Polymerizations of methyl methacrylate (MMA) initiated by PhOCu/n-BuLi in tetrahydrofuran solution have been carried out. The PMMAs synthesized were characterized by GPC and ¹H NMR spectra. The results show that MMA can be rapidly polymerized with high monomer conversion initiated by PhOCu/n-Buli. The ratio of PhOCu and n-BuLi and polymerization temperature have large effect on initiator efficiency, molecular weight distribution (MWD) and microstructure of PMMA. At －40 ℃, PMMA with relative narrow MWD and high syndiotactic can be synthesized, but at the same time, the initiator efficiency of PhOCu/n-BuLi is low, about 15%. The low initiator efficiency and broad MWD was related to association state of initiator. The relationships of molecular weight and monomer concentration, initiator concentration show that the polymerization reaction system has the characteristic of living polymerization.

Key words: lithium organocuprate, methyl methacrylate, anionic polymerization