Mathematical Modeling of Free-radical Six-component Bulk and Solution Polymerization
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The purpose of this project is to reexamine established free-radical polymerization theories and build a mechanistic reactor model for multi-component (up to six monomers) bulk and solution polymerizations under batch/semi-batch reactor configurations. The six-monomer system of interest is: Styrene (Sty), n-Butyl acrylate (BA), Butyl methacrylate (BMA), Hydroxyethyl acrylate (HEA), Hydroxybutyl acrylate (HBA), and Acrylic acid (AA). In order to develop a flexible, comprehensive, and user-friendly model, not only a physical/kinetic database of individual monomers and ingredients such as solvents, initiators, and chain transfer agents, but also a co-polymer database of reactivity ratios, and glass transition temperatures were built and combined with the modeling steps. Through an extensive literature search for polymerization models and kinetics, the simulation model was developed in a general way to cover the range from homo- to hexa-polymerization at both regular and elevated temperature levels, and explain various polymerization kinetics and characteristics. Model testing was conducted with experimental data as much as possible to check the model’s reliability. Due to limited experimental data for higher multi-component polymerizations, the simulation model was tested with homo-polymerizations and other available cases of combinations of two to four monomers. Very reasonable agreement was found between model predictions and experimental data on rate of polymerization, molecular weight, polymer composition, sequence length, etc. through the entire conversion. This multi-component modeling study continuously requires experimental checkups and parameter fine-tuning for better predictions. Further literature search or experimental studies still remain necessary for the hydroxyalkyl acrylate kinetic database and model testing of the depropagation feature. Sensitivity analysis also could be performed to locate critical parameters. This model should find use in industry for analyzing and optimizing reactor conditions as well as in the academic field as a research and educational tool.