Of thermotropic main chain polymer liquid

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... 

Aromatic polyesters were particularly well suited candidates for this new field of thermotropic main-chain polymers since the relatively low energy of association of the ester groups led to low inter-chain forces. A typical representation of liquid crystalline polyester structure can be given in Figure 8.5. Terephthaloyl chloride and hydroquinone reacts in straight configuration to form the LC polyester. 

This paper presents some of our results on the synthesis and structure of thermotropic main-chain liquid crystalline polyethers based on bis(4-hydroxy-phenoxy)-p-xylene. It also deals with two areas in the field of liquid crystalline polymers that have received only little attention, namely the dielectric relaxation (5-10 and Gedde, U.W. Liu, F. Hult, A. Gustafsson, A. Jonsson, H. Boyd, R.H. Polymer submitted) and the kinetics of isotropic-mesomorphic state transitions (11-14. 32). They are both very important for the understanding of the nature of the mesomorphic state in polymers and for the understanding of similarities and differences of physical phenomena between liquid crystalline and semi-crystalline polymers. 

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. 

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. 

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. 

Heino, M. (1994) Blends of thermotropic main-chain liquid crystalline polymers and thermoplastics. Acta Polytechnica Scandinavica, Chemical Technology and Metallurgy Series, No. 220, 1-49 (+ 7 appended publications). 

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. 

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). 

In the procedures below, methodology is described to facilitate medium scale (ca. 100 g) synthesis of a main-chain thermotropic liquid crystalline polymer containing ethylene glycol units as a flexible spacer between the rigid aromatic units. Two methods are described melt polymerization, and polymerization in a heat-transfer solvent with an inorganic medium (Claytone). For melt polymerization, the material is obtained as an extremely rigid solid, while in the... 

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 7. Typical DSC thermogram of a main chain thermotropic liquid ciystalline polymer.

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-...

The thermal reaction of cobalt polymers 4.28 with isocyanates at 120 °C leads to 2-pyridone-containing polymers such as 4.30 [70]. Well-characterized, yellow polyesters 4.31 containing skeletal (cyclobutadiene)cobalt moieties in the main chain have been prepared by interfacial polycondensation approaches [73]. The use of solubilizing alkoxy substituents R afforded materials with Mn = 5,400-16,300 (PDI = 1.3-1.8). Analogous materials to 4.31 with a 1,3-disposition of the main-chain substituents on the cyclobutadiene ligands have also been studied [73, 74]. Thermotropic liquid crystallinity was detected by polarizing microscopy, with, in some cases, mesophases stable over the temperature range from about 110 to >250°C. 

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. 

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)... 

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