Side-chain liquid-crystalline polyphosphazenes

SINGLERETAL. Side-Chain Liquid-Crystalline Polyphosphazenes... 

At the present time, only a few side-chain liquid crystal polyphosphazenes have been synthesized and investigated. Opportunities exist to prepare a wide variety of side-chain liquid crystalline polyphosphazenes, based on the polymerization-substitution process outlined in Figure 2. Alternative approaches, such as side chain modification of polyphosphazenes prepared by the thermal decomposition of N-silylphosphoranimines (19), may provide even further options for preparing liquid crystal polyphosphazenes. 

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. 

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. 

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... 

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