Polymer chemistry book

POLYMER CHEMISTRY Alka L Gupta PRAGATI PUBLICATIONS PRAGATIPRAKASHAN Educational Publishers Head Office: PRAGATI BHAWAN, 240, W K Road, Meerut-250001 Tele Fax: 0121-2643636, 2640642 Phone: 0121-6544642,6451644 Regd Office: New Market, Begum Bridge, Meerut-250001 Phone: 0121-2661657 Kindly visit us : www.pragatiprakashan.in e-mail: pragatiprakashan@gmail.com Revised Edition: 2010 ISBN No : 978-81-8398-998-5 IINTRODUCTION 1-10 BASICS Importance of Polymers 11 Monomers and Repeat units 12 Degree of Polymerisation 14 Classification of Polymers 14 Linear Polymers 15 Branched Polymers 15 Cross-linked or Network Polymers 16 Addition Polymers 16 Condensation Polymers 16 Chain-Growth Polymers 17 Step-Growth Polymers 18 Elastomers 18 Fibres 20 Thermoplastics 20 Thermosetting Polymers 20 Nomenclature of Polymers 21 Polymerisation 23 Addition (chain) Polymerisation 23 Free-radical Addition Polymerisation 24 Ionic-Polymerisation 29 Cationic Polymerisation 29 Anionic Polymerisation 31 Coordination Polymerisation 32 Condensation (Step) Polymerisation 33 Polycondensation Polymerisation 34 Polyaddition Polymerisation 35 Ring-opening Polymerisation 36 Copolymerisation 37 Free-radical Copolymerisation 38 Monomer Reactivity Ratios 40 Reactivity-ratios and Copolymerisation Behaviour Ionic Copolymerisation 46 Copolycondensation 47 Types of Copolymers 48 Polymer Reactions 50 Hydrolysis 50 Acidolysis 51 Aminolysis 51 Hydrogenation 51 Addition reactions 52 Substitution reactions 53 Reaction of Ketonic Groups 54 Reactions of Carboxylic Groups 54 Reactions of Aldehyde Groups 54 11-76 43 (vi) Reaction' of Nitric Group 55 Reaction of Amino Group 55 Reaction of Aromatic-Ring 55 Reaction of Amide Group 56 Cyclisation Reaction 56 Cross linking Reactions 57 Vulcanisation 58 Reaction with Ammonium acetate 59 Reaction with Ni-carbon compound 59 Reaction Introducing Aromatic group 60 Reaction with succinic anhydride 60 Nucleophilic substitution reaction 60 Polymerisation in Homogeneous and Heterogeneous Systems Homogeneous System 61 Heterogeneous System 63 Suspension Polymerisation 63 Emulsion Polymerisation 63 Interfacial Polycondensation Polymerisation 65 Solid and Gas Phase Polymerisation 66 Miscellaneous Polymerisation 67 Group Transfer Polymerisation 67 Metathetical Polymerisation 68 Electrochemical Polymerisation 69 Ziegler-Natta Polymerisation 71 fl POLYMER CHARACTERIZATION Average Molecular Weight Concepts 77 Number-Average Concept 78 Weight-Average Concept 79 Viscosity-Average Molecular Weight 80 Polydispersity and Molecular Weight Distribution 81 The Practical Significance of Molecular Weight 82 Measurement of Molecular Weights 84 End-group Analysis 84 Viscometry 85 Light Scattering Method 88 Osmometry 89 Ultracentrifugation Method 94 Chemical Analysis of Polymers 97 Mass Spectrometry 98 Gas Chromatography 98 Spectroscopic Methods 98 1R 98 NMR 99 EPR 100 X-ray diffraction 100 Microscopy 101 Thermal Analysis 101 Differential Calorimetric ~alysis 102 Thermal Gravimetric Analysis 102 Physical Testing 102 Tensile Strength 102 Fatigue 103 61 77-103 (vii) Impact 103 Teat Resistance 103 Harlmess 103 Abtasion Resistance 103 " I STRUCTURE AND PROPERTIES 104-139 Morphology and Order in Crystalline Polymers 104 Configurations of Polymer chains 104 Crystal Structure of Polymers 111 Morphology of Crystalline Polymers 115 Strain-Induced Morphology 117 Polymer Structure and Physical Properties 120 Crystalline Melting Point (Tm) 120 Melting-Point of Homologous Series 121 Effect of Chain Flexibility and Other Sterle Factors 121 Chain Flexibility 121 Side-Chain Substitution 123 Glass Transition Temperature (Tg) 123 Experimental Demonstration of Tg 124 Glassy Solids and Glass Transition 124 128 Relationship between Tg and Tm Effect of molecular weight on Tg 129 Effect of Plasticizers on Tg 129 Effect of copolymers on Tg 130 Effect of chemical structure on Tg 130 Effect of chain topology on Tg 131 Effect of chain branching and crosslinking on Tg 131 Factors Influencing Glass Transition Temperature 131 Determination of Glass Transition Temperature 135 Importance of Glass Transition Temperature 137 Property Requirements and Polymer Utilization 137 EM POLYMER PROCESSING Plastics 140 Thermosetting Plastics 142 Elastomers 143 Fibres 145 Compounding 148 Processing Techniques 148 Calendering 149 Oiecasting 150 Rotational Casting 150 Film Casting 151 Injection Moulding 151 Blow Moulding 153 Extrusion Moulding 154 Compression Moulding 155 Thermoforming 155 Foaming 156 