可熔体加工热塑性聚酰亚胺研究进展

王　凯1　　詹茂盛1　　高生强2　　杨士勇2(1　,　100083)(2　,　100080)　　从发展航空航天、微电子、汽车及电器等高技术领域先进材料的角度,阐述了可熔体加工热塑性聚酰亚胺的发展现状和最新进展;报告了热塑性聚酰亚胺的挤出成型、注射成型、纺丝、涂覆等工艺;讨论了热塑性聚酰亚胺的分子结构对聚酰亚胺热性能的影响;介绍了几种最新热塑性聚酰亚胺的特点和典型应用实例;指出开发新型热塑性聚酰亚胺应综合考虑可加工性、耐热性、成本以及原料来源。　聚酰亚胺,热塑性,熔体加工DevelopmentofMelt-processableThermoplasticPolyimidesWangKai1　　ZhanMaosheng1　　GaoShengqiang2　　YangShiyong2(1　SchoolofMaterialScience&Engineering,BeijingUniversityofAeronautics&Astronautics,Beijing　100083)(2　TheStateKeyLaboratoryofEngineeringPlastics,InstituteofChemistry,ChineseAcademyofSciences,Beijing　100080)Abstract　Developmentandthemostresentresearchonmelt-processablethermoplasticpolyimides(TPIs)arepre-sentedinviewoftheprocessingofadvancedmaterialsusedinthefieldofaerospace,microelectronics,automobileandelectricalequipments.Extrusion,injection,spinningandcoatingconditionsofTPIsarereported.Theeffectsofmolecu-larstructuresonthethermalpropertiesofpolyimidesarediscussedaswell.SeveralnewTPIsandsomeexamplesofcom-mercialTPIsareintroducedinthispaper;themelt-processability,thermalresistibility,costandsourceofstuffshouldbeconsideredfornewTPlsdevelopment.Keywords　Polyimide,Thermoplastic,Melt-processable1　(PI),,。,。()、、,、、。,、,1[1～3]。。,,(、),(),。,,。:2003-06-30,1979,,—5—　2004　31　Tab.1　Applicationsofpolyimides　、、、、、、、、、、、。2.4Ma,177℃,60000h,50%,30t,、,TN-LCD、STN-LCD、TFT-LCD　　,:、PMR[4～9]。,。。,,,,。。2　,(GE),1982(PEI),Ultem®[10]。、,2、3[11]。Ultem®A,,Tg217℃,150℃～180℃,。,。2　Ultem®1000Tab.2　InjectionmoldingparametersofUltem®1000/℃/h/h/%/%////℃/℃/℃/MPa/r·min-11494.0～6.0240.02040～60332～399/338～399/343～399/343～399349～399135～1630.34～0.6940～703　Ultem®1000Tab.3　ExtrusionmoldingparametersofUltem®1000/℃/h(1/2/3)/℃/℃/MPa1494.0324～349/329～357/329～357329～3578.27～48.23　　Amoco(PAI),Torlon®,、、,。,,15.9mm。Torlon®、、、,3.2mm～50.8mm,4.8mm～25.4mm。15.9mm,,381mm,OI914mm,76.2mm。,,4[12]。4　Torlon®Tab.4　InjectionmoldingparametersofTorlon®/℃/h/MPa/s/MPa/MPa/r·min-1(///)/℃/℃121(177)24(16)41～553～921～346.950～100304/327/343/371163～190—6—　2004　3　　NASA(LaRc)LaRcTM-IA,,,5[13]。5　LaRcTM-IATab.5　MeltextrusionspinconditionsofLaRcTM-IA/℃/h(//)/℃/r·min-119224340/350/36010　　[1],2060YHPI,70YS20,GE。[14],,。,,,,。2080,Aurum®,,Tg(250℃),、6～8[15,16]。6　Aurum®Tab.6　MeltfluidityofAurum®1)/mPa·s1)/g·(10min)-14003000～400012.0～18.045060004.5～7.5500100002.5～4.5　　:1)400℃。