Sustainable Framework of Chitosan–Benzoxazine with Mutual Benefits: Low Curing Temperature and Improved Thermal and Mechanical Properties

Abstract

Polybenzoxazines (PBzs) are emerging as a highly promising and superior class of thermoset polymers for a variety of applications. However, it remains a significant challenge to substantially lower the ring-opening polymerization (ROP) temperature with an ease in processability. On the other hand, biomacromolecule chitosan (CS) is explored extensively, but its practical applications have been precluded by poor thermal and mechanical properties. Here, we developed a fully biobased copolymer of vanillin benzoxazine (V-fa) monomer with CS, which is effective in providing mutual benefits, effective lowering in ROP temperature of benzoxazine (70 °C), and an enhanced thermal stability of CS (by 85 °C, and with char yield of ∼32%). To understand this unusual lowering in ROP temperature, we investigated the structural interaction mechanism between solvated CS and V-fa using in situ NMR studies. The analysis of fully intercalated co-structure demonstrated that there is a strong preference for ROP over Schiff base ...