EUROPEAN POLYMER JOURNAL, vol.104, pp.164-169, 2018 (SCI-Expanded)
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 degrees 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 (k(app) = 4 x 10(-4) s(-1)). The resulting copolymers had a nearly perfect alternating structure over a very wide range of comonomer feed compositions (f(MAF-TBE) = 0.05-0.95) until complete consumption of one of the monomers. The reactivity ratios were measured to be: r(MAF-TBE) = 0 and r(VAc )= 0.014 at 40 degrees C and the Alfrey and Price parameters for MAF-TBE were calculated (Q(MAF-TBE) = 1.18 and e(MAF-TBE) = 1.84).