Analogy between liquid crystal side chain polysiloxanes and liquid crystal twins with siloxane spacers

Abstract

The goal of this present work was to compare the properties of dimers with a siloxane spacer to those of side chain polysiloxanes including the same mesogenic groups and the same dilution with dimethylsiloxane segments. A systematic study of the influence of the dilution parameter on the mesomorphic and structural properties of dimers and diluted side chain polysiloxanes, as well as on the behaviour of their solutions with low molar mass liquid crystals is reported.     

Photochromism of side-chain liquid crystal polymers containing spironaphthoxazines

Side-chain liquid crystal polyacrylates and polysiloxanes containing different photochromic spironaphthoxazine side groups were synthesized. Thermodynamic, spectral and kinetic properties of the polymers were investigated. The structure of the mesophase is discussed.     

Liquid crystal side chain polysiloxanes containing various proportions of non-mesogenic units

Recent studies have established that side chain polymeric liquid crystals composed of mesogenic and non-mesogenic side groups keep their liquid-crystalline properties even for a low proportion of mesogens. We show that the detailed structures of three kinds of new diluted liquid crystal polysiloxanes depend on the nature of the co-substituent as well as on the proportion of the silicon sites occupied by the mesogenic groups. Mixtures of these systems with low molar mass liquid crystals were also investigated in terms of compatibility and/or stabilization of smectic A phases.     

Liquid-crystalline monomers, dimers and side group polymers containing phenylpyrimidine mesogens

Phenylpyrimidine derivatives were used to synthesize monomers, dimers and side group polymers. Only a few monomers and dimers show liquid-crystalline behaviour whereas almost all of the polysiloxanes, polyacrylates and polymetha-crylates prepared possess enantiotropic Hquid-crystalline phases. The structure of the main chain and of the mesogenic unit as well as the length of the spacer and of the terminal groups were modified. The relation between structure and phase behaviour is discussed.     

Liquid crystal side chain polysiloxanes containing various proportions of non-mesogenic units

Abstract

Recent studies have established that side chain polymeric liquid crystals composed of mesogenic and non-mesogenic side groups keep their liquid-crystalline properties even for a low proportion of mesogens. We show that the detailed structures of three kinds of new diluted liquid crystal polysiloxanes depend on the nature of the co-substituent as well as on the proportion of the silicon sites occupied by the mesogenic groups. Mixtures of these systems with low molar mass liquid crystals were also investigated in terms of compatibility and/or stabilization of smectic A phases.     

The influence of a γ-oxygen in the spacer of liquid crystal side group polysiloxanes on their ferroelectric properties

Two types of side group polysiloxanes which differ in their spacer between backbone and mesogenic part were synthesized via polymer analogous reaction. The impact of an oxygen atom localized in the γ position to the siloxane main chain on the ferroelectric properties was investigated. In addition, the link between the terminal chiral moiety and the mesogenic part in each series was varied. The phase transition behaviour, spontaneous polarization and the electro-optical response time for the two series of polymers are compared. The mesophase structures were determined by X-ray measurements on magnetically oriented samples at different temperatures. The additional oxygen atom in the spacer near to the main chain leads to broader range smectic C* phases and shorter electro-optical response times, which suggests that the ether linkage promotes a better decoupling between main chain and mesogenic side group.     

液晶聚合物的单层与Langmuir-Blodgett膜

系统研究了手性液晶聚硅氧烷和光致变色液晶聚硅氧烷两个毓的侧链液晶聚合物在空气/水界面的单层行为和Langmuir-Blodgett(LB)膜沉积特性,对LB膜结构与存在的聚集现象进行了系统的表征,并初步探讨了LB膜中液晶聚合物表现的功能性。     

From monomeric to polymeric ferroelectric liquid crystals A comparative study of ferroelectric properties

