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

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 (Mw = 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.