Study on the polymerizations of methyl methacrylate and styrene initiated with chlorotrimethylsilane and CuCl/N,N,N′,N″,N″-pentamethyldiethyltriamine

Methyl methacrylate (MMA) and styrene (St) have been radically polymerized in the presence of chlorotrimethylsilane and CuCl/N,N,N′,N″,N″-pentamethyldiethyltriamine (Me3SiCl/CuCl/PMDETA). An analysis of the resultant polymers by 1H NMR discloses terminal silyl group and chlorine atom in all the obtained polymers. Kinetics studies have been carried out by measuring monomer conversions and polymer molecular weights against polymerization time. The results indicate that, for both MMA and St polymerizations, the monomer conversions exhibit a quasi-linear relationship with polymerization time, and the polymer number-average molecular weight (Mn) also increases with monomer conversion. The molecular weights of both PS and PMMA exceed one hundred thousand. Regardless of molecular weight, all the polymers show narrow molecular distributions (Mw/Mn = 1.2–1.5). These polymerization reactions are speculated to follow a mechanism similar to that of atom transfer radical polymerization (ATRP).