TEXTBOOK
`
`OF POLYMER SCIENCE.
`
`Second Edition
`
`Wiley- Interscience, a Division of John Wiley and Sons, Inc.
`New York I London I Sydney I Toronto
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`~
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`. Copyright © 1962, 1971, by John Wiley & Sons, Inc.
`
`All rights reserved.
`
`Reproduction or translation of any part of this work beyond that
`permitted by Sections 107 or 108 of the 1976 United States Copy(cid:173)
`right Act without the permission of the copyright owner is unlaw(cid:173)
`ful. Requests for permission or further information should be
`addressed to the Permissions Department, John Wiley & Sons, Inc.
`
`Library of Congress Catalog Card Number: 78-142713
`
`ISBN 0 471
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`07296 6
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`Printed in the United. States of America
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`10 9 8
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`Contents
`
`Part 1 Polymer Chains and their Characterization
`Chapter 1 The Science of Large Molecules 3
`A Basic Concepts of Polymer Science 3
`B History of Macromolecular Science 10
`C Molecular Forces and Chemical Bonding in Polymers 14
`Chapter 2 Polymer Solutions 23
`A Criteria for Polymer Solubility 23
`VJ( Conformations of Dissolved Polymer Chains 27
`C Thermodynamics of Polymer Solutions 32
`D Phase Separation in Polymer Solutions 39
`E Fractionation of Polymers by Solubility 47
`F Gel Permeation Chromatography 53
`Chapter 3 Measurement of Molecular Weight and Size 62
`A End Group Analysis 62
`B Colligative Property Measurement 64
`'-C Light Scattering 75
`'D Solution Viscosity and Molecular Size 84
`E Ultracentrifugation 90
`F Polyelectrolytes 95
`Chapter 4 Analysis and Testing of Polymers 105
`A Analytical Chemistry of Polymers 105
`B
`Infrared Spectroscopy 106
`C X-Ray Diffraction Analysis Ill
`D Nuclear Magnetic and Electron Paramagnetic Resonance
`Spectroscopy 114
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`xii
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`CONTENTS
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`E Thermal Analysis 120
`F Microscopy 123
`G Physical Testing 126
`
`Part II Structure and Properties of Bulk Polymers
`Chaptet;--S Morphology and Order in Crystalline Polymers 141
`\ -~ Configurations of Polymer Chains 141
`\___.../viR Crystal Structures of Polymers 146
`C Morphology of Polymer Single Crystals 154
`D Structure of Polymers Crystallized from the Melt 159
`E Crystallization Processes 165
`F Orientation and Drawing 174
`Chaptf!r 6 Rheology and the Mechanical Properties of Polymers 185
`//A Viscous Flow 186
`~ B Kinetic Theory of Rubber Elasticity 191
`C Viscoelasticity 199
`D The Glassy State and the Glass Transition 207
`E The Mechanical Properties of Crystalline Polymers 211
`Chapteyi_. Polymer Structure and Physical Properties 220
`
`A The Crystalline Melting Point 221
`
`The Glass Transition 228
`C Properties Involving Large Deformations 232
`D Properties Involving Small Deformations 235
`E Property Requirements and Polymer Utilization 241
`
`Part III Polymerization
`Chapter 8 Step-Reaction (Condensation) Polymerization 255
`J A Classification of Polymers and Polymerization Mechanisms 255
`J B Chemistry of Stepwise Polymerization 257
`v'C Kinetics and Statistics of Linear Stepwise Polymerization 264
`D Polyfunctional Step-Reaction Polymerization 272
`V Cht/pter 9. Radical Chain (Addition) Polymerization 280
`A Chemistry of Vinyl Polymerization 280
`B Laboratory Methods in Vinyl Polymerization 287
`C Steady-State Kinetics of Vinyl Radical Polymerization 289
`D ~bsolute Reaction Rates 297
`~ Molecular Weight and Its Distribution 301
`F
`·Thermochemistry of Chain Polymerization 304
`;Chapter 10
`Io?ic and Coordination Chain (Addition) Polymerization 311
`A Chemistry of Nonradical Chain Polymerization 311
`.
