导电高分子PPT讲稿.ppt
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1、导电高分子第1页,共85页,编辑于2022年,星期六Introduction第2页,共85页,编辑于2022年,星期六Polymerswerethoughtofaselectrialinsulatorsuntilthediscoverythatiodine-dopedpolyacetylene(聚乙炔)exhibitedelectricalconductivitymanyordersofmagnitudehigherthanneutralpolyacetylene.ThisdiscoverywaspublishedbyShirakawa,H.,Louis,E.,MacDiarmid,A.,He
2、eger,A.,(1977).Asaresultofthispioneeringwork,theyreceivedthe2000NobelPrizeinChemistry.Introduction第3页,共85页,编辑于2022年,星期六Nobel Prize in Chemistry 2000“For the discovery and development of conductive polymers”G.MacDiarmid H.Shirakawa J.Heeger第4页,共85页,编辑于2022年,星期六黑格(黑格(Alan J.Alan J.Heeger,1936Heeger,19
3、36 )美美国国加利福尼亚大学的加利福尼亚大学的著名物理学家,著名物理学家,20002000年年1010月月1010日,因对导日,因对导电聚合物的发现和发电聚合物的发现和发展而获得诺贝尔化学展而获得诺贝尔化学奖。奖。Introduction第5页,共85页,编辑于2022年,星期六麦克迪尔米德(麦克迪尔米德(Alan Alan G.MacDiarmidG.MacDiarmid,19371937 )美国美国宾夕法尼亚大宾夕法尼亚大学的学的著名化学家,著名化学家,20002000年年1010月月1010日,日,因对导电聚合物的发因对导电聚合物的发现和发展而获得诺贝现和发展而获得诺贝尔化学奖。尔化学
4、奖。Introduction第6页,共85页,编辑于2022年,星期六白川英树白川英树(Hideki(Hideki ShirakawaShirakawa,19361936 )日本筑波大学的著名日本筑波大学的著名化学家,化学家,20002000年年1010月月1010日,因对导电日,因对导电聚合物的发现和发聚合物的发现和发展而获得诺贝尔化展而获得诺贝尔化学奖。学奖。Introduction第7页,共85页,编辑于2022年,星期六ConductivityIntroduction第8页,共85页,编辑于2022年,星期六Thediscoveryofconductivepolymersisuniqu
5、einitsaccomplishmentasapossiblesubstitute(替代物替代物)formetallicconductorsandsemiconductors.Scientistsfrommanydisciplinesarenowcombiningexpertise(专门技术)tostudyorganicsolidsthatexhibitremarkableconductingproperties.Alargenumberoforganiccompounds,whicheffectivelytransportchargeareroughlydividedintothreegro
6、upsi.e.chargetransfercomplexes/ionradical(基基)salts,organometallicspeciesandconjugatedorganicpolymers.Introduction第9页,共85页,编辑于2022年,星期六Electronicallyconductingpolymersdifferfromallthefamiliarinorganiccrystallinesemiconductorsintwoimportantfeaturesthatpolymersaremolecularinnatureandlacklongrangeorder.
7、Akeyrequirementforapolymertobecomeintrinsically(本征本征)electricallyconductingisthatthereshouldbeanoverlapofmolecularorbitalstoallowtheformationofdelocalized(离域离域)molecularwavefunction.Besidesthis,molecularorbitalsmustbepartiallyfilledsothatthereisafreemovementofelectronsthroughoutthelattice.Introducti
8、on第10页,共85页,编辑于2022年,星期六Conductingpolymerscontain-electronbackboneresponsiblefor(是的原因)theirunusualelectronicpropertiessuchaselectricalconductivity,lowenergyopticaltransitions,lowionizationpotentialandhighelectronaffinity.Thisextended(延长延长)-conjugatedsystemoftheconductingpolymershavesingleanddoublebo
9、ndsalternatingalongthepolymerchain.Thehighervaluesoftheelectricalconductivityobtainedinsuchorganicpolymershaveledtothenamesyntheticmetals.Introduction第11页,共85页,编辑于2022年,星期六IntroductionThedevelopmentofpolymerswithconductivitiesequaltosemiconductorsandmetalshavebeenpresentedinTable1andtheircorrespondi
10、ngstructuresareshowninFig.1.第12页,共85页,编辑于2022年,星期六Introductionisothianaphthene:异硫茚;异硫茚;azulene:甘菊蓝;甘菊蓝;furan:呋喃呋喃第13页,共85页,编辑于2022年,星期六IntroductionPoly-acetylenePolypyrrolePolythiophenePolyanilinePoly-p-phenylenePoly-phenylenevinylenePoly-p-phenylenesulphidePoly-iso-thianaphthene第14页,共85页,编辑于2022年,星
11、期六Historical background of electronically conducting polymers第15页,共85页,编辑于2022年,星期六Historical background of electronically conducting polymersResearchonconductingpolymersintensified(增强)soonafterthediscoveryofpoly(sulphurnitride)(SN)xin1975whichbecomessuperconductingatlowtemperatures(Greeneetal.,1975
12、).Although,conductingpolymercomplexesintheformoftetracyano(四氰基)andtetraoxalato-platinates(四草酸铂酸盐),theKrogmansaltschargetransfercomplexeshadbeenknownearlier,thesignificanceliesintherediscoveryofPAin1977(initiallydiscoveredbyShirakawaetal.,1977usingaZieglerNattatypepolymerizationcatalyst)byMacDiarmida
