Multiscale approach to investigate the radiochemical degradation of epoxy resins under high‐energy electron‐beam irradiation

A multiscale investigation of the degradation mechanism of two epoxy systems exposed to electron‐beam irradiation under a helium atmosphere was carried out with a variety of analytical methods, including high‐resolution solution‐ and solid‐state NMR spectroscopy, NMR relaxometry, infrared spectroscopy, sterical exclusion chromatography, and differential scanning calorimetry. As a first step, we studied a linear phenoxy polymer, poly(2‐hydroxyether of bisphenol A), which provided a basis for the investigation of the degradation of a more complex, insoluble epoxy–amine network, diglycidyl ether of bisphenol A/triethylene tetramine. Among different structural modifications, the main degradation process was shown to produce in both cases a chain scission. For the phenoxy resin, the hydroxypropylidene moiety was identified as the fragile site leading to the formation of two phenolic chain ends and acetone and isopropyl alcohol as low‐molecular‐weight products. All methods, ranging from molecular to supramolecular scales, were shown to correlate both qualitatively and quantitatively. Experimental results obtained with diglycidyl ether of bisphenol A/triethylene tetramine evidenced a different degradation scheme occurring at the ethylene amine part and producing a dangling vinyl amine as the major degradation product. A selective increase in the molecular mobility at this site was confirmed by a two‐dimensional, local‐field wide‐line separation experiment. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 865–887, 2006