环氧乙烷和环氧丙烷开环聚合

:20061,:20062*(No.2004C31058)**e-mail:[e-mail]环氧乙烷和环氧丙烷开环聚合*张治国**尹红(浙江大学联合化学反应工程研究所杭州310027)环氧乙烷和环氧丙烷的开环聚合产物在表面活性剂工业和聚氨酯工业得到了极为广泛的应用本文综述了近几年来发展的用于环氧乙烷和环氧丙烷开环聚合的各类催化剂体系,分别讨论了各类催化剂体系对环氧乙烷和环氧丙烷的不同作用机制,考察了反应物结构对反应活性和选择性的影响,重点介绍了配位络合催化剂体系在环氧乙烷和环氧丙烷开环聚合反应中的应用,并指出了今后研究的方向环氧乙烷环氧丙烷开环聚合反应机理配位催化剂:O6315:A:1005-281X(2007)01-0145-08Ring-OpeningPolymerizationofEthyleneOxideandPropyleneOxideZhangZhiguo**YinHong(UNILABResearchCenterofChemicalReactionEngineering,ZhejiangUniversity,Hangzhou310027,China)AbstractPolyether(primarilyhomopolymersandcopolymersofethyleneoxideandpropyleneoxide)whichhasthepropertiesofexcellentsurfaceactivity,flexibilityofhydrophile_lipophilebalance(HLB)andlowtoxicityhasbeenwidelyusedinsurfactantandpolyurethaneindustries.Theprogressinthecatalyticring-openingpolymerizationofethyleneoxideandpropyleneoxideisreviewedinthispaper.Thedifferentcatalyticmechanismsofcationiccatalysts,anioniccatalystsandcoordinationcatalystsarediscussedrespectively.Theapplicationofcoordinationcatalystsinthecatalyticring-openingpolymerizationisintensivelyintroducedandthefurtherresearchtrendsarepointedout.Keywordsethyleneoxide;propyleneoxide;ring-openingpolymerization;reactionmechanism;coordinationcatalysts1,,30,;1939ScretleWotter;1940,,Du-Pont1953;Wyandotte1954(Pluronic)(Tetronic),,[16]80,,,Lewis,,,19120071化学进展PROGRESSINCHEMISTRYVol.19No.1Jan.,2007[714],3:2[9,14],(),,[7,8]RO-(1):,(),,,-2(42),SN2(5)(5)(6),,,,,,,,,,,,,,,;ROH,(5),,,(5000),4000050000(),,,,,,[15,16]Price[17],()(7)Simons[18]Steiner[19],,146化学进展19,,(8,9)Simons,,,,,;,Gee[20],(10,11)80,Conoco,[2126][27,28],,,,[2933]:,,,,,(12)(12),,,,,,,,3,,[811,14]:(1):,(13)(14)(),,(2)Lewis:LewisBF3SnCl4BF3H2OBF3OH2,(3):,,R+A-H+A-(4):,1471,,,,,(15),,(16),[34],,[12],,2-,4412060,DMC,doublemetalcyanidecomplexcatalysts[35],90,,DMC,,,DMC,[3639]2004,ImpactImpact,,Impact[40]DMC[37,38]Zn3[Co(CN)6]2xZnCl2yH2Ozcomplexingagents,DMC1[41]1tBuOHROHDMC[41]Fig.1ThestructureofDMCcatalystpreparedbyusingtBuOHandROH[41]DMCDMC,,148化学进展19,[42],,,,DMC,DMC,DMC[38](17)(20),S*,C*,,,[41]4270[43]()5,10,15,20-(TPPA-lX),2[44]2[44]Fig.2Aluminum-tetraphenylporphyrincomplex[44][4446]TPPA-lCl,[47]:::,AlO,AlO,-,,,,[48,49],,Lewis,,,43AlEt3Al(iBu)3ZnEt2MgEt2,,1491[50]-(Fe(acac)3-Al(iBu)3)[5154],,R2Al(acac)-H2O-Et2Zn,AlOAl,3[50]3R2Al(acac)-H2O-Et2Zn[50]Fig.3ThestructureofR2Al(acac)-H2O-Et2Zn[50],LewisLewis,,,,,[52](23)441985,,Ziegler()[55,56]Nd(P204)3-Al(iBu)3-H2O[57][4][4]--[58,59],[59][56],Nd(P204)3-Al(iBu)3-H2O,,Al(iBu)3Nd(P204)3(24)NdOAl(25)45,(phosphazene,PZN),PN,[6062]DMC,,34[6062]4(a)[62],:QC1C20;DC1C20,P2DDQ;lmn003,,,,,4(b)[61,6366],,RC1C10,N2R;ad003;Zn-n,,,,150化学进展194[6062]Fig.4Thestructuresofphosphazenecatalysts[6062]4(c)[67],POP+O-,[68]Dow,-,[69]46Peretti[70]Co,,,55,23,,,5Co[70]Fig.5Synthesisofcobaltcatalystandisospecificpolymerizationofrac-propyleneoxide[70],,,,,[1](QianBZ).