导电性核壳型高分子材料的合成,导电性核壳型高分子材料的合成,.pdf

導電性核殼型高分子材料的合成、導電性核殼型高分子材料的合成、分析與應用分析與應用王立義國立台灣大學凝態科學研究中心講講 題題 大大 綱綱?導電性高分子簡介導電性高分子簡介?導電性高分子之應用介紹導電性高分子之應用介紹?核殼型導電高分子之結構與特性核殼型導電高分子之結構與特性?可撓式透明導電電極可撓式透明導電電極?製備與分析技術製備與分析技術PlasticsPlasticsPliability Lightweight strength Cheap cost of production Good electrical insulationInsulator in electricity cableInsulator in electricity cableHideki Shirakawa(Hideki Shirakawa(日本筑波大學材料學院日本筑波大學材料學院)Ziegler-NattaAcetylenePolyacetyleneTacticityTacticity-ControlControl100-fold excess of the Ziegler-Natta catalyst(By mistake)Silvery trans-polyacetylene film(Not Not a conductor)Copper coloured10-1010-9Scm-1toluenen-hexadecaneAcetyleneCCTi(Obu)4Et3Alciscis-PolyacetylenePolyacetylenetranstrans-PolyacetylenePolyacetyleneSilver coloured10-510-4 Scm-1T.Ito,H.Shirakawa and S.Ikeda,T.Ito,H.Shirakawa and S.Ikeda,J.Polym.Sci.,Polym.Chem.Ed.J.Polym.Sci.,Polym.Chem.Ed.1212,11,11-20(1974)20(1974)Alan Alan MacDiarmidMacDiarmid,Alan,Alan HeegerHeegerExplosive inorganic polymer:Explosive inorganic polymer:Poly(sulphurPoly(sulphur nitride)nitride)MetalMetal-Like Like Semiconductor at lowSemiconductor at low-T TPolyacetylenePolyacetyleneAgAg、CuCu10106 6S/cmS/cmTeflonTeflon1010-1616S/cmS/cm.+.103 S/cmI2or AsF5(oxidation)10-6 S/cmLi(reduction).Phys.Rev.Phys.Rev.LettLett.,39,1098(1977).,39,1098(1977)The 2000 Nobel Prize in ChemistryThe 2000 Nobel Prize in ChemistryThe Royal Swedish Academy of Sciences has decided to award the Nobel Prize in Chemistry for 2000 jointly toAlan J.HeegerUniversity of California at Santa Barbara,USA,Alan G.MacDiarmidUniversity of Pennsylvania,Philadelphia,USA,Hideki ShirakawaUniversity of Tsukuba,Japan for the discovery and development of conductive polymersfor the discovery and development of conductive polymersAdvantagesAdvantages?Light weight?Flexible?Easy Process?Cheap?VersatileExamples of currently widely used types of Examples of currently widely used types of conducting polymersconducting polymersConductivity of various metallic,semiconductor,Conductivity of various metallic,semiconductor,and insulting materialsand insulting materialsConductivities of conducting polymers vary widelyConductivities of conducting polymers vary widelyPotential Industrial Applications for Potential Industrial Applications for Conducting PolymersConducting Polymers?Antistatic Coatings?Cable Shielding?Electrodes,Sensors?Rechargeable Batteries?Electrochromic Smart-Windows?Flexible Light-Emitting Diodes?Field-Effect Transistor?Flexible Solar CellsPolypyrrolePolypyrrole-Coated Knitted Nylon FabricCoated Knitted Nylon Fabric?Static Dissipation?EMI Shielding?Radar-absorption?Highly efficient microwave absorptionPolymerPolymerColorColorUndopedUndopedDopedDopedblueblueblueblue-blackblackgreengreenlightlight-yellowredredyellowyellow-greengreenbluebluebluePolythiophenePolypyrrolePolyanilinePolyisothianaphtheneyellowblueElectrochromic WindowElectrochromic WindowGlassGlassPolymer electrolytePolymer electrolyteVGlassGlassITOITOConducting polymerConducting