Thermotropic liquid crystalline properties of (hydroxypropyl)cellulose derivatives with butyryl and heptafluorobutyryl substituents

(Hydroxypropyl)cellulose (HPC) derivatives with butyryl (Bu) and heptafluorobutyryl (7FBu) substituents were prepared in various proportions of the Bu/7FBu groups and at a fixed total DS (DSBu + DS7FBu) of 3.0. Thermotropic liquid crystallinity of the derivatives (Bu7FBu-HPC) was investigated to specify the effect of the fluoroacylation on the mesophase behavior. Thermal transition data were collected using differential scanning calorimetry and polarized light microscopy. The Bu7FBu-HPC samples formed a chiral nematic phase between their glass transition and isotropization temperatures, T-g and Ti-a, respectively; these transition temperatures rose moderately as the 7FBu proportion increased (T-g = -44 to -27 degrees C and Ti-a = 158-190 degrees C for DS7FBu = 0.04-1.60). The structural property of the mesophase was examined at 70 degrees C by circular dichroism and other optical measurements. The chiral nematic pitch (P) sensitively increased with increasing 7FBu proportion, while the supramolecular helical arrangement remained right-handed. Selective light-reflection colors were observed for the samples of DS7FBu = 0.04-0.8, covering an entire spectrum range from violet to red. Temperature dependence of P was also examined for selected samples below Ti-a, and it was found to increase with increasing temperature; however, there was no indication of inversion in the handedness of the helical structure. Wide-angle X-ray diffractometry revealed that the increases of P responding to the increases in DS7FBu and temperature were attributable to the decrease of the twist angle between adjacent thin nematic layers.