The effect of a single atom in the terminal position of a fluorocarbon chain on liquid crystalline properties

Eight series of chiral compounds with semi-fluorocarbon chains have been synthesized. The compounds were characterized by IR, ¹H NMR, ¹⁹F NMR and mass spectroscopies and elemental analysis. Their phase transition behaviour was investigated by differential scanning calorimetry and polarizing optical microscopy. Their clearing points increase with an increase of the length of fluorocarbon chain. For a certain compound, when the terminal hydrogen atom in the semi-fluoroalkyl chain was substituted by a chlorine atom, both the clearing point and melting point were increased, and the thermal stability of the chiral smectic C (SmC*) phase was enhanced. However, the clearing point decreased and the melting point increased with the introduction of a triple bond into the core.     

2,3-二氟代联苯类液晶化合物的合成与性能

以4-烷基环己基甲酸和4-溴-2,3-二氟苯酚为原料,经格氏、黄鸣龙还原、碘代、芳基硼酸化、Suzuki偶联、威廉姆逊和酯化等反应,合成24种侧向二氟取代联苯类液晶化合物,总收率4.2%～8.7%,产物的分子结构经核磁（1H NMR,13C NMR）、红外和质谱确认。 利用差示扫描量热仪（DSC）和偏光显微镜（POM）对目标化合物进行了液晶性能测试。 结果表明,烷基链的长度不仅影响化合物的熔点和清亮点,还影响液晶相态变化;端烯可以降低化合物的熔点（降低了3.7 ℃）,提高清亮点（提高了24.8 ℃）,拓宽向列相区间（由54.1 ℃拓宽到82.6 ℃）;酯基的引入可以提高清亮点,有助于消除近晶相。 该系列化合物在垂直取向(VA)和平面转换(IPS)显示模式中具有潜在的应用前景。     

Liquid crystalline derivatives of galactose and galactitol: dependence of thermotropic mesomorphism on carbohydrate form

An almost complete homologous series of the acyclic, open-chain 6- O - n -alkyl-D-galactitols has been prepared. Most homologues in this series exhibit an enantiotropic smectic A* phase. The liquid crystal transition temperatures of these open-chain carbohydrates are compared with those of the corresponding homologues in the cyclic form, i.e., with those of the 6- O - n alkyl-alpha-D-galactopyranoses. In general the carbohydrates in the open-chain form exhibit higher clearing points than those of the analogous cyclic pyranoses. However, the melting point of the galactitols is generally significantly lower than that of the corresponding galactopyranoses. This leads to a much wider temperature range of the smectic A* phase for the carbohydrates in the pyranose form. The lowest clearing point was found for related galactoses in the furanose form. Alternation was found for the clearing point of the 6-O-n alkyl-alpha-D-galactopyranoses and the 6- O - n -alkyl-D-galactitols. Powder X-ray diffraction studies indicate a non-intercalated structure for the crystalline state and an interdigitated arrangement in the smectic A* phase with a degree of chain melting for both series.     

1,2-二芳基乙炔的简便合成及其结构与性能关系研究

1,2-Diarylacetylenes have been synthesized by a facile method consisting of an addition of diaryl ketone with acetyl chloride and the elimination of resultant ethene chloride. Correlation between physical properties and structure of the 1,2-diarylacetylene has been studied by differential scanning calorimeter （DSC）, refractor and electro-optical parameter test instrument. The results show that birefringence was increased with inserting cyclohexyl into the skeleton, but mesophase range, melting and clearing points were reduced with introducing the ethylene bridge in the molecule, and birefringence, viscosity, clearing point and mesophase range could all be decreased with perfluoro alkyl/alkoxyl terminal instead of alkyl/alkoxyl moiety.     

