Hodges Mercie N, Elardo Matthew J, Seo Jinyoung, Dohoda Alexander F, Michael Forrest E, Golder Matthew R
Department of Chemistry, University of Washington, 36 Bagley Hall, Seattle, WA 98195, USA.
Department of Chemistry & Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, MA 02138, USA.
Angew Chem Int Ed Engl. 2023 May 8;62(20):e202303115. doi: 10.1002/anie.202303115. Epub 2023 Apr 12.
Accumulation of end-of-life plastics presents ongoing environmental concerns. One strategy to solve this grand challenge is to invent new techniques that modify post-consumer waste and impart new functionality. While promising approaches for the chemical upcycling of commodity polyolefins and polyaromatics exist, analogous approaches to repurpose unsaturated polymers (e.g., polybutadiene) are scarce. In this work, we propose a method to upcycle polybutadiene, one of the most widely used commercial rubbers, via a mild, metal-free allylic amination reaction. The resulting materials have tunable thermal and surface wetting properties as a function of both sulfonamide identity and grafting density. Importantly, this approach maintains the parent alkene microstructure without evidence of olefin reduction, olefin transposition, and/or chain scission. Based on these findings, we anticipate future applications in the remediation of complex elastomers and vulcanized rubbers.
废弃塑料的积累给环境带来了持续的问题。解决这一重大挑战的一种策略是发明新技术，对消费后的废弃物进行改性并赋予其新功能。虽然存在一些有前景的用于商品聚烯烃和聚芳烃化学升级循环的方法，但对不饱和聚合物（如聚丁二烯）进行重新利用的类似方法却很少。在这项工作中，我们提出了一种通过温和的无金属烯丙基胺化反应将聚丁二烯（一种应用最广泛的商用橡胶）进行升级循环的方法。所得材料的热性能和表面润湿性可根据磺酰胺特性和接枝密度进行调节。重要的是，这种方法能保持母体烯烃的微观结构，没有烯烃还原、烯烃转位和/或链断裂的迹象。基于这些发现，我们预计该方法在复杂弹性体和硫化橡胶的修复方面将有未来应用。
