Mechanisms of antioxidant action: Antioxidant behaviour of nickel complex u.v. stabilisers

The antioxidant mechanisms involved in the u.v. stabilising activity of two nickel complexes, nickel dibutyl dithiocarbamate (NiDBC) and nickel acetophenone oxime (NiOx), have been investigated both by oxygen absorption measurements and in peroxide decomposition studies. NiDBC gives rise to a powerful catalyst for non-radical hydroperoxide decomposition; the rate of the reaction is faster in the presence than in the absence of light although the overall mechanisms appear to be very similar. NiOx is decomposed by hydroperoxides in a series of stoichiometric reactions which involve the consumption of at least six molecules of hydroperoxide per molecule of NiOx. Again the reaction is catalysed by light but the mechanism, which does not involve free-radical formation, is the same in the presence and absence of light. NiOx also appears to have weak radical trapping properties. Attempts to show that NiDBC and NiOx might interact sacrificially with photo-excited states of molecules (triplet carbonyl and singlet oxygen) were unsuccessful; the rates of photo-destruction of both complexes were unaffected by the presence of ketones both in the presence and absence of oxygen. This work confirms earlier conclusions that the nickel complex u.v. stabilisers function by auto-synergistic mechanisms involving u.v. screening and conventional chain-breaking and preventive antioxidant processes which operate during thermal processing operations as well as during environmental exposure. Although excited state quenching processes may occur, they appear to be less important in the overall scheme than the well established antioxidant mechanism.