07 June 2024 | Junheng Zhang, Can Jiang, Guoyan Deng, Mi Luo, Bangjiao Ye, Hongjun Zhang, Menghe Miao, Tingcheng Li & Daohong Zhang
A strategy was developed to create strong and tough epoxy supramolecular thermosets with rapid reprocessing and room-temperature closed-loop recyclability. These thermosets were constructed using a vanillin-based hyperbranched epoxy resin (VanEHBP) through the introduction of intermolecular hydrogen bonds and dual dynamic covalent bonds, as well as the formation of intramolecular and intermolecular cavities. The supramolecular structures provided remarkable energy dissipation, leading to high toughness and strength. The thermosets could be rapidly reprocessed at 120°C within 30 seconds and efficiently depolymerized at room temperature, with recovered materials retaining their structural integrity and mechanical properties. This strategy enables the design of tough, closed-loop recyclable epoxy thermosets for practical applications.
Epoxy thermosets with excellent mechanical and thermal performance have been widely studied in fields such as coatings, adhesives, and structural components. However, the covalent crosslinked structure of epoxy thermosets hinders reprocessing and recycling, leading to economic and environmental issues. Covalent adaptable networks (CANs) offer a solution by allowing the fabrication of cross-linked healable and recyclable epoxy thermosets. Various dynamic covalent-bond-forming processes have been used to construct CANs, enabling reprocessable and chemically recyclable epoxy thermosets. Despite efforts, the reprocessing of CANs often requires a catalyst, high temperature, and pressure, leading to unwanted side reactions and loss of physical properties. Therefore, constructing CANs that are mechanically strong and thermochemically stable and can be rapidly reprocessed under mild conditions without a catalyst remains challenging.
Dynamic covalent crosslinking enables the resulting crosslinked epoxy thermosets to depolymerize into the original monomers and oligomers, which can then regenerate the thermosets. However, these technologies usually require high temperatures, prolonged reaction times, and substantial separation and purification. There is a critical need to explore efficient, low-cost recycling technologies to achieve closed-loop chemical recycling through depolymerization into monomers and oligomers, followed by full repolymerization of these monomers and oligomers.
Imine bonds and hyperbranched topological structures were used to construct the epoxy supramolecular thermosets. The hyperbranched topological structure of VanEHBP provided efficient hydrogen-bonding interactions and denser hydrogen bonds, leading to excellent mechanical properties, creep resistance, and chemical resistance. The incorporation of reversible noncovalent interactions such as multiple hydrogen bonds into CANs not only endows these polymers with excellent mechanical performance but also provides recyclability and self-healing capacity. Hyperbranched topological structures have also been applied to effectively improve the strength, toughness, solvent resistance, and dimensional stability of CANs.
The epoxy supramolecular thermosets were synthesized by reacting vanillin derivatives with epichlorohyA strategy was developed to create strong and tough epoxy supramolecular thermosets with rapid reprocessing and room-temperature closed-loop recyclability. These thermosets were constructed using a vanillin-based hyperbranched epoxy resin (VanEHBP) through the introduction of intermolecular hydrogen bonds and dual dynamic covalent bonds, as well as the formation of intramolecular and intermolecular cavities. The supramolecular structures provided remarkable energy dissipation, leading to high toughness and strength. The thermosets could be rapidly reprocessed at 120°C within 30 seconds and efficiently depolymerized at room temperature, with recovered materials retaining their structural integrity and mechanical properties. This strategy enables the design of tough, closed-loop recyclable epoxy thermosets for practical applications.
Epoxy thermosets with excellent mechanical and thermal performance have been widely studied in fields such as coatings, adhesives, and structural components. However, the covalent crosslinked structure of epoxy thermosets hinders reprocessing and recycling, leading to economic and environmental issues. Covalent adaptable networks (CANs) offer a solution by allowing the fabrication of cross-linked healable and recyclable epoxy thermosets. Various dynamic covalent-bond-forming processes have been used to construct CANs, enabling reprocessable and chemically recyclable epoxy thermosets. Despite efforts, the reprocessing of CANs often requires a catalyst, high temperature, and pressure, leading to unwanted side reactions and loss of physical properties. Therefore, constructing CANs that are mechanically strong and thermochemically stable and can be rapidly reprocessed under mild conditions without a catalyst remains challenging.
Dynamic covalent crosslinking enables the resulting crosslinked epoxy thermosets to depolymerize into the original monomers and oligomers, which can then regenerate the thermosets. However, these technologies usually require high temperatures, prolonged reaction times, and substantial separation and purification. There is a critical need to explore efficient, low-cost recycling technologies to achieve closed-loop chemical recycling through depolymerization into monomers and oligomers, followed by full repolymerization of these monomers and oligomers.
Imine bonds and hyperbranched topological structures were used to construct the epoxy supramolecular thermosets. The hyperbranched topological structure of VanEHBP provided efficient hydrogen-bonding interactions and denser hydrogen bonds, leading to excellent mechanical properties, creep resistance, and chemical resistance. The incorporation of reversible noncovalent interactions such as multiple hydrogen bonds into CANs not only endows these polymers with excellent mechanical performance but also provides recyclability and self-healing capacity. Hyperbranched topological structures have also been applied to effectively improve the strength, toughness, solvent resistance, and dimensional stability of CANs.
The epoxy supramolecular thermosets were synthesized by reacting vanillin derivatives with epichlorohy