羟基氟硅油改性聚氨酯的合成、结构及性能的研究

上海交通大学硕士学位论文羟基氟硅油改性聚氨酯的合成、结构及性能的研究姓名：包天宇申请学位级别：硕士专业：材料学指导教师：王新灵20070101IPUD3FKH550IRVPOTGASEMIIPTMGIIIABSTRACTThepolyurethaneelastomerhasexcellentabrasionresistance,tenacity,fatiguedurability,chemicalresistanceandhighimpactresilience,etc.It’sakindofengineeringmaterialswithbroadapplications.Thetraditionalwayofmakingpolyurethanehasmanydisadvantages,suchasheatresistance,soitsetboundstoitsfurtherapplicationinengineeringtechnology.Polysiloxanepolymerspossessimportantphysicalandchemicalpropertiesduetoitsuniquestructure.Thesepropertiesincludelowglass-transitiontemperature,verygoodresistancetotemperatureandoxidantagents,goodelectricalinsultingqualitiesandthermalstability,highpermeabilitytogases,biocompatibilityandetc.Thefluorosiliconehasbettersurfaceperformance.Butexhibitratherpoormechanicalpropertiesandlowadhesiveforce,whichrestrictitsapplicationveryseriously.Sofromnowonwecanseebothhavesomekindsofmeritsanddemerits,howevercopolymerofpolysiloxaneandpolyurethanecombiningtheiradvantagescanimprovethepropertiesofpolysiloxaneandpolyurethane.Polysiloxane-polyurethanecopolymerwhichwouldrenderbetterheatresistanceandlowertemperatureflexibilitythanpolyurethanesthemselvesandbettermechanicalstrengthandabrasioncharacteristicsthanpolysiloxanehasthepotentialapplicationasnewmaterial.IVInthisarticle,weopenringD3Ftoformhydroxyfluorosilcone,andthenwesynthesisamine-terminatedfluorosiliconebyusingKH550.Also,weuseinfraredopticalspectrumandgasphasepermeabilitymethodandsomeothercharacterizationtoobtainakindofmolecularweightmine-terminatedfluorosilicone.Byusingitassoftsegmenttoreactwithdifferentkindsofurethaneprepolymer,thenweusemanykindsofcharacterizationmethodtoresearchontheirstructureandproperties.Wefindthattheheatresistanceandsurfacecontactangleofmodifiedpolyurethanehaveimproved.comparedtodifferentkindsofpolyurethanewecanseethepolyurethanemodifiedbyPTMGandamine-terminatedfluorosiliconehasgoodcombinedproperties,andwebelieveithasbroadapplicationincomingdays.Keywords:fluorosilicone,polyurethane,heatresistance,surfacecontactangle2007118□□√“√”2007118200711811.1[1-2]70025022020020004.625024.812.64026.59.64200211055~60[3-6]1.2[7].1.2.1404060261621.2.2[8]1.2.35.5~6200518.35.7122310.35501.2.4,,,,;,,,;PU,,,,,,PUPU;PU,,,,,PUA,,,;,,,;,,,,PAPU,PUA[9].31.2.5[10]1.2.6400%800%300%95%10%1.2.7[11]1.31.3.14ROCONH—CH2—ROCO—O—CNHOHNCNHONCOORCNHONCOONHCNHO[11]()()50901050(domain)[12]1.3.251.3.2.180120130[13]-62~711.3.2.2351031-4Taber6figure1-1Taberwearvalueofmaterials1-1Taber[14]/mg/mg0.53.5146610161601817711241872920542ABS275442807032412266366CS171000g/5000r/min23601.3.2.323[14]A10D75A60100.1.3.2.471.3.2.51.3.31.3.3.1[15]1.3.3.2808figure1-2Theheatdecompositiontemperature1-2HNCNHO260NCOORCNHO146ROCONH240NCOONHCNHO1441-51.3.3.3[16]91.3.3.4≥TDIMDI,[17]1.3.3.5NCO/OHNCO/OH1.4101.4.1[18][19][20][21][22][23]SiO2PDMS/PU[24][25],,-PDMSCooper[26-29]1.4.2(PC),,[30]Harris[31]Gunatilake[32](1,6-)[33-34][36]PCU11PUPUPUPUPU[37-39]1.4.3[40],PUPAPUA-PUAPUAMasakazu[41]--1.4.4[42],[43]A[44-45]121.4.5/[46][47][48-50]/Ni[51]/TiO2[52]/CeO2[53]/[54]1.4.6[55][56][57]1.5[58](1)[59-61]PU,,PU,,,PU(2)[62](3),,,PU(4),[63][63-64]13PUPUPU[65][66]PU,,,,Si-OC-F[67]D3FD3F-OHKH570TDINCOMOCA14[1],·.:.1999,6[2]Zhang,Y.C.,etal.,Reviewofpolyurethane/layeredsilicatenanocomposites.ProgressinChemistry,2006.18(1):p.59-65.[3]..2002[4]Galbany,J.,etal.,ComparativeanalysisofdentalenamelpolyvinylsiloxaneimpressionandpolyurethanecastingmethodsforSEMresearch.MicroscopyResearchandTechnique,2006.69(4):p.246-252.[5]Digar,A.,etal.,Studyofionicconductivityandmicrostructureofacross-linkedpolyurethaneacrylateelectrolyte.Polymer,2002.43(3):p.681-691.[6]Mishra,J.K.,S.Raychowdhury,andC.K.Das,Heat-shrinkablepolymerblendsbasedongraftedlow-densitypolyethyleneandpolyurethaneelastomer.PartI.PolymerInternational,2000.49(12):p.1615-1623.[7]..:,1992,1~4[8]..:.2001.94[9],..:,1996.250~435[10]..1991,14(6):437[11].[M].1994.[12]1993.[13].199449.[14]VoelkerTHPeterBallingElastonters&Plastics1987193219.[15]..1988,(2):23[16],.1998,13(3);1-4[17]19955(3)39.[18],,.20011533.[19]YilgorI,Sha’abanAK,WarrenPS.JPolymer,1984,25,1800[20]SummerJD,ArnoldCA,BottRH.JPloymPrepr.1986,27(2):403.[21]TangSH,MeineckeEA,RiffleJS,etal.JRubberChemTechnol,1984,57[22],.,1991,4(1)19.[23].20042561.[24],,,,.,1996,12(1):54.[25].[26]YuX-H,NagarajanMR,GraselTG,etal.JPolymSciPolymPhysEd,1985,23(11):2319.[27]YuX,NagarajanMR,LiC,etal.JPolymSci,PartB:PolymPhys,1986,24(12):2681.[28]LiC,YuX,SpeckhardTA,etal,JPolymSci,PolymPhysEd,1988,26(2):315.15[29]..2003610.[30]HarrisRF,JosephMD,DavidsonC,etal.JApplPolymerSci1990,41:487.[31]GunatillakePA,MeijsGF,MccarthySJ,etal.JApplPolymerSci,1997,69:1621.[32],.,1993,(4):13.[33],,,.,1993,16(4):199.[34],,,.200218637.[35],,,.,1995,36(8):426.[36].199411565.[37].198474320.[38]CuveL,PascaultJP,BolteuxGetal.Polymer,1991,32343.[39].20053346.[40]MatsumraA,OcahitaA.JP:10204134,1998.[41].(2).:,1996.443.[42].2005225538.[43],,.,1999,4:391.[44]LinMS,WangMW,ChengLN.PolymDegrStab,1999,66(3):343.[45]200414516.[46],,.2003346638.[47].2003126.[48],,,