研究生课件for copy-ATRP

1、,FUDAN,Atom Transfer Radical Polymerization,Atom transfer radical polymerization,FUDAN,The first paper:,Mechanism of ATRP,FUDAN,Molecular weight and distribution,FUDAN,Kinetics,FUDAN,Monomers: wider suitability,FUDAN,Styrenics:,Methacrylates:,Monomers: wider suitability,FUDAN,Acrylates:,Initiators,F

2、UDAN,1. Alkyl halides:,Initiators,FUDAN,2. -haloesters, ketons and nitriles,Initiators,FUDAN,3. Sulfonyl halides: much faster initiation, easy to generate, hard to terminate, high efficiency.,Theoretical results,FUDAN,Ligands,FUDAN,Metal complexes,FUDAN,Macromolecular engineering by ATRP,FUDAN,Termi

3、nal functionalization:,Dendritic-linear diblock copolymer,FUDAN,Polymer brushes: densely grafted copolymers,FUDAN,ATRP,Star-like polymers,FUDAN,Hyperbranched polymers,FUDAN,Self-condensing vinyl polymerization:,Compositional control,FUDAN,Summary,FUDAN,Synthetic strategy of star polymers using ATRP,

4、FUDAN,Star polymers with exact number of arms; Star polymers with crosslinked core;,Linear macroinitiator as the chain precursor:,FUDAN,“Arm first” approach,Linear macromonomer as the chain precursor:,Synthetic strategy of star polymers using ATRP,“Core first” approach,Linear macroinitiator vs. macr

5、omonomer:,FUDAN,“Arm first” approach,Steric saturation state,Chain end-linking:,FUDAN,Macroinitiator approach,Core cross-linking:,Drawback: Star-Star coupling,An example of “Arm first” synthesis,Core functionalized star polymer:,FUDAN,“Arm first” approach,FUDAN,The crosslinkers,By “in-out” method:,F

6、UDAN,Miktoarms,By “co-linking” method:,FUDAN,“Core-first” approach,Star from in-situ generated core,FUDAN,One-pot synthesis of hairy nanoparticles in emulsion,Hairy nanoparticles,FUDAN,Comparison of different systems,In atom transfer radical copolymerization, or any kind of living copolymerization,

7、of vinyl and divinyl monomer, the addition of the latter determines the structure of the final product.,FUDAN,More homogenous gels by CRP:,FUDAN,Crosslinking reaction: synthesis of networks,Some featured systems developed by Matyjaszewski Based on PRE,FUDAN,Reverse ATRP,Mtn+1XY /L,Mtn Y /L,an exampl

8、e of St polymn. at 110 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 Gao, H.; Matyjaszewski, K.,Polymerization of BA,AGET ATRP in miniemulsion,FUDAN,PMA macroinitiator,FUDAN,AGET ATRP in miniemulsion,Difference between SR B: Mn insensitive to voltage; C: living mann