Secondary Network Formation in Epoxidized Natural Rubber with Alternative Curatives

Epoxidized natural rubber (ENR) offers a unique combination of strength, sustainability, and versatile structure, making it a good candidate for creating sacrificial and reformable bonds via secondary curatives. These curatives should be simple and compatible with other rubber ingredients and industrial mixing processes. Although many alternative curatives, including zinc chloride, zinc dimethacrylate (ZDMA), and sebacic acid (SA), have been proven to be successful, they have never been compared in the same compound. Moreover, the effectiveness of these alternative curatives on network formation, including their interactions with the other ingredients of a rubber compound, such as fillers, coupling agents, and traditional curatives, has not been fully studied yet. Based on the current study, these secondary curatives alone cannot provide a sufficient level of vulcanization. However, adding ZDMA or SA together with sulfur curatives allowed improving the tensile properties and showed microlevel self-healing behavior during cyclic loading. The addition of 10 phr (parts per hundred rubber) ZnCl₂ created weak, short, and rigid bonds in ENR detectable by simple Payne measurements. However, that led to active interaction with all compounding ingredients and deterioration of the physical properties. Reducing the ZnCl₂ load to 1 phr allowed full recovery of stress after the cyclic test and fair tensile strength of the compound.