Synthesis and liquid crystalline properties of novel laterally connected trimesogens and tetramesogens

Three types of laterally connected triplet mesogens and one quadruplet mesogen incorporating rigid p-terphenyl units have been synthesized. Their liquid crystalline behaviour was investigated by polarizing microscopy, differential scanning calorimetry and X-ray scattering. The lateral fixation of three rod-like 4,4'-didecyloxy-p-terphenyl units mostly gives liquid crystalline materials with considerably increased mesophase stabilities with respect to the parent 4,4'-didecyloxy-2'-methyl-p-terphenyl. The mesophase stability strongly depends on the type of connection. The highest clearing temperatures were observed for triplets which are connected in line with each other (type I) and triplets which are laterally connected in a peripheral manner. Only the oligomesogens of type III are not liquid crystalline. All compounds incorporating exclusively decyloxy chains exhibit smectic phases (S_A and S_c). For the ethoxy derivatives the nematic phase was found.     

Synthesis and liquid crystalline properties of novel pyridine derivatives

The treatment of 4‐hydroxypyridine with cholestery p‐(ω‐bromoalkyloxy)benzoates in N,N‐dimethylformamide containing K₂CO₃ gave cholestery p‐[ω‐(4‐pyridyloxy)alkyloxy]benzoates, which exhibited liquid crystalline properties     

Synthesis and properties of some laterally substituted liquid crystals

This paper presents a number of laterally substituted liquid crystalline compounds which have been synthesized by systematically varying both the position and the type of the lateral substituent. The influences of such structural changes on the physico-chemical properties of new compounds are discussed and compared with those of the corresponding laterally unsubstituted analogues.     

Synthesis and mesomorphic properties of novel fishbone-like liquid crystalline polysilsesquioxanes VI. Fishbone-like,ester-based liquid crystalline polysilsesquioxanes

Two novel kinds of fishbone-like, ester-based, liquid crystalline, random copolysilsesquioxanes, LC₁-CH₃-P and LC₂-CH₃-P, have been synthesized for the first time by stepwise coupling polymerization (SCP) from trichlorosilane monomers (RSiCl₃) containing mesogenic ester groups, using three main steps including preaminolysis, hydrolysis and polycondensation. Two new monomers 4-(11-trichlorosilylundecloyloxy)phenyl 4-methoxybenzoate (M₁) and 4-(3-trichlorosilylpropoxy)phenyl 4-methoxybenzoate (M₂) have been synthesized by hydrosilylation reaction of trichlorosilane and the mesogens 4-n-undecenoyloxyphenyl 4-methoxybenzoate and 4-allyloxyphenyl 4-methoxy-benzoate, respectively, in the presence of dicyclopentadienylplatinum(II) chloride (Cp₂Ptcl₂) catalyst. The structures and mesomorphic properties of LC₁-CH₃-P and LC₂-CH₃-P were investigated by FTIR, ¹H NMR, ¹³C NMR, ²⁹Si NMR, gel permeation chromatography, polarizing optical microscopy, differential scanning calorimetry and X-ray diffraction. It is proposed from the characterization data that these two polymers not only have an ordered ladder-like, double main chain, but also show thermotropic smectic behaviour with high clearing points and wide mesophase ranges (ΔT), which may hold promise for potential applications as highly stable gas chromatographic stationary phases.     

Synthesis and properties of liquid crystalline polyurethanes

Liquid crystalline polyurethanes were prepared from 4,4′-bis(2-hydroxyethoxy)biphenyl (BHBP) and 2,4-tolylene diisocyanate (TDI). The effect of partial replacement of BHBP by 25–75 mol % poly(oxytetramethylene) diol (PTMO, M _n = 250) on the liquid crystalline properties was studied. The BHBP/TDI/PTMO polyurethanes were obtained by one- and two-step polyaddition. The polyurethanes were investigated by DSC, polarizing microscopy, x-ray, and IR spectroscopy. The molecular weight distribution was determined by GPC. The morphology of the polymers was investigated by the SALS method. Thermogravimetric investigations of the polyurethanes were also performed. All polyurethanes containing BHBP units have liquid crystalline properties. Partial replacement of BHBP by PTMO-250 considerably changes the phase transition temperatures and the range of mesophase occurrence. More homogeneous polyurethanes were obtained, if the two-step polyaddition method was applied. The polyaddition method affects the phase transition temperatures. © 1993 John Wiley & Sons, Inc.     

