Theoretical studies on anhydride dynamic covalent bond exchange mechanisms

Anhydrides have been utilised to synthesize covalent adaptable networks (CANs), enabling the recycling of thermosets and immiscible plastic wastes due to their dynamic bond exchange properties. However, the exact bond exchange mechanism involving anhydrides remains unclear. Herein, we identify the bond exchange mechanism behind anhydride-based CANs through a comprehensive study of the anhydride bond exchange mechanism under uncatalysed and acid-catalysed reaction conditions using density functional theory (DFT) methods. Careful conformational samplings of structures and transition states have been performed to ensure accurate determination of the key rate-determining step. The bond exchange barrier increases from 44.1 kcal mol^-1 at 25 °C to 52.8 kcal mol^-1 at 200 °C for the uncatalysed route and from 25.9 kcal mol^-1 to 33.0 kcal mol^-1 over the same temperature range for acid-catalysed route. Our results implicate that anhydrides can be good dynamic covalent bond linker candidates in CANs for high temperature applications and acid catalysts may be used as mediators to assist low-temperature reprocessing and recycling.