Plasticized Cellulosic Films by Partial Esterification and Welding in Low-Concentration Ionic Liquid Electrolyte

Abstract

Alternatives to petroleum-based plastics are of great significance not only from the point of view of their scientific and practical impact but to reduce the environmental footprint. Inspired by the composition and structure of wood's cell walls, we used phenolic acids to endow cellulosic fibers with new properties. The fiber dissolution and homogeneous modification were performed with a recyclable ionic liquid (IL) (tetrabutylammonium acetate ([N 4444 ][OAc]):dimethyl sulfoxide) to attain different levels of reaction activity for three phenolic acids (p-hydroxybenzoic acid, vanillic acid, and syringic acid). The successful autocatalytic Fischer esterification reaction was thoroughly investigated by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, elemental analysis, and nuclear magnetic resonance spectroscopy ( 13 C CP-MAS, diffusion-edited 1 H NMR and multiplicity-edited heteronuclear single quantum coherence). Control of the properties of cellulose in the dispersed state, welding, and IL plasticization were achieved during casting and recrystallization to the cellulose II crystalline allomorph. Films of cellulose carrying grafted acids were characterized with respect to properties relevant to packaging materials. Most notably, despite the low degree of esterification (DS < 0.25), the films displayed a remarkable strength (3.5 GPa), flexibility (strains up to 35%), optical transparency (>90%), and water resistance (WCA ∼90°). Moreover, the measured water vapor barrier was found to be similar to that of poly(lactic acid) composite films. Overall, the results contribute to the development of the next-generation green, renewable, and biodegradable films for packaging applications.