高分子化学英文PPT课件下载(红102页)

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Chapter1Introduction1.1Foreword1.2Typesofpolymersandthenomenclature1.3Polymerization1.5StructureofPolymers1.4MolecularweightanditsdistributionThemodificationofnaturalpolymersDirectapplicationofnaturepolymerssynthesisofpolymerTimeofpolymerprotein、starch、cottonfibers、bamboon、woodetc.Vulcanizationofnaturalrubber,synthesisofnitrocellulosepolycondensation，radical、coordination、ionicpolymerization1.1.1Historyofpolymerscience1.1IntroductionLordToddTheNobelPrizeinChemistry1957Iaminclinedtothinkthatthedevelopmentofpolymerizationisperhapsthebiggestthingthatchemistryhasdone,whereithashadthebiggesteffectoneverydayLife.Introducedtheconceptof“polymer”intoscientificfield,andsetuptheequationbetweentheviscosityofpolymersolutionanditsmoleculeweight.setupthetheoryofpolycondensationcoordinationpolymerizationofethylene、propylene（1963Nobel）Relationsbetweenthemechanicalpropertiesandstructureofpolymers(1974Nobel)Discoveryanddevelopmentofconductivepolymers（2000Nobel）。HermannStaudingerCarothersKarlZiegler,GiulioNattaKarlZiegler,GiulioNattaPaulJ.FloryHidekiShirakawa,AlanG.MacDiarmid,AlanJ.HeegerPolymerSciencePolymerChemistryFocusonthemechanismofpolymerizationandpolymericchemicalreaction.Selectrawmaterials,figureoutroute,seekcatalyst,andsetupsynthesisplan.Researchtherelationshipbetweenstructureandmechanicpropertiesofpolymers,andprovidetheoreticinstructionfordesigningspecificfunctionalpolymers.PolymerPhysicsPolymerProcessingResearchtheprincipleandmethodologyofpolymerprocessing.PolymerscienceisapplyingscienceaswellasbasicsubjectwhichisanewfieldonthebasesofOrganicChemistry,PhysicsChemistry,Biochemistry,PhysicsandKinetics.1.1.2IntroductionofpolymerscienceRestraintsSolutions（1）Elongatethedurableyears（2）Recycle（3）NaturaldegradationEnvironmantalpollutionofpolymericjunkGeneraldefinition:plastic,rubber,fibre,coating,adhesionForchemists：Polymersaremacromoleculesbuiltupbythelinkingtogetheroflargenumbersofmuchsmallermolecules.1.1.3Basicconception1.1.3.1DefinitionCH2CHCl[]nMonomerMonomerunitStructuralunitRepeatingunitChain1.1.3.2ConceptDegreeofPolymerization,DPmolecularweight1.2ClassificationandnomenclatureBasedonuseBasedontheheatingwaymainchainPolymersNomenclatureNon-IUPACIUPACBasedonsourceBasedonstructureTradenamesBasedonmonomer：homopolymerization、copolymerizationBasedonReactingcentre：radicalandionicpolymerization（cationic、anionic）Basedonreaction：linear、open-loop、cyclization、transitioin、isomerizationpolymerizationBasedonElements：additionpolymerization、polycondensationBasedonkinetics：chain、stepsPolymerization：MonomerPolymer1.3PolymerizationFloryPolymerizationBasedonstructuralandcompositionaldifferencesbetweenmonomersandpolymersAdditonpolymerizationPolycondensationBasedonpolymerizationmechanismChainpolymerizationSteppolymerizationCarothers:1.4MolecularweightandMolecularweightDistributionAveragemoleculeweightDistributionMolecularWeightDistribution（MWD）DistributionIndex（HI）Moleculeweightdistributiondiagram(MWD)1.5PolymerstructureOpticalisomerismPolymerstructureMaocromoleculeChainstructureAggregationstructureMacro-structureMicrostructurelinealBranchedCrosslinkedrepeatedunitsSequentialstructureCubicisomerismrotamerismConformationcrystalizationAmor-phousglassyelastomericviscousControlbasicconceptofpolymer。