Chiral Combined LC Polymers

The first chiral combined lc polymers prepared for this purpose showed the desired cholesteric and chiral smectic C phases only at high temperatures (8) (the melting point was always above 100°C). By using lateral substituents (see Figure 3) it is possible however to suppress the melting temperature and to obtain polymers with a glass transition temperature of about room temperature, without losing the cholesteric and chiral smectic C phases (9). 

Due to the interesting LC properties of combined LC polymers (i.e. broad LC phases, and the occurrence of different smectic phases and a nematic phases at different temperatures) and their intermediate nature between that of side-chain and that of main-chain polymers, a lot of research has been undertaken on these materials. Most of the research has been directed towards the preparation of cross-linkable polymers and LC elastomers [3-11] and of chiral combined LC polymers [4, 6, 7, 9, 12-16]. 

Because of the interest in chiral LC phases in general, which give rise to selective reflection of light (cholesteric phase) or fer-roelectricity (chiral smectic C phase), chiral combined LC polymers were prepared quite early on [4]. Polymers with cholesteric and chiral smectic C phases could be prepared easily. As these polymers were synthesized using to the polycondensation process shown in Scheme 1, the chiral groups had to be selected carefully in order to prevent racemization during polycondensation [4, 7, 12, 13]. 

Scheme 2. Synthesis of chiral combined LC polymers by esterification of chiral acids with a preformed polyphenolic polymer. DCC, dicyclohexylcarbodi-imide.

The investigation of combined FLCPs was initiated by Zentel et al. [91-93] as a part of their approach to ferroelectric LC elastomers [94]. Figure 12 shows typical structures of combined FLCPs and cross-linkable chiral combined LC polymers. Poths et al. [67] used that approach to synthesize combined polymers with axially chiral mesogenic side groups (similar to the acrylic side-chain polymer above). The smectic C structure of polymers has been identified by optical microscopy and x-ray data, but no ferroelectric properties of the polymers have been reported yet. 

In order to make more labile (referring to racemization) chiral groups accessible, a new synthetic route to combined LC polymers was developed (Scheme 2), which involves the esterification of chiral acids with... 

The first success was achieved when optically active (chiral) monomeric units were combined with a nematic LC polymer 105,123,143,144). The approach was based on the idea that a cholesteric mesophase may actually be realized as a helical nematic structure. Then by chemical binding of chiral and mesogenic units into a chain, accomplished by copolymerization or copolycondensation (in case of linear polymers) of nematogenic and optically active compounds, it was found feasible to twist a nematic mesophase and obtain copolymers of cholesteric type (Table 13). 

Chiral lc-polymers can be prepared by a proper functionalization of lc-polymers with chiral and reactive groups. These elastomers are interesting, because they combine the mechanical orientability of achiral lc-elastomers with the properties of chiral lc-phases, e.g. the ferroelectric properties of the chiral smectic C phase. The synthesis of these elastomers was very complicated so far, but the use of lc-polymers, which are functionalized with hydroxyl-groups, has opened an easy access to these systems. Also photocrosslinkable chiral lc-polymers can be prepared via this route. 

The general concept of preparing such materials involves the synthesis of combined chiral-photochromic LC copolymers or obtaining cholesteric mixtures based on nematic polymers and low-molecular-mass chiral and photochromic dopants. 

Aromatic imide groups are known to be nearly planar, rigid, polar, and thermostable. However, aromatic imide structures are also known to be non-mesogen in nature. Poly(ester-amide) (PEI) derived from N- (4 -carboxyphenyl) trimellitimide and aliphatic spacers are not thermotropic, whether the spacer used is chiral or not. Semi-aliphatic spacers are observed to exhibit both a smectic and a nematic LC phase in the resultant thermotropic PEIs. The semi-aliphatic chiral spacers exhibit both chiral smectic phase (A or C ) and cholesteric phase. Such a chiral smectic LC-phase, which may be ferroelectric in nature, is extremely rare for LC-main-chain polymers [27]. It is a particular advantage of polar imide mesogens to favor the formation of layer-structures when combined with non-polar species [28]. 

To produce novel LC phase behavior and properties, a variety of polymer/LC composites have been developed. These include systems which employ liquid crystal polymers (5), phase separation of LC droplets in polymer dispersed liquid crystals (PDLCs) (4), incorporating both nematic (5,6) and ferroelectric liquid crystals (6-10). Polymer/LC gels have also been studied which are formed by the polymerization of small amounts of monomer solutes in a liquid crystalline solvent (11). The polymer/LC gel systems are of particular interest, rendering bistable chiral nematic devices (12) and polymer stabilized ferroelectric liquid crystals (PSFLCs) (1,13), which combine fast electro-optic response (14) with the increased mechanical stabilization imparted by the polymer (75). 

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