Of thermotropic main chain polymer liquid crystals

TABLE 5.3 Chemical Constitution Typical of Thermotropic Main-Chain-Polymer Liquid Crystals, i.e., [4]... 

Group Arrangements Typical of Thermotropic Main-Chain Polymer Liquid Crystals... 

ELASTIC MODULI OF THERMOTROPIC MAIN CHAIN POLYMER LIQUID CRYSTALS... 

In the following, attention is focused only on some results obtained for solutions of thermotropic PLCs, and particularly on those of side group polymer liquid crystals (SGPLCs) since main chain polymer liquid crystals (MCPLCs) are normally difficult to dissolve and at least are insoluble in non-protonated solvents. The inclusion of lyotropic systems would be beyond the scope of this chapter and also would give no contribution to solving the question of how the properties of solutions of PLCs differ from those of non-LC polymers with similar molecular design. 

The first examples of thermotropic main-chain liquid crystal polymers were produced by Roviello and Sirigu in 1975 when they reacted alkyl acylchlorides with p, p dihydroxy-a,-(x -dimethylbenzalazine, giving the stmcture (I), which exhibited anisotropic fluid phases after melting. 

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)... 

SINCE the discovery of liquid crystalline phenomenon for low molecular weight liquid crystals (LMWLCs) more than 100 years ago, anisotropic ordering behaviors of liquid crystals (LCs) have been of considerable interest to academe [1-8], In the 1950s, Hory postulated the lattice model for various problems in LC systems and theoretically predicted the liquid crystallinity for certain polymers [1-3], As predicted by the Hory theory, DuPont scientists synthesized lyotropic LCPs made of rigid wholly aromatic polyamide. Later, Amoco, Eastman-Kodak, and Celanese commercialized a series of thermotropic main-chain LCPs [2]. Thermotropic LCPs have a unique combination of properties from both liquid crystalline and conventional thermoplastic states, such as melt processibility, high mechanical properties, low moisture take-up, and excellent thermal and chemical resistance. Aromatic main-chain LCPs are the most important class of thermotropic LCPs developed for structural applications [2,4-7]. Because they have wide applications in high value-added electronics and composites, both academia and industry have carried out comprehensive research and development. 

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). 

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. 

Figure 24. Biomesogenic structures a) (Bio)meso-gens displaying order-disorder distributions in CPK-presentation (left to right and top to bottom) hexa-n-alkanoyl-oxybenzene discoid - Chandrasekar s first non-rodlike liquid crystal [28 a, 51c] enantiomeric cholesteric estradiol- and estrone-derivatives [ 17 a, c, d, 26 f, 51 a, s, u] Reinitzer s cholesterolbenzoate [21, 22] - together with the acetate the foundation stones of liquid crystal history [21, 22] Kelker s MBBA -first liquid crystal fluid at ambient temperature [ 13 f, g] Gray s cyanobiphenyl nematics for electrooptic displays [25 a, 51 e] lyotropic lecithin membrane component [7 a, 14, 27 d, 52 a] and valinomycin-K -membrane carrier [7 a, 35] thermotropic cholesteryl-side-chain-modifiedpolysiloxanes with the combination of flexible main-chain and side-chain spacers [51 a, h] thermotropic azoxybenzene polymers with flexible main-chain spacers [51a] thermotropic cya-...

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. 

From such a background, the structure and dynamics of the main chain and side chains of LC polymers have been sophisticatedly characterized by solid-state NMR and pulse field-gradient spin-echo (PFGSE) NMR to understand an important role for formation of the thermotropic liquid crystals [21-25], Details of these works will be introduced. 

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. 

Class a, longitudinal liquid crystal polymers, earlier called main-chain polymers. A new name is necessary to distinguish them from the following classes jS and y and the subclasses (S, (R and Al. There are numerous examples of class a. We do not discuss them here in any detail since the entire Chapter 8 by MacDonald is devoted to thermotropic ones, while Chapter 6 by Northolt and Sikkema deals with lyotropic PLCs of the same class. Orientational and conformational order in longitudinal PLCs is discussed by Frangoise Lauprete in Section 3.1.3.1 would only like to note an account of the history of first polyesters in this class and of future perspectives by Jackson. ... 

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