Polymers of intrinsic microporosity(PIMs) are a class of porous organic polymer(POP) that form microporous solids due to the inefficient packing of their rigid and contorted macromolecular chains. In contrast to other types of POP, PIMs are not comprised of a network of cross-linked covalent bonds so that they can be dissolved in organic solvents and processed into robust films,coatings or fibres. Here, over twelve years’ accumulated research on the synthesis of PIMs is reviewed. To date, three types of polymerisation reaction have been used successfully to prepare PIMs of sufficient molecular mass to form robust self-standing films. These involve the formation of dibenzodioxin, Tr鰃er抯 base and imide linkages between monomeric units. This rapid development of synthetic methods for preparing PIMs has been driven by their rich potential for numerous diverse applications and this synergistic relationship between synthesis and functionality is set to continue.
