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EnglishThe basic features of the mechanism of the solid state radiolysis of the title polyethers have been elucidated with an ESR study using the matrix isolation and spin-trapping techniques. The species identified at 77 K are α-alkoxy radicals arising from hydrogen abstractions probably involving the primary ether cation-radicals; chain scission radicals are formed on warming as a consequence of the thermal decomposition of the α-alkoxy radical precursors. The formation of acyl and α-keto radicals, which is observed on warming near room temperature, is identified with cage hydrogen abstraction reactions taking place between the products of the β-scission of the α-alkoxy radicals. Direct information on the stability and ESR properties of the polymeric ether cation-radicals, which are thought to be important intermediates in the radiolysis mechanism, have been obtained by irradiation in the CFCl3 matrix.
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| Titolo: | The mechanism of gamma-radiolysis of polymethylene, polypropylene and poly-n-butylene oxides: An ESR investigation | |
| Autori: | ||
| Data di pubblicazione: | 1992 | |
| Rivista: | ||
| Abstract: | The basic features of the mechanism of the solid state radiolysis of the title polyethers have been elucidated with an ESR study using the matrix isolation and spin-trapping techniques. The species identified at 77 K are α-alkoxy radicals arising from hydrogen abstractions probably involving the primary ether cation-radicals; chain scission radicals are formed on warming as a consequence of the thermal decomposition of the α-alkoxy radical precursors. The formation of acyl and α-keto radicals, which is observed on warming near room temperature, is identified with cage hydrogen abstraction reactions taking place between the products of the β-scission of the α-alkoxy radicals. Direct information on the stability and ESR properties of the polymeric ether cation-radicals, which are thought to be important intermediates in the radiolysis mechanism, have been obtained by irradiation in the CFCl3 matrix. | |
| Handle: | http://hdl.handle.net/11571/468664 | |
| Appare nelle tipologie: | 1.1 Articolo in rivista |
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