Collection of Czechoslovak Chemical Communications - digital archive 

Abstract

The kinetic data of decay of alkyl macroradicals in two temperature regions in isotactic polypropylene exposed to gamma radiation at 77 K were interpreted in terms of the model of diffusion-limited reactions at the activation energy level. The potential molecular mechanisms of transfer of the radical centres were tested from the point of view of their physical and/or chemical migration. Two mechanisms are suggested for the mutual approach of the centres in macroradical decay regions I and II in the amorphous zones of the matrix. Both of them involve the contribution of segmental conformational motions, the mobility of the terminal segments being of importance in region I whereas in region II the mutual nearing of the reactants proceeds in a relay way via intermolecular H-abstraction in conjunction with crank and crankshaft motions of the end and inner segments of the chain.