题目: PHOTOACTIVATION WITH COPPER(II) AND DISPROPORTIONATION OF COPPER(I) TOACHIEVE EXCELLENT LIVING POLYMERISATION OF ACRYLAMIDES AND ACRYLATES
报告人：Prof. David MHaddleton，University of Warwick
报告时间：2015年9月17日（星期四）下午 14:00
报告地点： 独墅湖校区907号楼1101室
Two new methods of using coppercomplexes at ambient and sub ambient temperature will be presented 1) usingvisible light with copper(II) complexes and 2) utilising rapiddisproportionation of copper(I) in water and aqueous media. Photo-activatedliving radical polymerization of acrylates, in the absence of conventionalphoto-initiators or dye sensitizers upon irradiation with UV radiation (λmax ∼ 360nm) will be described. In the presence of low concentrations of copper(II)bromide and an aliphatic tertiary amine ligand (Me6-Tren), near-quantitativemonomer conversion (> 95%) is obtained within 80 minutes yieldingpoly(acrylates) with dispersities as low as 1.05 and excellent end groupfidelity (>99%). The control retained during polymerization is confirmed byMALDI-ToF-MS and exemplified by in situ chain extension upon sequential monomeraddition furnishing higher molecular weight polymers with an observed reductionin dispersity (Ð = 1.03). Similarly, efficient one-pot block copolymerizationby sequential addition of PEGA480- to a poly(methyl) acrylate (PMA)macroinitiator without prior work-up or purification is also reported. Minimalpolymerisation in the absence of light confers temporal control and alludes topotential application at one of the frontiers of materials chemistry wherebyprecise spatiotemporal “on/off” control and resolution achieved.
A new approach to performsingle-electron transfer living radical polymerization (SET-LRP) in water willbe also described. The key step in this process is to allow fulldisproportionation of CuBr/Me6TREN to Cu(0) powder and CuBr2 in water prior toaddition of both monomer and initiator. This provides an extremely powerfultool for the synthesis of functional water-soluble polymers with controlledchain length and narrow molecular weight distributions (PDI approx. 1.10),including poly- NIPAM, DMA, acrylamide, zwiterionic monomers, PEG acrylate, HEAand an acrylamido glyco monomer. (1, 2)
(1) Zhang, Q.; Wilson, P.; Li, Z.; McHale, R.; Godfrey, J.; Anastasaki, A.;Waldron, C.; Haddleton, D. M. Journal of the American Chemical Society 2013,135, 7355.
(2) Zhang, Q.; Li, Z.; Wilson, P.; Haddleton, D. M. Chemical Communications2013, 49, 6608.
报告人简介：
David Mark Haddleton教授主要从事高分子化学和材料科学方向的研究， 2003年-2009年担任《Chemical Communications》编辑，2002年-2009年担任《European PolymerJournal》主编、2004年-2010年担任《Soft Matter》的编辑，现为华威大学化学系无机及材料部门主管，《Polymer Chemistry》主编以及《J. Pol. Sci. Part A, Polym.》编辑。先后于2005年荣获Chemistry World、“Entrepreneur of theYear”、Lord
(报告联系人：陈红老师课题组）
