FREE-RADICAL POLYMERIZATION OF STYRENE WITH A BINARY MIXTURE OF SYMMETRICAL BIFUNCTIONAL INITIATORS

The kinetics of bulk styrene polymerization catalyzed by a binary mixture of symmetrical bifunctional initiators has been investigated. When the bifunctional initiators having different thermal stabilities are mixed, an unsymmetry in the initiator functions is formed in situ via propagation, chain transfer, and termination reactions. For the quantification of the polymerization kinetics, a kinetic model has been developed using the molecular species modeling technique. For various polymerization conditions, good agreements between the model predictions and experimental data have been obtained. It is shown that polymerization rate and molecular weight can be easily regulated under isothermal reaction condition by changing the initiator composition. A comparison of the detailed kinetic model with a simple kinetic model for monofunctional initiators has also been made to illustrate the molecular weight increasing effect of the bifunctional initiator system.