Reactions between Molecular Chlorine and Acrylates over a Wide Range of Temperatures

Abstract

EPR, UV, VIS spectroscopy, chromatography, calorimetry, elemental analysis, and gravimetry are used to show that radicals formed spontaneously upon low temperature (77 K) interaction between molecular chlorine and methyl acrylate and/or methyl methacrylate initiate reactions of polymerization and chlorination that proceed under heating in a monomer system + Cl₂ prepared at 77 K. It is established that beginning at the premelting temperature of chlorine, both reactions mostly proceed at the temperatures of monomer melting, and the main reaction products are oligomers. It is concluded that chloroalkyl radicals formed spontaneously at 77 K react more readily with monomer molecules than do chlorine radicals in a cell.