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- W2169476871 abstract "Radical formation was observed in purified cis-1.4-poly(butadiene) after irradiation in vacuo at 77°K with UV light from a medium pressure mercury lamp. The free radicals were studied by electron spin resonance (ESR). The ESR spectra obtained were interpreted as due mainly to radicals formed by scission of the CC bond midway between the double bonds: A minor part was assigned to radicals formed by hydrogen abstraction from one of the α-methylene groups. These radicals are believed to be twisted, resulting in bad overlapping between the π-electron cloud and the p-orbital of the unpaired electron, i.e. the radicals give spectra of the alkyl type:documentclass{article}pagestyle{empty}begin{document}$ = {rm CH} - {rm dot CH} - {rm CH}_2 - $end{document}. In addition the spectra contained a weak signal interpreted as due to polyenyl radicals documentclass{article}pagestyle{empty}begin{document}$ - {rm (CH = CH)}_{rm n} - {rm dot CH}_2 $end{document} At liquid nitrogen temperatures all radicals formed were stable, but at temperatures near the glass transition range, the radicals disappeared rapidely. One radical type showed much less stability and rearranged on heating the sample to 114°K; these radicals were formed by hydrogen abstraction from the α-methylene groups. The changes in the infrared and ultraviolet absorption spectra observed by other authors are discussed in relation to the radicals identified here. In gereinigtem cis-1.4-Polybutadien wurde nach Bestrahlung mit ultraviolettem Licht einer Mitteldruck-Quecksilberlampe Radikalbildung beobachtet. Die freien Radikale wurden mit Hilfe der Elektronenspinresonanz (ESR) untersucht. Die erhaltenen ESR-Spektren werden hauptsächlich auf die Gegenwart von Radikalen zurückgeführt, die durch die Aufspaltung einer CC-Bindung entstehen, die in der Mitte zwischen zwei benachbarten Doppelbindungen des Polymeren liegt; Bei Temperaturen des flüssigen Stickstoffs sind alle gebildeten Radikale stabil, wärend sie in der Nähe des Glasumwandlungsgebietes rasch verschwinden. Einer der Radikaltypen zeigt vie1 geringere Stabilitat und lagert sich urn, sobald die Probe auf 114°K erwarmt wird; diese Radikale bilden sich durch Wasserstoffabspaltung aus den α-Methylengruppen. Die Äderungen in den IR- und UV-Absorptionsspektren, die von anderen Autoren beobachtet wurden, werden uuter Bezugnahme auf die hier identifizierten Radikale erörtert." @default.
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- W2169476871 date "1971-03-18" @default.
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- W2169476871 doi "https://doi.org/10.1002/macp.1971.021420111" @default.
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