A Comprehensive Kinetic Model for the Free-Radical Polymerization of Vinyl Chloride in the Presence of Monofunctional and Bifunctional Initiators

A comprehensive kinetic model is developed for the suspension free-radical polymerization of vinyl chloride (VC) initiated by a mixture of monofunctional and bifunctional initiators. The model predicts the monomer concentrations in the gas, aqueous, and polymer phases; the overall monomer conversion; the polymerization rate; the polymer chain structural characteristics (e.g., number- and weight-average molecular weights, short chain branching, and number of terminal double bonds); the reactor temperature and pressure; and the coolant flow rate and temperature in the reactor’s jacket over the whole batch polymerization cycle. The capabilities of the model are demonstrated by a direct comparison of model predictions with experimental data on monomer conversion, number- and weight-average molecular weights, and reactor pressure. It is shown that high molecular weights and high polymerization rates can be obtained in the presence of a mixture of monofunctional and bifunctional initiators. Moreover, the use of bifunctional initiators results in a significant reduction of the polymerization time without impairing the final molecular weight properties of the polymer. To our knowledge, this is the first comprehensive kinetic modeling study on the combined use of monofunctional and bifunctional initiators on the free-radical suspension polymerization of VC. Taking into consideration the excellent agreement of the model predictions with the experimental measurements, the proposed model should find wide application in the design, optimization, and control of industrial poly(vinyl chloride) batch reactors.