
%0 Journal Article
%A Busfield, W. Ken 
%A Busfield, W. Ken 
%A Jenkins, Ian D. 
%A Jenkins, Ian D. 
%A Monteiro, Michael J. 
%A Monteiro, Michael J. 
%T Initiation Processes in Copolymerization Studied by the Nitroxide Radical-Trapping Technique: Ethyl Vinyl Ether and Acrylonitrile
%J Australian Journal of Chemistry
%D 1997/03/05
%V 50
%N 1
%P 1-8
%K 
%R https://doi.org/10.1071/C96016
%U https://www.publish.csiro.au/paper/C96016 
%X The nitroxide free-radical trapping technique has been applied to an investigation of the initiation mechanism of the copolymerization of ethyl vinyl ether and acrylonitrile initiated by t-butoxyl radicals. In addition to a range of products normally produced from reactions with individual monomers, four new trapped products each involving both monomers have been observed. These arise because the strongly electron-accepting acrylonitrile reacts so fast with the strongly nucleophilic ethyl vinyl ether radical end groups that the reaction competes successfully with radical trapping. t-Butoxyl radicals react 3-6 times faster with ethyl vinyl ether than with acrylonitrile depending on solvent, illustrating the strong electrophilic nature of the t-butoxyl radicals. Reactions carried out in non-olefinic solvents show that polarity is not a major factor in the solvent e&reg;ect. It is more likely to be due to selective interaction of one monomer with the radical end enhancing its electrophilic nature. A similar e&reg;ect is caused by a hydrogen-bonding solvent. 
