Cellulose liquid crystal solutions

Solvent viscosity vs, concentration plots for cellulose dissolved in TFA-CH2CI2 (70/30, v/v) do not exhibit a maximum (1I,S1) in contrast to the typicid behavior of polymer liquid crystal solutions. This same behavior is exhibited by other cellulose-solvent systems (52,fiQ). Conio et al. (59) si gest that due to the close proximity of the cholesteric mesophase to its solubility limit, it is only observed in a metastable condition. 

Here we describe some recent work on liquid crystal solutions of cellulose and cellulose triacetate in TFA-CH2CI2 solvent mixtures. 

Sixou, P. Bosch, A.T. Lyotropic liquid crystal solutions of cellulose derivatives. In Cellulose Structure, Modification and Hydrolysis Young, R.A., Rowell, R.M., Eds. Wiley New York, 1986 205-219. 

Phase transition at heating of liquid crystal solutions of acetates of cellulose in trifluoroacetic acid. Vysokomol. Soedin., B. Vol. 24, No.6, pp. 414-418. 

Of particular interest are the ternary systems of ethylcellulose dissolved in a mixed solvent (acrylic acid - water or acrylic acid - glacial acetic acid) and ethylcellulose/ acrylic acid solution blended with a flexible polymer, polyacrylamide. The conclusions of these studies is that, for cellulosic liquid crystals application, the morphology and optical properties of lyotropic liquid crystals can be adjusted by solvent mixing and blending with other 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... 

Lyotropic liquid crystals are those which occur on the addition of a solvent to a substance, or on increasing the substance concentration in the solvent. There are examples of cellulose derivatives that are both thennotropic and lyotropic. However, cellulose and most cellulose derivatives form lyotropic mesophases. They usually have a characteristic "critical concentration" or "A point" where the molecules first begin to orient into the anisotropic phase which coexists with the isotropic phase. The anisotropic or ordered phase increases relative to the isotropic phase as the solution concentration is increased in a concentration range termed the "biphasic region." At the "B point" concentration the solution is wholly anisotropic. These A and B points are usually determined optically. 

Since Robinson [1] discovered cholesteric liquid-crystal phases in concentrated a-helical polypeptide solutions, lyotropic liquid crystallinity has been reported for such polymers as aromatic polyamides, heterocyclic polymers, DNA, cellulose and its derivatives, and some helical polysaccharides. These polymers have a structural feature in common, which is elongated (or asymmetric) shape or chain stiffness characterized by a relatively large persistence length. The minimum persistence length required for lyotropic liquid crystallinity is several nanometers1. 

Solid formulations for sustained drug release may contain mesogenic polymers as excipients. The mesogenic polymers form a matrix, which is usually compressed into tablets. Some of the most frequently used excipients for sustained release matrices include cellulose derivatives, which behave like lyotropic liquid crystals when they are gradually dissolved in aqueous media. Cellulose derivatives such as hydroxy-propyl cellulose or hydroxy-propylmethyl cellulose form gel-like lyotropic mesophases in contact with water, through which diffusion takes place relatively slowly. Increasing dilution of the mesophase with water transforms the mesophase to a highly viscous slime and then to a colloidal polymer solution. 

Discovery of the formation of liquid crystalline solutions by cellulosics in the mid-1970s has resulted in attempts to develop new cellulosics products with properties superior to those of conventional cellulosic. Following the first observation of mesophases formed in aqueous solutions of hydroxypropyl cellulose (HPC), a variety of other cellulose derivatives have been reported to form liquid crystals. Liquid crystalline solutions of cellulose and its derivatives provide a potential route to high-modulus and high-tenacity cellulosic fibers, films, and other high-performance products. 

Liquid crystalline (LC) solutions of cellulose derivatives form chiral nematic (cholesteric) phases. Chiral nematic phases are formed when optically active molecules are incorporated into the nematic state. A fingerprint texture is generally observed under crossed polarizers for chiral nematic liquid crystals when the axis of the helicoidal structure is perpendicular to the incident light (Fig. 2). 

Werbowyj, R.S. Gray, D.G. Liquid crystalline structure in aqueous hydroxypropyl cellulose solutions. Molec. Crystals Liquid Crystals 1976, 34 (4), 97-103. 

Suto, S. Tateyama, S. Transient shear response of liquid crystal-forming hydroxypropyl cellulose solution in dimethylacetamide. I. Stress growth and relaxation behavior. J. Appl. Polym. Sci. 1994, 53 (2), 161-168. 

One of the main features of nonionic water-soluble cellulose derivatives is that they exhibit, like some other polyethers, an inverse solubility-temperature behavior, i.e. there is phase separation on heating above the so-called lower critical solution temperature (LCST). The temperature at which a polymer-rich phase separates is normally referred to as the cloud point (CP). For ideal solutions, this temperature corresponds to the theta-temperature. Actually, for some derivatives, the cloud point may be preceded, if the concentration is not too low, by a sol-gel transformation with an increase in viscosity and possibly formation of liquid crystals (see Sect. 3.5). As it will be seen later, this reversible thermotropic behavior may be detrimental to the performance of the derivatives or can be advantageneously utilized to develop applications. 

The implications of the existence of liquid crystals in water-soluble cellulosic gels has not been fully studied in the field of biological applications. In particular, the models developed for water transport in hydrogels do not consider the presence of mesophases. The same is true for solute (drug) release models... 

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). 

Cellulose triacetate-trifluoroacetic acid cholesteric solutions - This kind of lyotropic polymer liquid crystals undergoes a mesomorphic-isotropic phase transition upon heating. The peak is well defined but very small The determination of N for this... 

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. 

Specific inter- and intramolecular bonding are not necessary for ordered structures to persist in dilute solution. Ordered structures, that lead to highly asymmetric molecules, can be perpetuated by severe steric repulsions of substituents or an inherent restraint to rotations about single bonds. Such structures are known, even among synthetic macromolecules, and they form liquid-crystal systems. Some examples are polymeric aramides, poly(N-alkyl isocyanates) and some cellulose derivatives. 

FIGURE 5.3 Viscosity dependence on concentration for a liquid crystal polymer solution. (Adapted from Appaw Collins. Rheology and microstructure of cellulose acetate in mixed solvent systems. Dissertation at Graduate Faculty of North Carolina State University, 2004, http //repository.lib.ncsu.edU/ir/bitstream/1840.16/3487/l/etd.pdf.)... 

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