Solid-state thermal polymerization of the heterocyclic HC7N7 acid

The preparation of a new type of thermally stable (up to 385°C) heterocyclic polymer, containing a five-membered fused ring system, is described. The ultraviolet, visible, and infrared spectra indicate that this solid-state polymerization probably proceeds via formation of an azomethine-type intermolecular crosslink, rather than via opening of the C₄N₄ ring system. The reaction is facilitated by the presence of reactive protons, which act as an efficient catalyst for this nucleophilic addition to the nitrile group. It is suggested that this type of solid-state polymerization may possibly be carried out on a single HC₇N₇ crystal resulting in a fully ordered macroscopic polymer single crystal.