Features of the processes occurring during low-temperature reactions between molecular chlorine and monomers and during the heating of mixtures

Abstract

Using EPR, UV, VIS, and IR spectroscopy; chromatography; calorimetry; elemental analysis; and gravity, it has been shown that low-temperature reactions between molecular chlorine and some acetylenic and/or vinyl monomers lead to the spontaneous formation of radicals without involving any external energy impact. The resulting radicals initiate polymerization and chlorination reactions that occur during the heating of mixtures prepared at 77 K. In mixtures where the monomers are solids under normal conditions, the polymerization and chlorination reactions occur in the range of the melting point of chlorine. In mixtures where the monomers are liquids, the reactions begin at temperatures below the melting point of chlorine (170 K) and occur at a maximum rate in the region of the melting point of the monomer. The main reaction products are oligomers. The last-mentioned fact suggests that the spontaneously formed chloroalkyl radicals more readily react with the monomer molecules than with the caged chlorine radical.