Liquid crystalline compounds in the thiophene series. VIII. Synthesis and characterization of liquid crystalline vinylenes with thiophene moieties and carbaldehyde groups

New thermotropic liquid crystal compounds, with one and two mesogenic groups, have been synthesized and characterized. The structural elements of the compounds consist of thiophene ring systems, vinylene units and, for some compounds, carbaldehyde groups. Mesogenic groups involving three thiophene ring systems are normally not liquid crystalline. Only in the case of E,E-5-[5-(5-butyl-2-thienylvinyl)-2-thienylvinyl]-2-thiophenecarbaldehyde could a monotropic nematic phase be easily observed. By replacing thiophene ring systems in the core with a benzene ring system, or by attaching one carbaldehyde group at the moieties, or by doubling the mesogenic groups via an alkylene spacer, the temperature ranges of the mesophases of the compounds with thiophene ring systems can be enlarged or liquid crystal phases induced. The small values for δS_NI, which have been observed for the low molecular weight compounds, indicate a very low order in the nematic phases.     

A liquid crystal microlens obtained with a non-uniform electric field

A homogeneously aligned nematic liquid crystal cell with a hole-patterned electrode and with an indium-tin oxide (ITO-) coated counter-electrode has been prepared. A non-uniform electric field can be produced by the asymmetrical electrode structure. The liquid crystal director can be reoriented by applying a voltage across the electrodes, and this produces an axially symmetrical profile of the refractive index. This liquid crystal cell is expected to have a lens effect and so its optical properties have been investigated. The profile of the output light intensity was measured by using a detecting system with an optical fibre. Some relationships between the lens properties, the diameter of the hole and the thickness of the liquid crystal layer have been examined. The liquid crystal cell becomes a convex (converging) lens with a relatively low voltage. A focal length of several millimetres can be obtained by applying voltages of 3-4 V. As the applied voltage increases, the focal length becomes longer, and the cell changes to a concave (diverging) lens when a high voltage is applied (≳ 20 V). These properties are discussed from the viewpoint of the director orientation effects resulting from the non-uniform electric fields in the cell.     

A liquid crystal microlens obtained with a non-uniform electric field

Abstract

A homogeneously aligned nematic liquid crystal cell with a hole-patterned electrode and with an indium-tin oxide (ITO-) coated counter-electrode has been prepared. A non-uniform electric field can be produced by the asymmetrical electrode structure. The liquid crystal director can be reoriented by applying a voltage across the electrodes, and this produces an axially symmetrical profile of the refractive index. This liquid crystal cell is expected to have a lens effect and so its optical properties have been investigated. The profile of the output light intensity was measured by using a detecting system with an optical fibre. Some relationships between the lens properties, the diameter of the hole and the thickness of the liquid crystal layer have been examined. The liquid crystal cell becomes a convex (converging) lens with a relatively low voltage. A focal length of several millimetres can be obtained by applying voltages of 3-4 V. As the applied voltage increases, the focal length becomes longer, and the cell changes to a concave (diverging) lens when a high voltage is applied (? 20 V). These properties are discussed from the viewpoint of the director orientation effects resulting from the non-uniform electric fields in the cell.     

Mischungsverhalten von polyvinylchlorid und polyepichlorhydrin

The system poly(vinyl chloride) (PVC)/polyepichlorohydrin (PECH) has been studied. From a study of the sorption of acetone vapour by PVC, PECH and their mixtures, the Gibbs free energy of mixing of the two polymers has been calculated. The values of ΔG^M are positive indicating lack of miscibility. Thermodynamic aspects of the PVC/PECH system are discussed.     

Chirality-induced phase transitions in some liquid crystalline binary mixtures

Novel binary mixtures have been prepared between an optically active antiferroelectric liquid crystal, (S)-4-(1-methylheptyloxycarbonyl)phenyl 4'-octyloxy-biphenyl-4-carboxylate, and an optically active twin liquid crystal, (R)-3-methyladipic acid bis[4-(5-octyl-2-(pyrimidinyl)phenyl] ester, and the liquid crystalline properties investigated. The stability of each liquid crystal phase was found to decrease by mixing these two liquid crystalline materials. Furthermore, a phase diagram between these compounds showed a clear discontinuity in phase sequences. These results indicate that the liquid crystal phases are different in nature between these materials. The mixture consisting of the antiferroelectric material (40 per cent) and the twin material (60 per cent) shows an unusual liquid crystal phase, where the texture is similar to that reported for the twist grain boundary (TGB) phase. Related binary mixtures have been prepared between optically active or racemic materials, where the chirality of the system is expected to be altered systematically. The TGB phase was found to be induced only in the mixture between the optically active materials. Two kinds of effect on the appearance of the TGB phase, i.e. a strong helical structure induced by the optically active twin liquid crystal and a decrease of the smectic layer strength achieved by mixing between two types of liquid crystalline materials, are discussed.     

