Conformation, environment and reactivity of radicals in copolymerization of methyl methacrylate/ethylene glycol dimethacrylate

The electron spin resonance (e.s.r.) spectra of radicals observed during the copolymerization of methyl methacrylate (MMA) and ethylene glycol dimethacrylate (EGDMA) consist of 13 lines in the initial liquid phase, but change to 9 lines as the copolymerization proceeds. The experimental spectra have been simulated by use of a model based upon a Gaussian distribution of dihedral angles about a most stable conformation. The simulations suggest that the e.s.r. spectra are superpositions of spectra arising from three types of radicals: a liquid-phase radical giving rise to a 13-line spectrum and two solid-phase radicals giving rise to two slightly different 9-line spectra. The two types of 9-line spectra correspond to terminal radicals on EGDMA and MMA residues. The ratio of the two types of solid-phase radicals is correlated with the degree of disorder of the reacting system, which accounts for the observed dependence of both initiator efficiency and final radical concentration upon the weight fraction of EGDMA. When copolymerization proceeded to medium conversion, ultra-violet irradiation of the samples reinitiated the reaction and caused a temporary reappearance of the 13-line spectrum, indicating that some propagating radicals are trapped in the polymer matrix.