POLYMER CHEMISTRY - GBV
T H I R DE D I T I O NPOLYMERCHEMISTRYAN INTRODUCTIONMalcolm P. StevensUniversity of HartfordNew YorkOxfordOXFORD UNIVERSITY PRESS1999
CONTENTSPreface,PART IxviiPOLYMER STRUCTURE A N D PROPERTIESI. Basic principles,31.11.21.3Introduction and historical development,Definitions, 6Polymerization processes, 101.4Step-reaction polymerization,1.5Chain-reaction polymerization,1.61.7Step-reaction addition and chain-reaction condensation,Nomenclature, 1.8.41213Vinyl polymers, 17Vinyl copolymers, 20Nonvinyl polymers, 21Nonvinyl copolymers, 24End groups, 24Abbreviations, 25Industrial polymers,25Plastics, 25fifaers, 27Rubber (elastomers), 28Coatings and adhesives, 291.9Polymer recycling,References, 31Review exercises,3032vii315
ContentsVlll2. Molecular w e i g h t and p o l y m e r Solutions,352.1Number average and weight average molecular weight,2.2Polymer Solutions,2.3Measurement of number average molecular weight,2.4372.3.1End-group analysis,2.3.2Membrane osmometry,2.3.3Cryoscopy and ebulliometry,462.3.4Vapor pressure osmometry,462.3.5Mass spectrometry,2.3.6Refractive index measurements,42434648Measurement of weight average molecular weight,2.4.1Light ,2.6Molecular weight distribution,50532.6.1Gel permeation chromatography (GPC),2.6.2Fractional Solution,2.6.3Fractional preäpitation,2.6.4Thin-layer chromatography (TLC),References,575858593. Chemical s t r u c t u r e and p o l y m e r m o r p h o l o g y ,3.1Introduction,3.2Molecular weight and intermolecular forces,3.3The amorphous State—rheology,3.4Glass transition 7Liquid crystallinity,3.8Chemical crosslinking,3.9Physical crosslinking,3.10Polymer blends,References,5358Review exercises,747991Review exercises,61619383878586427063624835
Contentsix4. Chemical structure and polymer properties,4.1Introduction, 964.2Fabrication methods,96964.3Mechanical properties,4.44.5Thermal stability, 106Flammability and flame resistance,1004.64.7Chemical resistance,Degradability, I 144.8Electrical conductivity,4.9Nonlinear optical properties,I 10I 12I 171204.10 Additives, 121References, 124Review exercises, 1275. Evaluation, characterization, and analysis of polymers,5.1Introduction,5.2Chemical methods of analysis,5.3Spectroscopic methods of frared, 131Raman, 133Nuclear magnetic resonance, 134Electron spin resonance, 138Ultraviolet (UV)-visible, 139Fluorescence, 1395.4X-ray, electron, and neutron scattering,5.5Characterization and analysis of polymer 1Scanning electron microscopy (SEM), 143Attenuated total reflectance spectroscopy (ATR), 143Photoacoustic spectroscopy (PAS), 144Electron spectroscopy for chemical analysis (or applications)(ESCA) and Auger electron spectroscopy (AES), 145Secondary-ion mass spectrometry (SIMS) and ion-scattering spectroscopy (ISS), 147Atomic force microscopy (AFM), 148Thermal analysis, 1495.6.1Differential scanning calorimetry (DSC) and differentialthermal analysis (DTA), 149
ContentsX5.6.25.6.35.6.45.6.55.7Thermomechanical analysis (TMA), 152Thermogravimetric analysis (TGA), 152Pyrolysis-gas chromatography (PGC), 153Flammability testing, 154Measurement of mechanical properties,1565.8Evaluation of chemical resistance, 1595.9Evaluation of electrical properties, 159References, 160Review exercises,PART II163V I N Y L POLYMERS6. Free radical polymerization,6.1Introduction, 1676.2Free radical Peroxides and hydroperoxides, 169Azo Compounds, 171Redox initiators, 171Photoinitiators, 172Thermal polymerization, 172Electrochemical polymerization, 173Techniques of free radical polymerization,6.3.16.3.26.3.36.3.4Bulk, 174Suspension, 174Solution, 174Emulsion, 1756.4Kinetics and mechanism of polymerization,6.5Stereochemistry of polymerization,6.6Polymerization of dienes, 1886.6. /Isolated dienes, 1886.6.2Conjugated dienes, 1896.7Monomer view exercises,202191194186176