Liquid crystal properties of some substituted pyrazines

A number of biphenyl, terphenyl analogues and ethynes which contain a pyrazine ring have been made and their liquid crystal transition temperatures, together with examples of birefringence measurements, are reported. All the 2,5-disubstituted pyrazine systems are liquid crystalline showing high birefringence values for the biphenyl and terphenyl analogues, whereas the 1,5-disubstituted systems are not liquid crystalline. The pyrazine ethyne systems exhibit very high birefringence values. X-ray diffraction has been used to identify the liquid crystal phases of 2-n-nonyloxy-5-(4'-propylbiphenyl-4-yl)pyrazine.     

乙烷类三环体系液晶的合成及其相变规律的研究

以反式-4-烷基环己烷甲酸为原料,合成了两个系列共14种乙烷类三环体系液晶。利用NMR、IR、DSC等确定了化合物的结构及相变温度,讨论了化合物的结构对相变温度的影响。     

Polarized infrared spectroscopic study on changes in molecular orientation and interaction during phase transitions of a ferroelectric liquid crystal with a naphthalene ring

Temperature-dependent polarized infrared spectra were measured over the temperature range 105-30°C for a ferroelectric liquid crystal with a naphthalene ring (FLC-1) in the isotropic, smectic A (SmA), and chiral smectic C (SmC*) phases to investigate its molecular conformation, interactions, and alignment in each phase. It has been found, from the temperaturedependent spectral changes in the 1610-1600 cm^-1 region, that the degree of twist between the naphthalene and benzene rings of FLC-1 changes with temperature. The peak intensity of the band at 1606 cm^-1 containing contributions from both the benzene and naphthalene ring stretching modes begins to decrease, not suddenly but gradually, upon going from the SmA phase to the SmC* phase, suggesting that the molecular orientation of the two rings changes gradually between the two phases. The frequencies of two CH₂ stretching bands suggest that the disorder of the alkyl chain of FLC-1 is similar for the liquid crystal phase and the isotropic liquid phase. The splitting of the core C=O stretching band indicates that the resonance system consisting of the benzene ring and the C=O group in the core part of FLC-1 is involved in two kinds of intermolecular interaction between adjacent molecules in the liquid crystal phase.     

Internal orientations in externally deformed nematic polymer liquid crystals

The system of linear polymer liquid crystal (PLC) macromolecules, each modeled by semiflexible chain of alternate connected flexible and stiff rodlike sequences, is externally deformed. As a result, two orientation phases for hard rods are generated. One of them is nematic N+ with orientation parameter s>0; this has the place in monomer liquid crystal (MLC) systems and in PLCs. The nematic N- phase with s>0 appears in deformed PLCs only. This causes the fact that orientation of PLC chains, as a whole, is generated also by the system deformation. A discussion of that effect is the main goal of this article. The change of orientation is also discussed dependent on changes of the system temperature and parameters of the chain structure, such as the liquid crystal component concentration, contour lengths of stiff and flexible parts, and internal interactions parameters. Average shape of PLC chain and the shape anisotropy are calculated and discussed.     

新型弯曲形双偶氮苯类液晶合成及光致异构性能研究

弯曲形偶氮苯液晶由于其偶氮键独特的光致可逆异构化性能,已成为光电子信息材料研究的热门课题,但光响应速度慢已成为制约其发展的关键因素.目前报道的弯曲型偶氮类液晶化合物的偶氮键都距离中心核较远的位置,光致异构的响应时间较长,大都在分钟以上,不利于光敏器件应用研究.本工作试图以2-甲基-1,3-间苯二胺为中心核,将偶氮键紧挨中心核两边,末端为直链烷基,设计合成了一系列新型弯曲形双偶氮苯类液晶化合物,以期缩短光响应时间.通过IR, 1H NMR, 13C NMR和ICP-MS光谱鉴定这些化合物的分子结构,经差示扫描量热仪(DSC)和偏光显微镜(POM)测定其液晶相变温度和相态织构;并通过测定2-甲基-1,3-双(4-((4-庚基苯基)酯基)-1-(E)-偶氮苯基)苯(2c)的紫外-可见光的吸收光谱研究其光致异构化性能,通过UV-Vis光谱仪和偏光显微镜(POM)测定其液晶化合物以及掺杂向列相液晶材料的光致异构现象和响应时间.实验结果表明,所有设计合成的弯曲形双偶氮苯类液晶化合物均具有近晶相相态,且相态温度范围较宽,当近晶相态化合物2c掺杂到向列相混合液晶中时,其光致异构响应时间为2~3 s,在日光下液晶态恢复时间为3~4s,在乙酸乙酯稀溶液中时10s可达到光稳态.说明这类弯曲形双偶氮液晶化合物具有较快的光致异构响应速度.     

