This tutorial review describes recent research directed towards the synthesis of polymer-based organic microporous materials termed Polymers of Intrinsic Microporosity (PIMs). PIMs can be prepared either as insoluble networks or soluble polymers with both types giving solids that exhibit analogous behaviour to that of conventional microporous materials such as activated carbons. Soluble PIMs may be processed into thin films for use as highly selective gas separation membranes. Preliminary results also demonstrate the potential of PIMs for heterogeneous catalysis and hydrogen storage.

Microporous materials can be derived directly from soluble polymers whose randomly contorted shapes prevent an efficient packing of the macromolecules in the solid state.

Microporous polymers of extreme rigidity are required for gas-separation membranes that combine high permeability with selectivity. We report a shape-persistent ladder polymer consisting of benzene rings fused together by inflexible bridged bicyclic units. The polymer's contorted shape ensures both microporosity-with an internal surface area greater than 1000 square meters per gram-and solubility so that it is readily cast from solution into robust films. These films demonstrate exceptional performance as molecular sieves with high gas permeabilities and good selectivities for smaller gas molecules, such as hydrogen and oxygen, over larger molecules, such as nitrogen and methane. Hence, this polymer has excellent potential for making membranes suitable for large-scale gas separations of commercial and environmental relevance.

A polymer with a rigid, randomly contorted molecular structure (see Figure), incorporating fused rings connected by spiro‐centres, may be precipitated or cast from solution to give microporous powders and membranes stable up to temperatures of 350 °C, with apparent surface areas > 600 m2 g–1. Organophilic membranes may be formed, as demonstrated by the separation of phenol from water by pervaporation.

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The past decade has seen the development of microporous materials (i.e., materials containing pores of dimensions <2 nm) derived wholly from organic components. Here we review this nascent area with a particular emphasis on amorphous polymers that possess intrinsic microporosity (IM), which is defined as microporosity that arises directly from the shape and rigidity of component macromolecules. Although IM can be readily identified within soluble non-network polymers and oligomers, for network polymers it is harder to differentiate IM from template effects that are responsible for the microporosity within hyper-cross-linked networks. The numerous examples of microporous polymers assembled from rigid monomers by the formation of rigid linking groups are surveyed and their IM assessed. The potential applications of these materials are highlighted.

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Ultrapermeable benzotriptycene-based PIMs show exceptional gas selectivities that define new positions for the CO2/CH4 and CO2/N2 Robeson upper bounds.