胆甾相液晶的合成

本文使用了二氯亚砜先制成酰氯,然后再与胆甾醇化合合成胆甾酯的方法制得胆甾相液晶。并使用了红外(IR)和热重／差热分析仪(TGA／SDTA)对所制得的胆甾酯进行了分析。     

Determination of the order parameter in cholesteric liquid crystalline phase cellulose derivatives solutions by refractometry

The macroscopic order parameter S in the cholesteric liquid crystalline phase of hydroxypropyl cellulose (HPC) and ethyl cellulose (EC) solutions was calculated using refractive index data. Haller's extrapolation approach was used. The S calculated was compared with the S predicted from Doi's theory. The calculated values of S for HPC and EC solutions were in the range of 0.4–0.8 within our experimental range, and agreed with the predicted values of S obtained with Doi's theory. This result suggests that Haller's approach is valid for determining S for liquid crystalline solutions of HPC and EC, despite the scattering of the data at higher temperatures.     

Birefringence measurement on the liquid crystal by phase modulation technique

A convenient and accurate technique for measuring the birefringence of liquid crystal (LC) is developed. The birefringence of LC was obtained with only one experimental run by using phase modulation technique, which is an expansion of PMFB (Phase Modulated Flow Birefringence) technique developed elsewhere [1], The basic principle of the method is based on the determination of the phase differences which occur when a phase modulated monochromatic polarized light propagates through a medium with an anisotropic refractive index. Birefringence measurements with red light (wavelength: 0.6328μm) for commercial liquid crystal material (Merck, ZLI 3201-000) are reported.     

Structural chirality of cholesteric liquid crystal produces atropisomerism: Chiroptical polyisocyanides from achiral monomer in cholesteric liquid crystal matrix

1-Naphthyl isocyanide was polymerized with Ni(II) catalyst in a cholesteric matrix at the liquid crystal (LC) temperature range. The resultant polymers showed optical activity. In this reaction, the structural chirality of cholesteric LC effectively functions to impart one-handed helicity on the corresponding polymers as an optically active atropisomer.     

Preparation of composites of polymer liquid crystal/cholesteric liquid crystal and their photochemical switching and memory properties by photoisomerization of a chiral azobenzene molecule

A chiral azobenzene compound was synthesized, and mixing the chiral azobenzene compound in a host nematic liquid crystal (LC) induced a cholesteric phase. The twisting power of the trans‐form of the chiral azobenzene compound was larger than that of its cis‐form produced by ultraviolet irradiation. A low molecular weight compensated nematic LC was then prepared by mixing of the chiral azobenzene and a nonphotochromic chiral compound, thus giving mutual opposite helical sense in the host LC. Reversible optical switching between transparent and opaque was achieved by ultraviolet and visible light irradiation. However, the photochemically switched opaque state was not stable even in the dark. Stability of the opaque state was found to be improved by adding polymer LC to the low molecular weight compensated nematic LC. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2577–2580, 2004     

聚硅氧烷侧链胆固醇酯液晶聚合物的合成及性能研究

设计、合成了一种烯丙氧基联苯甲酸胆固醇酯液晶单体(V1OBEG),并通过巯基-乙烯基点击加成反应,将其接枝到聚(3-巯丙基甲基硅氧烷)(PMMS)上,得到一种新型的以聚硅氧烷为主链的侧链高分子液晶(PMMS-V1OBEG)。通过红外光谱、核磁共振氢谱、差示扫描量热仪和偏光显微镜分别对液晶单体和聚合物的分子结构及液晶行为进行表征。结果表明,液晶单体的熔点和清亮点分别为189.37℃和277.99℃,在升温过程中先后出现胆甾相的玫红色油丝织构和蓝色油丝织构,继续升温时呈指纹织构,降温过程中出现焦锥织构;聚合物的玻璃化转变温度和清亮点分别为103.71℃和278.16℃,在升温过程中出现胆甾相液晶,降温过程中无液晶相。     

