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1、JOURNALOFCATALYSIS125,390-400(1990)MechanismofActive-SiteFormationinCopper-CatalyzedSynthesisofTrimethoxysilanebytheReactionofSiliconwithMethanolEIICHISUZUKIANDYOSHIOONODepartmentofChemicalEngineering,TokyoInstituteofTechnology,Ookayarna,Meguro-ku,Tokyo152,JapanReceivedJa
2、nuary3,1990;revisedApril23,1990Thedirectsynthesisoftrimethoxysilanewascarriedoutbyfeedingmethanolat513Ktoamixtureofsiliconandcopper(l)chloridewhichhadbeenheat-treatedunderaheliumstreaminafixed-bedreactorat533-773Kfor3h.Siliconconversionincreased,butselectivitytowardtrimet
3、hoxysilanedecreasedwithincreasingtemperatureoftheheattreatment.Maximumyieldwasobtainedafterthetreatmentat723Kwithasiliconconversionof98%andaselectivityof82%in3h.Whentheheat-treatmentiscarriedoutabove623K,theformationoftrimethoxysilanestartsjustafterthefeedofmethanol,while
4、aninductionperiodisobservedwhenthetemperatureoftheheat-treatmentisbelow573K.Intheformercase,thesurfaceofsiliconisexposedtocopper(I)chloridevapororthemelttogiveanintermetallicphase,Cu3Si.Inthelattercase,methanoltakespartintheformationoftheintermetallicphase.Uponthesilicon-
5、methanolreaction,pitsareformedonthesiliconsurface.Theirsizeincreaseswithincreasingsiliconconversion.©1990AcademicPress,Inc.INTRODUCTIONconandcopper(I)chloride.Thus,a90%selectivityfortrimethoxysilanetogetherThecopper-catalyzedreactionofsiliconwithahighsiliconconversionwaso
6、btainedwithmethylchloridetogivemethylchlorosi-whenmethanolwasfeddropwiseintoasus-laneswasdiscoveredbyRochow(1,2)inpensionofsiliconandcopper(I)chloridein,1945.Thedirectsynthesisisakeystepine.g.,dodecylbenzeneordiundecylbenzenethesynthesisofsilicon-containingmaterialsat493-
7、513Kfor5.5-10h(6-9).However,suchassiliconepolymersandnumerousor-whenthereactionwasconductedinafluid-ganosiliconchemicals(3).izedbedreactorat618Kusingasili-Siliconisknowntoreactalsowithmetha-con-copper(I)chloride-zincmixturewhichnol.Thus,in1948,Rochow(4)reportedthathadbeen
8、preheatedat623Kpriortothetetramethoxysilanewasobtainedwhensili-contactwithmethanolvapor,trimetho