Synthesis and properties of liquid crystalline polyurethanes

1,4-Bis(p-hydroxybenzoate)phenylene was prepared using 1,4-bis(trimethylsiloxy)benzene and p-hydroxybenzoyl chloride as starting materials. A series of novel 1,4-bis(p-hydroxyalkoxybenzoate)phenylene were synthesized by reaction of 1,4-bis(p-hydroxybenzoate) phenylene with 3-brompropanol and 4-bromobutanol, respectively. The liquid crystal polyurethanes were prepared by 1,4-bis(p-hydroxyalkoxybenzoate)phenylene with MDI (p-methylene diphenylenediisocyanate) and 2,4-TDI(2,4-toluenediisocyanate), respectively. The thermotropic properties, the melting point (T _m) and the isotropization temperature (T _i) of the synthesized polyurethanes were characterized by DSC, IR and POM. It showed that all of the polyurethane polymers exhibited thermotropic liquid crystalline properties between 144°C and 260°C. The transition temperature (T _m and T _i) decreased with an increase in the length of the methylene spacer. __________ Translated from Journal of Qingdao University of Science and Technology, 2006, 27(1) (in Chinese)     

Synthesis and properties of novel thermotropic liquid crystalline copoly(ester-imide)s

Four novel copoly(ester-imide)s based on 3,3',4,4'-biphenyltetracarboxylic dianhydride,bis(trimellitic acid anhydride) phenyl ester and di-p-aminophenyl ester of dicarboxylic acids were synthesized via two-step method in order to investigate whether two imide mesogenic units with different conformation and polarity could control the formation of LC-phase.Polarizes light microscopy(PLM) and differential scanning calorimetry(DSC) have shown that three polymers formed the nematic phase with thread schlieren...     

Synthesis and properties of cholesteric liquid crystalline elastomers

The synthesis of new side-chain cholesteric liquid crystalline elastomers, containing the flexible non-mesogenic crosslinking agent M-1 and the cholesteric monomer M-2, is described by a one-step hydrosilication reaction. The chemical structures of the monomers and network polymers obtained were confirmed by FT-IR spectroscopy. Their mesogenic properties and phase behavior were investigated by differential scanning calorimetry, polarizing optical microscopy, and x-ray diffraction measurements. The influence of the crosslinking units on the phase behavior is discussed. The network polymers showed elasticity, reversible phase transitions, and cholesteric Grandjean texture. The experimental results demonstrated that the glass transition temperatures and isotropization temperatures of network elastomers decreased as the concentration of crosslinking units was increased, but the cholesteric phase was not disturbed.     

Structural studies of laterally attached liquid crystalline polymers

Abstract

Structural studies of a series of laterally attached side chain liquid crystalline polysiloxanes have been made by X-ray diffraction. All but one exhibit a nematic phase with S_C-like short range ordering. The diffraction has been interpreted in terms of a model in which the mesogenic units form a ‘jacket’ around the polymer backbone. The backbone conformation has been studied by small angle X-ray scattering from oriented samples of mesomorphic solutions and by infrared dichroism measurements on oriented samples of the polymers. In both cases the results were consistent with the mesogens being oriented parallel to the backbone which is consistent with the ‘mesogen jacket’ model.     

Electrooptical properties of liquid crystalline side chain polymers with laterally attached mesogenic units

The electrooptical properties of side-chain liquid crystalline polymers were investigated for the case that the mesogenic units were attached laterally rather than longitudinally to a flexible chain backbone via flexible spacer units. The experimental finding is that these polymers display unusual electrooptical properties within the isotropic phase in the neighborhood of the transition into the nematic phase. The polymers are characterized by the occurrence of a fast and a slow electrooptical response both of which show a critical divergence of the Kerr constant and the Kerr relaxation time. In addition, they show deviations between the rise and the decay values of the Kerr constants and in certain cases also of the Kerr relaxation times. Finally an overshoot of the induced birefringence following a sudden stepwise increase of the applied electric field has been found for one of these polymers. All these features can be accounted for on the basis of a newly developed theoretical approach that considers the particular dipolar and optical polarization configurations of these polymers.     

