Lyotropic polymers phase equilibria

Figure 6 shows the phase diagrams plotting temperature T vs c for PHIC-toluene systems with different Mw or N [64], indicating c( and cA to be insensitive to T, as is generally the case with lyotropic polymer liquid crystal systems. This feature reflects that the phase equilibrium behavior in such systems is mainly governed by the hard-core repulsion of the polymers. The weak temperature dependence in Fig. 6 may be associated with the temperature variation of chain stiffness [64]. We assume in the following theoretical treatment that liquid crystalline polymer chains in solution interact only by hardcore repulsion. The isotropic-liquid crystal phase equilibrium in such a solution is then the balance between S and Sor, as explained in the last part of Sect. 2.2. 

Phase Equilibrium in a Rigid-Chain Polymer-Solvent System 2.1 Lyotropic and Thermotropic Liquid Crystals... 

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). 

---