A series of phosphorus-containing main-chain thermotropic liquid crystalline copolyesters named poly(4,4′-biphenylene decanedioate-co-4,4′-(phenylphosphoryl)dibenzoate) (PBPDP) were synthesized by random polycondensation from mesogenic diol 4,4′-biphenol (BP), decanedioic acid (DA) and phosphorus-containing non-coplanar diacid named 4,4′-(phenylphosphoryl)dibenzoic acid (PPDBA). Chemical structures and physical properties of PBPDPs were characterized by Fourier-transform infrared spectroscopy (FTIR), proton and 31P nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC) and X-ray diffraction (WAXD). Thermal stability of the copolyesters was determined via thermogravimetric analysis (TGA), and the liquid crystalline behaviours were observed using polarizing optical microscopy (POM). Results showed that the introduction of PPDBA into the copolyester could decrease the liquid crystalline temperature (Tlc) and the isotropic temperature (Ti) as a result of both copolymerization and the non-coplanar structure of PPDBA; furthermore, when the molar ratio of PPDBA reached 15%, the copolyester turned into a semi-crystalline polymer and lost its liquid crystallinity. Thermal stability of the copolyester increased with increasing the content of PPDBA, due to the positive contribution of the phosphorus-containing structure.
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