Control of polymer chain architecture and polymer product morphology through manipulation of complex kinetics, thermodynamics, and the reactor environment

A comprehensive model was developed for “living” free radical polymerization carried out in both tank and tubular reactors. The kinetic model was validated against experimental data available from the literature. The model was used as a tool for practical applications. A mathematical model was developed also for Reversible Addition Fragmentation Transfer (RAFT) living free radical polymerization chemistry. The model was used to examine different operation modes using this chemistry.; A mathematical model combining anionic polymerization kinetics with an axial dispersion model was developed for tubular reactors. The model was used to study the effect of the reactor residence time distribution and used as a design tool for developing new products.; A computer model for the study of the effects of changing morphology in polymerization induced phase separation was developed and used to investigate the role of polymerization kinetics, thermodynamics, and the reactor environment. Once phase separation occurs as a result of polymerization, a coarsening process quickly dominates, reducing the high interfacial area. After the buildup of the dispersed phase to a certain threshold, phase inversion occurs as predicted by the model. The model employing an extended Cahn-Hilliard equation predicts the various morphologies that have been found in commercial HIPS products and reported in patents. It is expected that this fundamental model will aid in the understanding and improvement of product properties using reactive blending techniques.