Deconstruction of rubber via C-H amination and aza-Cope rearrangement

• 成果类型: Article
• 署名作者: Towell, Sydney E.; Ratushnyy, Maxim; Cooke, Lauren S.; Lewis, Geoffrey M.; Zhukhovitskiy, Aleksandr V.
• 署名单位: University of North Carolina; University of North Carolina Chapel Hill; University of North Carolina School of Medicine; University of Michigan System; University of Michigan
• 刊物名称: Nature
• ISSN/ISSBN: 0028-1700
• DOI: 10.1038/s41586-025-08716-6
• 发表日期: 2025-04-10
• 关键词: opening metathesis polymerization; allylic amination; green chemistry; BEHAVIOR; olefins; resins

摘要

Limited strategies exist for chemical recycling of commodity diene polymers, like those found in tyres1, 2-3. Here we apply C-H amination and backbone rearrangement of polymers to deconstruct these materials into precursors for epoxy resins. Specifically, we develop a sulfur diimide reagent4,5 that enables up to about 35% allylic amination of diene polymers and rubber. Then, we apply the cationic 2-aza-Cope rearrangement to deconstruct aminated diene polymers. In a model system, we see molecular weight reduction from 58,100 to approximately 400 g mol-1, and aminated post-consumer rubber is deconstructed over 6 hours into soluble amine-functionalized polymers, which can be utilized to prepare epoxy thermosets with similar stiffnesses to commercial bisphenol A-derived resins6. Altogether, this work demonstrates the power of C-H amination and backbone rearrangement to enable chemical recycling of post-consumer materials.