Acrylonitrile Copolymerization. VIII. Radical Determination by the Spin-Trapping Technique

The technique of spin trapping of polymer radicals by 2-methyl-2-nitrosopropane has been applied to the study of acrylonitrile copolymerization. Provided the concentration of the spin trapping agent is kept low, and the samples are kept at low temperature during storage before obtaining the ESR spectra, quantitative studies of styrene-acrylonitrile copolymerization are possible. However, the spin-trapping reaction is a competitive one, and the trapping efficiency is dependent on the reactivity of the radicals present. In the case of acrylonitrile copolymerization with either vinyl chloride or vinyl acetate, these two last radicals are trapped preferentially. Furthermore, the cyclization reaction observed with many acrylonitrile copolymerization is nearly eliminated in the presence of the spin-trapping agent.