Linking MCLCP

All Liquid Crystal Polymers are characterised by the fact that they contain stiff meso-genic groups, often inserted in flexible chain systems (so called "spacers") and connected to them by linking functional groups the mesogenic unit is inserted either in the main chain or in the side chains or (in exceptional cases) in both. We shall discuss MCLCPs and SCLCPs. A schematic representation of common structures of LCPs is displayed in Fig. 6.14 (Jansen, 1996). An example of a SCLCP with disc-like mesogens is displayed in Fig. 6.15 (Franse et al., 2002, 2004). 

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. 

Completely rigid rod-like molecules such as poly(4-oxybenzoyl) or poly( p-phenylene terephthalate) tend to be highly crystalline and intractable, with melting points above the decomposition temperature of the polymers (>450°C). The problem of thermotropic MCLCP design is to disrupt the regularity of the intractable para-linked aromatic polymers to the point at which mesomorphic behaviour is manifested below the decomposition temperature and the materials can be processed in fluid yet ordered states. The disruption must not, however, be taken to the stage where conventional isotropic fluid behaviour is preferred. These requirements that the polymer must retain some rod-like nature but at the same time be melt-processable below 400-450°C have limited thermotropic MCLCPs mainly to polymers based on the linear ester or ester/amide bonds. With polyester/ polyesteramides, disruption is normally achieved by the th ee copolymerization techniques outlined in Fig. 8.1, i.e. frustrated chain packing, flexible spacers and non-linear links. 

The third common strategy for lowering in MCLCPs is to introduce non-linear units into the polymer backbone. These can take the form of met a- or ortho-substituted phenyls, 1,6- or 2,5-linked naphthy-lenes " or the incorporation of kinked bonds within the monomer unit such as —C(CH3)2—, —CH2—, —O—, —S—, —SO2—, —CO—This method of disruption is especially effective at lowering Tm, but the introduction of large amounts of such bent units will lead ultimately to loss of liquid crystallinity. In general, the stereochemistry of the bisphenol containing a kinked bond is more important than the polar... 

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