ABSTRACT:Semi-rigid polyesters based on twin biphenyl analogues of 1,3,4-thiadiazole (2-phenyl-1,3,4-thiadiazoles) with hepta-and octamethylene chains in the central part were synthesized by melt polycondensation of bismethyl ester derivatives of twin 2-phenyl-1,3,4-thiadiazole with a ,w-alkylenediols and dioxydialcohol derivatives of bi phenyl. The relationship between polymer structure and thermotropic liquid-crystallinity (LC) was investigated by differential scanning calorimetry (DSC), polarizing microscope observations, miscibility tests and temperature-dependent X-ray analysis. All the polymers derived from a ,w-alkylenediols appeared to form enantiotropic or monotropic nematic phase independent of the lengths of aliphatic chains. Among the polyesters containing the bi phenyl unit, most polymers with octamethylene segment between the twin 2-phenyl-1,3,4-thiadiazoles showed the nematic phase, but polymers composed of the twin bi phenyl analogue having the central heptamethylene chain had no LC melts.KEY WORDS Semi-Rigid Polyester/ 2-Phenyl-1,3,4-thiadiazole / Melt Polycondensation / Bismethyl Ester Derivative/ Liquid-Crystallinity / Nematic Phase/ Differential Scanning Calorimetry Measurement/ A terphenyl analogue of 1,3,4-thiadiazole (2,5-diphenyl-1,3,4-thiadiazole), a five-membered heterocyclic unit containing sulfur and nitrogen atoms, is a calamitic mesogen. 1 Derivatives composed of mesogen with flexible chains on both sides, twin terphenyl analogues of the 1,3,4-thiadiazole having alkylenedioxy segments in the center 2 -5 and main-6 -8 or side-chain 9 polymers containing the mesogen form nematic and smectic mesophases in spite of its bent molecular structure. 2 · 10 -12 Our previous articles described that twin 2,5-diphenyl-1,3,4-thiadiazole derivatives linking an octamethylenedioxy chain to the center 5 have stable nematic and smectic phases. Side-chain polymers with the 2,5-diphenyl-1,3,4-thiadiazole as a mesogen represent cholesteric and chiral smectic C * phases.9 Enantiotropic thermotropic liquid-crystalline (LC) phases emerge in semi-rigid polyesters derived from diacylchloride of the 2,5-diphenyl-1,3,4-thiadiazole and aliphatic diols, 8 although wholly aromatic polyesters consisting of calamitic mesogen have no LC melts. 13Biphenyl analogues of 1,3,4-thiadiazole (2-phenyl-1,3,4-thiadiazoles) have the monotropic smectic A phase, 1 · 14 · 15 although LC temperature range was narrow. 2 In recent years, Tschierske et al. found that homoand heterotrimeric or tetrameric derivatives with the 2-phenyl-1,3,4-thiadiazole ring linked to central flexible chains show the smectic C phase. 14 · 15 Thermotropic LC phases appear in semi-rigid LC polyesters based on twin biphenyl analogue of 1,3,4-thiadiazole having decamethylene chain in the central part. 16 The polymer with octamethylene spacer displayed the monotropic nematic phase and those having decamethylene and dodecamethylene chains showed enantiotropic smectic phases, but LC temperature range was narrow.The present work describes the synthesis of vario...