xiContents7. lonic .3.37.3.4205Cationic initiators, 205Mechanism, kinetics, and reactivity in cationicpolymerization, 207Stereochemistry of cationic polymerization, 21 3Cationic copolymerization, 215Isomerization in cationic polymerization, 217Anionic polymerization,7.3.17.3.27.4205Introduction, 205Cationic polymerization,217Anionic initiators, 217Mechanism, kinetics, and reactivity in anionicpolymerization, 219Stereochemistry of anionic polymerization, 223Anionic copolymerization, 225Group transfer polymerization,References,227230Review exercises,2318. Vinyl polymerization with complex coordination catalysts,8.1Introduction,8.2Heterogeneous Ziegler-Natta eterogeneous catalysts, 236Mechanism and reactivity in heterogeneouspolymerization, 238Stereochemistry of heterogeneous polymerization, 242Polymerization ofdienes, 243Homogeneous Ziegler-Natta polymerization,8.3.18.3.2234245Metallocene catalysts, 245Mechanism and reactivity with metallocenecatalysts, 246Stereochemistry of metallocene-catalyzedpolymerization, 2488.4Ziegler-Natta copolymerization,2498.58.68.7Supported metal oxide catalysts, 251Alfin catalysts, 252Metathesis polymerization, 252
xiiContents8.7.18.7.2Ring-opening metathesis polymerization, 253Acyclic diene metathesis polymerization, 255References, 255Review exercises,2579. Reactions of vinyl polymers,2599.1Introduction,9.2Functional group reactions,9.2.19.2.2259Introduction of new functional groups, 260Conversion of functional groups, 2619.3Ring-forming 59.5265Vulcanization, 265Radiation crosslinking, 267Photochemical crosslinking, 267Crosslinking through labile functional groups, 271lonic crosslinking, 272272Block copolymers, 272Graft copolymers, 273Polymer degradation,9.6.19.6.29.6.3276Chemical degradation, 276Thermal degradation, 277Degradation by radiation, 278References, 279Review exercises,PART III263Block and graft copolymer formation,9.5.19.5.29.6260281N O N V I N Y L POLYMERS10. Step-reaction and ring-opening polymerization,10.1 Introduction, 28510.2 Step-reaction polymerization—kinetics,10.3Stoichiometric imbalance,29010.410.5Molecular weight distribution,Network step polymerization,10.610.7Step-reaction copolymerization,Step polymerization techniques,292295297298285285
Contents10.8 Dendritic polymers, 30110.9 Ring-opening polymerization,References, 306Review exercises,30430711. Polyethers, polysulfides, and related polymers, 309l l . l Introduction, 309I 1.2 Preparation of polyethers by chain-reaction and ring-openingpolymerization, 30911.2.1/1.2.2/1.2.3/1.2.411.3Preparation of polyethers by step-reaction ization of carbonyl Compounds, 309Stereochemistry ofaldehyde polymerization, 313Polymerization ofcyclic ethers, 3 14Stereochemistry of epoxide polymerization, 320321Synthesis of polyethers from glycols and bisphenols, 321Polyacetals and polyketals, 322Poly(phenylene oxide)s, 324Epoxy resins, 326Polysulfides, poly(alkylene polysulfide)s, and polysulfones,32911.4.1 Polysulfides, 32911.4.2 Poly(alkylene polysulfide)s, 331/1.4.3 Polysulfones, 332References, 333Review exercises,12. Polyesters, 33812.1 Introduction,12.2334338Linear polyesters,12.2.112.2.2/ 2.2.312.2.4341Preparation of polyesters by polycondensation reactions, 341Polycarbonates, 346Preparation of polyesters by ring-opening polymerizavon, 348Microbial polyesters, 35212.3Hyperbranched polyesters,12.4Crosslinked polyesters,35335412.4.1 Saturated polyester resins, 35412.4.2 Unsaturated polyesters, 356References, 359Review exercises,360
