Table Of ContentPolymer Synthesis: Theory and Practice
.
Dietrich Braun (cid:129) Harald Cherdron
Matthias Rehahn (cid:129) Helmut Ritter
Brigitte Voit
Polymer Synthesis: Theory
and Practice
Fundamentals, Methods, Experiments
Fifth Edition
DietrichBraun HaraldCherdron
TechnischeUniversit€atDarmstadt Wiesbaden
Darmstadt Germany
Germany
HelmutRitter
MatthiasRehahn Heinrich-Heine-Universit€at
TechnischeUniversit€at D€usseldorf
Darmstadt Institutf€urOrganischeChemie
Ernst-Berl-Institutf€ur undMakromolekulareChemie
Technischeund D€usseldorf
MakromolekulareChemie Germany
FGderPolymeren
Darmstadt
Germany
BrigitteVoit
Leibniz-Institutfu¨r
PolymerforschungDresdene.V.
Dresden
Germany
ISBN978-3-642-28979-8 ISBN978-3-642-28980-4(eBook)
DOI10.1007/978-3-642-28980-4
SpringerHeidelbergNewYorkDordrechtLondon
LibraryofCongressControlNumber:2012949897
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Preface to the Fifth Edition
The focus of the previous edition was on a broader description of the general
methods and techniques for the synthesis, modifications and characterization of
macromolecules.Thiswassupplementedbyselectedanddetailedexperimentsand
bysufficienttheoreticaltreatmentsothatnoadditionaltextbookbeneededinorder
to understand the experiments. In addition to the preparative aspects, we had also
tried to give the reader an impression of the relation of chemical structure and
morphologyofpolymerstotheirproperties.Thisconceptisalsomaintainedinthis
edition.
Inrecentyears,theso-calledfunctionalpolymers(whichhavespecialelectrical,
electronic, optical and biological properties), have attracted a lot of interest. We,
therefore, felt, that a textbook should exist that would contain recipes which
describethe synthesis ofthesematerials.Forthisreason, weaddedanewchapter
“FunctionalPolymers”.
Together with new experiments in Chaps. 3, 4 and 5, the book now contains
morethan120recipesthatdescribeawiderangeofmacromolecules.
Thecompletionofthe5thEditionwasaidedbythecontributionofanumberof
scientists. Our special thanks are due to Dr. M. Tabatabai for her arduous task of
checking, assembling and formatting the manuscript. We wish to express our
sincerest appreciation to Prof. Dr. M. Buchmeiser for contribution chapter 3.3.3,
Dr.B.Mu¨ller,Dr.J.ZhouandMs.Dr.Z.Rezaieforproductionofchapter2.3.4and
6.1; Dr. J. Pionteck, Dr. P. Po¨tschke, and Dr. F. Bo¨hme for contributing to and
readingofthechapter1and5.WealsothanktheChemistryEditorialandProduc-
tionDepartmentofSpringer-Verlagforanexcellentcooperation.
September2012 D.Braun,Darmstadt
H.Cherdron,Wiesbaden
M.Rehahn,Darmstadt
H.Ritter,Du¨sseldorf
B.Voit,Dresden
v
.