Reinforcing 157 Fiber Spinning 161 140-1641 ~ "i ~ (viii) 165-2341 PROPERTIES OF COMMERCIAL POLYMERS Polyethylene 165 Polyvinyl chloride 169 Polyarnides 171 Polyesters 173 'phenolic Resins 175 Epoxy ~esins 178 Silicone Polymers 179 Electrically Conducting Polymers Functional Polymers 183 Fire-Retardmg Polymers 184 Biomedical Polymers 188 Contact Lens 196 Dental Polymers 206 Artificial Heart 218 Artificial Kidney 220 Artificial Skin 225 Artificial Blood 230 180 Ii POLYMER ADDITIVES 235-2431 Types of Fillers 236 Miscellaneous Mineral Fillers ' 237 Plasticizers 238 Properties of Plasticizers 238 Importamt Plasticizers 238 Antioxidants 239 UV-Stabilizers and Absorbers 242 Fire Retardants 243 Colourants 243 I' NATURAL POLYMERS 244-2531 Polysaccharides and Lignin 244 Reactions of Cellulose 245 Starch 246 Lignin 247 Glycogen 248 Proteins 248 Nucleic Acids 250 Conformation of the Nucleic Acids 251 Segments of RNA and DNA Polymers 252 IAPPENDICES Appendix 1: Polymer Degradation 254 Appendix 2: Photodegradation of Polymers 255 Appendix 3: Current and Promising Polymer Research Topics ISUGESTED READINGS ISUBJECT INDEX 254-2571 '( 256 258-260 (i)-(iv) I,· I INTRODUCTION PROLOGUE • Historical Background • Basic Tenns and Definitions • Polymer • Polymer Synthesis • Polymer Structure • Chain Linearity Polymers science and engineering deal with the chemistry, molecular stru~ture, physical properties, the applications and processing in the useful forms and the biological significance of materials It is the chemistry of large molecules-macromolecules each containing from thousands to millions of atoms The atoms are typically linked in a sequence of repeating structural units, derived from certain molecules of small units, i.e., monomers The polymer is thus a long chain, in some polymer may coil, branch, cross-linked to other chains or take part in other orders or structural complexity The chemical and physical interactions among the atoms of polymer are governed by the same laws that describe systems of small molecules, but extreme molecular size introduces a new realm of properties The diversity of macromolecular structure represented by a given chemical composition increases with the number of monomeric units present and statistical considerations must enter the description of even the simplest polymer chain The extreme length of macromolecular chain inhibits their crystallization, hence diverse stable solid states occur which may be rubbery, glassy or semicrystalline New combinations of properties emerge, such as rubbery elasticity and strength, combined with flexibility and optical clarity Fabrication methods are found with polymers which facilitate their shaping into desired forms Polymers made by man, and their fabrication into finished products have become the basis of a major industry world wide Life itself is a basis of large molecules The remarkable adaptations of collagen and cellulose to structural functions, the specificity and efficiency of enzymes as catalysts, the binding and release of oxygen by hemoglobin and (1) 2• POLYMER CHEMISTRY myoglobin, and the encoding of specific genetic information by the nucleic acids, all have their origins in the polymeric nature of the molecules involved Polymer study and research is thus interdisciplinary, with major contributions from chemistry, physics, several branches of engineering, biomedical science and molecular biology Polymers are essential in fulfilling a broad range of national needs, present and prospective, in such categories as energy, transportation, construction, agriculture and food processing, medicine and national defense The history of polymer science and engineering is replete with unforeseen discoveries of major consequence, and the future of this field is bright one promising For example, the recent break throughs in understanding the structure and invivo synthesis of biopolymers still have to make their major impact on synthetic polymers, and the theory and application of composite materials based on polymers are still in their infancy Enormous studies have been made in the field of biopolymers, since the discovery of the DNA double helical structure in 1953 This was followed by various advances: the determination of the detailed sequence structure of nucleic acids and proteins, the recognition of nucleic acids as the carriers of heredity and the solid-state synthesis of sizable protein molecules Further progress has continued in many related areas, including such vital aspects as the