Xanthate Disulfide-Mediated RAFT Polymerization Toward Oxygen Tolerance

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 (¹H-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.