Hydrogen bond recombination regulated by strongly electronegative functional groups in demulsifiers for efficient separation of oil–water emulsions

Tight oil extraction and offshore oil spills generate large amounts of oil-water emulsions, causing serious soil and marine pollution. In such oil-water emulsions, the resin molecules are bound by π-π stacking and bind to interfacial water molecules via hydrogen bonds, which impede the aggregation between water droplets and thereby the separation of the emulsion. In this study, strongly electronegative oxygen atoms (in ethylene oxide, propylene oxide, esters, and hydroxyl groups) were introduced through poly(propylene glycol)-block-polyether and esterification with acrylic acid to attract negative charges in order to form electron-rich regions and enhance interfacial hydrogen bond recombination. The potential distribution in the demulsifier molecules and their space occupancy were regulated by the polymerization reaction to destroy the π-π stacking interaction between resin molecules. The results show that the binding energies (binding free energy and hydrogen bonding energy) of oxygen-containing demulsifier molecules with water molecules were higher than those of resin molecules with water molecules, resulting in the fission of the hydrogen bonds between resin and water molecules. The introduction of demulsifier molecules that occupied large interfacial space reduced the binding energy between resin molecules from -2176.06 to -110.00 kJ·mol-1. Noteworthy, the binding energy between demulsifier molecules and resin molecules was -1076.36 kJ·mol-1 lower than that between resin molecules (-110.00 kJ·mol-1), indicating the adsorption of the surrounding interfacial resin molecules by the demulsifier molecules and destruction of the π-π stacking between them, thus favoring the collapse of the interfacial structure of the oil-water emulsion and achieving its separation. This study provides important theoretical support for the treatment of oil-contaminated soil and offshore oil spill pollution.