polymerGlassGlassITOITOLightLight-emitting emitting polymerpolymerMetal(CaMetal(Ca、MgMg、AlAl)UltrafastUltrafast,Reversible,Reversible,MetastableMetastable PhotoPhoto-Induce eInduce e-TransferTransfer?Strong luminescence of MEH-PPV is quenched by a factor in excess of 103?Luminescence decay time:0:550ps 60ps?ESR:triplet-triplet absorption signal(1.35 ev)disappearstrong spin:1/2 signalEnhance the charge carrier generationPrevent charge recombinationQuantum yield of photo-induced charge generation100 Photovoltaic DevicePhotovoltaic DeviceGlassGlassConducting polymerFullerenceFullerenceAlAlITOITOFlexible Solar CellFlexible Solar CellPV elements on flexible ITO coated PET(6 6 cm)MDMO-PPV/PCBMQ2%DisadvantagesDisadvantages?Rigid?Infusible?InsolubleImproving MethodsImproving Methods?Poly(alkyl-sbstituted aniline)?Doped with long alkyl chain acids?Blended with polymersPoly(alkylPoly(alkyl-substituted aniline)substituted aniline)HNNRRRNNRnH?Steric effect between side groupsSteric effect between side groups?Nonplanar conformationNonplanar conformation?Lower crystallinityLower crystallinity?Lower conductivityLower conductivityDoped with Functionalized Protonic AcidDoped with Functionalized Protonic AcidNNNNnHHHH+.+.SO3-RSO3-RCH3CH3H2COC12H25R=?Soluble in a variety of common organic solvents,such Soluble in a variety of common organic solvents,such as mas m-cresol,cresol,xylenexylene,chloroform,chloroform?Good conductivityGood conductivityY.Y.CaoCao et al.Synthetic Metal 48,91(1992)et al.Synthetic Metal 48,91(1992)Electron micrographs of extracted PANIElectron micrographs of extracted PANI-CSACSA-PMMA polyblends films initially PMMA polyblends films initially containing different concentration(in wt.%)of the PANIcontaining different concentration(in wt.%)of the PANI-CSA complex.CSA complex.(b)(b)(a)(a)(a)28.0%,(b)16.2%,(c)3.7%,(d)1.9%,(e)0.96%,(f)0.48%PANI-CSA(c)(c)(d)(d)(e)(e)(f)(f)Polyaniline/Polycaprolactone(PCL)Polyaniline/Polycaprolactone(PCL)Polyaniline/Poly(ethyleneterethphalate)Polyaniline/Poly(ethyleneterethphalate)ShackletteShacklette et al.et al.Synthetic MetalSynthetic Metal,55,3532(1993),55,3532(1993)Polyaniline ColloidsPolyaniline ColloidsCoreCore-Shell StructureShell StructurePotential ApplicationsPotential Applications?Corrosion inhibitorCorrosion inhibitor?Antistatic coatingAntistatic coating?Conducting adhesiveConducting adhesive?Flexible transparent conducting electrodeFlexible transparent conducting electrode透明導電膜的主要用途透明導電膜的主要用途液晶顯示器液晶顯示器有機發光二極體有機發光二極體高分子發光二極體高分子發光二極體電漿顯示器電漿顯示器電致發光體電致發光體有機太陽電池有機太陽電池電致變色材料電致變色材料觸控面板觸控面板車用防霜加熱條車用防霜加熱條航空器窗戶防霧航空器窗戶防霧透明導電膜種類透明導電膜種類InIn2 2O O3 3/polyester resin/polyester resin無機填充高分子膜無機填充高分子膜Polyethyleneglycol/LiClOPolyethyleneglycol/LiClO4 4離子性複合膜離子性複合膜PolypyrrolePolypyrrolePolythiopenePolythiopene derivativesderivatives導電性高分子膜導電性高分子膜有機有機材料材料InIn2 2O O3 3(Sn)(Sn)、ZnO(AlZnO(Al)氧化物半導體薄膜氧化物半導體薄膜TiOTiO2 2/Ag/TiO/Ag/TiO2 2BiBi2 2O O3 3/Au/Bi/Au/Bi2 2O O3 3複合膜複合膜CuCu、AgAg、AuAu、PdPd等等金屬薄膜金屬薄膜無機無機材料材料實實例例導導 電電 材材 