Organophosphorus antioxidants action mechanisms and new trends

Abstract

AbstractPhosphite and phosphonite esters can act as antioxidants by three basic mechanisms depending on their structure, the nature of the substrate to be stabilized and the reaction conditions. All phosph(on)ites are hydroperoxide‐decomposing secondary antioxidants. Their efficiency in hydroperoxide reduction decreases in the order phosphonites > alkylphosphites > arylphosphites > hindered arylphosphites. Five‐membered cyclic phosphites are capable of decomposing hydroperoxides catalytically due to the formation of acidic hydrogen phosphates by hydrolysis and peroxidolysis in the course of reaction. Hindered aryl phosphites can act as chain‐breaking primary antioxidants being substituted by alkoxyl radicals and releasing hindered aryloxyl radicals which terminate the radical chain oxidation. At ambient temperatures, the chain‐breaking antioxidant activity of aryl phosphites is lower than that of hindered phenols, because the rate of their reaction with peroxyl radicals and their stoichiometric inhibition factors are lower than those of phenols. In oxidizing media at medium temperatures, however, hydrolysis of aryl phosph(on)ites takes place giving hydrogen phosph(on)ites and phenols which are effective chain‐breaking antioxidants.2,2,6,6‐Tetramethyl‐ and 1,2,2,6,6‐Pentamethylpiperidinyl phosphites and phosphonites (HALS‐phosph(on)ites) surpass many common phosphites, phenols and HALS compounds as stabilizers in the thermo‐ and photo‐oxidation of polymers. Their superior efficiency is probably due to an intramolecular synergistic action of the HALS and the phosph(on)ite moieties of their molecules.