Electron paramagnetic resonance characterization and thermal decay of radicals trapped in a photopolymerized triacrylate monomer

Abstract

Radicals trapped during the photopolymerization and photo-cross-linking of 2-ethyl-2-hydroxymethylpropane-1,3-diol triacrylic ester have been studied by EPR spectroscopy at different temperatures (25–180 °C) and their thermal decay has been followed at 120 °C and 150 °C. Performing a fitting procedure on the EPR signals showed that they are composed of two kinds of patterns, which superimpose with the same g value. One of them is a single-line spectrum, while the other is hyperfine-structured. An exchange between two radical conformations is revealed by the latter, with the rate depending both on temperature and on the molar fraction of radicals giving the single-line spectrum. This suggests that both species are involved in the exchange mechanism. Termination occurs preferentially between radicals giving the same EPR pattern. Second-order termination rate constants depend on the photoinitiator concentration in the irradiated photoreactive mixture and give information about the microstructure of the polymer.