Engineering sterilization-resistant and fouling-resistant porous membranes by the vapor-induced phase separation process using a sulfobetaine methacrylamide amphiphilic derivative

Abstract

The in-situ modification of polyvinylidene fluoride (PVDF)-based membranes with zwitterionic copolymers for environmental applications remains challenging because of the large polarity difference between PVDF and zwitterionic materials. Besides, common zwitterionic units such as sulfobetaine methacrylate fail when exposed to elevated temperatures, limiting their range of applications in biomedical engineering. We designed an amphiphilic copolymer containing sulfobetaine methacrylamide (SBAA), styrene and ethylene glycol methyl ether methacrylate (EGMA) groups. Once the appropriate composition determined, membranes were prepared by vapor-induced phase separation (VIPS), a process permitting fine control over formation mechanisms, hence over the matrix structure. Sorption, mapping FT-IR and DSC tests indicated that even a low proportion of SBAA (< 10 mol%) in the P(S-r-EGMA-r-SBAA) copolymer significantly increases the proportion of non-freezable water and enhances the strength of the hydration layer, compared to a system containing styrene and EGMA groups only, P(S-r-EGMA). The modification also resulted in a large increase in membrane hydration capacity (> 550 mg/cm3 vs. < 25 mg/cm3 for the virgin membrane). Consequently, the zwitterionic copolymer could efficiently mitigate biofouling by fibrinogen (76% drop), Escherichia coli (99% decrease) or whole blood (82% reduction), even after a steam sterilization process, while the control zwitterionic sulfobetaine methacrylate material failed at maintaining its performances. Separation tests carried out with bacterial solutions revealed the ability of the zwitterionic copolymer to significantly decrease irreversible fouling (27%), compared to a commercial membrane (47%). All in all, their porous structure, hydration capacity and their ability to withstand steam sterilization make these novel porous zwitterionic membranes ideal candidates for biomedical (blood filtration) or environmental applications (water treatment).