Bodachivskyi I. Synthesis, properties, and application of oleochemical polysulfanes

Did a new method of a chemical conversion of vegetable oils and fats via alcoholysis with concomitant sulfuration of fatty acid alkyl esters, or their sequential vulcanisation with benzoyl peroxide and elemental sulfur was developed. By a means of IR-spectroscopy, NMR, differential scanning calorimetry and rheological readings, the structure of the synthesised products in response to the reaction conditions and presence of accelerants was explored. The achieved data reveals that oleochemical sulfanes are complex structures with a various cross-linking degree and contain sulfur-rich cyclic and linear derivatives. An optimisation of the structure of possible compounds and evaluation of energy data of potential reaction pathways were performed using quantum-chemical methods. It has been proposed that the addition to carbon-carbon double bonds occurs via intermediate zwitterions of octasulfur. In turn, a substitution of allylic hydrogens is likely to take place of due to the interaction of alkenes with biradicals of disulfur followed by the formation of hydropolysulfanes. The latest molecules can be converted into cyclic polysulfanes via inner-molecular cyclisation or to the linear products through the interaction with air oxygen.