Structural aspects of the topochemical polymerization of diacetylenes

The present state of knowledge of the topochemical polymerization of diacetylenes is reviewed with regard to structural properties. Principles and mechanisms of topochemical reactions are described. Solid-state polymerization of diacetylenes utilizes the special packing properties of monomer units in their crystals. Rules relating reactivity in the solid-state and packing properties are given and the relation between reaction mechanism, molecular mobility and polymer morphology are discussed. The growth of the macromolecules in the monomer crystal, the molecular weight and its distribution with regard to the reaction kinetics and phase transitions are outlined. The electronic structure of the polydiacetylene chain is best represented by the acetylene resonance structure consisting of alternating double, single and triple bonds.

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