The role of dislocations in the solid‐state polymerization of monomers having conjugated triple bonds: A study of 2,4‐hexadiyne‐1,6‐diol bis( p ‐toluene sulfonate)

The crystal structure of the monomer bis( p ‐toluene sulfonate) ester of 2,4‐hexadiyne‐1,6‐diol (pT) is conducive from the viewpoint of both the separation distances and molecular configuration, to polymerization, irrespective of whether initiation is thermal, photochemical, or mechanical. The dislocations present in the monomer and polymer structures have been characterized by employing optical microscopic techniques. The slip system (102)[010] is found to be present in both monomer and polymer crystals but the (010)[001] system is found only in the monomer. On this basis a crystal structure for the monomer is proposed based on existing crystallographic information relating to the structure of the polymer. Dislocations are thought, on energetic grounds, to facilitate nucleation of product in the thermal polymerization but have no observable influence on the photoinduced reaction which proceeds homogeneously through the bulk.