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

The use of supercritical CO2 (scCO2) as alternative to traditional organic solvents and the valorization of biomass are interesting approaches to reduce the ecological footprint of chemical processes. On the other hand, emulsions offers many advantages over bulk and solution processes for polymerization reactions including limited environmental impact, ease of products recovery and increased reaction rate. In this context, this thesis aims to design novel fluorinated sugar-based surfactants able to stabilize water/CO2 (W/C) emulsion systems and explore their potential as template for polymerization reactions.
Such surface active agents were prepared either by lipase-catalyzed esterification of mannose with fluorinated acid derivatives or following chemoenzymatic approaches involving very efficient and versatile "click" chemistries like the thiol-Michael addition or the thiol-ene/-yne reactions. The W/C interfacial activity of these novel glycosurfactants was confirmed by tensiometry as well as their ability to form stable W/C microemulsions. Then, we tested a range of these neutral fluorinated carbohydrate esters as stabilizers for the CO2-in-water (C/W) emulsion polymerization. In particular, the radical polymerization of acrylamide was performed in the continuous aqueous phase of a C/W high internal phase emulsion (HIPE) leading to highly interconnected macroporous polymer matrices, also called polyHIPEs. In this case, we emphasized a clear dependence of morphology of the porous structure with the concentration and the structure of the glycosurfactant. Thanks to the electrical neutrality of these fluorinated glycosurfactants which confers them a lower sensitivity to the ionic forces compared to their ionic counterparts, we could extend this system to the polymerization of ionic liquid monomers. Porous poly(ionic liquid)s were thus formed by emulsion polymerization for the first time and exhibit spherical cells interconnected by pores with size (~ 1 μm) among the lowest reported for polyHIPEs produced from C/W emulsions. The emulsion C/W templating methodology based on the designed fluorinated glycosurfactants thus appears as a technique of choice for the preparation of valuable macroporous polymer matrices.