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WO2017071575A1 - 具有负介电各向异性的液晶化合物及其应用 - Google Patents

具有负介电各向异性的液晶化合物及其应用 Download PDF

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WO2017071575A1
WO2017071575A1 PCT/CN2016/103328 CN2016103328W WO2017071575A1 WO 2017071575 A1 WO2017071575 A1 WO 2017071575A1 CN 2016103328 W CN2016103328 W CN 2016103328W WO 2017071575 A1 WO2017071575 A1 WO 2017071575A1
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liquid crystal
compound
dielectric anisotropy
negative dielectric
crystal composition
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PCT/CN2016/103328
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English (en)
French (fr)
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韩文明
徐爽
王盼盼
徐海彬
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江苏和成显示科技股份有限公司
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Publication of WO2017071575A1 publication Critical patent/WO2017071575A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D309/04—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • C09K19/44—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing compounds with benzene rings directly linked
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/137—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering

Definitions

  • the present invention relates to a liquid crystal compound, particularly a liquid crystal compound having negative dielectric anisotropy, a method for synthesizing the same, and an application thereof.
  • the liquid crystal display element can be used in various household electric appliances, measurement equipment, automobile panels, word processors, computers, printers, televisions, and the like represented by watches and clocks and electronic calculators.
  • PC phase change
  • TN tunnel nematic
  • STN super twisted nematic
  • ECB electrically controlled
  • Birefringence electronically controlled birefringence
  • OCB optical compensated bend
  • IPS in-plane switching
  • VA vertical alignment
  • CSH color super homeotropic
  • the PM is divided into static (static) and multiplex (multiplex) types.
  • the AM is classified into a TFT (thin film transistor), a MIM (metal insulator metal), and the like.
  • the types of TFTs are amorphous silicon and polycrystalline silicon. The latter is classified into a high temperature type and a low temperature type according to a manufacturing process.
  • the liquid crystal display element is classified into a reflection type using natural light, a transmission type using a backlight, and a semi-transmissive type using both natural light and backlight depending on the type of the light source.
  • the IPS mode, the ECB mode, the VA mode, or the CSH mode are different from the conventional TN mode or the STN mode in that the former uses a liquid crystal material having a negative dielectric anisotropy.
  • an AM-driven VA-type display is used in a display element requiring a high-speed and wide viewing angle, and among them, the most desirable one is application to a liquid crystal element such as a television.
  • the liquid crystal material used is required to have a low driving voltage, a high response speed, a wide operating temperature range, a large absolute value of negative dielectric anisotropy, a high phase transition temperature, and good mutual solubility.
  • a highly conjugated molecular structure has a tendency to be inferior in compatibility with other liquid crystal materials, and is difficult to be used as a constituent element of a liquid crystal composition having good electrical characteristics.
  • a liquid crystal compound used as a constituent element of a liquid crystal composition requiring light stability such as a liquid crystal display device of a thin film transistor type is required to have high stability.
  • a liquid crystal display element containing a liquid crystal composition having a large absolute value of dielectric anisotropy can lower the basic voltage value, lower the driving voltage, and further reduce the power consumption.
  • a large number of hydrogen-substituted liquid crystal compounds on a benzene ring have been studied for a long time as a component of a liquid crystal composition having negative dielectric anisotropy which can be used for a liquid crystal display element.
  • the side fluorine-containing negative compounds such as Ref.2 and Ref.3 avoid the disadvantages of the bis-cyano-negative compound, the negative dielectric anisotropy value is too small (Ref. 2 dielectric anisotropy literature). The value is -4.1, and the Ref. 3 dielectric anisotropy literature value is -6.0). Therefore, compounds with large negative dielectric side fluorine species still need to be explored.
  • low temperature stable liquid crystal compound such that the composition containing the liquid crystal compound has large dielectric anisotropy, low threshold voltage, fast response speed, high contrast, good mutual solubility, and good light stability And low temperature stability.
  • Another object of the present invention is to provide a method of synthesizing the above liquid crystal composition.
  • Still another object of the present invention is to provide use of the above liquid crystal compound for preparing a liquid crystal composition and a display containing the same.
