Acid-functionalized PVA composite membranes for pervaporation-assisted esterification

Composite flat-sheet membranes functionalized with imidazolium-based ionic liquids (ILs) grafted to poly(vinyl alcohol)/glutaraldehyde as a catalytic layer were developed to enhance the esterification between n-butanol and acetic acid. The functionalized membranes were produced via dip-coating commercial pervaporation membranes, and two distinct Brønsted-acidic ILs with an imidazolium-based cation and different (hydrogen sulfate [HSO₄]^- or bromide [Br]^-) anions were compared. Compact, 12 μm-thick, defect-free catalytic layers were observed on top of the pervaporation membrane supports, and the determined penetration depth of the ILs confirmed their presence in the upper part of the coating. While both ILs could significantly promote the esterification of n-butanol and acetic acid, the [HSO₄]^- anion catalyzed the formation of butyl acetate more effectively than [Br]^--based species, resulting in yields of up to 50% over 15 h. Furthermore, the coated membranes exhibited enhanced water separation factors compared to the unfunctionalized one owing to the reduced swelling of the coated membranes accompanied with their diminished wettability.