PRINCIPLES OF POLYMERIZATION Fourth Edition GEORGE ODIAN College of Staten Island City University of New York Staten Island, New York A JOHN WILEY & SONS, INC., PUBLICATION PRINCIPLES OF POLYMERIZATION Fourth Edition PRINCIPLES OF POLYMERIZATION Fourth Edition GEORGE ODIAN College of Staten Island City University of New York Staten Island, New York A JOHN WILEY & SONS, INC., PUBLICATION Copyright#2004byJohnWiley&Sons,Inc.Allrightsreserved. PublishedbyJohnWiley&Sons,Inc.,Hoboken,NewJersey. PublishedsimultaneouslyinCanada. 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LibraryofCongressCataloging-in-PublicationData: PrinciplesofPolymerization,FourthEdition GeorgeOdian ISBN0-471-27400-3 PrintedintheUnitedStatesofAmerica 10 9 8 7 6 5 4 3 2 1 CONTENTS PREFACE xxiii 1 INTRODUCTION 1 1-1 TypesofPolymersandPolymerizations / 1 1-1a PolymerCompositionandStructure / 2 1-1b PolymerizationMechanism / 6 1-2 NomenclatureofPolymers / 9 1-2a NomenclatureBased onSource / 10 1-2b NomenclatureBased onStructure (Non-IUPAC) / 11 1-2c IUPACStructure-BasedNomenclature System / 11 1-2d TradeNamesandNonnames / 16 1-3 Linear,Branched,andCrosslinked Polymers / 17 1-4 MolecularWeight / 19 1-5 PhysicalState / 24 1-5a CrystallineandAmorphousBehavior / 24 1-5b DeterminantsofPolymerCrystallinity / 27 1-5c ThermalTransitions / 29 1-6 Applications ofPolymers / 32 1-6a MechanicalProperties / 32 1-6b Elastomers, Fibers,andPlastics / 35 References / 36 v vi CONTENTS 2 STEPPOLYMERIZATION 39 2-1 Reactivity ofFunctionalGroups / 40 2-1a BasisforAnalysis ofPolymerizationKinetics / 40 2-1b Experimental Evidence / 41 2-1c Theoretical Considerations / 43 2-1d EquivalenceofGroupsinBifunctionalReactants / 44 2-2 KineticsofStepPolymerization / 44 2-2a Self-Catalyzed Polymerization / 46 2-2a-1 ExperimentalObservations / 47 2-2a-2 ReasonsforNonlinearityinThird-OrderPlot / 48 2-2a-3 MolecularWeightofPolymer / 50 2-2b ExternalCatalysisofPolymerization / 51 2-2c StepPolymerizationsOtherthanPolyesterification: CatalyzedversusUncatalyzed / 53 2-2d NonequivalenceofFunctionalGroupsinPolyfunctional Reagents / 54 2-2d-1 ExamplesofNonequivalence / 54 2-2d-2 Kinetics / 57 2-3 Accessibility ofFunctionalGroups / 63 2-4 EquilibriumConsiderations / 65 2-4a ClosedSystem / 65 2-4b Open,DrivenSystem / 67 2-4c KineticsofReversible Polymerization / 69 2-5 CyclizationversusLinear Polymerization / 69 2-5a PossibleCyclizationReactions / 69 2-5b CyclizationTendencyversusRingSize / 70 2-5c ReactionConditions / 72 2-5d ThermodynamicversusKineticControl / 73 2-5e OtherConsiderations / 74 2-6 MolecularWeightControlinLinearPolymerization / 74 2-6a NeedforStoichiometric Control / 74 2-6b QuantitativeAspects / 75 2-6c KineticsofNonstoichiometricPolymerization / 79 2-7 MolecularWeightDistributioninLinearPolymerization / 80 2-7a DerivationofSizeDistributions / 80 2-7b Breadth ofMolecular WeightDistribution / 82 2-7c Interchange Reactions / 83 2-7d AlternateApproaches forMolecular-WeightDistribution / 83 2-7e EffectofReactionVariablesonMWD / 86 2-7e-1 UnequalReactivity ofFunctionalGroups / 86 2-7e-2 ChangeinReactivity onReaction / 86 2-7e-3 NonstoichiometryofFunctionalGroups / 86 CONTENTS vii 2-8 ProcessConditions / 87 2-8a PhysicalNatureofPolymerizationSystems / 87 2-8b DifferentReactant Systems / 89 2-8c InterfacialPolymerization / 90 2-8c-1 DescriptionofProcess / 90 2-8c-2 Utility / 92 2-8d Polyesters / 92 2-8e Polycarbonates / 96 2-8f Polyamides / 97 2-8g HistoricalAspects / 101 2-9 MultichainPolymerization / 101 2-9a Branching / 101 2-9b MolecularWeightDistribution / 102 2-10 Crosslinking / 103 2-10a CarothersEquation:X !1 / 105 n 2-10a-1 StoichiometricAmountsofReactants / 105 2-10a-2 ExtensiontoNonstoichiometricReactant Mixtures / 106 2-10b Statistical ApproachtoGelation:X !1 / 108 w 2-10c Experimental GelPoints / 111 2-10d ExtensionsofStatistical Approach / 112 2-11 MolecularWeightDistributionsinNonlinearPolymerizations / 114 2-12 CrosslinkingTechnology / 117 2-12a Polyesters,UnsaturatedPolyesters, andAlkyds / 118 2-12b PhenolicPolymers / 120 2-12b-1 ResolePhenolics / 120 2-12b-2 NovolacPhenolics / 124 2-12b-3 Applications / 126 2-12c AminoPlastics / 126 2-12d EpoxyResins / 128 2-12e Polyurethanes / 130 2-12f Polysiloxanes / 132 2-12g Polysulfides / 134 2-13 StepCopolymerization / 135 2-13a TypesofCopolymers / 135 2-13b MethodsofSynthesizingCopolymers / 138 2-13b-1 StatisticalCopolymers / 138 2-13b-2 AlternatingCopolymers / 138 2-13b-3 BlockCopolymers / 139 2-13c UtilityofCopolymerization / 140 2-13c-1 StatisticalCopolymers / 141 2-13c-2 BlockCopolymers / 142