Liquid crystalline polymeric synthesis

The design and synthesis of new liquid crystalline polymeric materials endowed with intrinsc chirality deserve attention, as chirality can offer probes of the supermolecular structure and a tool for modulating specific responses of the polymers (1). The chemical transformation of preformed thermotropic polymers can add novel opportunities for the realization of various molecular architectures conventionally unfeasible and best suited for mesophase modification. 

Order and Mobility are two basic principles of mother nature. The two extremes are realized in the perfect order of crystals with their lack of mobility and in the high mobility of liquids and their lack of order. Both properties are combined in liquid crystalline phases based on the selforganization of formanisotropic molecules. Their importance became more and more visible during the last years in Material science they are a basis of new materials, in Life science they are important for many structure associated functions of biological systems. The main contribution of Polymer science to thermotropic and lyotropic liquid crystals as well as to biomembrane models consists in the fact that macromolecules can stabilize organized systems and at the same time retain mobility. The synthesis, structure, properties and phototunctionalization of polymeric amphiphiles in monolayers and multilayers will be discussed. 

Cho et al. described the synthesis and polymerization of 4,8-cyclododeca-dien-l-yl-(4 -methoxy-4-biphenyl) terephthalate VIII [54,55]. Polymerization was carried out with WCl4(OAr)2/PbEt4. The double bonds in the polymer backbone were subsequently hydrogenated with H2/Pd(C), leading to a SCLCP with a fully saturated hydrocarbon backbone. This polymer system had a very flexible polymer backbone but a stiff connection between the main chain and the mesogenic unit. The distance between two adjacent side chains was about 12 methylene units. This very flexible main chain allowed the polymer to organize into a LC mesophase. Both polymers - the unsaturated and the saturated -showed smectic liquid crystalline mesophases with almost the same transition temperatures (see Table 5). 

The two-step synthesis process shown in Figure 2 affords several possibilities for preparing new side-chain liquid crystal polymers. The polymerization process allows one to vary the molecular weight and molecular weight distribution (MWD), and potentially change the properties of the liquid crystalline state. Most of the polyphosphazenes reported in the literature, including the examples in this paper, are derived from the bulk uncatalyzed process this... 

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... 

It is not necessary to carry out synthesis, if the triggering photochromic compound has good affinity to the polymer matrix. A mixture of the polyacrylate with BMAB which exhibits an excellent function as trigger is equally photoresponsive. While the monomer model compound (i.e. the acrylate before polymerization) does not provide a liquid crystalline phase, the polymer shows a clear nematic - isotropic transition at ca. 61 °C and the glass transition temperature at 24 °C as shown in Fig. 4. Tj j depends very much on the length of the alkyl spacer. In comparison with the... 

Figure 3.6. Polymerizations and polymer reactions for synthesis of side-group type liquid crystalline polymers.

First, the lyotropic phase is used as a template for the preparation of a bicontinuous silica structure, from which the polymer is removed by calcination or extraction. In the second step the porous inorganic structure is filled with monomer and crosslinker which is polymerized to form a bicontinuous organic polymer network from which the silica template is removed by treatment with hydrofluoric acid. An example for the preparation of hierarchical structures is the synthesis of bicontinuous pore structures by using two templates simultaneously [115]. In this case a liquid crystalline lyotropic phase of an amphiphilic block copolymer is used as a template together with suspended latex particles. The sol-gel process with subsequent calcination leads to a bicontinuous open pore structure with pores of 300 nm and 3 nm. 

Liquid crystals combine properties of both liquids (fluidity) and crystals (long range order in one, two, or three dimensions). Examples of liquid crystalline templates formed by amphiphiles are lyotropic mesophases, block copolymer mesophases, and polyelectrolyte-suxfactant complexes. Their morphological complexity enables the template synthesis of particles as well as of bulk materials with isotropic or anisotropic morphologies, depending on whether the polymerization is performed in a continuous or a discontinuous phase. As the templating of thermotropic liquid crystals is already described in other reviews [47] the focus here is the template synthesis of organic materials in lyotropic mesophases. 

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