The polymerization of crystalline trioxane. II. experiments with irradiated trioxane (and tetraoxane) calculation of the crystal field of trioxane

Abstract

The physics of the polymerization of irradiated trioxane crystals have been studied experimentally and theoretically. A geometrical comparison of the monomer and polymer crystal lattices suggests that growth of the polymer twins must occur in a synchronized fashion. The crystal field in the polar trioxane lattice has been calculated. The results are highly suggestive of its important role in the polymerization. Experiments with tritiated water show that this contaminant resides specifically on the crystal surface. Trioxane has been found to have no phase transitions between room temperature and the melting point. The heat of the polymerization is 21 cal g⁻¹. Partly polymerized trioxane shows a melting behaviour, suggesting the occurrence of trioxane in two different phases. Tetraoxane can be polymerized in a similar way as trioxane. The heat of the reaction is 23 cal g⁻¹.