Nematic siloxane liquid-crystalline polymer

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. 

An accepted experimental proof for the existence of a biaxial nematic phase in a thermotropic liquid crystal remained missing for a very long time. However, in recent years, biaxial nematic phases have been found in liquid crystalline polymers as well as in liquid crystals made of rod-disc mesogens, banana-shaped (bent-core) molecules, and organo-siloxane tetrapodes. Here, some characteristics of these systems and the corresponding experimental procedure for the investigation of phase biaxiality will be introduced. Further details for the individual systems can be found in the cited literature. 

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. 

In a recent publication, these findings have been nicely confirmed by deuterium NMR investigations of a spin probe dissolved in the organo-siloxane tetrapodes [40], where the same sample-flip technique was applied as in [4, 11], In their study, the authors point out that the mode of stabilization of the biaxial nematic phase in tetrapodes and liquid-crystalline side-chain polymers, i.e., the lateral fixation of the mesogenic group, may in fact be similar. 

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