質質種類種類工研院材料所工研院材料所透明導電膜基本特性需求表透明導電膜基本特性需求表0.50.5以下以下cc/mcc/m2 2-24hr24hr-atmatm氧氣氧氣、濕氣測定儀濕氣測定儀氣體透過率氣體透過率1515以下以下nmnm相位差儀相位差儀相位差值相位差值1.051.05倍倍8mm8mm，收捲來回收捲來回5050次次表面電阻變化值表面電阻變化值耐曲撓性耐曲撓性1.021.02倍倍摩擦摩擦100100次次表面電阻變化值表面電阻變化值耐磨耗性耐磨耗性1.01.0以下以下倍倍150150，3 3小時小時表面電阻變化值表面電阻變化值耐熱性耐熱性300300表面電阻計表面電阻計導電性導電性8585%分光光度計分光光度計(波長波長600 600 nm)nm)透明性透明性典型值典型值量測單位量測單位試驗法試驗法項目項目Display 1,58(1995)透明導電膜製作法透明導電膜製作法濺鍍法濺鍍法IonIon-platingplating真空蒸著法真空蒸著法成長法成長法化學蒸著法化學蒸著法塗佈法塗佈法網印印刷法網印印刷法成膜法成膜法方法方法製法種類製法種類透明導電膜製作法比較透明導電膜製作法比較較差較差良好良好薄膜性能薄膜性能較易較易難難塗佈時同時形成塗佈時同時形成線路圖形線路圖形高高低低原料利用率原料利用率大大小小成膜面積成膜面積簡單簡單複雜複雜儀器設備儀器設備塗佈法塗佈法成長法成長法比較項目比較項目ITOITO透明導電膜規格透明導電膜規格86862020-303015015083834040-6060808080807070-9090303082829090-13013025258585150150-19019014148080230230-2702707 77575310310-3503505 5透光率透光率(%550nm)(%550nm)ITOITO膜膜厚厚(nm)(nm)表面電阻表面電阻Display 1,42(1995)玻璃及塑膠面板性質比較玻璃及塑膠面板性質比較10101 1耐衝擊力耐衝擊力(相對相對)-3080 3080-3080 3080 儲存溫度範圍儲存溫度範圍-2070 2070-20702070作業溫度範圍作業溫度範圍在在40 40,95%RH95%RH下下10001000個小時個小時在在40 40,95%RH95%RH下下10001000個小時個小時可靠性可靠性250ms250ms250ms250ms反應時間反應時間8:18:18:18:1對比對比1.3g1.3g1.8g1.8g3.4g3.4g4.3g4.3g基板基板1.6g1.6g2.1g2.1g3.7g3.7g4.6g4.6gCellCell重量重量0.2mm0.2mm0.4mm0.4mm0.4mm0.4mm0.7mm0.7mm基板基板0.95mm0.95mm1.35mm1.35mm1.35mm1.35mm1.95mm1.95mmCellCell厚度厚度塑膠面板塑膠面板玻璃面板玻璃面板工研院材料所資料塑膠液晶顯示器構造圖塑膠液晶顯示器構造圖Insulating film(top coat)Insulating film(top coat)Hard CoatHard CoatGas BarrierGas Barrier塑膠基材ITOITOAlignment LayerAlignment LayerPolarizerPolarizerPolymer SubstratePolymer SubstrateSeal agentSeal agentLiquid CrystalLiquid CrystalLCDLCD用塑膠基材基本結構圖用塑膠基材基本結構圖Sputtering/EB PVDSputtering/EB PVDSolSol-gel/nano tech.gel/nano tech.阻氣性阻氣性2.52.5Gas BarrierGas BarrierExtrusionExtrusionFlowFlow-castingcastingSupportSupport200200-400400PlasticPlasticWet Coat/UVWet Coat/UV(nano tech)(nano tech)抗濕層抗濕層耐傷性耐傷性ITOITO密著性密著性耐溶劑性耐溶劑性5 5-1010Hard CoatHard CoatSputteringSputteringSolSol-gelgel導電層導電層0.050.05-0.10.1透明導電層透明導電層製法製法功能功能厚度厚度(m)m)層別層別可撓式可撓式LCDLCD對基材特性的需求對基材特性的需求TolueneTolueneMEKMEKAcetoneAcetoneEthanolEthanolMethanolMethanolChemical ResistanceChemical Resistance 1010nmnmSurface RoughnessSurface Roughness 3H3HPencil HardnessPencil Hardness 5050ppmppm/K/KCoefficient of Linear ExpansionCoefficient of Linear Expansion 150 150Glass Transition Temp.Glass Transition Temp.9090%Total Light Transmittance(at 550nm)Total Light Transmittance(at 550nm)0.5 0.5%HazeHaze 10 10nmnmBirefringenceBirefringence 15 15nmnmRetardationRetardation 1.5 1.5Refractive IndexRefractive Index 0.1 0.1cc/mcc/m2 2-daydayO O2 2PermeabilityPermeability 0.15 0.15g/mg/m2 2-daydayWater Vapor PermeabilityWater Vapor Permeability 0.20.2%Water AbsorptionWater Absorption100100-200200mmThicknessThicknessHard CoatHard CoatUnitUnit可撓式基材特性比較可撓式基材特性比較AlcoholAlcoholButylacetateButylacetateAcetoneAcetoneAcidAcidAlkalineAlkaline耐藥性耐藥性0.10.10.10.10.10.10.10.1g/mg/m2 2-dayday透溼度透溼度-151515151515cc/mcc/m2 2-atmatm-dayday透氧度透氧度1010 15 15 15 15 15 90 90%透光率透光率 10 10 10 10 10 10 1010NmNm表面平整性表面平整性100/200100/200100/150100/150100/130100/130 Pixel size/20 Pixel size/20ppmppm/溫度溫度熱收縮率熱收縮率505060606565 