Characterization of Metallocene Epdm Terpolymers with High Diene and Propylene Content Crosslinked by Dicumyl Peroxide and β‐Radiation

Abstract

Summary: Two metallocene EPDMs with the same weight fraction of ethylene but differing in diene content were crosslinked, either by dicumyl peroxide (DCP) or β‐radiation. The effect of different diene and propylene content on the molecular structure and the mechanical properties once the materials were crosslinked was studied. The final gel content was very high due to the large level of unsaturations. The crosslinking process was monitored by FTIR spectroscopy by following the decay of unsaturations and the variation of the carbonyl groups that are related to the oxidation grade. It was found that β‐radiation crosslinked samples exhibited a lower oxidation grade than those crosslinked by DCP. An oscillant disc rheometer was employed to follow the evolution of the rheological properties, the scorch time, and the time corresponding to full cure during the crosslinking reaction with DCP. In addition, in order to characterize the state of cure we have studied the rheological properties in shear employing a dynamic parallel plate geometry. These results were correlated with those obtained from the molecular characterization of the soluble fraction by size exclusion chromatography. The experiments indicate that, at low irradiation doses, there is a high rate of chain scission reactions that cause an important decrease in storage modulus. Whereas, at high irradiation doses the rate of chain scission reactions diminishes, thus the storage modulus increases but it still remains at lower levels than those corresponding to the original terpolymers. The tensile properties, hardness (Shore A) and compression set tests also suggest the presence of chain scission reactions.Storage modulus (G′) versus frequency for a β‐irradiated sample.magnified imageStorage modulus (G′) versus frequency for a β‐irradiated sample.

Influence of PE/PP ratio and ENB content on the degradation kinetics of γ-irradiated EPDM

“…Both materials have the same PE/PP ratio, but the diene content of SC matrix is 5.2 times larger than the one of the P matrix. This difference confirms the major role of the diene in the cross-linking process [30,31]. This is consistent with a lower M c in SC-X-CR than in A-X-CR: since, during thermal crosslinking, more ENB units are consumed in SC-X-CR than in A-X-CR (cf.…”