Enhancement of CO(2) Affinity in a Polymer of Intrinsic Microporosity by Amine Modification

[Image: see text] Nitrile groups in the polymer of intrinsic microporosity PIM-1 were reduced to primary amines using borane complexes. In adsorption experiments, the novel amine–PIM-1 showed higher CO(2) uptake and higher CO(2)/N(2) sorption selectivity than the parent polymer, with very evident dual-mode sorption behavior. In gas permeation with six light gases, the individual contributions of solubility and diffusion to the overall permeability was determined via time-lag analysis. The high CO(2) affinity drastically restricts diffusion at low pressures and lowers CO(2) permeability compared to the parent PIM-1. Furthermore, the size-sieving properties of the polymer are increased, which can be attributed to a higher stiffness of the system arising from hydrogen bonding of the amine groups. Thus, for the H(2)/CO(2) gas pair, whereas PIM-1 favors CO(2), amine–PIM-1 shows permselectivity toward H(2), breaking the Robeson 2008 upper bound.