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CatalysiswithIonicLiquids:ProgressandProspectsYouquanDENGCentreforGreenChemistryandCatalysisLanzhouInstituteofChemicalPhysicsChineseAcademyofSciencesLanzhou,730000,China1.INTRODUCTION:WhatareionicliquidsRoomtemperatureILscontainorganiccationsandinorganicanionsNNR2R1R3R5R4NR1R6R5R4R3R2NR1R4R3R2+PR1R4R3R2+N-alkylimidazoliumN-alkylpyridiniumquaternaryammoniumquaternaryalkylphosphoniumFunctionalgroupse.g.X=NH2,SO3H,CO2H,etc.incorporateduponthesidechainofImidazolium[CF3COO]-[CF3SO2]-[BF4]-[PF6]-[(CF3SO2)2N]-AirandwaterstableDecreasingcoordinatingabilibityIncreasinghydrophobicitySecondgenerationILsTypicalcations[AlCl4]-[AuCl4]-[PdCl4]2-TypicalanionsReactivetowaterFirstgenerationILsFunctionalILsThirdgenerationILsNew!ChloroaluminateNNR2R1R-XR5R41.INTRODUCTION:PropertiesofionicliquidsLowermeltingpoint:＜-90oCNegligiblevaporpressure:GreensolventsLargeliquidrange＞200oCSelectivedissolvability:‘liquid’zeoliteDesignable:Acidity,Density,HydrophilityDiversity:overatrillionpossibleGoodelectrechemicalsatbility:E.W.ca5VHighthermalstability400oCILscontaning1-alkyl-3methylimidazoliumcationsStrongcoulombicforce:MuchdifferentfrommolecularsolventsILspossesssomespecialphysicalandchemicalpropertiesreasonablygoodelectricalconductivity(25mS/cm)1.INTRODUCTION:GeneralsituationofILsresearchca.200papershaveappearedonthe226thACSNationalMeetingHundredspatentsonILshavealsobeenissuedCatalysisOrganicsynthesisSeparation&analysisFunctionalmaterialslifesciencesThefigureillustratesthegrowthinpublicationsonILsAtleastanother500paperswillappearedbytheendof2003TherehasbeenmuchworkperformedonILsasreactionmediaorfunctionalmaterialsLubricants,sensing&opticalmaterialsStationaryphaseforGC,treatingnuclearwasteElectrochemistryNanotechnologyCleanenergyHeack,BeckmannetcNano-metalparticles,filmElectrolytes,ElectrodepositionElectrolytesforsolarcell,batteryArtificialmuscle,drugreservoirs1.INTRODUCTION:GeneralresearchsituationofcatalysiswithILsILsascatalystsorreactionmediahavebeenreportedtohaveexcellentperformancesformanycatalyticreactionsCatalyticreactionsusingILsasreactionmediaCatalyticactivityenhancedSelectivityimprovedEnzymecatalysisCatalyststabilityimprovedILsbiphasicsystemSeparationofdesiredproductsfromreactionwassimplifiedILsusedassubstituteofvolatileorganicsolventsCatalyticreactionmaybecomegreener2.PROGRESS:CatalysiswithILs—BiocatalysisinILsLipase-CatalyzedPolytransesterificationofDVAandBDTheuseofILstoreplaceorganicsolventsinbiocatalyticprocesseshasrecentlygainedmuchattention+nHOOHdivinyladipateButanediollipaseOOOOOOOO()n2n-1+OHCH3CHOJ.Am.Chem.Soc.,2003,byA.J.RusselletalPolyesterThefigureillustratesLipasepossesshigheractivityandstabilityinBMIMPF6ILthanthatintetrahydrofuranNoreactionoccurredinthehydrophilicILSinvestigated,egBMIMNO3DVABDNovozym435&porcinepancreaticlipaseintetrahydrofuranNovozym435&porcinepancreaticlipaseinBMIMPF6At50oCinthepresenceofDVAandBD2.PROGRESS:CatalysiswithILs—FunctionalILsRecently,functionalILs,egBronstedacidicILsusedassolvent-catalystweredevelopedJ.Am.Chem.Soc.,2002,byJ.H.Davis,Jr.etalSulfonicacidgroupwasincorporatedSolidacids,duetonon-volatility,arebeingmorewidelyused,buttheyhaveshortcomingsaswellSuchBronstedacidicILhasnegligiblevaporpressure,andissomekindof‘solidlike’liquidacidNearly100％ofesterselectivityachievedIsolationofdesiredproductscanbeobtainedbyasimpledistillationTheILcouldbereusedSuchBronstedacidicILsisalsoaneffectivecatalystsforesterificationofalkeneswithaceticacidOHO+OOOOContinuous-flowhydromylationinaScCO2-ILbiphasicsystemhasbeensuccessfullyestablished2.PROGRESS:CatalysiswithILs—CombinationwithScCO2Science,2003,byD.J.Cole-HamiltonAdiagramofcontinuous-flowhydromylationinaScCO2-ILbiphasicsystemHigheraldehydeselectivityHigherratioofthelinear:thebranchedHydroformylationofhexenecatalysedbyRhcatalystSolventCon.%Sel.%1:bBMImPF69915.72:4BMImPF6+scCO24083.56:1PROGRESS:CatalysiswithILs—DimerizationofalkenesTheInstitutFrancaisduPétrole,IFPlaunchedthefirstcommercialprocessbasedonILs,knownastheDifasolprocess+NicomplexionicliquidTypicalDifasolprocess:butenesdimerizationtooctenesbasedonnickel(II)saltinionicliquid.IFPclaimthattheDifasolprocesswasmuchbetterthanotherdimerisationprocessesandwithoutanyothersolventAcontinuousrunhasbeencarriedoutoveraperiodof5500h,andbuteneconversionandselectivitywerestablePhaseseparatorDifasolreactionsectionSeparationofILandproductoccursrapidlyandcompletelyduetoinsolubilityIonicLiquidsinsynthesis,2002,byP.Wasserscheidetal2.PROGRESS：CatalysiswithIonicliquidsonlargescaleBASF'SSMARTIL:thefirstcommercialuseoftheILsinanorganicprocessIntelligentILseparatesaslowerphasefromproductROHR3PClNNNHN+Cl-NHN+Cl-R3PORdeprotonation&recyclingR3PClROHNNR3PORNHN+Cl-+++UsingN-methylimidazoletoscavengeacidthatisformedintheprocess.N-methylimidazoleisalsoacatalystHmIm-ClIL,formedduringreaction,separateasaclearliquidphasefromtheproductHmIm-Cl,afterdeprotonation,itcanbedistilledlikeanyotherorganicsolventandcanberecycledSuchprocessisonamultitonscaleinbatchreactorwithoutproducingsolidsManufacturingProcessofalkoxyph