Smectic C* side chain liquid-crystalline

Finkelmann reported synthesis of a novel cross-linked smectic-C main-chain liquid-crystalline elastomer that was formed by polycondensation of vinyloxy-terminated mesogens, tetramethyldi-siloxane, and pentamethyl-pentaoxapentasilicane. The introduction of the functional vinyloxy group allows the synthesis of well-defined networks with good mechanical properties due to ehmination of side reactions as in the case of vinyl groups [60]. 

The redox properties of the ferrocene unit were also used to control the liquid-crystalline organization of side-chain liquid-crystalline poly(methacrylates) the reduced polymer gave rise to smectic C and smectic A phases whereas the oxidized polymer showed a nematic phase. ... 

Lee, K.-J. Hsiue, G.-H. Wu, J.-L. Sha, Y.-A., Molecular Structure of Side-Chain Liquid Crystalline Polysiloxane in the Smectic C Phase from X-Ray Diffraction and Molecular Modeling Polymer 2007,48,5161-5173. 

Arehart SV, Pugh C (1997) Induction of smectic layering in nematic liquid crystals using immiscible components. 1. laterally attached side-chain liquid crystalline poly(norbomene)s and their low molar mass analogs with hydrocarbon/fluorocarbon substituents. J Am Chem Soc 119 3027-3037... 

Yu ZQ, Lam JWY, Zhu CZ, Chen EQ, Tang BZ. Side-chain liquid crystalline polyacetylenes with increasing length of alkyl tails from highly ordered smectic to smectic C phase. Macromolecules 2013 46 588-96. 

The systematic synthesis of non amphiphilic l.c.-side chain polymers and detailed physico-chemical investigations are discussed. The phase behavior and structure ofnematic, cholesteric and smectic polymers are described. Their optical properties and the state of order of cholesteric and nematic polymers are analysed in comparison to conventional low molar mass liquid crystals. The phase transition into the glassy state and optical characterization of the anisotropic glasses having liquid crystalline structures are examined. 

McArdle, C. B., ed.. Side Chain Liquid Crystal Polymers, Blackie, Glasgow, 1989. Ciferri, A ed.. Liquid Crystallinity in Polymers, VCH Publishers, New York, 1991. Gray, G. W., and Goodby, J. W., Smectic Liquid Crystals—Textures and Structures, Heyden Son, Philadelphia, 1984. 

With these three different examples it has been demonstrated that the systematics observed for the polymorphism of m-l.c. s is also valid for the side chain polymers, provided that a flexible spacer connects the rigid mesogenic moieties to the polymer main chain. Deviations from this behavior are observed, when the mesogenic moieties are directly linked to the backbone. Under these conditions, normally no liquid crystalline behavior is to be expected, according to the model considerations mentioned in Chap. 2.1. Some examples, however, proved l.c. properties for such systems, which are characterized by two striking properties Very high glass transition temperatures and only smectic structures even in case of short substituents... 

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). 

Characterization. The liquid crystalline properties of the side-chain monomers (III) and polymers (I) have been studied by Differential Scanning Calorimetry (DSC), Polarized Optical Microscopy (POM) and X-ray diffraction. The thermal transition data and phase types for all monomers (III) and polymers (I) are summarized in Table HI. A representative DSC scan for the monomer (El) and polymer (p with a four-carbon tail (n=4) and six-carbon flexible spacer (m=6) are shown in Figures 1 and 2 respectively. The first peak at -24°C shown in Figure 1 is the crystal to smectic... 

Liquid crystalline polymers containing ferrocene in their side chains have been reported.235-240 Deschenaux used free-radical synthesis to prepare thermotropic liquid crystalline polymethacrylates containing ferrocene (Scheme 2.46).235 Polarized light microscopy showed that monomer 171 and its corresponding polymer 172 exhibited enantiotropic smectic A and C phases. 

The ease of forming the smectic mesophase by this class of side-group type liquid crystalline polymers has rendered a great possibility in synthesizing polymeric chiral smectic materials useful in non-linear optics, transducers, pyroelectric detectors and display devices (Chapter 6). The first polymer forming a chiral smectic-C phase was synthesized by Shibaev et al. (1984). It has a polymethacrylate main chain, a long polymethylene spacer, and a mesogenic unit attached at the end with a chiral moiety (polymer (3.60)). Since then, a lot of polymers with chiral mesophases have been synthesized and studied (Le Barny and Dubois, 1989). 

The texture of polymeric chiral liquid crystalline phases. The chiral liquid crystalline phases include the chiral smectics and the chiral nematic or cholesteric phase. Poly(7-benzyl-L-glutamate) and derivatives of cellulose are popular examples of polymers that form a chiral mesophase. Side-chain type copolymers of two chiral monomers with flexible spacers of different, lengths and copolymers of one chiral and the other non-chiral mesogenic monomers may also form a cholesteric phase (Finkelmann et al., 1978 1980). In addition, a polymeric nematic phase may be transformed to a cholesteric phase by dissolving in a chiral compound (Fayolle et al., 1979). The first polymer that formed a chiral smectic C phase was reported by Shibaev et al. (1984). It has the sequence of phase transition of g 20-30 Sc 73-75 Sa 83-85 I with the Sc phase at the lower temperature side of Sa- More examples of Sc polymers are given by Le Barny and Dubois (1989). 

An initial approach to supramolecular H-bonded mesogenic polymer complexes involves a polyacrylate with 4-oxybenzoic acid moieties via a hexamethylene spacer 29 [26]. The 1 1 complexation of the side chain of the polymer and stilbazole 3 n - 2) (nematic, 168-216 °C) results in the formation of an extended supramolecular mesogen in the side chain (Fig. 11). Side-chain polymer complex 30 exhibits a nematic phase up to 252 °C, which shows that a significantly stabilized mesophase is achieved by the complexation of two different components. Liquid-crystalline properties have been examined for the series of complexes formed between polyacrylates and trans-4-alkoxy-4 -stilbazoles [33, 78]. Figure 12 shows transition temperatures against the carbon number of the alkyl chain for the series of complexes 31 [33]. They exhibit thermally stable smectic liquid-crystalline phases. For example, smectic E, B, and A phases are observed until 192 °C after the glass transition at 38 °C for the complex with m = 6 [78a]. 

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