three-dimensional structure of enzymes, its connection to binding of specific molecules, and thus its catalytic function The production of polymers on a volume basis now exceeds that of steel, and its growth rate (8.5% per year) is four times that of steel and nonferrous metals Polymer industries add $ 90 billion per year of value added by manufacture and employ 3.4 million people Polymers also have a high technology aspect which will be increasingly important in the future and may have a critical impact on fulfilling national needs • HISTORICAL BACKGROUND The polymer science is a coherent subject since 1950 Prior to 1930, a number of national products now recognized as polymers (e.g., cellulose, starch, proteins, rubber) had been studied with the relatively primitive instrumentation but highly ingenious methods of chemical experimentation and reasoning then available Emil Fischer, after his classic researches on the stereochemistry and synthesis of the sugars, turned in 1899 to the linkage of the amino acids known to be combined in proteins He succeeded not only in getting two amino acids to combine synthetically (as an amide), but by 1907 he had synthesized a polypeptide chain containing as many as 18 amino acids residues, linked in known linear sequence His synthetic polypeptide prove to behave in every respect by corresponding natural intermediate products derived from the hydrolysis of proteins Important synthetic derivatives of natural polymers had been discovered, among them vulcanized rubber by C Good year in 1839, cellulose nitrate in 1870 by J.W Hyatt, cellulose acetate by C and H Dreyfus in 1919, and even the first commercially successful class of entirely synthetic polymers, the thermosetting phenolic resins by L.H Baeke land in 1909 The structure of these amorphous, plastic, nonvolatile, slow diffusing materials was that they consisted of micellar aggregates of small molecules, a colloidal state, cohering through I I INTRODUCTION "'" intermolecular forces of non-chemical origin There was a prejudice against believing that stable molecules of indefinitely large dimensions could exist The clear concepts of macromolecules, are attributed to Hermann Staudinger In 1920's, Staudingers did work on styrene, convinced that the amorphous material readily forms on standing or heating consists of styrene units covalently bonded in long chains through a chemical reaction involving opening of the vinylic double bond He succeeded in preparing of polystyrenes of varying degrees of polymerization (i.e., number of styrene units per chain) as reflected in their average molecular weight and molecular weight distributions He demonstrated a corelation of molecular size with the viscosity of their dilute solutions in suitable solvents The fundamental principles of vinyl polymerization were outlined by J.F Paul in 1937 in terms of chain reaction sustained by a free-radical mechanism A landmark in polymer science and engineering was the commercial development in 1939 of nylon 66, discovered by carothers This entirely synthetic aliphatic polyamide, resembling natural silk but with controllable structural regularity and attendant desirable physical properties, proved to be a product for which a demand rapidly became evident C.S Marvel pioneered in the organic chemistry of polymers and made outstanding contributions to polymer synthesis His research on polymers stable on high temperatures and on polymers with heterocyclic structures has led to concepts and materials of major commercial significance An unexpected break through in polymer research was achieved in 1955, when Karl Ziegler discovered polymerization catalysts based on various coordination compounds of transition metals With such a catalyst, Ziegler found that polyethylene could be synthesized from ethylene rapidly at ambient temperature and pressure Furthermore, this polyethylene was almost entirely linear unlike the branched low density polyethylene known since 1935, which is produced only at elevated temperatures and pressure in excess of a thousand atmospheres Giulio Natta then succeeded with catalysts of this type in polymerizing propylene and discovered the first synthetic stereospecific polymerization Natural stereospecific reactions occur in the formation of proteins and other polymer of biologic origin such as rubber and Gutta-percha (which are stereoisomers of each other) In polypropylene, all the propylene units are aligned 'head to tail', i.e., pendant methyl groups occur at the same end of