RAFT Polymerization of Methyl Acrylate in Carbon Dioxide

Abstract

Abstract Summary: Reversible addition fragmentation chain transfer (RAFT) polymerizations of methyl acrylate (MA) in solution containing either 22 vol.‐% CO 2 or toluene were performed at 80 °C and 300 bar using cumyl dithiobenzoate (CDB) at concentrations between 1.8 × 10 −3 to 2.5 × 10 −2 mol · L −1 as the RAFT agent. Product molecular weight distributions and average molecular weights indicated the successful control of MA polymerization in CO 2 , even at low CDB concentrations. RAFT polymerization rates were strongly retarded by CDB and were lower in CO 2 than in toluene solution. The enhanced fluidity associated with the addition of CO 2 to the polymerizing system provided access to mechanistic details of RAFT polymerization. The data of the present study into MA, together with our recent results on RAFT polymerization of styrene in solution of CO 2 and of toluene, suggest that self‐termination of intermediate RAFT radicals is responsible for retardation in case of high concentrations of this intermediate and in case of enhanced fluidity, which may be achieved by polymerization in solution of CO 2 . magnified image