Novel Copolymers of Vinyl Acetate and Halogen Ring‐Substituted 2‐Phenyl‐1,1‐dicyanoethylenes

Abstract

Electrophilic trisubstituted ethylene monomers, some ring‐substituted 2‐phenyl‐1,1‐dicyanoethylenes, RC₆H₄CH˭C(CN)₂ (where R is 2‐Br, 3‐Br, 4‐Br, 2‐Cl, 3‐Cl, 4‐Cl, 2‐F, 3‐F, 4‐F) were synthesized by piperidine catalyzed Knoevenagel condensation of ring‐substituted benzaldehydes and malononitrile, and characterized by CHN elemental analysis, IR, ¹H‐and ¹³C‐NMR. Novel copolymers of the ethylenes and vinyl acetate were prepared at equimolar monomer feed composition by solution copolymerization in the presence of a radical initiator (ABCN) at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, ¹H and ¹³C‐NMR, GPC, DSC, and TGA. High T _g of the copolymers, in comparison with that of polyvinyl acetate, indicates a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. The gravimetric analysis indicated that the copolymers decompose in the 220–800°C range.

Keywords:

• trisubstituted ethylenes; radical copolymerization; vinyl acetate copolymers

Acknowledgments

We thank the National Science CCLI A&I program (Grant No. DUE0310624) for support in purchasing our Bruker NMR spectrometer. We are grateful to acknowledge that the project is partly supported by the Coatings Industry Education Foundation (CIEF), Chicago Society of Coating Technology and Office of Sponsored Programs and Research of DePaul University. S.M.R. was supported by a CIEF graduate fellowship.