Catalytic effectiveness of azobisisobutyronitrile/[SiMes)Ru(PPH3)(Ind)Cl2 initiating system in the polymerization of methyl methacrylate and other vinylic monomers

The catalytic system of azo-bis-isobutyronitrile (AIBN) combined with (SiMes)Ru(PPH3)(Ind)Cl-2 [M-20] was investigated for the controlled radical polymerization of methyl methacrylate (MMA) in solution. Various factors that may influence the catalytic polymerization process, such as the aging time of the initiating system, AIBN/M-20 ratio, concentration of monomer, polymerization time, temperature, and the nature of solvent were examined. The results showed that the yield, molecular weight, and molecular distribution are practically unaffected by these parameters; however, the syndiotactic stereo-structure tendency that characterizes the produced poly(methyl methacrylate) (PMMA) varied with temperature. The optimum conditions for PMMA synthesis were determined to produce an essentially syndiotactic material with uniformly high molecular weights. It was also revealed that the kinetics of MMA polymerization is of first order with respect to the concentration of monomer. A comparison was also made for some vinylic polymers synthesized either with the AIBN alone or with the AIBN/M-20 initiating system under the same conditions