`"':1
`B Cationic Polymerization 313
`C Anionic Polymerization 316
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`CONTENTS
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`xiii
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`D Coordination Polymerization 319
`E Ring-Opening Polymerization 324
`vChapter 11 Copolymerization 328
`A Kinetics of Copolymerization 328
`B Composition of Copolymers 337
`C Chemistry of Copolymerization 341
`D Block and Graft Copolymers 350
`Chapte; 12 Polymerization Conditions and Polymer Reactions 355
`f..-'1\ Polymerization in Homogeneous Systems 355
`~ Polymerization in Heterogeneous Systems 357
`C Diene and Divinyl Polymerization 364
`D Chemical Reactions of Polymers 368
`E Degradation of Polymers 369
`F Radiation Chemistry of Polymers 372
`Part IV Properties of Commercial Polymers
`Chapter 13 Hydrocarbon Plastics and Elastomers 379
`A Low-Density (Branched) Polyethylene 379
`B High-Density (Linear) Polyethylene 385
`C Polypropylene 386
`·
`D Other Olefin Polymers 388
`E Natural Rubber and Other Polyisoprenes 391
`F Rubbers Derived from Butadiene 394
`G Other Synthetic Elastomers 397
`·· Chapter 14 Other Carbon-Chain Polymers 404
`A Polystyrene and Related Polymers 404
`B Acrylic Polymers 409
`C Poly(vinyl Esters) and Derived Polymers 415
`D Chlorine-Containing Polymers 419
`E Fully Fluorinated Fluorocarbon Polymers 423
`F Other Fluorine-Containing Polymers 427
`Chapter 15 Heterochain Thermoplastics 433
`A Polyamides 433
`B Other Noncyclic Heterochain Thermoplastics 438
`C Cellulosic Polymers 443
`D Aromatic Heterochain Thermoplastics 452
`E Heterocyclic, Ladder, and Inorganic Polymers 457
`Chapter 16 Thermosetting Resins 468
`A Phenolic Resins 468
`B Amino Resins 473
`C Unsaturated Polyester Resins 475
`D Epoxy Resins 478
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`CONTENTS
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`E Urethane Foams 480
`F Silicone Polymers 482
`G Miscellaneous Thermosetting Resins 485
`Part V Polymer Processing
`Chapter 17 Plastics Technology 491
`A Molding 491
`B Other Processing Methods 494
`C Fillers, Plasticizers, and Other Additives 499
`D Tables of Pastics Properties 503
`Chapter 18 Fiber Technology 513
`A Textile and Fabric Properties 514
`B Spinning 518
`C Fiber After-Treatments 525
`D Table of Fiber Properties 529
`Chapter 19 Elastomer Technology 533
`A Compounding and Elastomer Properties 535
`B Vulcanization 539
`C Reinforcement 544
`D Table of Elastomer Properties 549
`Appendixes
`I. List of Symbols 551
`II. Table of Physical Constants 561
`Author Index 563
`Subject Index 577
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`,··
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`,..
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`I
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`Polymer Chains and their
`
`Characterization
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`I
`
`The Science of large Molecules
`
`A. Basic Concepts of Polymer Science
`
`Over half a century ago, Wilhelm Ostwald (1914)* coined the phrase "the
`land of neglected dimensions" to describe the range of sizes between molecu(cid:173)
`lar and macroscopic within which occur most colloidal particles. The term
`"neglected dimensions" might have been applied equally well to the world
`of polymer molecules, the high-molecular-weight compounds so important to
`man and his modern technology. It was not until the 1930's that the science
`of high polymers began to emerge, and the major growth of the technology
`of these materials came even later. Yet today polymer dimensions are
`neglected no more, for industries associated with polymeric materials employ
`more than half of all American chemists and chemical engineers.
`The science of macromolecules is divided between biological and non(cid:173)
`biological materials. Each is of great importance. Biological polymers form
`the very foundation of life and intelligence, and provide much of the food
`on which man exists. This book, however, is concerned with the chemistry,
`physics, and technology of nonbiological polymers. These are primarily the
`synthetic materials used for plastics,, fibers, and elastomers, but a few natur(cid:173)
`ally occurring polymers, such as rubber, wool, and cellulose, are included.
`Today, these substances are truly indispensable to mankind, being essential
`to his clothing, shelter, transportation, and communication, as well as to
`the conveniences of modern living.
`A polymer is a large molecule built up by the repetition of small, simple
`chemical units. In some cases the repetition is linear, much as a chain is
`
`* Parenthetical years or names and years refer to items in the bibliography at the end of
`the chapter.