each unit, an orientation of the chain which as favoured by the reaction kinetics, but they may assume either of two different mirror-image-configurations depending on the orientation of the pendent methyl group about the chain The Ziegler-Natta catalyst permits the synthesis of stereoregular polymers, in which the monomeric units have either the same or regularly alternating configurations, or the synthesis of isomeric randomly oriented polymers, which have quite different physical properties Some stereoregular synthetic polymers may occur in a semicrystalline state, the randomly oriented polymers are always amorphous The Ziegler-Natta catalysts were used primarily to produce new forms of earlier polymers rather than polymers of new chemical composition This has been a major trend in more recent developments, i.e., existing polymer types have been vastly improved by chemical and physical modification For example, modification of polymer glasses to produce tough, impact-resistant materials, increase in the elastic modulus of polyethylene 250 • POLYMER CHEMISTRY Steps! repeated r-n }-CH2-J r NHJ 1{-NHBlg TR ! Hydrolysis )-CH20H+HJf{-NHJ 1- {-NH2 R TR BIg = Blocking group ) = Polymer bead Solid phase synthellis of poly(peptide) • NUCLEIC ACIDS The nucleic acids are the condensation products of nucleoside triphosphates, and it contains heterocyclic bases The nucleic acids are of two types: (a) DNA and (b) RNA DNA is deoxyribose nucleic acid It contains the heterocyclic bases; such as adenine, guanine, thymine, and cytosine RNA is the ribose nucleic acid It contains adenine, guanine, uracil and cytosine In DNA, thymine is present, while in RNA, uracil is present, i.e., only one of the heterocyclic bases is different The names of the two nucleic acids are based on the sugar moiety present in them Thus, DNA and RNA differ in that one contains the carbohydrate D-2-deoxyribose, and the other contains D-ribose The early work on the separation of nucleic acids from the human cells was initiated by Miescher in 1868 In 1930, it was recognized that there were two types of these acids During 1940s and 1950s, special techniques of separation, namely, paper and ion-exchange chromatography were discovered, and this provided the progress in the chemistry of nucleic acids HOC~H HOC~H OH OH OH H (D-Ribose) (Deoxyribose) Sugar moieties NATURAL POLYMERS ):' O~NjJ (Adenine) (A) (Guanine) (G) o HN~ OANjJ H (Cytosine) (C) H (Uracil) (U) 251 o HN~CH3 OANjJ H (Thymine) (T) BASES Nucleosides On enzymatic hydrolysis, RNA gives four nudeosides, namely, adenosine, guanosine, uridine and cytidine; which on acid hydrolysis gives D-ribose and the four bases, ~amely, adenine, guanine, uracil and cytosine, respectively On a similar reaction with an enzyme, DNA yields the four nucleosides deoxyadenosine, deoxyguanosine, deoxycitidine and deoxythymidine Acid hydrolysis of the nucleosides yield besides deoxy D-2-ribose, the four heterocyclic bases, adenine, guanine, cytosine and thymine Nucleotides : On hydrolysis with specific enzymes (or very mild chemical hydrolysis) nucleic acids yield a mixture of nucleotides These were shown to be phosphate esters of nucleosides, which had been obtained under more drastic hydrolysis Conformation of the Nucleic Acids NH2 N~N~ ~NJlN> o II HO-P-O-CH2 I OH OH OH (Adenosine) (a-nucleoside) OH H (Cytosine deoxyribonucleotide) (a-nucleotide) The chemical structure of nucleic acids was settled by 1950 The accepted conformation of DNA was put forward by F.H.C Crick and J.D Watson They suggested that DNA consisted of n:vo poly (nucleotide) chains wound helically in opposite directions around a central axis They postulated that the nitrogen bases in each linear chain of the helix were paired across the axis of the helix with the nitrogen bases in the other linear chain In each case the pairing was made by hydrogen bonding between the bases Since only a purine paired with a pyrimidine would conveniently fit the dimensions across the axis of the helix, this model also explained the regular ratios of the base compositions 252 • POLYMER CHEMISTRY Segments of RNA and DNA Polymers NATURAL POLYMERS -4 % 3.4 A 253 A-T pair (b) R =DEOXY RIBOSE H I ~N, r II H, NVN", ':i'O GUANINE R II H, N N ~ "H, (a) CYTOSINE ~H AN I N/ I R G-CPair (c) (a) Double helix of DNA (b) and (c) base pairs in DNA ••• APPENDICES \ eQQ*i.)