通过C-H胺化和aza-Cope重排对橡胶进行解构，这一成果由北卡罗来纳大学Aleksandr V. Zhukhovitskiy小组经过不懈努力而取得。相关论文于2025年3月26日发表在《自然》杂志上。

在这里，该课题组应用碳氢胺化和主链重排聚合物解构这些材料成环氧树脂的前驱体。具体来说，研究团队开发了一种硫二亚胺试剂，使二烯聚合物和橡胶的烯丙基胺化率高达35%。然后，该研究团队应用阳离子2-aza-Cope重排来解构胺化二烯聚合物。在一个模型系统中，我们看到分子量从58100降低到约400g mol，胺化的消费后橡胶在6小时内分解成可溶性胺官能化聚合物，可用于制备硬度与商业双酚a衍生树脂相似的环氧热固性树脂。总之，这项工作证明了碳氢胺化和主干重排的力量，使消费后材料的化学回收成为可能。

据悉，商品二烯聚合物的化学回收策略有限，如轮胎中发现的那些。

附：英文原文

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

Author: Towell, Sydney E., Ratushnyy, Maxim, Cooke, Lauren S., Lewis, Geoffrey M., Zhukhovitskiy, Aleksandr V.

Issue&Volume: 2025-03-26

Abstract: 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 400gmol1, and aminated post-consumer rubber is deconstructed over 6hours 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.

DOI: 10.1038/s41586-025-08716-6

Source: https://www.nature.com/articles/s41586-025-08716-6