Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, Frontiers Science Center for Materiobiology and Dynamic Chemistry, Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, China.
Key Laboratory for Advanced Materials and Joint International Research Laboratory for Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, Centre for Computational Chemistry and Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, China.
Angew Chem Int Ed Engl. 2023 Mar 6;62(11):e202215329. doi: 10.1002/anie.202215329. Epub 2023 Jan 24.
Poly(1,2-dithiolane)s are a family of intrinsically recyclable polymers due to their dynamic covalent disulfide linkages. Despite the common use of thiolate-initiated anionic ring-opening polymerization (ROP) under basic condition, cationic ROP is still not exploited. Here we report that disulfide bond can act as a proton acceptor, being protonated by acids to form sulfonium cations, which can efficiently initiate the ROP of 1,2-dithiolanes and result in high-molecular-weight (over 1000 kDa) poly(disulfide)s. The reaction can be triggered by adding catalytic amounts of acids and non-coordinating anion salts, and completed in few minutes at room temperature. The acidic conditions allow the applicability for acidic monomers. Importantly, the reaction condition can be under open air without inert protection, enabling the nearly quantitative chemical recycling from bulk materials to original monomers.
聚 1,2-二硫杂环戊烷是一类具有固有可回收性的聚合物，这是因为其含有动态的二硫键连接。尽管巯基引发的阴离子开环聚合（ROP）通常在碱性条件下进行，但阳离子 ROP 仍未得到开发。在这里，我们报告称二硫键可以作为质子受体，被酸质子化形成锍阳离子，从而可以有效地引发 1,2-二硫杂环戊烷的 ROP，得到高分子量（超过 1000 kDa）的聚（二硫代）。该反应可以通过加入催化量的酸和非配位阴离子盐来引发，在室温下几分钟内即可完成。酸性条件允许使用酸性单体。重要的是，反应条件可以在开放空气中进行，无需惰性保护，从而可以从大块材料中几乎定量地进行化学回收，得到原始单体。
