Effect of Third Monomer Type and Content on Peroxide Crosslinking Efficiency of EPDM

Peroxide crosslinking of EPDM is commonly applied in rubber practice. Although the presence of a diene termonomer is not a prerequisite for peroxide crosslinking, it does provide a significant increase of the peroxide crosslinking efficiency. Different explanations for the effect of the type and the amount of the third monomer on the peroxide curing efficiency have been put forward; but, a comprehensive overview and an acceptable explanation of all the effects observed are still lacking. In the present paper, this gap is filled by combining results from low-molecular-weight model studies and rheometer experiments with information from the literature. It is shown that peroxide crosslinking of EPDM proceeds via the combination of two EPDM macro-radicals and the addition of an EPDM macro-radical to the residual EPDM unsaturation. The extent to which the latter radical addition occurs, is governed by the amount of the third monomer and by the steric hindrance of the residual unsaturation of the EPDM, i.e. the lower the number of ipso- and β- alkyl substituents on the unsaturation, the higher the rate of addition. This explains why EPDMs containing termonomers with terminal unsaturations are more reactive than those with internal unsaturations. The same approach was followed to assess the peroxide curing efficiency of polydiene elastomers. It was found that the same steric effects govern peroxide crosslinking of polydiene elastomers, such as NR, IR and BR.