  • the present invention provides a compound having a negative dielectric anisotropy, the compound having the structure of Formula I:
  • R 1 and R 2 are the same or different and each independently represents an alkyl group of 1 to 10 carbon atoms;
  • X 1 and X 2 are each different and independently represent -O- or -CH 2 -;
  • R 1 and R 2 are the same or different and each independently represents an alkyl group of 1 to 6 carbon atoms.
  • the Z represents a single bond, -CH 2 O- or -CH 2 CH 2 -.
  • the Z represents a single bond or -CH 2 CH 2 -.
  • the compound of Formula I is selected from the group consisting of one or more of the following Formulae I-A through I-F:
  • the R1 and R2 are the same or different and each independently represents an alkyl group of 1 to 6 carbon atoms.
  • the compound of Formula I is preferably selected from the group consisting of one or more of the following formulae:
  • the R1 and R2 are the same or different and each independently represents an alkyl group of 1 to 6 carbon atoms.
  • the compound of Formula I-A is preferably selected from the group consisting of one or more of the following structures:
  • the compound of Formula I-B is preferably selected from the group consisting of one or more of the following structures:
  • the compound of Formulas I-C is preferably selected from the group consisting of one or more of the following structures:
  • the compound of Formulas I-D is preferably selected from the group consisting of one or more of the following structures:
  • the compound of Formulas I-E is preferably selected from the group consisting of one or more of the following structures:
  • the compound of Formulas I-F is preferably selected from the group consisting of one or more of the following structures:
  • Another aspect of the present invention provides a liquid crystal composition comprising the liquid crystal compound of the formula I of the present invention.
  • the liquid crystal composition further comprises a group consisting of one or more of Formulas II, III, and/or IV:
  • the R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are the same or different and each independently represents a substituted or unsubstituted linear or branched alkyl or alkoxy group of 1 to 10 carbon atoms. a substituted or unsubstituted linear or branched alkenyl or alkenyloxy group of 2 to 10 carbon atoms, wherein one or more -CH 2 - may be substituted by -O-, provided that the oxygen atom is not Directly connected;
  • the m and n are the same or different and each independently represents 0 or 1.
  • Another aspect of the present invention provides a display device comprising the liquid crystal composition of the present invention.
  • Another aspect of the present invention provides an application comprising the liquid crystal composition of the present invention in VA, FFS, IPS, PSVA display modes.
  • the liquid crystal compound of the formula I provided by the present invention and other negative liquid crystal compounds of the prior art Compared with a larger absolute value of dielectric anisotropy, a low viscosity, and a high voltage holding ratio, the composition containing the liquid crystal compound has large dielectric anisotropy, low threshold voltage, and fast response speed. High contrast, good mutual solubility and good light stability and low temperature stability; and the preparation process of the liquid crystal compound of the formula I of the invention, the raw materials are easy to obtain, the synthesis route is simple and easy, and it is suitable for large-scale industrial production.
  • the refractive index anisotropy was measured at 25 ° C under a sodium light (589 nm) light source using an Abbe refractometer; the dielectric test box was a TN90 type, and the cell thickness was 7 ⁇ m.
  • ⁇ ⁇ - ⁇ , where ⁇ is the dielectric constant parallel to the molecular axis, ⁇ is the dielectric constant perpendicular to the molecular axis, test conditions: 25°C, 1KHz, test box is TN90 type, box thickness 7 ⁇ m.
  • VHR (initial) is tested using TOY06254 liquid crystal physical property evaluation system; pulse voltage: 5V 6HZ, test temperature is 60 ° C, test unit period is 166.7 ms;
  • liquid crystal compounds of the general formula I prepared by the following examples were tested for optical anisotropy and clearing points and the extrapolation parameters were determined as follows:
  • the commercial liquid crystal No. TS023 produced by Jiangsu Hecheng Display Technology Co., Ltd. was selected as the precursor, and the liquid crystal compound represented by Formula I was dissolved in the parent liquid crystal (10% by weight) to test the optical anisotropy of the mixture. Clearing point and dielectric anisotropy, and liquid crystal performance data of the liquid crystal compound represented by Formula I was extrapolated according to a linear relationship according to the ratio added in the matrix.
