Enzyme Catalysis for RAFT Polymerization and Functionalization: a Sustainable Strategy for Synthesis of Precision Polymers

Enzymes are well-known biological catalysts able to catalyze chemical processes in a mild, efficient and selective manner. Controlled radical polymerization (CRP) techniques have revolutionized the field of polymer chemistry, enabling unprecedented access to various polymer architectures with controlled molar mass, topology, sequence, composition and functionality. The combination of enzyme catalysis and reversible addition-fragmentation chain transfer (RAFT) polymerization is a sustainable strategy for synthesis and functionalization of precision polymers, which has attracted extensive attention in the field of polymer syntheses in recent years. Our group has carried out the following series of work in this field. (i) Enzyme catalysis has been used to initiate RAFT polymerization for synthesis of well-defined polymers with controlled molar mass and low dispersity in benign solvents under mild conditions. (ii) Enzyme cascade catalysis has enabled the synthesis of multiblock and ultrahigh-molecular-weight (UHMW) polymers with oxygen tolerance. (iii) Interestingly, the promiscuity of enzyme can be employed for synthesis and functionalization of well-defined polymers via three different catalytic reactions mediated by one single enzyme. In this feature article, we highlight the recent development on enzyme catalysis for RAFT polymerization and functionalization. At last, perspectives in this field and some future research directions along this exciting theme are proposed.