Synthesis and properties of thermotropic polyesters modified with a non-mesogenic rigid group

Four series of copolyesters, namely BB6-DMT, BB5-DMT, BB6-DMI and BB5-DMI series, were prepared by melt polycondensation of dimethyl 4,4′-bibenzoate (BB) with a dimethyl phthalate (DMT: dimethyl terephthalate or DMI: dimethyl isophthalate) and an alkanediol (1,6-hexanediol or 1,5-pentanediol). The homopolyesters poly(hexamethylene 4,4′-bibenzoate) (BB6) and poly(pentamethylene 4,4′-bibenzoate) (BB5) exhibit a smectic phase. The thermotropic liquid crystalline and crystalline properties of the copolyesters are significantly influenced by the presence of the non-mesogenic rigid phthalate unit. All BB6-DMT copolyesters remain crystalline. As x, the molar fraction of the phthalate units in the diacid units, ≧ 0.7 the mesophase of the BB6-DMT copolyesters is destroyed completely. For BB5-DMT copolyesters, the mesophase disappears as x ≧ 0.4, and the copolyesters become amorphous as 0.5 ≦ x ≦ 0.8. The mesophase and the crystallinity of the BB6-DMI copolyesters are destroyed completely as x > 0.5. The BB5-DMI copolyesters lose the mesophase as x ≧ 0.3, and become amorphous as x ≧ 0.4. The results indicate that the non-linear isophthalate unit destroys mesophase and crystallinity of the copolyesters to a greater extent than the para-linked terephthalate unit.