Iron-Catalyzed C–H Amination of Polyethylenes

Polyethylene is one of the most widely produced polymers due to its low cost and outstanding performance such as resistance to harsh chemicals. However, this same chemical resistance also challenges its chemical transformation to value-added materials. Postpolymerization functionalization offers a promising solution to create novel materials from polyolefins. Despite the ability to introduce various functional groups onto the polyethylene backbone, forming C–N bonds remains a significant challenge. In this study, we present an iron-catalyzed amination of both commodity and postconsumer polyethylene using nitrosoarenes as the N-source under visible light. This protocol facilitates the synthesis of mono- and bifunctional polyethylene materials with diverse polar groups under mild conditions. Oxidation and chlorination reactions occur concomitantly with amination reactions, while the introduced oxy and chloro groups can be smoothly further transformed, thus broadening the diversity of functionalized polyethylene materials. These functionalized materials exhibit new properties, not present in the original polyethylene, such as the ability to form cross-linked polyolefin networks and enhanced adhesive properties, therefore enabling the upcycling of waste polyolefins.