Abstract
Biocatalysis is promising for sustainable production of polymers. Enzyme-initiated reversible addition–fragmentation chain transfer (RAFT) polymerization is reported. Horseradish peroxidase (HRP) catalyzes oxidation of acetylacetone (ACAC) by hydrogen peroxide to generate ACAC radicals, which in the presence of a suitable chain transfer agent initiate efficient and well-controlled RAFT polymerization in aqueous buffer solution at room temperature. The versatility of HRP-initiated RAFT polymerization was demonstrated by controlled polymerization of a wide range of monomers, including both more and less activated monomers, under a variety of conditions, including both homogeneous solution polymerization and heterogeneous dispersion polymerization conditions. In all cases, the polymerization afforded excellent pseudo-first-order kinetics, predictable molecular weights, and narrow molecular weight distributions. Operation via RAFT mechanism of this HRP-initiated polymerization was confirmed by a combination o...
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