Hierarchically Porous Microspheres by Thiol-ene Photopolymerization of High Internal Phase Emulsions-in-Water Colloidal Systems

A facile method for the preparation of hierarchically porous spherical particles using high internal phase water-in-oil-in-water (w/o/w) double emulsions via the photopolymerization of the water-in-oil high internal phase emulsion (w/o HIPE) was developed. Visible-light photopolymerization was used for the synthesis of microspherical particles. The HIP emulsion had an internal phase volume of 80% and an oil phase containing either thiol pentaerythritol tetrakis(3-mercaptopropionate) (PETMP) or trimethylolpropane tris(3-mercaptopropionate) (TMPTMP) and acrylate trimethylolpropane triacrylate (TMPTA). This enabled the preparation of microspheres with an open porous morphology, on both the surface and within the microsphere, with high yields in a batch manner. The effect of the thiol-to-acrylate ratio on the microsphere diameter, pore and window diameter, and degradation was investigated. It is shown that thiol has a minor effect on the microsphere and pore diameter, while the acrylate ratio affects the degradation speed, which decreases with increasing acrylate content. The possibility of free thiol group functionalization was demonstrated by a reaction with allylamine, while the microsphere adsorption capabilities were tested by the adsorption of methylene blue.