Table Of ContentSecond Edition
Chemistry and
Technology of
Emulsion
Polymerisation
A. M. van Herk
Editor
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Chemistry and
Technology of
Emulsion
Polymerisation
Second Edition
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Chemistry and
Technology of
Emulsion
Polymerisation
Second Edition
Editor
A.M. van Herk
Institute of Chemical and Engineering Sciences, Singapore
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Thiseditionfirstpublished2013
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ISBN:9781119953722
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Contents
ListofContributors xi
Abbreviations xiii
ListofFrequentlyUsedSymbols xvii
IntroductiontotheSecondEdition xix
IntroductiontotheFirstEdition xxi
1 HistoricOverview 1
FinnKnutHansen
1.1 TheEarlyStages 1
1.2 TheSecondHalfoftheTwentiethCentury 9
1.2.1 ProductDevelopment 9
1.2.2 KineticTheory 11
1.2.3 EmulsionPolymerisationinMonomerDroplets 19
1.2.4 IndustrialProcessControlandSimulation 21
2 IntroductiontoRadical(Co)Polymerisation 23
A.M.vanHerk
2.1 MechanismofFreeRadicalPolymerisation 23
2.2 RateofPolymerisationandDevelopmentofMolecular
MassDistribution 25
2.2.1 RateofPolymerisation 25
2.2.2 KineticChainLength 26
2.2.3 ChainLengthDistribution 27
2.2.4 TemperatureandConversionEffects 30
2.3 RadicalTransferReactions 31
2.3.1 RadicalTransferReactionstoLowMolecularMass
Species 31
2.3.2 RadicalTransferReactionstoPolymer 32
2.4 RadicalCopolymerisation 34
2.4.1 DerivationoftheCopolymerisationEquation 34
2.4.2 TypesofCopolymers 37
2.4.3 PolymerisationRatesinCopolymerisations 39
2.5 ControlledRadicalPolymerisation 41
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vi Contents
3 EmulsionPolymerisation 43
A.M.vanHerkandR.G.Gilbert
3.1 Introduction 43
3.2 GeneralAspectsofEmulsionPolymerisation 44
3.3 BasicPrinciplesofEmulsionPolymerisation 46
3.4 ParticleNucleation 47
3.5 ParticleGrowth 51
3.5.1 TheZero-OneandPseudo-BulkDichotomy 52
3.5.2 Zero-OneKinetics 53
3.5.3 Pseudo-BulkKinetics 55
3.5.4 SystemsbetweenZero-OneandPseudo-Bulk 57
3.6 IngredientsinRecipes 57
3.6.1 Monomers 58
3.6.2 Initiators 58
3.6.3 Surfactants 58
3.6.4 OtherIngredients 59
3.7 EmulsionCopolymerisation 59
3.7.1 MonomerPartitioninginEmulsionPolymerisation 59
3.7.2 CompositionDriftinEmulsionCo-and
Terpolymerisation 63
3.7.3 ProcessStrategiesinEmulsionCopolymerisation 64
3.8 ParticleMorphologies 66
3.8.1 Core–ShellMorphologies 68
4 EmulsionCopolymerisation,ProcessStrategies 75
JoseRamonLeizaandJanMeuldijk
4.1 Introduction 75
4.2 MonomerPartitioning 79
4.2.1 SlightlyandPartiallyWaterMiscibleMonomers 79
4.2.2 ConsequencesofMonomerPartitioningfortheCopolymer
Composition 84
4.3 ProcessStrategies 86
4.3.1 BatchOperation 86
4.3.2 Semi-BatchOperation 89
4.3.3 ControlOpportunities 92
5 LivingRadicalPolymerisationinEmulsionandMiniemulsion 105
BernadetteCharleux,MichaelJ.Monteiro,andHansHeuts
5.1 Introduction 105
5.2 LivingRadicalPolymerisation 106
5.2.1 General/FeaturesofaControlled/LivingRadical
Polymerisation 106
5.2.2 ReversibleTermination 108
5.2.3 ReversibleChainTransfer 116
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Contents vii
5.3 Nitroxide-MediatedPolymerisationinEmulsionandMiniemulsion 119
5.3.1 Introduction 119
5.3.2 ControlofMolarMassandMolarMassDistribution 120
5.3.3 SynthesisofBlockandRandomorGradientCopolymersvia
(Mini)EmulsionPolymerisation 125
5.3.4 Surfactant-FreeEmulsionPolymerisationUsingthe
Polymerisation-InducedSelf-AssemblyTechnique 126
5.4 ATRPinEmulsionandMiniemulsion 126
5.4.1 Introduction 126
5.4.2 DirectATRP 127
5.4.3 ReverseATRP 130
5.4.4 NextGenerationATRPTechniques:SRNIandAGET 132
5.4.5 SomeConcludingRemarksonATRPinEmulsion 135
5.5 ReversibleChainTransferinEmulsionandMiniemulsion 136
5.5.1 LowC ReversibleChainTransferAgents 136
ex
5.5.2 HighC ReversibleChainTransferAgents 137
ex
5.6 Conclusion 143
6 ParticleMorphology 145
YuriReyesMercado,ElenaAkhmastkaya,JoseRamonLeiza,andJoseM.Asua
6.1 Introduction 145
6.2 SynthesisofStructuredPolymerParticles 146
6.2.1 EmulsionPolymerisation 146
6.2.2 MiniemulsionPolymerisation 147
6.2.3 PhysicalMethods 148
6.3 Two-PhasePolymer–PolymerStructuredParticles 148
6.3.1 EffectofGrafting 152
6.4 Two-PhasePolymer–InorganicParticles 153
6.5 MultiphaseSystems 156
6.6 EffectofParticleMorphologyonFilmMorphology 162
6.6.1 ModellingFilmMorphology 165
Acknowledgements 165
7 ColloidalAspectsofEmulsionPolymerisation 167
BrianVincent
7.1 Introduction 167
7.2 TheStabilisationofColloidalParticlesagainstAggregation 168
7.3 Pair-PotentialsinColloidalDispersions 170
7.3.1 Core–CoreInteractions 170
7.3.2 StructuralInteractions:(i)ThoseAssociatedwiththeSolvent 171
7.3.3 StructuralInteractions:(ii)ElectricalDoubleLayerOverlap 173
7.3.4 StructuralInteractions:(iii)AdsorbedPolymerLayerOverlap 175
7.4 WeakFlocculationandPhaseSeparationinParticulateDispersions 179
7.5 AggregateStructureandStrength 184
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viii Contents
8 AnalysisofPolymerMoleculesincludingReactionMonitoring
andControl 187
PeterSchoenmakers
8.1 SamplingandSampleHandling 188
8.1.1 Sampling 188
8.1.2 SamplePreparation 188
8.2 MonomerConversion 189
8.3 MolarMass 190
8.3.1 Molar-MassDistributions 191
8.4 ChemicalComposition 197
8.4.1 AverageChemicalComposition 197
8.4.2 Molar-MassDependentChemicalComposition 199
8.4.3 Chemical-CompositionDistributions 202
8.4.4 Two-DimensionalDistributions 207
8.5 DetailedMolecularCharacterization 210
8.5.1 ChainRegularity 210
8.5.2 Branching 212
9 ParticleAnalysis 213
OlaKarlssonandBrigitteE.H.Schade
9.1 Introduction 213
9.2 ParticleSizeandParticleSizeDistribution 214
9.2.1 Introduction 214
9.2.2 AverageParticleDiameter 216
9.2.3 ParticleSizeDistribution 216
9.3 Sampling 216
9.4 ParticleSizeMeasurementMethods 217
9.4.1 EnsembleTechniques 218
9.4.2 ParticleSeparationMethods 224
9.5 ComparisonofMethods 233
9.5.1 ChoiceofaMethod 235
9.6 ParticleShape,StructureandSurfaceCharacterisation 236
9.6.1 IntroductiontoParticleShape,StructureandSurface
Characterisation 236
9.6.2 ClassificationoftheSamples 238
9.6.3 GeneralConsiderations–SamplePreparationIftheLatex
isFilmForming 238
9.7 DiscussionoftheAvailableTechniques 239
9.7.1 OpticalMicroscopy(OM) 239
9.7.2 AtomicForceMicroscopy(AFM) 240
9.7.3 ElectronMicroscopy 243
9.7.4 IndirectAnalysisofParticleMorphology 248
9.7.5 SurfaceCharacterisation 249
9.7.6 CleaningofLatexes 250
9.7.7 AnalysesofParticleCharge 250
