Aromatic thermotropic polyesters

K.F. Wissbrun, "Observations on the Melt Rheology of Thermotropic Aromatic Polyesters," paper presented at Symposium on Liquid Crystal Polymers, Leeds, July 16-17, 1980, Br. Polym, J., 163-169 (Oec. 1980). 

Windle AH, Viney C, Golombok R, Donald AM, Mitchel G (1985) Molecular correlation in thermotropic copolyesters. Chem Soc 79 161-173 Wissbrun KF (1980) Observations on the melt rheology of thermotropic aromatic polyesters. Br Polym J 12 163-169... 

In the late 1980s, new fully aromatic polyester fibers were iatroduced for use ia composites and stmctural materials (18,19). In general, these materials are thermotropic Hquid crystal polymers that are melt-processible to give fibers with tensile properties and temperature resistance considerably higher than conventional polyester textile fibers. Vectran (Hoechst-Celanese and Kuraray) is a thermotropic Hquid crystal aromatic copolyester fiber composed of -hydroxyben2oic acid [99-96-7] and 6-hydroxy-2-naphthoic acid. Other fully aromatic polyester fiber composites have been iatroduced under various tradenames (19). 

Aromatic polyesters were particularly good candidates for this new field of thermotropic main-chain polymers, since the relatively low energy of association of the ester groups led to low inter-chain forces. Further research led to the discovery that incorporation of 2,6-naphthylene or of 4,4 -biphenylyl groups, in addition to p-phenylene groups, as components of aromatic polyesters, introduced a useful new degree of randomness. Particularly useful, and the basis of the commercial products Vectra (polymer) and Vectran (fibre) from Hoechst-Celanese and Kuraray, are the copolymers formed by polymerisation of mixtures of p-acetoxybenzoic acid and 6-acetoxy-2-naphthoic acid. Within a range of... 

Unusual properties of fully aromatic polyesters are observed if they have at least partially a rigid planar chain structure. In particular, they can form thermotropic liquid crystalline states (see Example 4-5). As already discussed in Sect. 1.2.4 an important structural prerequisit for LCPs of Type A in order to attain the liquid crystalline state of aromatic polyesters (and aromatic polyamides, see Example 4-14), is a rigid main chain according to the following construction principle ... 

It was, however, observed that such systems under appropriate conditions of concentration, solvent, molecular weight, temperature, etc. form a liquid crystalline solution. Perhaps a little digression is in order here to say a few words about liquid crystals. A liquid crystal has a structure intermediate between a three-dimensionally ordered crystal and a disordered isotropic liquid. There are two main classes of liquid crystals lyotropic and thermotropic. Lyotropic liquid crystals are obtained from low viscosity polymer solutions in a critical concentration range while thermotropic liquid crystals are obtained from polymer melts where a low viscosity phase forms over a certain temperature range. Aromatic polyamides and aramid type fibers are lyotropic liquid crystal polymers. These polymers have a melting point that is high and close to their decomposition temperature. One must therefore spin these from a solution in an appropriate solvent such as sulfuric acid. Aromatic polyesters, on the other hand, are thermotropic liquid crystal polymers. These can be injection molded, extruded or melt spun. 

We already have reported on the replacement of the terephthalic acid with kinked diphenylether dicarboxylic acids (4). 3,4 - and 4,4 -Dicarboxydiphenylether (3,4 -0 and 4,4 -0) were synthesized and all-aromatic polyesters were prepared represented by structure 1. These polyesters were thermotropic with melt transitions decreasing to about 200°C with increasing replacement of the terephthalic acid with the kinked monomers. The polymers generally were thermally stable without measurable weight loss until well over 400°C. We wish here to supplement our previous studies with rheological measurements and fiber spinning of the polymers, including some measurements of fiber properties. 

Although studies concerning main chain liquid crystalline polymers were originated by Onsager (la) and Ishihara (lb) in the late 1940 s, extensive work in this field did not really begin until the early 1970 s. Jackson and Kuhfuss (2) reported the first thermotropic polyester by modifying polyethylene terephthalate with various amounts of p-hydroxybenzoic acid (HBA). They found that the copolyester with HBA content of at least 35 mole % have opaque melts. Subsequent studies in the area of aromatic polyesters by various authors resulted in a large number of patents and publication. (3.) These polymers were all derived from unsubstituted and... 

The preparations of thermotropic polyester-amides from comparable monomers as those of thermotropic polyesters were a logical extension of a series of studies in thermotropic polyesters and lyotropic polyamides. (4.) However the inclusion of carbonates had rarely been explored.(5) Because of the flexibility of carbonate compared to substituted aromatic rings, it should be an even more effective approach in lowering the melting temperatures of the unmodified all aromatic polyesters into the easily processable range. 

Aromatic polyesters undoubtedly represent the most important class of thermotropic nematics. Fully aromatic rod-hke homopolymers such as poly(p-oxybenzoate) or poly (p-phenylene terephthalate) melt at temperatures which are too high to form a stable nematic mesophase. However if the regular chemical structure of the homopolymer is disrupted, the melting temperature is reduced and it is possible to obtain thermotropic nematics. ... 

It is far beyond the scope of this chapter to present a comprehensive overview on the different structures of aromatic main chain LCPs and take into account the various property and application aspects. The objective of this chapter is to discuss the impact of structural concepts in modifying the properties of aromatic LCPs, focusing here on aromatic thermotropic LC polyesters. This will be discussed for selected examples. Conclusions from the work on polyesters are transferrable to other classes of thermotropic and lyotropic aromatic polymers. 

The same structural modification concepts, which were utilized to modify the properties of para-linked aromatic LC polyesters, have also been applied to aromatic polyamides. Para-linked aromatic polyamides are an important class of LC polymers. In contrast to thermotropic LC polyesters, para-linked aromatic polyamides form lyotropic solutions. Due to the formation of intermolecular hydrogen bridges, these polymers are in most cases unable to melt below their thermal decomposition temperature. Infusibility and limited solubility of unsubstituted para-linked aromatic polyamides are characteristic properties which limit synthesis, characterization, processing, and applications. 

Aromatic polyesters forming thermotropic smectic mesophases, J.Polym.Sci., Polym.Lett.Ed. 20 109 (1982). 

Thermotropic polyester backbone chemistry is characterized by a high degree of aromaticity, planarity, and linearity in the chain backbone. Most common moieties are p-phenylene, 1,4-biphenyl, and 2,6-naphthalyl moieties linked by ester or amide linkages. Polymers that form liquid crystal phases in the melt are thermotropic, whereas those that form liquid crystalline phases in solution are lyotropic. The all-aromatic polyester homopolymers tend to be intractable, decomposing at temperatures well below their melting points and insoluble in most... 

The thermotropic group consists of a crystalline liquid formed during cooling of a dry melt (similar to the processing of thermoplastics)—the first having been the aromatic polyesters (1972). When a disordered melt cools in a region of proper transition temperature (Tj), a liquid crystal phase (mesophase) is formed. It is characterized by high order (anisotropic) that creates turbidity. 

Calundann Gordon, Meet, W. Processable Thermotropic Wholly Aromatic Polyester Containing Polybenzoyl Units US Patent 4067852. 

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