近代高分子科學(xué)

導(dǎo)電高分子材料聚苯胺研究進(jìn)展×××

××工程××××××1目錄OUTLINE聚苯胺發(fā)展歷史聚苯胺合成方法聚苯胺應(yīng)用領(lǐng)域聚苯胺發(fā)展前景12342聚苯胺發(fā)展歷史anilineblackemeraldine1984年，賓夕法尼亞大學(xué)Macdiaemid重新開發(fā)51910年，Perkin,得到過氧化anilineblack,此物質(zhì)不能還原為emeraldine41862年，Letheby發(fā)現(xiàn)在電解苯胺硫酸鹽時(shí)，陽極生成darkblue產(chǎn)物31840-1843,Fritzsche發(fā)現(xiàn)用鉻酸氧化苯胺鹽時(shí)，darkgreen變?yōu)閎lush(淺藍(lán))black21824年，Runge發(fā)現(xiàn)加熱CuCl2與苯胺硝酸鹽混合物到100℃，顏色由darkgreen變?yōu)閎lack16......non-greeninganilineblack1947年，Brown首次在文章中提及polyamine3H.Letheby,JournaloftheChemicalSociety15(1862)161.

E.Noelting,ScientificandIndustrialHistoryofAnilineBlack,WM.J.Matheson&Co,1889

4深藍(lán)色部分氧化導(dǎo)體綠色部分氧化質(zhì)子導(dǎo)體綠色部分氧化質(zhì)子導(dǎo)體無色全還原絕緣A.G.MacDiarmid,J.C.Chiang,A.F.Richter,A.J.Epstein,SyntheticMetals18(1987)285

5還原單元氧化單元結(jié)構(gòu)單元可表示為其中y表示氧化-還原程度。氧化度不同的聚苯胺表現(xiàn)不同的組分、結(jié)構(gòu)、顏色及電導(dǎo)特性。如從完全還原態(tài)(Leucoemeraldiline,LBy=1)向完全氧化態(tài)(Pernigraniline,PBy=0)轉(zhuǎn)化的過程中,隨氧化度的提高聚苯胺依次表現(xiàn)為黃色、綠色、深藍(lán)、深紫色和黑色。6聚苯胺合成方法Scheme3.Monomericanddimericproductsofanilineoxidation:1)nitrobenzene,2)phenazine,3)2-aminodiphenylamine,4)hydrazobenzene,5)azobenzene,6)azoxybenzene,7)potassiumorthoaminophenylsulfate,8)benzidine,9)4-aminodiphenylamine,10)N-phenyl-1,4-benzoquinonediimine,11)indophenol,12)1,4-benzoquinone,13)1,4-benzoquinoneimine,14)4-aminophenol,15)phenylhydroxylamine,and16)nitrozobenzene.G.A.Planes,J.L.Rodríguez,M.C.Miras,G.García,E.Pastor,C.A.Barbero,PhysicalChemistryChemicalPhysics12(2010)10584

