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This short Perspective conveys to the general reader of Macromolecules basic approaches of materials science of polymeric membranes for gas and vapor separation. The relations between the polymer structure and transport properties of rubbery and glassy membrane materials are considered. On the basis of acquired information, several methods for quantitative prediction of permeability were developed, and their comparative analysis is given in the Perspective. The past decade was marked by the appearance of a number of novel interesting membrane materials, which will be briefly described in the text. In conclusion, novel approaches for achieving highly permeable and permselective materials (e.g., mixed matrix membranes) will be considered as well as several relevant but not solved so far problems of membrane gas separation.

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The present paper deals with a molecular modeling-based characterization of the distribution of free volume in a number of different stiff chain glassy polymers including ultrahigh free volume and conventional materials. The free volume distribution was analyzed for the validated packing models and compared with respective positron annihilation data (if available). It will be shown that the molecular modeling approach permits a more detailed insight into free volume distributions. There the observed distributions reach from more or less symmetric monomodal (with maximum probability at free volume element radii of about 3 Å) via monomodal distributions with extended tails toward larger radii up to distinctly bimodal distributions with a tendency toward a continuous nanoporous free volume phase besides "conventional", free volume organized in isolated holes of radii up to a few angstroms. The described sequence roughly corresponds to the trend of measured permeabilities for small molecules in the investigated materials.

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A range of polyimides with characteristics similar to a polymer of intrinsic microporosity (PIM) were prepared by reaction with various aromatic diamines of a bis(carboxylic anhydride) incorporating a spiro-center. The polymers exhibited high surface area, as determined by nitrogen adsorption, and high thermal stability. Membrane gas permeation experiments showed PIM-polyimides to be among the most permeable of all polyimides and to have selectivities close to the upper bound for several important gas pairs. A group contribution method was used to predict permeability coefficients and separation factors for further PIM-polyimide structures, revealing worthwhile targets for future synthetic efforts.

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Polymers of intrinsic microporosity (PIMs) are receiving increasing attention from the membrane community because of their high gas and vapor permeability. Recently a novel ethanoanthracene-based PIM synthesized by Troger's base formation (PIM-EA-TB) was reported to have exceptional transport properties, behaving as a polymer molecular sieve membrane. In the present work, an extensive investigation of the structural, mechanical, and transport properties of this polymer, both by experimental analysis and by molecular simulation, offers deep insight into the behavior of this polymer and gives an explanation for its remarkable performance as a membrane material. Transport properties were determined by the barometric time-lag method, by the volumetric method with gas chromatographic or mass spectrometric gas analysis, and by gravimetric sorption measurements, yielding all basic transport parameters, permeability (P), diffusivity (D), and solubility (S). Upon alcohol treatment, PIM-EA-TB exhibited a much stronger permeability increase than archetypal "benchmark" polymer PIM-1, with performance above the Robeson upper bound for several gas pairs. This is in part due to an extremely high gas solubility in PIM-EA-TB, higher than in PIM-1. The experimental data were supported by extensive modeling studies of the polymer structure and the spatial arrangement of its free volume. Modeling confirms that the high gas permeability must be attributed to the large fractional free volume of the polymer. The simulated free volume size distribution in PIM-EA-TB is in agreement with the average experimental free volume elements size determined by PALS and 129 Xe NMR analysis. The modeled spatial arrangement of the free volume revealed a slightly lower interconnectivity of the FV elements in PIM-EA-TB compared to PIM-1. Along with its higher chain rigidity, determined by analysis of the torsion angles in the polymer model, this was identified as the main reason for its stronger size sieving behavior and relatively high permselectivity. A number of peculiarities in the behavior of PIMs will also be discussed here, explaining discrepancies between results published in the literature by different laboratories, the effect of their thermomechanical history, aging, or conditioning, and the influence of the measurement technique and of the experimental conditions on the results. This makes this study of inestimable value for unifying the results of different experimental techniques and fully understanding the transport properties.