High-performance functionalized polymer of intrinsic microporosity (PIM) composite membranes with thin and stable interconnected layer for organic solvent nanofiltration

Abstract A novel polymer of intrinsic microporosity, acyl chloride-functionalized polymer of intrinsic microporosity (PIM-COCl), was obtained by hydrolysis under alkaline conditions and acylation in thionyl chloride of PIM-1. PIM-COCl is soluble in common organic solvents, and it is used for the first time for organic solvent nanofiltration (OSN). The acyl chloride groups in PIM-COCl can be further cross-linked with an amine-functionalized polyacrylonitrile (APAN) ultrafiltration membrane to form an interconnected layer, which shrinks pore size and provides better structural stability and selectivity. The PIM-COCl composite membranes exhibit high rejection and alcohol flux during OSN. Compared with the reported PIM OSN membranes, APAN-90-3@PIM-0.1 exhibits higher rejection for crystal violet (408 g mol−1, over 94%) in ethanol and several times higher alcohol flux. The membrane shows outstanding stability in ethanol for 14 days. PIM provides a microporous structure, while the interconnected layer maintains this structure in organic solvents via hydrogen bonding, electrostatic interactions and covalent cross-linking. Other PIMs can readily undergo acyl chloride functionalization, which provides them with high reactivity towards amine groups to form stable interconnected layers. This work offers new strategies for the design and preparation of high performance OSN membranes.