Preparation of pH-Responsive PET TeMs by Controlled Graft Block Copolymerisation of Styrene and Methacrylic Acid for the Separation of Water–Oil Emulsions

To develop membranes capable of efficient and switchable emulsion separation under variable pH conditions, pH-responsive surfaces were engineered on poly(ethylene terephthalate) track-etched membranes (PET TeMs) via a two-step UV-initiated RAFT graft polymerization process. Initially, polystyrene (PS) was grafted to render the surface hydrophobic, followed by the grafting of poly(methacrylic acid) (PMAA) to introduce pH-responsive carboxyl groups. Optimized conditions (117 mM MAA, RAFT:initiator 1:10, 60 min UV exposure at 10 cm) resulted in PET TeMs-g-PS-g-PMAA surfaces exhibiting tunable wettability, with contact angles shifting from 90° at pH 2 to 65° at pH 9. Successful grafting was confirmed by FTIR, AFM, SEM, TGA, and TB dye sorption. The membranes showed high degree of rejection (up to 98%) for both direct and reverse emulsions. In direct emulsions, stable flux values (70 ± 2.8 to 60 ± 2.9 L m−2 h−1 for cetane-in-water and 195 ± 8.2 to 120 ± 6.9 L m−2 h−1 for o-xylene-in-water) were maintained over five cycles at 900 mbar, indicating excellent antifouling performance. Reverse emulsions initially exhibited higher flux, but stronger fouling; however, flux recovery reached 91% after cleaning. These findings demonstrate the potential of PET TeMs-g-PS-g-PMAA as switchable, pH-responsive membranes for robust emulsion separation.