Liquid crystalline polymers structure

In the past few years a considerable number of papers were published which were concerned with liquid crystalline structures in polymeric systems. Different routes were employed to obtain polymers with liquid crystalline structures or even thermodynamically stable liquid crystalline phases 1,, In general monomers containing mesogenic groups - groups which are known to have a tendency towards the formation of liquid crystalline structures, or rigid groups were used. Cases are known where the monomers exhibit liquid crystalline phases Z) In that case the polymerization can be performed in anisotropic melts frozen-in liquid crystalline structures and textures can be obtained in many instances i . In other cases the monomers do not display liquid crystalline phases. The formation of liquid crystalline polymer structures may nevertheless be possible due to the restriction of the motions of the individual repeat units -3),... 

Many engineering thermoplastics (e.g., polysulfone, polycarbonate, etc.) have limited utility in applications that require exposure to chemical environments. Environmental stress cracking [13] occurs when a stressed polymer is exposed to solvents. Poly(aryl ether phenylquin-oxalines) [27] and poly(aryl ether benzoxazoles) [60] show poor resistance to environmental stress cracking in the presence of acetone, chloroform, etc. This is expected because these structures are amorphous, and there is no crystallinity or liquid crystalline type structure to give solvent resistance. Thus, these materials may have limited utility in processes or applications that require multiple solvent coatings or exposures, whereas acetylene terminated polyaryl ethers [13] exhibit excellent processability, high adhesive properties, and good resistance to hydraulic fluid. 

Another natural polymer that needs a fresh look into its structure and properties is bitumen [123], also called asphaltines, that are used in highway construction. Although a petroleum by-product, it is a naturally existing polymer. It primarily consists of polynuclear aromatic and cyclocaliphatic ring systems and possesses a lamellar-type structure. It is a potential material that requires more study, and high-performance materials such as liquid crystalline polymer (LCP) could be made from it. 

In order to make polymers behave as liquid crystals it is necessary to introduce some structural rigidity. A typical polymer which has the required rigidity is poly(phenylenetetraphthalamide) (10.7). This material belongs to a class of polymer known as the aramids. Other liquid crystalline polymers are the thermotropic polyesters derived from /7-hydroxybenzoic acid, p, p -biphenol and terephthalic acid (10.8). 

A review of the literature demonstrates some trends concerning the effect of the polymer backbone on the thermotropic behavior of side-chain liquid crystalline polymers. In comparison to low molar mass liquid crystals, the thermal stability of the mesophase increases upon polymerization (3,5,18). However, due to increasing viscosity as the degree of polymerization increases, structural rearrangements are slowed down. Perhaps this is why the isotropization temperature increases up to a critical value as the degree of polymerization increases (18). 

Saminathan, M. and Pillai, C.K.S. (2000) Synthesis of novel liquid crystalline polymers with cross-linked network structures. Polymer, 41 (8), 3103—3108. 

Figure 8 Liquid-crystalline polymers in which the mesomorphic sequences occur in the side-chain (middle), in the chain backbone (top), or in both (bottom) ( combination structures).

FIGURE 5.7 Schematic Representation of typical, (partially) electroluminescent LC polymer architectures. (a) Rodlike structure, (b) Hairy-rod structure, (c) Combined main-chain-side-chain system, (d) Semiflexible segmented structure, (e) Semiflexible segmented structure with disklike mesogen. (After Weder, C. and Smith, P., Main-chain liquid-crystalline polymers for optical and electronic devices, in Encyclopedia of Materials Science and Technology, Buschow, K.H., Cahn, R.W., Flemings, M.C., Ilschner, B., Kramer, E.J., and Mahajan, S., Eds., Elsevier Science, New York, 2001.)... 

Amoskov, V. M. and Birshtein, T. M. (2000). Homeotropic and planar structures in liquid-crystalline polymer brushes, Vysomolekul. Soedin. A B, 42, 612-626. 

While no direct evidence of liquid crystallinity in PET-BB copolymers has been reported, the high-BB-content copolymers have been shown to possess morphologies similar to those of liquid crystalline polyesters [40], and show major changes in both melt relaxation times and fiber tensile moduli, suggestive of structural organization in a frustrated liquid crystalline polymer (LCP) (Table 6.3 and Figure 6.4) [41, 42],... 

