Improving aging resistance of PIM-1 thin films by nano-TiO2 filler used for robust solvent permeation

Polymers of intrinsic microporosity (PIMs) are promising materials for membrane separation because their special rigid and contorted structures contribute to high permeability. However, their chain rearrangement to fill excessive free volume makes the permeability stability a tough challenge. In this work, we report on a new use of rutile nano-TiO₂ to mitigate the physical aging of PIM-1 (a typical PIM) nanofilms for stable permeability by mixing matrix. It was shown that the PIM-1 membrane incorporated with nano-TiO₂ displayed remarkably higher aging resistance with a lower swelling degree in long-term ethanol soaking, having more stable ethanol permeance with only a 5% decrease after 35 days, lower than 25% of the pure one. The mechanism of anti-aging was revealed by molecular simulation, thermal, tensile mechanical, and dynamic mechanical analysis. It was found that nano-TiO₂ had good compatibility with PIM-1 due to strong coordination interaction, making its uniform dispersion in polymer. Additional solvent permeation channels were also created to increase solvent permeance without compromising solute rejection. Due to the reliable interaction of nano-TiO₂, which makes particles serve as physical crosslinking points, the movement of PIM-1 chains was limited partially to mitigate aging, enabling PIM-1-based membranes to have robust solvent permeation.