Liquid crystalline copolyesters, rigid

From practical considerations, two properties are of prime interest The effect of liquid crystalline behavior on viscosity and the ability of the polymer to retain the ordered arrangement in the solid state. Liquid crystalline behavior during the melt results in lower viscosity, because the rigid polymeric mesophases align themselves in the direction of the flow. As a result, the polymer is easier to process. Also, retention of the arrangement upon cooling yields a material with greatly improved mechanical properties. Several thermotropic liquid crystalline copolyesters are now available commercially. 

Further theoretical studies by Floryconcerned the clarification of phase transitions for the systems with a definite distribution of macromolecules over the length and also the analysis of equilibrium for a model system composed of macromolecules in which rigid blocks are separated by flexible units. An example of such systems are copolyesters exhibiting the thermotropic transition into the liquid crystalline state in the absence of a solvent... 

The unique molecular packing of rod-like chains in liquid crystalline polymers (LCP) closely resembles the extended chain structure of highly oriented flexible chain polymers, suggesting that these materials are good candidates for barrier applications. Thermotropic LCP s, first developed in the early 1970 s, have been the object of much interest because of their excellent mechanical properties and ease of product fabrication. Preliminary observations have shown that a commercially available wholly aromatic thermotropic copolyester has gas permeability coefficients that are lower than those of polyacrylonitrile (4.). These results raise some fundamental questions as to the nature of the mechanism for transport of small molecules through a matrix of ordered rigid rod-like chains. 

In a study of the effects of temperature on the melt viscosities of copolyesters of terephthalic acid, i sophthalic acid, and methylhydroquinone, McFarlane and Davis observed that minima in the melt viscosity versus temperature curves occurred at about 340 to 360°C in compositions containing 40 to 60 mol % isophthallc acid (total diacids equal 100 mol %). The increase in the melt viscosities with increasing temperature after the minima presumably is due to the Increase in the isotropic content of the polymers and the decrease in the degree of liquid crystallinity. We did not observe this phenomenon in the rigid-rod, all-aromatic, liquid crystalline polyesters that did not contain any meta component because of the high temperatures involved (above the decomposition temperatures of the polyesters). A poly(terephthalate-Isophthalate) of methylhydroquinone containing 70 mol % isophthallc acid was not liquid crystalline and, therefore, did not exhibit a minimum in a plot of melt viscosity versus temperature... 

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