Nematic phase lyotropic polymers

The development is reviewed of liquid-crystalline polymers whose mesophase formation derives from the nature of the chemical units in the main chain. The emphasis lies primarily on highly aromatic condensation polymers and their applications. The general properties of nematic phases formed by such polymers are surveyed and some chemical structures capable of producing nematic phases are classified in relation to their ability to form lyotropic and thermotropic systems. The synthesis, properties, physical structure and applications of two of the most important lyotropic systems and of a range of potentially important thermotropic polymers are discussed with particular reference to the production and use of fibres, films and anisotropic mouldings. 

Academic and industrial interest in liquid-crystalline polymers of the main-chain type has been stimulated by certain special properties shared by lyotropic and thermotropic systems that exhibit a nematic phase. Although these special properties affect both the processing into fibres and other shaped articles and the physical behaviour of the products, the product behaviour is at least partly attributable to the novel processing behaviour. 

Both lyotropic and thermotropic liquid-crystalline synthetic polymers have been widely studied. Aromatic polyamides constitute the most important class forming liquid-crystalline solutions the solvents are either powerfully protonating acids such as 100% sulphuric acid, chloro-, fluoro- or methane-sulphonic acid, and anhydrous hydrogen fluoride, or aprotic dipolar solvents such as dimethyl acetamide containing a small percentage, usually 2-5 %, of a salt such as lithium chloride or calcium chloride. Such solutions constitute a nematic phase within certain limits. Some criteria for formation of a nematic instead of an isotropic phase are ... 

Lyotropic polymers consisting solely of ring structures are also known, and are exemplified by poly(p-phenylene benzobisthiazole) (IV), which forms a nematic phase in several strongly protonating acids including polyphosphoric acid. Its synthesis and application, like those of the aromatic amide polymers, are discussed later. 

The isotropic-to-nematic transition is determined by the condition [1 — (2/3)TBBWBB/k T] = 0 whereas the spinodal line is obtained when the denominator of XAA is equal to zero. These conditions are evaluated in the thermodynamic limit (Q = 0) in Fig. 7 for a Maier-Saupe interaction parameter Web/I bT = 0.4xAb and for NA = 200, N = 800, vA = vB = 1. When the volume fraction of component A(a) is low, the isotropic-to-nematic phase transition is reached first whereas at high < >A the spinodal line is reached first. In the second case, the macromolecules do not have a chance to orient themselves before the spinodal line is reached. This RPA approach is a generalization of the Doi et al. [36-38] results (that were developed for lyotropic polymer liquid crystals) to describe thermotropic polymer mixtures. Both approaches cannot, however,... 

For lyotropic LCPs, there is a hiphasic window of concentrations over which nematic and isotropic phases coexist, t he polymer concentrations in the coexisting isotropic and nematic phases are designated by C (or = Trd Lv /A) and Cj (or (pj = jrd Lv2/A), respectively. There is also a theoretical concentration C, at which the isotropic phase becomes unstable to orientational fluctuations. According to the Onsager theory, 02/0 = 1.047 and 02/0i = 1.27 (see Section 2.2.2). Thermotropic LCPs often have a biphasic window of temperatures over which isotropic and nematic phases coexist. This biphasic window exists in nominally single-component thermotropics because of polydispersity the nematic phase is typically enriched in the longer molecules relative to the coexisting isotropic phase (D Allest et al. 1986). 

The fairly good quality of the fits validates both Leadbetter s assumptions and the Maier-Saupe distribution function. However, the values of S obtained and even the quality of the fits obviously depend on the odd or even number of (CH2) groups in the flexible spacer. This odd-even effect is widespread and well known in the field of main-chain LCPs and will be discussed later in this article. The nematic order parameter of main-chain LCPs may reach values as high as 0.85 which demonstrates the very high orientation of the nematic phase of these polymers. Such a large orientation is undoubtedly responsible for the good mechanical properties of this type of materials. The treatment described above therefore provides a very easy way of characterizing the orientational order of a nematic phase. It has also been tested for thermotropic side-chain LCPs and found to be satisfactory as well [15]. Unfortunately, it has not been used yet in the case of lyotropic LCPs except for some aqueous suspensions of mineral ribbons (Sect. 5) which are not quite typical of this family of materials. 

Observed structures of a lyotropic material are classified into three categories nematic, smectic, and cholesteric. Nematic and cholesteric mesophases can be readily identified by microscopic examination. The existence of a smectic mesophase is not well defined and is only suggested in some cases. Solvent, solution concentration, polymer molecular weight, and temperature all affect the phase behavior of lyotropic polymer solutions. In general, the phase transition temperature of a lyotropic solution increases with increasing polymer molecular weight and concentration. It is often difficult to determine the critical concentration or transition temperature of a lyotropic polymer solution precisely. Some polymers even degrade below the nematic isotropic transition temperature so that it is impossible to determine the transition temperatures. Phase behavior is also affected by the polymer molecular conformation and intermolecular interactions. 

These theoretical considerations have led to the following view on a nematic solution, in particular of a solution of a para-aromatic polyamide in sulfuric acid [38]. In a quiescent solution of a lyotropic polymer the chains are more or less aligned parallel inside domains of microscopic size, see Fig. 3. The degree of orientation inside the domain, as represented by the order parameter (Pj), is determined by the concentration and temperature. The excluded volume entropy term leads to the formation of oriented blobs with a size of the order of Lp, the persistence length. These blobs line up due to their anisotropic polarizability, which implies that the formation of the anisotropic phase is governed by a dipole-dipole type of interaction, immediately leading to the Maier-Saupe mean-field potential. The entropy or excluded volume interaction merely tells us... 

The zero shear viscosity of flexible linear polymers varies experimentally with and theoretically with [20]. Due to the highly restricted rotational diffusion, the viscosity of TLCPs is much more sensitive to the molecular weight than that of ordinary thermoplastics as discussed in section 3. Doi and Edwards predicted that the viscosity of rod-like polymers in semi-dilute solutions scales with A/ [see Equation (12)] [2]. Such a high power dependence of viscosity on the molecular weight has been experimentally observed both for lyotropic LCPs [14,15] and for TLCPs [16-18]. The experimental values of the exponent range from 4 to 7 depending on the chemical structure, the chain stiffness, and the domain or defect structure of the liquid crystalline solution or melt. The anisotropicity of the liquid seems to have little effect on the exponent. A slightly smaller exponent for the nematic phase than for the isotropic phase (6 in the nematic phase versus 6.5 in the isotropic... 

Still in the isotropic phase, but closer to the phase transition temperature, a shear induced transition to the nematic phase occurs, see Fig. 6. Based on the equations presented here, such a behavior has been predicted theoretically quite some time ago [20, 21]. This phenomenon has been observed in lyotropic liquid crystals, in particular with wormlike micelles [5] and in side-chain liquid-crystalline polymers [35]. In Fig. 6, results are presented for = 1.3. For comparison, the highest temperature for which a metastable nematic phase exists, -d = 9/8 = 1.125, is included. For imposed shear rates, shear stress and consequently the viscosity jump smaller values at the induced phase transition. For imposed shear stress there is a jump to higher shear rates. 

By Heck-type coupling liquid crystalline rigid-rod polymers containing [1,3-(diethynyl)cyclobutadiene] cyclopentadienyl moieties were prepared [202]. One example is the reaction of the diethynyl derivative 41 with a 2,5-diodothiophene 42 to the polymer 43 [equation (21)] which show lyotropic nematic phases. 

---