(ChemicalPropellants&PolymericMaterials),2004,2(6):5153[2](ZhangW).(ChemicalTechnologyMarket),2003,26(12):57[3](ZhangJ).(ChinaSurfactantSoapandDetergent),2004,(6):6870[4]BurridgeE.Eur.Chem.News,2004,80(2095):17[5]BurridgeE.Eur.Chem.News,2004,80(2100):15[6]XiZW,ZhouN,SunY,LiKL.Science,2001,292:11391141[7](ZhangZG),(YinH),(ChenZR).:(ActaPetroleiSinica:PetroleumProcessingSection),2005,21(1):3136[8](ZhangZG),(YinH),(ChenZR).(ActaChimiaSinica),2004,62(20):19881992[9]OdianG.PrinciplesofPolymerization.3rded.NY:JohnWiley&Sons,1991.532558[10]WorsfoldDJ,EasthamAM.J.Am.Chem.Soc.,1957,79(4):897899[11]WorsfoldDJ,EasthamAM.J.Am.Chem.Soc.,1957,79(4):9009021511[12]KuranW.Prog.Polym.Sci.,1998,23:919992[13]BoileauS.ComprehensivePolymerScience(eds.EastmondGC,LedwithA,RussoS,etal).London:PergamonPress,1989.467487[14](ZhuSX).(Ring-OpeningPolymerization).:(Beijing:ChemicalIndustryPress),1987.4772[15](WangM),(WeiXZ),(HuangPC).(ChemicalWorld),1997,38(2):5964[16]DegeGJ,HarrisRL,MackenzieJS.J.Am.Chem.Soc.,1959,81(13):33743379[17]PierreLES,PriceCC.J.Am.Chem.Soc.,1956,78(14):34323436[18]SimonsDM,VerbaneeJJ.J.Polym.Sci.,1960,44(144):303311[19]SteinerEC,PelletierRR,TrucksRO.J.Am.Chem.Soc.,1964,86(21):46784686[20]GeeG,HigginsonWCE,TaylorKJ,TrenholmeMW.J.Chem.Soc.,1961,42984303[21]YangK,NieldGL,WashecheckPH.US4223164,1980[22]YangK.US4239917,1980[23]YangK,NieldGL,WashecheckPH.US4302613,1981[24]YangK,NieldGL,WashecheckPH.EP49358,1982[25]YangK,WashecheckPH,NieldGL.EP34648,1981[26]YangK,NieldGL,WashecheckPH.EP85167,1983[27]SmithG,SawyerWMJR,MorrisRC.US3682849,1982[28]McCainJH,TheilingJLF.US4453023,1984[29]ReikichiW,HiromutsuW.J.Am.Chem.Soc.,1976,98(13):37643768[30]ShozoY,KazutomoT,MitsuoO.Bull.Chem.Soc.Jpn.,1977,50(6):13861390[31]MathesonKL,CoxMF.RivistaItalianadelleSostanzeGrasse,1995,72(9):391395[32]SallayP,MorgosJ,FarkasL,etal.TensideDetergents,1980,17(6):298300[33]ZiegenhainWC,JacksonRT,RoseL.US4254287,1981[34]YodhifaNN.JP02227426,1991[35]JohnstonHR.US3278459,1966[36](WuLC),(YuAF),(ZhangM).(ActaPolymericaSinica),2003,(6):871874[37](YanZR),(YangSY),(YuAF).(PolymerBulletin),2001,(5):16[38](HuangYJ),(QiGR),(FengLX).(ActaPolymericaSinica),2002,(3):271275[39]Paz