Polymerization of N‐vinylcarbazole by chlorides and oxychlorides of some group V elements. II. Kinetics and mechanism of the polymerization initiated by arsenic trichloride

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Abstract
The polymerization of N‐vinylcarbazole (NVC) initiated by AsCl3 in benzene and nitrobenzene solvents was studied at 33°C. Rp is proportional to the first power of the initiator concentration. Rp varies in a first‐order manner with NVC concentration up to a certain optimum concentration of the latter, after which it falls and ultimately levels off. The rate and the molecular weight are depressed by the addition of various amines, preformed poly‐NVC, and water. HCl does not have any cocatalytic effect on the system. Rate and the molecular weight are increased in nitrobenzene. The degree of polymerization stays independent of the initiator and NVC concentration and also of increasing conversion. These results suggest a conventional cationic mechanism, and overrule the possibility of a cation radical initiation. A suitable kinetic scheme has been proposed in conformity with the findings.