Liquid crystals (LCs) may be divided into two subgroups: (1) lyotropic LCs, formed by mixing rigid rodlike molecules with a solvent, and (2) thermotropic LCs, formed by heating. One finds in the literature such terms as mesomorphs, mesoforms, mesomorphic states, and anisotropic liquids. The molecules in LCs have an orderly arrangement, and different orders of structures (nematic, smectic, or cholesteric structure) have been observed, as schematically shown in Figure 9.1. The kinds of molecules that form LCs generally possess certain common molecular features. The structural characteristics that determine the type of mesomorphism exhibited by various molecules have been reviewed. At present, our understanding of polymeric liquid crystals, often referred to as liquid-crystalline polymers (LCPs), is largely derived from studies of monomeric liquid crystals. However, LCPs may exhibit intrinsic differences from their monomeric counterparts because of the concatenation of monomers to form the chainlike macromolecules. The linkage of monomers inevitably means a loss of their translational and orientational independence, which in turn profoundly affects the dynamics of polymers in the liquid state. These intramolecular structural constraints are expressed in the flexibility of the polymer chain. Generally speaking, the chemical constitution of the monomer determines the flexibility and equilibrium dimensions of the polymer chain (Gray 1962). Figure 9.2 illustrates the variability of chain conformation (flexible chain, semiflexible chain, and rigid rodlike chain) forming macromolecules. Across this spectrum of chain flexibility, the persistence in the orientation of successive monomer units varies from the extreme of random orientation (flexible chains) to perfect order (the rigid rod). Hence, efforts have been made to synthesize LCPs that consist of rigid segments contributing to the formation of a mesophase and flexible segments contributing to the mobility of the entire macromolecule in the liquid state (Ober et al. 1984). From the point of view of molecular architecture, as schematically shown in Figure 9.3, two types of LCP have been developed: (1) main-chain LCPs (MCLCPs), having the monomeric liquid crystals (i.e., mesogenic group) in the main chain of flexible links, and (2) side-chain LCPs (SCLCPs), having the monomeric liquid crystals attached, as a pendent side chain, to the main chain.
Phase Transitions of Side Chain Liquid Crystalline Polymers Having a Terminal Alkyl Chain.