Interaction of Polymeric Hydroperoxides with NO

The phenomenon of hydroperoxide decomposition under the action of NO was studied using macromolecular peroxides and their low-molecular analogues [65, 66]. It has been shown [66] that NO-induced decomposition of polypropylene (PP) hydroperoxides leads to the formation of low-molecular hydrocarbons, which is indicative of the degradation of macromolecules. The primary stage of the decomposition is represented by the reaction [65, 66]  

The reaction of hydroperoxides with NO can also proceed with the formation of peroxy radicals  

At high hydroperoxide concentrations in solution, the process was described as decomposition of hydroperoxide dimers by NO [65]  

Pryor and co-workers [67] gave evidence that NO, which is a more active radical as compared with NO, cannot directly decompose hydroperoxides. The reaction is induced by non-paramagnetic dimers of N O. In this context, the scheme including the reactions (Equations 3.72-74) is not evident. 

The character of the kinetic curves cannot be explained from the mechanism presented by the reactions (Equation 3.72-74). According to these reactions, based on the direct interaction of hydroperoxides with NO, the rate of decomposition is maximal at the beginning of the process and decreases with a decrease in the concentration of ROOH. The shape of the kinetic curves is characteristic of autoaccelerated reactions with an induction period. 

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