Creation of Self-Semi-Interpenetrating Network Structures in PIM-1 Membranes for Enhanced Physical Aging Resistance

A series of self-semi-interpenetrating network (ssIPN) thin films based on PIM-1 structure were developed by end-cross-linking telechelic PIM-1 oligomers end-capped with curable carboxylic acid groups to form model networks, which are penetrated by linear high-molecular-weight PIM-1 chains. ssIPN films with systematically varied network content ranging from 10 to 30 wt % were comprehensively examined on their microstructure and gas permeation properties. Fresh PIM-1 ssIPN films exhibited gas separation performances close to those of as-cast linear PIM-1, where the films closely followed the upper bound trade-off line, gaining as much selectivity as they lose gas permeability as the network content increases. This indicates that gas permeability is largely preserved despite cross-linking. Wide-angle X-ray scattering supported this observation, with peaks shifting toward lower <i>d</i>-spacing as oligomer content increased, suggesting tighter chain packing with higher cross-linkable oligomer loading. In physical aging studies over two months, all ssIPN films outperform linear PIM-1 for H₂/CH₄ and O₂/N₂ separations. Notably, the PIM-1 ssIPN with 10 wt % network content showed the best physical aging resistance, with negligible permeability loss even after one month. These findings highlight a promising macromolecular strategy for enhancing the physical aging resistance of microporous polymer membranes for gas separation.