As a method for overcoming the challenge of rigorous deoxygenation in copper‐mediated controlled radical polymerization processes [e.g., atom‐transfer radical polymerization (ATRP)], reported here is a simple Cu⁰‐RDRP (RDRP=reversible deactivation radical polymerization) system in the absence of external additives (e.g., reducing agents, enzymes etc.). By simply adjusting the headspace of the reaction vessel, a wide range of monomers, namely acrylates, methacrylates, acrylamides, and styrene, can be polymerized in a controlled manner to yield polymers with low dispersities, near‐quantitative conversions, and high end‐group fidelity. Significantly, this approach is scalable (ca. 125 g), tolerant to elevated temperatures, compatible with both organic and aqueous media, and does not rely on external stimuli which may limit the monomer pool. The robustness and versatility of this methodology is further demonstrated by the applicability to other copper‐mediated techniques, including conventional ATRP and light‐mediated approaches.

中文翻译：

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铜介导的聚合反应，无需外部脱氧或除氧剂

作为克服铜介导的受控自由基聚合过程[例如，原子转移自由基聚合（ATRP）]中严格脱氧挑战的方法，此处报道的是一种简单的Cu ⁰‐RDRP（RDRP =可逆失活自由基聚合）系统，无需外部添加剂（例如，还原剂，酶等）。通过简单地调节反应容器的顶部空间，可以以可控的方式聚合各种单体，即丙烯酸酯，甲基丙烯酸酯，丙烯酰胺和苯乙烯，以生成具有低分散性，接近定量转化率和高端基的聚合物保真。值得注意的是，这种方法是可扩展的（约125 g），耐高温，与有机和水性介质均兼容，并且不依赖于可能限制单体池的外部刺激。这种方法的鲁棒性和多功能性还通过其他铜介技术的适用性得到了证明，包括传统的ATRP和光介方法。