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.

Automated summary

Polymerizations of styrene were performed in Pickering emulsions using DVB and VBS, resulting in polydisperse spheroid copolymer nanoparticles and microspheres with core-shell structures; adjusting the pH and DVB content in the emulsions could control the final morphology of the products; this work presents a new strategy for preparing hybrid percolated scaffolds with bi-continuous porosity using Pickering emulsion polymerization.