Abstract
The experimental data on investigations of the cage effect in polymers are examined for the decomposition of 2,2′-azoisobutyronitrile and lauroyl peroxide. The kinetic schemes taking into account only translational motion of radicals are shown not to describe the cage effects in polymers. The experimental dependence of the cage effect on molecular mobility in polymers may be explained on the basis of schemes taking into account both the rotational and translational motions of particles. The study of cage effects in oriented polymeric films proves an important role of the form of the cage. In polymers the molecular mobility influences the rate of slow reactions. This is explained for the scope of the model of a rigid cage where orientation of the particles depends on the form of the cage.
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