£I~ Polymer Degradation A plastic item with thirty years of exposure to heat and cold, brake fluid, and sunlight, notice the discoloration, swollen dimensions, and tiny splits running through the material Polymer degradation is a change in the propertiestensile strength, colour, shape, etc of a polymer or polymer based product under the influence of one or more environmental factors such as heat, light or chemicals It is often due to the hydrolysis of the bonds connecting the polymer chain, which in turn leads to a decrease in the molecular mass of the polymer These changes may be undesirable, such as changes during use, or desirable, as in biodegradation or deliberately lowering the molecular mass of a polymer Such changes occur primarily because of the effect of these factors on the chemical composition of the polymer Ozone cracking and UV degradation are specific failure modes for certain polymers The degradation of polymers to form smaller molecules may proceed by random scission or specific scission The degradation of polyethylene occurs by random scission-that is by a random breakage of the linkages (bonds) that hold the atoms of the polymer together When heated above 450 Celsius it degrades to form a mixture of hydrocarbons Other polymers-like polyalphamethylstyrene-undergo 'specific' chain scission with breakage occurring only at the ends The literally unzip or depolymerize to become the constituent monomer However the degradation process can be useful from the view points of understanding the structure of a polymer or recycling/reusing the polymer waste to prevent or reduce environmental pollution Polylactic acid and Polyglycolic acid, for example, are two polymers that are useful for their ability to degrade under aqueous conditions A copolymer of these polymers is used for biomedical applications such as hydrolysable stitches that degrade over time after they are applied to a wound These materials can also be used for plastics that will degrade over time after they are used and will therefore not remain as litter (254) APPENDICES • 255 (;1QQM't'W, Photodegradation of Polymers I In ordinary sunlight, ultraviolet light radiations are present, which consist of wavelength less than 400 nm It corresponds the energy about 390 kJ/mole The energy required to break a C-H, C-C and C=C bonds is 99, 83 and 145 kcallmol respectively If unsaturated aromatic or carbonyl group is present in a polymer, it causes homolytic bond fusion and forms free-radicals These free-radicals can then react with any oxygen present, leading to the oxidation of polymer chain The polymers, degraded in presence of UV light can be discussed in the following examples: (1) Degradation of Copolymer of Ethylene and Carbon Monoxide: In a copolymer of ethylene and carbon monoxide, a carbonyl group is present On irradiation in UV light, the carbonyl group makes it most photo-labile In the first step of reaction, the chain scission takes place in the adjacent carbonyl group to forms radicals directly The second step is non-radical reaction, which results in chain scission by way of a six-membered ring transition state, forming a methyl ketone and unsaturated vinyl compound The photo-degradation of the polymer occurs as follows : (2) Photodegradation in ~olyamide Polymer: In photo-degradation reactions of polyamides, both cross-linking and chain scission take place, although it has been reported that this is wavelength dependent In the first step, scission occurs at the bonds between carbon and nitrogen atoms It forms carbon monoxide and amine groups In the second step, cross-linking occurs, it follows abstraction of hydrogen atoms from the methylene groups, which are present at the adjacent of -NH groups The entire reactions are as follows : 256 • POLYMER CHEMISTRY Scission : -CH2-CH2-CH3 + NH -CH2 + R' CO+R' Cross-linking : o1/ o 1/ -CH2 -CH2 -CH2 -C-NH-CH-CH2- I -CH2-CH2-CH2-C-NH-CH2-CH2.b4 -CH2-CH2-CH2-C-NH-CH-CH21/ o The methylene group adjacent to the nitrogen atom is most reactive group, hence the hydrogen atom abstracted from it, resulting in subsequent cross-linking reaction in the polyamide polymer APPENDIX Current and Promising Polymer Research Topics The following summary list of current and promising polymer research topics is necessarily quite brief The field is large and will continue to have a great impact on all levels of society for the foreseeable future • Growing use of polymers as biomaterials - Seasickness patches - Proxtheses-hip cups, lenses, blood vessels, orthopedic implants, denture bases, fillings, cultures, heart valves organs, vascular grafts, hernia mesh, catheters, syringes, diapers, blood