Anionic polymerization of MMA initiated by organolithium/cuprum diphenylphosphide (Ph2PCu) and synthesis of its block copolymer

Organolithium/cuprum diphenylphosphide (Ph2PCu) 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/Ph2PCu, Ph2PCu/Li (Ip)3‐6Li/Ph2PCu, and PSLi/Ph2PCu were studied in detail. The polymerization of alkyl methacrylate initiated by n‐BuLi/Ph2PCu 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/Ph2PCu]. After the second monomer addition, the molecular weight increased proportionally while the MWD remained constantly narrow. These results reveal partial living characteristics. Ph2PCu/Li (Ip)3‐6Li/Ph2PCu 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/Ph2PCu for styrene was low. The macromolecular initiator PSLi/Ph2PCu was prepared and PS‐b‐PMMA with a narrow distribution was synthesized.