Catalyst-Free Biodegradable Chitosan-Based Dual Dynamic Covalent Networks with Self-Healing and Flame-Retardant Properties

Synthesizing covalent adaptable networks (CANs) from chitosan has been difficult due to its inherent insolubility in organic solvents. In this study, we report a facile approach for obtaining biobased flame-retarding CANs using chitosan as the starting material without dissolving it. These novel CANs were prepared via a dual cross-linking strategy in which chitosan consecutively reacted with citric acid and a vanillin-based cross-linker containing a flame-retarding moiety. The chitosan-based CANs attained dual dynamic bond-exchange sites resulting from generation of amide and ester linkages, which enabled them to perform self-healing and recyclability. They also possessed remarkable flame-retarding performance (e.g., limiting oxygen index of 41.5% and UL-94 V-0 rating), surpassing other chitosan-based flame retardants reported in the literature to date. By investigating the CAN’s response to fire in both gas and condensed phases, their flame-retarding mechanisms were uncovered. This study pinpoints a promising approach to make biobased, biodegradable, and multifunctional CANs from chitosan.