Electronic effects of substituents on the properties of recyclable epoxy resins containing aromatic acetal groups

Abstract

Both environmental and economic concerns are pioneering the development of recyclable thermosetting polymers. In this study, three liquid acetal-containing di-epoxide monomers (ADEs) with different para-substituted (-OCH3, -Cl and –NO2) phenyl groups were synthesized. The refractive indices and viscosities of the three di-epoxide liquids increase in the sequence of ADE-3 (-OCH3), ADE-1 (-Cl) and ADE-2 (-NO2). Once cured with methylhexahydrophthalic anhydride, the three cured ADEs exhibit high glass transition temperatures (181–218 °C). Due to the presence of dynamic acetal bonds, all three cured ADEs are reprocessable, repairable, weldable, and degradable. Interestingly, the electronic effect of the substituents on the phenyl group significantly impacts the structural configuration, reprocessability and degradation behaviors of the resultant cured ADEs. As the electron-withdrawing effect of the substituents on the phenyl group increases, the stress relaxation rates of the cured ADEs decrease at the same temperature. Under optimized reprocessing conditions, the reprocessed ADE-1 (-Cl) and ADE-2 (-NO2) resins show the highest (117 %) and lowest (67 %) retention rates for tensile strength, respectively. The degradation rates of the three cured ADEs in the acidic solutions decrease with increasing the electron-withdrawing effect of the substituent on the phenyl group. Finally, a di-epoxide curing system based on ADE-3 was applied to prepare carbon fiber-reinforced composites, and nondestructive recovery of the carbon fibers was attained by degradation of the resin matrix.