Controlled Radical Polymerization in the Dispersed Phase
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Controlled radical polymerization (CRP) has emerged as a powerful method of creating polymers with tailored molecular architectures under mild reaction conditions. However, production of these polymers efficiently at an industrial scale will likely require them to be synthesized in the dispersed phase. Three types of CRP are explored, Atom Transfer Radical Polymerization (ATRP), Nitroxide Mediated Polymerization (NMP) and Catalytic Chain Transfer (CCT) to elucidate the intricacies of creating these novel polymer colloids. Compartmentalization in an ATRP dispersed phase system is explored theoretically to understand the effects of particle size and catalyst concentration on the polymerization. The results suggest that there is an optimal range of particle sizes where the rate of polymerization is greater than that in an equivalent bulk system while maintaining both a lower PDI (polydispersity index) and higher livingness. All three factors are desirable in ATRP but generally cannot be achieved simultaneously in bulk. Compartmentalization manifests itself differently in CCT dispersed phase systems, where the segregation of the CCT agents into different polymer particles leads to multimodal molecular weight distributions. Control over the particle size is notoriously difficult for nitroxide mediated polymerization, as it is challenging to decouple an increase in the particle size with an increase in target molecular weight using a two stage emulsion polymerization approach. This often leads to colloidally unstable latexes for low molecular weight, high solids conditions which are the result of superswelling. We offer several strategies to minimize this problem and create colloidally stable, high solids, n-butyl acrylate latexes by NMP with moderate to high molecular weight targets (>70 kg/mol). Using this synergy between target molecular weight and particle size, high solids (>40 wt.%), high molecular weight (<200 kg/mol) microemulsions (~20 nm) of methyl methacrylate-co-styrene were prepared. Finally, the monomer type and nucleation mechanisms also play a role in determining the particle size distribution in NMP emulsion systems. Using n-butyl methacrylate in emulsion with surfactant concentrations above the critical micelle concentration yields latexes with bimodal particle size distributions. However a surfactant-free approach allows monomodal latexes to be created.