Thermotropic Side Chain Liquid Crystal Polymers

Side-Chain Thermotropic Liquid Crystal Polymers... 

The last volume is devoted to polymeric liquid crystals (with chapters about main-chain and side-group thermotropic liquid crystal polymers), amphiphilic liquid crystals, and natural polymers with liquid-crystalline properties. 

Thermotropic side-chain ionic liquid-crystalline polymers are particularly attractive when the aim is that of merging the liquid-crystalline characteristics of the low molecular weight mesogen side groups with the mechanical properties of the polymeric main chain. It is not surprising, then, that they attracted most of the research efforts in the polymeric ionic liquid crystals field. 

FIGURE 5.4 Examples of thermotropic liquid crystal polymers showing multiphase transitions (a) main-chain polymer (b) side-chain polymer. 

To our knowledge, this is the first example of the coexistence of both twisted smectic and cholesteric phases in thermotropic liquid crystal polymers. Previous preparations of thermotropic polymers by the use of chiral derivatives both incorporated in the macromolecular backbone and pendant to it as side chain substituents (comb-like polymers) resulted in either cholesteric or smectic " polymeric products. 

Shibaev, V.P., Freidzon, S., Kostromin, S.G. Molecular architecture and structure of thermotropic liquid crystal polymers with mesogenic side chain groups. In Shibaev, V.P., Lam, L. (eds.) Liquid Crystalline and Mesomorphic Polymers, pp. 77-120. Springer-Verlag, New York (1993)... 

In Part I we present a survey of the work done in the preparation and characterization of synthetic and semi-synthetic chiral thermotropic liquid crystal polymers. For convenience, we have grouped the polymeric materials (until now reported) according to the nature of the repeat unit and relevant position of the mesogen, side chain and main chain polymers. In Part II we report on the results obtained in our laboratories on optically active thermotropic polyesters containing mesogenic aromatic dyads or triads based on / -oxybenzoic acid. 

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)... 

The main part of the side group in these macromolecules consists of the alkoxy-benzoic acid moiety. This acid may form thermotropic liquid crystals. The investigation of the hydrodynamic properties of PPhEAA molecules in dilute solutions has revealed that the equilibrium rigidity of their main chains is relatively low (Table 12). Hence, since for all flexible-chain polymers, the shear optical coefficient An/Ar in PPhEAA solutions is independent of molecular weight the segmental anisotropy - tt2 and the anisotropy of the monomer unit Aa may be determined by use ofEq. (67). 

Both thermotropic and lyotropic liquid crystal polymers exhibit characteristic features with regard to their microstructureJ Anisometrical monomers such as rods or discs are connected to chains in an appropiate manner. These anisometrical monomers are considered to be the mesogens and may be part of main chain LCP, side chain LCP, or of both types together (Fig. 6). Between the mesogens are located flexible spacers of non-mesogenic character. Sufficient flexibility is a prerequisite for liquid crystal formation, with an increase in either temperature or solvent concentration. 

Thermotropic liquid crystals can then be furflier subdivided into high molecular mass, main and side-chain polymers [10] and low molecular mass, the latter class of compounds being one of the areas of this review. The phases exhibited by the low molecular mass molecules are then properly described with reference to the symmetry and/or supramolecular geometry of the phases, which are briefly introduced here and are discussed in more detail further below. Thus, the most disordered mesophase is the nematic (N), which is found for calamitic molecules (N), discoidal molecules (Nq) and columnar aggregates (Nc), among others. The more ordered lamellar or smectic phases (S) [11, 12] are commonly shown by calamitic molecules, and there exists a variety of such phases distinguished by a subscripted letter (e. g. Sa, Sb)- Columnar phases (often, if incorrectly, referred to as discotic phases) may be formed from stacks of disc-like molecules, or from... 

A convenient way to get information about the dynamics of polymers is to measure Ti, Tip and T2 by H pulse NMR. Figure 7.15 shows the side chain length-dependence of the H T2 value measured at 80°C for the side chain of poly(y-n-alkyl L-glutamate)s [26]. As seen from this figure, T2 is almost constant for n = 5-9 and suddenly becomes double for n = 10. It is easy to find the discontinuity between n = 9 and n = 10. Based on BPP theory, T2 increases as the correlation time for the motion decreases. A sudden increment of T2 means that there is a large difference in the side chain mobility between n 9 and n 10. These polymers become a thermotropic liquid crystal if the number of carbon atoms in the alkyl side chain is more than... 

At 80°C, the polymers with more than 10 carbon atoms are in the liquid crystalline state. Low mobility of the side chain prevents the polymers of n 9 to be in the thermotropic liquid crystal. The existence of the discontinuity is evidence for the solvent like nature of the side chains in the thermotropic liquid crystalline phase. 

Liquid crystals (LCs) are described as a fluid phase that flows like a liquid and is oriented in a crystalline manner. LCs are divided into two types thermotropic LCs, where the LC phase transition is dependent on temperature or lyotropic LCs, where the LC phase transition occurs as a function of solvent concentration. To introduce liquid crystallinity to conjugated polymers, LC moieties can be introduced to the polymer side chains for side chain-type liquid crystallinity. On the other hand, designing conjugated polymers with rigid main chain structures with flexible alkyl side chains for solubility enables main chain-type liquid crystallinity. 

The extrapolated line of log S-log C crossed each other at a critical concentration Cq at which S stays constant and independent of temperature. These results suggest that the temperature dependence of the cholesteric pitch would inflect at the concentration higher than Cq This is analogous to the behavior of thermotropic liquid crystals composed of cholesteric solute and nematic solvent, where the sign of dS/dT reverses at a critical concentration. It is understood that the behavior of both thermotropic and lyotropic liquid crystals is comparable provided that the nematic substances of the former are substituted with the solvents of the latter. The critical concentration Cq is about 0.41 vol/vol and this value is very close to the concentration at which the side chains on neighboring molecules of the polymer come to contact each other ( refer to fig.5 ). From these results, it is expected that the origin or mechanism of twist would change at this concentration Cq. The... 

C. Noel and J. Virlet, "DSC, Miscibility and X-ray Studies of the Thermotropic Liquid Crystalline Polyesters with Aromatic Moieties and Flexible Spacers in the Main Chain", in "Liquid Crystals and Ordered Fluid, A. Griffin and A. Johnson eds., Plenvim Press, New-York, vol. 1+, 1+01 (198I+) Finkelmann, "Synthesis, Structure, and Properties of Liquid Crystalline Side Chain Polymers", in "Polymeric Liquid Crystals", A. Ciferri, W.R. Krigbaum and R.B. Meyer eds. Academic Press, New-York (I982)... 

Much of the current research on polymeric liquid crystals is directed towards thermotropic liquid crystals which are formed when certain polymer melts are cooled. Many of those polymers includes chemical groups similar to low-molecular-weight nematics either along the main chain or in the side chains. These materials are technologically interesting because of their ease of processing. Theoretically, these materials are expected to show curious behaviours which are a mixture of their... 

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