热塑性弹性体的研究与产业化进展_佘庆彦

31220122MATERIALSCHINAVol.31No.2Feb.20122011－03－012009BAE77B012011CB60600319751969100029、、。TPE、TPE、TPE、TPE、TPE、、。TQ334A1674－3962201202－0024－09StudyofThermoplasticElastomerandItsIndustrializationSHEQingyanTIANHongchiHANJibinCHENWenquanWUShemaoTIANMingZHANGLiqunCollegeofMaterialsScienceandEngineeringBeijingUniversityofChemicalTechnologyBeijing100029ChinaAbstractVarietiesmarketsituationindustrializedprogressandlatestresearchdirectionofchemicalsynthesistypeTPEandrubber-plasticblendingtypeTPEarereviewed．NewthermoplasticelastomerproductssuchaspolyamideTPEthermallyreversiblecovalentcrosslinkingTPEmetallocenecatalyticpolyolefinTPEmesogen-jacketedliquidcrystallineTPEbiobasedTPEandnewthermoplasticvulcanizateetc．withbroadapplicationprospectsareintroduced．Preparationmethodsperformancecharacteristicsandmarketdevelopmentofnewthermoplasticelastomerproductsarealsodiscussedindetail．Furthermoretheapplicationfieldsandtheindustrializationdevelopmentofthenewthermoplasticelastomerproductsarepredicted．KeywordsthermoplasticelastomernewTPEproductindustrialization1ThermoplasticElastomerTPE。、TPE1/425%～40%10～20。、、、、、、。1958Bayer1TPUTPE1963。Freedonia6.3%2013420t。2。、。ThermoplasticOlefinTPOThermoplasticVulcanizateTPV2。22.12。2。SBCTPE2013SBC200tTPE3。SBC、、、、、。SBC、SBC－－SBS、－－SISSEBSSEPS4－5。PSSBC。SBC。RAFT6、、、SBC。TPU、27－9。TPU、、、、、、、、。TPUTPE200935t6t、9t、2t、14t。TPU。、、10－13TPUTPU14－15TPU16－17。TPEEPBTPLLA、PGA、PCLPEG、PPG、PTMG18－19。TPEE2040DuPond1972Hytrel。、、TPEE10DuPontDSMLGGEEastmanchemical。TPEE2070、20。TPEETPE、－70～200℃。TPEE、、、、。2010TPEE14t2.3t。TPEE、TPEETPEE。2.2、、、。、、。。3、。TPO2070DuPontGoodrichPPTPO21。、。0～40℃80℃。。DynamicVulcanization。5231GesslerPP22。Fisher23－25EPDMPPTPEPPEPDM。Uniroyal“TPR”TPE、、、TPOEPDM50%。TPE50%TPE。。CoranTPV26－27。7×10－5mol/mL97%。2、、、。。PP/EPDMTPVTPV90%。2080TPV15%。2010TPV42t。、。2080、、11t。3。3.1TPAE28。TPAEHüls1979。Upjohn、ATO、Emaser、、TPAE。TPAE、66、、、、、29－31。、、TPAE。TPAE、TPAE、、、TPAE、。、TPAE。。Alla32、、TgTm－36℃281℃。TPAEDowPESATPAEUpjohn、、Es-tamindTPAE。EliAtochemPebaxTPAE。TPAE、、、、、。TPAE2t。TPAE。3.2－Diels-Alder1CPDCPD622CPDDCPD－C－C－。1Diels-AlderFig.1Diels-AlderreactionofcyclopentadieneKennedy33－34CPDPIB-CPD。。35－37CPDEA、A-CPDEADCPD。CPD。CPD38DGDCAECH、、190℃。Kennedy39Me2AlCPDCl-IIRCl-EPR－CPD150170℃。CPDDCPD。CPDDCPD。Ruckenstein40－41KDCPDCA、。4288.75%CER。43CPDDCPDACM、CIRCR2～3。CPDDCPDCPDDCPD、CPDDCPDC=C、、Diels-Alder20%～50%。CPDDiels-Alder。DCPDCPD、。DCPD1。“”。