Diamines, CS2 and Monoisocyanide-participated Polymerizations for Large-scale Synthesis of Polythioureas and Thioformamide

Multicomponent polymerizations (MCPs) are powerful tools to synthesize functional polymers with great structural diversity, low cost and high efficiency, which usually generate single polymer product. Herein, a robust one-pot diamines, CS 2 and monoisocyanide-participated catalyst-free polymerization was developed at room temperature to produce polythiourea and thioformamide simultaneously in equal equivalent, which was featured with cheap monomers, simple operation and mild condition, affording various polythioureas with high M w s of up to 47500 g/mol in high yields of up to 98%. Polythioureas with varied chain composition and sequence-controlled structure could be synthesized in 62 g-scale from copolymerization or multicomponent tandem polymerization, enabling facile tuning of thermal property, crystallinity, mechanical property, and fluorescence. The abundant irregular hydrogen bonds endowed the polythioureas excellent glassy state self-healing property at room temperature or below 0 °C. This polymerization provided an efficient and economic approach to access functional polythioureas.