Liquid Chromatography Quadrupole Time-of-Flight Mass Spectrometry Analysis of Eutectic Bis(2,2-dinitropropyl) Acetal/Formal Degradation Profile: Nontargeted Identification of Antioxidant Derivatives.

In the eutectic mixture of bis(2,2-dinitropropyl) acetal (BDNPA) and bis(2,2-dinitropropyl) formal (BDNPF), also known as nitroplasticizer (NP), -phenyl-β-naphthylamine (PBNA), an antioxidant, is used to improve the long-term storage of NP. PBNA scavenges nitrogen oxides (e.g., NO radicals) that are evolved from NP decomposition, hence slowing down the degradation of NP. Yet, little is known about the associated chemical reaction between NP and PBNA. Herein, using liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF), we thoroughly characterize nitrated PBNA derivatives with up to five NO moieties in terms of retention time, mass verification, fragmentation pattern, and correlation with NP degradation. The propagation of PBNA nitration is found to depend on the temperature and acidity of the NP system and can be utilized as an indirect, yet reliable, means of determining the extent of NP degradation. At low temperatures (<55 °C), we find that the scavenging efficiency of PBNA is nullified when three NO moieties are added to PBNA. Hence, the dinitro derivative can be used as a reliable indicator for the onset of hydrolytic NP degradation. At elevated temperatures (≥55 °C) and especially in the dry environment, the trace amount of water in the condensed NP (<700 ppm) is essentially removed, which accelerates the production of reactive species (e.g., HONO, HNO and NO ). In return, the increased acidity due to HNO formation catalyzes the hydrolysis of NP and PBNA nitro derivatives into 2,2-dinitropropanol (DNPOH) and nitrophenol/dinitrophenol, respectively.