Zwitterionic Alternating Polymerization to Generate Semicrystalline and Recyclable Cyclic Polythiourethanes
Da‐Wei Tan, Xin Hu, Zheng Cao, Ming Luo, Donald J. Darensbourg
Abstract
Synthesis of cyclic, semicrystalline, and recyclable polythiourethanes was realized via the catalyst-free zwitterionic alternating copolymerization of N-alkyl aziridines with carbonyl sulfide (COS) under mild conditions. The copolymerization proceeded efficiently at room temperature and generated copolymers with fully alternating linkages in more than 99% selectivity in 5 min under solvent-free conditions. Notably, the copolymers are typical semicrystalline thermoplastics with melting temperatures up to 137 °C (n-butyl-substituted) or 170 °C (ethyl-substituted). The resulting polythiourethanes are predominantly cyclic as evidenced by 1H NMR and MALDI-TOF mass spectroscopies. Remarkably, the cyclic copolymers could be recycled into N-substituted cyclic thiourethanes in quantitative yield by heating at 250 °C for 2 h.