Two new ferroelectric oligosiloxanes, a cyclic tetramer and a twin, have been synthesized. By a comparative study with their corresponding monomer and side chain polysiloxanes, the influence of oligo- and polymerization on the liquid crystalline and ferroelectric properties have been investigated. Polymerization leads to a stabilization of LC phases through increase of the clearing temperatures and suppression of crystallization. Oligomerization also leads to mesophase broadening, but, due to the low degree of polymerization, the effect is inferior to the linear polysiloxanes. The low viscosity of the oligosiloxanes ensures response times in the microsecond region, thus being comparable with their monomer and conventional LMWFLCs. It is found that polymerization increases the spontaneous polarization P_s. This is attributed to the density increase after polymerization, enhancing the inter-mesogenic interactions. The collective and local dynamics of the OFLCs are influenced differently with respect to their molecular structures. Each oligomer is already a good model for its corresponding polymer concerning the soft mode dynamics. For the local β-relaxation a similar temperature dependence of the relaxation times τ for the cyclic tetramer and for the side chain polysiloxanes is observed. The long axial rotation of the twin, having a very efficient decoupling, is significantly faster, thus resembling the monomer.     

From monomeric to polymeric ferroelectric liquid crystals A comparative study of ferroelectric properties

Abstract

Two new ferroelectric oligosiloxanes, a cyclic tetramer and a twin, have been synthesized. By a comparative study with their corresponding monomer and side chain polysiloxanes, the influence of oligo- and polymerization on the liquid crystalline and ferroelectric properties have been investigated. Polymerization leads to a stabilization of LC phases through increase of the clearing temperatures and suppression of crystallization. Oligomerization also leads to mesophase broadening, but, due to the low degree of polymerization, the effect is inferior to the linear polysiloxanes. The low viscosity of the oligosiloxanes ensures response times in the microsecond region, thus being comparable with their monomer and conventional LMWFLCs. It is found that polymerization increases the spontaneous polarization P _s. This is attributed to the density increase after polymerization, enhancing the inter-mesogenic interactions. The collective and local dynamics of the OFLCs are influenced differently with respect to their molecular structures. Each oligomer is already a good model for its corresponding polymer concerning the soft mode dynamics. For the local β-relaxation a similar temperature dependence of the relaxation times τ for the cyclic tetramer and for the side chain polysiloxanes is observed. The long axial rotation of the twin, having a very efficient decoupling, is significantly faster, thus resembling the monomer.     

Synthesis and characterization of chiral smectic C liquid crystalline terpolysiloxanes

A number of tailor-made side chain liquid crystalline terpolysiloxanes, containing chiral cyanohydrin ester, phenyl pyrimidine and fluorinated phenylbenzoate as the side groups, have been synthesized for potential applications as ferroelectric liquid crystal polymers. All the polysiloxanes exhibit the mesomorphic sequence of crystal-chiral smectic C-smectic A-isotropic phases.     

Cyclic versus linear siloxane liquid crystalline oligomers: phase behaviour

The phase behaviour of cyclic and linear liquid crystalline polysiloxanes containing two different cholesteric mesogens is reported. The thermal properties of the synthesized monomers and oligomers were investigated by polarizing optical microscopy and differential scanning calorimetry. The influence of the structure of cyclic siloxane on the mesomorphic properties of cyclic liquid crystalline polysiloxanes is discussed. Similar trends in the thermal transitions of cyclic and linear compounds containing the same mesogenic composition were observed, though the cyclic oligomers showed poorer mesomorphic properties as compared with their linear analogues.     

The synthesis and properties of side‐chain liquid‐crystal polymers with a chiral center

The synthesis and mesomorphic properties of six monomers and six side‐chain liquid‐crystal polymers with a chiral center are described. The polysiloxanes were prepared by the hydrosilation of monomers with poly(hydromethylsiloxane)s. Most of the polymers exhibit a wide range of the chiral smectic C phase (SmC*). © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1609–1617, 2000     

Cyclic versus linear siloxane liquid crystalline oligomers: phase behaviour

The phase behaviour of cyclic and linear liquid crystalline polysiloxanes containing two different cholesteric mesogens is reported. The thermal properties of the synthesized monomers and oligomers were investigated by polarizing optical microscopy and differential scanning calorimetry. The influence of the structure of cyclic siloxane on the mesomorphic properties of cyclic liquid crystalline polysiloxanes is discussed. Similar trends in the thermal transitions of cyclic and linear compounds containing the same mesogenic composition were observed, though the cyclic oligomers showed poorer mesomorphic properties as compared with their linear analogues.     

