Silica-Supported Styrene-Co-Divinylbenzene Pickering Emulsion Polymerization: Tuning Surface Charge and Hydrophobicity by pH and Co-Aid Adsorption

In this work, polymerizations of styrene (St) in the presence of divinylbenzene (DVB) as a crosslinking agent and sodium 4-vinylbenzenesulfonate (VBS) have been performed in Pickering emulsions, using silica nanoparticles (SNps) as stabilizing agents and ammonium persulfate as a hydrophilic initiator. In oil-in-water Pickering emulsions with alkaline continuous phase (pH = 9) at 1, 2, and 3 wt% DVB (relative to St), polydisperse spheroid copolymer submicronic nanoparticles were obtained. Comparatively, polymerizations performed in Pickering emulsions with acidic continuous phase (pH = 5) allowed preparing St-co-DVB microspheres with core–shell structures at 1 wt% DVB and St-co-DVB hybrid monoliths with bi-continuous morphologies at 2 and 3 wt% DVB. It is noteworthy that this work reports Pickering emulsion polymerization as a new strategy for preparing hybrid percolated scaffolds with bi-continuous porosity. The proposed mechanisms originated by pH, DVB, and VBS and the drastic impact caused on the final morphology obtained, either hybrid particles or monoliths, are discussed herein.