Thermotropic cholesteric liquid crystalline polymers

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. 

Main chain cholesteric liquid crystalline polymers 

D-3-methyl-glyoxal is a common chiral spacer. In addition, D-butane-1, 3-diphenol, L-propane-1, 2-diphenol, and their dimers and trimers are used as the chiral spacers in cholesteric liquid crystalline polymers as well. 

High viscosity is the main drawback for cholesteric liquid crystalline polymers in applications. However, cholesteric polymers have their advantages. They may exhibit the memory effect. These polymers make processing and handling easily. Therefore, cholesteric liquid crystalline polymers have become the new materials for optical filters, temperature indicators, etc. The Merck product with the trade name Transmax is actually associated with the cholesteric liquid crystalline polymers. 

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Stiff rod-like helical polymers are expected to spontaneously form a thermotropic cholesteric liquid crystalline (TChLC) phase under specific conditions as well as a lyotropic liquid crystal phase. A certain rod-like poly(f-glutamate) with long alkyl side chains was recently reported to form a TChLC phase in addition to hexagonal columnar and/or smectic phases [97,98]. These properties have already been observed in other organic polymers such as cellulose and aromatic polymers. 

Banded texture is generally observed in relaxed polymer liquid crystal solutions or melts after shearing or annealing of the melts of the thermotropic polymer liquid crystal. For the cholesteric liquid crystalline phase of cellulose derivatives in crosslinkable solvents, the banded texture can be fixed by crosslinking. When polymerizable solvents were used for the preparation of cholesteric liquid crystalline composites films, the... 

Emoto A, Uchida E, Fukuda T (2012) Optical and physical applications of photocontrollable materials azobenzene-containing and liquid crystalline polymers. Polymers 4 150-186 Ericson LM, Fan H, Peng HQ, Davis VA, Zhou W, Sulpizio J, Wang Y, Booker R, Vavro J, Guthy C et al (2004) Macroscopic, neat, single-walled carbon nanotube fibers. Science 305 1447-1450 Etchegoin P (2000) Blue phases of cholesteric liquid crystals as thermotropic photonic crystals. Phys Rev E 62 1435-1437... 

Kricheldorf [17] studied liquid-crystalline cholesteric copoly(ester-imide)s based on 1 or 2. The comonomers to obtain these chiral thermotropic polymers were N-(4-carboxyphenyl)trimellitimide, 4-aminobenzoic trimellitimide, 4-aminocinnamic acid trimellitimide, adipic acid, 1,6-hexanediol, and 1,6-bis(4-carboxyphenoxyl) hexane. Apparently the poly (ester imide) chains are so stiff that the twisting power of the sugar diol has little effect. 

The article covers synthesis, structure and properties of thermotropic liquid-crystalline (LC) polymers with mesogenic side groups. Approaches towards the synthesis of such systems and the conditions for their realization in the LC state are presented, as well as the data revealing the relationship between the molecular structure of an LC polymer and the type of mesophase formed. Specific features of thermotropic LC polymers and copolymers of nematic, smectic and cholesteric types are considered. 

The phase behavior is similar to that of a lower critical solution temperature (LCST), hence it is different from the above systems. The HPC/water system is an interesting model system because of the rich variety of phase structure 01 the material. HPC is a semicrystalline polymer in the solid state (7), but exhibits thermotropic liquid crystalline character at elevated temperatures below the melting point (8). It shows isotropic phase in dilute solutions, but forms an ordered liquid crystalline phase with cholesteric structure in concentrated solutions (4). 

Liquid crystals are broadly classified as nematic, cholesteric and smectic (I)- There are at least nine distinct smectic polytypes bearing the rather mundane labels smectic A, B, C,... I, by the chronological order of their discovery. Some of the smectics are actually three-dimensional solids and not distinct liquid-crystal phases at all. There are three t s of liquid crystals. Thermotropic liquid-crystal phases are those observed in pure compounds or homogeneous mixtures as the temperature is changed they are conventionally classified into nematic, cholesteric, and smectic phases in Fig.2. Lyotropic liquid-crystal phases are observed when amphiphilic molecules, such as soaps, are dissolved in a suitable solvent, usually water. Solutions of polymers also exhibit liquid-crystalline order, the polymeric phases. Most of our knowledge about liquid crystals is based on the thermotropic phases and much of this understanding can be transferred to elucidate polymeric and lyotropic phases. 

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 ... 

Many cellulose derivatives form lyotropic liquid crystals in suitable solvents and several thermotropic cellulose derivatives have been reported (1-3) Cellulosic liquid crystalline systems reported prior to early 1982 have been tabulated (1). Since then, some new substituted cellulosic derivatives which form thermotropic cholesteric phases have been prepared (4), and much effort has been devoted to investigating the previously-reported systems. Anisotropic solutions of cellulose acetate and triacetate in tri-fluoroacetic acid have attracted the attention of several groups. Chiroptical properties (5,6), refractive index (7), phase boundaries (8), nuclear magnetic resonance spectra (9,10) and differential scanning calorimetry (11,12) have been reported for this system. However, trifluoroacetic acid causes degradation of cellulosic polymers this calls into question some of the physical measurements on these mesophases, because time is required for the mesophase solutions to achieve their equilibrium order. Mixtures of trifluoroacetic acid with chlorinated solvents have been employed to minimize this problem (13), and anisotropic solutions of cellulose acetate and triacetate in other solvents have been examined (14,15). The mesophase formed by (hydroxypropyl)cellulose (HPC) in water (16) is stable and easy to handle, and has thus attracted further attention (10,11,17-19), as has the thermotropic mesophase of HPC (20). Detailed studies of mesophase formation and chain rigidity for HPC in dimethyl acetamide (21) and for the benzoic acid ester of HPC in acetone and benzene (22) have been published. Anisotropic solutions of methylol cellulose in dimethyl sulfoxide (23) and of cellulose in dimethyl acetamide/ LiCl (24) were reported. Cellulose tricarbanilate in methyl ethyl ketone forms a liquid crystalline solution (25) with optical properties which are quite distinct from those of previously reported cholesteric cellulosic mesophases (26). 

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