A strong viscosity increase upon polymerization hinders cavitation and subsequent radical formation during an ultrasound-induced bulk polymerization. Ultrasound-induced radical polymerizations of methyl methacrylate (MMA) have been performed in CO2-expanded MMA, as well as in bulk MMA. For this purpose, the phase behavior of CO2/MMA systems has been determined. With temperature oscillation calorimetry, the influence of CO2 on the viscosity and on the reaction kinetics of ultrasound-induced polymerizations of MMA has been studied. In contrast to polymerizations in bulk, this technique shows that a low viscosity is maintained during polymerization reactions in CO2-expanded MMA. As a consequence, a constant or even increasing polymerization rate is observed when pressurized CO, is applied. (c) 2005 American Institute of Chemical Engineers.