文献类型：期刊文献

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

作者：Li, Pengyun[1];Li, Chong[1];Lei, Mengying[1];Gu, Ruirui[1];Tian, He[1];Qu, Da-Hui[1]

机构：[1]East China Univ Sci & Technol, Inst Fine Chem,Key Lab Adv Mat & Joint Int Res Lab, Feringa Nobel Prize Scientist Joint Res Ctr,Sch Ch, Frontiers Sci Ctr Materiobiol & Dynam Chem, Shanghai 200237, Peoples R China

年份：2025

卷号：12

期号：12

外文期刊名：NATIONAL SCIENCE REVIEW

收录：;EI(收录号：20260119848718);WOS:【SCI-EXPANDED(收录号:WOS:001642483300001)】；

基金：This work was supported by the National Natural Science Foundation of China (22025503, 22588101, 22571084, 22205064 and 22220102004), the Science and Technology Commission of Shanghai Municipality (24DX1400200), the Innovation Program of Shanghai Municipal Education Commission (2023ZKZD40), the Programme of Introducing Talents of Discipline to Universities (B16017), the Fundamental Research Funds for the Central Universities, and the CNPC Innovation Found (2024DQ02-0410).

语种：英文

外文关键词：dynamic covalent chemistry; polar olefin bonds; entropy-driven ring-opening polymerization; closed-loop chemical recycling

摘要：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. Bio-based macrocycles bearing dynamic polar-olefin bonds undergo entropy-driven ring-opening polymerization to yield cyclic polymers that can be depolymerized on demand, offering a practical route to circular plastics.