Liquid-crystalline siloxane polymers

Cyclic liquid crystalline siloxanes can be considered as a class of the liquid crystalline (LC) side-chain polymers with a low degree of polymerization. 

F.-H. Kreuzer, Ch. Brauchle, A. Miller, A. Petri, "Cyclic Liquid-Crystalline Siloxanes as Optical Recording Media", in Polymers as Electrooptical and Photooptical Active Media (Ed. V. Shibaev), Springer, Berlin, 1996, p. 111. 

K.D. Gresham, C.M. McHugh, T.J. Running, R.J. Crane, H.E. Klei, E.T. Samulski, Phase behaviOT of cyclic siloxane-based liquid crystalline compounds. Polym. Sci. Part A Poljrm. Chem. 32, 2039-2047 (1994)... 

Liquid crystalline main chain polymers with siloxane spacer groups were obtained by the hydrosilation of (Si—H) terminated polydimethylsiloxane oligomers and mesogenic groups with terminal double bonds as shown in Reaction Scheme XVII-(a). Reactions were usually carried out in THF with the Wacker Oil catalyst 255). Completion of the reactions was followed by the disappearance of the strong (Si—H) absorption band at 2140 cm-1 using IR spectroscopy. 

Finkelmann et al. 256 274,2781 have also investigated the synthesis and the characteristics of siloxane based, crosslinked, liquid crystalline polymers. This new type of materials displays both liquid crystallinity and rubber elasticity. The synthesis of these networks is achieved by the hydrosilation of dimethylsiloxane-(hydrogen, methyl)siloxane copolymers and vinyl terminated mesogenic molecules in the presence of low molecular weight a,co-vinyl terminated dimethylsiloxane crosslinking agents156 ... 

Optical and electro-optical behavior of side-chain liquid crystalline polymers are described 350-351>. The effect of flexible siloxane spacers on the phase properties and electric field effects were determined. Rheological properties of siloxane containing liquid crystalline side-chain polymers were studied as a function of shear rate and temperature 352). The effect of cooling rate on the alignment of a siloxane based side-chain liquid crystalline copolymer was investigated 353). It was shown that the dielectric relaxation behavior of the polymers varied in a systematic manner with the rate at which the material was cooled from its isotropic phase. 

Incorporation of flexible siloxane spacers into side chain or main chain liquid crystalline polymers have been shown to drastically reduce the transition temperatures 255,267,271,272,277) anc[ aiso increase the response time of the resultant systems to the applied thermal, optical or electrical fields 350-353>. In addition, siloxanes also provided elastomeric properties and improved the processibility (solution or melt) of the resulting liquid crystalline copolymers. 

It is intriguing that even some flexible siloxane polymers form mesomorphic (liquid-crystalline) phases.34 139-166 Some illustrative data are given in Table 4.2. Both poly(diethylsiloxane) and pol y(di-n-propylsiloxane) show two crystalline modifications as well as a mesomorphic phase. (The other major class of semi-inorganic polymers, the polyphosphazenes, are also relatively flexible, and show similarly interesting behavior.)10167... 

The study by Percec, Tomazos and Willingham (15) looked at the influence of polymer backbone flexibility on the phase transition temperatures of side chain liquid crystalline polymethacrylate, polyacrylate, polymethylsiloxane and polyphosphazene containing a stilbene side chain. Upon cooling from the isotropic state, golymer IV displays a monotropic nematic mesophase between 106 and 64 C. In this study, the polymers with the more rigid backbones displayed enantiotropic liquid crystalline behavior, whereas the polymers with the flexible backbones, including the siloxane and the polyphosphazene, displayed monotropic nematic mesophases. The examples in this study demonstrated how kinetically controlled side chain crystallization influences the thermodynamically controlled mesomorphic phase through the flexibility of the polymer backbone. 

Extensive studies on photochromic liquid-crystalline polymers have been made by Krongauz et al,2 Liquid-crystalline phases caused marked colour changes of poly(acrylates)98 and poly(siloxanes) substituted with spiropyran side chains upon UV irradiation owing to the aggregation of the photomerocyanines." In contrast, spirooxazines attached to liquid-crystalline polymer backbones displayed no aggregation and hence exhibited normal photochromism similar to that in solution. Fulgimides bound covalently to the side chains of nematic liquid-crystalline polymers also showed normal photochromism. 

The following examples describe two different approaches to developing liquid crystalline elastomers. The hrst two examples, developed at Reading, utilize the acrylate-based polymer described in Protocol 4 the hnal technique, invented in Freiburg utilizes siloxane-based polymers. This latter process is particularly useful where high levels of orientation are required (and of course room temperature liquid crystalline phases). 

Most main chain liquid crystalline polymers are composed of mesogenic units linked by spacers with varying degrees of flexibility, such as repeated methylene, oxyethylene, or siloxane groups, etc., in order to reduce the... 

Commonly, polymers with a poly(siloxane) backbone and pendant side chain liquid crystalline groups are used. The side chain liquid crystalline groups are organic complexes with zinc, nickel, or crown ethers. This type of polymers is addressed as mesomorphic poly(siloxane). Side chains based on 4-biphenyl-4-allyloxybenzoate exhibit a special separation performance for racemic compounds. ... 

The switching properties of liquid crystalline side chain polymers with either siloxane or acrylic groups as main chain are described, especially in relation to the possibility of dualfrequency addressing of fields effects. Also the optical birefringence data are reported. 

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