Structural studies of laterally attached liquid crystalline polymers

Structural studies of a series of laterally attached side chain liquid crystalline polysiloxanes have been made by X-ray diffraction. All but one exhibit a nematic phase with S_C-like short range ordering. The diffraction has been interpreted in terms of a model in which the mesogenic units form a 'jacket' around the polymer backbone. The backbone conformation has been studied by small angle X-ray scattering from oriented samples of mesomorphic solutions and by infrared dichroism measurements on oriented samples of the polymers. In both cases the results were consistent with the mesogens being oriented parallel to the backbone which is consistent with the 'mesogen jacket' model.     

Synthesis of a novel liquid crystalline bisindenocarbazole derivative

In this paper we describe the synthesis of four new bisindenocarbazole derivatives, prepared by selective bromination of bisindenocarbazole in the 7- and 7'-positions, followed by Suzuki crosscoupling with alkyl-substituted phenyl, biphenyl and fluorene units. From this new class of fused aromatics a liquid crystalline derivative is reported for the first time. The bisindenocarbazole with two 4-hexylphenyl side groups exhibits a broad nematic phase between 180 and 250°C, whereas the other derivatives are crystalline or form molecular glasses. All bisindenocarbazoles exhibit high thermal stabilities above 300°C and show excellent electrochemical stability. HOMO and LUMO levels of -5.4 eV and -2.3 eV, respectively, were determined by cyclic voltammetry and optical spectroscopy. The bisindenocarbazoles display a strong blue fluorescence with up to 56% quantum yield in solution.     

Synthesis and X-ray investigation of liquid crystalline polymers containing laterally methyl-substituted tolane-based mesogenic side groups

A series of polymethacrylates containing laterally methyl-substituted 4-alkoxy-4-nitrotolane, 4-alkoxy-4'-cyanotolane, and 4-alkoxy-4'-trifluoromethyltolane as mesogenic side groups are presented. The thermal behaviours of the prepared compounds were characterized by differential scanning calorimetry, optical polarized microscopy and X-ray diffraction. All of the obtained methacrylate monomers exhibit no mesophase, while most of the synthesized polymers reveal enantiotropic mesomorphism. The polymer containing 4-propyloxy-2'-methyl-4'-nitrotolane side groups was the only one to show no mesomorphic behaviour. The spacer length and the nature of terminal group have a profound influence on the type of mesophase formed and the thermal stability. Incorporation of a lateral methyl-substituent into the mesogenic groups reduces the thermal stabilities of the mesophases. X-ray diffraction reveals that polymers with a smectic A or smectic E phase have the inclination to form a bilayer structure. Increasing the temperature within the smectic phase range, the intermolecular spacing increases while the layer spacing decreases. On the other hand, introducing a lateral substituent into the mesogenic side groups leads to increase in both layer and intermolecular spacing.     

新型噻二唑类液晶的合成与研究

合成了以酰胺键为中心桥键的三芳环1,3,4-噻二环系共8个新化合物。液晶性质测试证明它们均为具有高相变温度和宽相变范围的稳定的液晶化合物。     

Synthesis and liquid crystalline properties of T-shaped dimesogenic compounds

Two series of new dimesogenic liquid crystalline compounds were synthesized and their LC and other thermal properties were characterized. These compounds consist of two mesogenic units connected through polymethylene spacer of varying length in the shape of the letter ‘T’. The difference between the two series is in the structure of tail groups attached on the pendant azobenzene mesogens; one of which is n-butyl and the other is phenyl. The compounds were characterized for their liquid crystallinity by the differential scanning calorimetry (DSC), X-ray diffractometry and visual observation of the melts on a hot-stage attached to a polarizing microscope. All these compounds were found to form only the nematic phase enantiotropically.     

