Polymerization of methyl methacrylate by metallocenes

Abstract

Attempts at polymerizing methacrylate using metallocenes are reported. Polymerization is successful using ferrocene in a ketone solution, but not in benzene or without a solvent. Ketones are effective in the order: methyl ethyl ketone < cyclohexanone < cycloheptanone. Carbon tetrachloride has an accelerative effect on the polymerization in benzene and methyl ethyl ketone solutions, but no effect in cyclohexanone solution. Some binary systems, which consist of ferrocene and higher valence compounds such as cobalt trisacetylacetonate, are effective redox initiators. Cobaltocene polymerizes methyl methacrylate in the presence of carbon tetrachloride; zirconocene dichloride induces polymerization of methyl methacrylate in a cyclohexanone solution; whereas neither nickelocene nor titanocene dichloride are effective. Styrene and acrylonitrile were not polymerized by the metallocenes examined.