多功能性聚吡咯复合膜

:20061,:20065*e-mail:[e-mail]多功能性聚吡咯复合膜谢允斌黄美荣李新贵*(同济大学材料学院先进土木工程材料教育部重点实验室材料化学研究所上海200092)聚吡咯具有较高的电导率与良好的环境稳定性,被视为继聚苯胺之后最有工业化应用前景的导电高分子材料之一聚吡咯与常规聚合物基体如聚乙烯醇聚氯乙烯等形成的复合膜不仅可以综合聚吡咯奇异的多功能性与常规聚合物的易成膜性和低成本性于一体,而且可望发挥两者的协同效应,从而大大拓宽其应用领域该研究已经成为导电聚合物研究领域中的又一新热点作者系统论述了这类功能复合膜的两种典型制备方法,并在分析各自特点的基础上提出了改进与发展方向,指出聚吡咯复合膜具有广泛可调的电导率快速的电学响应性以及稳定的电致变色性等多种功能,在透明导电膜化学传感器生物分离膜电致变色膜领域具有诱人的应用前景聚吡咯多功能性复合膜:0633;TB383:A:1005-281X(2006)12-1677-07MultifunctionalPolypyrroleCompositeFilmsXieYunbinHuangMeirongLiXingui*(InstituteofMaterialsChemistry,KeyLaboratoryofAdvancedCivilEngineeringMaterials,TongjiUniversity,Shanghai200092,China)AbstractPolypyrrolehasbeenconsideredoneofthemostprospectiveconductingpolymersforindustrialapplicationsfollowingpolyanilineforitshighconductivityandgoodenvironmentalstability.Compositefilmsfrompolypyrroleandsomeconventionalpolymermatrixessuchaspoly(vinylalcohol)andpoly(vinylchloride),couldnotonlyintegratetheexcitingmultifunctionalityofpolypyrroleaswellasthegoodfilm-formabilityandmuchlowercostofthematrixpolymers,butalsoproduceanovelcoadjutanteffectofbothpolymers.Thereforethesekindsofcompositefilmshavewidenedapplicationfields,andhavebecomeanewresearchhotspotinthefieldsofconductingpolymers.Twotypicalpreparationmethodsoftheseconductivepolypyrrolecompositefilmshavebeensystematicallyreviewed.Accordingtocarefulanalysisoftheirindividualcharacteristics,thepossibleimprovementanddevelopmentareproposed.Havingavarietyofexcellentfunctionssuchaswidely-variableelectroconductivity,fastelectricalresponseandstableelectrochromism,thepolypyrrolecompositefilmshaveshownagreatattractionofpotentialapplicationsinmanyfieldsincludingtransparentconductingfilms,chemicalsensors,bioseparation,andelectrochromicfilms.Keywordspolypyrrole;multifunctionality;compositefilms(PPY)P(1),,1(PPY)PFig.1TheP-conjugatedstructureofpolypyrrole(PPY)1812200612化学进展PROGRESSINCHEMISTRYVol.18No.12Dec.,20061Table1Polypyrrolecompositefilmspreparedbyin-situpolymerizationmethodmatrixPPY*(wt%)conductivity(SPcm)ref.chemicalpoly(vinylalcohol),PVA~101005oxidativepoly(vinylchloride),PVC~810-16polymerizationpoly(vinylacetate),PVAc5107poly(ethyleneterephthalate),PET~1010-28poly(methy-lmethacrylate),PMMA403.279poly(ethylene-co-vinylalcohol),PEVOH106.5@10-110crosslinkedpoly(methylacrylate-co-hydroxyethylacrylate),PMPHEA~410011crosslinkedpoly(styrenePbutylacrylatePacrylicacid),PSBA~42.212crosslinkedpoly(styrene-butylacrylate-hydroxyethylacrylate),PSBH2.61513crosslinkedcellulose4.210014electrochemicalPVA~2010015oxidativePVC10-116polymerizationpolystyrene,PS5010-317poly(bisphenolAcarbonate),PCR5010-3poly(etherurethane),PEU~1010-118PEVOH~1010-4poly(vinylmethylketone),PVMK1510019thiorubber,TR~1010120*theprefix/~0meansthegivendataisapproximatelycalculatedbythedataintheliterature,PPY(PVC)(,/0/PPY0)PPY,,PPY[1)4],PPY;PPY[5)8],PPY,,1(2):,,;,,1preparationmethodsofpolypyrrolecompositefilmsin_situpolymerizationchemicaloxidation:solutionimpregnation,direct_contactmethod,etc.electrochemicaloxidation:one_step,two_stepmethod,etc.blendingmeltingblendingsolutionblending2Fig.2Preparationmethodsofpolypyrroleconductingcompositefilms1.11.1.1,:(1)(),;(2)(),,()PVCPETPPY(1)1,,10-1SPcm,PPY,,:FeCl3PMMA#1678#化学进展18,,PMMAPPY,PPY,,,3.27SPcm(PPY40%),[9]9@10-2SPcm(PPY30%)PPYPPU,,1.1.2,(),,/0,PPYPMMAPVAPVCPEUPEVOH(1);/010-1SPcm(1);/0,,[20]/0,()SH)(TR),,10SPcmPPYPTRPPY,PPY1.2,,[21,22],,:[23)25][26]PPY;,,;101SPcm[24]PPY,,;,[27]22.1PPY,10-5SPcm)101SPcm(1)PPY(fp),,PPY,fp10%[17,19];,fp,PPY(PDLLA)fp3%[28],,PVCfp1%,fp,PPY,PPY,2,PPYPVCNylon-66SPS()PSBAPSBH,,,PPY,,PPYPSPSSPS:160eSPS106Pa,SPSPPPY7@107Pa[22]#1679#122PPYTable2MechanicalpropertiesofPPYanditscompositefilmsconductingfilmsPPY(wt%)thickness(Lm)conductivity(SPcm)mechanicalproperties*Ry(MPa)St(MPa)Eb(%)EY(MPa)ref.PPY100)53)46.378.62@10-26PPYPPVC104)75011.87.62214.47@10-210~1010-138)141.73@10329PPYPNylon-66751.1@10-68.0@104)3502.6@10330PPYPSPS7)82007@10-53223.4)1.1@10322PPYPPSBA))2.2)6.294.790.712PPYPSBH))15)10.3170178.913*Ry:yieldstress,St:tensilestrength,Eb:strainatbreak,EY:Young.smodulus,PPYPET[8],313@10-2SPcm,70%(633nm);PVA[31],100SPcm,~80%(500)700nm)2.2,K+[26]NH3[32,33][34][23,25][23],,,PPYPPMMANH350s680LA440LA,240LA;NH30.1%,160LA[32]PPYPPVA,PVAPPYPPVA:715gPL510gPL1010gPL110gPL0gPL(PPY)PVA,[34]213PPYP(P,3)/yy0PPY3PPYP[28]Fig.3DopingPdedopingprocessofPPY4PPY(ECD)($T)[18]Fig.4Differenceintransmittanceat800nmbetweenthedoped(+3V)andundoped(-3V)stateswiththecyclenumberswitchingvoltage(?3V,1Hz)forECDusingPPYPEVOHandPPYPPEUcompositefilmsrespectively[18],,,,[35],[18],,PEUPPYPPEU3000,PEVOHPPYPPEVOH8000(4)#1680#化学进展183311,PPY(PET)-6(PA6)(PVA)(PC)3,10-2SPcm70%,PPYPPCPPY12nmPPY,PPY1%90%,10-3SPcm,[36]3PPYTable3TransparencyandconductivityofPPYcompositefilmsPPYcompositefilmPPY(wt%)thickness(Lm)transparency(%)(K,nm)conductivity(SPcm)ref.PPYPPET~103070(633)313@10-28PPYPPA6))75())2135@10-131PPYPPVA~52~80(500)700)1005PPYPPC1012790(300)800)10-336PPY,,,312,,;PPY,,PPY[23,37](4),PPYPMMAPVANH3,2min,PPYPPY,,PPY,[38],,PPY(),PPY4PPYTable4SensitivityofPPYanditscomposi