Effects of keto acid crosslinking on the structure and properties of chitosan based casted and hot-pressed films

Crosslinking is one of the most effective ways to enhance the performance of bio-based films, and suitable crosslinking agents are crucial for the enhancement. In this study, four α-ketoacids, namely glyoxylate, pyruvate, oxaloacetate, and α-ketoglutarate were used to crosslink chitosan at room temperature. The effects of crosslinking on the structure and properties of chitosan films were studied, and the reaction mechanism was explored. Fourier Transform Infrared spectroscopy and X-ray Photoelectron Spectroscopy indicated that ion attraction and Schiff base reactions occurred between keto acids and chitosan. Glyoxylate developed the most effective covalent crosslinking with chitosan, whereas α-ketoglutarate had the highest ionic crosslinking ratio. Keto acid crosslinking reduced the orderliness of chitosan, improved the uniformity of the film matrix and increased its UV-blocking capacity. Glyoxylate-crosslinked chitosan film demonstrated excellent tensile strength (160 MPa), water stability (water solubility about 11.71 %), and extremely low oxygen permeability (2.65 × 10^-16 cm³·cm/cm^-2·s^-1· Pa^-1). Despite the weakened thermal stability and water barrier property, glyoxylate crosslinking shows great potential for the preparation of high-strength and high‑oxygen-resistance chitosan films. Furthermore, the glyoxylate-crosslinked chitosan film could be produced by hot pressing and performed satisfactorily.