Vinyl polymerization. 294. Decomposition of tetramethyltetrazene in the presence of p‐substituted benzyl chlorides

Abstract

AbstractA study was made of the polymerization of acrylonitrile in dimethylformamide (DMF) initiated by the binary systems of tetramethyltetrazene (TMT) and p‐substituted benzyl chlorides. The polymerization rate increased linearly with the σ‐constants of substituents as electron‐releasing groups were introduced to the phenyl ring of benzyl chloride. In order to elucidate the initiation mechanism of the polymerization, a kinetic investigation was also undertaken of the decomposition of TMT in the presence of p‐substituted benzyl chlorides in DMF. The decomposition rate was first‐order in TMT and first‐order in p‐substituents benzyl chloride. The decomposition rate also increased with the σ constants of substituents as electron‐releasing groups were introduced. On the basis of the results, the initiation mechanism for the polymerization was discussed.