1.3.5- Trioxane. thermal decomposition

The thermolysis of a variety of 1,2,4-trioxanes in methanol has been followed by mass spectrometry and provided evidence of the corresponding products. A smdy of the thermal decomposition of 3,6-diphenyl-1,2,4,5-tetroxane in toluene and methanol revealed a significant solvent effect that supported a homolytic stepwise mechanism instead of a concerted process. ... 

The industrial production of copolymers of trioxane with ethylene oxide or di-oxolane (1-5%) is conducted as a bulk polymerization in special equipment. The incorporation of small amounts of C-C bonds into the C-0 chain has a remarkable effect on the thermal and chemical stability. In homopolymers the thermal decomposition starts at the semiacetal end groups ( unzipping ) and leads to a complete destruction of the polymer chain, whereas this reaction stops in copolymers already at the first C-C bond. A thermally stable OH end group is thus formed which, in addition, contributes to a much better alkali resistance compared to ester group-terminated homopolymers (see Examples 3-40 and 5-13). 

Tricyclic trioxanes, synthesis, 282, 283 Tricyclohexylgermyl hydroperoxide, thermal decomposition, 822-3 Triethylsilane, oxidation, 807-8 Triethylsilyl hydrotrioxide... 

The thermal decomposition reaction of 1,2,4-trioxane, along with others, was studied in toluene solution over a wide temperature range <2000MOL360>. The reaction follows a first-order kinetic law up to ca. 50% peroxide conversion. Only the linear dependence of activation enthalpies and entropies of this unimolecular reaction is reported with a slope of 130.4 °C as the isokinetic temperature . 

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