13、ndHeeger,UniversityofPennsylvania(宾夕法尼亚).重视第16页,共85页,编辑于2022年,星期六TheywereabletoenhancetheelectricalconductivityofPA(109Scm1)byseveralordersi.e.105Scm1bysimpledopingwithoxidizingagentse.g.I2,AsF5,NOPF6(p-doping)orreducingagents(n-doping)e.g.sodiumnapthalide(萘钠).Thishasgeneratedrenewedinterestofthesci
14、entificcommunitytowardsthestudyanddiscoveryofnewconductingpolymericsystems.Historical background of electronically conducting polymers第17页,共85页,编辑于2022年,星期六Poly-paraphenylene(对苯基)wassynthesizedbyIvoryetal.(1979).Itformshighlyconductingchargetransfercomplexeswithbothnandptypedopants.DopingwithAsF5inc
15、reasesitsconductivitytoitsvaluesfrom105to500Scm1.TheoreticalmodelsandelectronspinresonancemeasurementsindicatethatthechargetransportinPPPisapolaron(极化子)/bipolaron.PPS(聚苯硫醚)wasthefirstnon-rigid,butnotfullycarbonbackbonelinkedconductingpolymer.Itsdiscoverywasparticularlyexciting,sinceitspropertyofsolu
16、tionprocessabilityopenedthedoorforpotentiallyobtainingcommerciallyviableconductingplastics(Raboltetal.,1980).Historical background of electronically conducting polymers第18页,共85页,编辑于2022年,星期六Amongstpolyheterocyclines(聚杂环聚杂环),polypyrrole(PPY)hasbeeninvestigatedthemost.Theelectrochemicaloxidationofpyrr
17、oleinaqueousH2SO4canbecarriedoutonplatinumelectrode.TheproductisaconductingpolymerknownasPyrroleBlackKanazawaetal.(1979)producedcoherentfilmsofPPYwithaconductivityof100Scm1andexhibitedexcellentairstability.Butthemainhindrance(障碍)ofitsprocessabilityisinitsinsolubilityinanyorganicsolvents.Historical b
18、ackground of electronically conducting polymers第19页,共85页,编辑于2022年,星期六PTH(聚噻吩)showsremarkablestabilityofbothoxidized(p-doped)conductingformanditsneutral(undoped)insulatingforminbothairandwater.Itshowshighdopinglevelupto50%whichmaybeattributedtoitspartiallycrystallinenaturethathasbeenconfirmedbyX-rayp
19、hotoelectronspectroscopystudies.Manyotherconductingpolymerssuchaspolyfuran(聚呋喃聚呋喃),polyindole(聚吲哚聚吲哚),polycarbazole(聚咔唑聚咔唑),polyanilineetc.havealsobeensynthesized.StructuresofsometypicalconductingpolymershavebeenshowninFig.1.Historical background of electronically conducting polymers第20页,共85页,编辑于202
20、2年,星期六Synthesis of conducting polymers第21页,共85页,编辑于2022年,星期六Thereisnosingularmethodforsynthesisingpolymersthatcanbetransformedintoconductivepolymers,theincorporationofextended(延长延长)-electronconjugation(共轭共轭)isofforemostimportance.Conductivepolymersexceptionomeric(离子交联的)polymersmaybesynthesisedusings
21、tandardmethodsofpolymerisationincludingconventionalaswellasspecificrouteswhichincludeWitting(维狄希),Horner(霍纳)andGrignard(格林尼亚)reactions,polycondensationprocessesandmetalcatalysedpolymerisationtechniques.Oxidativecoupling(偶合)withoxidisingLewisacidcatalystsgenerallyleadstopolymerswitharomaticorheterocy
22、clicbuildingblocks(构件构件).Synthesis of conducting polymers第22页,共85页,编辑于2022年,星期六Conductivepolymersmaybesynthesisedbyanyoneofthefollowingtechniques:1.Chemicalpolymerisation2.Electrochemicalpolymerisation3.Photochemicalpolymerisation4.Metathesis(复分解)polymerisation5.Concentratedemulsion(浓乳液浓乳液)polymeris
23、ation6.Inclusion(夹杂)polymerisation7.Solid-statepolymerisation8.Plasma(等离子体)polymerisation9.Pyrolysis(高温分解)10.Solubleprecursor(前体)polymerpreparationSynthesis of conducting polymers第23页,共85页,编辑于2022年,星期六Amongalltheabovecategories,chemicalpolymerisationisthemostusefulmethodforpreparinglargeamountsofcon
24、ductivepolymers,sinceitisperformedwithoutelectrodes.Chemicalpolymerisation(oxidativecoupling)isfollowedbytheoxidationofmonomerstoacation(阳离子)radicalandtheircouplingtoformdicationsandtherepetition(重复)ofthisprocessgeneratesapolymer.Alltheclassesofconjugatedpolymersmaybesynthesisedbythistechnique.Synth
25、esis of conducting polymers第24页,共85页,编辑于2022年,星期六Electrochemicalpolymerisationisnormallycarriedoutinasingle-ordual-compartment(隔间隔间)cellbyadoptingastandardthree-electrodeconfigurationinasupportingelectrolyte,bothdissolvedinanappropriate(适当的适当的)solvent.Electrochemicalpolymerisationcanbecarriedoutpote
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