Functionalization of Polyolefins via Catalytic Nitrene Addition

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.