Mesomorphic flexible chain polymers based on silicon

Poly(dialkylsiloxane)s and poly(dialkylsilane)s form a similar type of columnar mesophase. Although, the polysilanes are stiffer than polysiloxanes, both classes of polymers may be considered to be flexible due to the ability to form chain-folded crystals. Chain flexibility rather than the presence of chain stiffness determines whether the columnar mesophase is formed. A certain amphiphilic character does not appear to be required, as polysiloxanes with short side groups, e.g. polydiethylsiloxane display the same mesophase behaviour as polydialkylsilanes with long side chains and other nonpolar flexible chain molecules. The importance of the entropy gain upon conformational disordering is reflected in the increase in temperature stability with increasing alkyl side group length and the absence of mesophase behaviour in the case of the dimethyl substituted polymers     

Distinctive dielectric properties of nematic liquid crystal dimers

ABSTRACT

We provide an overview of the effect of the molecular structure on the dielectric properties of dimers exhibiting nematic and twist-bend nematic phases with special focus on how the conformational distribution changes are reflected by the dielectric behaviour. Nematic dimers show distinctive dielectric properties which differ from those of archetypical nematic liquid crystals, as for example, unusual temperature dependence of the static permittivity or dielectric spectra characterised by two low-frequency relaxation processes with correlated strengths. The interpretation of such characteristic behaviour requires that account is taken of the effect of molecular flexibility on the energetically favoured molecular shapes. The anisotropic nematic interactions greatly influence the conformational distribution. Dielectric behaviour can be used to track those conformational changes due to dependence of the averaged molecular dipole moment on the averaged molecular shape. Results for a number of dimers are compared and analysed on the basis of the influence of details of the molecular structure, using a recently developed theory for the dielectric properties of dimers.     

A series of azo-type side-chain liquid crystalline polysiloxane–palladium complexes

A series of azo-type side-chain liquid crystalline polysiloxanes (AZLCPs) were synthesized, starting from organic polysiloxane and azo-type mesogenic compounds having an end allyl group. The AZLCPs were further used to coordinate with palladium dichloride and potassium chloride, by which a series of palladium complexes of AZLCPs (Pd–AZLCPs) were prepared. The mesogenic properties of all of the liquid crystalline polymers were characterized by using differential scanning calorimetry, polarized microscope and wide-angle X-ray diffraction. It was found that all of the polymer ligands and their palladium complexes showed thermotropic liquid crystallinity and that the incorporation of the palladium ions gave positive effects to the mesogenic properties of their polymer ligand counterpart. Compared with the corresponding AZLCPs, the Pd–AZLCPs have higher isotropization temperatures and a broader mesophase temperature range. The mesogenic properties of the liquid crystalline polymer ligands and their palladium complexes were also varied gradually by changing the length of the alkoxy groups on the side chain. The polymers that have a color emissive group and a highly flexible polysiloxane main chain may potentially be used as nonlinear optical materials.     

