Influence of polar solvent in formation and organic solvent separation performance of novel fluorine-containing polyamide membranes

Polyamide thin film composite (PA-TFC) membranes have shown great potential in organic solvent separations. However, the intrinsic polar feature of the amide group limits their permeability to specific solvents, such as nonpolar solvents. In this study, we used a fluorine-containing monomer [4,4'-oxybis(3-(trifluoromethyl)aniline), OTFA] to conduct interfacial polymerization (IP) with trimesoyl chloride, resulting in the fabrication of novel PA-TFC membranes with permeability to both polar and nonpolar solvents. Interestingly, by simply adjusting the composition of OTFA solvents [DMF and DMF/water (1:1, v : v)], we obtained two PA-TFC membranes (OTFA-D and OTFA-DH, respectively) featuring completely different structures and surface properties, including PA layer thickness, water contact angle, surface element composition, surface charge, and polarity. Due to their distinct structures and surface features, the two membranes exhibited different performances in organic solvent nanofiltration (OSN). The OTFA-DH membrane showed higher permeability to polar solvents (e.g., methanol), while the OTFA-D membrane was more permeable to nonpolar solvents (e.g., toluene). The mechanism on the formation of the two PA layers was clarified by combining the experimental results with the molecular dynamics simulations. The significantly different interfacial properties and monomer diffusion during IP led to the substantial differences in the formation of the PA network. This work provides a strategy to fabricate tailored PA-TFC membranes for various OSN scenarios by simply adjusting the solvent compositions.