5050ppmppm/K/K熱膨脹係數熱膨脹係數180180160160130130150150連續使用溫度連續使用溫度PESPESPARPARPCPC基版基材基版基材要求要求水準水準單位單位項目項目=good,=poor,=only contactAGFAAGFA s s OrgaconOrgaconTMTM與與ITOITO透明導電膜比較透明導電膜比較可小至可小至1 1mm以下以下20 20 mm目前最小有效線寬目前最小有效線寬酸鹼液酸鹼液NaClO,KMnONaClO,KMnO4(aq)4(aq)蝕刻液蝕刻液10109 910101414不導電區域電阻不導電區域電阻凹凸排列凹凸排列平坦表面平坦表面(相對相對)線路作成後線路作成後表面形狀表面形狀蝕刻法蝕刻法將不須導通的區域將不須導通的區域予以氧化予以氧化deactivatedeactivate作線路方式作線路方式低低(金屬氧化物易剝落金屬氧化物易剝落)高高耐彎折能力耐彎折能力金屬氧化物金屬氧化物(ITO/IZO)(ITO/IZO)導電高分子導電高分子(PEDOT)(PEDOT)導電機制導電機制金屬氧化物透明導電膜金屬氧化物透明導電膜AGFAAGFA s s OrgaconOrgaconTMTM工研院材料所資料Optical Properties of Optical Properties of OrgaconOrgacon ELEL-350350Colloidal dispersions of conducting polymersColloidal dispersions of conducting polymers?StericSteric stabilizationstabilization-this involves polymers added to the system adsorbing onto the particle surface and causing repulsion.?This approach was used to produce stable dispersions,and improving the processability.Conducting polymer coreConducting polymer coreAdsorbed stabilizer layerAdsorbed stabilizer layerGeneral Criteria for Effective StabilizersGeneral Criteria for Effective Stabilizers?Strongly anchored to the particle surface for Strongly anchored to the particle surface for preventing desorption or surface migration of the preventing desorption or surface migration of the polymer during polymer during interparticleinterparticle collisioncollision?High surface coverageHigh surface coverage?Sufficient anchored layer thickness to the Sufficient anchored layer thickness to the minimum potential energy minimum potential energy GGminmin0.0.?The loops and tails of the anchored polymer The loops and tails of the anchored polymer should be associated with a good solvent should be associated with a good solvent environment in order to optimize the layer environment in order to optimize the layer thickness.thickness.Stabilizers for Polyaniline ColloidsStabilizers for Polyaniline Colloids?Water soluble polymersWater soluble polymers?TailorTailor-made polymersmade polymers?Particulate stabilizersParticulate stabilizers?SurfactantsSurfactantsWater soluble polymersWater soluble polymers?CarboxymethylcelluloseCarboxymethylcellulose?Ethy(hydroxyethyl)celluloseEthy(hydroxyethyl)cellulose?HydroxypropylcelluloseHydroxypropylcellulose?MethycelluloseMethycellulose?PolyacrylamidePolyacrylamide?Poly(acrylic acid)Poly(acrylic acid)?Poly(ethylene oxide)Poly(ethylene oxide)?Poly(methy vinyl ether)Poly(methy vinyl ether)?Poly(styrenesulfonic acid)Poly(styrenesulfonic acid)?Poly(vinyl alcohol)Poly(vinyl alcohol)?Poly(NPoly(N-vinylpyrrolidonevinylpyrrolidone)?Poly(vinylPoly(vinyl alcoholalcohol-coco-vinyl acetate)vinyl acetate)?ProteinProteinPolyaniline dispersion particles stabilized with hydroxypropylcellulose.PolymerPolymer 40(1999)248740(1999)2487TailorTailor-made polymersmade polymers?Graft copolymersGraft copolymers?Block copolymersBlock copolymers?Reactive polymersReactive polymersPolyaniline particles Prepared from Reactive Polyaniline particles Prepared from