Combining Enzymatic Monomer Transformation with Photoinduced Electron Transfer - Reversible Addition-Fragmentation...

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.