Membranes with high permeability to gases are formed from polyimides with rigid backbones that incorporate a spiro-centre. A route to this new range of high-free-volume polyimides is demonstrated, and exceptional performance is obtained for a polymer containing a dimethyl binaphthyl unit.

A novel triptycene-based polymer of intrinsic microporosity (Trip-PIM) displays enhanced surface area (1065 m2 g(-1)) and reversibly adsorbs 1.65% hydrogen by mass at 1 bar/77 K and 2.71% at 10 bar/77 K.

The challenge of storing hydrogen at high volumetric and gravimetric density for automotive applications has prompted investigations into the potential of cryo-adsorption on the internal surface area of microporous organic polymers. A range of Polymers of Intrinsic Microporosity (PIMs) has been studied, the best PIM to date (a network-PIM incorporating a triptycene subunit) taking up 2.7% H(2) by mass at 10 bar/77 K. HyperCrosslinked Polymers (HCPs) also show promising performance as H(2) storage materials, particularly at pressures >10 bar. The N(2) and H(2) adsorption behaviour at 77 K of six PIMs and a HCP are compared. Surface areas based on Langmuir plots of H(2) adsorption at high pressure are shown to provide a useful guide to hydrogen capacity, but Langmuir plots based on low pressure data underestimate the potential H(2) uptake. The micropore distribution influences the form of the H(2) isotherm, a higher concentration of ultramicropores (pore size <0.7 nm) being associated with enhanced low pressure adsorption.

The performance of polymeric membranes for gas separation is mainly determined by the free volume. Polymers of intrinsic microporosity are interesting due to the high abundance of accessible free volume. We performed measurements of the temperature dependence of the positron lifetime, generally accepted for investigation of free volume, in two polymers of intrinsic microporosity (PIM‐1 and PIM‐7) in the range from 143 to 523 K. The mean value of the free volume calculated from the ortho‐positronium lifetime is in the range of typical values for high free volume polymers. However, the temperature dependence of the local free volume is non‐monotonous in contrast to the macroscopic thermal expansion. The explanation is linked to the spirocenters in the polymer. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)