A study of the solid-state polymerization of trithiane

Abstract

The temperature dependence of the rate of solid-state polymerization of trithiane was investigated in conjunction with calorimetric measurements of the heat capacity of the irradiated monomer as a function of temperature. It was found that the rate of change of entropy with temperature exhibited a maximum at about 175°C. The curve of per cent polymerization versus isochronal, post-irradiation polymerization temperature also peaked at some 175°C. Finally, the existence of a crystalline phase-transition in the monomer at about 194°C was discovered by DSC and was confirmed by X-ray powder diffraction and by optical microscopy. Two models which may interrelate this set of phenomena are suggested.