聚硅氧烷侧链胆固醇酯液晶聚合物的合成及性能研究

设计、合成了一种烯丙氧基联苯甲酸胆固醇酯液晶单体(V1OBEG),并通过巯基-乙烯基点击加成反应,将其接枝到聚(3-巯丙基甲基硅氧烷)(PMMS)上,得到一种新型的以聚硅氧烷为主链的侧链高分子液晶(PMMS-V1OBEG)。通过红外光谱、核磁共振氢谱、差示扫描量热仪和偏光显微镜分别对液晶单体和聚合物的分子结构及液晶行为进行表征。结果表明,液晶单体的熔点和清亮点分别为189.37℃和277.99℃,在升温过程中先后出现胆甾相的玫红色油丝织构和蓝色油丝织构,继续升温时呈指纹织构,降温过程中出现焦锥织构;聚合物的玻璃化转变温度和清亮点分别为103.71℃和278.16℃,在升温过程中出现胆甾相液晶,降温过程中无液晶相。     

Magneto-optically active polythiophene derivatives bearing a stable radical group from achiral monomers by polycondensation in cholesteric liquid crystal

Chiral π-conjugated polymers bearing a stable radical group are successfully prepared by chiral inductive asymmetric polymerization using a cholesteric liquid crystal medium. The polymers thus synthesized form “structural chirality”, with the structure of the polymer being analogous to that of the one-handed helical form of the cholesteric liquid crystal. Chirality and magnetic properties of the present polymers were elucidated.     

Dimensional stability of polystyrene/polymeric liquid crystal blends

Recovery experiments above T_g have been performed on polymeric liquid crystal (PLC) - polystyrene (PS) blend sheets obtained from extrusion and subsequent hot drawing. The data reported show that a significant improvement of the dimensional stability of a drawn thermoplastic material can be obtained by adding a low percentage of non-compatible polymeric liquid crystals that are oriented during the hot drawing process. The fibrils formed act as a constraint for a certain amount of polymer surrounding them and consequently these highly oriented sheets, once exposed to high temperature, will mainly stress relax and do not creep. This effect disappears when the melting temperature of the oriented crystalline phase is reached. Compatible PLC-PS blends do not show any improvement on the dimensional stability compared to the unfilled matrix.     

Interfacial conversion for poly(para‐phenylenevinylene) at a cholesteric liquid crystal surface

A new approach for the preparation of poly (para‐phenylenevinylene) (PPV) with an ordered structure is presented. PPV is synthesized by a precursor method using a cholesteric liquid crystal medium. The resultant PPV film is observed to have a cholesteric fingerprint‐like texture, indicating replication of the cholesteric liquid crystal medium. Infrared absorption measurements confirm that the PPV has essentially the same molecular structure as normal PPV film. Ultraviolet–visible absorption measurements show that the absorption band due to π?π* transition of the conjugated main‐chain is located at 402 nm. The conversion is found to occur at the interface with the cholesteric liquid crystal medium as a mechanical process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and phase behavior of cholesteric liquid crystal polymers containing glutamic acid in main‐chain

Four polymers (P₀–P₃) containing peptide chain as polymer backbone were synthesized by condensation reaction with bis(trichloromethyl)carbonate and triethylamine. The chemical structures of the monomers M₀–M₃ were confirmed by FTIR and ¹H‐NMR. The structure–property relationships of the monomers and polymers are discussed. Their phase behavior and optical properties were investigated by differential scanning calorimetry, thermogravimetric analysis, and polarizing optical microscopy. Monomers M₁–M₃ and polymers P₁–P₃ displayed cholesteric phases. The results demonstrated that the melt temperature and clear point of monomers (M₁–M₃) and polymers (P₁–P₃) decreased with the increase of the flexible spacer length in the side‐chain, and the mesophase temperature range of the polymers increased with the increase of the flexible spacer length. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Self-assembly of a liquid crystal ABA triblock copolymer in a nematic liquid crystal solvent

