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Combining Enzymatic Monomer Transformation with Photoinduced Electron Transfer − Reversible Addition–Fragmentation Chain Transfer for the Synthesis of Complex Multiblock Copolymers

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journal contribution
posted on 15.07.2014, 00:00 by Changkui Fu, Jiangtao Xu, Lei Tao, Cyrille Boyer
A novel and facile method, involving enzymatic monomer synthesis and a photocontrolled polymerization technique, has been successfully employed for the preparation of high-order multiblock copolymers. New acrylate monomers were synthesized via enzymatic transacylation between an activated monomer, i.e., 2,2,2-trifluoroethyl acrylate (TFEA), and various functional alcohols. These synthesized monomers were successfully polymerized without further purification via photoinduced electron transfer–reversible addition–fragmentation chain transfer (PET-RAFT) polymerization under low energy blue LED light (4.8 W) in the presence of an iridium-based photoredox catalyst (fac-[Ir­(ppy)3]). In this condition, PET-RAFT allows us to achieve high monomer conversion (∼100%) with excellent integrity of the end group (>80%). Different multiblock (co)­polymers, including poly­(hexyl acrylate) pentablock homopolymer, poly­(methyl acylate-b-ethyl acrylate-b-n-propyl acrylate-b-n-butyl acrylate-b-n-pentyl acrylate) pentablock copolymer, and poly­(3-oxobutyl acrylate-b-methyl acrylate-b-3-(trimethylsilyl)­prop-2-yn-1-yl acrylate) triblock copolymer containing functional groups were rapidly prepared via sequential addition of monomers without purification steps.