Linking Intrinsic Filler Properties to Gas Separation Performance in Polyimide-Based Mixed-Matrix Membranes

Mixed-matrix membranes (MMMs) incorporating porous organic fillers into high-performance polyimides were developed to investigate the influence of free volume and molecular architecture on gas transport. Four structurally rigid, intrinsically porous fillers (TFAP-Trp, Is-Trp, TFAP-TPB, and Is-TPB) were incorporated into a range of polymer matrices (P84^®, Matrimid^®, Pi-DAPOH, Pi-DAROH, Pi-HABAc, Pi-DAM, and PIM-1), enabling the development of a matrix-independent methodology for estimating intrinsic filler permeabilities for five gases (He, O₂, N₂, CH₄, and CO₂). This comprehensive multi-matrix, multi-gas study reveals a strong correlation between filler fractional free volume (FFV), BET surface area, and gas permeability, with isatin-based fillers exhibiting particularly high CO₂ permeability. Filler incorporation generally resulted in substantial permeability enhancements (100-350%) while maintaining selectivity, often with only minor losses or even favorable improvements in CO₂/CH₄ and He/CH₄ separation performance. Several MMMs, particularly those based on Pi-DAPOH and Pi-DAROH polyimides, approached or exceeded the Robeson upper bound. Analysis of permeability as a function of gas kinetic diameter further elucidated clear structure-property relationships, confirming that filler-induced disruption of polymer chain packing and the creation of additional transport pathways are the primary factors governing separation performance. Overall, these findings demonstrate that rationally designed porous organic fillers provide a robust and broadly applicable strategy for mitigating the permeability-selectivity trade-off in polymer membranes and enhancing gas separation efficiency.