Liquid crystalline polymers smectic crystals

Shibaev, V. P., Moiseenko, V. M., Plate, N. A. Thermotropic liquid crystalline polymers, 3, Comb-like polymers with side chains simulating the smectic type of liquid crystals. Makromol. Chem. 181, 1381 (1980)... 

In general, for side chain liquid-crystalline polymers, macroscopic molecular alignment is not easy and therefore clear evidence of electronic charge carrier transport was confirmed first in liquid crystals with low molecular weight. In the 1990s, fast electronic conduction was verified in discotic columnar phases of triphenylene derivatives [79,80] and hexabenzocoronene derivatives [81,82] as well as smectic phases of 2-phenylbenzothiazole [83, 84] and 2-phenylnaphthalene derivatives [85], as shown in Fig. 14. Carrier... 

Because of the additional translational order, the dislocations can exist in the cholesteric and smectic liquid crystals, which makes the texture of these liquid crystals even more complicated. Each liquid crystal phase shows characteristic textures and thus the optical texture becomes an important means to differentiate the phase of the liquid crystals. Liquid crystalline polymers have the same topologically stable defects as small molecular mass liquid crystals do, but the textures may be different due to the difference in the energetic stability of the same topological defects in both low molecular mass and polymeric liquid crystals (Kleman, 1991). In Chapter 3 we will discuss the textures in detail. 

In the latter two phases backbones have the spindle-like conformation, i.e., the prolate shape with (R%) > R p), the characteristic of main chain liquid crystalline polymers. Important means of investigating the conformations of side chain liquid crystalline polymers include small angle neutron scattering from deuterium-labeled chains (Kirst Ohm, 1985), or small angle X-ray scattering on side chain liquid crystalline polymers in a small molecular mass liquid crystal solvent (Mattossi et al., 1986), deuterium nuclear resonance (Boeffel et al., 1986), the stress- or electro-optical measurements on crosslinked side chain liquid crystalline polymers (Mitchell et al., 1992), etc. Actually, the nematic (or smectic modifications) phases of the side chain liquid crystalline polymers have been substantially observed by experiments. 

The liquid crystalline polymer has since developed far beyond imagination that a decade ago. The liquid crystalline polymer family has so far included the main chain-, side chain-, and crosslinked- (i.e. network or elastomer) types, and their solutions and gels. The liquid crystal phases cover nematic, cholesteric and smectics. Although the science of the liquid crystalline polymer is not fully mature, it has attracted significant research interests and has already made tremendous progress. As investments and human resources continue, the liquid crystalline polymer is expected to have an even brighter future. 

FIGURE 5.3 Schematic representation of (a) nematic phase and (b) smectic phase for main-chain liquid crystalline polymers, showing the director as the arrow. The relative ordering is the same for side-chain-polymer liquid crystals. 

Perhaps one of the most important applications of chiral induction is in the area of liquid crystals. Upon addition of a wide range of appropriate chiral compounds, the achiral nematic, smectic C, and discotic phases are converted into the chiral cholesteric (or twisted nematic), the ferroelectric smectic C and the chiral discotic phases. As a first example, we take the induction of chirality in the columns of aromatic chromophores present in some liquid-crystalline polymers. " The polymers, achiral polyesters incorporating triphenylene moieties, display discotic mesophases, which upon doping with chiral electron acceptors based on tetranitro-9-fluorene, form chiral discotic phases in which the chirality is determined by the dopant. These conclusions were reached on the basis of CD spectra in which strong Cotton effects were observed. Interestingly, the chiral dopants were unable to dramatically influence the chiral winding of triphenylene polymers that already incorporated ste-reogenic centers. 

Until now there was no obvious correlation found between the monomer structure and the resulting pol qner phase. No.theorr retical structural conditions were described which would result in a liquid crystalline polymer with a definite ordered phase e.g. with a nematic a smectic or a cholesteric phase as in conventional liquid crystals. Although previous examples have established (8 9) the existence of enantiotropic liquid crystalline side chain polymers additional considerations are in order for a systematic synthesis of such polymers. 

The molecule is a liquid crystalline polymer with chiral smectic C phase forming parts attached as side chains. The field required to switch the direction of polarization of the polymer is very low (0.3 MVm ). There is a lot of interest in liquid crystalline ferroelectric polymers, because of their possible use for fast-switching electro-optical devices. More information about ferroelectric liquid crystals can be found in references [36,37]. 

Smectic liquid crystalline polymers have more ordered structures than nematic liquid crystalline polymers, as their molecular arrangements have not only long-range orientational order, but also positional order. The positional order refers to the layer packing structures of the polymers. The less ordered smectic liquid crystals, such as smectic A, are true one-dimensional crystals. The packing structure of the smectic A is illustrated in Figure 5.6. The smectic A phase can be considered as convolution of a layer of two-dimensional liquid, i.e., a layer of randomly packed hard rods that are uniaxially oriented in the direction of the layer normal, and a one-dimensional lattice as shown in Figure 5.7. 

The equations presented above are derived based on the least ordered smectic liquid crystalline polymers, i.e., the smectic A liquid crystals. The more ordered smectic systems may generate X-ray scattering patterns similar to those of crystal structures. 

Having discussed the theory behind X-ray scattering from nematic and smectic liquid crystalline polymers, in the following sections, applications of X-ray scattering in studies of phase behavior, crystallization, and orientation of liquid crystalline polymers will be discussed. 

In summary, TPPs show complicated phase transition behaviors. Their phase diagrms are established and various phases are identified via the thermodynamic transition properties obtained from DSC, the structural order and symmetry determined by WiOCD, and morphology and defects observed under PLM and TEM. In particular, the WAXD fiber patterns in different phases play the most important role in determining the phase structures and symmetry. It is evident that the concepts of highly order smectic phases developed in small-molecule liquid crystals can also be utilized in the main-chain liquid crystalline polymers. 

Watanabe, J., and Kinoshita, S., A distinct smectic C2 liquid crystal observed in main-chain liquid crystalline polymer, J. Phys. II (Fr.) 2, 1237-1245 (1992). 

The surface-stabilized ferroelectric liquid crystals in the smectic C (SmC ) phase are among the most interesting types of liquid-crystalline systems because of their potential applications in high-resolution flat panel displays and fast electro-optical devices [73-76]. Within this class of compounds, ferroelectric liquid-crystalline polymers (FLCPs) have gained theoretical and practical interest as systems which combine the properties of polymers and ferroelectric liquid crystals. This combination is achieved by attaching the ferroelectric mesogen to a main chain via a flexible spacer... 

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