Peroxide cross-linking of EPDMs having high fractions of ethylenic units

The considerable amount of research in the literature has practically allowed the elucidation of the mechanism of peroxide cross-linking of ethylene–propylene–diene–monomer rubber (EPDM), which occurs through a radical chain reaction initiated by the thermal decomposition of the peroxide molecule. According to this radical chain reaction, all types of labile hydrocarbon bonds (i.e., allylic, methynic, and methylenic CH bonds) would be exposed to alkoxy radicals and involved in the formation of the elastomeric network. However, for high fractions of ethylenic units (typically ≥60 mol.%), simple chemical kinetics and thermochemical analyses have shown that the radical attack would essentially occur on the methylenic CH bonds. Starting from this assertion, a simplified mechanistic scheme has been proposed for the three commercial EPDMs under study. The corresponding kinetic model, derived from this new scheme by using the basic concepts of the chemical kinetics, provides access to the changes in concentration of the main reactive chemical functions (against exposure time), among which are double bonds and changes in cross-linking density. The validity of these predictions has been eventually successfully verified by five distinct analytical techniques frequently used for studying the cross-linking of rubbers