Lyotropic liquid crystalline polymers properties

The development is reviewed of liquid-crystalline polymers whose mesophase formation derives from the nature of the chemical units in the main chain. The emphasis lies primarily on highly aromatic condensation polymers and their applications. The general properties of nematic phases formed by such polymers are surveyed and some chemical structures capable of producing nematic phases are classified in relation to their ability to form lyotropic and thermotropic systems. The synthesis, properties, physical structure and applications of two of the most important lyotropic systems and of a range of potentially important thermotropic polymers are discussed with particular reference to the production and use of fibres, films and anisotropic mouldings. 

Academic and industrial interest in liquid-crystalline polymers of the main-chain type has been stimulated by certain special properties shared by lyotropic and thermotropic systems that exhibit a nematic phase. Although these special properties affect both the processing into fibres and other shaped articles and the physical behaviour of the products, the product behaviour is at least partly attributable to the novel processing behaviour. 

The rigid rod chains in para-aramids tend to form so-called liquid crystals when they are dissolved in polar solvents or heated to certain temperatures. The polymers showing liquid crystalline behavior in melts are called the thermotropic liquid crystalline polymers, and those showing similar properties in solution are called the lyotropic liquid crystalline polymers. These liquid crystals exist in three distinct phases according to their specific structures (Fig. 12.25). 

Liquid crystallinity can be attained in polymers of various polymer architectures, allowing the chemist to combine properties of macromolecules with the anisotropic properties of LC-phases. Mesogenic imits can be introduced into a polymer chain in different ways, as outhned in Fig. 1. For thermotropic LC systems, the LC-active units can be connected directly to each other in a condensation-type polymer to form the main chain ( main chain liquid crystalline polymers , MCLCPs) or they can be attached to the main chain as side chains ( side chain liquid crystalline polymers , SCLCPs). Calamitic (rod-Uke) as well as discotic mesogens have successfully been incorporated into polymers. Lyotropic LC-systems can also be formed by macromolecides. Amphiphihc block copolymers show this behavior when they have well-defined block structures with narrow molecular weight distributions. 

Because biopolymers may have properties uncommon in synthetic systems, they can be very attractive as model systems to test specific ideas. An early example of this can be seen in the work on PBLG, a synthetic polypeptide. Although the motivation for its original synthesis failed, it provided a firm basis for many of the early studies on lyotropic liquid crystalline polymers. It was one of the first systems to have its phase diagram characterised, for comparison with Flory s predictions, and a study of its viscosity demonstrated that there is a non-monotonic increase in viscosity with concentration as the liquid crystalline phase is entered. 

The most important development in lyotropic liquid crystalline polymers after Kevlar is probably the synthesis of poly [benzo(l,2-d 4,5-d ) bisthiazole-2,6-diyl]-l,4-phenylene, or for short, poly(p-phenylene benzo-bisthiazole) ( PBT Wolfe and Loo, 1980 Wolfe et al., 1981), and the closely related poly [benzo(l,2-d 5,4-d )bisoxazole-2,6-diyl]-l,4-phenylene or poly(p-phenylene benzobisoxazole) ( PBO Helminiak and Arnold, 1977 Wolfe and Arnold, 1981). Both PBT and PBO are lyotropic liquid crystalline and can be spun into fibers with mechanical properties even superior to that of Kevlar fibers. The molecular structures of these polymers are shown in Figure 5.2. 

It should be noted that some polymers may generate crystallinity at a certain concentration of their solution (lyotropic) or under melting conditions (thermotropic). These are known as liquid crystalline polymers and behave like an isotopic liquid. They exhibit high strength properties. 

Thermotropic, main-chain, liquid-crystalline polymers (LCPs) have attracted considerable attention as a result of their high stiffness and mechanical properties. There has been interest in combining the LCPs with other materials. In one area, LCPs are used, in relatively low concentration, to reinforce less-stiff materials. In another case, a second component is used as a solvent to increase the mobility in the LCP and form lyotropic liquid-crystalline materials. There are now two reports, from Kricheldorf s group, of blends of PCL with liquid-crystalline polyesters [156,157]. 

Liquid crystalline polymers have been discussed in many texts and review papers [65, 400-413] during the last decade, in which the synthesis, processing, morphology, orientation and structure-property relations are described. The major applications of these materials have been as high modulus fibers and films, with unique properties due to the formation of ordered lyotropic solutions or thermotropic melts which transform easily into highly oriented, extended chain structures in the solid state. 

There are several commercial thermotropic polyesters that exhibit outstanding high-temperature capabilities. These include (14,15) an increasing number of fibers and high temperature plastics. Similar to the lyotropic liquid crystalline polymers, the thermotropics exhibit unusually low viscosities because of orientation and lack of entanglement. Of course, the orientation serves to improve their mechanical properties. The chemical structure can be varied significantly. 

Liquid crystalline polymers are termed liquid crystal from the fact that the polymers exhibit crystalline properties as a liquid. In LCPs there is little entwining of molecules. LCPs are polymers having a degree of molecular order either in solution (lyotropic) or in a melt (thermotropic) intermediate between those of a solid crystals and those of isotropic liquids and are called liquid crystalline. Most... 

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