Polymerization and copolymerization of allyl ethenesulfonate

Abstract

Allyl ethenesulfonate (AES) has been polymerized by radical initiators under different conditions. The polymers consist of 67 to 86 yo 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 following copolymerization parameters were found : r l (AES) 0.23 & 0.03 ; r2 (styrene)1.6 f 0.1 r i (AES) 0.07 f 0.02; r 2 (methyl acrylate) 10.7 i 0.2 r l (AES) 3.6 f 0.2 ; r2 (vinyl acetate)0.38 f 0.08 vinylsulfonat ; bei der Copolymerisation mit Vinylacetat ist AES reaktiver als Butylvinylsulfonat. Dieser Anstieg der Reaktivitat wird der Bildung cyclischer Radikale zugeschrieben. AES ist ein weiteres Beispiel fiir ein unsymmetrisches 1.6-Dien, in welchem die Reaktivitat der weniger reaktiven Doppelbindung grol3er ist als in analogen Monomeren, in welchen nur diese eine Doppelbindung vorkommt.

Polymers fromS-vinyl monomers: reactivities and properties

“…In general, homo-or copolymerization have been demonstrated to be initiated by azo initiators but as well by peroxides. [180][181][182][183][184] The studies on the copolymerization behavior of butyl vinyl sulfonate in 1950 revealed a similar reactivity as observed for vinyl acetate and vinyl chloride. 181 However, it can also be copolymerized with styrene, methacrylates, and vinylidene chloride, although the copolymerization is significantly retarded.…”

Radical cyclo‐ and cyclocopolymerization

“…In a similar study of allyl ethenesulfonate, k,/k; = 45 M/I. at 45OC in benzene [21]. Under thesameconditions, allyl ethanesulfonate did not polymerize and propyl ethenesulfonate polymerized at about the same rate as allyl ethenesulfonate.…”

“…In unsymmetrical monomers, where the double bonds differ significantly in reactivity, it is possible to neglect initiation or intermolecular propagation reaction involving the less reactive double bond. This permits a simplification of the kinetic expressions which describe these systems, and such have been applied to vinyl trans-cinnamate [20], allyl ethenesulfonate [21], N-allylmethacrylamide [27], N-allylacrylamide [23], allyl methacrylate [24], allyl acrylate [25], and vinyl trans-crotonate [26]. For these monomers, only one type of repeating unit is formed, and the simplified kinetic expressions could be used.…”