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`4
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`POLYMER CHAINS AND THEIR CHARACTERIZATION
`
`built up from its links. In other cases the chains are branched or inter(cid:173)
`connected to form three-dimensional networks. The repeat unit of the polymer
`is usually equivalent or nearly equivalent to the monomer, or starting material
`from which the polymer is formed. Thus (Table 1-1) the repeat unit of
`poly(vinyl chloride) is -CH 2 CHCl-; its monomer is vinyl chloride,
`CH2=CHCI.
`The length of the polymer chain is specified by the number of repeat
`units in the chain. This is called the degree of polymerization (DP). The
`molecular weight of the polymer is the product of the molecular weight of
`the repeat unit and the degree of polymerization. Using poly( vinyl chloride)
`as an example, a polymer of degree of polymerization 1000 has a molecular
`weight of 63 x 1000 = 63,000. Most high polymers useful for plastics,
`rubbers, or fibers have molecular weights between 10,000 and 1,000,000.
`Unlike many products whose structure and reactions were well known
`before their industrial application, some polymers were produced on an
`industrial scale long before their chemistry or physics was studied. Empiri(cid:173)
`cism in recipes, processes, and control tests was usual.
`Gradually the study of polymer properties began. Almost all were first
`called anomalous because they were so different from the properties of low-
`
`TABLE 1-1. Some linear high polymers, their monomers, and their repeat units
`
`Polymer
`
`Monomer
`
`Repeat Unit
`
`Polyethylene
`Poly(vinyl chloride)
`Polyisobutylene
`
`Polystyrene''
`
`CHz=CHz
`CH2=CHCI
`CH3
`I
`CH 2 =C
`I
`CH3
`
`-CHzCHz-
`-CH2CHCI-
`CH3
`I
`-CHz-C-
`1
`CH3
`
`Polycaprolactam (6 nylon)
`
`Polyisoprene (natural rubber)
`
`H-N(CH2)sC-OH -N(CHz)sC-
`II
`II
`I
`1
`H
`0
`0
`H
`CH2=CH-C=CH2 -CHzCH=C-CH2-
`I
`I
`CH3
`CH3
`
`* By convention, the symbol Q is used throughout to represent the benzene ring,
`
`double bonds being omitted.
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`THE SCIENCE OF LARGE MOLECULES
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`5
`
`molecular-weight compounds. It was soon realize"d, .however, that polymer
`molecules are many times larger than those of ordinary substances. The
`presumably anomalous properties of polymers were shown to be normal for
`such materials, as the consequences of their size were included in the theoreti(cid:173)
`cal. treatments of their properties.
`Primary chemical bonds along polymer chains are entirely satisfied. The
`only forces between molecules are secondary bond forces of attraction,
`which are weak relative to primary bond forces. The high molecular weight
`of polymers allows these forces to build up enough to impart excellent
`strength, dimensional stability, and other mechanical properties to the
`substances.
`
`Polymerization processes The processes of polymerization were divided by
`Flory (1953) and Carothers (Mark 1940) into two groups known as condensa(cid:173)
`tion and addition polymerization or, in more precise terminology (Chapter
`SA), step-reaction and chain-reaction polymerization.
`Condensation or step-reaction polymerization is entirely analogous to
`condensation in low-molecular-weight compounds. In polymer formation
`the condensation takes place between two polyfunctional molecules to
`produce one larger polyfunctional molecule, with the possible elimination of
`. a small molecule such as water. The reaction continues until almost all of
`one of the reagents is used up; an equilibrium is established which can be
`shifted at will at high temperatures by controlling the amounts of the reac(cid:173)
`tants and products.
`Addition or chain-reaction polymerization involves chain reactions in
`which the chain carrier may be an ion or a reactive substance with one un(cid:173)
`paired electron called afree radical. A free radical is usually formed by the
`decomposition of a relatively unstable material called an initiator. The free
`radical is capable of reacting to open the double bond of a vinyl monomer
`and add to it, with an electron remaining unpaired. In a very short time
`(usually a few seconds or less) many more monomers add successively to the
`growing chain. Finally two free radicals react to annihilate each other's
`growth activity and form one or more polymer molecules.
`With some exceptions, polymers made in chain reactions often contain
`only carbon atoms in the main chain (homochain polymers), whereas poly(cid:173)
`mers made in step reactions may have other atoms, originating in the mono(cid:173)
`mer functional groups, as part of the chain (heterochain polymers.)
