CO2和环氧化合物合成环碳酸酯的研究

SynthesisofChloropropeneCarbonatefromCO2andEpichlorohydrinCatalyzedbyMagnesiumPorphyrinsspeaker:ChenXiaolinghost:LiuJinping2013/10/22IntroductionExperimentalResults＆discussionConclusionOutlineItroduction•chemicalfixationofcarbondioxide(CO2)fromcarbonresourcesandenvironmentalproblems.•inwhichthemostsuccessfulexampleistheatom-economycouplingreactionofCO2andepoxidestogeneratecycliccarbonates.IntroductionMaterials:•CO2epichlorohydrinCH2ClOReactionequation:IntroductionChloropropeneCarbonateTEA:triethylamineco-catalystCatalyst:meso-tetraphenylporphyrinmagnesium(MgTPP)IntroductionExperimental•step1SynthesisofMgTPPTPP(1mmol)Mg(Ac)2(6mmol)＋MgTPPrefluxing、stirring、recrystallizationExperimentalstep2Synthesisofthechloropropenecarbonateepichlorohydrin(50mmol)MgTPP(5.0×10-3mmol)TEA(6.25×10-3mmol)reactorCO21.5MPA140°C，8h.productcool++ResultsandDiscussionFourfactors:catalystamountreactiontemperaturereactionpressurereactiontimeEffectofthecatalystamount•withoutthecatalyst,only7%yield•theoptimalamountofcatalystwas5×10-3mmolbasedonthehigheryieldEffectofthereactiontemperature80°CyieldwasverylittleT↑,conversion↑,yield↑140°C↑,yield↓theoptimalreactiontemperaturewas140°CEffectofthepressurepressure↑,reactionrate↑,theconversion↑,andtheyield↑,tothemaximumatthepressureofCO2at1.5MPa(Entry4).EffectofthereactiontimeTheconversionincreasedwiththereactiontime.reached92%,whenthereactioncontinuedfor8h.Figure4UV-visspectraofmagnesiumporphyrininthecouplingreactionofCO2andepichlorohydrinItalsocouldbeconcludedthatthevalenceofmagnesiumionmaybeunchangedinthecouplingreactionaswell.ConclusionInsummary,anefficientmethodforpreparingchloropropenecarbonatehasbeendeveloped.Theoptimalreactionconditions:(epichlorohydrin50mmol,MgTPP5.0×10-3mmol,TEA6.25×10−3mmol,140°C,1.5MPa,8h),92%yieldofchloropropenecarbonatecouldbeobtainedandtheTONofcatalystwashighupto9200.References1.Ma,J.,Sun,N.N.,Zhang,X.L.,Zhao,N.,Mao,F.K.,Wei,W.,Sun,Y.H.,“AshortreviewofcatalysisforCO2conversion”,Catal.Today,148,221-231(2009).2.North,M.,Pasquale,R.,Young,C.,“SythesisofcycliccarbonatesfromepoxidesandCO2”,GreenChem.,12,1514-1539(2010).3.Xu,X.D.,Moulijn,J.A.,“MitigationofCO2bychemicalconversion:Plausiblechemicalreactionsandpromisingproducts”,EnergyFuels,10,305-325(2010).4He,L.N.,Wang,J.Q.,Wang,J.L.,“Carbondioxidechemistry:Examplesandchallengesinchemicalutilizationofcarbondioxide”,PureAppl.Chem.,81(11),2069-2080(2009).5Tian,J.S.,Miao,C.X.,Wang,J.Q.,Cai,F.,Du,Y.,Zhao,Y.,He,L.N.,“Efficientsynthesisofdimethylcarbonatefrommethanol,propyleneoxideandCO2catalyzedbyrecyclableinorganicbase/phosphoniumhalide-functionalizedpolyethyleneglycol”,GreenChem.,9(6),66-571(2007).6Ion,A.,Parvulescu,V.,Jacobs,P.,deVos,D.,“ScandZn-catalyzedsynthesisofcycliccarbonatesfromCO2andepoxides”,Appl.Catal.AGen,363,40-44(2009).Thankyouforyouratteneion!