Abstract
Addition reaction of photo-generated organic radicals to maleic anhydride (MA), that is a common monomer in polymerization, was studied by time-resolved (TR)- and pulsed electron paramagnetic resonance (EPR) spectroscopic methods. The radicals examined are 2-hydroxypropyl (2Hy-Pr), diphenylphosphine oxide (DPPO) and hydroxycyclohexyl (Hy-CyH). Analysis of TR-EPR spectra gave the structures of adduct radicals. The addition rate constants of the radicals generated by the photolysis of initiators were measured by electron spin echo detection method. It was found that the addition reaction rate constants of 2Hy-Pr, DPPO and Hy-CyH radicals to MA show exceptionally smaller values than those estimated by the theoretical reaction model based on enthalpy and polar effects.
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