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

Abstract

Abstract 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 (M 1 )–vinyl acetate (M 2 ), r 1 = 0.42, r 2 = 1.29; allyl butyrate (M 1 ) –vinyl acetate (M 2 ), r 1 = 0.64, r 2 = 0.97; allyl isobutyrate (M 1 )–vinyl acetate (M 2 ), r 1 = 0.51, r 2 = 1.04; allyl valerate (M 1 )–vinyl acetate (M 2 ), r 1 = 0.58, r 2 = 1.07; allyl trimethylacetate (M 1 ) –vinyl acetate (M 2 ), r 1 = 0.34, r 2 = 1.15. The Q‐e parameters were calculated from the allyl esters (M 1 )–vinyl acetate (M 2 ) 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) × 10 4 .