The idea of combining the anisotropic behaviour of liquid crystalline materials with the properties of macromolecular systems was first suggested by Onsanger and subsequently Flory. The actual realization that such systems could exist came from studies of natural polymers such as the tobacco mosaic virus. Interest in these systems intensified with the development of highstrength systems, based on rigid-rod systems, notably the aramid fibres, however, liquid crystallinity in such systems occurs only at high temperatures, usually close to the decomposition point of the polymer. It was only in the late 1970s that the design criteria for liquid crystalline polymers became apparent, the secret being largely in the decoupling of the rigid aromatic groups which give rise to the anisotropic behaviour. As a result of these ideas two classifications of liquid crystalline materials were described. Main-chain liquid crystalline polymers, are those in which rigid aromatic molecules form part of the polymer backbone, either as a continuous chain or separated by a series of methylene groups in order to lower temperature at which liquid crystalline phase behaviour is observed. Side-chain systems resemble the comb-like systems studied by Shibaev and Plate, and have the rigid aromatic groups attached as a side-chain. In general, the monomer systems required for main-chain liquid crystalline polymers are relatively simple; synthetically these systems are prepared by step-growth methods and the main challenge is often maintaining sufficient solubility to allow suitable chain-lengths to be grown (an example of how such problems might be overcome is given in Chapter 4). Side-chain systems tend to be produced from more complex structural sub-units, and may be produced either by polymerization of the appropriate monomer or by functionalization of a preformed polymer backbone. Examples of both approaches are given in this chapter. From a practical viewpoint, the advantage of side-chain systems is that they tend to be much more soluble in common organic solvents and also that thermal phase transitions occur at reasonable temperatures (reasonable being well below the temperature at which the polymer decomposes). A further advantage of such side-chain systems is that the phase behaviour can be effectively tuned through the chemical modifications of the three components, namely the side-group, the flexible coupling chain and the polymer backbone.
A columnar liquid crystal with permanent polar order