Polyesters thermotropic type

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 ... 

Thermotropic liquid crystalline polymers, like polyesters containing mesogenic units on the main chain, may not be described by the wormlike chain model (cf. Sect. 1.2). The present article does not consider this type of polymers. 

Iimura, K., Koide, N., Ohta, R. and Takeda, M. Synthesis of thermotropic liquid crystalline polymers, 1, azoxy and azo-type polyesters. Makromol. Chemie 182, 2563 (1981)... 

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. 

Among the many different classes of thermotropic polymers, only a limited number of polyesters based on aromatic ester type mesogenic units have been studied by rheological methods, beginning with the publication by Jackson and Kuhfuss of their work on the p-oxybenzoate modified polyethylene terephthalate, PET, copolymers. They prepared a series of copolyesters of p-hydroxybenzoic acid, HBA, and PET and measured the apparent melt viscosity of the copolymers as a function of their composition by use of a capillary rheometer. On inclusion of low levels of HBA into PET, the melt viscosity increased because of partial replacement of the more... 

Table VI compares the key properties of these two types of thermotropic polymers category by category. The samples compared had the same melting ranges, but were very different in reduced viscosities and solubility characteristics. The data compared were those processed under the most favorable conditions. Interestingly enough, the as-spun fibers from the polyester-carbonate can be heat-treated more efficiently than those fibers (of same tenacity) spun from the polyester. Both of them gave fiber properties far superior to those of nylons and polyethylene terephthalate. These two classes of polymers also had comparative properties (such as tensile strength, tensile modulus, flex modulus, notched Izod impact strength) as plastics and their properties were far superior to most plastics without any reinforcement.

Ringsdorf s research group have prepared novel types of rigid-rod polyesters and polyamides 56 with a disc-like mesogen in tte mainchain [75]. Most polymers with six lateral substituents appear to be thermotropic liquid crystals. Polyamides with Z = H and having four substituents on the diamine component are not liquid crystalline. The two substituents on the diacid component seem to contribute to decrease further the intermolecular hydrogen bonding. 

Perhaps the most obvious characteristic of thermotropic polyesters Is their bulk appearance. These polyesters, whether aliphatic-aromatic as the X7G type or the wholly aromatic structures, all have a fibrous, almost wood-like texture. The fracture surface of a strand shows the typical highly fibrillar morphology. If such a strand Is put through a conventional cutting process, a fuzzy and very fibrillar chip often results. Another plainly visible characteristic of thermotropic polyesters Is the opalescent, almost metalllc-1 Ike surface sheen. 

A lot of molecular structures give rise to thermotropic liquid crystallinity, but only the aromatic ester type polymers and copolymers are successfully prepared as structural materials. Aromatic polyesters can be classified into three types based on their molecular composition and thermomechanical property [74]. 

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