Oxygen-Driven Atom Transfer Radical Polymerization

In traditional atom transfer radical polymerization (ATRP), oxygen must be meticulously eliminated due to its propensity to quench radical species and halt the polymerization process. Additionally, oxygen oxidizes the lower-valent Cu catalyst, compromising its ability to activate alkyl halides and propagate polymerization. In this study, we present an oxygen-driven ATRP utilizing alkylborane compounds, a method that not only circumvents the need for stringent oxygen removal but also exploits oxygen as an essential cofactor to promote polymerization. This approach exhibits broad compatibility in organic or aqueous media, yielding well-defined polymers with low dispersity (Đ as low as 1.11) and molecular weights closely aligned with theoretical values. Triethylborane (Et₃B) and its air-stable triethylborane-amine complex (Et₃B-DMAP) facilitate controlled polymerization under open-to-air conditions, demonstrating efficiency across a wide range of monomers. Moreover, the technique enables the successful synthesis of protein–polymer conjugates and supports surface modifications of nanoparticles and silicon wafers under aerobic conditions. This oxygen-driven ATRP represents a robust and versatile platform for precision polymerization with far-reaching implications in materials science, biomedicine, and advanced surface engineering.