Topochemical polymerization is a polymerization method performed by monomers aligned in the crystal state. In this process, the monomers are crystallised and polymerised under external stimuli such as heat, light, or pressure. Compared to traditional polymerisation, the movement of monomers was confined by the crystal lattice in topochemical polymerisation, giving rise to polymers with high crystallinity, tacticity, and purity. Topochemical polymerisation can also be used to synthesise unique polymers such as polydiacetylene that are otherwise hard to prepare.
Various reactions have been adopted in the field of topochemical polymerisation, such as [2+2], [4+2], [4+4], and [3+2] cycloaddition, linear addition between dienes, trienes, diacetylenes. Other than linear polymers, they can also be applied to the synthesis of two dimensional covalent networks.