Abstract: Series of thermotropic liquid crystalline poly(aryl ether ketone)s were synthesized by mucleophilic substitution reactions of 4,4'-biphenol and substituted hydroquinone with different difluoromonomers. The relationship between structure and properties of the novel copolymers was investigated. For the copolymers with liquid crystalline properties, their melting transition temperatures show no great change with increase the content of the crystal-disrupting unit. The reason is that the crystal phase is directly transformed from the ordered liquid crystal phase. Side-groups have important effect on mesophase stability. The temperature range of mesophase stability for the chloro-polymers is smaller than those of other series of copolymers(p-phenyl,t-butyl, methoxy, 3-trifluoromethylbenzene). This behavior indicates that the effect of geometric repulsive factor on the thermodynamic stability of the mesophase is much larger than that of the polarizability attractive factor. Different ordered liquid crystal phases are observed in the polymers with different molecular weights. At low molecular weight, highly ordered smectic liquid crystal phases form. With increasing the molecular weight, the ordered degree of the liquid crystals decreases, and only the nematic liquid crystal phase is observed in the polymer with higher molecular weight.

Key words: Poly(aryl ether ketone)s, Liquid crystalline polymers, Structure and properties