Reversible addition‐fragmentation chain‐transfer (RAFT) copolymerization of vinylidene chloride and methyl acrylate

The reversible addition‐fragmentation chain‐transfer (RAFT) copolymerization of vinylidene chloride and methyl acrylate was investigated at 70 °C in benzene. Three dithioesters were synthesized in high yield by a simple and straightforward transesterification method. These dithioesters were successfully used as reversible chain‐transfer agents, as demonstrated by the increase of molecular weight with conversion, a relatively low polydispersity index ( I p = 1.5) in comparison with a blank experiment ( I p = 1.9), first‐order polymerization kinetics and efficient chain extension. Nevertheless, a transfer reaction to vinylidene chloride monomer was considered to address the limitations of the RAFT process for this system. Moreover, a retardation effect was noticeable on the kinetics, depending on the structure and concentration of the transfer agent, leading to lower rate of polymerization for lower targeted molecular weights.