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.

The mechanism of gamma-radiolysis of polymethylene, polypropylene and poly-n-butylene oxides: An ESR investigation

FAUCITANO, ANTONIO;BUTTAFAVA, ARMANDO;MARTINOTTI, FAUSTA;FERLONI, PAOLO;MAGISTRIS, ALDO
1992-01-01

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.
File in questo prodotto:
Non ci sono file associati a questo prodotto.

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11571/468664
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus ND
  • ???jsp.display-item.citation.isi??? ND
social impact