Flexible Aliphatic–Aromatic Polyamide Thin Film Composite Membrane for Highly Efficient Organic Solvent Nanofiltration

Membranes with strong solvent resistance and efficient molecular separation are desirable in industries. Especially the fractionation of organic molecules in harsh organic solvents still remains a challenge in the pharmaceutical industry. Here, we report a flexible aliphatic–aromatic polyamide thin-film composite (TFC) membrane with high stability, permeability, and precise selectivity in mild solvents as well as in polar aprotic solvents. This composite organic solvent nanofiltration (OSN) membrane integrates a cross-linked sub-100 nm nanofilm and a nanofibrous sublayer. The flexible aliphatic chains in the polyamide network render the selective layer with a tunable free volume in different organic solvents. Consistent with the solvent swelling degrees, the membrane shows a cutoff in a sequence of dimethyl sulfoxide (DMSO, MWCO: 814 g mol–1) > N,N-dimethylformamide (DMF, MWCO: 648 g mol–1) > methanol (MWCO: 506 g mol–1, with DMF activation) > methanol (MWCO: 327 g mol–1). The membrane can precisely fractionate two molecules with difference in molar mass of <166 g mol–1 in a polar aprotic solvent, DMSO. Long-term filtration tests in DMF further demonstrate that the TFC membrane has an outstanding chemical stability and molecular selectivity in aggressive organic media. This work provides an efficient way to control OSN membrane separations by introducing flexible alkane chains into the rigid polymer structure followed by solvent activation. Additionally, the high permeance and excellent separation efficiency of the TFC membrane highlight its great potential for molecular separation in pharmaceutical and chemical industries.