Zum mechanismus des strahlenchemischen abbaus von polytetrafluorethylen

The present work studies the changes in polymer structure and the mechanism of the decomposition of polytetrafluoroethylene resin (PTFE) exposed to high energy radiation (electron beam). Spectroscopic and kinetic observations are used to interpret the degradation process. For the first time the decomposition of PTFE has been carried out on a preparative scale and new results obtained by analysing the degradation products. The radiation-induced degradation of PTFE is accompanied by thermal degradation under certain irradiation conditions. This is due to an increase in temperature of the polymer caused by retardation of highly accelerated electrons (heat accumulation effect).The kinetics are discussed in terms of the reactions and recombination of radicals produced by high-energy radiation both in the polymer melt and the polymer surface. These are related to the overall rate of decomposition.The primary radicals formed by decomposition of PTFE in an inert atmosphere (N₂, Ar) react to produce perfluorinated alkanes and alkenes. In the presence of reactive gases the decomposition fragments originated will react rapidly; e.g. if oxygen is present in the reactive area the radicals form perflourinated peroxyl and oxyl radicals which finally stabilize themselves by CC-scission to perfluorocarbon acid fluorides and carbonyldifluorides.     

Alternierende Copolymerisation von Styrol und Benzylmethacrylat in Gegenwart von Ethylaluminiumsesquichlorid

Zusammenfassung Die alternierende Copolymerisation von Styrol und Benzylmethacrylat in Gegenwart von Ethylaluminiumsesquichlorid als Katalysator zeigt im Anfangsstadium der Reaktion ein vom weiteren Verlauf abweichendes Verhalten. So nehmen die Zusammensetzung und die Grenzviskositäten der Produkte sowie die Reaktionsgeschwindigkeit erst nach der Anfangsphase konstante Werte an.Die¹H-NMR-Spektren von alternierenden und statistischen Copolymeren gleicher Bruttozusammensetzung zeigen deutliche Unterschiede. Das Spektrum des alternierenden Copolymeren bestätigt die alternierende Struktur und spricht gleichzeitig für einen ataktischen Kettenaufbau.

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The alternating copolymerization of styrene and benzylmethacrylate shows a different behaviour at the beginning of the reaction and later on. Thus the composition and the intrinsic viscosity of the products as well as the reaction rate become constant only after the initial stage.The¹H-NMR-spectra of alternating and statistical copolymers with equal composition show distinct differences. The spectrum of the alternating copolymer confirms the alternating structure as well as an atactic chain configuration.