近日，华东理工大学曲大辉团队报道了通过熵驱动开环聚合和闭环化学回收的动态共价极性烯烃大环的生命周期。2025年11月6日出版的《国家科学评论》杂志发表了这项成果。

全球塑料污染危机迫切需要闭环化学回收战略。虽然通过烯烃分解可回收聚合物已被广泛探索，但开发在温和条件下操作的无金属方法仍然是一个重大挑战。

研究组提出了极性烯烃衍生大环的生命周期设计，作为能够通过有机碱催化极性烯烃键的复分解进行可逆熵驱动开环聚合（ED-ROP）的新型单体。采用体熔体聚合法制备了高分子量聚合物。动力学研究和质量分析表明，通过插入和环扩张形成环状聚合物拓扑结构，聚合的热力学驱动是构象熵的增加。通过改变稀溶液中极性烯烃复分解的平衡，这些聚合物可以实现高效的闭环解聚和单体回收。这种方法建立了一个基于极性烯烃化学的多功能平台，推进了具有定制动态功能的可回收材料的设计。

附：英文原文

Title: Lifecycle of dynamic covalent polar-olefin macrocycles via entropy-driven ring-opening polymerization and closed-loop chemical recycling

Author: Li, Pengyun, Li, Chong, Lei, Mengying, Gu, Ruirui, Tian, He, Qu, Da-Hui

Issue&Volume: 2025-11-06

Abstract: The global plastic pollution crisis urgently demands closed-loop chemical recycling strategies. While recyclable polymers via olefin metathesis have been widely explored, the development of metal-free methods operating under mild conditions remains a significant challenge. Here, we present the lifecycle design of polar-olefin-derived macrocycles as novel monomers capable of undergoing reversible entropy-driven ring-opening polymerization (ED-ROP) through organic base-catalyzed metathesis of polar olefin bonds. High-molecular-weight polymers were efficiently produced via bulk melt polymerization. Kinetic studies and mass analyses indicated the formation of cyclic polymer topologies through insertion and ring expansion, with polymerization thermodynamically driven by an increase in conformational entropy. By shifting the equilibrium of polar-olefin metathesis in dilute solution, these polymers enable efficient closed-loop depolymerization and monomer recovery. This approach establishes a versatile platform based on polar olefin chemistry, advancing the design of recyclable materials with tailored dynamic functionalities.

DOI: 10.1093/nsr/nwaf484

Source: https://academic.oup.com/nsr/advance-article/doi/10.1093/nsr/nwaf484/8316130searchresult=1