Synthesis of a novel polymer and design of carboxylate-terminated hyperbranched PEI-incorporated PVDF membranes for efficient oil-in-water emulsion separation

Polyvinylidene fluoride (PVDF) membranes utilizing ultrafiltration (UF) and microfiltration (MF) configurations have widely been used in many separation processes, including oil/water emulsions. Recently, there have been tremendous research interests in designing PVDF membranes on their structural-property relations as well as high separation performances. Herein we report the synthesis of a novel carboxylate-terminated hyperbranched polyethylenimine (CHPEI) using a facile three-step one-pot strategy to enhance the characteristics of PVDF membranes for oil/water emulsion separation. The first step involved the production of one amide and one carboxylate functional group per maleic anhydride molecule on the outer surface of polyethylenimine (PEI). The second step involved producing two additional carboxylate groups via amine-based Michael addition of alkenes using aspartic acid dimethyl ester hydrochloride, followed by basic hydrolysis. CHPEI-n-PVDF membranes having various CHPEI contents are further fabricated by a phase-inversion process, obtaining as free-stable flatsheet membranes. The synthesized polymer and membranes were thoroughly characterized by FTIR and 1 H NMR, SEM, EDX, mapping, AFM, and contact angle analysis. The incorporation of CHPEI into PVDF positively enhanced the hydrophilicity, and the WCA was significantly reduced from 80.6 degrees to 59.5 degrees . The maximum permeation flux was obtained using CHPEI-3-PVDF membranes, which was 200 % more than that obtained using pristine PVDF. The CHPEI-2-PVDF membranes exhibited a rejection performance of >99 % for separating oil-inwater emulsions. The incorporation of CHPEI into PVDF significantly improved the antifouling characteristics of the membranes. After 5 h of operation in separating oil-in-water emulsions, the flux recoveries of CHPEI-2-PVDF and CHPEI-3-PVDF were found to be 92 % and 97 %, respectively. CHPEI has demonstrated a considerable positive influence in improving the PVDF membrane 's performance, making it an excellent candidate for oily wastewater treatment because of its high rejection performance and excellent flux recovery ratio.