硅氧烷的水解-缩聚反应动力学

:(2003111A03);:(1982-),,,;*梁志超1,詹学贵2,单国荣1*,邵月刚2,翁志学1(1浙江大学化工系化学工程联合国家重点实验室(聚合反应工程实验室),杭州310027;2浙江新安化工集团股份有限公司,建德311600):():;;;,[1~3]:1硅氧烷的水解动力学2080,,[3]80,13CNMR29SiNMR,[3]11R3SiOR,,[4]RnSi(OR)4-n(0n3),Keefer[5]:OHOR,SiOR,SiOH,OR,Si(OR)44,,SiOSi[6,7]Kay[6],(TMOS),,TMOSORRo[7],(TEOS),McNeil[8]C6H5Si(OR)3[9]Pouxviel[10],TEOS,,PouxvielSanchez[11],TEOSTMOS,,,,[11]Sanchez[11](SN2):,H2OSi(),Si(OR)4SN2,:,OHOR,SiOH3111,Si,;,,OHOR,;,ORSi,O+RH,[11],[12,13],SN2,,,,ClCH2Si(OCH2CH2OCH3)3C3H7Si(OCH2CH2OCH3)31600[3],,,(HEODS)SiTEOS,[11],[14]TEOSMTEOS()DMDEOS(),,12TEOS[10,11,15,16],11~16kcalmol[7,11]Sanchez[11]:([HCl]110-3M),TEOS;Sefck[17]([HCl]110-2M),,;([HCl]=110-2M),[17]TEOS,[NH3]=056molL,[18],TEOS,,,[23]TEOS[18~22]TEOS,[TEOS][H2O]1[23][14]TEOS25kJmolOsterholtz[3]Taft,,*s5;,p*sSN213,,[5~7,9~11,24],Rankin[23]:ii+1,,,,(TMEOS)[4]Rankin[25],TMEOS,:(1)i;(2)i(i+1)2硅氧烷的缩聚反应动力学21211,,[3,26~28]Smith[29](MTMOS),,32200611Nishiyama[30],,Savard[26]Sefck[4],,29SiNMRDevreux[27]VTES()MTEOSTEOS,Vainrub[31],SiOHRankin[25],,,,;,,212Assink[32],TEOS,TEOS,,,,[10,16,32,33]TMOS[6],[34],TMOS;,,[34]Sefck[17][HCl],K=40;,,TEOS,,K=20;,TEOS,,;,[17]213Kelts[35]29SiNMRSanchez[36]TEOS,Baney[37](T)Zhang[38]MTEOS,Brus[39]TEOSNg[40](Q)Ng[41]Rankin[25](D)T,,,Ng[41]DTQ,Q,,TQ[36]D,,[25],,[(Et)2SiO]3[(Me)2SiO]3[32]D,[25]22,:[42]Rankin[43]MTEOSDMDEOS,,,Prabakar[44]29SiNMR17ONMRTEOS(Q)RTEOS(T)(),TQ,(kTTkTQkQQ),[42]Fyfe[45]TEOS3311MTEOS,:MTEOS080015TEOS1002,,,OH;,,;,[25]Sugahara[46],TQ,Rankin[25]:TQ,,,;,,[25],;DeWitte[47]TQDQ,:,,[25],,,TEOS[48],[25]3结束语(),,,,,,,参考文献:[1]Nikolic'L,Radonjic'L.CeramicsInternational,1998,24:547.[2],,.,1996,2:120.[3]OsterholtzFD,PohlER.JAdhedionSciTechnol,1992,6:127.[4]SefckJ,RankinSE,KirchnerSJ,McCormickAV.JNonCrystSolids,1999,258:187.[5]KeeferKD.BetterCeramicsThroughChemistry,ElsevierNorthHolland:NewYork,1984,p15.[6]KayBD,AssinkRA.JNonCrystSolids,1988,99:359;1988,104:112;1988,107:35.[7]RoJC,ChungJ.JNonCrystSolids,1989,110:26.[8]McNeilKJ,DiCapriJA,WalshDA,PrattRF.JAmChemSoc,1980,102:1859.[9]YangH,DingZ,JiangZ,XuX.JNonCrystSolids,1989,112:449.[10]PouxvielJC,BoilotJP.JNonCrystsolids,1987,94:374.[11]SanchezJ,McCormickAV.JPhysChem,1992,96:8973.[12]HookRJ.JNonCrystSolids,1996,195:1.[13]SchmidtH,ScholzeH,KaiserA.JNonCrystSolids,1984,63:1.[14]LiuRL,XuY,WuD,etal.JNonCrystSolids,2004,343:61.[15]DamrauU,MarsmannHC.JNonCrystSolids,1994,168:42.[16]FyfeCA,ArocaPP.ChemMater,1995,7:1800.