ContentsXIV13. Polyamides and related polymers,13.1 Introduction, 36413.2Polyamides,36436613.2.1 Preparation ofpolyamides by polycondensationreactions, 36613.2.2 Polymerization oflactams, 36913.2.3 Miscellaneous methods of preparing polyamides, 37213.313.4Properties of polyamides,Polyureas, 37713.513.6Polyurethanes, 378Polyhydrazides, 38213.7 Polyimides,References, 388Review exercises,37438239014. Phenol-, urea-, and melamine-formaldehyde yde polymers: resoles, 396Phenol-formaldehyde polymers: novolacs, 39914.4Chemical modifications of phenolic resins,39539540214.5 Urea-formaldehyde polymers, 40414.6 Melamine-formaldehyde polymers, 406References, 407Review exercises,40815. Heterocyclic polymers,15.1 Introduction, 40940915.2Polypyrrole, polyfuran, and polythiophene,15.315.4Polycyanurate and polyphthalocyanine resins, 413Heterocyclic polymers formed from precursor polymers,15.5Heterocyclic polymers formed from polyfunctional 7412Polybenzimidazoles, 415Polybenzoxazoles and polybenzothiazoles, 417Polyhydantoins, 418Poly(parabanic aäd)s, 418Polyquinoxalines and polypyrazines, 419Polypyrazoles and polyimidazoles, 419Poly(as-triazine)s and polytriazolines, 420414415
Contents15.5.8 Polyquinolines and polyanthrazolines, 421References,421Review exercises,42216. Inorganic and partially inorganic polymers,16.1 Introduction, 42516.216.316.4Poly(sulfur nitride), 426Polysiloxanes, 427Polysilanes, 43016.5Polyphosphazenes,42543116.6 Carborane polymers, 43416.7 Organometallic polymers, 43616.8 Coordination polymers, 438References, 442Review exercises,44417. Miscellaneous organic polymers,17.1 Introduction, 44717.2Miscellaneous unsaturated polymers,/ 7.2.1/ 7.2.2/ 7.2.3/ 7.2.4/ 7.2.517.3447447Polycarbodiimides, 447Polyimines, 449Polymers containing carbon-carbon double bonds, 450Azo polymers, 450Polymers containing carbon-carbon triple bonds, 451Poly(p-phenylene) and poly(p-xylylene),452/ 7.3.1 Poly(p-phenylene), 452/ 7.3.2 Poly(p-xylylene), 45417.417.5Friedel-Crafts polymers, 455Cycloaddition polymerization, 456/ 7.5.1 Diels-Alder polymerization, 456/ 7.5.2 2 2 Cycloaddition polymerization, 45917.6Polyanhydrides,17.717.8Polyamines, 461Charge-transfer polymers,17.9 lonic polymers,References, 469Review exercises,471460467464
Contentsxvi18. Natural polymers, 47618.1 Introduction, 47618.2Miscellaneous natural 76Rubber, 476Lignin, humus, coal, and kerogen, 479Asphaltenes, 481Shellac, 481Amber, 482Tall oil-derived polymers, 482Polysaccharides,48418.3.1 Cellulose, 48418.3.2 Regenerated cellulose, 48518.3.3 Derivatives of cellulose, 48618.3.4 Starch, 48918.3.5 Derivatives of starch, 49018.3.6 Other Polysaccharides, 491184Proteins, 492/ 8.4.1 Amino acids, Polypeptides, and proteins, 49218.4.2 Protein structure, 49518.4.3 Synthesis of Polypeptides and proteins, 49818.4.4 Wool, silk, Collagen, and regenerated protein, 50018.5Nucleic acids, 50218.5.1 Nucleic acid structure, 50218.5.2 Nucleic acid synthesis, 50718.6 Conclusion, 510References, 510Review exercises, 513Appendix AAppendix BCommonly used polymer abbreviations,Polymer literature, 517Appendix CSources of laboratory experimentsin polymer chemistry, 526Index,535515
PART I POLYMER STRUCTURE AND PROPERTIES I. Basic principles, 3 1.1 Introduction and historical development, 3 1.2 Definitions, 6 1.3 Polymerization processes, 10 1.4 Step-reaction polymerization, 12 1.5 Chain-reaction polymerization, 13 1.6 Step-reaction addition and chain-reaction conde
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