`
`In both chain and stepwise poly(cid:173)
`Molecular weight and its distribution
`merization, the length of a chain is determined by purely random events. In
`step reactions, the chain length is determined by the. local availability of
`reactive groups at the ends of the growing chains. In radical polymerization,
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`POLYMER CHAINS AND THEIR CHARACTERIZATION
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`chain length is determined by the time during which the chain grows before it
`diffuses into the vicinity of a second free radical and the two react.
`In either case, the polymeric product contains molecules having many
`different chain lengths. For some types of polymerization the resulting
`distribution of molecular weights can be calculated statistically. It can be
`illustrated by plotting the weight of polymer of a given size against the chain
`length or molecular weight (Fig. 1-1).
`
`Number average, Mn
`
`Weight average, Mw
`
`1 Q)
`0 -c:
`
`E
`~
`0 a.
`
`:::J
`0
`E
`<C
`
`Molecular weight~
`
`Fig. 1-1. Distribution of molecular weights in a typical polymer.
`
`Since a distribution of molecular weights exists in any finite sample of
`polymer, the experimental measurement of molecular weight can give only
`an average value. Several different averages are important. For example,
`some methods of molecular-weight measurement in effect count the number
`of molecules in a known mass of material. Through knowledge of Avogadro's
`number this information leads to the number-average molecular weight· M n
`of the sample. For typical polymers the number average lies near the peak
`of the weight-distribution curve or the most probable molecular weight.
`In other experiments, such as light scattering, the contribution of a
`molecule to the observed effect is a function of its mass. Heavy molecules
`are favored in the averaging process; a weight-average molecular weight M w
`results. M w is equal to or greater than M n. The ratio M w! M n is sometimes
`used as a measure of the breadth of the molecular weight distribution. Values
`of M,../Mn for typical polymers range from 1.5-2.0 to 20-50.
`The molecular weight averages shown in Fig. 1-1 are defined mathemati-
`cally in Chapter 3.
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`THE SCIENCE OF LARGE MOLECULES
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`7
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`In contrast to the-linear-chain molecules
`Branched and network polymers
`discussed so far, some polymers have branched chains, often as a result of
`side reactions during polymerization (Fig. I-2a). The term branching implies
`that the individual molecules are still discrete; in still other cases crosslinked
`or network structures are formed (Fig. I-2b), as in the use of monomers con(cid:173)
`taining more than two reactive groups in stepwise polymerization. If, e.g.,
`
`(a)
`
`(b)
`
`Fig. 1-2. Schematic representation of (a) branched and (b) network polymers.
`
`glycerol is substituted for ethylene glycol in the reaction with a dibasic acid,
`a three-dimensional network polymer results. In recent years, a variety of
`branched polymer structures, some with outstanding high-temperature
`properties, has been synthesized (Chapter 15, Fig. 1-3).
`In commercial practice crosslinking reactions may take place during the
`fabrication of articles made with thermosetting resins. The crosslinked net(cid:173)
`wbrk extending throughout the final article is sta12Le~_!o-~~ancLc~nnoJ_be
`~de to flo\V C>_E..JP_dt.-, In contrast, most linear polymers --can be made to
`soften and take on new shapes by the application of heat and I>Rs.s__l1re. They
`are said to be thermoplastic.
`-
`-
`
`The texture of polymers The geometrical arrangement of the atoms iri a
`polymer chain can be divided conveniently into two categories:
`·a. Arrangements fixed by the chemical bonding in the molecule, such
`as cis and trans isomers, or d- and /-forms. Throughout this book, such
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`POLYMER CHAINS AND THEIR CHARACTERIZATION
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`+ Cruciform
`
`II
`
`I I[
`
`Random comb
`
`Double cruciform
`
`1111 11
`Regular comb
`
`I I I I I I I I
`
`Ladder
`
`Semiladder
`
`Fig. 1-3. Some possible model structures for branched polymers (Tawn 1969).
`
`arrangements are described as configurations. The configuration of a poly(cid:173)
`. mer chain cannot be altered unless chemical bonds are broken and reformed.
`b. Arrangements arising from rotation about single bonds. These
`arrangements, including the manifold forms that the polymer chain may have
`in solution, are described as conformations.