侧链型丙烯酸酯共聚物相变的正电子湮没谱研究

利用正电子湮没技术对侧链型热致高分子液晶丙烯酸酯共聚物进行了变温相变研究．除实验标识出样品的相变温度点外，根据试样中自由体积随温度的变化关系，对高分子液晶材料内部立链、侧链以及介晶基元的相变行为特点进行了探讨，并就与小分子液晶变化特点的一些不同做了解释．     

New liquid-crystalline isothiocyanates with high clearing points, low viscosities and strong nematic character

Bi-, tri- and tetra-ring liquid-crystalline compounds with an isothiocyanate group in the terminal position of the molecule and with an ethylene group in the central position have been synthesized. Phenyl, cyclohexyl, bicyclo[2,2,2]octyl, 1,3-dioxane and pyrimidinyl were used as the ring systems. Their transition temperatures and melting enthalpies have been determined. The relationship between the order of the rings in the molecule and the clearing points and melting points of the compounds is discussed. It is shown that these compounds are valuable components of liquid crystal mixtures, since they effectively raise their clearing points yet only have a small effect on the viscosity.     

New liquid-crystalline isothiocyanates with high clearing points,low viscosities and strong nematic character

Abstract

Bi-, tri- and tetra-ring liquid-crystalline compounds with an isothiocyanate group in the terminal position of the molecule and with an ethylene group in the central position have been synthesized. Phenyl, cyclohexyl, bicyclo[2,2,2]octyl, 1,3-dioxane and pyrimidinyl were used as the ring systems. Their transition temperatures and melting enthalpies have been determined. The relationship between the order of the rings in the molecule and the clearing points and melting points of the compounds is discussed. It is shown that these compounds are valuable components of liquid crystal mixtures, since they effectively raise their clearing points yet only have a small effect on the viscosity.     

Schiff碱类向列液晶熔融与清亮过程热力学

用差示扫描量热法及热台显微镜法研究了Schiff碱类向列液晶PEBAB及PBAPB的熔融与清亮过程.给出PEBAB的Tm=378.53K,△Hm=26.48±0.20kJ/mol,△Sm=69.96±0.53J/K.mol,Tc=399.80K,△Hc=929±53J/mol,△Sc=2.32±0.13J/K.mol;对于PBAPB,Tm(II)=352.86K,Tm(I)=354.74K,Tc=384.54K,△Hc=866±25J/mol,△Sc=2.25±0.07J/K.mol.在通过二次加热法消除熔前效应后,得到△Hm(I+II)=12.36±0.17kJ/mol,它不随升温速率改变而变化.本工作测得的清亮焓,在3%的偏差范围内符合平均场理论要求;△H1/△H2=T1/T2;所得清亮熵也与大多数向列型液晶相近.在PBAPB中,在318K左右,还观察到固→固相变等情况,相变焓是13.96±0.35kJ/mol.     

Liquid crystalline behaviours of some 3-perfluoroalkylbenzoate esters

A series of 3-perfluoroalkylbenzoate esters are synthesised. They tend to exhibit enantiotropic SmA and SmC phases. The clearing points are decreased with increasing the alkoxy chain length and show odd-even effect. With increasing the fluorocarbon chain length, the melting and clearing points increase; however, the SmC phase is suppressed.     

New isothiocyanato liquid crystals containing thieno[3,2-b]thiophene central core

New isothiocyanato liquid crystal (LC) materials based on thieno[3,2-b]thiophene core have been synthesised and characterised. Their mesomorphic and physical properties were evaluated. The results indicate that most of the new compounds exhibit only enantiotropic smectic A phases with high clearing points, and the difluorinated compounds (A3 and A6), in particular, also display a stable nematic phase with low melting points. Compared with the corresponding biphenyl and thiophene-phenyl analogues, these thieno[3,2-b]thiophene-based compounds possess increased birefringence (the highest value found to be 0.40) and mesogenic phase intervals. These new thieno[3,2-b]thiophene-based LCs exhibit a high birefringence and a high clearing point and are of potential use as components of high birefringence mixtures.     

