Free radical polymerization models for simulating reactive processing

Abstract

AbstractThe generally accepted kinetic mechanism for free radical copolymerization was simplified by various assumptions and restrictions to give several realistic and easily evaluated models for the simulation of industrial molding. Six assumptions, including conversion‐dependent rate coefficients and constant comonomer concentration ratios, were used to obtain a simplified model. Special cases of this simplified model were obtained by the following additional constraints: (1) Restriction C, consecutive inhibition and radical generation reactions; (2) Restriction I, constant initiator decomposition rate; (3) Restriction Z, zero termination rate for free radicals; and (4) Restriction K or P, all rate coefficients independent of conversion or only polymerization rate coefficient dependent on conversion. For various combinations of these restrictions, the time and concentration variables in the simplified model are separated and solved; the separate solutions are then combined in various ways to give models capable of predicting a wide variety of behavior. Many of these models have analytical solutions that greatly facilitate the evaluation of rate constants. Models based on restrictions KCI, PCI, and PCZ are shown to give good agreement with isothermal DSC data plotted as reaction rate versus time and, in a more sensitive test, as reaction rate divided by monomer concentration versus fractional conversion. Because of their predictive ability and ease of evaluating constants. Models PCI and PCZ are recommended for simulating industrial processing; they are particularly well suited for simulating compression molding of sheet molding compound.