Polymerization liquid crystal solvents

The same authors 369,3701 also obtained similar results if the liquid crystal solvent was aligned by flow during the polymerization. They showed that the polymerization conditions lead to alignment of the fibrils within the polymer mass and of the chains within the fibrils polymers produced in this way could also be doped to a conductivity of 104 S cm-1 371). The morphology of polyacetylene produced by polymerization in a liquid crystal solvent, aligned both magnetically and by flow, has been studied by Montaner et al. 371). They show that the polymer film is made up of very long fibrils built from microfibrils. In one fibril, the orientation of microcrystalline domains with respect to the fibril axis is very well defined, whilst the orientation of the different fibrils in the sample spreads over 20°. 

The effect of polymer-solvent interactions on the mesophase can be derived from the rigidity of the polymer chain, the critical concentration to form liquid crystalline phase, and relaxation studies. After shearing a rigid polymeric liquid crystal, a banded texture is formed in which the direction of the bands... 

As described in Section II.B.l above, doping causes a drastic change in the electrical properties of polyacetylene. The initial values of electrical conductivity were of the order of 10 S cm" for unoriented materials d24-i30 when doped by iodine and AsFs, were enhanced to the order of 10 S cm, which was obtained in the parallel direction of the doped films oriented by mechanical stretching 31 Improvements in polymerization methods and in the catalyst systems also enhanced the electrical conductivity. Highly oriented films prepared in liquid crystal solvents (Section II.A.l.d.iii) exhibited a conductivity higher than 10 S cm, as did also a well stretch-oriented film prepared by Ti(OBu)4-EtsAl dissolved in silicon oil and aged at 120°C. In further studies Naarmann and Theophilou and Tsukamoto and coworkers attained a conductivity of ca 10 S cm k... 

A modification of the oriented polymer network systems are polymer stabilized liquid crystals (PSLC) 4) being studied in detail because of their application in flat-panel displays. In these materials, photopolymerizable diacrylate monomers are usually dissolved at a concentration less than 10% in non-reactive low-molar-mass liquid crystal solvents, commonly available, along with a small concentration of photoinitiator. Typically, the addition of small amounts of monomers and photoinitiator reduces the transition temperatures of the pure low-molar-mass liquid crystals slightly, suggesting that the order in the system is not dramatically altered by the addition of monomers or initiator. In application, this solution is aligned in a particular desired state and then photopolymerized. Photopolymerization is preferred to thermal free-radical polymerization, because photopolymerizations are very fast and because the temperature of photopolymerization can be controlled more easily to optimize processing of the display. 

In some cases, solvents do remain in the final product One sueh example oeeurs in the preparation of liquid vanillin composition used in food and cosmetics production. The preparation of such a solution is complex. The solution must be pourable at room temperature, have high solids concentration (50-70%), be mechanically and chemically stable, be easy to dilute, be transparent, be stable to bacteria, and inexpensive. The solvents include water, ethanol, and propylene glycol. Polymeric liquid crystals are prepared by dispersing polysaccharide in water. These liquid crystals arc used for perfumes. Xanthan gum is also in use for thickening cosmetics. ... 

Fig. 4. Phase diagram for mesomorphic phase transition for a liquid crystal polymer A (degree of polymerization = 100, persistence length q = 1D] in solution in a liquid crystal solvent B ( ) exact ( ] Landau de Gennes...

The papers presented in this symposium give some indication of the wide variety of polymers which are now known to form liquid crystalline phases Polymeric liquid crystals are usually classified according to the mesophase structure e g., nematic, cholesteric, smectic A, etc ). However, these classes are quite broad For example, the cholesteric lyotropic phases formed by synthetic polypeptides in suitable solvents differ markedly from the cholesteric thermotropic phases formed from silicone polymers with cho-lesteryl ester side chains. In particular, the driving forces behind the formation of the mesophases are quite different for these two examples, being essentially due to chain stiffness in the first case and to anisotropic dispersion force interactions in the second case It may therefore be useful to classify polymeric liquid crystals according to the polymer chain structure ... 

In the last section of the book, lyotropic systems are treated. These concern derivatives of cellulose in various solvents as well as solutions of synthetic PLCs in low molecular mass liquid crystal solvents and polypeptide solutions in water. The last article illustrates the tremendous variety of polymeric bio-mesogens encountered in living matter. 

Non-polymeric, liquid crystals are divided into thermotropic and lyotropic liquid crystals. Compounds which have liquid crystalline behavior in solution are called lyotropic liquid crystals. The amount of solvent is then the most important variable. Mainly thermotropic liquid crystals will be discussed here. 

The liquid crystal polymerization method was modified to prepare a vertically aligned poly acetylene film [58]. As a result, a film with a very curious morphology was formed that was composed of two layers. The layer on the solvent side had a vertically oriented fibrillar structure, whereas the layer on the acetylene gas side had a randomly oriented one. The modified method is very promising for visualizing the polymer growth process and clearly demonstrates that PA chains grow in a liquid crystal solvent. 

Araga, K., Polymerization of acetylene in liquid crystal solvent, Chem. Lett, 7, 1141-1142 (1984). 

The backbone types of polymeric liquid crystals may be lyotropic, requiring a solvent for entrance into the liquid crystalline phase, or thermotropic, requiring heat for entrance into the hquid crystalline phase. However, when dry and at service temperature, both types ordinarily exhibit three-dimensional crystalline order. 

This section pertains to reports on oriented molecules in which phases other than the usual thermotropic nematics have been used. Studies in chiral, smectic, columnar, lyotropic and polymeric liquid crystals as well as other unusual phases have been presented. The use of carbon-proton heteronuclear selective refocusing 2D NMR experiment designed for the spectral analysis of enantiomers dissolved in weakly ordering chiral liquid crystal solvents has been proposed." The method permits the extraction of carbon-proton residual dipolar couplings for each enantiomer from a complex or unresolved proton-coupled... 

Fig. 3. Liquid-crystal solvents used in the oriented polymerization of acetylene.

To produce novel LC phase behavior and properties, a variety of polymer/LC composites have been developed. These include systems which employ liquid crystal polymers (5), phase separation of LC droplets in polymer dispersed liquid crystals (PDLCs) (4), incorporating both nematic (5,6) and ferroelectric liquid crystals (6-10). Polymer/LC gels have also been studied which are formed by the polymerization of small amounts of monomer solutes in a liquid crystalline solvent (11). The polymer/LC gel systems are of particular interest, rendering bistable chiral nematic devices (12) and polymer stabilized ferroelectric liquid crystals (PSFLCs) (1,13), which combine fast electro-optic response (14) with the increased mechanical stabilization imparted by the polymer (75). 

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