Abstract
Abstract Polymerization of acrylonitrile initiated by thallium(III) per-chlorate was investigated in aqueous perchloric acid medium in the temperature range 55–70°C. The rate of polymerization was evaluated by varying the concentrations of monomer, initiator, and perchloric acid. The rate of polymerization was found to increase steadily with an increase of monomer concentration. The effect of solvents; micelles of cationic, anionic, and nonionic surfactants; and inhibitors on the rate of polymerization was also studied. Molecular weights and chain lengths of purified polyacrylonitrile were determined by viscometry. The chain transfer constants for the monomer (CM) and that for the solvent dioxane (C) were calculated to be 1.7 × lo4 and 1.6 × lo4, respectively. From the Arrhenius plot, the overall activation energy was found to be 13.2 kcal/mol. A suitable kinetic scheme has been proposed and a rate equation has been derived.
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