C─H Amination of Polypropylene with Sodium <i>N</i> ‐Chloro‐Amides

Abstract Polypropylene (PP) is one of the most produced polymers. To meet the requirements of many modern technologies, it is very urgent to introduce diverse functional groups onto PP. Selective C─N bonds forming via C─H functionalization have been considered as a universal platform; however, it remains a significant challenge. Herein, we report a mild, catalyst‐free, and light‐free C─H amination of both commodity and postconsumer PP using sodium N ‐chloro‐amides as nitrogen sources. This method allows the efficient preparation of a variety of aminated PP materials (up to 2.4 mol% LOF) via direct functionalizations and subsequent functional group transformations. These aminated materials retain crystallinity and molecular weight while exhibiting new properties not present in virgin PP, such as improved compatibility in mixed plastic blends, enhanced adhesion to metals, and fluorescence properties. This work also provides a sustainable strategy to expand the use of PP waste.