高分子化学课件：for copy-ATRP.ppt

1、Atom Transfer Radical PolymerizationAtom transfer radical polymerizationThe first paper:Mechanism of ATRPMolecular weight and distributionKineticsMonomers: wider suitabilityStyrenics:Methacrylates:Monomers: wider suitabilityAcrylates:Initiators1. Alkyl halides:Initiators2. -haloesters, ketons and ni

2、trilesInitiators3. Sulfonyl halides: much faster initiation, easy to generate, hard to terminate, high efficiency.Theoretical resultsLigandsMetal complexesMacromolecular engineering by ATRPTerminal functionalization:Dendritic-linear diblock copolymerPolymer brushes: densely grafted copolymersATRPSta

3、r-like polymersHyperbranched polymersSelf-condensing vinyl polymerization:Compositional controlSummarySynthetic strategy of star polymers using ATRPStar polymers with exact number of arms;Star polymers with crosslinked core;Linear macroinitiator as the chain precursor:“Arm first” approachLinear macr

4、omonomer as the chain precursor:Synthetic strategy of star polymers using ATRP“Core first” approachLinear macroinitiator vs. macromonomer:“Arm first” approachSteric saturation stateChain end-linking:Macroinitiator approachCore cross-linking:Drawback:Star-Star couplingAn example of “Arm first” synthe

5、sisCore functionalized star polymer:“Arm first” approachThe crosslinkersBy “in-out” method:MiktoarmsBy “co-linking” method:“Core-first” approachStar from in-situ generated coreOne-potsynthesis of hairy nanoparticles in emulsionHairy nanoparticlesComparison of different systemsIn atom transfer radica

6、l copolymerization, or any kind of livingcopolymerization, of vinyl and divinyl monomer, the addition of the latter determines the structure of the final product. More homogenous gels by CRP:O OHCrosslinking reaction: synthesis of networksReverse ATRPMtn+1XY /LMtn Y /Lan example of St polymn. at 110

7、 C:PRE shifts the equilm. to dormant species.Are PRE affects ATRP? YES !Catalyst very easy to be oxidized by O2.Simultaneous reverse and normal initiation:SR&NI ATRPAn example of SR&NI ATRPBlock copolymerization of SR&NI in miniemulsionICAR ATRPinitiators for continuous activator regeneration(ICAR)

8、ATRPMatyjaszewski, K. et al PNAS 2006, 103, 15309-15314Theoretical PDI:Results of ICAR ATRPMatyjaszewski, K. et al PNAS 2006, 103, 15309-15314NORkdkcNOR+Results of ICAR ATRP of styreneMatyjaszewski, K. et al PNAS 2006, 103, 15309-15314Activators generated by electron transfer:AGET ATRPMin, K.; Gao,

9、H.; Matyjaszewski, K. Polymerization of BA AGET ATRP in miniemulsionPMA macroinitiatorAGET ATRP in miniemulsionDifference between SR&NI and AGET ATRPsARGET ATRPActivators regenerated by electron transfer:Matyjaszewski, K. et al with greatly reduced amount of Cu (ppm) !ARGET ATRP of MMAMatyjaszewski,

10、 K. et al Kinetics and GPC tracesMatyjaszewski, K. et al Synthesis of block copolymers by ARGET ATRPMatyjaszewski, K. et al Compare different systemsNew development: eATRPMatyjaszewski, K. et al Science 2011, 332, 81-84Electrochemically mediated ATRP:An externally applied electrochemical potential can reversibly activate the copper catalyst by a one-electronreduction of Cu(II)/ligandeATRP of MA in MeCNA: Rp sensitive to voltage;B: Mn insensitive to voltage;C: living manner.Switch the polymerization on demandcomonomers: acrylates, acrylonitrile, N-vinylcarbazole, 4-vinylpyridine, etc.