`
`In dilute solution, where the polymer chain is surrounded by small
`molecules, or in the melt, where it is in an environment of similar chains,
`the polymer molecule is in continual motion because of its thermal energy,
`assuming many different conformations in rapid succession. As a polymer
`melt is cooled, or as this molecular motion so characteristic of polymers is
`restrained through the introduction of strong interchain forces, the nature
`of the polymer sample changes systematically in ways that are important in
`determining its physical properties and end uses (Fig. 1-4).
`·
`In the molten state, polymer chains move freely, though often with
`enormous vi~asrone another if a force is applied. This is the prin(cid:173)
`ciple utilized in the fabrication of most polymeric articles, and is the chief
`example of the plasticity from which the very name plastics is derived. If
`the irreversible flow characteristic of the molten state is inhibited by the
`introduction of a tenuous network of primary chemical-bond crosslinks in
`the process commonly called vulcanization (Chapter 19), but the local free(cid:173)
`dom of motion of the polymer chains is not restricted, the product shows the
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`THE SCIENCE OF LJ}.RGE MOLECULES
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`9
`
`High
`
`LOWL-------------------------------------
`Intermolecular
`High
`forces
`
`____ __,..
`
`Low
`
`Fig. 1-4. The interrelation of the states of bulk polymers. The arrows indicate the direc(cid:173)
`tions in which changes from one state to another can take place (Billmeyer 1969).
`
`elastic properties we associate with typical rubbers. If, however, the inter(cid:173)
`chain forces result from secondary bonds, such as the interaction of polar
`groups, rather than primary chemical bonds, the rubber is not one of high
`elasticity but has the properties of limpness and flexibility: a familiar example
`is the vinyl film widely used alone or in coated fabrics. ,Secondary bond
`forces are capable of forming and breaking reversibly as the temperature is
`changed, as indicated by the arrows in Fig. 1-4.
`Continued primary-bond crosslinking in the postpolymerization step of
`vulcanization co'nverts rubber into hard rubber or ebonite, while crosslinking
`concurrent with polymerization produces a wide variety of thermosetting
`materials. Common examples are the phenol-formaldehyde and amine(cid:173)
`formaldehyde families widely used as plastics.
`As the temperature of a polymer melt or rubber is lowered, a point
`known as the glass-transition temperature is reached where polymeric materials
`undergo a mfrked change in propeitleS~t~d with the virtual cessation
`Ofillolecular motion on the local scale. Thermal energy is required for seg(cid:173)
`ments of a polymer chain to move with respect to one another; if the tem(cid:173)
`perature is low enough, the required amounts of energy are not available.
`Below their glass-transition temperature, polymers have many of the proper(cid:173)
`ties associated with ordinary inorganic glasses including hardness, stiffness,
`hrittleness, and transparency.
`In addition to undergoing a glass transition as the temperature is
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`10
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`POLYMER CHAINS AND THEIR CHARACTERIZATION
`
`lowered, some polymers can crystallize at temperatures below that designated
`as their crystalline melting point. Not all polymers are capable of crystal(cid:173)
`lizing; to oversimplify somewhat, the requirements for crystallizability in a
`polymer are that it have either a geometrically regular structure, or that
`any substituent atoms or groups on the backbone chain be small enough so
`that, if irregularly spaced, they can still fit into an ordered structure by
`virtue of their small size (see Chapter 5).
`The properties of crystalline polymers are highly desirable. Crystalline
`polymers are strong, tough, stiff, and generally more resistant to solvents
`and chemicals than their noncrystalline counterparts. Further improvements
`in these desirable properties can be brought about in at least two ways:
`
`First, by increasing intermolecular forces through the selection of highly
`polar polymers, and by using inherently stiff polymer chains, crystalline
`melting points can be raised so that the desirable mechanical properties
`associated with crystallinity are retained to quite high temperatures. There
`is a large research effort in this direction at the present time, leading to
`plastics capable of competing with metals and ceramics in engineering
`applications (Chapters 7 and 15).
`Second, the properties of. crystalline polymers can be improved for
`materials in fiber form by the process of orientation or drawing. The result
`is the increased strength, stiffness, and dimensional stability associated with
`synthetic fibers (Chapter 18).
`
`GENERAL REFERENCES:
`
`Mark 1940; Flory 1953, Chaps. Il-l, II-2; Mark 1966; Margerison 1967.
`
`B. History of Macromolecular Science
`
`Early investigations
`
`Natural polymers Natural polymers have been utilized throughout the
`ages. Since his beginning man has been dependent on animal and vegetable
`matter for sustenance, shelter, warmth, and other requirements and desires.