Banana-shaped molecules peculiarly oriented in a magnetic field: (2)H NMR spectroscopy and quantum mechanical calculations.

The orientational properties of the banana-shaped liquid crystal 4-chloro-1,3-phenylenebis{4-[4'-(10-undecenyloxy)]benzoyloxy} benzoate (ClPbis11BB) are reported in the nematic phase under the effect of an external magnetic field. A new hypothesis, which states that the central ring of the aromatic core is oriented perpendicularly to the external magnetic field, is proposed. In support of this hypothesis, a series of studies based on (2)H NMR spectroscopy, both in the bulk and in solution, are discussed. (2)H NMR measurements on three selectively deuterium-labelled isotopomers are presented, together with DFT results from B3LYP/cc-pvDz calculations performed on the aromatic core. The rather flat shape of the investigated intramolecular energy surface allows for several different conformations to be populated, the computed magnetic susceptibilities of which are consistent with the proposed hypothesis of peculiar orientation of banana-shaped molecules. Moreover, the orientation of the magnetic susceptibility tensor is shown to be strongly dependent on the internal conformation of the banana-shaped molecules.     

Liquid crystal properties of new ionic liquid crystal compounds having a 1,3-dioxane ring

New pyridinium type chiral ionic liquid crystal materials having a 1,3-dioxane ring in the central core, (+)- N -2-methylbutyl-4-(5-alkyl-1,3-dioxan-2-yl)pyridinium bromides ( 6 ), were synthesized. Mixture A was made by adding 5.9 wt % of compound 6-3 to the ferroelectric liquid crystal mixture Merck 4655-100; its phase transitions and some liquid crystal properties were measured. In spite of a large decrease of P s for mixture A, its response time A was the same as that of Merck 4655-100. The dielectric constants perpendicular to the molecular axis for the smectic C* and smectic A phases were measured for the mixture and Merck 4655-100: in the smectic C phase, these dielectric constants were almost the same (4.5~5.5), but in the smectic A phase, the perpendicular dielectric constant of the mixture was 47.0 and that of Merck 4655-100 was 4.5.     

The versatile,functional polyether,polyepichlorohydrin: History,synthesis, and applications

Polyepichlorohydrin (PECH) is a functional polyether first synthesized in the 1950's by the catalytic ring opening polymerization of epichlorohydrin (ECH), its inexpensive epoxide pre-cursor. PECH elastomers are used in diverse commercial applications due to their unique combination of properties including low temperature flexibility and heat and oil resistance. PECH holds an interesting place in polymer history as its synthesis led to the discovery of highly effective aluminum-based catalysts for epoxide polymerizations and a new class of high molecular weight polyether elastomers by an exceptional polymer chemist, Edwin J. Vandenberg. ECH is an ideal feedstock for polymer materials as it is functional, inexpensive, and produced through environmentally friendly means. However, due to the alkyl chloride pendant, polymerizations involving ECH are difficult and limited synthetic advancement has occurred until very recently. This focused review will discuss modern polymerization methods involving ECH while giving a historical perspective on the evolution of these techniques. We will also review applications of ECH-based polymers and discuss the future development of these materials. We hope to convince the reader to explore ECH-based materials in their own work.     

Polarized infrared spectroscopic study on changes in molecular orientation and interaction during phase transitions of a ferroelectric liquid crystal with a naphthalene ring

Temperature-dependent polarized infrared spectra were measured over the temperature range 105-30°C for a ferroelectric liquid crystal with a naphthalene ring (FLC-1) in the isotropic, smectic A (SmA), and chiral smectic C (SmC*) phases to investigate its molecular conformation, interactions, and alignment in each phase. It has been found, from the temperaturedependent spectral changes in the 1610-1600 cm^-1 region, that the degree of twist between the naphthalene and benzene rings of FLC-1 changes with temperature. The peak intensity of the band at 1606 cm^-1 containing contributions from both the benzene and naphthalene ring stretching modes begins to decrease, not suddenly but gradually, upon going from the SmA phase to the SmC* phase, suggesting that the molecular orientation of the two rings changes gradually between the two phases. The frequencies of two CH₂ stretching bands suggest that the disorder of the alkyl chain of FLC-1 is similar for the liquid crystal phase and the isotropic liquid phase. The splitting of the core C=O stretching band indicates that the resonance system consisting of the benzene ring and the C=O group in the core part of FLC-1 is involved in two kinds of intermolecular interaction between adjacent molecules in the liquid crystal phase.     

