Huang Yuzhang, Yu Yongjiang, Hu Rongrong, Tang Ben Zhong
State Key Laboratory of Luminescent Materials and Devices, Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates, South China University of Technology, Guangzhou 510640, China.
School of Science and Engineering, Shenzhen Institute of Aggregate Science and Technology, The Chinese University of Hong Kong, Shenzhen, Guangdong 518172, China.
J Am Chem Soc. 2024 May 29;146(21):14685-14696. doi: 10.1021/jacs.4c02155. Epub 2024 May 8.
The exploration of new polymer materials required the development of efficient, economic, robust, and scalable synthetic routes, taking energy consumption, environmental benefit, and sustainability into overall consideration. Herein, through retro-polymerization analysis of functional aromatic polythioureas, a multicomponent reaction of elemental sulfur, CHCl, and aromatic amines was designed with the assistance of fluoride, and efficient, economic, and robust multicomponent polymerizations (MCPs) of these three abundantly available cheap monomers, elemental sulfur, CHCl, and aromatic diamines, were developed to realize scalable conversion directly from sulfur to a series of functional aromatic polythioureas with high molecular weights ( up to 50,800 g/mol) in excellent yields (up to 98%). The synergistic cooperation of the strong and selective coordination of thiourea with gold ions and the redox property of aromatic polythiourea enable in situ reduction of Au to elemental gold under a normal bench condition. Furthermore, the functional aromatic polythiourea could be chemically recycled through aminolysis with NH·HO to afford a diamine monomer in 83% isolated yield. The development of elemental sulfur-based MCP has brought the opportunity to access cost-effective and sustainable sulfur-containing functional polymer materials, which is anticipated to provide a solution for the utilization of sulfur waste and making profitable polymer materials.
新型聚合物材料的探索需要开发高效、经济、稳健且可扩展的合成路线，同时要全面考虑能源消耗、环境效益和可持续性。在此，通过对功能性芳香族聚硫脲进行逆聚合分析，借助氟化物设计了硫单质、CHCl和芳香胺的多组分反应，并开发了这三种大量可得的廉价单体（硫单质、CHCl和芳香二胺）的高效、经济且稳健的多组分聚合反应（MCP），以实现从硫直接到一系列高分子量（高达50,800 g/mol）的功能性芳香族聚硫脲的可扩展转化，产率优异（高达98%）。硫脲与金离子的强选择性配位以及芳香族聚硫脲的氧化还原特性之间的协同作用，使得在常规实验室条件下能够将金原位还原为单质金。此外，功能性芳香族聚硫脲可以通过与NH·HO进行氨解反应进行化学循环，以83%的分离产率得到二胺单体。基于硫单质的MCP的开发为获取具有成本效益和可持续性的含硫功能聚合物材料带来了机遇，有望为硫废料的利用和生产盈利性聚合物材料提供解决方案。
