Fabrication of a Modified Polyethersulfone Membrane with Anti-Fouling and Self-Cleaning Properties from SiO--PHEMA NPs for Application in Oil/Water Separation.

To prepare anti-fouling and self-cleaning membrane material, a physical blending modification combined with surface grafting modification has been carried out; first, poly (2-hydroxyethyl methacrylate) grafted silica nanoparticles (SiO--PHEMA NPs) were synthesized using surface-initiated activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) and used as a blending modifier to fabricate a polyethersulfone (PES)/SiO--PHEMA organic-inorganic membrane by the phase-inversion method. During the membrane formation process, hydrophobic PES segments coagulated immediately to form a membrane matrix, and the hydrophilic SiO--PHEMA NPs migrated spontaneously to the membrane surface in order to reduce interfacial energy, which enhanced the hydrophilicity and anti-fouling properties of the PES/SiO--PHEMA membrane. Importantly, the membrane surface contained abundant PHEMA segments, which provided active sites for further surface functionalization. Subsequently, the carboxyl-terminated fluorocarbon surfactant (fPEG-COOH) composed of hydrophilic polyethyleneglycol segments and low-surface-energy perfluorinated alkyl segments was synthesized via the esterification of fPEG with succinic anhydride. Lastly, the PES/SiO--PHEMA/fPEG membrane was prepared by grafting fPEG-COOH onto surface of the PES/SiO--PHEMA. Thus, a versatile membrane surface with both fouling-resistant and fouling-release properties was acquired. The PES/SiO--PHEMA/fPEG membrane has a large oil-water flux (239.93 L·m·h), almost 21 times that of PES blank membrane and 2.8 times of the PES/SiO--PHEMA membrane. Compared with the unmodified PES membrane, the flux recovery ratio increased from 45.75% to 90.52%, while the total flux decline ratio decreased drastically from 82.70% to 13.79%, exhibiting outstanding anti-fouling and self-cleaning properties. Moreover, the grafted fPEG segments on the membrane surface show excellent stability due to the presence of stable chemical bonds. The grafted segments remain at the surface of the membrane even after a long shaking treatment. This suggests that this PES/SiO--PHEMA/fPEG membrane material has potential for application in oil/water separation.