Mesogenic units

Only a few building blocks are available for the synthesis of ester-containing rigid mesogenic units, namely dihydroxy-, dicarboxy-, or (hydroxy, carboxy)-l,4-phenylenes, 4,4,-biphenylenes, and 2,6-, 1,4-, or 1,5-naphthylenes (Table 2.15). 

TABLE 2.15 Building Blocks Used in Main-Chain Polyester LCP Mesogenic Units... 

Macromolecules dendritic, 285 hyperbranched, 284-286 Main-chain liquid crystalline polymers, 49 Main-chain polyester LCP mesogenic units, 50... 

In general terms, high molar mass liquid crystals are classified according to the location of the mesogenic unit in the polymer. Thus, they are either incorporated into the main chain (main-chain liquid crystal polymers - MCLCP Fig. 5A) or they are pendant from the main chain (side-chain liquid crystal polymers - SCLCP Fig. 5B). 

Poly(epichlorohydrin) (PECH) and poly(2,6 - dimethyl-1,4-phenylene oxide) (PPO) containing pendant mesogenic units separated form the main chain through spacers of zero to ten methylene units were synthesized and characterized in order to test the "spacer concept." Both polymers were modified by phase transfer catalyzed esterifications of the chloromethyl groups (PECH) or the bromobenzyl groups (brominated PPO) with potassium co -(4-oxybiphenyl) alkanoates and potassium u-(4-methoxy-4-oxybiphenyl)-alk.an oates. While PPO required ten methylene units as a spacer and 4,4 -methoxybiphenyl as mesogen to present thermotropic liquid crystalline mesomorphism,... 

In order to determine the necessity and/or the length of the spacer that is required to achieve liquid crystalline behavior from flexible vs. rigid polymers, we have introduced mesogenic units to the backbones of a rigid [poly(2,6-dimethyl-l,4-phenylene oxide) (PPO)] and a flexible [poly(epichlorohydrin) (PECH)] polymer through spacers of from 0 to 10 methylene groups via polymer analogous reactions. 

The attachment of mesogenic units to a polymer backbone via polymer analogous reactions is not a new concept, although they are much less frequently used than the polymerization of mesogen containing monomers. Liquid crystalline polyacrylates,... 

The mesogenic units with methylenic spacers were prepared by reacting the sodium salt of either 4-methoxy-4 -hydroxybiphenyl or 4-phenylphenol with a bromoester in DMF at 82° C for at least 4 hours in the presence of tetrabutylammonium hydrogen sulfate (TBAH) as phase transfer catalyst. In this way, ethyl 4-(4-oxybi-phenyl)butyrate, ethyl 4-(4-methoxy-4 -oxybiphenyl)butyrate, ethyl 4-(4-oxybiphenyl)valerate, ethyl 4-(4-methoxy-4 -oxybiphenyl)-valerate, n-propyl 4-(4-oxybiphenyl)undecanoate and n-propyl 4-(4-methoxy-4 -oxybiphenyl)undecanoate were obtained. These esters were hydrolyzed with base and acidified to obtain the carboxylic acids. The corresponding potassium carboxylates were obtained by reaction with approximately stoichiometric amounts of potassium hydroxide. Experimental details of these syntheses were described elsewhere (27). 

In a model study aimed at elucidating the behavior of the polymers, Watanabe found that the dimer polymethylene diol diesters of type 7 (Figure 8.18) formed smectic phases.38 When the spacer between the two mesogenic units in the dimer had an odd number of methylene groups (diester 7 has nine methylenes in the spacer), then an intercalated tilted smectic structure with all anticlinic layer interfaces was formed. This structure is often termed SmC2 in the literature. As for the B6 phase, all of the layer interfaces in this structure are equivalent, and the X-ray layer spacing is less than half the fully... 

Another, more direct approach to overcome the problem of surface reconstruction, is the variation of the mesogenic unit of the surface active molecule. Instead of using flexible n-alkyl moieties with high conformational freedom, SAMs formed from molecules featuring a rigid mesogen in which conformational disorder has been eliminated as completely as possible should be suitable for the preparation... 

Fig. 9.18 The polymer spacer concept for the construction of a biomimetic cell membrane on solids. Mesogenic units, coupling groups and the flexible polymer can be combined either in form of a statistical terpolymer (above). Variation of the ratio of the three monomers allows an easy tuning of the system. In an alternative system, an end-functio-nalized linear hydrophilic polymer chain bearing a coupling group at the proximal and the mesogen at the distal end was employed.

Polymer containing mesogenic units in their main chains but not in side-chains. 

Polymer, the molecules of which have mesogenic units only in the side-groups or side-chains. 

Flexible segment used to link successive mesogenic units in the molecules of MCPLCs or to attach mesogenic units as side-groups onto the polymer backbone of SGPLCs. 

Note 2 The term is also used for the group linking two or more mesogenic units in liquid-crystal oligomers. 

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