NaOH‐Assisted Multicomponent Reaction and Polymerizations of Elemental Sulfur, Diisocyanides, and Diols to Access Functional Poly(<i>O</i>‐thiocarbamate)s

Sulfur-containing polymers with unique structures and fascinating properties have attracted much attention recently, the efficient and economic synthetic approaches for various sulfur-containing polymers have rapidly developed. Herein, the multicomponent reaction of elemental sulfur, isocyanide, and alcohol was designed at mild condition in the presence of NaOH, and the corresponding NaOH-assisted multicomponent polymerization of elemental sulfur, diisocyanides, and diols were developed at room temperature or 40 °C in air, to produce poly(O-thiocarbamate)s with well-defined structures, high molecular weights (M_ws up to 32 500 g/mol) and high yields (up to 99 %). The facilely available monomers, mild condition, and high efficiency of this MCP enabled scale-up synthesis of poly(O-thiocarbamate)s, and 7.33 g polymer was obtained in 98 % yield. These functional poly(O-thiocarbamate)s could enrich Au³⁺ from aqueous solution with high enrichment capacity (983 mg⋅Au³⁺/g) and high efficiency (>99.77 %) in 1 min, demonstrating superior gold enrichment performance and their potential industrial and economic values.