A highly gas permeable polymer with exceptional size selectivity is prepared by fusing triptycene units together via a poly­merization reaction involving Tröger's base formation. The extreme rigidity of this polymer of intrinsic microporosity (PIM‐Trip‐TB) facilitates gas permeability data that lie well above the benchmark 2008 Robeson upper bounds for the important O2/N2 and H2/N2 gas pairs.

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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 CO2 uptake and higher CO2/N2 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 CO2 affinity drastically restricts diffusion at low pressures and lowers CO2 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 H2/CO2 gas pair, whereas PIM-1 favors CO2, amine–PIM-1 shows permselectivity toward H2, breaking the Robeson 2008 upper bound.

Ionic liquid polymeric gel membranes containing from 20 wt % to 80 wt % of the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][TFSI]) in poly(vinylidene fluorideco-hexafluoropropylene) (p(VDF-HFP)) were prepared by solvent casting from a solution in acetone. The effect of the ionic liquid on the performance and properties of the membranes was discussed and compared with the neat polymer. In the presence of an excess of ionic liquid, p(VDF-HFP) membranes swell in a significant way, especially above 70°C, becoming completely soluble above 90°C. DSC analysis shows a gradual decrease of the melting point of the gel and a decrease in the overall melting enthalpy with increasing IL content, whereas the melting enthalpy normalized for the polymer fraction shows an initial drop and then a gradual increase. In the presence of the ionic liquid, the elastic modulus and break strength decrease dramatically, while the maximum deformation first increases due to higher flexibility of the plasticized polymer and then rapidly decreases above 40 wt % of IL as a consequence of the progressive decrease of the number of entanglements. X-ray studies demonstrate a reduction in the overall crystal content. The position of the strongest diffraction peak remains unaltered in all samples, suggesting that only the polymer chains crystallize and that no cocrystallization of ionic liquid and polymer takes place. Preliminary gas permeation measurements show a significant increase of the permeability in the presence of [EMIM][TFSI], especially for carbon dioxide. This suggests a potential application in gas separation membranes, for instance for natural gas treatment or for CO 2 sequestration from flue gas.

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