| Abstract: | A homologous series of main‐chain thermotropic liquid‐crystalline polyesters containing rigid biphenyl mesogen and flexible methylene spacers were synthesized with the AB‐type self‐polycondensation approach. The polyesters were characterized with 1H NMR, gel permeation chromatography, thermogravimetric analysis, differential scanning calorimetry, polarized light optical microscopy, and X‐ray diffraction. These polyesters, containing trimethylene spacers on the acid side and various spacers on the alcohol side of the biphenyl mesogen, showed an odd–even effect in the transition temperatures and mesophase type. The even members showed higher transition temperatures than the odd ones. A normal smectic mesophase was observed for the even members, whereas the odd‐membered counterparts exhibited a tilted smectic mesophase. To study the effect of connectivity, the mesophase characteristics of these polyesters were compared with those of the isomeric AB‐type polyesters without any methylene spacer on the acid side of the biphenyl moiety. The mesophase characteristics were insensitive to whether the mesogen was connected to a carboxyl unit or a methylene unit. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2734–2746, 2004 |
