Vinyl Polymerization. 371. Polymerization of Methyl Methacrylate Initiated by the System of Polyvinylferrocene and Carbon Tetrachloride

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Abstract
The polymerization of vinyl monomers initiated with the system of polyvinylferrocene (PVFc) and carbon tetrachloride (CCl4) was carried out in dark. Methyl methacrylate (MMA) and acrylonitrile (AN) could be polymerized, while styrene (St) was hardly polymerized under the conditions used. The polymerization proceeded through a free-radical mechanism and was concluded to be initiated by attack of vinyl monomer, having a polarized vinyl group, on the charge-transfer complex of PVFc/CCl4. In the polymerization of MMA, the initiating ability of PVFc was much larger than that of ferrocene (Fc-H) or poly(ferrocenylmethyl methacrylate) (PFMMA) and was comparable to that of polyferrocenylenemethylene (PFM). The overall activation energy was estimated to be 34.2 kJ/mole.

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