Polymer synthesis and processing using supercritical carbon dioxide

Carbon dioxide is a clean and versatile solvent for the synthesis and processing of a range of materials. This review focuses on recent advances in polymer synthesis and processing using liquid and supercritical CO2. The synthetic techniques discussed include homogeneous solution polymerisation, precipitation polymerisation, dispersion and emulsion polymerisation, and bulk polycondensation. The formation of porous polymers and polymer blends is also considered, and the specific advantages of CO2 in these processes are evaluated in each case. The use of CO2 as a solvent for polymer processing is reviewed from a materials perspective, with particular attention being given to the formation of polymers with well defined morphologies. The variable solvent strength associated with supercritical fluids has been utilised in areas such as polymer fractionation and polymer extraction. Plasticisation phenomena have been exploited for the impregnation and heterogeneous chemical modification of polymeric materials. The formation of microcellular polymer foams by pressure induced phase separation is considered, as is the use of CO2 for polymer particle formation, spray coating, and microlithography. The aim of the review is to highlight the wide range of opportunities available to the materials chemist through the use of carbon dioxide as an alternative solvent.