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Abstract Polymer materials suffer mechano-oxidative deterioration or degradation in the presence of molecular oxygen and mechanical forces. In contrast, aerobic biological activities combined with mechanical stimulus promote tissue regeneration and repair in various organs. A synthetic approach in which molecular oxygen and mechanical energy synergistically initiate polymerization will afford similar robustness in polymeric materials. Herein, aerobic mechanochemical reversible-deactivation radical polymerization was developed by the design of an organic mechano-labile initiator which converts oxygen into activators in response to ball milling, enabling the reaction to proceed in the air with low-energy input, operative simplicity, and the avoidance of potentially harmful organic solvents. In addition, this approach not only complements the existing methods to access well-defined polymers but also has been successfully employed for the controlled polymerization of (meth)acrylates, styrenic monomers and solid acrylamides as well as the synthesis of polymer/perovskite hybrids without solvent at room temperature which are inaccessible by other means. 

Spatial and temporal regulations of ATRP by external stimuli are presented. Various ATRP techniques, e ATRP, photoATRP, and mechanoATRP, are controlled by electrical current, light, and mechanical forces, respectively. Conversely, ARGET and SARA ATRP are controlled by chemical reducing agents. ICAR ATRP is a thermally regulated process through decomposition of a radical initiator. The aim of this review is to highlight the use of external regulations in ATRP and to summarize the state-of-the-art and future perspectives, focusing on mechanistic aspects, synthetic procedures, preparation of polymers with complex architectures and functional materials, and their applications.