An ABA type triblock copolymer, consisting of liquid crystalline polymer (LCP, poly(4-cyanobiphenyl-4-oxyundecylacrylate)) ‘A’ end blocks and a deuterated polystyrene (dPS) ‘B’ mid block (LCP–dPS–LCP) was successfully synthesized by atom transfer radical polymerization (ATRP). The number average molecular weight (M_n) of LCP–dPS–LCP was LCP (7.1 K)–dPS (19.4 K)–LCP (7.1 K) with a polydispersity index (PDI) of 1.41. LCP–dPS–LCP was self-assembled in a nematic liquid crystal solvent of 4-pentyl-4′-cyanobiphenyl (5CB) into spherical micelles with a LCP corona and a dPS core, in which dPS was folded to produce a V-shape structure. Micellar structures of LCP–dPS–LCP in 5CB were examined by small angle neutron scattering at various block copolymer concentrations and temperatures using a curve fitting method. The critical micelle concentration was 0.25 wt% and the self-assembled micelles dissociated into unimers at 33 °C, which is lower than the nematic to isotropic transition temperature (T_ni) of 5CB (36 °C). The entropic penalty imposed on dPS by the ordered nematic state of the 5CB solvent caused phase separation of the flexible dPS block to form micelles, which vanished above the T_ni of the 5CB solvent. Magnetic field-induced global orientation of 5CB revealed the structure of the dPS core of the micelle to be prolate (an elongated sphere) oriented with its long axis along the direction of the applied magnetic field.     

胆甾液晶弹性体的合成及液晶性能研究

以胆甾液晶单体和向列液晶交联剂与含氢聚硅氧烷接枝聚合制备了一系列弹性体.通过红外光谱(FT-IR)、核磁氢谱(1 H-NMR)确定了液晶单体及弹性体的化学结构.通过差热扫描量热仪(DSC)、偏光显微镜(POM)以及X-射线衍射研究了其介晶性质及液晶相行为.结果表明,弹性体的玻璃化转变温度随着向列液晶交联剂的加入先降低后升高.随着向列液晶交联剂的加入,系列弹性体的X-射线衍射峰弥散,且最大反射波长略微变长,说明液晶分子间的有序性受到干扰.     

Standard color liquid crystal displays by a dimming technology

Dimming technologies have been used in liquid crystal display (LCD) products, especially for mobile applications, to reduce power consumption. It is widely known that dimming technologies tend to degrade the color accuracy. This article, however, presents that color performance of a dimmed LCD is better than a conventional one. We show a max method, one of dimming methods, converting an input digital data into higher values that have less color shift phenomenon. We propose how to compare the color performance of original and dimmed colors based on a modified standard. The average value of measured Δu′v′ of 25 dimmed colors was 0.0040, whereas that of the original colors was 0.0190. In addition, the average value of measured Δ of 25 dimmed colors was 2.40, whereas that of the original colors was 9.24. The measured results prove that the dimming technology can make LCD better in not only power consumption but also color performance. This article is the world's first report that breaks the usual stereotype on dimming technologies. This work proposes a dimmed LCD as a standard color display. © 2013 Wiley Periodicals, Inc. Col Res Appl, 39, 480–485, 2014     

Dynamic viscoelastic behavior of cholesteric liquid crystalline side-chain copolymers

Summary The rheological behavior of the cholesteric side-chain copolysiloxane whose two kinds of mesogenic groups consist of cholesteryl units and biphenyl benzoate units was investigated for three different compositions: 31:69, 35:65, 37:63 (in mol%). On the frequency dependence diagram of G′ for the copolymers at various temperatures, G′ decreases with decreasing frequency. The slope of G′ in a higher frequency region at lower temperatures (110°–130°C) is similar to that in the flow region of amorphous polymer melts. However, the slope of G′ in a lower frequency region at higher temperatures (140°–160°C) is relatively small, and the G′ curves in this region can not be superposed on to a single master curve. This deviation seems to be due to change in stability of the domain structure of the cholesteric phase. Furthermore, on the temperature dependence curve of G′, G′ showed a maximum near T _c1 . This maximum of G′ curve seems to be caused by molecular organization of a blue phase.     

Metallization of a liquid crystal polymer by PVD using a nickel interlayer

In this paper metallization of a liquid crystal polymer (LCP) substrate by physical vapor deposition (PVD) is described. Pretreatment of LCP substrates with oxygen-containing plasma improves the adhesion strength between the PVD copper layer and substrate. When a nickel interlayer was used, the adhesion was improved further. Still higher adhesion was also achieved with appropriate bias used during deposition of the nickel interlayer by PVD. Even after 1000 cycles of thermal shock the adhesion strength of Cu/Ni on LCP pretreated with oxygen plasma was still high.     

