Controlled radical polymerizations in miniemulsions: Advances in the use of RAFT

The goal of this work is to increase the current understanding of Controlled Radical Polymerizations (CRPs) in two areas. Progressing closer towards employing an aqueous system, specifically miniemulsion, to produce poly(vinyl acetate) via reversible addition fragmentation chain transfer (RAFT) chemistry constitutes the first part of this goal. Presented are the results of miniemulsion polymerizations using both water and oil-soluble initiators. Limiting conversions in both are examined and explained in terms of radical loss. The second part of the goal is to further the understanding of the nature of the RAFT/miniemulsion system when employed in continuous tubular reactors. The development of the recipe using mixed surfactants, the results of styrene homopolymerizations in batch and tube, and the results of a chain extension experiment demonstrating the living nature of the chains formed in the tubular reactor are presented. Kinetic anomalies are addressed, as well as polydispersity differences between batch and tube. Flow phenomenon and their influence on residence time distribution and by implication the PDI of the polymer formed are offered as explanations for the variance in PDI and are subsequently quantified. A model of RAFT in laminar flow is presented and the results and implications are discussed in general terms. The flow profile of the reactor is examined using a tracer technique developed specifically for this system. Experiments are presented directly relating the residence time distribution to the polydispersity of the polymer. Transient behavior of the reactor in isolated plug flow is explained in terms of initiator loss. Both experimental data and a model are used to support this hypothesis. Finally, conclusions and implications are presented and unanswered questions and the ideas for future work that they generated are addressed.