Alkyl chloride initiators for SET‐LRP of methyl acrylate

Single‐electron transfer living radical polymerization (SET‐LRP) proceeds by an outer‐sphere single‐electron transfer mechanism that induces a heterolytic bond cleavage of the initiating and propagatingR‐X (where X = Cl, Br, and I) species. Therefore, unlike the homolytic bond cleavage mechanism claimed for ATRP, SET‐LRP is expected to show a small dependence of the nature of the halide group on the apparent rate constant of activation. This means theR‐X with X = Cl, Br, and I must all be efficient initiators for SET‐LRP and no chain transfer must be observed in the case of initiators with X = Br and I. Here, we report the SET‐LRP of methyl acrylate initiated with the alkyl chlorides methyl‐2‐chloropropionate (MCP) and chloroform (CHCl3) and catalyzed by Cu(0)/Me6‐TREN/CuCl2in DMSO at 25 °C. A combination of kinetic and structural analysis was used to elucidate the MCP and CHCl3initiating behavior under SET‐LRP conditions, and to demonstrate the very small dependence of the SET‐LRP apparent rate constant of propagation on X while providing polymers with well defined architecture.