Synthesis of thermoplastic chitin hexanoate-graft-poly(ε-caprolactone).

Herein, we report that chitin hexanoate-graft-poly(ε-caprolactone) (ChHex-g-PCL) is thermoplastic, as confirmed by the formation of a melt-pressed film. Chitin hexanoates with degrees of substitution (DSs) of 1.4-1.8 and bearing free hydroxy groups were first prepared by the hexanoylation of chitin using adjusted feed equivalents of hexanoyl chloride in the presence of pyridine and N,N-dimethyl-4-aminopyridine in 1-allyl-3-methylimidazolium bromide, an ionic liquid. Surface-initiated ring-opening graft polymerization of ε-caprolactone from the hydroxy groups of the chitin hexanoates was conducted in the presence of tin(II) 2-ethylhexanoate as the catalyst at 100 °C to produce (ChHex-g-PCL)s. The feed equivalent of the catalyst, reaction time, and DS value were found to affect the molar substitution and degree of polymerization of the PCL graft chains. Longer PCL graft chains formed their crystalline structures and the (ChHex-g-PCL)s largely contained uncrystallized chitin chains. Accordingly, these (ChHex-g-PCL)s exhibited melting points associated with the PCL graft chains, leading to thermoplasticity.

Synthesis of mixed chitin esters with long fatty and bulky acyl substituents in ionic liquid.

This study revealed that mixed chitin esters with long fatty and bulky acyl substituents were efficiently synthesized by acylation using acyl chlorides in the presence of pyridine and N,N-dimethyl-4-aminopyridine in an ionic liquid, 1-allyl-3-methylimidazolium bromide (AMIMBr), at 100 °C for 24 h. A stearoyl group was selected as the first substituent, which was combined with different long fatty and bulky acyl groups as the second substituents. In addition to IR analysis of the products, which suggested progress of the acylation, 1H NMR measurement was allowed for structural confirmation for high degrees of substitution (DSs) of the desired derivatives in CDCl3/CF3CO2H solvents. Crystalline structures and thermal property of the products were evaluated by powder X-ray diffraction and differential scanning calorimetry measurements, respectively. All the products showed film formability by casting from solutions in chloroform or chloroform/trifluoroacetic acid solvents. The occurrence of halogen exchange between acyl chlorides and AMIMBr in the present system was speculated to produce highly reactive acyl bromides in situ, which efficiently reacted with hydroxy groups in chitin to obtain high DS products.