Reactive PolymersPolymersNH2NH2Add oxidantAdd oxidantActivation of pendant Activation of pendant aniline graft sitesaniline graft sitesAdd AnilineAdd AnilineIn situ polymerizationIn situ polymerizationPolyaniline Polyaniline particle coreparticle corePolyelectrolyte stabilizer containing Polyelectrolyte stabilizer containing reactive pendant aniline groupsreactive pendant aniline groupsPolyaniline particles using reactive polyelectrolyte stabilizers.EurEur.Polym.J.Polym.J.33(1997)24533(1997)245Inorganic Particulate StabilizerInorganic Particulate StabilizerParticle coreStabilizer overlayerStabilizer overlayer(A)(A)(B)(B)(C)(C)(D)(D)Aniline oligomersColloidal silicaParticulate stabilizersParticulate stabilizers?Silica?Manganese()oxide?Zirconium dioxide?Titanium dioxide?Polymer latexesPolyaniline Particles Stabilized with Nanocolloidal Silica.Free silica is visible on the background.MacromoleculesMacromolecules 29(1996)681429(1996)6814SurfactantsSurfactants?Sodium dodecyl sulfateSodium dodecyl sulfate?Dodecylbenzenesulfonic acidDodecylbenzenesulfonic acid?AOTAOTColloidal polyaniline particles prepared in the presence of dodecylbenzenesulfonic acidJ.Polym.Mater.J.Polym.Mater.18(2001)22518(2001)225Particle ShapeParticle ShapeThe particle shape and morphology of polyaniline may be affected by several factors-?StabilizerStabilizerNeedle-shape polyaniline particles(stabilizer:PVA)Spherical polyaniline particles(stabilizer:NaPSS)Anal.ChemAnal.Chem.69(1997)1030.69(1997)1030?StabilizerStabilizerNeedle-shape polyaniline particles using poly(ethylene oxide),M=300000,as stabilizer.Rice-grain polyaniline particles using a graft copolymer stabilizer based on poly(ethylene oxide).Chem.Commun.(1990)683Chem.Commun.(1990)683?OxidantOxidantTEM MicrographsTEM MicrographsRice-grain shaped PANI colloids,using KIO3as oxidantSpherical PANI colloids,using(NH4)2S2O8as oxidantJ.Colloid Interface Sci.J.Colloid Interface Sci.150(1992)134150(1992)134?TemperatureTemperature?The morphology of polyaniline particles may be different by changing the polymerization temperature of aniline.?The micrograph shows the particles formed in dispersion polymerization of aniline hydrochloride at different temperatures.20.40.0.Polymer Polymer 40(1999)248740(1999)2487?TemplateTemplate?Sun et al.found that the polymerization of aniline in a solution of poly(styrene sulfonic acid)yielded the globular structure while in the presence of poly(acrylic acid)it resulted in distinct coral-like morphology attributed to the template control in polymerization.TEM of PSSA-PANI complexSEM of PAA-PANI complexPolym.Prepr.Polym.Prepr.33(1992)37933(1992)379?SolventSolvent?Chattopadhyay found that the morphology of PANI particles stabilized with cellulose ethers was controlled by the composition of ethanol/water mixture.TEM of ethyl(hydroxyethyl)cellulosestabilized PANI dispersions prepared in 70%ethanol.TEM of ethyl(hydroxyethyl)cellulosestabilized PANI dispersions prepared in waterLangmuirLangmuir 14(1998)154414(1998