Structure Evolution of Epoxidized Natural Rubber (ENR) in the Melt State by Time-Resolved Mechanical Spectroscopy.

In this work, time-resolved mechanical spectroscopy (TRMS) was used to accurately characterize the rheological behavior of an epoxidized natural rubber (ENR) containing 25 mol% of epoxy groups. Conventional rheological tests are not suitable to characterize with accuracy the frequency-dependent linear viscoelastic behavior of materials, such as ENR, in a transient configurational state. For this reason, TRMS was used to determine the true rheological behavior of ENR, as well as to gain some insights into the changes of its macromolecular architecture under the dynamic conditions experienced during the measurements. The constructed master curves for the moduli revealed a gradual transition of the ENR rheological state from liquid-like to solid-like through the formation of an "elastic gel" throughout the bulk of the polymer. Furthermore, the evolution of the stress relaxation modulus revealed a slow relaxation mechanism, resulting from thermally activated reactions in the molten state attributed to the formation of crosslinks. Finally, the crosslink density evolution was estimated from the TRMS data and compared with results derived from equilibrium solvent-swelling measurements. These demonstrated the accuracy of the TRMS data in the prediction of the structural changes that can take place in polymers during processing.