Viscosity reduction of polymeric liquid by dissolved carbon dioxide

The viscosities of polydimethylsiloxane (PDMS)/CO₂ solutions were measured over the range of pressures of 1–3 MPa and at the ambient temperature. The viscosities were measured by using a specially designed falling ball viscometer (FBV). The Stokes equation was used to determine the viscosities and the Stokes force expressing the viscous drag of the sphere was corrected for the effect of the lateral cylindrical wall. The Kelley-Bueche (KB) free-volume treatment of the viscosities of polymeric solutions was modified to account for the gas solvent and applied to interpret our data on PDMS/CO₂ systems. It was shown that the theoretical equation, based on the assumption of the additivity of free volumes of the components, was capable of predicting with remarkable accuracy the concentration and pressure dependence of the viscosities of the investigated polymeric solutions. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 459–466, 1997     

Synthesis and characterization of cholesteric thermotropic liquid crystalline polyesters

Cholesteric liquid crystalline polyesters were successfully synthesized from isosorbide, methyl hydroquinone, and isophthaloyl chloride. Homo/copolyesters were synthesized by the solution polycondensation method, for which a mild organic base such as pyridine was employed. Inherent viscosities of polyesters P‐3–P‐5 were in the range of 0.31–0.39 dL/g at 25°C in chloroform, and polyesters P‐1 and P‐2 were insoluble in chloroform. Homo/copolyesters based on isosorbide, methyl hydroquinone, and isophthalic acid had thermal stability at more than 300°C on the basis of 10% weight loss. The thermotropic liquid crystalline properties were examined by differential scanning calorimetry and polarizing optical microscopy. Wide‐angle X‐ray diffraction study demonstrated that polyesters P‐1, P‐2, and P‐3 were semicrystalline, whereas the degree of crystallinity of polyesters P‐4 and P‐5 was less than 5%. Copolyester P‐4 showed formation of a yellow iridescent streak at 209°C on heating and development of a Grandjean texture at 270°C on heating. These are typical textures of the cholesteric liquid crystalline phase. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1232–1237, 2007     

Non-isothermal flow of a polymeric liquid through rounded L-channels

Abstract

The non-isothermal creeping flow of nylon-6 in L-channels with rounded corner has been studied numerically. A differential-type, non-isothermal White-Metzner constitutive equation is used for this flow simulation. Computational results were obtained by the elastic-viscous split-stress (EVSS) finite element method, incorporating the streamline-upwind Petrov-Galerkin (SUPG) scheme. The generated thermal field is entirely due to viscous heating. Essential flow characteristics, including temperature distribution in the flow field, are predicted. The resulting local Nusselt numbers along the walls and dimensionless bulk temperature along the channel are predicted. Furthermore, the effects of flow-rate, temperature-thinning, and geometry are investigated. In the curved elbow, the local heat transfer coefficient is higher along the outer wall than along the inner, and the difference is more significant for higher flow-rate. The local Nusselt number and bulk temperature distributions increase with flow-rate, but decrease with fluid temperature-thinning. The effect of elbow radius on these two values is only significant in the curved elbow.     

Molecular structure and cholesteric liquid crystalline behavior of ethyl-cyanoethyl cellulose

Summary Ethyl-cyanoethyl cellulose [(E-CE)C] can form lyotropic cholesteric liquid crystals in acrylic acid (AA) and the liquid crystalline behavior is influenced by the concentration and (E-CE)C molecular structure. The critical concentration C₁ increases with increasing (E-CE)C molecular weight and is also influenced by the degree of substitution for cyanoethyl. The C₁ is lowest when the degree of substitution for cyanoethyl is 0.26. The pitch of cholesteric phase decreases with increasing both the (E-CE)C concentration and the degree of substitution for cyanoethyl and can not be influenced by the molecular weight of (E-CE)C in the molecular weight region of 6x10⁴–5x10⁵.