Stable Free Radical Polymerization Conducted In Emulsion Polymerization Systems
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Free radical polymerization is the most common polymerization technique that is used for the manufacturing of polymers, due to the ease of the polymerization initiation, wide latitude of the material design for a large variety of monomers, and the excellent process robustness for commercial production. In the 1990’s, research activities for the precise control of radical polymerization process resulted in the discovery of ‘Living Radical Polymerization’. The discoveries opened the door for the next generation of radical polymerizations. Extensive research has been conducted to understand the mechanisms and kinetics for numerous practical applications, particularly for polymerization in bulk and solution systems. However, despite the interest of industry, the mechanistic understanding in aqueous dispersed systems such as emulsion and miniemulsion polymerization is far behind the aforementioned two systems. There are still major challenges from the production viewpoint. One reason for the poor understanding is the complexity of the heterogeneous system, which includes multiple reaction phases that are accompanied by the segregation and transfer of the reaction species among different phases. The purpose of this research was to investigate living radical polymerization or “Stable Free Radical Polymerization” (SFRP) in aqueous dispersed systems to obtain better mechanistic understanding of how the heterogeneous nature of the system interacts with the novel living radical chemistry. The theoretical and experimental feasibility of the SFRP emulsion process were studied in this research, in particular, focusing on the compartmentalization effect. Particle size influence on the polymerization kinetics and the polymer livingness was experimentally confirmed, and compared to bulk polymerization. In addition, a comprehensive mathematical model including all major chemical and physical events was developed to further our mechanistic understanding. Based on the results from the experimental and modeling studies, it was shown that rate reduction in the smaller particles is the primary cause of difficulty in implementing a conventional emulsion process (i.e. ab initio emulsion polymerization). Finally, for overcoming this difficulty, a new approach using a combination of TEMPO with highly hydrophobic 4-stearoyl TEMPO was proposed for a coagulum free ab initio emulsion process.