Controlled, radical reversible addition–fragmentation chain‐transfer polymerization in high‐surfactant‐concentration ionic miniemulsions

Living free‐radical polymerization of methacrylate and styrenic monomers with ionic surfactants was carried out with reversible addition–fragmentation chain transfer in miniemulsion with different surfactant types and concentrations. The previously reported problem of phase separation was found to be insignificant at higher surfactant concentrations, and control of the molar mass and polydispersity index was superior to that of published miniemulsion systems. Cationic and anionic surfactants were used to examine the validity of the argument that ionic surfactants interfere with transfer agents. Ionic surfactants were suitable for miniemulsion polymerization under certain conditions. The colloidal stability of the miniemulsions was consistent with the predictions of a specific model. The living character of the polymer that comprised the latex material was shown by its transformation into block copolymers.