Direct Graft Copolymerization of Cellulose Acetate Membrane with Bio-Based Itaconic Acid for Pollutant Removal from...

Cellulose acetate (CA) is a promising bio-derived membrane material for water treatment; however, its limited availability of active functional sites can restrict its affinity toward dissolved pollutants. In this study, a cellulose acetate membrane was fabricated by phase inversion and subsequently functionalized through novel direct graft copolymerization with bio-based itaconic acid (IA) using potassium persulfate (KPS) as an initiator in an aqueous medium. The grafting approach introduced carboxylic functional groups into the CA matrix, providing additional active sites for pollutant removal. The successful grafting was confirmed by UV-Vis and 1H NMR spectroscopy, while XRD indicated changes in the structural organization of the polymer matrix. SEM/EDS characterization further revealed morphological changes associated with grafting, and cross-sectional SEM showed the development of finger-like, continuous pore channels within the modified membrane. The effects of reaction time, IA concentration, and KPS concentration on the grafting percentage were systematically evaluated, with grafting increasing up to an optimum range before declining at excessive monomer or initiator concentrations. Thermal analysis demonstrated improved stability after grafting, with the 6.6% grafted CA-g-IA membrane exhibiting an initial decomposition temperature of 351 °C and a reduced weight loss of 85% at 500 °C, compared with 344 °C and 91%, respectively, for pristine CA. The 6.6% CA-g-IA membrane was subsequently evaluated for the removal of Cu(II) and methylene blue (MB) from aqueous solutions. Cu(II) uptake was strongly influenced by contact time, solution pH, initial concentration, and grafting percentage, with the highest performance observed around pH 6 and 240 min contact time. The membrane also maintained its Cu(II)-binding performance over four regeneration cycles following HNO₃ treatment. Overall, direct IA grafting provides a simple bio-based functionalization strategy for enhancing the pollutant-binding functionality of cellulose acetate membranes, demonstrating potential for the removal of metal ions and cationic dyes from contaminated water.