1DCPDTable1VarietiesofDCPDderivativesthermallyreversiblecovalentcrosslinkingagentDCPderivativesInitialdedimerizationtemperatureTdb/℃CompletededimerizationtemperatureTdc/℃DCPD120170DCPDCH2CH2OH2139218DCPS-CH2CH2CH2OH142217DCPDCH2nCOOH2139232DCPDCOOM2－2203.3TPEDowInsite1994TPE44。、、Ziegler-Natta45。TPEEtiND2ZrCl2/MAOiPPαPP46。TPETPE7231MontellAdflex、UCCFlexomers－、ExxonMobilExact－、DuPont-DowEngage－47。48－49。DowInsiteOBC50－52。Insite“”“”。POEOBC1253。2OBCPOETable2CharacteristicsofOBCandPOEthermalperformancePolymerTotaloctenex/%Mw/kg·mol－1Mw/MnI2a/10－1·g·min－1Density/g·cm－3Tm/℃ΔHmbXccw/%Tgd/℃OBC8812.21242.11.40.87951184917－42BO8711.61112.11.00.87240613813－36aMeltflowindexbHeatofmeltingfromthefirst-heatingendothermcCrystallinityfromheatofmeltingdGlasstransitiontemperaturefromdynamicmechanicalthermalanalysistanδ2OBCPOE－Fig.2Engineeringstress-straincurvesofOBCOBC88andPOEEO87at23℃3.4。。53MesogenJacketedLiquidCrys-tallinePolymerMJLCP。3。“”。54PMPCSAPnBABABAPMPCS-b-PnBA-b-PMPCS3。、。PDMSPDMS-b-PMPCS55。3PMPCS-b-PnBA-b-PMPCSFig.3MolecularstructureofPMPCS-b-PnBA-b-PMPCS。822。56。、。3.5。。。HytrelBio-PDO40%～60%Bio-PBO。、、、13－、14－、。57、58－59、60－61、62－63。。2、、、、、、。3.6TPVEPDM/PPTPVTPVTPV、TPV。IIR/PATPVTPV4。、64－65。IIR/PATPV60%10。IIR/PATPV、。AESIIR/PPTPVGOODYEAR。。2008。4Fig.4SchematicdiagramofmeridiantireIIR/PPTPVTPV。15%、。。IIR/PPTPVIIR/PPTPVIIR/PPTPV。IIR/PPTPV1t60001～2×103t。20116tAESIIR/PPTPVIIR/PPTPV。2009。92314。TPE、。。References1SchollenbergerCSScottHMooreGR．PolyurethanVCAVirtuallyCross-LinkedElastomerJ．RubberWorld1958137549－555．2HoldenGLeggcNRQuirkRetal．ThermoplasticElastomersM．BeijingChemicalIndustryPress2000．3QianBozhang．－－J．ShanghaiChemicalIndustry2009341031－33．4LiYufangLiMing．J．WorldRubberIndustry2008351141－48．5WuZhiyong．－－J．SyntheticRubberIndustry2004274201－204．6ZhouQiLuoYingwu．RAFTJ．ActaPolymericaSinica2008128－31．7KorodiTMarcuN．PolyurethaneMicrocellularElastomers1．EffectofChemicalcompositiononTensileStrengthandElongationatBreakofPolyethylene-butyleneadipateBasedSystemsJ．Polymer198324101321－1326．8KorodiTMarcuNTirnaveanuA．PolyurethaneMicrocellularElastomers2．EffectofChainExtenderontheMechanicalProp-ertiesJ．Polymer19842581211－1213．9ChattopadhyayDKWebsterDC．ThermalStabilityandFlameRetardancyofPolyurethanesJ．ProgPolymSci200934101068－1133．10YeganehHShamekhiMA．PolyUrethane-Imide-ImideaNewGenerationofThermoplasticPolyurethaneElastomerswithEnhancedThermalStabilityJ．Poly