Use of Diels–Alder Chemistry for Thermoreversible Cross-Linking of Rubbers: The Next Step toward Recycling of Rubber Products?

A proof of principle for the use of Diels–Alder chemistry as a thermoreversible cross-linking tool for rubber products is demonstrated. A commercial ethylene-propylene rubber grafted with maleic anhydride has been thermoreversibly cross-linked in two steps. The pending anhydride rings were first modified with furfurylamine to graft furan groups onto the rubber backbone. These pending furans were cross-linked with a bismaleimide via a Diels–Alder coupling reaction. The newly formed Diels–Alder cross-links break at elevated temperatures (>150 °C) and can be re-formed by thermal annealing (50–70 °C). Reversibility of the rubber network was proven with infrared spectroscopy and on the basis of the mechanical properties. Furthermore, reversibility was also shown in a practical way, i.e., by cutting the used material into pieces and pressing them into new samples displaying comparable mechanical properties (impossible for conventionally cross-linked rubbers). The physical properties of the resulting products are comparable to those of conventionally cross-linked EPDM rubber and superior compared to those of their non-cross-linked precursors.