含全氟烃基的联苯酯类液晶的合成及其介晶性

全氟烃或半氟烃链无手性液晶化合物可能呈现铁电液晶性, 具有较大的学术及应用价值而受到研究人员的重视. 合成了全氟己基苯甲酸联苯酯类液晶化合物: ROC₆H₄C₆H₄O₂CC₆H₄C₆F₁₃ (3a～3e), C₃H₇C₆H₄C₆H₄O₂CC₆H₄C₆F₁₃ (6a)及其烃衍生物. 用差示扫描量热法(DSC)和偏光显微镜(POM)对其介晶性研究发现: 烃衍生物呈有序度较低的向列相, 熔点较高, 清亮点较低, 液晶相较窄. 全氟烃基取代的化合物出现多个有序度较高的近晶相, 熔点较低, 清亮点高, 介晶相温度范围宽.     

Mesophase behaviour and thermal stability of octa-alkoxy substituted phthalocyaninatocobalt (II) complexes

Cobalt (II) phthalocyanines substituted with eight alkoxy chains in the peripheral (2, 3, 9, 10, 16, 17, 23, 24) positions were prepared. The alkoxy chain length was varied between n-butyloxy (C₄H₉O) and n-octadecyloxy (C₁₈H₃₇O). Studies by polarizing optical microscopy and high temperature X-ray diffraction revealed that all the complexes are liquid crystalline and that they exhibit a hexagonal columnar mesophase (Col_h). Transition enthalpies were determined by differential scanning calorimetry. The clearing point could only be observed for compounds with a chain length longer than C₁₃H₂₇O. Both the melting and clearing points decrease with increasing chain length. The transition temperatures of these discotic metallomesogens are higher than those of the corresponding metal-free phthalocyanines, but are comparable with those of the corresponding copper (II) compounds. The thermal decomposition of the compounds was studied by thermogravimetry.     

Synthesis and characterization of novel fluorinated bistolane-type liquid crystals

Three series of fluorinated bistolane-type liquid crystals have been synthesized. Their mesomorphic properties were studied by optical polarizing microscopy and DSC. These compounds exhibit only a broad nematic phase with high clearing points, wide phase transition temperatures and low melting points. The effects of lateral fluoro-substitution and the introduction of the tetrafluorophenylene moiety are discussed in detail.     

Synthesis and characterization of novel fluorinated bistolane-type liquid crystals

Three series of fluorinated bistolane-type liquid crystals have been synthesized. Their mesomorphic properties were studied by optical polarizing microscopy and DSC. These compounds exhibit only a broad nematic phase with high clearing points, wide phase transition temperatures and low melting points. The effects of lateral fluoro-substitution and the introduction of the tetrafluorophenylene moiety are discussed in detail.     

Synthesis and characterization of side chain liquid crystalline polymers exhibiting cholesteric and blue phases

A series of cyclosiloxane-based cholesteric liquid crystalline (LC) polymers were synthesized from a cholesteric LC monomer cholest-5-en-3-yl(3β) 4-(2-propenyloxy)benzoate and a nematic LC monomer butyl 4-[4-(2-propenyloxy)benzoxy]benzoate. All the polymers exhibit thermotropic LC properties and show cholesteric phases. Most of the polymers display four types of phase transition behaviour corresponding to glass transition, melting point, cholesteric phase-blue phase transition and clearing point. The mesophase temperature range of the blue phases are as broad as 20°C. The blue phase was confirmed by the apperance of planar textures and cubic packings. With an increase of non-chiral component in the polymers, the clearing point decreases slightly, while the glass transition and melting temperatures change little. In the reflection spectra of the polymer series the reflected wavelength broadens and shifts to longer wavelength with increase of the non-chiral component in the polymer systems, suggesting that the helical pitch P lengthens.     