Controlthemechanismofstep,chain,additionpolymerizationandpolycondensation.Understandthenomenclature,classificationofpolymersandtheirmonomersUnderstandthemoleculeweightexpressionandmoleculeweightdistribution。UnderstandtheaggregationofpolymerKeys补充习题1、在聚合反应过程中，分子量随转化率变化规律是，随转化率提高，自由基聚合的分子量，逐步聚合分子量，阴离子聚合的分子量是。2、聚合物是的混合物，其分子量是一平均值，这种分子量的不均一性称做3、尼龙-810是由和缩聚而成的，“8”代表；“10”代表。其反应机理是。4、何谓分子量的多散性？如何a聚合物分子量的多分散性？3KSHermannStaudinger（1881～1965）1920，issuethepaperof“Discussionofpolymerization”1932，editthebookpolymericorganiccompounds1953，NobelPrizeWallace HumeCarothers（1896～1937)1935：InventNylon66GiulioNatta（1903～1979）KarlZiegler(1898～1973)Coordinationpolymerizationofethyleneandpropylene1963Nobelprize,Chem1974Nobelprize:RelationsbetweenthemechanicalpropertiesandstructureofpolymersPaulJ.Flory（1910～1985）ShirakawaHideki（1936～）AlanJ.Heeger（1936～）AlanG.MacDiarmid（1929～）2000NobelPrizeDiscoveryanddevelopmentofconductivepolymersLordToddTheNobelPrizeinChemistry1957Iaminclinedtothinkthatthedevelopmentofpolymerizationisperhapsthebiggestthingthatchemistryhasdone,whereithashadthebiggesteffectoneverydayLife.NaturalPolymers硫化Thefirsttruesyntheticplastic再生真皮(硅橡胶)液晶显示裸鼠背上的人工耳朵(硅橡胶)plasticrubbermonomer：smallmoleculePolymerMonomerCH2CHCl[]nCH2CH[]n[OCH2CH2OOC]OnC--HOCH2CH2OHHOOCCOOHstructuralunitPolymerStructuralUnitCH2CHCl[]nCH2CH[]n[OCH2CH2OOC]OnCrepeatingunitCH2CHCl[]nCH2CH[]n[OCH2CH2OOC]OnC--PolymerRepeatingunitmonomerunitPolymerMonomerunitCH2CHCl[]nCH2CH[]n[OCH2CH2OOC]OnC--?：chainPolymerChainCH2CHCl[]nCH2CH[]n[OCH2CH2OOC]OnC--DegreeofpolymerizationBasedonrepeatingunit:Basedonstructuralunit:DPDPnXnXPolymerDegreeofpolymerization(n)CH2CHCl[]nCH2CH[]nnXDPnnXDPnnXDPn2/MolecularweightM=DPM0OrM=XnM1M0:ThemoleculeorrepeatingunitM1:ThemoleculeofstructuralunitDP:ThenumberofrepeatingunitXn:ThenumberofstructuralunitBasedonusePolymerPlasticRubberCoatingAdhesionFibreCoatingFilmformerPaintSolventAccessoryingredientBasedonheatingwayThermoplasticsExamples:PP,PVC,PS,etc.ThermosetExamples:Phenolicresin,Epoxyresin,Urea-formaldehyderesin.Basedonmainchainstructure1）Carbonchainpolymer：ThemainchainismadeofC.Suchas:PVC,PBD,etc.2）Heterochainpolymer：BesidesC,themainchainismadeofotheratomsasO,NandS.Suchas:polyester,polyether,polyurethane,thiorubber,etc.3）Elementorganicpolymer：ThemainchainisnotmadeofC,it’smadeofSi,B,Al,O,N,Sandsoon.Butthereareorganicgroupsonthesidechain.Suchas:Siliconerubber4）Abio-macromolecule：TherearenoCinthemainchainorsidechain.Suchas:SilicateNaturalrubberPlasticsCurrencyplastics：PVCPSPPPMMAEngineeringplastics:NylonPCCurrencyrubber：naturalrubberSpecialrubber：butyronitrilerubber,siliconerubber,chlorobutadienerubber.butadienestyrenerubbercis1.4polybutadienerubberfiber：cotton,hair,silk,hemp,etc.：Vicosefiber,Cellulosefiber,etc.：terylene、nylon、acrylon、vinylonnaturefiberrayonsyntheticfiberAdhesionNon-IUPAC：easytoremember,butcouldnotexpressthestructural[OCH2CH2]n[OCH2CH2]nCH2CH2O¿ª»·HOCH2CH2OH[OCH2CH2]nÍÑË®ClCH2CHOH[OCH2CH2]nHClClCH2OCH3[OCH2CH2]nHClNon-IUPAC:Polycyclic-ethaneBasedonstructure:PolyoxidizedethyleneAdvantagesanddisadvantagesofnon-IUPACNomenclaturebasedonsourceSuchpolymersarenamedbyaddingthenameofthemonomerontotheprefix“poly”withoutaspaceorhyphen.