Polymer Synthesis: Theory and Practice: Fundamentals, Methods, Experiments PDF
Preview Polymer Synthesis: Theory and Practice: Fundamentals, Methods, Experiments
Polymer 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 #Springer-VerlagBerlinHeidelberg2001,2005,2012,2013 Thisworkissubjecttocopyright.AllrightsarereservedbythePublisher,whetherthewholeorpartof the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation,broadcasting,reproductiononmicrofilmsorinanyotherphysicalway,andtransmissionor informationstorageandretrieval,electronicadaptation,computersoftware,orbysimilarordissimilar methodologynowknownorhereafterdeveloped.Exemptedfromthislegalreservationarebriefexcerpts inconnectionwithreviewsorscholarlyanalysisormaterialsuppliedspecificallyforthepurposeofbeing enteredandexecutedonacomputersystem,forexclusiveusebythepurchaserofthework.Duplication ofthispublicationorpartsthereofispermittedonlyundertheprovisionsoftheCopyrightLawofthe Publisher’s location, in its current version, and permission for use must always be obtained from Springer.PermissionsforusemaybeobtainedthroughRightsLinkattheCopyrightClearanceCenter. ViolationsareliabletoprosecutionundertherespectiveCopyrightLaw. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publicationdoesnotimply,evenintheabsenceofaspecificstatement,thatsuchnamesareexempt fromtherelevantprotectivelawsandregulationsandthereforefreeforgeneraluse. While the advice and information in this book are believed to be true and accurate at the date of publication,neithertheauthorsnortheeditorsnorthepublishercanacceptanylegalresponsibilityfor anyerrorsoromissionsthatmaybemade.Thepublishermakesnowarranty,expressorimplied,with respecttothematerialcontainedherein. Printedonacid-freepaper SpringerispartofSpringerScienceþBusinessMedia(www.springer.com) 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
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