Radical copolymerization of 2-acetoxyacrylates with nitrile monomers and properties of the copolymers

Radical copolymerization of captodatively (cd) substituted methyl and ethyl 2-acetoxyacrylates (MAA and EAA) with electron-withdrawing olefins including vinylidene cyanide and acrylonitrile is studied using azobisisobutylonitrile as a radical initiator at 60 °C, and the structure of copolymers is examined by 13C NMR spectra. It is found that the copolymerization of MAA and EAA with vinylidene cyanide provides a 1:1 alternating copolymer with ε-tacticity of 0.540 and 0.517, respectively, but that with acrylonitrile gives a random copolymer containing a larger amount of acetoxyacrylate unit. Addition of zinc chloride to the copolymerization of MAA and acrylonitrile, however, leads to the increase of acrylonitrile unit contents in the copolymer. Dielectric constant, gas permeability, and deformation by elongation of the copolymer film of MAA and vinylidene cyanide are also examined.