Functionalization of Polyolefins via Catalytic Nitrene Addition

Abstract The post‐polymerization functionalization of polyolefins has emerged as a key tool for obtaining new materials with enhanced properties. With an array of approaches being already reported, the incorporation of N‐containing fragments en route to the generation of amino groups in yet scarce and not disclosed for the metal‐catalyzed nitrene transfer strategy. Here we introduce such tactics employing silver‐based catalysts for the incorporation of nitrene NTs (Ts = p ‐toluenesulfonyl) groups to commercially available polybutadienes. The process occurs at room temperature without appreciable chain scission or cross‐linking processes and enables precise control of the degree of functionalization. Thermal analyses demonstrate a correlation between such degree and the T g values of the functionalized polymers.