bags, artificial limbs, ligaments, packaging - Controlled release - Diagnostics • Emerging electronic properties of polymers - Dielectrics - Synthetic metals and battery materials - Sensors - Lithographic resists - Photonic materials - Light-emitting diodes and displays - Electrophotography - Holography APPENDICES • • • • • 257 - Fuel cells - Solar cells Emergence of synthetic means for control of polymer structures - Coordination catalysts - Biocatalysis, enzyme synthesis, biological organisms for synthesizing monomers and polymers - Ring-opening metathesis polymerization - Hybrid organic-inorganic materials synthesis, sol gel formation - Dendritic polymers - Composites with tailored transport, electrical, or optical properties Growing use of blends and composites to obtain "tailored" properties - High-strength, high-modules fibers - Enhanced matrix choices - "Tailored" mechanical properties - High-stability toughening additives - High-temperature options - Understanding of failure mechanisms Enhanced characterization capability through computer and electronic advances - Molecular colligative, light scattering, centrifuged separation, NMR, UV, FTIR, RAMAN - Solutions, merits; rheology, diffusion, neutron scattering - Solid state synchrotron x-ray and electron spectroscopy, TEM, soft x-ray microscopy, mechanical testing - Surface analysis: XPS, depth profiling SIMS, SFA, AMF, LFM - Folding: NMR - New microscopies: confocal and scanning tunneling Evolution of polymer theory with emphasis on computer modeling and simulation - States of matter, solutions, crystalline, amorphous, LCs, blends, block polymers, copolymers, interfaces, surfaces ••• SUGGESTED READINGS The following books and articles are suggested for further readings : Mark, H.F., Giant Molecules, Time-Life Books, New York, 1966 Bawn, C.E.H., The Chemistry of High Polymers, Butterwo~th London, 1948 Flory, P.J., Principles of Polymer Chemistry, Cornell University Press, New York, 1953 Billmeyer, Jr., F.W., Text Book of Polymer Science, John Wiley New York, 3rd edition, 1984 Allen, P.E.M and Patrick, C.M., Kinetics and Mechanisms of Polymerization Reactions, John Wiley, New York, 1974 Bamford, C.H., Jenkins, AD.; Barb, W.G., Onyon, P.F.; The Kinetics of Vinyl Polymerization by Radical Mechanisms, Butterworth, London, 1958 '7 Bevington, J.c., Radical Polymerization, Academic Press, New York, 1961 Ham, G.E., Vinyl Polymerization, I, Park I, Marcel Dekker, New York, 1967 Odian, G., Principles of Polymerization, John Wiley, New York, II edition, 1981 10 Natt., G., Giannini, u., Coordination Polymerization in Encyclopaedia of Polymer Science and Technology, 4, Willey-Interscience, New York, 1966, pp 137-50 11 Alfrey, Jr., T Bohrer, J.J and Mark, H., Copolymerization Interscience, New York, 1952 12 Ceresa, R.J., Block and Graft Copolymers, Butterworth, London, 1962 13 Stille, J.K., Introduction of Polymer Chemistry, John Wiley, New York, 1962 14 Natta, G., Dannisso, F., Stereoregular Polymers and Stereospecific Polymerization, Pergamon, Oxford, 1967 15 Bovey, F.A, Polymer Conformation and Configuration Academic Press, New York, 1969 16 Jenkins, AD., Ladewith, A, Reactivity, Mechanism and Structure in Polymer Chemistry, Chapter 12, Wiley-Interscience, London, 1974 17 Vollmert, B., Polymer Chemistry, Springer-Verlag, New York, 1973 18 Allen, P.W., Techniques of Polymer Characterization, Butterworth, Londong, 1959 (258) SUGGESTED READINGS • 19 Bonner, R.V., Dimbat, M., Stross, Wiley-Interscience, New York 1950 F.H., Number-average Molecular 259 Weights, 20 Chien-Jen-Yuen, Determination of Molecular Weights of High Polymers, Oldboume, London, 1963 21 D'Alelio, G.F., Fundamental Principles of Polymerization "Rubbers, Plastics, and Fibers", John-Wiley, New York, 1952 22 Rodriguez, F., Principles of Polymer Systems, MacGraw Hill, New York 1970 23 Ravve, A, Organic Chemistry of Macromolecules, marcel Dekker, New York, 3rd edition, 1967 24 Tager, A, Physical Chemistry Of Polymers, Mir Publishers, Moscow, 1972 25 Schildknecht, C.E (Ed.) Polymer Processes, Interscience New York, 1965 26 Morton, M., Rubber Technology, 2nd edition, Van-Nostrand-Reinhold, New York, 1981 27 Braun, D., etat., Encyclopaedia of Polymer Science and Technology, "Rubber Natural", 12, Wiley-Interscience, New York, 1970, pp 178-256 28 Moor, J.A, Reactions of Polymers, (Reidel Dordrecht (1973) 29 Odian, G., Principles of Polymerization, John Wiley, New York, 3rd edition 30 Seymour, R.B., Carraher, C.E., Polymer Chemistry: An Introduction, Marcel