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Fig. 2-20 Molecular ordering in nematic and smectic liquid crystals compared to liquid. After Brown and Crooker [1983] (by permission of American Chemical Society, Washington, DC).
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Rigid-rod liquid crystal polymer molecules result from having rigid groups either within the polymer chain or as side groups on the polymer chain. These two types of LC polymers, referred to as main-chain and side-chain LC polymers, respectively, are depicted in Fig. 2-21. The rigid groups are referred to as mesogens or mesogenic groups. The mesogens are shown as rigid-rod groups, but other shapes (e.g., disks) are also possible. The collection of mesogenic units results in a molecule that is a rigid rod with molecular shape anisotropy and liquid crystal behavior. Liquid crystal behavior in polymers has practical consequences. Liquid crystal melts or solutions have lower viscosities than melts or solutions of random-coil polymers and are easier to process. More importantly, the extension and orientation of polymer chains during processing yields highly crystalline products with high modulus and high strength. The moduli and strengths of chain-extended LC polymers is considerably higher than those of
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Fig. 2-21 Main-chain and side-chain liquid crystal polymers.
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the chain-folded crystalline polymers formed from non-LC polymers. LC polymers also have signi cantly increased crystalline melting temperatures as a result of the extended-chain morphology. Thus, the synthetic guidelines are the same for synthesis of heat-resistant and LC polymers build rigid polymer chains. Poly(1,4-oxybenzoyl) (LII) [IUPAC: poly(oxy-1,4-phenylenecarbonyl), obtained by selfreaction of p-hydroxybenzoic acid, and the various aramids (Sec. 2-8f) were among the rst LC polymers studied. The experience in commercializing poly(1,4-oxybenzoyl) and the
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aramids illustrates that one can have too much of a good thing. None of these polymers can be melt processed since they undergo decomposition before melting (Tm > 500 C). The aramids are spin processed into bers using lyotropic solutions in sulfuric acid. It would be preferable to melt-process the polymers or, at least, to use a less aggressive or less dangerous solvent, but these options do not exist. Poly(1,4-oxybenzoyl) (Ekonol) has found limited utility due to a lack of easy processability. It does not have suf cient solubility even in an aggressive solvent to allow solution processing. It can be processed by plasma spraying or powder sintering. There is a need to decrease the crystalline melting temperature in such very-high-melting LC polymers to achieve a degree of processability. Copolymerization is used to alter the polymer chains in the direction of decreased rigidity but one needs to do it carefully to retain as high modulus, strength, and Tm as possible. Chain rigidity can be lowered by reducing molecular linearity by incorporating a less symmetric comonomer unit (o- and m- instead of p- or naphthalene rings, other than 1,4-disubstituted, instead of the 1,4-phenylene unit), a comonomer containing a exible spacer (single bond, oxygen, or methylene between mesogenic monomer units) or a comonomer with exible side groups [Jin and Kang, 1997; Yamanaka et al., 1999]. This approach has been successfully applied to poly(1,4-oxybenzoyl). Two copolyesters are commercial products. Vecta is a copolymer of p-hydroxybenzoic acid with 6-hydroxy-2-naphthoic acid; Xydar is a copolymer of p-hydroxybenzoic acid with p; p0 biphenol and terephthalic acid. These polymers have continuous service temperatures up to 240 C and nd applications for microwave ovenware, automotive components, components for chemical pumps and distillation towers, and electronic devices. Many of the polymers discussed in the following sections exhibit liquid crystal behavior.
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5-Membered Ring Heterocyclic Polymers
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Polyimides are obtained from amine and carboxyl reactants when the ratio of amine to acid functional groups is 1 : 2. If reactants with the reverse ratio of amine to acid functional groups are employed, polybenzimidazoles (PBI) are produced; for instance, polymerization of 3,30 diaminobenzidine and diphenyl isophthalate yields poly[(5,50 -bi-1H-benzimidazole]2,20 -diyl)-1,3-phenylene] (LIIIa) (Eq. 2-216) [Buckley et al., 1988; Hergenrother, 1987;
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