Dual‐Dynamic Chemistries‐Based Fast‐Reprocessing and High‐Performance Covalent Adaptable Networks

Covalent adaptable networks (CANs) possess multiple functions including reprocessing (or recyclability), self‐healing, welding, shape shifting, 3D printing, etc., due to the network rearrangement from dynamic bonds, and favorable performance from their cross‐linked feature, and they are supposed to be as sustainable alternatives to thermosets. However, the thermal and mechanical properties, and stability of CANs are often sacrificed for rapid network rearrangement. In this paper, fast‐reprocessing CANs with high performance are facilely constructed by in situ polymerization and dynamic cross‐linking of styrene (St), maleic anhydride (MA), and acetal diol (BHAD). The rigid and hydrophobic polymer backbone endow the materials with high glass transition temperatures, mechanical performance, and water resistance. Besides, carboxylic group‐catalyzed dual dynamic ester and acetal‐based networks exhibit faster stress relaxation and realize extrusion reprocessing. This work provides an ingenious and simple strategy of construction of CANs combining rapid network rearrangement and excellent comprehensive performance, which is beneficial for the application of CANs. Fast‐reprocessing and high‐performance covalent adaptable networks (CANs) are facilely constructed. The CANs exhibit rapid network rearrangement and realize fast reprocessing because of synergetic catalysis of carboxylic group on transesterification and acetal exchange. Meanwhile, the rigid and hydrophobic polymer backbone imparts the materials with high glass transition temperature, mechanical performance, and superior water resistance.