Synthesis and liquid crystalline properties of novel compounds containing a 3-fluoro-4-cyanophenoxy group

A series of novel compounds containing a 3-fluoro-4-cyanophenoxy group were synthesized and fully characterized by IR and ¹H NMR, and their mesomorphic properties were studied. Seven compounds exhibited enantiotropic nematic phases and three compounds exhibited monotropic nematic phases, as confirmed by differential scanning calorimetry and polarizing optical microscopy. Selected properties of the liquid crystalline compounds synthesized were calculated by ab initio methods at a HF/6-31G level. The bond lengths, bond angles and dihedral angles of the fragments with the same structure change little between the compounds. All the compounds with a terminal alkoxy chain approached a planar structure.     

Synthesis,properties and photopolymerization of liquid crystalline dioxetanes

The synthesis and photopolymerization of various liquid crystalline dioxetanes is described. The effects of the spacer length, structure of the mesogenic group and oxetane group on the liquid crystalline properties, polymerization behaviour and optical properties (birefringence) of the oriented and crosslinked network formed in photo-polymerization are discussed. Thermally stable films with birefringence values up to 0.13 can be formed from these materials. The dioxetanes show significantly lower polymerization shrinkage than do structurally related diacrylates.     

Synthesis, properties and photopolymerization of liquid crystalline dioxetanes

The synthesis and photopolymerization of various liquid crystalline dioxetanes is described. The effects of the spacer length, structure of the mesogenic group and oxetane group on the liquid crystalline properties, polymerization behaviour and optical properties (birefringence) of the oriented and crosslinked network formed in photo-polymerization are discussed. Thermally stable films with birefringence values up to 0.13 can be formed from these materials. The dioxetanes show significantly lower polymerization shrinkage than do structurally related diacrylates.     

Synthesis and properties of liquid crystalline copolyarylates containing phenylhydroquinone

Copolycondensations of TPA, PhHQ, and several aromatic diacid and diol modifiers were examined for which kind of the modifiers incorporated is more effective to reduce the transition temperatures of the resulting copolyesters and how they affect the temperatures. The acid modifiers are more effective than the diol ones, significantly when they have substituents. As another type of modifier, HBA forming the ester bond of an AB structure different from the AABB structure of TPA/PhHQ polyester was also effective, and the lowering effect on the temperatures was varied by the mode of copolycondensations, being most remarkable when HBA was randomly introduced. The results obtained were discussed in terms of the disturbance and thereby weakening of the interchain dipole–dipole interaction between the carbonyl groups in the ester linkages due to the introduction of the diacid modifiers and of HBA having an ester bond of a different directionality. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 621–626, 1999     

近红外电致变色胆甾相液晶高分子的设计、合成及旋光开关性质

通过单体4′-甲氧基苯基-4-烯丙氧基苯甲酸酯(M1)、(S)-(-)-N-(5-己烯基)-6-(4′-(2-甲基丁氧基)苯基)-蒽醌-2,3-二羧酸酰亚胺(M2)与聚甲基氢硅氧烷间的硅氢加成反应,制得了3个新的具有近红外电致变色性质的侧链型液晶共聚物(PC5A10,PC5A20CB,PC5A30CB),并对其液晶性,电化学,光谱电化学和旋光开关性质进行了表征.当M2单体的含量为10mol%,20mol%时,共聚物可形成胆甾相液晶,而当其含量为30mol%时,所能形成的液晶相为近晶A相.3个共聚物的循环伏安曲线均出现了两对可逆的氧化还原峰,分别对应于蒽醌酰亚胺基团得电子而形成自由基阴离子和二价阴离子.中性态时,共聚物在420nm处有较强吸收,而当被还原为自由基阴离子后,在近红外区域840nm出现了新的强烈的吸收.以聚合物为阴极电致变色层,普鲁士蓝为离子储存层的全固态电致变色器件在800nm有较好的光学调制性.此外,本文还就该器件的电化学调控手性光开关性质进行了初步研究.