复旦 高分子化学课件for copy NMRP.pptxVIP

Controlled/“living”radicalpolymerizationAnewtoolformacromoleculardesign高等高分子化学

ContentsFUDANIntroduction:conventionalandcontrolledradicalpolymerization(CRP)briefhistoryofCRPNitroxidemediatedradicalpolymerization(NMP)NMP:mechanismandelementaryreactionsNMP:specifickinetics–thepersistentradicaleffect(PRE)LimitationsofNMPExploringthenewnitroixdesMacromoleculardesignbyNMPReversibleradicalcoupling:ausefulreaction..Industrialapplication9.

Kineticfeature:slowinitiationfastpropagationrapidterminationCtMnCWiMnConventionalradicalpolymerizationFUDAN三个问题：1)MMA端基；2)MMA+St；3)无kt

Non-livingPolymn.LivingPolymn.Controlled/“Living”RadicalPolymn.ConventionalRadicalPolymn.ConventionalandcontrolledradicalpolymerizationFUDAN(ATRP)(RAFT)(NMRP)Anionic

IdeaforcontrolledradicalpolymerizationFUDANTheoriginofthenon-livingnessofconventional:Protectingthepropagatingradicals!!

1980s.Otsu:initiator-transfer-terminator:iniferter1987.CSIROgroup:.auNitroxideinMMAPolymn.1993.Georges:NitroxideinSt.Polymn.XeroxinCanada1995.Hawker:AlkoxyamineIBMAlmaden1995.WangandMatyjaszewski:ATRPCarnegieMellonSawamotoandcoworkers:1998.CSIROgroup:RAFT-basedPolymn.dithioesterHistoryofCRPFUDANSFRP

FUDANTerminology…Namesthathavebeenusedintheliterature:Controlledradicalpolymerization;livingradicalpolymerization;Controlled/”living”radicalpolymerization.IUPACrecommendation:Reversible-deactivationradicalpolymerization(RDRP).IUPACpermitted:Controlledradicalpolymerization(CRP).IUPACdiscouraged:Nameswith“living”Livingradicalpolymerization;Controlled/”Living”radicalpolymerization;Quasi-livingradicalpolymerizationSpecificnomenclaturerecommendedbyIUPAC:Stableradicalmediatedpolymerization(SRMP);Nitroxidemediated(radical)polymerization(NMPorNMRP);Organometallic-mediatedradicalp