CO-,2-與環(huán)氧丙烷不對稱共聚二元催化體系的設計及合成.pdf

1、大連理工大學碩士學位論文CO與環(huán)氧丙烷不對稱共聚二元催化體系的設計及合成姓名：彭雪明申請學位級別：碩士專業(yè)：應用化學指導教師：張英菊呂小兵20070620O＆與環(huán)氧丙烷不對稱共聚二元催化體系的設計及合成DesignandsynthesisofbinarycatalystsystemsfortheasymmetriceopolymerizationofCOzandpropyleneoxideAbstractThetetradentateS

2、chiifbasecompounds(designatedasSalenligand)，formedbythecondensationofsaUcylhydrideOritsderivativesandvariousdiaminocompounds，caneasilycomplexwithtransitionmetaliORSManyeffortshasbeendenotedtotheuseofbinarycatalystsystemc

3、onsistedofaSalenM(111)complexandanionicammoniumsaltororganicbaseinthecopolymerizationofC02andpropyleneoxideTheimprovedcatalyticactivity髂wellashighpolymerseleetivityandnarrowmolecularweightdistributionWerCusuallyobtainedi

4、nthesesystemsProminentamongthesebinarycatalystssystemsbeingthemostefficientforCOdepoxidescopolymerizationandinsomeeasesapproachtotheregio—and／orstereoselectivepolymerizationButtherestillremainsomeproblemstobefurthersolve

5、d，suchasthelowenantioseleetivity(eevalue)ofpoly(propoylenecarbonate)withregardtothelOWkineticresolutioncoefficient(廚d)Inthisthesis，onthebasisof‘doublechiralcentersinduction’，achiralbicyclicguanidineWasfirstsynthesizedand

6、usedaschimlnuclcophileofbinarycatalystsystembasedOnchiralSalenCo(111)N03aseleetrophilefortheasymmetrycopolymerizationofC02andracemicpropyleneoxideUnfortunately，compared、Ⅳiththeresultofthepreviousworkinourgroup，theenantio

7、selactivityoftheresultedpolycarbonatesdidnotshowobservableimprovement，probablybecausethechimlinductioneffectofchiralbicycliegnanidinetopropyleneoxideonlyaffectsattheverybeginningofthecopolymerizationduetothe“polymerchain

8、endcontrol”mechanismAlso，thesyntheticprocessofthechiralbieyelieguanidiuewasfurtheroptimizedFurthermore，anewchiralSalenCo(1lI)complexwasdesignedandsynthesizedBytheformationofCoObondofthephenyloxylinthediaminebackbonetothe

9、centralmetalionthetwistofthediaminebackbonehappened，andtheothersubstituentgroupofthediaminebackbonecouldbeforcedtoaxialpositionthustoincreasethestefichindrancen壕resulting($S)SalenCo(IHlcomplexinconjunctionwimanionicammon

10、iumsaltwasappliedinasymmetrycopolymerizationofC02andmcemicpropyleneoxide，butallthecatalyticactivity‰andpolymerselectivityarelowTheseresultsarereasonableaSsumpationthathigh《terichindranceofthe@固SalenCo([I])complexandlacko