Thiyl radical reversible-deactivation polymerization via degenerative transfer with vinyl sulfides

Precise control over thiyl radical polymerizations remains a significant challenge in polymer chemistry, particularly within the framework of traditional reversible-deactivation radical polymerization (RDRP) techniques. In this work, we introduce a novel thiyl radical reversible-deactivation polymerization (SRDP) strategy that employs vinyl sulfides as degenerative transfer agents to reversibly deactivate the propagating thiyl radicals, thus enabling direct and efficient control over the thiyl radical polymerizations to afford polymers with tunable molecular weights and low dispersities. The controlled nature of this polymerization was further confirmed by first-order kinetics, a linear relationship between molecular weight and conversion, and efficient chain extension. In addition, density functional theory calculations offered valuable insights into the reversible-deactivation ability of vinyl sulfides. The versatility of the SRDP method was demonstrated through its compatibility with a wide range of thiyl radical polymerizations and its successful application in synthesizing structurally diverse copolymers. This study represents a new reversible-deactivation pattern for thiyl radical polymerizations and would lead to a powerful platform for the precise synthesis of complex functional materials.