Enhanced Solubility of Polyvinyl Esters in scCO2 by Means of Vinyl Trifluorobutyrate Monomer

The novel monomer, vinyl trifluorobutyrate (VTFBu), when polymerized in a controlled fashion by RAFT/MADIX polymerization with a xanthate transfer agent, yields poly(vinyl ester)s with improved solubility in supercritical carbon dioxide. The thermodynamic parameters controlling the solubility of VTFBu/vinyl acetate statistical copolymers are discussed based on ab initio calculations, glass transition temperatures of the copolymers, and surface tension measurements. The enhanced solubility of this new class of CO2-philic polymer combined with its good chemical stability render it attractive for the preparation of next-generation macromolecular surfactants for the formation of waterscCO(2) emulsions.