Mediation of water-soluble oligoaniline by phenol in the aniline–persulfate system under alkaline conditions

Abstract

Although synthesis of oligoaniline (OANI) by persulfate and aniline has been investigated in the recent years, the impact of phenol on the synthesized soluble OANI is still not clear. In this study, our results indicate that phenol and pH mediate the production of the blue water-soluble OANI (OANI_blue) in the reaction between sodium persulfate (SPS) and aniline under alkaline conditions, and the yields of OANI_blue increase with increasing concentrations of phenol and pH values. Quenching experiments rule out the contributions of SO₄˙⁻ and ˙OH to aniline oxidation and imply that the non-radical activation of SPS is an important pathway in the formation of OANI_blue. MALDI-TOF-MS analysis indicates that phenol apparently inhibits the polymerization degree of aniline in that the molecular weights of OANI_blue gradually decrease from 1586.4 to 684.6 when phenol is increased from 0 to 2.0 mM. FTIR and Raman analyses confirm the structure of aniline oligomers in OANI_blue and indicate that phenol inhibits the phenazine-like structure in OANI_blue and facilitates the transformation of benzenoid rings to quinoid rings in the oxidation products. However, simultaneous activation of SPS by phenol and aniline is likely to occur in the reaction system with the formation of PhNH˙, as indicated by DFT calculations. The high scavenging reactivity of phenol towards both PhNH₂˙⁺ and PhNH˙ implies that PhNH₂˙⁺ and PhNH˙ are not the intermediates in the formation of OANI_blue. DFT calculations also reveal that apart from the one-electron transfer pathway between aniline and SPS, the two-electron transfer pathway is also likely to occur in the presence of phenol, resulting in the formation of PhNH⁺/PhN˙˙ without producing PhNH₂˙⁺ and PhNH˙. The produced PhNH⁺/PhN˙˙ intermediates then couple with aniline, PhNH⁺, aminophenyl sulfate and its hydrolysate to form dimers, trimers, oligomers, and eventually OANI_blue. This study not only describes a novel method to prepare water-soluble OANI, but also gives new insight on the importance of phenol in the production of OANI_blue.