Cu2O nanoparticle-catalyzed tandem reactions for the synthesis of robust polybenzoxazole

Abstract

We report the synthesis of Cu₂O nanoparticles (NPs) by controlled oxidation of Cu NPs and the study of these NPs as a robust catalyst for ammonia borane dehydrogenation, nitroarene hydrogenation, and amine/aldehyde condensation into Schiff-base compounds. Upon investigation of the size-dependent catalysis for ammonia borane dehydrogenation and nitroarene hydrogenation using 8–18 nm Cu₂O NPs, we found 13 nm Cu₂O NPs to be especially active with quantitative conversion of nitro groups to amines. The 13 nm Cu₂O NPs also efficiently catalyze tandem reactions of ammonia borane, diisopropoxy-dinitrobenzene, and terephthalaldehyde, leading to a controlled polymerization and the facile synthesis of polybenzoxazole (PBO). The highly pure PBO (M_w = 19 kDa) shows much enhanced chemical stability than the commercial PBO against hydrolysis in boiling water or simulated seawater, demonstrating a great potential of using noble metal-free catalysts for green chemistry synthesis of PBO as a robust lightweight structural material for thermally and mechanically demanding applications.