Synthesis of Thermoplastic Mixed Chitin Esters.

Abstract

Mixed chitin esters, that is, chitin benzoate stearates, exhibiting thermoplasticity, were synthesized by the acylation of chitin using benzoyl and stearoyl chlorides in the presence of pyridine and N,N-dimethyl-4-aminopyridine for 1 h + 24 h at 100 °C in an ionic liquid, 1-allyl-3-methylimidazolium bromide. IR and 1H NMR spectroscopic analyses confirmed the formation of the desired chitin benzoate stearates. Powder X-ray diffraction analysis of the products indicated that the crystalline structures of the chitin main-chains and stearoyl side-chains were strongly affected by the benzoyl/stearoyl substituent ratios. Introducing a small number of benzoyl groups, in addition to a large ratio of stearoyl groups, contributed to disrupting the intrinsic chitin crystals and enabling the chitin main chains and stearoyl side chains to form regularly controlled layered and parallel arrays, respectively. The resulting products exhibited meting points, associated with regular stearoyl packings, and formed melt-pressed films during the melt-pressing process. These results suggest that chitin benzoate stearates with appropriate benzoyl/stearoyl substituent ratios exhibit thermoplasticity.