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Equimolar alternating copolymers of vinyl acetate and electrophilic trisubstituted ethylene monomers, halogen ring‐disubstituted methyl (E)‐2‐cyano‐3‐phenyl‐2‐propenoates, RC 6 H 3 CH&dbnd;C(CN)CO 2 CH 3 (where R=2,3‐dichloro, 2,4‐dichloro, 2,6‐dichloro, 3,4‐dichloro, 3,5‐dichloro, 2,4‐difluoro, 2,5‐difluoro, 2,6‐difluoro, and 3,4‐difluoro) were prepared via copolymerization in solution with radical initiation (ABCN) at 70°C. The compositions of the copolymers were calculated from nitrogen analysis and the structures were analyzed by IR, 1 H‐ and 13 C‐NMR. High glass transition temperatures of the copolymers in comparison with that of polyvinyl acetate indicate a decrease in chain mobility of the copolymers due to the high dipolar character of the trisubstituted ethylene monomer unit. The gravimetric analysis indicated that the decomposition of the copolymers occurs in two steps. The first step is relatively fast weight loss in 272–370°C range followed by very slow decomposition of the formed residue in 370–950°C range. [ABSTRACT FROM AUTHOR]