A highly gas permeable polyimide with improved molecular sieving properties is produced by using a bisanhydride monomer based on the rigid ethanoanthracene unit. The polymer (PIM-PI-EA) demonstrates enhanced selectivity for gas separations so that its gas permeability data lie above the 2008 Robeson upper bounds for the important O₂–N₂, H₂–N₂, CO₂–CH₄ and CO₂–N₂ gas pairs.

Polymers of intrinsic microporosity (PIMs) have been identified as potential next generation membrane materials for the separation of gas mixtures of industrial and environmental relevance. Based on the exceptionally rigid methanopentacene (MP) structural unit, a Polymer of Intrinsic Microporosity (PIM-MP-TB) was designed to demonstrate high selectivity for gas separations. PIM-MP-TB was prepared using a polymerisation reaction involving the formation of Tröger's base linking groups and demonstrated an apparent BET surface area of 743 m² g⁻¹ as a powder. The microporosity of PIM-MP-TB was also characterized by chain packing simulations. PIM-MP-TB proved soluble in chlorinated solvents and was cast as a robust, free-standing film suitable for gas permeation measurements. Despite lower gas permeability as compared to previously reported PIMs, high selectivities for industrially relevant gas pairs were obtained, surpassing the 2008 Robeson upper bound for H₂/CH₄ and O₂/N₂, (e.g., P O₂ = 999 Barrer; α O₂/N₂ = 5.0) and demonstrating a clear link between polymer rigidity and selectivity. Upon aging, the permeability data move parallel to the Robeson upper bounds with a decrease of permeability, compensated by a related increase in selectivity. Mixed gas permeation measurement for CO₂/CH₄ and CO₂/N₂ mixtures confirmed the excellent selectivity of PIM-MP-TB for potentially relevant separations such as biogas upgrading and CO₂ capture from flue gas. Importantly, unlike other high performing PIMs, PIM-MP-TB is prepared in four simple steps from a cheap starting material.