Abstract: | Thermotropic homopolyesters were prepared through interfacial polycondensation of 4,4′‐dihydroxybiphenyl with sebacoyl chloride. The optimal conditions of the process, in terms of the best yield, were studied through investigating the type of organic phase, amount of phase transfer agent, time and temperature of reaction, and volume ratio of aqueous to organic phase. The structure of the sample that had the best yield (53.235% ± 5%) was determined by means of elemental analysis, infrared spectra, and X‐ray. The effect of the molar ratio of the monomers on the yield and inherent viscosity was investigated. The inherent viscosity of the samples varied between 0.095 and 0.25 dL/g. The mesophase formed at elevated temperatures was studied by differential scanning calorimetry, polarized light microscopy, and depolarizing transmittance measurements. Our observations revealed that poly(4, 4′‐diphenyl sebacate), in contrast to previous reports that suggest this polymer is smectgenic, could produce nematic phase. It could be concluded that the chemical structure ordering of the poly(4, 4′‐diphenyl sebacate) plays a significant role in its liquid crystalline behavior. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1594–1606, 2005 |