Facile and green preparation of hemicellulose-based film with elevated hydrophobicity via cross-linking with citric acid

Abstract

Hemicellulose has shown great potential in food packaging due to its excellent biodegradability and low oxygen permeability. However, its strong hydrophilicity leads to poor moisture resistance and hinders its wide application. To address this issue, herein a ternary carboxylic acid, citric acid (CA), was incorporated into hemicellulose as esterifying agent to form a crosslinking structure via the esterification reaction. The CA-modified hemicellulose films showed an increased contact angle of 87.5° (vs. 40.5° for unmodified film), demonstrating that the hydrophobicity of hemicellulose had been improved significantly. In addition, the esterification/cross-linking modification enhanced oxygen barrier performance with oxygen permeability decreasing from 1053 (cm³ μm) (m² d kPa)⁻¹ to 1.8 (cm³ μm) (m² d kPa)⁻¹. Moreover, the tensile strength rose to a peak value and then fell back at higher CA content. Effect of CA addition on elongation at break exhibited an opposite trend. The modified hemicellulose films with 20% CA addition possessed the highest tensile strength and the lowest elongation at break. Morphology observation with scanning electron microscopy indicated that at CA content exceeding 20%, the modified films were dense with a smooth surface, illustrating the improvement of phase compatibility. A possible mechanism for esterification/cross-linking was proposed to elucidate the connection between CA addition and film performances.