AbstractA detailed study of gas permeation, thermodynamic properties and free volume was performed for a novel polymer of intrinsic microporosity (PIM-1). Gas permeability was measured using both gas chromatographic and barometric methods. Sorption of vapors was studied by means of inverse gas chromatography (IGC). In addition, positron annihilation lifetime spectroscopy (PALS) was employed for investigation of free volume in this polymer. An unusual property of PIM-1 is a very strong sensitivity of gas permeability and free volume to the film casting protocol. Contact with water in the process of film preparation resulted in relatively low gas permeability (P(O2) = 120 Barrer), while soaking with methanol led to a strong increase in gas permeability (P(O2) = 1600 Barrer) with virtually no evidence of fast aging (decrease in permeability) that is typical for highly permeable polymers. For various gas pairs (O2/N2, CO2/CH4, CO2/N2) the data points on the Robeson diagrams are located above the upper bound lines. Hence, a very attractive combination of permeability and selectivity is observed. IGC indicated that this polymer is distinguished by the largest solubility coefficients among all the polymers so far studied. Free volume of PIM-1 includes relatively large microcavities (R = 5 Å), and the results of the PALS and IGC methods are in reasonable agreement.