[17]SefckJ,McCormickAV.CatalysisToday,1997,35:205.[18]BakaliI,RhessE,RousselotC,MercierR.CanJChem,1992,70:1612.34200611[19]BaileyJK,MecartneyML.ColloidsSurf,1992,63:151.[20]MatsoukasT,GulariE.JColloidInterfaceSci,1988,124:252.[21]BogushGH,ZukoskiCF.JColloidInterfaceSci,1991,142:1.[22]YoonHS,ParkHS,KimSH.HwahakKonghak,1994,32:557.[23]RankinSE,MacskoCW,McCormickAV.AIChEJ,1998,44,1141.[24]JadaSS.JAmCeramSoc,1987,70:298.[25]RankinSE,McCormickAV.ChemEngSci,2000,55:1955.[26]SavardS,BlanchardLP,LeonardJ,PrudhommeRE.PolymComposites,1984,5:242.[27]DevreuxF,BoilotJP,ChaputF.PhysRevLett,1990,65:614[28]BrinkerCJ.JNonCrystSolids,1988,100:31.[29]SmithKA.Macromolecules,1987,20:2514.[30]NishiyamaN,HorieK,AsakuraT.JColloidInterfaceSci,1988,124:14;1989,129:113.[31]VainrubA,DevereuxF,BoilotJP,etal.MaterSciEngB,1996,37:197.[32]AssinkRA,KayBD.ColloidsSurfA,1993,74:1.[33]SanchezJ,RankinSE,McCormickAV.IndEngChemRes,1996,35:117.[34]AssinkRA,KayBD.BetterCeramicsthroughChemistry,1990,p21.[35]KeltsLW,ArmstrongNJ.JMaterRes,1989,4:423.[36]SanchezJ,McCormickAV.JNonCrystSolids,1994,167:289.[37]BaneyRH,ItohM,SakakibaraA,SuzukiT.ChemRev,1995,95:1409.[38]ZhangZ,TanigamiY,TeraiR.JNonCrystSolids,1995,189:212.[39]BrusJ,KarhanJ,KotlkP.CollecCzechChemCommun,1996,61:691.[40]NgLV,ThompsonP,SanchezJ,etal.Macromolecules,1995,28:6471.[41]NgLV,McCormickAV.JPhysChem,1996,100:12517.[42]ParbakarS,AssinkRA.JNonCrystSolids,1997,211:39.[43]RankinSE,MacoskoCW,McCormickAV.JPolymSciPartA:PolymerChemistry,1997,35:1293.[44]ParbakarS,AssinkRA,RamanNK,etal.JNonCrystSolids,1996,202:53.[45]FyfeCA,ArocaPP.JPhysChemB,1997,101:9504.[46]SugaharaY,TanakaY,SatoS,KurodaK,KatoC.MaterResSocSympProc,1992,271:231.[47]DeWitteBM,CommersD,UytterhoevenJB.JNonCrystSolids,1996,202:35.[48]KimJ,PlawskeyJL,VanWagenenE,KorenowskiGM.ChemMater,1993,5:1118.KineticsoftheHydrolysisandPolycondensationofAlkoxysilanesLIANGZhiChao1,ZHANXueGui2,SHANGuoRong1,SHAOYueGang2,WENGZhiXue1(1StateKeyLaboratoryofChemicalEngineering,PolymerReactionEngineeringDivisionDepartmentofChemicalandBiochemicalEngineering,ZhejiangUniversity,Hangzhou310027,China;2ZhejiangXinanChemicalIndustryGroupCo.LTD,Jiande311600,China)Abstract:Inthispaper,areviewoftheliteraturesispresentedforthekineticsofthehydrolysisofalkoxysilanesandthecondensationofhomoandhetroalkoxysilanes.Themainfactorsthataffectthekineticsofhydrosisofalkoxysilanesarediscussed.Keywords:Alkoxysilanes;Hydrolysis;Polycondensation;Kinetics3511