Alternating radical copolymerization of vinyl acetate and tert-butyl-2-trifluoromethacrylate

Abstract

Alternating conventional radical copolymerization of tert-butyl-2-trifluoromethacrylate (a non-homopolymerizable fluoromonomer under radical conditions) with vinyl acetate, initiated by 2,2′-azo-bis(4-methoxy-2,4-dimethyl valeronitrile) at 40 °C is presented. The study of the kinetics of the copolymerization using various [VAc]0/[MAF-TBE]0 feeds showed that an equimolar feed of comonomers led to the highest apparent copolymerization rate (kapp = 4 × 10−4 s−1). The resulting copolymers had a nearly perfect alternating structure over a very wide range of comonomer feed compositions (fMAF-TBE = 0.05–0.95) until complete consumption of one of the monomers. The reactivity ratios were measured to be: rMAF-TBE = 0 and rVAc = 0.014 at 40 °C and the Alfrey and Price parameters for MAF-TBE were calculated (QMAF-TBE = 1.18 and eMAF-TBE = 1.84).