Vinyl polymerization. 198. A kinetic study on the polymerization of acrylonitrile initiated by tetramethyl tetrazene in presence and absence of acetic anhydride

The polymerization of acrylonitrile (AN) was carried out in dimethyl formamide. The initiator was tetramethyl tetrazene (TMT) or a mixture of TMT and acetic anhydride (AA). The polymerization proceeded through a radical mechanism. The rate equations are: Adopting the value of (Ep ? 1/2 E_t) as ca. 5 kcal/mole, the activation energies for initiation, E_i, were estimated as ca. 40 kcal/mole for TMT and as ca. 15 kcal/mole for TMT/AA. TMT/benyl chloride or TMT/benzoic anhydride systems initiate a polymerization of AN more easily than TMT alone.