Liquid Crystal Polymers. V. Thermotropic Polyesters with Either Dyad or Triad Aromatic Ester Mesogenic Units and Flexible Polymethylene Spacers in the Main Chain

Abstract

The thermal properties of two new series of thermotropic, liquid crystalline polyesters were studied by differential scanning calorimetry and on a hot-stage of a polarizing microscope. The first series contained an aromatic ester triad with a central terephthaloyl and two terminal oxybenzoyl units connected by a flexible polymethylene spacer containing from two to ten methylene units. The second series contained a head-to-head tail-to-tail aromatic ester dyad with one terephthaloyl and one oxybenzoyl unit and either a dimethylene or hexamethylene spacer. The melting temperatures and the transition temperatures for conversion from the mesophase to the isotropic phase (the clearing temperature) of the polyesters in the first series initially decreased in a zig-zag manner for polymers with up to nine methylene units but increased for the decamethylene polymer. The temperature ranges over which the mesophase formation occurred were generally broader for polymers containing an odd number of methylene units than for those with an even number of units. Most, if not all, of the polymers in both series formed nematic states on melting. The enthalpy and entropy changes for the clearing transition both increased with the length of the polymethylene spacer. Polymers of the second series possessed lower transition temperatures and narrower temperature ranges for mesophase formation, as would be expected for the shorter mesogenic unit.