Nematic phase thermotropic polymers

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. 

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 ... 

Above 110 °C, this arrangement becomes mobile, and a smectic C liquid-crystalline phase is entered. Samples cooled down from the isotropic melt (140 °C) show Schlieren and banded textures when viewed under crossed polarizers (Figure 8). These textures look similar to nematic Schlieren textures, but from the X-ray diffraction data it is clear that 12c forms a homeotropically oriented smectic C phase. In a nematic phase, the small-angle diffraction peak would be absent, and a broad scattering feature, a nematic streak , would be observed. Polymer 12c was the first example of a PPE derivative for which three states of matter, i.e. crystalline, thermotropic liquid crystalline, and a highly viscous isotropic liquid, were accessible [46]. 

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,... 

Low polarisation ratios (<2 1) for absorption had also been found for amorphous PPV (1) deposited from solution by spin-coating on rubbed poly(tetrafluoroethylene) [PTFE]. It is evident that this could be improved on by making use of the high order parameter and self-organising properties of the nematic phase of liquid crystalline electroluminescent polymers such as those (16, 28 and 78-82) shown in Table 6.16. - 2 ° This was then found subsequently to be the case using thermotropic liquid crystalline polyfluorenes, such as 28 and 80 shown in Table 6.6 and segmented PPV derivatives, such as 81. The nematic phase exhibits the lowest viscosity of... 

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). 

PEIs derived from AT-(4-carboxyphenyl) trimellitimide and aliphatic spacers (11) are not thermotropic, irrespective of whether the spacer is chiral or not. If the spacers are semi-aliphatic and contain a benzene ring, then thermotropic PEIs may be formed with both a smectic and nematic phase. If chiral spacers are then used a chiral smectic A or C phase may additionally be obtained. Such phases may be ferroelectric, which is extremely rare for main-chain polymers [26]. Examples of chiral and non-chiral spacers used in the copolymers (12) are ... 

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. 

NMR spectroscopy to characterize thermotropic PLCs was first reported by McFarlane et al. [21] and Calundann and Jaffe [22], although the first actual measurements of the nematic order parameter (i.e. the domain order parameter of the nematic polymer and the fraction of nematic phase (in the biphasic region) was first made by Blumstein and CO workers [23-25] and Samulski [26] using and D-NMR. The nematic order parameter was calculated on the basis of the dipolar and quadrupolar splitting of the NMR spectrum when cooling from the isotropic phase. 

Severing, K., Saalwachter, K. Biaxial nematic phase in a thermotropic liquid-crystalline side-chain polymers. Phys. Rev. Lett. 92(14), 125501 (2004)... 

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