聚合物分散液晶膜

聚合物分散液晶膜是将液晶和聚合物结合,得到的一种综合性能优异的膜材料,液晶分子赋予了聚合物分散液晶膜显著的电光特性,使其受到了广泛的研究,并有着广阔的应用前景。而聚合物作为成膜材料,起着辅助但是重要的作用,其结构和固化过程是影响聚合物分散液晶膜电光特性的重要因素。本文简要综述了聚合物分散液晶膜的制备方法、电光特性的影响因素及研究手段。     

Biaxial smectic phases in non-linear optical properties and phase behaviour of an oxdiazole liquid crystal

A symmetric, low-molecular-mass liquid crystal based on the oxadiazole ring was synthesized and characterized. The symmetric position of the heterocyclic group in the centre of the liquid crystal, bis(4-hexyloxyphenyl)4,4-(1,3,4-oxadiazole-2,5-diyl)dicarboxylate, yields a very rigid and non-linear mesogenic core. Despite this non-linear structure, a broad liquid crystalline range with a smectic C and a smectic A phase was found. Conoscopic experiments on freely suspended films revealed the existence of two optical axes in the smectic A phase, indicating a phase symmetry anticipated for either a 'McMillan' biaxial smectic phase or a biaxial (achiral) ferroelectric smectic phase.     

非离子表面活性剂体系的液晶与自发乳化(I)

乳状液广泛用干工、农业、医药、食品与化妆品生产中．近年来，许多研究集中在如何制备颗粒细小、均匀的乳状液方面．用通常的机械法制备细小乳状液，需要较昂贵的设备和消耗较多能量，其颗粒分布仍不够均匀．近来，一些研究发现，有可能采用物理化学方法，而不需乳化机械，只要选用合适的乳化剂，在轻微的搅拌下，可制得颗粒细小而均匀的微小乳状液[1，2]．我们在采用反相乳化法和自发形成O／W型微小乳状液的研究中发现，在自发乳化的中间过程中常有液晶棺和粘稠的胶状物形成[3，4]．有关液晶对乳状液的稳定作用前人有过较多研究[5]，但在…     

Fluorene‐based liquid crystalline networks with linearly polarized blue emission

A series of fluorene‐based luminophores containing methacrylic end groups have been prepared and incorporated into uniaxially oriented liquid crystalline films by in situ photopolymerization. Various structural modifications on the 2‐(4‐cyanophenyl)fluorene core, which include alkyl chains at the 9‐position and elongation of the rigid core with one additional phenyl ring, have been investigated to generate emitters with adjusted liquid crystal compatibility, improved luminescence and dichroic properties. Polarized blue‐emitting films were produced that had an acceptable photostability, and it was found that the polarization emission was better for samples with low (5%) cross‐linker contents. Polarization of the luminescence was favored by the liquid crystalline properties of the luminophore. In addition, the detrimental effect of the alkyl substituent at the fluorene core on the mesomorphism and on the emission polarization can be overcome by lengthening the π‐system. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4804–4817, 2007     

A single-cell-gap transflective liquid crystal display with a vertically aligned cell

A single-cell-gap transflective liquid crystal display with a vertically aligned cell using square ring electrode is demonstrated. The top substrate has a top planar common electrode, a square ring pixel electrode is coated on the bottom substrate, while a bumpy reflector is coated under the bottom substrate. In this device, the planar common electrode and square ring pixel electrode generate a strong longitudinal electric field in the transmissive region (T region) and a weak fringe field in the reflective region (R region). As result, the T and R regions accumulate the same optical phase retardation. The simulation results show that the display exhibits reasonably low operating voltage, high transmittance and well-matched voltage-dependent transmittance and reflectance curves. Besides, fabrication process of the transflective liquid crystal display is very simple.     

Spontaneously created ring structures in free-standing liquid crystal films and their dependence on temperature and material parameters

A rotating electric field can induce a spontaneous formation of ring structures in free-standing ferroelectric liquid crystal films. A phase delay between the field rotation and the director movement on the smectic cone is the reason for the ring creation. The appearance of these structures depends on the field parameters, on the material parameters of the liquid crystal compound used, and on the temperature. The temperature dependence of the pattern formation and of material parameters (spontaneous polarization, rotational viscosity, pitch) have been investigated in more detail. It could be shown that the rotational viscosity of the liquid crystal is the most important parameter with respect to the influence of temperature. The experimental results are compared with the theoretical interpretation of the ring formation.