Polymers having stable radicals. I. Synthesis of nitroxyl polymers from 4‐methacryloyl derivatives of 2,2,6,6‐tetramethylpiperidine

Abstract

Abstract Polymers having stable nitroxyl free radicals, poly‐4‐methacryloylamino‐ and poly‐4‐methacryloyloxy‐2,2,6,6‐tetramethylpiperidine‐1‐oxyls, were synthesized from their precursor polymers by oxidizing them in a methanolic solution of hydrogen peroxide. The precursor polymers were prepared by radical polymerization of 4‐methacryloyl‐amino/oxy‐2,2,6,6‐tetramethylpiperidines in various solvents. These polymerizations in acetic acid were found to yield polymers of high molecular weight. The copolymers of the precursor monomers with styrene and methyl methacrylate were also prepared as precursor copolymers. These precursor polymers of a piperidine type were converted to the polymers having stable nitroxyl free radicals by the hydrogen peroxide method. In this report, it was assumed that the post‐oxidation reaction introduced a nitroxyl group smoothly and quantitatively at room temperature. Elucidations of the stable radical formation and the electron spin behavior of the stable radical polymers were made in terms of elemental analyses, infrared, ultraviolet, and ESR spectroscopy.