`Natural resins and gums have been used for thousands of years. Asphalt
`was utilized in pre-Biblical times; amber was known to the ancient Greeks;
`and gum mastic was used by the Romans.
`About a century ago the unique properties of natural polymers were
`recognized. The term colloid was proposed to distinguish polymers as a class
`from materials which cc;>Uld be obtained in crystalline form. The concept
`was later broadened to that of the "colloidal state of matter," which was
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`THE SCIENCE OF LARGE MOLECULES
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`II
`
`considered to be like the gaseous, liquid, and solid stat,es. Although useful
`for describing many colloidal substances, such as gold sols and soap solu(cid:173)
`tions, the concept of a reversibly attainable colloidal state of matter has no
`validity.
`The hypothesis that colloidal materials are very high in molecular weight
`is also quite old, but before the work of Raoult and van't Hoff in the 1880's
`no suitable methods were available for estimating molecular weights. When
`experimental methods did become available, molecular weights ranging
`from I 0,000 to 40,000 were obtained for such substances as rubber, starch,
`and cellulose nitrate. The existence of large molecules implied by these
`measurements was not accepted by the chemists of the day for two reasons.
`First, true macromolecules were not distinguished from other colloidal
`substances that could be obtained in noncolloidal form as well. When a
`material of well-known structure was seen in the colloidal state, its apparent
`high molecular weight was considered erroneous. Thus it was assumed that
`Raoult's solution law did not apply to any material in the colloidal state.
`Second, coordination complexes and the association of molecules were often
`used to explain polymeric structures in terms of physical aggregates of small
`molecules.
`For example, the empirical formula C 5 H8 was found for rubber as early
`as I 826, and isoprene was obtained on destructive distillation of the poly(cid:173)
`mer in 1860. The presence of the repeating unit
`
`CH 3
`I
`CH 2-C=CH-CH 2-
`was demonstrated in the early 1900's. At that time rubber was thought to
`consist of short sequences of this unit arranged in either chains or cyclic
`structures. Obvious difficulties regarding end groups, which could not be
`found chemically; favored ring structures, leading to the concept of the
`rubber molecule being a ring like dimethylcycooctadiene. Large numbers
`of these were considered held together by" association" to give the colloidal
`material:
`
`"
`In the search by the early organic chemists for pure
`Synthetic polymers
`compounds in high yields, many polymeric substances were discovered and
`as quickly discarded as oils, tars, or undistillable residues. A few of these
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`12
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`POLYMER CHAJNS AND THEJR CHARACTERJZATION
`
`materials, however, attracted interest. Poly(ethylene glycol) was prepared
`about 1860; th~ individual polymers with degree of polymerization up to 6
`were isolated and their structures correctly assigned. The concept of extend(cid:173)
`ing the structure to very high molecular weights by continued condensation
`was understood.
`Other condensation polymers were prepared in succeeding decades. As
`the molecular aggregation theories gained in popularity, structures involv(cid:173)
`ing small rings held together by secondary bond forces were often assigned
`to these products.
`Some vinyl polymers were also discovered. Styrene was polymerized
`as early as 1839, isoprene in 1879, and methacrylic acid in 1880. Again
`cyclic structures held together by "partial valences" were assigned.
`
`The rise ofpolymer science
`
`Acceptance of the existence of macromolecules Acceptance of the macro(cid:173)
`molecular hypothesis came about in the I 920's, largely because of the efforts
`of Staudinger (1920), who received the Nobel Prize in 1953 for his champion(cid:173)
`ship of this viewpoint. He proposed long-chain formulas for polystyrene,
`rubber, and polyoxymethylene. His extensive investigations of the latter
`polymers left no doubt as to their long-chain nature. More careful molecular(cid:173)
`weight measurements substantiated Staudinger's conclusions; as did x-ray
`studies showing structures for· cellulose and other polymers which were
`compatible with chain formulas. The outstanding series of investigations by
`Carothers (1929, 1931) supplied quantitative evidence substantiating the
`macromolecular viewpoint.
`
`The problem of end groups One deterrent to the acceptance of the macro(cid:173)
`molecular theory was the problem of the ends of the long-chain molecul~s.
