Synthesis of polystyrene with mixtures of mono- and bifunctional initiators

This work studies the bulk and nonisothermic polymerization of styrene (S) using mixtures of mono- and bifunctional initiators. The effects on polymerization rate and on molecular weight averages after changes in the global initiator concentration and in the nature of the initiator mixtures were experimentally and theoretically analyzed. The mathematical model was adapted from the literature to admit initiator mixtures and to simulate the applied temperature profiles. Compared to the standard use of monofunctional initiators, the use of initiator mixtures that include bifunctional initiators presents the advantage of reducing the polymerization time, while not deteriorating the final polymer quality. The simulation program accurately describes the evolution of conversion, but exhibits some deviations with the average molecular weights. © 1996 John Wiley & Sons, Inc.