Abstract

AbstractEfficient stirring is needed to realize heat flow analysis with a thermally homogeneous medium. Because dispersion polymerization with supercritical fluids can be destabilized under stirring, a preliminary target has been to find a compromise between synthesis and basic reaction calorimetry requirements. This paper describes the use of poly (dimethylsiloxane) macromonomer with a molecular weight 5000 g/mol as stabilizer for the dispersion polymerization of methyl methacrylate in supercritical carbon dioxide. The effect of stirring speed and stabilizer concentration has been examined. This study has shown that poly (methyl methacrylate) can be produced at high yield and molecular weight using 10 wt% (respect to monomer) poly (dimethylsiloxane) macromonomer at stirring speeds up to 600 rpm. A polymerization enthalpy of −57.6±2 kJ/mol has been calculated being in good agreement with previously reported data. Thus, preliminary results for the heat balance using the newly developed high pressure reaction calorimeter for supercritical fluid applications have shown the important potential of reaction calorimetry to promote supercritical fluid technologies at industrial scale allowing for the determination of kinetics and thermodynamic and safety data, respectively.

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