Chitin derivatives. II. Time–temperature–transformation cure diagrams of the chitosan amidization process

The transformation of the salts of chitosan with acetic and propionic acid, chitosonium acetate and chitosonium propionate, into chitin or the respective homolog of amidized chitosan has been described on the basis of time–temperature–transformation (TTT) cure diagrams. The time to vitrification at various isothermal cure temperatures (T_c) was determined using dynamic mechanical thermal analysis. The time to full cure was derived using a T_g–T_c cure time relationship according to the method of Peng and Gillham, as well as by an extrapolation procedure. Consequently, TTT cure diagrams describing the temperature-driven regeneration process include full cure and vitrification curves. As in thermosets, this transformation displays an S-shaped vitrification curve, and the time to full cure increases with decreasing cure temperature. The time to full cure is very remote from the time to vitrification, and this is attributed to the tendency of vitrification to prevent full cure from being attained. The activation energies for vitrification of chitosonium acetate and chitosonium propionate derived from an Arrhenius equation are similar. This suggests that the same mechanism governs glass formation in the N-acetyl and N-propionyl-glucosamine derivatives. Additionally, the morphology of amidized chitosan and native chitin was examined using X-ray diffraction and FTIR analysis. X-ray diffraction results indicate that amidized chitosan is an amorphous material, whereas native chitin is crystalline. FTIR suggests the existence of hydrogen-bonded amide groups in native chitin but not in amidized chitosan. This difference in morphology between amidized chitosan and native chitin is accounted for in terms of the influence of glass formation in the former. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1879–1889, 1999