Free radical initiation mechanisms in copolymerisation studied by the nitroxide trapping technique

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Abstract
The initiation mechanism for the radical copolymerisation of vinyl acetate, a typical electron donor monomer, and acrylonitrile, a typical electron acceptor monomer, initiated by t‐butoxy radicals, has been investigated by the nitroxide radical trapping technique: 1,1,3,3‐tetramethyl‐1,3‐dihydroisoindol‐2‐yloxyl (T) was the radical trapping agent.Two adducts (diastereomers) containing both vinyl acetate and acryionitrile monomers were isolated. From a kinetic analysis of these and other products over a wide range of conditions, a mechanism involving separate monomer addition, which may be regarded as normal kinetic control of monomer addition, is shown to be most consistent with the observed results.