Novel Copolymers of Vinyl Acetate and Ring‐Substituted Methyl 2‐cyano‐3‐phenyl‐2‐propenoates

Equimolar alternating copolymers of vinyl acetate and electrophilic trisubstituted ethylene monomers, ring‐substituted methyl (E)‐2‐cyano‐3‐phenyl‐2‐propenoates, RC₆H₄CH˭C(CN)CO₂CH₃ (where R=4‐acetamido, 2‐cyano, 3‐cyano, 4‐cyano, 4‐diethylamino) 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, ¹H‐ and ¹³C‐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 257–370°C range followed by very slow decomposition of the formed residue in 370–950°C range.

Keywords:

• trisubstituted ethylenes
• radical copolymerization
• alternating copolymers
• vinyl acetate copolymers

Acknowledgements

We are grateful to acknowledge that the project was partly supported by the Coatings Industry Education Foundation (CIEF) and Chicago Society of Coatings Technology. Precious Wright and Margaret Smith were supported by the ACS SEED program. Gregory Kharas was supported by a DePaul University Research Council Grant. Xue Tian was supported by a CIEF graduate fellowship.