Dekker, New York, 2nd edition, 1988 31 Morawetz; H Micromolecules in Solution, Wiley-Interscience, New York, 3rd edition, 1984 32 Aklonis, J.J., Mcknight, W.J., Sten, M., Introduction Wiley-Interscience New York, 1982 to Polymer Viscoelasticity, 33 Rosen, S.L., Fundamental Principles of Polymeric Materials, Wiley-Interscience, New York, 1982 34 Hendrickson, J.E., Cram, D.J Hammond, G.S., Organic Chemistry, McGraw Hill, New York, 3rd edition, 1970 35 Walker, B.J., Organophosphorus Chemistry, Penguin, Hammonds worth, Middlesex, England., 1972 36 Grant, J., Cellulose, Pulp and Allied Products, Interscience, New York, 1959 37 Doty, P., Proteins in Organic Chemistry of Life, Freeman, New York, 137-146, 1973 38 Pinner, S.H., A Practical Course in Polymer Chemistry., Pergamon, New York, 1961 39 Sorensen, W., Campbell, T.W., Preparative Wiley-Interscience, New York, 2nd edition, 1968 Methods of Polymer Chemistry, 40 Collins, E.A, Bares, J., Billmeyer, Jr., F.W., Experiments in Polymer Science, Wiley-Interscience, New York, 1973 41 McCaffery, E.L., Laboratory Preparation for Macromolecular Chemistry, McGraw Hill, New York,1970 260· POLYMER CHEMISTRY 42 Redfam, CA., Bedford, J., Experimental Plastics, Iliffe, London, 1960 43 D'Alelio, G.F., Laboratory Manual of Plastics and Synthetic Resins, John Wiley, New York, 1943 44 Kline, G.M.E., Analytical Chemistry of Polymers Part I, Interscience, New York, 1959 45 Bovey, F.A., High Resolutions NMR of Macromolecules Academic Press, New York, 1972 46 Bovey, F.A., In Encyclopaedia in Polymer Science and Technology, "Nuclear Magnetic Resonance", 9, Wiley-Interscience, New York, 1968 47 Ritchie, PD., Plasticizers, Stabilizers, and Fillers, Butterworth, London, 1972 48 Frisse!, W.J., Enclopaedia of Polymer Science and Technology, "Filler", 6, Wiley-Interscience, New York, 1967 49 Buttery, D.N., Plasticizers, Franklin Publishing, Pollsides, New Jersey, 2nd edition, 1960 50 Segal, CL., High Temperature Polymers, Marcel-Dekker, New York, 1967 51 Jellinek, H.H.G., Aspects of Degradation and Stabilization of Polymers, Elsevier, Amsterdam, 1978 52 Grassie, N., Scott, G., Polymer Degradation and Stabilization, Cambridge-University Press, Cambridge, 1985 53 Grassie, N., Encyclopaedia of Polymer Science and Technology, "Degradation of Polymers", pp 647-716, Wiley-Interscience, 1966 :54 Dubois, J.H., John, F.W., Plastics, Reinhold, New York, 1981 55 Seymour, W.B., Modern Plastics Technolgy, Reston Publishing Co Reston., 1975 56 Moncrieff, R.W., Man Made Fibres, Halsted, New York, 1975 57 Melville, H.W., Big Molecules, G Ball, London, 1958 58 Mark, H.F., etal., Man Made Fibres, Sciene and Technology, 1,2,3; Wiley-Intescience, New York, 1967-68 59 Blow, CM., Rubber Technology and Manufacture, Butterworth, London, 1971 60 Copper., W., Encylopaedia of Polymer Science and Technology, "Elastomer synthetic", 5, Wiley-Interscience, New York, 406-482, 1966 61 Allcock Harry R., Lampe Frederick W and Mark James E "Contemporary Polymer Chemistry", Pearson Education, 3rd edition (2003) 62 Cowie J.M.G "Polymers: Chemistry and Physics of Modem Materials", Blackie (In USA: Chapman and Hall), 4nd edition (1991) 63 Ezrin, Meyer, Plastics Failure Guide: Cause and Prevention, Hanser-SPE (1996) 64 Lewis, Peter Rhys, Reynolds, K and Gagg, C, Forensic Materials Engineering: Case studies, CRC Press (2004) 65 Wright, David C, Environmental Stress Cracking of Plastics RAPRA (2001) ••• SUBJECT INDEX Abrasion resistance Absorbers 103 Cadaver skin Calendering 242 Addition polymer 16 Addition polymerisation Addition Reactions Adenine 13, 16, 23 29,31,70 235-237,239-242 Artificial blood 230-234 Artificial heart 218 99 Cold drawing 118, 112 243 Compounding 222 225 lOS, 106, 111 Bioengineered kidney Biomedical polymer 155 Condensation polymer 16, 18, 122 Configuration 104, 107-111 Conformation 104 221 Copolymer Blood oxygenator 195 Branched polyethylene 47, 48 35, 39 Cross-linked polyethylene Crosslinked polymer 153 15 Cyc1isation Reactions 167 Cytosine 251, 253 Decron 17, 18 168 15 Crystalline melting point Branched chain polymer 32, 33 13, 48 Copolymerisation 10, 49 Britle Copolycondensation 120 Block copolymer Blow moulding 10 Coordination polymerisation 165, 188 13, 16, 33 196 Contour length 4, 14 Birefringence 148 Compression moulding Contact lens 17, 18,21, 177 Bipolymer 165 Condensation polymerisation 236 Bakelite 10 Commercial polymer 194 23 Chemical shift Colourants 220 Artificial membrane Atactic 17,18, 207 Comb polymer Artificial heart