7Scheme4.Single-electronoxidationsofaniline(C),aniliniumcation(A),anilinecationradical(D)andanilineneutralradical(F),accompaniedwithcorrespondingacid/baseequilibria:aniliniumcation/aniline,aniliniumdicationradical(B)/anilinecationradical,anilinecationradical/anilineneutralradical,anilinedication(E)/anilinenitreniumcation(G),andanilinenitreniumcation/anilinenitrene(H–singletnitrene).8Scheme5.Majorproductsofpossibleanilineoxidativedimerizationreactions(A[138],B[138],C[139],D[115,122,139],E[138])determinedcomputationallybyusingAM1/COSMO[115,122,138,139]andPM3/COSMO[122,138,139]semiempiricalquantumchemicalmethods.9Scheme7.RedoxreactionsversusMichaeladditionreactionsofN-phenyl-1,4-benzoquinonediimineand/orhigheriminoquinonidoligoanilineswithanilineinhighlyacidic(pH<2)andalkaline/neutral/slightlyacidicsolutions(pH>2),respectively.Scheme6.Thereactionsofanilinenitreniumcationwithanilineandsulfateanion,giving4-ADPAandortho-aminophenylsulfate,respectively.10Fig.1.Molecularstructuresoflow-molecular-weightOANIsformed/precipitatedinAPS/anilinesysteminbuffersolutionsatpH2.5–10.0orunderfalling-pHconditions,proposedbyseveralresearchgroupsonthebasisofstructuralcharacterization(elementalanalysis,FTIR,Raman,UV–vis,and1H/13C/15NNMRspectroscopies,GC–MS,ESI-MSandMALDI-TOFMS)andsemiempiricalquantumchemicalpredictionsofoligomerizationmechanism:1化學(xué)氧化聚合法聚苯胺的化學(xué)氧化聚合法，是在酸性水溶液中用氧化劑使苯胺單體氧化聚合。化學(xué)氧化法能夠制備大批量的聚苯胺，也是最常用的一種制備聚苯胺的方法。質(zhì)子酸是影響苯胺氧化聚合的重要因素，它主要起兩方面的作用：提供反應(yīng)介質(zhì)所需要的pH值和以摻雜劑的形式進(jìn)入聚苯胺骨架賦予其一定的導(dǎo)電性。苯胺化學(xué)氧化聚合常用的氧化劑有：過氧化氫、重鉻酸鹽、過硫酸鹽、氯化鐵等，所得聚苯胺性質(zhì)基本相同。112電化學(xué)聚合法電化學(xué)法制備聚苯胺是在含苯胺的電解質(zhì)溶液中，選擇適當(dāng)?shù)碾娀瘜W(xué)條件，使苯胺在陽極上發(fā)生氧化聚合反應(yīng)，生成粘附于電極表面的聚苯胺薄膜或是沉積在電極表面的聚苯胺粉末。主要的電化學(xué)聚合法有：動(dòng)電位掃描法、恒電位法、恒電流法和脈沖極化電化學(xué)方法合成的聚苯胺純度高，反應(yīng)條件簡單且易于控制。但電化學(xué)法只適宜于合成小批量的聚苯胺。1213聚苯胺應(yīng)用領(lǐng)域防腐蝕涂料抗靜電和電磁屏蔽材料其它材料特殊分離膜

二次電池的電極材料

選擇電極應(yīng)用14Fig.2.(a)PartiallyprotonatedPANI-NF:zig-zaglinesandthegreendotsrepresentPANIchainsandCl?ions,respectively;thegrainfeatureofprotonatedregimesisimplicated.(b)AnillustrationofentangledPANI-NFs;theinternanotubularcontactsaremarkedinblueandaninsetshowsacloseviewoftheredrectanglearea.The3DgreenregimesintheinsetillustrateprotonatedgrainstructuresinasinglePANINF.(c)SEMimageofPANInanodevice.(Forinterpretationofthereferencestocolorinthisfigurelegend,thereaderisreferredtothewebversionofthearticle.)

15Fig.3.Top:Schemeoftheformationfornitrogen-dopedgraphenesheetsderivedfromPANIandCoprecursorsusingmultiwalledCNTs(MWCNTs)asatemplate.Bottom:SEM(a)andHR-TEM(b–d)imagesofthegraphene-richnanocompositesobservedinCo-N-MWCNTcatalysts.

G.Wu,N.H.Mack,W.Gao,S.Ma,R.Zhong,J.Han,J.K.Baldwin,P.Zelenay,ACSNano6(2012)9764

16S.Liu,J.Wang,D.Zhang,P.Zhang,J.Ou,B.Liu,S.Yang,AppliedSurfaceScience256(2010)3427

J.Yang,J.Choi,D.Bang,E.Kim,E.-K.Lim,H.Park,J.-S.Suh,K.Lee,K.-H.Yoo,E.K.Kim,Y.-M.Huh,S.Haam,AngewandteChemieInternationalEdition50(2011)441

Fig.4.Schematicillustrationofthepreparationoforganicphotothermalagentsbase