Thermotropics, solvents

In thermotropic (solvent-free) smectic-A phases, two types of distortion are permitted, namely, splaying of the director (which corresponds to bending of the layers) and layer compression. Note The material itself is assumed to remain incompressible only the layers compress.) For weak distortions, the free energy cost of these is given by (de Gennes and Frost 1993)... 

Properties. As prepared, the polymer is not soluble in any known solvents below 200°C and has limited solubiUty in selected aromatics, halogenated aromatics, and heterocycHc Hquids above this temperature. The properties of Ryton staple fibers are in the range of most textile fibers and not in the range of the high tenacity or high modulus fibers such as the aramids. The density of the fiber is 1.37 g/cm which is about the same as polyester. However, its melting temperature of 285°C is intermediate between most common melt spun fibers (230—260°C) and Vectran thermotropic fiber (330°C). PPS fibers have a 7 of 83°C and a crystallinity of about 60%. 

Some molecules ia a solvent form phases with orientational and/or positional order. In these systems, the transition from one phase to another can occur due to a change of concentration, so they are given the name lyotropic Hquid crystals. Of course temperature can also cause phase transitions ia these systems, so this aspect of thermotropic Hquid crystals is shared by lyotropics. The real distinctiveness of lyotropic Hquid crystals is the fact that at least two very different species of molecules must be present for these stmctures to form. 

A Hquid crystal compound in more cases than not takes on more than one type of mesomorphic stmcture as the conditions of temperature or solvent are changed. In thermotropic Hquid crystals, transitions between various phases occur at definite temperatures and are usually accompanied by a latent heat. 

The separation of Hquid crystals as the concentration of ceUulose increases above a critical value (30%) is mosdy because of the higher combinatorial entropy of mixing of the conformationaHy extended ceUulosic chains in the ordered phase. The critical concentration depends on solvent and temperature, and has been estimated from the polymer chain conformation using lattice and virial theories of nematic ordering (102—107). The side-chain substituents govern solubiHty, and if sufficiently bulky and flexible can yield a thermotropic mesophase in an accessible temperature range. AcetoxypropylceUulose [96420-45-8], prepared by acetylating HPC, was the first reported thermotropic ceUulosic (108), and numerous other heavily substituted esters and ethers of hydroxyalkyl ceUuloses also form equUibrium chiral nematic phases, even at ambient temperatures. 

This method is attractive, since polymers with good thermal stability are obtained, especially with aryl or halogeno substituents.165 174 Moreover, a number of substituted polyester LCPs exhibit solubility in common organic solvents, thus facilitating their structural characterization. However, the cost of starting monomers has hampered the commercial development of thermotropic polyesters based on substituted monomers. 

A compound which displays liquid crystal properties is referred to as a mesogen and said to exhibit mesomorphism. Liquid crystals may be considered either as disordered solids or ordered liquids, and their properties are very dependent on temperature and the presence or absence of solvent. In thermotropic liquid crystals the phases of the liquid crystals may be observed to change as the temperature is increased. In lyotropic liquid crystals the ordered crystalline state is disrupted by the addition of a solvent, which is very commonly water. For these systems temperature changes may also be... 

The liquid crystal state represents the fourth state of matter and exists between the solid and liquid states, which form its boundaries. The liquid crystal state is reached from the solid state either by the action of temperature (thermotropic liquid crystals) or of solvent (lyotropic liquid crystals) and it is the former that will be the subject of this chapter. 

Reinitzer discovered liquid crystallinity in 1888 the so-called fourth state of matter.4 Liquid crystalline molecules combine the properties of mobility of liquids and orientational order of crystals. This phenomenon results from the anisotropy in the molecules from which the liquid crystals are built. Different factors may govern this anisotropy, for example, the presence of polar and apolar parts in the molecule, the fact that it contains flexible and rigid parts, or often a combination of both. Liquid crystals may be thermotropic, being a state of matter in between the solid and the liquid phase, or they may be lyotropic, that is, ordering induced by the solvent. In the latter case the solvent usually solvates a certain part of the molecule while the other part of the molecule helps induce aggregation, leading to mesoscopic assemblies. The first thermotropic mesophase discovered was a chiral nematic or cholesteric phase (N )4 named after the fact that it was observed in a cholesterol derivative. In hindsight, one can conclude that this was not the simplest mesophase possible. In fact, this mesophase is chiral, since the molecules are ordered in... 

Liquid crystalline phases1 can be divided into two classes thermotropic phases are obtained by temperature variations and exist in a limited temperature interval (see Figure 7.1) lyotropic phases are instead formed by mixing two or more substances, for example, water and amphiphilic compounds or polymers and a solvent. Especially for amphiphilic compounds in water, temperature may play a role in determining the phase behavior. 

In the held of thermotropic cholesterics, the most promising approach seems to be that reported by Nordio and Ferrarini22 23 for calculating helical twisting powers. It allows one to tackle real molecules with rather complex structures and to describe them in detail. The model is currently being extended to include a better description of nematic solvents and specific solute-solvent interactions. Once tested also for conformationally mobile molecules, this model could allow the prediction of the handedness of single-component cholesterics, and, in the held of induced cholesterics, very interesting information on solute molecules could be obtained. 

M.J. Banach, R.H. Friend, and H. Sirringhaus, Influence of the casting solvent on the thermotropic alignment of thin liquid crystalline polyfluorene copolymer films, Macromolecules, 37 6079-6085, 2004. 

Recent solid state NMR studies of liquid crystalline materials are surveyed. The review deals first with some background information in order to facilitate discussions on various NMR (13C, ll, 21 , I9F etc.) works to be followed. This includes the following spin Hamiltonians, spin relaxation theory, and a survey of recent solid state NMR methods (mainly 13C) for liquid crystals on the one hand, while on the other hand molecular ordering of mesogens and motional models for liquid crystals. NMR studies done since 1997 on both solutes and solvent molecules are discussed. For the latter, thermotropic and lyotropic liquid crystals are included with an emphasis on newly discovered liquid crystalline materials. For the solute studies, both small molecules and weakly ordered biomolecules are briefly surveyed. 