Liquid Crystalline Polymers. One class of polymers that requires some special attention from a structural standpoint is liquid crystalline polymers, or LCPs. Liquid crystalline polymers are nonisotropic materials that are composed of long molecules parallel to each other in large clusters and that have properties intermediate between those of crystalline solids and liquids. Because they are neither completely liquids nor solids, LCPs are called mesophase (intermediate phase) materials. These mesophase materials have liquid-like properties, so that they can flow but under certain conditions, they also have long-range order and crystal structures. Because they are liquid-like, LCPs have a translational degree of freedom that most solid crystals we have described so far do not have. That is, crystals have three-dimensional order, whereas LCPs have only one- or two-dimensional order. Nevertheless, they are called crystals, and we shall treat them as such in this section. 

Figure 1.68 The structure of liquid crystalline polymers (a) nematic, (b) smectic and (c) cholesteric. Reprinted, by permission, from J. L. Fergason, Scientific American, 211(2), pp. 78, 80. Copyright 1964 by Scientific American, Inc.

Figure 1.69 General structure of main-chain (M.C.) and side-chain (S.C.) LCPs. Adapted from T. S. Chung, The recent developments of thermotropic liquid crystalline polymers. Polymer Engineering and Science, 26(13), p. 903. Copyright 1986, Society of Plastics Engineers.

The objective of this review is to characterize the excimer formation and energy migration processes in aryl vinyl polymers sufficiently well that the excimer probe may be used quantitatively to study polymer structure. One such area of application in which some measure of success has already been achieved is in the analysis of the thermodynamics of multicomponent systems and the kinetics of phase separation. In the future, it is likely that the technique will also prove fruitful in the study of structural order in liquid crystalline polymers. 

The development is reviewed of liquid-crystalline polymers whose mesophase formation derives from the nature of the chemical units in the main chain. The emphasis lies primarily on highly aromatic condensation polymers and their applications. The general properties of nematic phases formed by such polymers are surveyed and some chemical structures capable of producing nematic phases are classified in relation to their ability to form lyotropic and thermotropic systems. The synthesis, properties, physical structure and applications of two of the most important lyotropic systems and of a range of potentially important thermotropic polymers are discussed with particular reference to the production and use of fibres, films and anisotropic mouldings. 

It is reasonable to assume that the complementary units form the expected triply hydrogen bonded pairs, so that the entirely different behaviour of the pure compounds and of the 1 1 mixtures may be attributed to the spontaneous association of the complementary components into a polymolecular entity based on hydrogen bonding. The overall process may then be described as the self-assembly of a supramolecular liquid-crystalline polymer based on molecular recognition (Figure 40). The resulting species (TP2, TU2) is represented schematically by structure 174. 

Organic supramolecular materials may be devised on the basis of molecular components of various structures bearing recognition units [9.149, 9.235]. As shown above, liquid crystals and liquid crystalline polymers of supramolecular nature presenting various supramolecular textures are generated by the self-assembly of complementary subunits. 

Molecular recognition directed self-assembling of organized phases has been described recently in the formation 1) of mesophases by association of complementary molecular component, as in 13 (23) 2) of supramolecular liquid crystalline polymers of type 14 (24) and 3) of ordered solid state structures, such as that represented by 15 (25). In all these cases, the incorporation of NLO active groups may be expected to produce materials whose SHG properties would depend on molecular recognition induced self-organization. 

Abstract We describe mechanochromic and thermochromic photoluminescent liquid crystals. In particular, mechanochromic photoluminescent liquid crystals found recently, which are new stimuli-responsive materials are reported. For example, photoluminescent liquid crystals having bulky dendritic moieties with long alkyl chains change their photoluminescent colors by mechanical stimuli associated with isothermal phase transitions. The photoluminescent properties of molecular assemblies depend on their assembled structures. Therefore, controlling the structures of molecular assemblies with external stimuli leads to the development of stimuli-responsive luminescent materials. Mechanochromic photoluminescent properties are also observed for a photoluminescent metallomesogen and a liquid-crystalline polymer. We also show thermochromic photoluminescent liquid crystals based on origo-(/ -phenylenevinylene) and anthracene moieties and a thermochromic photoluminescent metallocomplex. 

First, we will consider the design of polyphosphazenes as side-chain liquid-crystalline materials.241 248 Side-chain liquid-crystalline polymers are a subclass of species described earlier as structure 3.72. Liquid crystallinity occurs when the rigid side groups become organized, usually in the semi-liquid state. The organization may be nematic (oriented but unlayered) or smectic (layered) as illustrated in Figure 3.25. 

Coatings derived from cholesteric liquid crystalline polymers are used commercially as reflective sheets and polarisers. The liquid crystal is cooled below the vitrification temperature resulting in a solid polymer that is amorphous but contains large regions of frozen liquid crystalline order. Such structures are also found in nature in the iridescent, almost metallic colours of beetles and other insects, which result from helical cholesteric structures in the outer layer of the carapace. 

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