Application of spin trapping technique to radical polymerization, 15. Photo‐decomposition of dibenzoyl disulfide and evaluation of relative reactivities of vinyl monomers toward the benzoylthiyl radical

The mechanism of photo‐decomposition of dibenzoyl disulfide (DBDS) in benzene or in monomers, and the evaluation of relative reactivities of various vinyl monomers toward the benzoylthiyl radical (4) were investigated by means of the spin trapping technique using 2‐methyl‐2‐nitrosopropane (BNO). When DBDS photo‐decomposed in benzene at 22±2°C in the presence of BNO, both 4 and benzoyl radicals were trapped as their nitroxyl radicals, indicating that both SS and CS bonds in DBDS were decomposed during its photolysis. However, when the photo‐decompositions were performed in the monomers, propagating radicals (7) were trapped, but no allyl‐type radicals (11). The coupling constants of the nitroxyl radicals of various propagating radicals were determined. From the ESR spectra of the systems DBDS/vinyl monomers/methyl methacrylate (as reference)/BNO the relative concentrations of the nitroxyls, [8]/[10, X = COOCH3], were determined by computer simulation, and the relative reactivities of the vinyl monomers toward 4 were estimated. It was found that the relative reactivities of these monomers are correlated with their e values to give a linear relationship with a negative slope, similar to those toward the tert‐butoxyl radical found in the previous paper.