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 SomeDefinitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.1.1 Monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.1.2 Oligomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.1.3 Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.2 ChemicalStructureandNomenclatureofMacromolecules . . . . . . 6
1.3 StatesofOrderinPolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.3.1 MacromoleculesinSolution . . . . . . . . . . . . . . . . . . . . . . 12
1.3.1.1 SolventsandSolubility . . . . . . . . . . . . . . . . . . . 14
1.3.1.2 Polyelectrolytes . . . . . . .. . . . . . . . . . . .. . . . . . 17
1.3.2 MacromoleculesintheMoltenState . . . . . . . . . . . . . . . . 18
1.3.3 MacromoleculesintheSolidState . . . . . . . . . . . . . . . . . . 21
1.3.3.1 MacromoleculesintheElastomericState . . . . . . 22
1.3.3.2 MacromoleculesintheAmorphous(Glassy)
State . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
1.3.3.3 MacromoleculesintheCrystallineState . . . . . . . 23
1.3.4 Liquid-CrystallinePolymers(LCP) . . . . . . . . . . . . . . . . . 27
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2 MethodsandTechniquesforSynthesis,Characterization,
Processing,andModificationofPolymers . . . . . . . . . . . . . . . . . . . . 33
2.1 MethodsforSynthesisofPolymers . . . . . . . . . . . . . . . . . . . . . . . 33
2.1.1 ChainGrowthPolymerizations . . . . . . . . . . . . . . . . . . . . 33
2.1.2 StepGrowthPolymerizations . . . . . . . . . . . . . . . . . . . . . 35
2.1.3 ModificationofPolymers . . . . . . . . . . . . . . . . . . . . . . . . 37
2.1.4 PolymerRecipesReferenceList . . . . . . . . . . . . . . . . . . . 37
2.2 TechniquesforManufacturingofPolymers . . . . . . . . . . . . . . . . . 37
2.2.1 ParticularitiesinthePreparationofPolymers . . . . . . . . . . 42
2.2.2 PolyreactionsinBulk . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
2.2.2.1 HomogeneousPolyreactionsinBulk . . . . . . . . . 49
2.2.2.2 HeterogeneousPolyreactionsinBulk . . . . . . . . . 49
2.2.3 PolyreactionsinSolution . . . . . . . . . . . . . . . . . . . . . . . . . 50
2.2.4 PolyreactionsinDispersion . . . . . . . . . . . . . . . . . . . . . . . 52
2.2.4.1 PolyreactionsinSuspension . . . . . . . . . . . . . . . . 52
2.2.4.2 PolyreactionsinEmulsion . . . . . . . . . . . . . . . . . 53
vii
viii Contents
2.2.5 GeneralLaboratoryTechniquesforthePreparation
ofPolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
2.2.5.1 SafetyintheLaboratory . . . . . . . . . . . . . . . . . . 57
2.2.5.2 WorkingwithExclusionofOxygen
andMoisture . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
2.2.5.3 PurificationandStorageofMonomers . . . . . . . . 58
2.2.5.4 ReactionVesselsforPolymerizationReactions . . 59
2.2.5.5 ControlandTerminationofPolymerization
Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
2.2.5.6 IsolationofPolymers . . .. . . . .. . . . .. . . . .. . . 63
2.2.5.7 PurificationandDryingofPolymers . . . . . . . . . . 65
2.3 CharacterizationofMacromolecules . . . . . . . . . . . . . . . . . . . . . . 65
2.3.1 DeterminationofSolubility . . . . . . . . . . . . . . . . . . . . . . . 66
2.3.2 MethodsforDeterminationofPolymerConstitution . . . . . 70
2.3.2.1 High-ResolutionNMRSpectroscopy . . . . . . . . . 70
