Abstract
A detailed kinetic model for the bulk polymerization of styrene initiated by unsysmmetrical bifunctional initiators is presented. When chain termination occurs via combination termination mechanism, 10 distinct polymeric species are identified for this initiator system according to the nature of polymer end units. It is shown that the unequal thermal decomposition characteristics of the labile groups in the bifunctional initiator system lead to the formation of polymers having considerbly higher molecular weight than those obtained by conventional monofunctional initiators or mixed initiator systems of those monofunctional initiators. It has also been found that high monomer conversion and high molecular weight can be obtained simultaneously within a short reaction time period by using the bifunctional initiators at high reaction temperature. This is due to the sequential decomposition of peroxides of different thermal stabilities distributed in various types of polymeric species.
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