  • the parent liquid crystal (host) is obtained by mixing the following compounds in a ratio of 20%:40%:40%:
  • the compound represented by the following Table 1 can be converted by the compound C and the compound A to obtain other target compounds:
  • liquid crystal properties of the above target compounds are as follows:
  • Example 1 Representative compound data of the formulae I-A, I-B, I-C and I-D are provided in Example 1, by the liquid crystal compounds I-A-9, I-A-11 of Example 1, The data of I-B-9, I-B-10, I-C-19 and I-D-19 can be seen that the liquid crystals contained in the formulae I-A, I-B, I-C and I-D The compounds all have large absolute values of dielectric anisotropy.
  • T -10 ° C indicates the storage stability of the mixture of the compounds I-A-9, I-A-11, I-B-9, V and the parent liquid crystal host in a ratio of 10:90 at -10 °C.
  • the compound of the invention Compared with the prior art compound V, the compound of the invention has a larger absolute value of dielectric anisotropy and higher Voltage retention and stable low temperature stability.
  • Example 3 The liquid crystal composition of Example 3 was prepared according to each compound and weight percentage listed in Table 3, and was filled in the performance test between the two substrates of the liquid crystal display.
  • the test data is shown in the following table:
  • Example 4 The liquid crystal composition of Example 4 was prepared according to each compound and weight percentage listed in Table 4, and was filled in the performance test between the two substrates of the liquid crystal display.
  • the test data is shown in the following table:
  • Example 5 The liquid crystal composition of Example 5 was prepared according to each compound and weight percentage listed in Table 5, and was filled in the performance test between the two substrates of the liquid crystal display. The test data are shown in the following table:
  • the liquid crystal composition has good liquid crystal properties, and the compound of the present invention has achieved very good technical effects.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Liquid Crystal Substances (AREA)

Abstract

本发明提供一种具有负介电各向异性的通式Ⅰ的液晶化合物，所述液晶化合物具有大的介电各向异性绝对值、高的电压保持率、良好的互溶性以及良好的光稳定性和低温稳定性，并且本发明通式Ⅰ的液晶化合物的制备过程，原料易得，合成路线简单易行，适合规模化工业生产，本发明还提供了一种包含所述液晶化合物的液晶组合物，所述液晶组合物具有良好的液晶性能。

Description

具有负介电各向异性的液晶化合物及其应用 技术领域
