Radiation‐induced postpolymerization of trioxane in the solid state. II. Kinetic study of radiation‐induced postpolymerization of trioxane in dry and high‐vacuum system

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Abstract
A kinetic study of the radiation‐induced postpolymerization of trioxane in the solid state has been made. Trioxane was purified by sublimation through Ag2O and Na–K alloy in vacuo and was both irradiated and polymerized in a super‐dry system under high vacuum. In the present study it was found that the initial rate of polymerization is larger than that reported previously. It is reasonably suggested that the postpolymerization of trioxane consists of two stages, i.e., a very large rate at the first stage and a relatively small one at the second stage. By using the kinetic scheme proposed previously kinetic parameters at the second stage were determined. It was found that trioxane can be postpolymerized even at a temperature below 30°C with good reproducibility and that the overall activation energy of the polymerization was less than 15 kcal/mole. No chain‐transfer reaction seems to occur except at low temperatures. These results have been discussed in comparison with data reported previously.

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