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A highly rigid and gas selective methanopentacene-based polymer of intrinsic microporosity derived from Tröger's base polymerization / Mariolino, Carta
Journal of Materials Chemistry A, Volume: 6, Issue: 14, Pages: 5661 - 5667
Swansea University Author: Mariolino, Carta
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Polymers of intrinsic microporosity (PIMs) have been identified as potential next generation membranematerials for the separation of gas mixtures of industrial and environmental relevance. Based on theexceptionally rigid methanopentacene (MP) structural unit, a Polymer of Intrinsic Microporosity (PI...
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Polymers of intrinsic microporosity (PIMs) have been identified as potential next generation membranematerials for the separation of gas mixtures of industrial and environmental relevance. Based on theexceptionally rigid methanopentacene (MP) structural unit, a Polymer of Intrinsic Microporosity (PIM-MPTB)was designed to demonstrate high selectivity for gas separations. PIM-MP-TB was prepared usinga polymerisation reaction involving the formation of Troger's base linking groups and demonstrated an ¨apparent BET surface area of 743 m2 g1 as a powder. The microporosity of PIM-MP-TB was alsocharacterized by chain packing simulations. PIM-MP-TB proved soluble in chlorinated solvents and wascast as a robust, free-standing film suitable for gas permeation measurements. Despite lower gaspermeability as compared to previously reported PIMs, high selectivities for industrially relevant gas pairswere obtained, surpassing the 2008 Robeson upper bound for H2/CH4 and O2/N2, (e.g., PO2 ¼ 999Barrer; aO2/N2 ¼ 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 andCO2/N2 mixtures confirmed the excellent selectivity of PIM-MP-TB for potentially relevant separationssuch as biogas upgrading and CO2 capture from flue gas. Importantly, unlike other high performingPIMs, PIM-MP-TB is prepared in four simple steps from a cheap starting materia
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