrene Poly(1-phenylethylene)
Polytetrafluoroethylene Polydifluoromethylene
Poly(vinylacetate) Poly(1-acetoxyethylene)
Poly(vinyl alcohol) Poly(1-hydroxyethylene)
Poly(vinyl chloride) Poly(1-chloroethylene)
Poly(vinyl butyral) Poly[(2-propyl-1,3-dioxane-4,6-diyl)methylene]
ß 2006 by Taylor & Francis Group, LLC.
Darvic, Elvic, Geon, Koroseal, Marvinol, Mipolam, Opalon, Pliofex, Rucon, Solvic, Trulon,
Velon, Vinoflex, Vygen, and Vyram are all trade names for poly(vinyl chloride) manufactured
by different companies. Some polymers are better known by their trade name than their
generic name. For instance, polytetrafluoroethylene is better known as Teflon, the trade name
held by DuPont.
Abbreviations, generally initials in capital letters, are also employed to describe polymers.
Table 3 contains a listing of some of the more widely used abbreviations and the polymer
associated with the abbreviation.
CHEMICAL ABSTRACTS–BASED POLYMER NOMENCLATURE
The most complete indexing of any scientific discipline is found in chemistry and is done by
Chemical Abstracts (CA). Almost all of the modern searching tools for chemicals and
TABLE 2
Linkage-Based Names
Family Name Linkage Family Name Linkage
Polyamide ÀNÀC
k
À
O
Polyvinyl
ÀCÀCÀ
Polyester ÀOÀC

k
À
O
Polyanhydride ÀC
O
k
ÀOÀC
k
À
O
Polyurethane
ÀOÀC
O
k
ÀN
j
À
H
Polyurea
j
H
ÀNÀC
O
k
ÀN
j
À
H
Polyether ÀOÀ Polycarbonate ÀOÀC
k

À
O
OÀ
Polysiloxane ÀOÀSiÀ Polysulfide ÀSÀ
TABLE 3
Abbreviations for Selected Polymeric Materials
Abbreviation Polymer Abbreviation Polymer
ABS Acrylonitrile–butadiene–styrene terpolymer CA Cellulose acetate
EP Epoxy HIPS High-impact polystyrene
MF Melamine–formaldehyde PAA Poly(acrylic acid)
PAN Polyacrylonitrile SBR Butadiene–styrene copolymer
PBT Poly(butylene terephthalate) PC Polycarbonate
PE Polyethylene PET Poly(ethylene terephthalate)
PF Phenyl–formaldehyde PMMA Poly(methyl methacrylate)
PP Polypropylene PPO Poly(phenylene oxide)
PS Polystyrene PTFE Polytetrafluoroethylene
PU Polyurethane PVA, PVAc Poly(vinyl acetate)
PVA, PVAl Poly(vinyl alcohol) PVB Poly(vinyl butyral)
PVC Poly(vinyl chloride) SAN Styrene–acrylonitrile
UF Urea–formaldehyde
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