Temperature dependence main chain crystalline polymers

Figure 6 shows the phase diagrams plotting temperature T vs c for PHIC-toluene systems with different Mw or N [64], indicating c( and cA to be insensitive to T, as is generally the case with lyotropic polymer liquid crystal systems. This feature reflects that the phase equilibrium behavior in such systems is mainly governed by the hard-core repulsion of the polymers. The weak temperature dependence in Fig. 6 may be associated with the temperature variation of chain stiffness [64]. We assume in the following theoretical treatment that liquid crystalline polymer chains in solution interact only by hardcore repulsion. The isotropic-liquid crystal phase equilibrium in such a solution is then the balance between S and Sor, as explained in the last part of Sect. 2.2. 

In main chain cholesteric liquid crystalline polymers, the mesogenic groups and flexible spacers are linked alternatively. The flexible units contain asymmetrical carbon atoms which enable the polymers to possess chirality and thus form cholesteric liquid crystals. By varying the ratio of chiral to non-chiral parts, the cholesteric temperature range and pitch can be changed. The cholesteric range depends on the mol fraction of the polymers. A typical main chain cholesteric liquid crystalline polymer is shown in Figure 6.27. 

Poly(3-decylthiophene) in crystalline powders has a co-planar structure, but the alkyl-chain planes are not co-planar with the thiophene backbone [89]. This polymer shows a temperature-dependent polymorphism with two crystalline and a (probably nematic) mesoscopic phase [90]. In the mesoscopic phase the side-chains can freely rotate, while the main chains can deviate from planarity. 

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. 

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