Aromatic liquid crystals with a trifluoromethyl group in the terminal chain for use in nematic LC mixtures

A new class of compounds suitable for LCD applications has have synthesized, incorporating a trifluoromethyl group in the terminal alkoxy or alkenyloxy chain. These compounds fulfil many of the specifications for use in TN-LCDs. Compounds containing several aromatic rings were synthesized with a view to producing compounds of high birefringence. This aspect also included the synthesis of compounds containing a carbon-carbon triple bond. Materials with three phenyl rings were also prepared in an attempt to produce nematic liquid crystals with a high clearing point and a high birefringence. Molecules containing a lateral fluoro substituent were synthesized in order to generate a high positive value of the dielectric anisotropy, a low melting point and no smectic mesophases. A series of compounds incorporating a carbon-carbon double bond was prepared in an attempt to produce compounds with a high nematic clearing point and a high birefringence.     

Aromatic liquid crystals with a trifluoromethyl group in the terminal chain for use in nematic LC mixtures

A new class of compounds suitable for LCD applications has have synthesized, incorporating a trifluoromethyl group in the terminal alkoxy or alkenyloxy chain. These compounds fulfil many of the specifications for use in TN-LCDs. Compounds containing several aromatic rings were synthesized with a view to producing compounds of high birefringence. This aspect also included the synthesis of compounds containing a carbon-carbon triple bond. Materials with three phenyl rings were also prepared in an attempt to produce nematic liquid crystals with a high clearing point and a high birefringence. Molecules containing a lateral fluoro substituent were synthesized in order to generate a high positive value of the dielectric anisotropy, a low melting point and no smectic mesophases. A series of compounds incorporating a carbon-carbon double bond was prepared in an attempt to produce compounds with a high nematic clearing point and a high birefringence.     

官能化苯并菲盘状液晶的合成及不饱柔链对介晶性的影响

合成了12个含不饱和软链的苯并菲盘状液晶化合物,C18H6（OC5H11）6-x（OR）x（x=1,2,3）,R=-C3H6CH=CH2（a）,-C3H6C≡CH（b）,-C2H4OCH=CH2（c）.化合物结构通过核磁共振氢谱和高分辨质谱表征.化合物热致液晶性通过偏光显微镜（POM）,差视扫描热量法（DSC）,和X射线衍射（XRD）进行了研究.结果显示目标化合物呈现有序的六方柱状介晶相.端炔基链化合物b系列熔点最高.乙烯氧基柔链化合物c系列有最高的清亮点和最宽的介晶性温度范围,且随着不饱和醚链数的增多,清亮点明显升高.对称苯并菲化合物sym-C18H6（OC5H11）3（OR）3比不对称化合物asym-C18H6（OC5H11）3（OR）3具有更高的熔点和清亮点.乙烯氧基柔链可极化的偶极相互作用对液晶稳定性有较大贡献.     

Liquid crystal polymers. 15. Synthesis and liquid crystalline properties of alkyl-substituted polyesters

Alkyl substitution in a series of main chain, liquid crystal polyesters strongly depressed their glass temperatures, melting points, clearing points, and mesophase thermal stabilities. Polymers with pendant n-alkyl substituents eight carbon atoms or longer did not form a liquid crystal phase.     

含氟丁烯联苯类液晶新方法合成及性能

含氟丁烯类液晶是一类新型具有低熔点和较高清亮点的液晶材料。 本文提出了一条新的方法合成关键中间体,采用以3-氟苄氯为起始原料,经Arbuzov、Wittig-Horner、催化氢化、锂化-硼酸化4步反应制备,避免了环己烷的异构化和脱氟副反应。 经过合成优化,总收率由4.5%提高到30%,具备较高的应用价值。 物理性能测试表明,该类化合物在配方中的虚拟清亮点达到127.7 ℃、展区常数K₁₁值高达19.7。 光电测试表明,该类化合物能够缩短10%的液晶总响应时间,与该类化合物粘弹系数小的特点相吻合。 新型含氟丁烯液晶为开发高性能混合液晶提供了新的单体液晶材料。