中国科学技术大学陈殿峰团队报道了单体设计实现了芳香硫代内酯阴离子开环聚合的机理映射。相关研究成果发表在2025年1月22日出版的《德国应用化学》。

可降解硫族化物聚酯，例如聚硫酯（PTEs），通常具有优良的热、机械和光学性能。然而，硫代内酯的阴离子开环聚合（ROP）是一种本质上有前景但尚未充分探索的制备PTEs的方法，但仍受到以下因素的限制：对金属催化剂的不耐受、对链生长的控制不足以及芳香体系的缺失。单体设计推动的机械研究可能会解决上述挑战。

该文中，研究人员介绍了一种由1,1′-联萘-2,2′-二醇（BINOL）合成的新型高活性硫代内酯。研究人员对聚合动力学和热力学的研究强调了快速引发的重要性，最终发现了2-萘基硫代甲酸四丁基铵作为一种独特的引发剂，能够实现硫内酯的真正可控和活性聚合。最终，BINOL固有的阻转异构性制备了具有定制分子量、对映体组成和拓扑结构的轴向手性PTE材材料。

附：英文原文

Title: Monomer Design Enables Mechanistic Mapping of Anionic Ring-Opening Polymerization of Aromatic Thionolactones

Author: Shaoqiu Zheng, Shu-Sen Chen, Yang-Yang Li, Minjian Liao, Xuhui Liang, Ke Li, Xiaopeng Li, Jinming Hu, Dian-Feng Chen

Issue&Volume: 2025-01-22

Abstract: Degradable chalcogenide polyesters, e.g., polythioesters (PTEs), typically exhibit improved thermal, mechanical, and optical properties. Anionic ring-opening polymerization (ROP) of thionolactones, an intrinsically promising yet underexplored approach to accessing PTEs, however, is still limited by: intolerance of metal catalysts, inadequate control over chain growth, and the absence of aromatic system. Monomer design-boosted mechanistic studies may address the above challenges. Here, we present a new and highly reactive thionolactone synthesized from 1,1′-binaphthyl-2,2′-diol (BINOL). Our investigations into polymerization kinetics and thermodynamics have underscored the importance of rapid initiation, eventually leading to the discovery of tetrabutylammonium 2-naphthyl-thiocarboxylate as a distinctive initiator that enables genuinely controlled and living polymerization of thionolactones. Ultimately, the atropisomerism inherent in BINOL has resulted in the creation of axially chiral PTE materials with tailored molecular weights, enantiomeric compositions, and topologies.

DOI: 10.1002/anie.202500581

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202500581