devices Asbestos 244-246 Chain polymerisation Anionic polymerisation Artificial kidney 29, 70 246 Chain linearity 246, 247 Artificial skin 238 Chain growth polymer 10, 49 246, 247 Antioxidant Camphor plasticizer Cellulose Alternating copolymer Amylose 136 Cellophane 225 Amylopectin 149 Calorimetric method Cationic polymerisation 52 251, 253 Allograpfts 225 120 56 103 Brush polymer 10 Bulk Polymerisation 61,62 Degree of polymerisation (i) 10, 14, 83 (ii) Dental adhesives 206, 213 Dental composites 206, 215 Dental polymers Deoxyribose Diads Geometric isomerism Glass Transition temperature 206 Glassy solids 250,253 Glycogen 105 Dialysis DNA 150 Graphite 135 10, 49 228 236 Group-transfer polymerisation Guanine 250-253 D-ribose Ductile 248 Graft skin Dilatometric method 251, 253 250 Hand-lay-up Technique 103 Hard contact lens Elastomer Hardness 18, 140, 143-145, 148 180 Heart valves Electrochemical polymerisation 69 Hemodialysis Emulsion polymerisation End-group Analysis Epoxy resins Inhibitors Filament-Winding Technique 158 28 151 Ionic copolymerisation Ionic polymerisation IR 151 Fire-retarding polymers 57, 184, 243 Flame resistant polymer 57, 184 Foaming 103 Injection moulding 235 Flow Temperature 232 154 18,20, 140, 145-147, 164 FiImcasting 240 13, 37, 49 Hyperbranched polyester 178 103 Fillers 105, 106 Homopolymer Impact Fibre 222 Hindered Phenol 63 84 Extrusion moulding Fatigue 196,201 194 Heterotactic 100 158 103 Electrically conducting polymer EMR 123 46 29, 70 98 Isotactic Jute fibre 106, 113, 114 237 156 Free-radical copolymerisation Free-radical polymerisation Fringed micelle Ladder polymer Lamellae 183, 184 Lathe cutting Lignin 196, 198 Gas-phase polymerisation 66 160 198, 199 Light-Scattering 84 Gas-permeable lens 57, 134 115, 116, 119 Laminating Technique 116 Functional polymer Functionality 39,47 24-29 123-138 124 Graft polymer 222, 223 Diecasting 109 88-89 244, 247 Linear Polyethylene Linear polymers 15 168 67 (iii) Mass spectrometry Plasticizer 98 Measurement of Mol wt Membrane osmometry 84 90 68 237 170 PMMA 198,202,207 Polyaddition polymerisation Microscopy 101 Mineral filler Polyamide 237 Mixed polymer MMA 140 Plastisol Metathetical polymerisation Mica Plastics 20, 238, 239 Polycondensation 13 Polydispersity 202,207 10, 77, 84, 85, 94 Molecular-weight distribution Monomers 34 81, 82 Polydispersity Index Molecular weight 81, 82 12 10 173, 112 Polyester Polyglycodic acid Polylactic acid 257 257 Polymer Additive 235 Natural polymer 14,58,244,207 Polymer degradation Network polymer 10, 15 Polymer drugs NMR 99 21 Nucleoside 251 Nucleotide 251 244 169,112 Polyvinylchloride 250,251 Nucleic acids Proteins 248 Pultrusion Technique Number-Average concept Random copolymer Nylon Rayon 18,20,21, 112, 133, 145, 146 Organosol 108 RNA 119, 120 Osmometry 84, 87, 89-93 12, 13, 14 122, 146 Ring-opening polymerisation 171 Orientation Pacemaker Scaffolding 195 SEM 230 Periodic copolymer 226,229-230 94, 95, 97 Peritoneal dialysis Phenolic resins 101 Silicone polymer Single crystal 10 223 175 36,37 250-253 Sedimentation Perfluoro carbon 10 157 Repeat units 215-218 100 245 Reinforcing Optical isomerism 160 Radiation counter method 78 Number-Average molecular weight 10,78,79,84 Organosilanes 257 196 Polysaccharides Nomenclature 35, 36 171 179 115, 116 Skin production 226-227 Soft contact lens 196, 203 / Photodegradation of polymer Photographic film 100 258 Solid-phase polymerisation Solution polymerisation 66 61, 62 (iv) Spherullites 117 Thymine Tm 161, 162 Spinning Spray-up Technique Star polymer Starch Triad 159 251, 253 118, 121, 125, 125-138, 146 105 10 246 Ultracentrifugation 94,95,97 164 Statistical copolymer 10,49 Uniaxial orientation Step growth polymer 1,18,207 Uracil Stereo block copolymer Substitution reactions Surfactants 50 UV-stabilizers Vapourphase osmometry Suspension polymerisation Svedberg equation 63 94 Viscose 14,58,207 84, 85, 87 245 Viscosity-Average molecular weight Vulcanisation Taktikos Tensile strength Tg 19, 58 105 Tear resistance Terylene 80,84,85 48, 59 Vulcanized rubber lOS, 107 92 194 Vascular grafts Viscometry 105-10 Synthetic polymer Tacticity 242 53 63-64 Syndiotactic 251 103 Weight Weight-Average concept 102 Wood flour 118,123-138, 146 Thermoforming 10,77,84,88 236 100-101 X-ray 155 Thermomechanical method Thermoplastics 79 Weight-Average molecular weight 17, 18, 20 Thermal Analysis 80, 84, 85 135 18, 20, 140 Thermosetting polymer 100, 119 18, 20, 140 Ziegler-Natta catalyst 67,71-76, 106 Ziegler-Natta polymerisation 70 DOD