Detailed study of the reversible addition–fragmentation chain transfer polymerization and co-polymerization of 2-methacryloyloxyethyl phosphorylcholine

In this paper, we report on a detailed study of the reversible addition–fragmentation chain transfer (RAFT) polymerization of 2-methacryloyloxyethyl phosphorylcholine (MPC). The RAFT polymerization conditions were carefully monitored and it was noted that well-defined homopolymers with ideal low polydispersity (M_w/M_n < 1.2) could be achieved in methanol using 4-cyanopentanoic acid dithiobenzoate (CTP) as a chain transfer agent and 4,4′-azobis(4-cyanovaleric acid) (ACVA) as an initiator. A series of well-defined block copolymers having a range of compositions and molecular weight were prepared using poly(MPC) as the macroCTA. Statistical MPC-based copolymers of biological relevance were also synthesized and characterized.