The liquid-crystalline properties of (acetoxypropyl)cellulose: Effect of chain length and degree of acetylation

Partially degraded (hydroxypropyl)cellulose methanolysates were acetylated in an acetic anhydride/dioxane mixture with a perchloric acid catalyst, yielding (acetoxypropyl)cellulose (APC) samples with an unit ester content per anhydroglucose unit of three. Eight APC samples of molar masses from 10,000 to 1.8 × 10⁵ g/mol were prepared. On heating, all the samples displayed biphasic behavior prior to isotropization. The isotropization temperature of the samples increased rapidly with molar mass, attaining a limiting value of 174°C. The substitution of hydroxyl groups of HPC by acetyl groups lowered the limiting value. Lyotropic mesophases of APC in dimethyl acetamide (DMAc) showed isotropization temperatures that increase nonlinearly with increasing APC concentration. For chains with contour lengths exceeding 72 nm, the critical concentration for mesophase formation, 0, does not depend on the chain length. However, for short chains the 0 value increases rapidly with decreasing chain length. The cholesteric reflection wavelength, λ₀, of a thermotropic APC sample of low molar mass is greater than that of a higher molar mass sample at a given temperature and increases with increasing temperature for all samples. Partially acetylated (hydroxypropyl)cellulose displays reflection colors at lower temperatures than the fully acetylated APC.