Oral: Leverage Long-term Physical Aging of Non-Equilibrium Microporous Polymeric Membranes for Complex CO2 and H2-based Separations

Physical aging in glassy polymers leads to densification, typically reducing a penetrant's permeability with minimal selectivity improvement. While usually seen as undesirable in membranes, the aging behavior of microporous hydrocarbon polymers synthesized via catalytic arene-norbornene annulation (CANAL) offers a unique advantage. After 150 days, these materials showed a 3300% increase in CO₂/CH₄ selectivity and a 1000% boost in H₂/CH₄ selectivity, surpassing upper bounds while maintaining superior gas permeability. We enhanced the size-sieving effects of CANAL membranes through aging, optimizing gas separation for complex CO₂ and H₂ mixtures. Stability was also assessed under industrial conditions, including gas mixtures and high temperatures. Prolonged aging significantly improved H₂/CO₂ selectivity, exceeding the 2008 upper bound. Simulations predict high H₂ permeability (15,000 barrer) without sacrificing H₂/CO₂ selectivity from 35°C to 190°C, a typical post-water-gas-shift condition. This positions aged CANAL membranes among the top H₂/CO₂ separation membranes. We also evaluated stability in high concentrations of plasticizing gases like CO₂ and H₂S. Concentration-dependent CO₂ plasticization reduced CO₂/CH₄ selectivity without affecting permeability, while time-dependent effects slightly reduced selectivity but increased permeability. This characterization of hyper-aged CANAL polymers provides valuable insights for industrial applications.