Design of sugar-based surface active agents for emulsion polymerization in supercritical carbon dioxide

The use of aqueous dispersed media, such as emulsions, has many advantages over solution processes for chemical transformations and polymerization reactions, i.e. limited environmental impact, ease of products recovery and increased reaction rate. Emulsions are usually implemented from a water/organic solvent mixture in the presence of a surfactant. However, supercritical carbon dioxide (scCO2) (Pc =74 bars; Tc = 31°C) constitutes an interesting alternative to the traditional organic solvents in these heterogeneous systems because it is inexpensive, non-toxic, non-inflammable and environmentally friendlier. In this context, we developed a novel class of surfactants for the stabilization of H2O/scCO2 emulsions, i.e. fluorinated modified carbohydrates. The hydrophilic head of the surfactant consists in a sugar moiety whereas a fluorinated tail is specifically located in the scCO2 phase. The strategies for the synthesis of these carbohydrates esters rely on selective lipase-catalyzed modifications of sugars and on the versatile thiol-Michael addition reaction. The ability of these molecules to decrease the H2O/scCO2 interfacial tension and to stabilize such emulsions will be presented. Finally, high internal phase scCO2-in-water emulsion (HIPE) were prepared with these new surfactants and used as template for the acrylamide polymerization. The monomer is polymerized in the continuous aqueous phase before removing the CO2 droplets (at least 70 % of the total volume). The resulting permeable porous polymers, called polyHIPEs, exhibit highly interconnected voids (cfr SEM picture) and should be valuable in many applications including support for catalyst, filtration process, immobilization of proteins, etc.