Nitroxide-Mediated Living Free Radical Miniemulsion Polymerization of Styrene

The miniemulsion technique was applied to the controlled/living free radical polymerization of styrene utilizing TEMPO-terminated oligomers of polystyrene (TTOPS) as a macroinitiator species to initiate the polymerization at 125 °C. Miniemulsion polymerizations of styrene using different amounts of TTOPS were studied. It was found that the polymerization rate of a miniemulsion containing no TTOPS was significantly faster than those containing TTOPS. In the latter reactions, the molecular weight of the polymer increased almost linearly with conversion up to 75% conversion. The slope of the molecular weight vs conversion curve increased with decreasing TTOPS concentration as expected. Particle size distributions were measured by both TEM and CHDF and were found to be broad. Using the kinetics and particle size data, the average number of active free radicals per particle ( n̄ in classical emulsion polymerization systems) was estimated and found to be low (≤0.005).