Thermal‐initiated reversible addition–fragmentation chain transfer polymerization of methyl methacrylate in the presence of oxygen

Abstract A novel reversible addition–fragmentation chain transfer polymerization (RAFT) of methyl methacrylate (MMA) in the presence of oxygen was carried out for the first time without added chemical initiators. The polymerization was mediated by 2‐cyanoprop‐2‐yl 1‐dithionaphthalate (CPDN) or cumyl dithionaphthalenoate (CDN) as RAFT agent. The polymerization demonstrated the features of a living/controlled radical polymerization. The polymerization rate increased with oxygen concentration. Polymers with molecular weight M n up to 520,000 g/mol, polydispersity M w / M n ∼1.46 and RAFT efficiency M n,th / M n,GPC ∼1.026 in the case of CPDN and M n ∼331,500 g/mol, M w / M n ∼1.35, and M n,th / M n,GPC ∼1.137 in the case of CDN were obtained. The possible mechanism of the thermal‐initiated RAFT polymerization of MMA in the presence of oxygen was discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3343–3354, 2006