Acrylonitrile polymerization initiated by Ce(IV)-cyclohexanone redox system in presence of surfactant

The rate of polymerization of acrylonitrile, using the Ce(IV)-cyclohexanone redox system as an initiator, was studied kinetically, in the presence of 0.015M sodium dodecyl sulfate (SDS), over a temperature range of 25-45degreesC. The rate of polymerization (R-p), percentage of monomer conversion, and rate of Ce(IV) consumption (-R-Ce) were found to increase with the concentration of SDS, above its CMC. The effect of [AN], [Ce(IV)], [H+], and the ionic strength were also studied. The overall activation energies for the polymerization processes were computed to be 23.14 and 17.64 kcal/mol in the absence and presence of 0.015M SDS. A suitable kinetic mechanistic scheme for the free-radical mechanism was proposed. (C) 2003 Wiley Periodicals, Inc.