Methylene- and ether-linked liquid crystal dimers II. Effects of mesogenic linking unit and terminal chain length

Four series of liquid crystal dimers have been prepared containing either ether-linked or methylene-linked spacers. Changing the spacer from being ether-linked, i.e. O(CH₂) _n O, to methylene-linked, i.e. (CH₂) _{n +2}, results in decreased nematic-isotropic transition temperatures, and this reduction is more pronounced for odd-membered spacers. By contrast, the entropy change associated with the nematic-isotropic transition is higher for an even-membered methylene-linked dimer than for the corresponding ether-linked material. This trend is reversed for odd members. These observations are completely in accord with the predictions of a theoretical model developed by Luckhurst and co-workers in which the only difference between the dimers is their shape. For the highly non-linear pentamethylene-linked dimers, only those with a short terminal chain exhibited fluid smectic behaviour, specifically, a monotropic alternating SmC structure which allowed for the efficient packing of the bent molecules. Once the terminal chain reached a value of m = 9, a modulated ordered smectic phase was observed. For even-membered dimers, which exhibit only nematic phases upon melting for short terminal chain lengths, smectic phase behaviour was promoted with increasing terminal chain length, as is conventionally observed. Even-membered ether-linked dimers exhibited a SmC phase whereas even-membered methylene-linked dimers exhibited an ordered smectic G/J phase. Thus, it would appear that the differences in the transitional properties of ether- and methylene-linked dimers can be accounted for largely in terms of geometrical factors.     

Thermotropic laterally attached liquid crystalline polymers: I. New stationary phases for high-performance liquid chromatography

Up to now thermotropic liquid crystalline side chain polymers have been seldom used as stationary phases in high-performance liquid chromatography (HPLC). The preparation of a new class of surface modified silica gels is reported. They are obtained by coating on the silica support liquid crystalline polysiloxanes with mesogenic side groups laterally attached to the polymer backbone through a flexible spacer. Their chromatographic behavior in reversed-phase HPLC is described for the separation of polycyclic aromatic hydrocarbons. The results show excellent planarity and rod shape recognition capabilities. Comparisons with low-molecular-mass liquid crystalline-bonded silica and longitudinally attached liquid crystalline polymer-coated stationary phase are also reported. Finally, comparisons to commercially available C₁₈ phases are described for the separation of complex mixtures.     

Symmetrical and asymmetrical liquid crystal dimers: synthesis,characterisation and mesomorphic behaviour

ABSTRACT

A series of new asymmetrical liquid crystal dimers, R_nO–S2O–OR_n (n = 2–10), linked by an ethylene spacer having carbothiol – COS – and carboxyl – COO – linkages to the core centre of the molecule and bearing different lengths of terminal alkoxy chains were synthesised in order to study the effects of the length of the terminal alkoxy chains on mesomorphic properties. As well as, five symmetrical and asymmetrical dimers linked by butylene spacers bearing different linkages to the core and various terminal chains were also synthesized in order to study the effect of the nature of the spacer and terminal groups. The structures of the synthesised dimers were confirmed by physico-chemical techniques, i.e. FTIR, NMR and mass spectra. Differential scanning calorimetry and polarising optical microscopy verified the liquid crystal behaviour transition temperatures. The isotropic transition temperatures of the dimers R_nO–S2O–OR_n (n = 2–10) decreased with increasing length of alkoxy chain. Structural effects on the mesomorphic and physical properties were investigated in terms of alteration of carboxylate and thioester groups linking the spacer. The mesomorphic investigation reveals that all the dimers formed an enantiotropic Nematic phase except for dimer HO2SH which is not a liquid crystal.     

Methylene-linked liquid crystal dimers

A range of symmetric liquid crystal dimers which differ in the nature of the link, either ether or methylene, between the spacer and mesogenic units has been prepared and their transitional properties characterized. The nematic-isotropic transition temperature, T _NI, and the associated entropy change, ΔS _NI/R, are sensitive to the chemical nature of this link. Specifically, T _NI falls on replacing ether links with methylene links for both odd and even members although this reduction is more pronounced for odd members. In comparison, ΔS _NI/R increases on changing ether links for methylene links for even dimers, but decreases for odd-membered dimers. These observations are completely in accord with the predictions of a model developed by Luckhurst and co-workers in which the difference between the ether-linked and methylenelinked dimers rests exclusively in their shapes. Furthermore, the highly non-linear pentamethylenelinked dimers show a greater tendency to exhibit smectic behaviour; this is interpreted in terms of molecular packing giving rise to an alternating smectic phase.