7　Aurum®Tab.7　ElectricwirecoatingconditionsforextrusionofAurum®/℃/MPa3904104104004103～5、、/m·min-130L/D=20～228　Aurum®Tab.8　TypicalinjectionmoldingconditionsforAurum®/g/℃/℃/MPa//s/r·min-1ARBURG-A220H(18Υ)Aurum®(450)()13380/390/400/400180/1801055/132002(0.5×4)380/390/400/410180/1801375/13200MEIKIM70AIISDM(28Υ)(JCN3030)62Υ13380/390/410/420210/2101474/5014079Υ210(25)390/400/420/420210/2101674/30140　　,Ul-tem®,360℃～380℃;LaRcTM-TPIAurum®。,,,、、、。3　GEUltem®,。Ultem®,,GE。GE—7—　2004　3Ultem®18100t/a,25800t/a。Ultem®,[17]。,[18],A,,A,,A。Aurum®250t/a,300t/a。[19],Aurum®。,;2004,500t/a。Ishikawajima-Harima()、NSK()、、、;、、、、、、、、、,75＄/kg～95＄/kg[20]。2003128Aurum®,SuperAurum,。Aurum®,SuperAurum,,359℃,(PET、PPS、PEEK),,250℃300℃。,,1999839t,5000。200044＄/kg,440＄/kg。,/。GEPlasticsUltem®、Aurum®、TI-5000BPAmocoTorlon®。1999GEPEI:/45%;25%;20%;5%;3%;2%。,、。4　,:(1);(2),,,;(3),,1000Pa·s。,、、,TPI。Ultem®1000()360℃3000Pa·s,400℃5760Pa·s。,。,。TPI,。1。1　Fig.1　Structuresofdianhydridesanddiamines—8—　2004　3　　、,。,,。,,,,、。4.1　,。S.Tamai[21]。、,9,2。9　Tab.9　EffectofdiaminesstructuresonthermopropertiesTg/℃Tm/℃H2NNH2326-H2NONH2242374H2NOONH2222428H2NOOONH2204332H2NNH2261491H2NONH2205-H2NOONH2189318H2NOOONH2181-H2NONH2205-H2NOONH2201341H2NOONH2168-2　Fig.2　StructuresofdiaminesSynthesisedbyS.Tamaietal　　,。Tg(9),∶∶0.97∶1∶0.06()。Tg、,Tg,10。Aurum®。[22]()。()。PI。,(—O—)(—CO—)-,-。(CT-complex),-。Zen-minShiMasatoshiHasegawa[23],ODPABEPA12,PA,DMTA。0.5dL/g,。ODPA4,4'-ODA、PTPEQ0.49dL/g,400℃470Pa·s。TgUl-tem®10007℃。—9—　2004　310　Tab.10　Structuresandpropertiesoftwomelt-processablepolyimidesPIη/dL·g-1Tg/℃Tm/℃T5d/℃1)/Pa·s0.48254-53945200.502503885504100　　:1)420℃、100kg。4.2　,,,TPI。2,3,3',4'-(a-BPDA,1),MasatoshiHasegawa[24～26]a-BPDA,。,Tg、。()。a-BPDAODPA(4∶1)3,4'-ODATPER(1∶1)(),PA,249℃,8200Pa·s,(Eb=66%)。390℃,Ultem®。4.3　,[7,27～30]。。,,,。(ATF)Avimid,AvimidN6FDA95%5%,Tg360℃,,,,。5　,。,。:(1)、、,TPI;(2),,、TPI、。,,。1　,..:,1998:283～2922　,,,..,2001;(4):16～193　,..,2002;32(3):6～104　KanagawaST,FukuokaMO,KanagawaAY.Readilypro-cessablepolyimideandpreparationprocessofsame.USPatent,5268446,1993-12-75　TerryLSt,FayCC,WorkingC.PolyimideFibers.US—10—　2004　3Patent,5840828,1998-11-246　LiBaozhong,HeTianbai,DingMengxian.Comparativestudyofinsolubleandsolublepolyimidethinfilms.Polymer,1999;40(3):789～7947　XieK,LiuJG,ZhouHWetal.Solublefluoro-polyimidesderivedfrom1,3'-bis(4-amino-2-trifluoromethyl-phenoxy)benzeneanddianhtdrides.Polymer,2001;42(17):7267～72748　,,..,2000;30(1):1～69　YokotaR,YamamotoS,YanoSetal.Moleculardesignofheatresistantpolyimideshavingexcellentprocessabilityandhighglasstransitiontemperature.HighPerformancePolymers,2001;13(2):S61～S7210　,,..,2001;(3):25～2811　=4&varAAA=4195&PI=1#NOTES12