2.3.2.2 IRSpectroscopy . . . . . . . . . . . . . . . . . . . . . . . . 74
2.3.2.3 UV–visSpectroscopy . . . . . . . . . . . . . . . . . . . . 77
2.3.2.4 FluorescenceSpectroscopy . . . . . . . . . . . . . . . . 78
2.3.2.5 Refractometry . . . . . . . . . . . . . . . . . . . . . . . . . . 78
2.3.2.6 ElementalAnalysis . . . . . . . . . . . . . . . . . . . . . . 79
2.3.2.7 CompositionofCopolymers . . . . . . . . . . . . . . . 79
2.3.3 DeterminationofMolecularWeightand
Molecular-WeightDistribution . . . . . . . . . . . . . . . . . . . . 80
2.3.3.1 ClassificationoftheMethodsfor
Molecular-WeightDetermination . . . . . . . . . . . . 84
2.3.3.2 AbsoluteMethods . . . . . . . . . . . . . . . . . . . . . . . 85
2.3.3.3 RelativeMethods . . . . . . . . . . . . . . . . . . . . . . . 96
2.3.3.4 DeterminationofMolecular-WeightDistribution
byFractionation . . . . . . . . . . . . . . . . . . . . . . . . 105
2.3.4 DeterminationofsizedistributionofPolymersDynamic
LightScattering(DLS) . . . . . . . . . . . . . . . . . . . . . . . . . . 109
2.3.5 PolymerCharacterizationinBulk . . . . . . . . . . . . . . . . . . 111
2.3.5.1 DeterminationofDensity . . . . . . . . . . . . . . . . . . 111
2.3.5.2 DeterminationofCrystallinity . . . . . . . . . . . . . . 112
2.3.5.3 GlassTransitionTemperature . . . . . . . . . . . . . . 112
2.3.5.4 SofteningPoint . . . . . . . . . . . . . . . . . . . . . . . . . 113
2.3.5.5 CrystalliteMeltingPoint . . . . . . . . . . . . . . . . . . 114
2.3.5.6 MeltViscosity(MeltFlowIndex) . . . . . . . . . . . 115
2.3.5.7 Thermogravimetry . . . . .. . . . .. . . . .. . . . .. . . 116
2.3.5.8 DifferentialScanningCalorimetry(DSC) . . . . . . 117
2.3.5.9 Small-andWide-AngleX-RayScattering
(SAXSandWAXS) . . . . . . . . . . . . . . . . . . . . . 120
2.3.5.10 PhaseContrastMicroscopy . . . . . . . . . . . . . . . . 121
2.3.5.11 PolarizationMicroscopy . . . . . . . . . . . . . . . . . . 122
Contents ix
2.3.5.12 ScanningElectronMicroscopy(SEM) . . . . . . . . 124
2.3.5.13 ScanningTransmissionElectronMicroscopy
(STEM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
2.3.5.14 TransmissionElectronMicroscopy(TEM) . . . . . 125
2.3.5.15 ScanningProbeMicroscopy . . . . . . . . . . . . . . . . 126
2.3.6 MechanicalMeasurements . . . . . . . . . . . . . . . . . . . . . . . 129
2.3.6.1 Stress–StrainMeasurements . . . . . . . . . . . . . . . . 130
2.3.6.2 Dynamic-MechanicalMeasurements . . . . . . . . . 133
2.3.6.3 ImpactStrengthandNotched
ImpactStrength . . . .. . . . . . . . . . . . . .. . . . . . . 135
2.3.6.4 Hardness . . . .. . . . . . . . . . .. . . . . . . . . .. . . . . 135
2.4 CorrelationsofStructureandMorphologywiththeProperties
ofPolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
2.4.1 Structure/PropertiesRelationshipsinHomopolymers . . . . 137
2.4.1.1 CorrelationswithSolutionProperties . . . . . . . . . 137
2.4.1.2 CorrelationwithBulkProperties . . . . . . . . . . . . 137
2.4.2 Structure/PropertiesRelationshipsinCopolymers . . . . . . . 141
2.4.2.1 StatisticCopolymers . . . . . . . . . . . . . . . . . . . . . 141
2.4.2.2 AlternatingCopolymers . . . . . . . . . . . . . . . . . . . 142
2.4.2.3 BlockCopolymers . . . . . . .. . . . . . . . . . .. . . . . 142
2.4.2.4 GraftCopolymers . . . . . . . . . . . . . . . . . . . . . . . 142
2.4.3 Morphology/PropertiesRelationships . . . . . . . . . . . . . . . . 143
