Advances in mathematical modelling of multicomponent free-radical polymerizations in bulk, solution and emulsion

A computer package has been developed to simulate free-radical multicomponent polymerization in bulk, solution and emulsion. The simulation package consists of two models, one for bulk and solution polymerization, and the other for emulsion polymerization. Databases of physicochemical parameter values for both models have been developed in parallel. The bulk/solution model's database includes 12 monomers and the database for the emulsion model consists of 5 monomers. Both databases also have many initiators, solvents (in bulk/solution model's database only), chain transfer agents and emulsifiers (in emulsion model's database only).; In the first stage of model development, the bulk/solution model was developed and extensively tested with a total of 15 copolymer systems. Several important aspects in copolymerization kinetics were discussed.; In the second stage of model development, terpolymerization kinetics in bulk/solution over the entire conversion range were investigated in detail. The bulk/solution copolymerization model was extended to simulate terpolymerization in bulk/solution and testing over the entire conversion range. Due to the scarcity of available experimental data in the literature, we were not able to test the model more extensively with other terpolymerizations.; In the third stage of model development, a general and comprehensive emulsion model has been developed. The model can describe the most important physicochemical phenomena occurring in emulsion polymerization. Difficult and challenging subjects in emulsion polymerization kinetics, such as monomer partitioning through thermodynamic equilibrium, particle nucleation, desorption, etc., have been solved satisfactorily in a general fashion. This model can predict important reaction characteristics (conversion profile and rate of polymerization) and polymer/latex properties.; The emulsion model has been tested with monomers of very different characteristics, like styrene and methacrylate. The model has also been tested for the copolymer system of styrene/methyl methacrylate. In most cases, simulation results are satisfactory compared to experimental data collected either from the literature or from this laboratory.; After this systematic effort in refining and testing our multicomponent simulation model/package/database, we strongly believe that the package can provide a very flexible and useful tool that could guide academic and industrial research and development, as extensively demonstrated in Gao and Penlidis (1996, 1998) for homo- and copolymerizations, and in the present thesis for terpolymerizations and emulsion case. (Abstract shortened by UMI.)...