Rigid chain polymers isotropic solutions

Orientational order appears in the solutions of rigid-chain polymers because a random mutual arrangement of their macromolecules is possible only up to a certain concentration of the solution. To retain a minimal volume (minimal free energy) above a certain critical concentration, asymmetric macromolecules must acquire an ordered mutual arrangement, which corresponds to a transition to the state typical for liquid crystals. In this case the solution becomes anisotropic. The degree of this anisotropy is still less than strict three-dimensional ordering typical of crystalline systems, but at the same time it differs from that of the isotropic state typical of amorphous systems. 

Figure 16 shows a schematic diagram of phase transformations for rigid-chain polymers separated from isotropic solutions by introducing a nonsolvent into the system (this is a usual method of obtaining fibres and films) (cf. >). The initial isotropic solution with the polymer concentration V2 and the value of the Huggins-Flory parameter is in the monophase region. The critical concentration of the transition into liquid crystalline state for this system is v. When a nonsolvent is introduced, i.e. when x is increased up to the value >0.5 (x ), two routes of the phase transition... 

The phase equilibrium in systems containing rigid-chain polymers is characterized by the formation of a liquid-crystalline state, which fact can be illustrated by the diagram due to Flory reproduced in Figure 3. At x values below 0,the polymer-solvent system forms either an isotropic (one-phase) solution mixture of... 

The polydispersion of the macromolecules, which results in their partial fractionation by lengths between the isotropic and anisotropic phases, plays an important role in nematic ordering in solutions of rigid-chain polymers [50-53, 115-117]. 

Precipitation of the polymer on addition of a nonsolvent or with any changes in the thermodynamic parameters in solutions whose conc tration is below the critical point of the transition to the liquid-crystalline state is the most typical case of the intermediate phase equilibrium in rigid-chain polymer-solvent systems. Instead of the anticipated establishment of isotropic-anisotrqric phase equilibrium, equilibrium of two amorphous (isotropic) phases initially arises if the parameter x attains values greater than +0.5. 

VISCOUS PROPERTIES OF ISOTROPIC SOLUTIONS OF FLEXIBLE-CHAIN AND RIGID-CHAIN POLYMERS... 

For a monodisperse solute with optically isotropic, identical solute, the full expression for R q,c) given by Equation 8.19, must be used, hi principle, though P q,c) may depend on c for a flexible chain polymer, such an effect is expected to be weak in a dilute solution, though not in a more concentrated solution [1,49], and such a dependence is, of course, nil for a rigid particle. Given that circumstance, an equivalent, but more convenient form for dilute solutions is given by [28,49] ... 

Lyotropic LCPs are polymers whose solutions exhibit liquid crystallinity, that is, anisotropic domains in a fluid system, over a characteristic range of concentrations. In more concentrated solutions the system may be multiphasic and contain crystalline particles, amorphous gel particles and anisotropic solution coexisting with one another. Upon dilution, the anisotropic liquid crystalline solution turns biphasic, where anisotropic and isotropic solutions of the same polymer in the same solvent coexist. Upon further dilution, the solution becomes fully isotropic. Polymers that exhibit lyotropic mesomorp-hicity are either stiff-backbone polymers with strong interchain interaction in the absence of solvent or polymers whose backbones are so extended and rigid that, upon breakup of their crystalline order by the addition of some solvent, the stiff polymer chains retain substantial measure of parallel alignment to remain in mobile anisotropic domains. 

Fib with a structure cmresponding to molecular composites can be formed from an isotropic solution of a mixture of polymers rigid-chain PBT and flexible-chain polybenzimidazole (PBI) with the formula... 

For a specific polymer, critical concentrations and temperatures depend on the solvent. In Fig. 15.42b the concentration condition has already been illustrated on the basis of solution viscosity. Much work has been reported on PpPTA in sulphuric acid and of PpPBA in dimethylacetamide/lithium chloride. Besides, Boerstoel (1998), Boerstoel et al. (2001) and Northolt et al. (2001) studied liquid crystalline solutions of cellulose in phosphoric acid. In Fig. 16.27 a simple example of the phase behaviour of PpPTA in sulphuric acid (see also Chap. 19) is shown (Dobb, 1985). In this figure it is indicated that a direct transition from mesophase to isotropic liquid may exist. This is not necessarily true, however, as it has been found that in some solutions the nematic mesophase and isotropic phase coexist in equilibrium (Collyer, 1996). Such behaviour was found by Aharoni (1980) for a 50/50 copolymer of //-hexyl and n-propylisocyanate in toluene and shown in Fig. 16.28. Clearing temperatures for PpPTA (Twaron or Kevlar , PIPD (or M5), PABI and cellulose in their respective solvents are illustrated in Fig. 16.29. The rigidity of the polymer chains increases in the order of cellulose, PpPTA, PIPD. The very rigid PIPD has a LC phase already at very low concentrations. Even cellulose, which, in principle, is able to freely rotate around the ether bond, forms a LC phase at relatively low concentrations. 

The intention of this brief survey has been to demonstrate that besides the "classical" aspects of isotropic polymer solutions and the amorphous or partially crystalline state of polymers, a broad variety of anisotropic structures exist, which can be induced by definable primary structures of the macromolecules. Rigid rod-like macromolecules give rise to nematic or smectic organization, while amphiphilic monomer units or amphiphilic and incompatible chain segments cause ordered micellar-like aggregation in solution or bulk. The outstanding features of these systems are determined by their super-molecular structure rather than by the chemistry of the macromolecules. The anisotropic phase structures or ordered incompatible microphases offer new properties and aspects for application. 

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