Allylic polymers. I. Copolymerization of allyl esters with vinyl acetate

The radical copolymerization of allyl esters with vinyl acetate has been studied in the range from 10 to 90 mol % allyl esters in the feed. The Kelen‐Tüdos method was employed to determine the monomer reactivity ratios. The following values were found for the reactivity ratios: allyl propionate (M1)–vinyl acetate (M2), r1 = 0.42, r2 = 1.29; allyl butyrate (M1)–vinyl acetate (M2), r1 = 0.64, r2 = 0.97; allyl isobutyrate (M1)–vinyl acetate (M2), r1 = 0.51, r2 = 1.04; allyl valerate (M1)–vinyl acetate (M2), r1 = 0.58, r2 = 1.07; allyl trimethylacetate (M1)–vinyl acetate (M2), r1 = 0.34, r2 = 1.15. The Q‐e parameters were calculated from the allyl esters (M1)–vinyl acetate (M2) reactivity ratios. The e parameters of allyl ester monomers have been found to be nicely correlated with parameters such as dissociation constants of carboxylic acids, which are constituents of allyl ester monomers, and Taft σ* constants of the alkyl group in the acids. The molecular weights of copolymers were measured by GPC and ranged from (1.0–15.0) × 104.