Dispersion polymerization of methyl methacrylate in supercritical carbon dioxide with a monofunctional pseudo-graft stabilizer

Krytox 157 FSL is an effective stabilizer for the free radical polymerization of methyl methacrylate in supercritical carbon dioxide. The interaction with polymethyl methacrylate is most likely via a hydrogen bond between the carbonyl of the methacrylate moiety and the terminal acid group of Krytox 157 FSL. Control experiments with a nonfunctionalized perfluoropolyether demonstrate that a terminal acid functionality is required for the stabilization of the polymerization reaction. Krytox is very easily removed from the polymethyl methacrylate product by supercritical fluid extraction.