Induced Dissociation of Peroxide Compounds

Being primary, stable, intermediate oxidation products and owing to the simplicity of their dissociation to free radicals, peroxide compounds HOOH, ROOH, ROOR (where R is alkyl, acyl, arylacyl fragments or their derivatives) possess favorable initiation properties in chain oxidation and polymerization reactions. 

As an example, dissociation of the most frequently applied di-/ t-butyl peroxide shall be considered (similarly, hydroperoxides dissociate) which independently of the fact, if the 

Nonehilbel and Walton [13] called such reactions producing free radicals induced dissociation processes. Hence, ROOH and ROOR dissociation is considered as induction of OH and other radicals by free radicals, generated in the chemical system by self-hemolytic break of their—O O-bond with formation of an active site (alkoxide). 

Let us ensure the accuracy of this interpretation of ROOR and ROOH dissociation mechanism in connection with a question that arises, i.e. how this statement correlates with the conditions under which chemical induction takes place. 

According to Nozari and Barlett s kinetic data [ 14], benzoyl peroxide dissociation competes with hemolytic decomposition and a reaction with free radical participation. The kinetic dissociation equation is as follows  

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