Yuan Pengjun, Sun Yangyang, Xu Xiaowei, Luo Yi, Hong Miao
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, China.
State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian, China.
Nat Chem. 2022 Mar;14(3):294-303. doi: 10.1038/s41557-021-00817-9. Epub 2021 Nov 25.
The development of sustainable polymers that possess useful material properties competitive with existing petroleum-derived polymers is a crucial goal but remains a formidable challenge for polymer science. Here we demonstrate that irreversible ring-opening polymerization (IROP) of biomass-derived five-membered thionolactones is an effective and robust strategy for the polymerization of non-strained five-membered rings-these polymerizations are commonly thermodynamically forbidden under ambient conditions, at industrially relevant temperatures of 80-100 °C. Computational studies reveal that the selective IROP of these thionolactones is thermodynamically driven by S/O isomerization during the ring-opening process. IROP of γ-thionobutyrolactone, a representative non-strained thionolactone, affords a sustainable polymer from renewable resources that possesses external-stimuli-triggered degradability. This poly(thiolactone) also exhibits high performance, with its key thermal and mechanical properties comparing well to those of commercial petroleum-based low-density polyethylene. This IROP strategy will enable conversion of five-membered lactones, generally unachievable by other polymerization methods, into sustainable polymers with a range of potential applications.
开发具有与现有石油衍生聚合物相媲美的有用材料性能的可持续聚合物是一个关键目标，但对聚合物科学来说仍然是一项艰巨的挑战。在此，我们证明生物质衍生的五元硫代内酯的不可逆开环聚合（IROP）是一种用于非张力五元环聚合的有效且稳健的策略——这些聚合反应在环境条件下以及80-100°C的工业相关温度下通常在热力学上是被禁止的。计算研究表明，这些硫代内酯的选择性IROP在开环过程中由S/O异构化在热力学上驱动。代表性的非张力硫代内酯γ-硫代丁内酯的IROP可从可再生资源中获得一种具有外部刺激触发降解性的可持续聚合物。这种聚（硫代内酯）还表现出高性能，其关键的热性能和机械性能与商业石油基低密度聚乙烯的性能相当。这种IROP策略将使通常无法通过其他聚合方法实现的五元内酯转化为具有一系列潜在应用的可持续聚合物。
