Functionalized cyclooctenes (FCOEs) are important monomers in ring-opening metathesis polymerization (ROMP). Herein, a new library of disubstituted FCOEs bearing adjacent heteroatoms were synthesized and applied in ROMP. To address the issues associated with the handling of the reactive thienyl chloride intermediate, a two-step continuous flow method has been developed to prepare 5-thio-6-chlorocyclooctene compounds from abundant cyclooctadiene starting materials. These newly synthesized FCOE monomers were subsequently polymerized through ROMP, giving rise to a range of functionalized polymers with high molecular weights. Furthermore, we demonstrated that the thermal properties of these polymers could be fine-tuned by changing the functional groups in the FCOE monomers. We expect that this functionalization-polymerization strategy will enable the preparation of a range of polymeric materials with complex structures.

中文翻译：

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连续流动条件下环辛二烯的不对称双官能化：扩大开环复分解聚合的范围†

功能化环辛烯 (FCOE) 是开环复分解聚合 (ROMP) 中的重要单体。在此，合成了一个新的带有相邻杂原子的二取代 FCOE 库，并将其应用于 ROMP。为了解决与反应性噻吩基氯中间体的处理相关的问题，已经开发了一种两步连续流动法，以从丰富的环辛二烯原料制备 5-硫代-6-氯环辛烯化合物。这些新合成的 FCOE 单体随后通过 ROMP 聚合，产生了一系列具有高分子量的功能化聚合物。此外，我们证明了这些聚合物的热性能可以通过改变 FCOE 单体中的官能团进行微调。