| Abstract: | Hindered Amine Light Stabilizers (HALS) are know to inhibit the photo-oxidation of polymers. A key reaction in their stabilization mechanism is believed to be the conversion of a hindered aminoether into a nitroxyl radical. Several different possible mechanisms for this conversion were explored. One, the elimination of the aminoether to form an olefin and hydroxylamine (an intermediate in the formation of a nitroxyl), while possible at high temperatures, cannot account for the inhibitory activity we observed for secondary and primary aminoethers. Direct radical displacement by peroxy radicals was also considered. However, the products predicted by this reaction pathway were not observed. Finally, oxidation of the nitrogen by a peroxy radical, by either electron transfer or a radical attack on the nitrogen, was investigated. While electron transfer was shown to be unlikely, direct oxidation of the aminoether nitrogen was supported by our results. A detailed mechanism for the reaction of both alkyl- and acyl-peroxy radicals with aminoethers is proposed. |