本发明涉及一种液晶化合物，尤其是具有负介电各向异性的液晶化合物及其合成方法及应用。
背景技术
液晶显示元件可以在以钟表、电子计算器为代表的家庭用各种电器、测定机器、汽车用面板、文字处理机、电脑、打印机、电视等中使用。作为夜景显示方式，在其代表性的方式中，可以列举PC(phase change，相变)、TN(twist nematic，扭曲向列)、STN(super twisted nematic，超扭曲向列)、ECB(electrically controlled birefringence，电控双折射)、OCB(optically compensated bend，光学补偿弯曲)、IPS(in-plane switching，共面转变)、VA(vertical alignment，垂直配向)、CSH(color super homeotropic，彩色超垂面)等类模式。根据元件的驱动方式分为PM(passive matrix，被动矩阵)型和AM(active matrix，主动矩阵)型。PM分为静态(static)和多路(multiplex)等类型。AM分为TFT(thin film transistor，薄膜晶体管)、MIM(metal insulator metal，金属-绝缘层-金属)等类型。TFT的类型有非晶硅(amorphous silicon)和多晶硅(polycrystal silicon)。后者根据制造工艺分为高温型和低温型。液晶显示元件根据光源的类型分为利用自然光的反射型、利用背光的透过型、以及利用自然光和背光两种光源的半透过型。
在这些显示方式中，IPS模式、ECB模式、VA模式或CSH模式等与现在常用的TN模式或STN模式不同在于，前者使用具有负介电各向异性的液晶材料。在这些显示方式中，尤其是通过AM驱动的VA型显示，在要求高速且宽视角的显示元件中的应用，其中，最值得期待的是在电视等液晶元件中的应用。
无论何种显示模式均要求所使用的液晶材料具有低的驱动电压、高的响应速度、宽的操作温度范围、负介电各向异性的绝对值较大、相转移温度高以及良好的互溶性。然而，现有技术中，具有高度共轭的分子结构，存在与其他液晶材料的相容性差的倾向，而难以用作具有良好电气特性的液晶组合物的构成要素。另外，对于作为薄膜晶体管方式的液晶显示元件等的要求光稳定性的液晶组合物的构成要素而使用的液晶性化合物而言，要求高稳定性。而含有介电各向异性的绝对值大的液晶组合物的液晶显示元件能够降低基础电压值、降低驱动电压，并能进一步降低消耗电功率。
长久以来，可用于液晶显示元件的具有负介电各项异性的液晶组合物的成分，已经研究了大量的苯环上的氢被取代的液晶化合物。
Osman,M.A.在Molec.crystals liq.Crystals,82,295.公开了Ref.1结构的负介电各向异性化合物：
Figure PCTCN2016103328-appb-000001
由于化合物Ref.1分子侧边的两个氰基，使该分子具有很大的负介电各向异性(文献值为-20)。该文献同时指出这类侧边双氰基的负介电各向异性化合物具有如下缺点：1)粘度大；2)与液晶单体互溶性差；3)光稳定性差。由于以上缺点，限制了该类负性化合物的应用。
Reiffenrath等在liquid crystals，1989，Vol.5,No.1,159-170中提出了Ref.2、Ref.3的含氟负性化合物，以避免双氰基负性化合物的缺点：
Figure PCTCN2016103328-appb-000002
虽然Ref.2、Ref.3这类侧边含氟负性化合物避免了双氰基负性化合物的缺点，但是导致了负介电各向异性值过小(Ref.2介电各向异性文献值为-4.1，Ref.3介电各向异性文献值为-6.0)的问题。所以，具有大的负介电的侧边含氟的化合物仍然需要探索。
因此，为了适应越来越高的应用需求，本领域内存在着持续改进负介电各向异性的液晶化合物的需求。
发明内容
发明目的：本发明的目的是提供了一种液晶化合物，所述液晶化合物具有大的介电各向异性绝对值、低的粘度、较高的电压保持率、良好的互溶性以及良好的光稳定性和低温稳定性的液晶化合物，使得包含所述液晶化合物的组合物具有大介电各向异性、低的阈值电压、快的响应速度、高的对比度、良好的互溶性以及良好的光稳定性和低温稳定性。
本发明的另一目的是提供一种合成上述液晶组合物的合成方法。
本发明的再一目的是提供上述液晶化合物制备液晶组合物及其含有液晶组合物的显示器中的应用。
技术方案：为了完成上述发明目的，本发明提供了一种具有负介电各向异性的化合物，所述化合物具有通式Ⅰ结构：
Figure PCTCN2016103328-appb-000003
其中，
R1和R2相同或不同，各自独立地表示1-10个碳原子的烷基；
X1和X2各不相同，独立地表示-O-或-CH2-；
Z表示单键、-CH2O-、-CH2CH2-、-COO-或-CH＝CH-。
在本发明的一些实施方式中，所述R1和R2相同或不同，各自独立地表示1-6个碳原子的烷基。
在本发明的一些实施方式中，所述Z表示单键、-CH2O-或-CH2CH2-。
在本发明的一些实施方式中，所述Z表示单键或-CH2CH2-。
在本发明的一些实施方式中，所述通式Ⅰ的化合物选自如下通式Ⅰ-A至Ⅰ-F中的一种或多种组成的组：
Figure PCTCN2016103328-appb-000004
Figure PCTCN2016103328-appb-000005
以及
Figure PCTCN2016103328-appb-000006
其中，
所述R1和R2相同或不同，各自独立地表示1-6个碳原子的烷基。
在本发明的一些实施方式中，所述通式Ⅰ的化合物优选自如下通式中的一种或多种组成的组：
