Xanthate Disulfide‐Mediated RAFT Polymerization Toward Oxygen Tolerance

Abstract In recent years, the fully oxygen‐tolerant reversible addition‐fragmentation chain transfer (RAFT) polymerization has been emerging as a versatile and powerful tool for preparing well‐defined polymers. In this contribution, the symmetrical diethyl xanthogen disulfide (XD) is successfully used as an initiator, chain transfer agent, and termination (iniferter) agent to directly regulate the open‐to‐air RAFT polymerization. The high end‐group fidelity of polymer demonstrated by nuclear magnetic resonance ( 1 H‐NMR) and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectra indicates that sulfur‐centered xanthate radical can initiate and regulate RAFT polymerization of methacrylate (MA) under open conditions. It is believed that sulfur‐centered xanthate radical initiation strategy provides a powerful and minimalist tool for fully oxygen‐tolerant RDRPs.