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The design of modern ways of sulfur transformation to different compounds (e.g., the polymer form having a number of valuable properties) is an important scientific task, because it can increase the global demand for elemental sulfur. The investigated sulfur-containing systems were heated with microwave radiation (microwave synthesizer Biotage Initiator+, microwave frequency 2.45 GHz). The researches of the systems were carried out by 31P NMR spectroscopy. It could be concluded that the microwave heating could lead to the sulfur polymerization or oligomerization with the sulfur chain opening and with the attaching of the ionic liquid fragments to the chain