Recently we have developed a new class of thermotropic liquid crystalline (LC) main-chain pol3rmers, i.e., polyethers of mesogenic bis-phenols(16-17.23-26). Since the obtained polymers are not soluble in dipolar aprotic solvents, the only available synthetic avenue for their preparation consists in the phase transfer catalyzed polyetherification. 

Starting with the crystalline state, the mesophase is reached by increasing the temperature or by adding a solvent. Accordingly, a differentiation can be made between thermotropic and lyotropic liquid crystals, respectively. As with thermotropic liquid crystals, a variation of the temperature can also cause a phase transformation between different mesophases with lyotropic liquid crystals. 

Lyotropic liquid crystals differ from thermotropic liquid crystals. They are formed by mesogens which are not the moleeules themselves but their hydrates or solvates as well as associates of hydrated or solvated molecules. In the presenee of water or a mixture of water and an organie solvent as the most important solvents for drug molecules, the degree of hydration or solvation, respectively, depends on the amphiphilic properties of a drug moleeule. Hydration of the mostly rod-shaped molecule— and the same holds for solvation—results in different geometries, eone or cylinder [5] (Fig. 3). 

Some drug substances can form mesophases with or without a solvent [19-26]. In the absence of a solvent, an increase in temperature causes the transition from the solid state to the liquid crystalline state, called thermotropic mesomorphism. Lyotropic mesomorphism occurs in the presence of a solvent, usually water. A further change in temperature may cause additional transitions. Thermotropic and/or lyotropic liquid crystalline mesophases of drug substances may interact with meso-morphous vehicles as well as with liquid crystalline structures in the human organism. Table 1 presents drug substances for which thermotropic or lyotropic mesomorphism has been proved. 

Note 2 The mesomorphic character of a lyotropic mesophase arises from the extended, ordered arrangement of the solvent-induced micelles. Hence, such mesophases should be regarded as based not on the structural arrangement of individual molecules (as in a non-amphiphilic or a thermotropic mesophase), but on the arrangement within multimolecular domains. 

Liquid crystalline materials can be divided into two large groupings thermotropic and lyotropic. Thermotropic LCs are formed when pure molecules such as cholesteryl form ordered structures upon heating. When LCs occur through mixing with solvents they are called lyotropic LCs. 

As compared to the cholesteric LC, the lyotropic LC consists of two or more components that exhibit liquid-crystalline properties (dependent on concentration, temperature, and pressure). In the lyotropic phases, solvent molecules fill the space around the compounds (such as soaps) to provide fluidity to the system. In contrast to thermotropic liquid crystals, these lyotropics have another degree of freedom of concentration that enables them to induce a variety of different phases. A typical lyotropic liquid crystal is surfactant-water-long-chain alcohol. 

These structures are extensively described in the current literature (Fanum, 2008 Friberg, 1976 Birdi, 2002 Holmberg, 2004 Somasundaran, 2006). Even within the same phases, their self-assembled structures are tunable by the concentration for example, in lamellar phases, the layer distances increase with the solvent volume. Lamellar structures are found in systems such as the common hand soap, which consists of ca. 0% soap + 20% water. The layers of soap molecules are separated by a region of water (including, salts etc.) as a kind of sandwich. The x-ray diffraction analysis shows this structure very clearly. Since lyotropic liquid crystals rely on a subtle balance of intermolecular interactions, it is more difficult to analyze their structures and properties than those of thermotropic liquid crystals. Similar phases and characteristics can be observed in immiscible diblock copolymers. 

Our understanding of lyotropic liquid crystals follows in a similar manner. The action of solvent on a crystalline substance disrupts the lattice structure and most compounds pass into solution. However, some compounds yield liquid crystal solutions that possess long-range ordering intermediate between solutions and crystal. The lyotropic liquid crystal can pass into the solution state by the addition of more solvent and/or heating to a higher temperature. Thermotropic and lyotropic liquid crystals, both turbid in appearance, become clear when they pass itno the liquid and solution states, respectively. 

Working with a solution is needed for polymers which above their melting point would degrade (example aromatic polyamide fibres such as Kevlar and Twaron). For fibres the removal of the solvent is not too problematic. In e.g. injection moulding applications solvents caimot be used here thermotropic LCP s have to be used. Since these would degrade during processing, they are diluted by copolymerisation (example poly-hydroxy-benzoic acid - co - PETP)... 

The mesogenic structures of glycolipids are due to the occurrence, on the same molecule, of a hydrophilic and a hydrophobic moiety often referred to as head and tail respectively. As a result, glycolipids are able to self-organize into a large variety of mesophases also called liquid crystals (Fig. 2) [ 10]. Supramolecular assemblies of mesogenic compounds can be caused by a rise in temperature (thermotropic liquid crystals) or by the addition of water (lyotropic liquid crystals) they result from different responses of the carbohydrate and the alkyl chain to temperature or solvent (water), respectively. 

Perhaps the most widely utilized (and studied) lyotropic LCP is poly j -phenylene terephthalamide (PPTA), more commonly known as Kevlar (see Figure 1.70). Kevlar belongs to the class of aramids that are well known for their LCP properties. Because these polymers are crystalline in solution, they are often spun into filaments, from which the solvent is subsequently removed in order to retain the aligned polymer structure. The result is a highly oriented, strong filament that can be used for a wide variety of structural applications. Most thermotropic LCPs are polyesters or copolymers that can be melted and molded into strong, durable objects. 

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