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1、474Macromolecules2007,40,474-481VersatilePathwaytoFunctionalTelechelicsviaRAFTPolymerizationandClickChemistrySudershanR.Gondi,AndrewP.Vogt,andBrentS.Sumerlin*DepartmentofChemistry,SouthernMethodistUniVersity,3215DanielAVenue,Dallas,Texas75275-0314ReceiVedAugust24,2
2、006;ReVisedManuscriptReceiVedNoVember14,2006ABSTRACT:Twonovelazidofunctionalizedchaintransferagents(CTAs)werepreparedandsubsequentlyemployedtomediatethereversibleaddition-fragmentationchaintransfer(RAFT)polymerizationsofstyrene(Sty)andN,N-dimethylacrylamide(DMA)und
3、eravarietyofconditions.Trithiocarbonate2-dodecylsulfanylth-iocarbonylsulfanyl-2-methyl-propionicacid3-azido-propylesteranddithioester4-cyano-4-methyl-4-thiobenzoyl-sulfanyl-butyricacid3-azido-propylestersuccessfullymediatedthepolymerizationsofStyandDMA.BothRAFTpoly
4、merizationsexhibitedpseudo-first-orderkineticsandalinearMndependencewithconversion.Theresultinghomopolymers(Mn)4-22103g/molandMw/Mne1.33)weredemonstratedtohaveretainedöendgroupfunctionality,asevidencedbythesuccessfulformationofblockcopolymers.TheR-azidoterminalpol
5、ymersandtheazidofunctionalizedCTAswerecoupledwithhighefficiencybyclickchemistrytovariousalkynes(propargylacrylate,propargylmethacrylate,andpropargylalcohol)inthepresenceofaCu(I)catalyst,demonstratingtheabilitytopreparearangeoffunctionaltelechelicsandCTAs.Introducti
6、onpolymerization(ATRP)ornitroxide-mediatedpolymerization.14,22-37Forexample,Lutzetal.demonstratedthepreparationofControlled/livingradicalpolymerization(CRP)techniquesö-functionaltelechelicsfrompolymerspreparedbyATRPviafacilitatethepreparationof(co)polymerswithprede
7、terminedendgroupsubstitutionwithNaN3andsubsequentcouplingwithmolecularweights,narrowmolecularweightdistributions,and1variousfunctionalalkynes.31Wereportedthepreparationofhighdegreesofchainendfunctionalization.Whileresultingö-(meth)acryloylmacromonomersviaATRPandazi
8、de-alkyneincontrolcomparabletolivingionicpolymerizations,CRPcoupling.38Whilethisapproachprovedanefficientandspecificmethodscanbeconductedunderles
