Polymerization and copolymerization of allyl ethenesulfonate

Allyl ethenesulfonate (AES) has been polymerized by radical initiators under different conditions. The polymers consist of 67 to 86% of cyclic recurring units for monomer concentrations going from 8.9 (bulk) to 0.28 mole·1−1. The amount of allyl groups taking part in the polymerization is much higher than expected from the composition of copolymers obtained from propyl ethenesulfonate and allyl ethanesulfonate. The allyl group of AES is incorporated in the polymer chain only via the cyclopolymerization mechanism. AES has been copolymerized with styrene, methyl acrylate, and vinyl acetate. The folowing copolymerization parameters were found: The percentage of cyclic recurring units is low in copolymers with methyl acrylate and with styrene but is high in those with vinyl acetate. In the copolymerization with styrene and with methyl acrylate the reactivity of AES is about equal to that of butyl thenesulfonate; in the copolymerization with vinyl acetate it shows a much higher reactivity than butyl ethenesulfonate. This increase in reactivity is attributed to the formation of cyclic radicals. AES is another example of an unsymmetrical 1.6‐diene wherein the reactivity of the less reactive double bond is greater than that observed in analogous monomers where only that double bond is present.