Incorporation into main-chain liquid-crystalline polymers

Incorporation of flexible siloxane spacers into side chain or main chain liquid crystalline polymers have been shown to drastically reduce the transition temperatures 255,267,271,272,277) anc[ aiso increase the response time of the resultant systems to the applied thermal, optical or electrical fields 350-353>. In addition, siloxanes also provided elastomeric properties and improved the processibility (solution or melt) of the resulting liquid crystalline copolymers. 

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. 

Liquid Crystalline Polymers are an important class of polymeric materials because they may exhibit optical properties similar to low-molar-mass liquid crystals and high mechanical properties of polymers. These polymers are broadly classified based on their molecular architecture, i.e. attachment of the mesogen to the polymeric backbone, as main-chain liquid crystal polymers (i) or side-chain liquid crystal polymers (2). In main-chain liquid crystal polymers, mesogens are incorporated into the backbone. The mesogens may be of different shapes and sizes, and are usually rodlike or disklike. Such polymers have not been used for optoelectronic applications because it is very difficult to reorient these materials by electric field. Instead, these materials find applications that use their exceptional mechanical properties. Even side-chain liquid crystal polymers, whose mesogen is attached to the polymer backbone through a flexible spacer switch too slowly for... 

In addition to the above mentioned lyotropic cholesteric liquid crystalline polymers composed of rigid polymers, there is a diversity of thermotropic cholesteric liquid crystalline polymers which consist of a flexible chain incorporated with a mesogenic and chiral units. The thermotropic cholesteric liquid crystalline polymers are classified into two categories main chain and side chain. 

Liquid crystalline polymers in which the mesogenic moiety is incorporated into the polymer main chain are of two types i) rigid segments joined by flexible segments ii) totally rigid segments (with very little or no chain flexibility)... 

Mesogenic groups can be incorporated into polymeric systems [7]. This results in materials of novel features like main chain systems of extraordinary impact strength, side-chain systems with mesogens which can be switched in their orientation by external electric fields or—if chiral groups are attached to the mesogenic units—ferroelectric liquid crystalline polymers and elastomers. The dynamics of such systems depends in detail on its molecular architecture, i.e. especially the main chain polymer and its stiffness, the spacer molecules... 

The other and most popular way is to copolymerize the flexible segment into the polymer main chains. De Gennes (1975) predicted that incorporation of both a rigid and a flexible segment in the repeating unit should afford semi-flexible polymers exhibiting thermotropic liquid crystallinity,... 

Physical cross-linking is easily incorporated into the structures of supramolecular side-chain polymers by using bi- or multifunctional molecules [9,31,93]. The complexation of the functionalized polyacrylates, a stilbazole, and bipyridine molecules form supramolecular side-chain cross-linked polymer 37 (Figure 27) [31,93]. Bis-imidazolyl compounds are also used for such cross-linking [105]. Reversible association-dissociation of the hydrogen bonding leads to the reversible thermal order-disorder transitions, which is an important feature of supramolecular materials. Liquid-crystalline main-chain supramolecular networks have been prepared from multifunctional components [32,123-126], which will be described in Section IV. 

The first liquid crystal polymers (LCPs), in which structural moieties known to lead to mesomorphic behavior in small-molecule liquid crystals have been incorporated into the main chain, were reported in early 1980s. The presence of the mesogenic units in the polymer chain enhances the tendency for the material to form the liquid crystalline state, and these polymers also show better thermal stability. Both the nematic and smectic phases can be observed in these materials, (see Fig. 4.12). 

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