Copolymerization of vinyl acetate and unsaturated acids in the presence of germanium tetrachloride in methanol

The influence of catalytic amounts of germanium tetrachloride on the copolymerization of vinyl acetate with acrylic acid and methacrylic acid in methanol is examined. It is shown that germanium tetrachloride exerts different effects on the formation rate, molecular-mass characteristics, and composition of copolymers formed in these systems. For example, at a germanium tetrachloride-to-acrylic acid ratio of 0.02 (mol/mol), an alternating copolymer is formed, whereas in the case of methacrylic acid, a copolymer considerably enriched with methacrylic acid units is produced at the same ratio. The results are explained by different copolymerization mechanisms for both systems.