Hydrolysis of p-Phenylenediamine Antioxidants: The Reaction Mechanism, Prediction Model, and Potential Impact on Aquatic Toxicity

Abstract

While p-phenylenediamine antioxidants (PPDs) pose potential risks to aquatic ecosystems, their environmental persistence and transformation remain ambiguous due to the undefined nature of PPD C–N bond hydrolysis. Here, we investigated the hydrolysis patterns of PPDs by analyzing their hydrolysis half-lives, hydrolysis products around neutral pH (pH 6.0–7.7), and the role of atoms within the C–N bonds in PPDs. Hydrolysis preferentially targets the aromatic secondary amine N with the strongest proton affinity and the C atom of C–N with the highest nucleophilic-attack reactivity. The hydrolysis half-life (t_1/2) shortens when the maximum proton affinity of N increases. These results are supported by theoretical calculations, demonstrating a hydrolysis reaction propelled by proton transfer from water to N and complemented by aromatic nucleophilic substitution of N in C–N by water hydroxyl. With the experimental results and the atom reactivity-based predictive model, the t_1/2 around neutral pH for 60 PPDs (monitored in environment, commercially available, or under investigation) is determined, showing variations ranging from 2.2 h to 47 days. The model prediction of primary C–N hydrolysis is confirmed through typical PPDs. With the elucidated mechanism and developed model, this research provides new insights into PPD hydrolysis, underscoring its significance in delineating environmental impacts.