Theoretical studies on the structure and property of alkylated dipenylamine antioxidants

Abstract

Diarylamines ( Ar 2 NH ) are generally used as antioxidants to inhibit or retard the auto-oxidation degradation of lubricating oil by trapping ROO• radicals. In the present study, 20 kinds of 4,4′-disubstituted diphenylamine compounds were investigated through density functional theory (DFT) calculations. The results indicate that the N – H bond dissociation enthalpy (BDE) linearly correlates its one-electron oxidation potential, the difference in Mulliken atomic charge on the two atoms of N – H bond, the reaction rate constant of hydrogen transfer from Ar 2 NH to peroxy radical, and the chemical hardness of the resulted Ar 2 N • radical, respectively. The substitution of alkyl groups (electron-donating groups) decreases the N – H BDE, one-electron oxidation potential and the reaction rate constant, while that of significant electron-withdrawing groups such as - NO 2 and - COOCH 3 increases these three parameters. The electron-donating groups such as alkyls could improve the antioxidation performance of 4,4′-disubstitued diphenylamines whereas electron-withdrawing groups have the contrary effect. In addition, the frontier molecular orbital of Ar 2 NH has been also analyzed.