软硬段对聚氨酯弹性体结构性能的影响

JournalofFunctionalPolymersVol.23No.220106:20091221:(1984),,,:Email:[e-mail]:,Email:[e-mail]区洁,田立颖,王新灵(上海交通大学化学化工学院,上海200240):采用本体聚合和溶液聚合两种方法,合成了一系列用聚乙二酸丁二醇酯二醇作为软段的聚氨酯弹性体研究了硬段含量和聚醚添加量对聚氨酯弹性体综合性能的影响利用红外光谱热分析力学性能测试记忆回弹性能和耐水解老化实验等测试手段对样品进行了表征与分析结果表明:硬段质量含量为31%~35%时,材料的力学性能较优,形状回复率可以达到75%~85%;软段中聚醚添加量在4%~5%(占软段的质量分数)时,弹性体具有较好的力学性能和耐水解性能:聚氨酯弹性体;硬段;软段;结构性能;微相分离:O63:A:10089357(2010)02016006EffectofHardandSoftSegmentonStructurePropertyofThermoplasticPolyurethaneElastomerOUJie,TIANLiying,WANGXinling(SchoolofChemistryandChemicalEngineering,ShanghaiJiaotongUniversity,Shanghai200240,China)Abstract:Aseriesofpolyurethane(PU)elastomersbasedonpolybutyleneadipate(PBA)assoftsegmentweresynthesizedbybulkpolymerizationandsolutionpolymerization.Theirmorphologies,shapememoryeffect,thermalstabilityandmechanicalpropertieswereanalyzedbymeansofFTIRspectra,AFM,TGA,tensiletestsandhydrolysisstabilitytesting.Polytetramethyleneglycol(PTMG)wasaddedintosoftsegmenttogetbetterperformanceofthespecimens.PUshowsdifferentperformancesbychangingthemolratioofMDIandBD(hardsegment)andthequantityofpolyetheraddingintothesoftsegment.Resultsshowthatbettermechanicalproperties,waterresistanceand75%-85%ofshaperecoveryareobtainedat31%-35%ofhardsegmentcontentand4%-5%ofPTMGcontent.Keywords:polyurethaneelastomer;hardsegment;softsegment;microphaseseparation(TPU),,,[1],80%~90%,1000~2000,,,,10%~20%,,,,,,,,,,160[23],,,,(PBA)(MDI),1,4(BDO),(PTMG),,,11.1MDI:;PTMG:DuPont,1000,,100!2h;PBA:2000,,100!12h;N,N(DMF):,,,60!2h,,,70~90!;BDO:2~3h1.2:Paragon1000(PerkinElmer),16,1000~3500cm-1:Nanoscope∀a,,X:RigakuD/Max2000X,40kV,20mA,(CuKa,=0.154nm),5#/min,2#~50#:Instron4465(Instron),GB/T5281998,500mm/min,,20mm,4mm,1~2mm,5[47]:Instron4465(Instron):70!(Tg+20),10mm/min100%(2L0),5min;20!(Tg-20),30min,L1;70!,10min,20!,L2Shaperetention=(L1-L0)∃100%/L0;Shaperecovery=(2L0-L2)∃100%/L0:100!8h,60!1d,,1.3,,,[4]1.3.1,,PBA80!,BDOMDI60!,,PBABDO,MDI,1000r/min,1~2min,,,70!8h,120!2h,1.3.2:,PBAPTMG500mL,N2,70!MDI70mLDMF,60~70!2h,,-NCO,1,4,70~80!1.5~2h,,70!1612,:DMF22.1PBA,,(HS)23%28%32%35%39%GPCMn=5.9∃104~6.9∃1042.1.11,3340~3336cm-1()N%H,1734cm-1,1176cm-1C%O%C,2270cm-1,%NCO,2953cm-12868cm-12%CH2%,1218cm-1O=C%O%C,1532cm-1%C=C%,,,1Fig.1FTIRspectraofTPUsamplesw(HS):a%23%;b%32%,(1702cm-1),(1730cm-1),,%C=O%HNCOO%,,,,,,,[8]2.1.22,,,,,,,,35%23%,,,,,,,2.1.33,,,,,,,,,,,,w(HS)(39%),,,,,,162232Fig.2AFMgraphsofTPUsamplesw(HS):a%23%;b%35%3,w(HS)31%~35%,20~18MPa,,700%,,2.1.44w(HS)23%39%,90%,,,,,3Fig.3TensilepropertiesofTPUsamples4Fig.4ShapememorycurvesofTPUsamples70%~80%,,,Tg20!,,,,,,,;,,,,,2.2w(HS)35%,,PTMG,,4%6%8%10%12%16%20%24%GPCMn=1.9∃104~3.9∃1042.2.15,,1222cm-11174cm-1PTMGC%O%C,1538cm-1,2962~2868cm-1PTMG%CH2%,1225cm-1,,1174cm-1C%O%C1632,:3338cm-1,,1732cm-1%C=O,1699~1702cm-1,%C=O,,,,;,,2.2.2X6,,2=20#,,PBA,,,5Fig.5FTIRspectraofTPUsamplesw(PTMG):a%0.04;b%0.08;c%0.206XFig.6WAXDcurvesofTPUsamplesw(PTMG):a%0.04;b%0.08;c%0.20,,,,,,,,,,2.2.37,,,,PBA,,,,PBAPTMG,,,,,,,,,,,2.2.48,,,85%~90%,75%~80%PBA,PTMG,,,,(4),w(HS)35%95%,,Tg,,,PTMG,,70!(Tg+20),,,,2.2.5016%1PBA,,,16423,,,,,04%,19.5%7%,,,4%~5%,,7Fig.7TensilepropertiesofTPUsamples8Fig.8ShapememorycurvesofTPUsamples1Table1TensilestrengthofTPUsamplesbeforeandafterhydrolysisw(PTMG)/(%)Tensilestrength/MPaBeforehydrolysisAfterhydrolysisMassloss/(%)018.514.919.5416.9215.737.0816.8415.498.01613.3412.754.43(1)w(HS)31%~35%,,78%~85%,w(HS)35%,,(2),,,4%~5%(),:[1],,.[J].,2007,5(1):4650.[2],.[J].,2008,17(6):1520.[3]LeeBS,ChunBC,ChungYC,etal.Structureandthermomechanicalpropertiesofpolyurethaneblockcopolymerswithshapememoryeffect[J].Macromolecules,2001,34(18):63416437.[4]AbouzahrS,Wilkes,GarthL.StructurepropertystudiesofpolyesterandpolyetherbasedMDIBDsegmentedpolyurethanes:Effectofonevs.twostagepolymerizationconditions[J].JApplPolymSci,1984,29(9):26952711.[5]FergusonJ,AhmadN.Chemicalstructureandphysicalpropertiesinpolyesterbasedsegmentedpolyurethanes:II.Tensileproperties[J].EurPolymJ,1977,13(11):865869.[6]FergusonJ,AhmadN.Chemicalstructureandphysicalpropertiesinpolyesterbasedsegmentedpolyurethanes[J].EurPolymJ,1977,13(11):859864.[7]KimBK,LeeSY,MaoXu.Polyurethanehavingshapememoryeffect[J].Polymer,1996,37(26):57815793.[8]LiYingjie,RenZhiyong,ZhaoMing,etal.Multiphasestructureofsegmentedpolyurethanes:Effectsofhardsegmentflexibility[J].Macromolecules,1993,26(4):612622.1652,: