中科院上海有机化学研究所洪缪团队报道了五元硫醇内酯异构化不可逆开环聚合制备高性能可持续聚合物。相关研究成果发表在2021年11月25日出版的《自然—化学》。

开发具有能够与现有石油衍生聚合物竞争的有用材料特性的可持续聚合物是一个关键目标，但仍然是聚合物科学的一个巨大挑战。

该文中，研究人员证明了生物质衍生的五元硫内酯的不可逆开环聚合（IROP）是非应变五元环聚合的有效且稳健的策略。在环境条件下，80–100°C的工业相关温度下，该聚合通常在热力学上被禁止。计算研究表明，该硫内酯的选择性IROP是由开环过程中的S/O异构化热力学驱动的。γ-硫诺丁酸内酯（一种典型的非应变硫诺内酯）的IROP提供了一种可再生资源的可持续聚合物，具有外部刺激触发的降解性。

该聚硫内酯也表现出高性能，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热性能和机械性能相当。该IROP策略将使五元内酯（通常无法通过其他聚合方法实现）转化为具有一系列潜在应用的可持续聚合物。

附：英文原文

Title: Towards high-performance sustainable polymers via isomerization-driven irreversible ring-opening polymerization of five-membered thionolactones

Author: Yuan, Pengjun, Sun, Yangyang, Xu, Xiaowei, Luo, Yi, Hong, Miao

Issue&Volume: 2021-11-25

Abstract: 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.

DOI: 10.1038/s41557-021-00817-9

Source: https://www.nature.com/articles/s41557-021-00817-9