Catalytic action of metallic salts in autoxidation and polymerization: 11. Polymerization of methacrylic acid esters with sodium hexanitrocobaltate in methanol-water

The polymerization of a series of methacrylic acid esters (methyl, ethyl, isopropyl and n-butyl) with sodium hexanitrocobaltate, Na₃[Co(NO₂)₆] was carried out in a methanol-water mixed solvent. The homogeneity of the polymerization system was dependent on the composition of the mixed solvent and greatly affected the rate of the polymerization. A maximum rate was obtained at approximately equimolar fractions of methanol and water in the polymerization of methyl methacrylate. The effect of bulkiness of ester groups on the polymerizability of each monomer was indistinguishable in the mixed solvent system. Kinetic study of the polymerization of methyl methacrylate in a mixed solvent of about an equimolar fraction of methanol and water gave the following polymerization equation: $\text{R}{}_{\mathrm{p}}\text{= k[l]}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{[}\text{M}\text{]}{}^2$, and an apparent activation energy of 10.6 kcal/mol. The copolymerization of methyl methacrylate and styrene with the initiator suggested that polymerization proceeded via a radical mechanism. The possibility of a certain interaction between initiator, solvent and monomer in the initial stage of the polymerization is discussed on the basis of the kinetic data, properties of oligomers of methyl methacrylate, spectroscopic and other data.