New synthetic route to α‐alkylacrylonitriles and a study of their homopolymerization and copolymerization reactions

Abstract

Aliphatic aldehydes have been condensed with cyanoacetic acid and the resulting olefin intermediates hydrogenated and then submitted to a Mannich‐type reaction to produce α‐alkylacrylonitriles with the alkyl groups ranging from C₁ to C₁₂. It was not necessary to isolate the intermediates when the reactions were carried out in acetonitrile solutions. The α‐alkylacrylonitriles with C₇ or higher alkyl groups in the chains would polymerize by radical initiation in emulsion to give polymers which were sticky, rubbery products and showed adhesive characteristics. Anionic initiation did not yield polymers with the α‐alkylacrylonitriles containing high alkyl groups but did convert the C₂ to C₄ alkyl‐substituted acrylonitriles to low molecular weight colored products. Some copolymers of α‐alkylacrylonitriles with acrylonitrile were prepared in emulsion by radical initiation. The monomer ratios in these copolymers were determined by nuclear magnetic resonance spectra.