`Since the degree of polymerization of a typical polymer is at least several
`hundred, chemical methods for detecting end groups were at first not success(cid:173)
`ful. Staudinger (1925) suggested that no end groups were needed to saturate
`terminal valences of the long chains; they were considered to be unreactive
`because of the size of the molecules. Large ring structures were also hypothe(cid:173)
`sized (Staudinger 1928), and this concept was popular for many years. Not
`until Flory (I 937) elucidated the mechanism for chain-reaction polymeriza(cid:173)
`tion did it become clear that the ends of long-chain molecules consist of
`normal, satisfied valence structures. The presence and nature of end groups
`have since been investigated in detail by chemical methods (Price 1942, .
`Joyce 1948, Bevington 1954).
`
`Molecular weight and its distribution Staudinger ( 1928) was among the first to
`recognize the large s!ze. of polymer molecules, and to utilize the dependence
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`THE SCIENCE OF LARGE MOLECULES
`
`13
`
`on molecular weight of a physical property, such a.s dilute-solution vis(cid:173)
`co~ity (Staudinger 1930), for determining polymer molecular weights. He
`also understood clearly that synthetic polymers are polydisperse (Staudinger
`1928): A few years later, Lansing (1935) distinguished unmistakably among
`the various average molecular weights obtainable experimentally.
`
`Configurations of polymer chain atoms Staudinger's name is also associated
`with the first studies (1935) of the configuration of polymer chain atoms.
`He showed that the phenyl groups in polystyrene are attached to alternate
`chain carbon atoms. This regular head-to-tail configuration has since been
`established for most vinyl polymers." The mechanism for producing branches
`in normally linear vinyl polymers was introduced by Flory (1937), but such
`branches were not adequately identified and characterized for another decade
`(see Chapter 3D). Natta (1955a,b) first recognized the presence of stereo(cid:173)
`specific regularity in vinyl polymers.
`
`Early industrial developments
`
`Rubber The modern plastics industry began with the utilization of natural
`rubber for erasers and in rubberized fabrics a few years before Goodyear's
`discovery of vulcanization in 1839. In the next decade the rubber industry
`. arose both in England and in the United States. In 1851 hard rubber, or
`ebonite, was patented ~nd commercialized.
`
`Derivatives of cellu.lose Cellulose nitrate, or nitrocellulose, discovered in
`1838, was successfully commercialized by Hyatt in 1870. His product,
`Celluloid, cellulose nitrate plasticized with camphor, could be formed into a
`wide variety of useful products by the application of heat and pressure.
`Nitrocellulose found application in the manufacture of explosives, photo(cid:173)
`graphic film, synthetic fibers (Chardonnet silk), airplane dopes, automobile
`lacquers, and automobile safety glass. Nitrocellulose in turn has been
`superseded in almost all these uses by more stable and more suitable
`polymers.
`Cellulose acetate, discovered in I 865, was not used commercially for
`several decades because of the low solubility and lack of dyeability of the
`early cellulose triacetate products. In the early I 900's the manufacture of
`less highly substituted, more readily soluble compositions opened the way
`for the commercial development of acetate rayon fibers and cellulose acetate
`plastics.
`Later still, processes were developed whereby cellulose itself could be
`dissolved and reprecipitated by chemical treatment. These processes led to the
`production of viscose rayon fiber and cellophane film.
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`TEVA PHARMACEUTICALS USA, INC. V. MONOSOL RX, LLC
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`14
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`POLYMER CHAINS AND THEIR CHARACTERIZATION
`
`Synthetic polymers The oldest of the purely synthetic plastics is _the family;
`of phenol-formaldehyde resins, of which Baekeland's Bakelite was the first
`commercial product. Small-scale production of phenolic resins and varnishes
`was begun in 1907.
`The first commercial use of styrene was in synthetic rubbers made by
`copolymerization with dienes in the early 1900's. Polystyrene was produced
`commercially in Germany about 1930 and successfully in the United States
`in 1937. Large-scale production of vinyl chloride-acetate resins began in
`the early 1920's also.
`Thus the last quarter-century has seen the development of all but a
`handful of the wide variety of synthetic polymers now in common use.
`
`GENERAL REFERENCES
`
`Mark 1940; Flory 1953, Chap. I; Purves 1954.
`
`C. Molecular Forces and Chemical Bonding in Polymers
`
`The nature of the bonds that hold atoms together in molecules is
`explained by quantum mechanics in terms of an atom consisting of a small
`nucleus, concentrating the mass and positive charge, surrounded by clouds
`or shells of electrons relatively far away. It is among the outermost, more
`loosely bound e