Relationship between structures and activities of silver salt–organic halide catalyst systems for styrene polymerization

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Abstract
The rate of bulk polymerization of styrene initiated by silver salt–organic halide systems was measured at 0°C. Neither of the catalyst components initiated the polymerization when used alone, while combined catalysts containing both components initiated the polymerization in the case that the components reacted with each other with precipitation of silver halide. The rate in the early stage of the polymerization increased with an increase in reaction time. Plots of yield against the second power of time gave a linear relation in the early stage of the polymerization. The slope of the line was taken as a measure of catalytic activity. The catalytic activity was markedly influenced by the kinds of the components. The activities of silver perchlorate–organic halide systems increased in the following order of halides: chloride < bromide < iodide in most cases. The activities of silver perchlorate–organic chloride systems increased with a decrease in ionization potentials of the organic groups of the chlorides. The activities of silver salt–benzyl bromide systems increased with a decrease in the pKa values of conjugate acids of silver salts. From these results, it was concluded that the facility of ionic dissociation of the catalyst components determined the activities.

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