Toward a General Methodology for Modeling Diffusive-Controlled Reactions in Free Radical Polymerization.

A mathematical model for describing the bulk free-radical polymerization of methyl-methacrylate was developed. This model includes a novel methodology for describing the diffusive step of the kinetic rate coefficients, which is based on geometric considerations and application of the Einstein diffusion Equation. The effect of polymer content and temperature on the Rp behavior is discussed in terms of the evolution of the interdependent parameters defining the Rp. The applicability of Smoluchowski equation and the importance of the translational diffusion of short radicals in the rate of termination reaction are questioned in this context. Similitudes and differences between the model results and experimental data are discussed including minima in the Rp curves at low conversions. [ABSTRACT FROM AUTHOR]