Thermotropic liquid‐crystalline poly(oxadiazole)s with poly(methylene) spacers: Preparation and extraordinary odd–even effect

A novel synthetic procedure for the preparation of poly(oxadiazole)s was developed with nucleophilic substitution of α,ω‐alkanediols with oxadiazole‐activated bisfluoride. Seven poly(oxadiazole)s were successfully prepared by the solution polymerization of 2,5‐bis(4‐fluorophenyl)‐1,3,4‐oxadiazole and various α,ω‐alkanediols [HO(CH2)nOH, n = 5–10 or 12] in diphenyl sulfone at temperature greater than 230 °C with K2CO3 as a catalyst. The reduced viscosities of the poly(oxadiazole)s were 0.14–0.51 dL/g, and the decomposition temperatures were greater than 350 °C and decreased from 436 to 379 °C with increasing spacer length (n). Corresponding model compounds, consisting of two terminal mesogenic 2,5‐bisphenyl‐1,3,4‐oxadiazole units and central poly(methylene) spacers, were also prepared for comparison. Both the polymers and model compounds exhibited an extraordinary odd–even effect: odd ones showed higher transition temperatures (melting and clearing temperatures). With differential scanning calorimetry, polarized optical microscopy (POM), and X‐ray diffraction, we found that the nematic mesophase was the only texture in the melts except for the polymers with longer methylene units (n = 9), in which smectic mesophases were observed.