Macromolecular stable free nitrogen radicals

✍ Scribed by Braun, D. ;Löflund, I. ;Fischer, H.

• Book ID: 104532156
• Publisher: John Wiley and Sons
• Year: 1962
• Weight: 640 KB
• Volume: 58
• Category: Article
• ISSN: 0022-3832
• DOI: 10.1002/pol.1962.1205816641

✦ Synopsis

Abstract

Low molecular stable free nitrogen radicals have been investigated frequently. There are, however, only a few records on corresponding high polymers. Preparation of macromolecular radicals of the diphenylpicrylhydrazyl type is described. Poly‐4‐fluorostyrene is nitrated to poly‐3,5‐dinitro‐4‐fluorostyrene, a compound in which the fluorine by analogy with similar low molecular compounds, is very reactive. By reaction with diphenylhydrazine, poly(α‐vinyldinitrophenyl‐β,β‐diphenyl hydrazine) is obtained; this can be oxidized without difficulty to the corresponding hydrazyl. The polymer is a stable free nitrogen radical. Its structure follows from the comparison of the absorption spectra and the electron spin resonance spectrum with suitable compounds. The polymer corresponds in its chemical behavior to the low molecular free nitrogen radicals, e.g., it easily oxidizes hydroquinone, ascorbic acid, or hydrazobenzene. It is a typical high polymer inhibitor for the polymerization of styrene, whereas the polymer hydrazine has no inhibiting effect.