Anionic polymerization of MMA initiated by organolithium/cuprum diphenylphosphide (Ph 2 PCu) and synthesis of its block copolymer

Organolithium/cuprum diphenylphosphide (Ph 2 PCu) was used as a novel initiator to polymerize methyl methacrylate (MMA) and styrene in tetrahydrofuran (THF) at −50 to −10°C. The polymerizations initiated by n ‐BuLi/Ph 2 PCu, Ph 2 PCu/Li (Ip) 3‐6 Li/Ph 2 PCu, and PSLi/Ph 2 PCu were studied in detail. The polymerization of alkyl methacrylate initiated by n ‐BuLi/Ph 2 PCu showed a narrow molecular weight distribution (MWD) (1.08–1.25) and 100% initiation efficiency. The experimental number average molecular weight increased linearly with increasing [MMA]/[ n ‐BuLi/Ph 2 PCu]. After the second monomer addition, the molecular weight increased proportionally while the MWD remained constantly narrow. These results reveal partial living characteristics. Ph 2 PCu/Li (Ip) 3‐6 Li/Ph 2 PCu showed a similar behavior and was used to prepare PGMA‐b‐PBMA‐b‐PMMA‐b‐PBMA‐b‐PGMA successfully. The initiation efficiency of n ‐BuLi/Ph 2 PCu for styrene was low. The macromolecular initiator PSLi/Ph 2 PCu was prepared and PS‐b‐PMMA with a narrow distribution was synthesized. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012