Mechanisms of Ozonation of N,N′-di-(1-Methylheptyl)-p-Phenylenediamine

Abstract

Abstract The ozonation products of a common rubber antiozonant, N,N′-di-(l-methylheptyl)-p-phenylenediamine (DOPPD), have been separated by liquid or gas chromatography. Molecular weights of about thirty LC separated components have been measured by field desorption mass spectroscopy. Elemental formulae have been determined by atomic composition mass spectroscopy. Other structural details have been elucidated by electron impact mass spectroscopy and attenuated total reflectance infrared spectroscopy. Two principal mechanisms appear to govern the ozonation of DOPPD. Amine oxide formation leads to observed nitrosoaryl and nitroaryl products. The second major mechanistic pathway is side chain oxidation. This leads to a number of low molecular weight components, including some that contain an amide moiety. A third (minor) mechanistic pathway involves a nitroxide radical intermediate and leads to the formation of a stable dinitrone species. The surface film formed on ozonation of a black loaded natural rubber sheet containing DOPPD has also been examined. The film contains appreciable quantities of unreacted DOPPD and many of the same low molecular weight components as observed in the ozonized liquid antiozonant. It is clear that DOPPD blooms to the rubber surface and acts as a scavenger for ozone. The results are consistent with a combined “scavenger-protective film” mechanism for antiozonant protection.