Self-Healing and Flame-Retardant Modifications of Epoxy Resins by the Diels-Alder Release-Delivery Strategy for a High-Efficiency and Green Application

The sustainability of epoxy thermosets (EPs) and EP-based composites is always limited by the evolution of internal microcracks and flammability. Herein, inspired by the drug release-delivery system for disease treatment, these symptoms of EP are solved efficiently by a multifunctional Diels-Alder (DA) release-delivery system. First, this novel system is fabricated by the cyclization reaction between the furan diene-containing phosphorus derivative and the maleimide dienophile. The resultant DA system is linked to the epoxy resin by the grafting reaction, thus ensuring its uniform dispersion. Being faced with the formation of inner microcracks, the maleimide dienophiles were released from the DA adducts under the mediated action of temperature and then were delivered to the targeted microcracks under the chemical potential difference derived from the variation of free volume. Then, the released maleimide molecules re-connect with the furan groups that existed near the microcracks to complete the repairing of the EP matrix. The skeletal structure of the EP was well preserved throughout the restoration process. Satisfactory flexural strength (105.5 MPa) and excellent crack-healing efficiency (104.5%) can be obtained for the modified EP. After three constant strain cycles, the stress retention rate can be readily maintained (more than 75%). In addition, due to the phosphorus-nitrogen synergistic flame-retardant effect from the DA system, not only the limited oxygen index of the DA-modified EP matrix can be improved to 27.5% but the lower peak release rate and lower total heat release are also observed compared with the unmodified EP.

Automated summary

The evolution of internal microcracks and flammability in epoxy thermosets (EPs) and EP-based composites are efficiently solved by a multifunctional Diels-Alder (DA) release-delivery system inspired by drug release-delivery system. The DA system is fabricated by the cyclization reaction between furan diene-containing phosphorus derivative and maleimide dienophile, and linked to epoxy resin by grafting reaction for uniform dispersion. The maleimide dienophiles are released from the DA adducts under temperature mediation and delivered to targeted microcracks, where they reconnect with furan groups to repair the EP matrix and preserve its skeletal structure. The modified EP exhibits satisfactory flexural strength (105.5 MPa) and excellent crack-healing efficiency (104.5%), as well as improved flame retardancy and reduced heat release.