[CH2CH]OHnCH2CHCl[]nCH2CH[]npolyvinylCloridepolystyrenepolyvinylalcoholResin:phenol+formaldehyde——phenolformaldehyderesinurea+formaldehyde——ureaformaldehyderesinRubber：butadiene+styrene——styrene-butadienerubberbutadiene+vinylcyanide——butadiene-vinylcyanideethylene+propylene——ethylene-propyleneCopolymer：nameofmonomer+“resin”or“rubber”assuffixNomenclaturebasedonstructureThenameofthepolymerisobtainedbyfollowingtheprefixploywithoutaspaceorhyphenwithparenthesesenclosingthenameofthestructuralgroupingattachedtotheparentcompound.—CONH—:polyamide—COO—:polyester—O—:polyether—SO2—:polysulfoneExamples:Anexampleoftrade-namenomenclatureistheuseofthenamenylonforthepolyamidesfromunsubstituted,nonbranchedaliphaticmonomers.TradenamesExamples:nylon6,6poly(hexamethyleneadipamide)nylon6,10poly(hexamethylenesebacamide)Thetradenameofsyntheticfiber,‘fiber’asthesuffixNylonPolyesterVinylonAcrylicPolyvinylchloridefiberPolyproylenefiberNylon-6PETPPVFPANPVCPPThebaseofIUPACpolymernomenclaturesystemistheselectionofapreferredconstitutionalrepeatingunit(abbreviatedasCRU).HereareasummaryofthemostimportantoftheIUPACrulesfornamingsingle-standorganicpolymers.1.2.2.2systematicnomenclaturesystema.ThenameofapolymeristheprefixpolyfollowedinparenthesesorbracketsbythenameoftheCRU.TheCRUisnamedbynamingitssubunits.SubunitsaredefinedasthelargestsubunitsthatcanbenamedbytheIUPACrulesforsmallorganiccompounds.b.TheCRUiswrittenlefttorightbeginningwiththesubunitofhighestseniorityandproceedinginthedirectioninvolvingtheshortestroutetothesubunitnextinseniority.c.Forheteroatomsoracyclicsubunitscontainingheteroatoms,theorderofdecreasingpriorityisO,S,Se,Te,N,P,As,Sb,Bi,Si,Ge,Sn,Pb,B,Hg.Theseniorityofotherheteroatomswithinthisorderisdeterminedfromtheirpositionsintheperiodictable.d.Forcarbocyclicringstheseniorityisaringsystemhavingthegreatestnumberofrings>theringsystemhavingthelargestindividualring>theringsystemhavingthegreatestnumberofatomscommontoitsring.e.Foragivencarbocyclicorheteroclicringsystem:(a)whenringsdifferonlyindegreeofunsaturation,seniorityincreaseswithdegreeofunsaturation;(b)forthesameringsystem,seniorityishigherfortheringsystemhavingthelowestlocationnumber,whichdesignatethefirstpointofdifferenceforringjunctionsf.TheseordersofseniorityaresupersededbytherequirementofminimizingthenumberoffreevalencesintheCRU,thatis,theCRUshouldbebivalentunitwhereverpossible.g.Wherethereisachoicesubunitsshouldbeorientedsothatthelowestlocantresultsforsubstituents•Forexample：－OCH2CH2-Poly（oxydizedethylene）—CH=CHCH2CH2—polybutadienepolyvinylchloridepolystyreneCHCH2ClCHCH2Usefulabbreviation PMMA：polymethylmethacrylateABS：acrylonitrile—butadiene—styreneSBR：styrene-butadienerubber)EPR：ethylene-propylenerubberEVA：ethylene—vinylacetatenCH2=CHClCH2CHCl[]nTheadditionandpolymerizationofalkenemonomers(polymerization)resultant——additionpolymerAdditionpolymerizationReactionofthemulti-stepcondensationandpolymerizationofmonomers，mainresultant——condensationpolymernH2N(CH2)6NH2+nHOOC(CH2)4COOH(2n-1)H2OHOH[NH(CH2)6NHCO(CH2)4CO]n+ReactionbetweenfunctionalgroupspolycondensationQ:Howeversomereactionarehardtobedetermined：(ringopening)CH2CH2O¿ª»·[OCH2CH2]n»·ÑõÒÒÍé¾Û»·ÑõÒÒÍénNH(CH2)5CO[NH(CH2)5CO]n¿ª»·¼º±ûõ£°·ÄáÁú-6HO(CH2)4OHnO=C=N(CH2)6N=C=O+·Ö×Ó¼äÇâתÒÆ£¨¾Û¼Ó³É£©¶¡¶þ´¼¶þÒìÇèËἺõ¥¾Û°±õ¥n[O(CH2)4OCONH(CH2)6NHCO]nCH2N[CH2]nN2+BF3¼ÓÈÈnH3CCH3600¡«1000¡æ[CH2CH2]+nH2neliminaationreaction:chainpolymerizationThedistinguishingcharacteristicofchainpolymerizationisthatpolymergrowthtakesplacebymonomerreactingonlywiththereactivecenter.Monomerdoesnotreactwithmonomerandthedifferent-sizedspeciessuchasdimer,trimer,tetramer,andn-merdonotreactwitheachother.relationbetweentimeandmoleculeweightchainpolymerizationtheconversionincreasesastimepasses，moleculedoesnothaveadramaticchangesteppolymerization——Thecharacteristicofsteppolymerizationthatdistinguishesitfromchainpolymerizationisthatreactionoccursbetweenanyofthedifferent-sizedspeciespresentinthereactionsystem.mostpolycondensationreactionsbelongtostep-mechanismconversion:00MMMCRelationbetweenconversionandtimesteppolymerization：moleculeweightincreasesslowlyasreactiongoesSynthesisofpolyurethane：mechanismofsteppolymerizationwithstructureofcondensationpolymerHO(CH2)4OHnO=C=N(CH2)6N=C=O+·Ö×Ó¼äÇâתÒÆ£¨¾Û¼Ó³É£©¶¡¶þ´¼¶þÒìÇèËἺõ¥¾Û°±õ¥n[O(CH2)4OCONH(CH2)6NHCO]nNH(CH2)5CO[NH(CH2)5CO]n¿ª»·¼º±ûõ£°·ÄáÁú-6Ringopeningreaction:mechanismchangeswithcatalystClassificationofsomepolymnerizationItisveryimportanttoclassifythereactionsaccordingtomechanism,sinceitpointsforwardtheessenceofpolymerizaion.Averagemoleculeweightnumber-averagemolecularweightweight-averagemolecularweightviscosity-averagemolecularweight•commonpolymersnVWMMM•monodispersitynVWZMMMMNumber-averagemolecularweightiiiiiiiinMNNMNNNNMNMNMNM212211N1,N2…Ni:ThenumberofpolymerwhosemoleculeareM1,M2…Mi;Ni:Thepecentofi.Weight-averagemolecularweightiiiiiiiiiiiiiiWMWMNMNMNMNMNMNMNMNWWWMWMWMWM22211222211212211W1，W2…Wi：TheweightofpolymerswhosemoleculeareM1，M2…Mi..Wi：Theweightpecentofi.MeasuringbylightscatteringmethodViscosity-averagemolecularweightMeasuringbyviscosimetry/1/11iiiiiiiVWMWMNMNMα:0.5～0.9HIHI=nMwM/Thelargertheratio,themorewidedistribution.Idealmonodispersepolymer:HI=1Polycondensate(suchaspolyester,polyamide,etc.):TheHIissmaller.Polymers(suchaspolyacrylonitrile,polyvinylchloride,etc.):TheHIislarger.TherangeoftheHIofpolymers:2～50.MWDDistributionofmoleculeweightinatypicalpolymersamplenVWMMMVMWMclosetothemostprobabledistributionnMnearto0.4Linear,branched,andcrosslinkedpolymersPolymerscanbeclassifiedaslinear,branched,orcrosslinkedpolymersdependingontheirstructure.Examples:PEPVCPETPANBranchedBranchedpolymersmoleculesarethoseinwhichtherearesidebranchesoflinkedmonomermoleculesprotrudingfromvariouscentralbranchpointsalongthemainpolymerchain.CrosslinkedWhenpolymersareproducedinwhichthepolymermoleculesarelinkedtoeachotheratpointsotherthantheirends,thepolymersaresaidtobecrosslinked.ThebasicfactortodeterminetheelementsandpropertiesofpolymersRepeatingunitPENylonCH2CHCH4CH2CH2CHOHCH2CHOHCH2CHOHCH2CHOHͷβͷͷββOHOHTheendtowhichattachesthesubstituent——headsequenceofstructuralunitinpolymerchains:•head-totail•headtohead•tailtotailsequentialstructureIsotactic（LLLL）（SSSS）Syndiotactic（SLSL）Random（SLSSLS）antimerisomerismRotamerismofpolyisopreneC=CC=CCH3CH3HHCH2CH2CH2CH2˳ʽ·´Ê½cistransrotamerismarousedbyinternalrotationofmacromoleculechain•spreadingchain•randomcoil•foldedchain•spiralchainconformationA—glassystate；B—highelasticstate；C—viscousstate•glassystate•highelasticstate•viscousstatePhysicandmechanicstateofamorphouspolymer•Tg——temperaturewhentransitionfromglassystatetohighelasticstatehappens•Tf——temperaturewhentransitionfromtohighelasticstatetoviscousstatehappensheattransitiontemperatureMeltingpointTm:temperaturewhenphasetransitionhappensTg—Highestusingtemperatureofamorphousplastic，50~75abovetheroomtemperature℃lowestusingtemperatureofrubber,75belowthe℃roomtemperatureTm—thehighestusingtemperatureofcrystallizedplasticplastic：highTg，aboveroomtemperature、rubber:lowTg、belowroomtemperaturefiber：highTm