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

Organolithium/cuprum diphenylphosphide (Ph sub(2)PCu) was used as a novel initiator to polymerize methyl methacrylate (MMA) and styrene in tetrahydrofuran (THF) at -50 to -10 degree C. The polymerizations initiated by n-BuLi/Ph sub(2)PCu, Ph sub(2)PCu/Li (Ip) sub(3-6)Li/Ph sub(2)PCu, and PSLi/Ph sub(2)PCu were studied in detail. The polymerization of alkyl methacrylate initiated by n-BuLi/Ph sub(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 sub(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 sub(2)PCu/Li (Ip) sub(3-6)Li/Ph sub(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 sub(2)PCu for styrene was low. The macromolecular initiator PSLi/Ph sub(2)PCu was prepared and PS-b-PMMA with a narrow distribution was synthesized. [copy 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012