Photostabilizing activity of sterically hindered piperidines—II: Radical trapping ability |
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Authors: | J. Sedlář J. Petrúj J. Pác A. Zahradníčková |
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Affiliation: | Research Institute of Macromolecular Chemistry, Tkalcovská 2, 656 49 Brno, Czechoslovakia |
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Abstract: | The abilities of both 2,2,6,6-tetramethylpiperidine (I) and its nitroxyl (II) to trap radicals involved in hydrocarbon photo-oxidations have been studied in cumene and 1,3,5-trimethylcyclohexane at 27° using AIBN, hydroperoxide and dialkylperoxide as initiators: the light was either the band 300–400 nm or 366 nm. Under conditions of photolysis of ROOH (degenerate branching), I is oxidized to II. II is capable of trapping R' radicals, the rate constant being ~50 times lower than that for RO.2 formation. RO.2 radicals react with neither I nor II. Under the condition of degenerate branching, II is capable of intercepting the radical fragments from decomposing hydroperoxide. The rate constant of this process is ~500 times higher than that for hydrogen abstraction by these fragments. A reaction mechanism is suggested: hydrogen bonded associates formed between an N-containing stabilizer and ROOH play a dominant role. The principal intermediates in this mechanism are represented by >NO., >NOH and >NOR species. |
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