2,2,6,6‐Tetramethylpiperydinyl‐1‐oxyl (TEMPO) Functionalized Benzoxazines Prepared with a One‐Pot Synthesis for Reactive/Crosslinkable Initiators of Nitroxide Mediated Polymerization

In this work, the incorporation of a 2,2,6,6‐tetramethylpiperydinyl‐1‐oxyl (TEMPO) group to a benzoxazine ring is performed using a one‐pot synthesis for the preparation of TEMPO‐functionalized benzoxazine compounds and polymers as reactive and crosslinkable initiators for nitroxide‐mediated polymerization (NMP). The TEMPO‐functionalization reaction of benzoxazine, traced with ¹H NMR, is conducted with sequential radical transfer and coupling reactions. Moreover, polystyrene‐grafted polybenzoxazine copolymers are prepared with the TEMPO‐benzoxazine initiator and NMP of styrene. The polymerization system exhibits the characteristics of controlled radical polymerization, including controlled molecular weights of products and ability for sequential polymerization. Moreover, based on the chemical reactivity and crosslinking ability of benzoxazine groups, the synthesis route developed in this work will widen the scope of the design and synthesis of functional and high‐performance polymers.