Sequence length distributions in vinylene carbonate-vinyl acetate copolymers

Polyvinylene carbonate is a linear polymer which can be dissolved with saponification in cold alkali. After precipitation the resultant amorphous polyvinylene glycol can only be dissolved in fused urea. Vinylene carbonate (M1)–vinyl acetate (M2) copolymers are higher melting than polyvinylacetate, and at 55° the reactivity ratios are r1 = 0.0579, r2 = 3.71. Expressions are derived relating periodate consumption and formic acid formation by hydrolyzed vinylene carbonate copolymers to the number-average sequence lengths predicted by copolymerization theory. Periodate consumption by the homopolymer and copolymers is complicated by the overoxidation of the intermediate malondialdehyde to carbon dioxide. When this side reaction is taken into account, periodate consumption and formic acid liberation are in reasonably good semi-quantitative agreement with theoretical predications of number-average sequence length.