2.5 ProcessingofPolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
2.5.1 SizeReductionofPolymerParticles . . . . . . . . . . . . . . . . 144
2.5.2 MeltProcessingofPolymers . . . . . . . . . . . . . . . . . . . . . . 144
2.5.2.1 PreparationofPolymerFilmsfromtheMelt . . . . 144
2.5.2.2 PreparationofFibersbyMelt-Spinning . . . . . . . 145
2.5.3 ProcessingofPolymersfromSolution . . . . . . . . . . . . . . . 145
2.5.3.1 PreparationofFilmsfromSolution . . . . . . . . . . 145
2.5.3.2 PreparationofFibersbySolutionSpinning . . . . . 146
2.5.4 ProcessingofAqueousPolymerDispersions . . . . . . . . . . 147
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
3 SynthesisofMacromoleculesbyChainGrowthPolymerization . .. . 149
3.1 RadicalHomopolymerization . . . . . . . . . . . . . . . . . . . . . . . . . . .149
3.1.1 PolymerizationwithPeroxoCompoundsasInitiators . . . . 157
Example3.1 ThermalPolymerizationofStyreneinBulk
(EffectofTemperature) . . . . . . . . . . . . . . . 158
Example3.2 PolymerizationofStyrenewithPotassium
PeroxodisulfateinEmulsion . . . . . . . . . . . 160
Example3.3 PolymerizationofVinylAcetatewith
AmmoniumPeroxodisulfateinEmulsion . . . 160
Example3.4 PolymerizationofVinylAcetatein
Suspension(BeadPolymerization) . . . . . . . 161
x Contents
Example3.5 PolymerizationofMethacrylicAcidwith
PotassiumPeroxodisulfateinAqueous
Solution . . . . . . . . . . . . . . . . . . . . . . . . . . 162
3.1.2 PolymerizationwithAzoCompoundsasInitiator . . . . . . . 162
Example3.6 BulkPolymerizationofStyrenewith2,20-
AzobisisobutyronitrileinaDilatometer . . . 163
Example3.7 PolymerizationofStyrenewith2,20-
AzobisisobutyronitrileinSolution
(EffectofMonomerConcentration) . . . . . . 165
Example3.8 PolymerizationofMethylMethacrylatewith
2,20-AzobisisobutyronitrileinBulk . . . . . . . 165
3.1.3 PolymerizationwithRedoxSystemsasInitiators . . . . . . . 166
Example3.9 PolymerizationofAcrylamidewitha
RedoxSysteminAqueousSolution . . . . . 168
Example3.10 FractionationofPolyacrylamidebyGel
PermeationChromatographyinWater . . . 168
Example3.11 PolymerizationofAcrylonitrilewith
aRedoxSysteminAqueousSolution
(PrecipitationPolymerization) . . . . . . . . . 169
Example3.12 PolymerizationofIsoprenewithaRedox
SysteminEmulsion . . . . .. . . . .. . . .. . . 171
3.1.4 PolymerizationUsingPhotolabileCompoundsasInitiators 171
Example3.13 PhotopolymerizationofHexamethylene
Bisacrylate . . . . . . . . . . . . . . . . . . . . . . . 172
3.1.5 PolymerizationofCyclodextrinHost-GuestComplexes
inWater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
Example3.14a FreeRadicalPolymerizationof
CyclodextrinHost–GuestComplexesof
ButylAcrylatefromHomogeneous
AqueousSolution(Precipitation
Polymerization) . . . . . . . . . . . . . . . . . . . 174
Example3.14bOxidativePolymerizationofaCyclodextrin
Host–GuestComplexofPyrrolefrom
HomogeneousAqueousSolution
(ConductingPolymer) . . . . . . . . . . . . . . . 175
3.1.6 ControlledRadicalPolymerization . . . . . . . . . . . . . . . . . . 175
Example3.15a ControlledRadicalPolymerization
(ARTP)ofMethylMethacrylatein
Miniemulsion . . . . . . . . . . . . . . . . . . . . 178
Example3.15b ControlledRadicalPolymerization
(RAFT)ofTrimethylsilylpropargyl
MethacrylateandSubsequentPolymer
AnalogousClickReaction . . . . . . . . . . . 180