Figure PCTCN2016103328-appb-000007
Figure PCTCN2016103328-appb-000008
以及
Figure PCTCN2016103328-appb-000009
其中，
所述R1和R2相同或不同，各自独立地表示1-6个碳原子的烷基。
在本发明的一些实施方式中，所述通式Ⅰ-A的化合物优选自如下结构中的一种或多种组成的组：
Figure PCTCN2016103328-appb-000010
Figure PCTCN2016103328-appb-000011
Figure PCTCN2016103328-appb-000012
以及
Figure PCTCN2016103328-appb-000013
在本发明的一些实施方式中，所述通式Ⅰ-B的化合物优选自如下结构中的一种或多种组成的组：
Figure PCTCN2016103328-appb-000014
Figure PCTCN2016103328-appb-000015
Figure PCTCN2016103328-appb-000016
以及
Figure PCTCN2016103328-appb-000017
在本发明的一些实施方式中，所述通式Ⅰ-C的化合物优选自如下结构中的一种或多种组成的组：
Figure PCTCN2016103328-appb-000018
Figure PCTCN2016103328-appb-000019
Figure PCTCN2016103328-appb-000020
Figure PCTCN2016103328-appb-000021
以及
Figure PCTCN2016103328-appb-000022
在本发明的一些实施方式中，所述通式Ⅰ-D的化合物优选自如下结构中的一种或多种组成的组：
Figure PCTCN2016103328-appb-000023
Figure PCTCN2016103328-appb-000024
Figure PCTCN2016103328-appb-000025
以及
Figure PCTCN2016103328-appb-000026
在本发明的一些实施方式中，所述通式Ⅰ-E的化合物优选自如下结构中的一种或多种组成的组：
Figure PCTCN2016103328-appb-000027
以及
Figure PCTCN2016103328-appb-000030
在本发明的一些实施方式中，所述通式Ⅰ-F的化合物优选自如下结构中的一种或多种组成的组：
Figure PCTCN2016103328-appb-000031
Figure PCTCN2016103328-appb-000032
Figure PCTCN2016103328-appb-000033
Figure PCTCN2016103328-appb-000034
以及
Figure PCTCN2016103328-appb-000035
本发明的另一方面提供一种包含本发明的通式Ⅰ的液晶化合物的液晶组合物。
在本发明的一些实施方式中，所述液晶组合物，还包含通式Ⅱ、Ⅲ和\或Ⅳ中的一种或多种组成的组：
Figure PCTCN2016103328-appb-000036
Figure PCTCN2016103328-appb-000037
以及
Figure PCTCN2016103328-appb-000038
其中，
所述R3、R4、R5、R6、R7和R8相同或不同，各自独立的表示1-10个碳原子的取代或未被取代的直链或支链烷基或烷氧基，2-10个碳原子的取代或未被取代的直链或支链烯基或烯氧基，其中，一个或多个-CH2-可以被-O-取代，其前提是氧原子不直接相连；
所述m和n相同或不同，各自独立的表示0或1。
本发明的另一方面提供一种包含本发明所述液晶组合物的显示器件。
本发明的另一方面提供一种包含本发明所述液晶组合物在VA、FFS、IPS、PSVA显示模式的中的应用。
有益效果：本发明所提供的具有通式Ⅰ的液晶化合物与现有技术其它负性液晶化合物 相比，具有更大的介电各向异性绝对值、低的粘度、高的电压保持率，包含所述液晶化合物的组合物具有大介电各向异性、低的阈值电压、快的响应速度、高的对比度、良好的互溶性以及良好的光稳定性和低温稳定性；并且本发明通式Ⅰ的液晶化合物的制备过程，原料易得，合成路线简单易行，适合规模化工业生产。
具体实施方式
以下将结合具体实施方案来说明本发明。需要说明的是，下面的实施例为本发明的示例，仅用来说明本发明，而不用来限制本发明。在不偏离本发明主旨或范围的情况下，可进行本发明构思内的其它组合和各种改良。
为便于表达，以下各实施例中，液晶化合物的基团结构用表1所列的代码表示：
表1液晶化合物的基团结构代码
Figure PCTCN2016103328-appb-000039
以下实施例中测试项目的简写代号如下：
                              清亮点(向列-各向同性相转变温
Cp：
                              度，℃)
Δn                           折射率各向异性(589nm，20℃)
Δε                          介电各向异性(1KHz，25℃)
VHR                           初始电压保持率(％)
其中，折射率各向异性使用阿贝折光仪在钠光灯(589nm)光源下、25℃测试得；介电测试盒为TN90型，盒厚7μm。
Δε＝ε‖-ε⊥，其中，ε‖为平行于分子轴的介电常数，ε⊥为垂直于分子轴的介电常数，测试条件：25℃、1KHz、测试盒为TN90型，盒厚7μm。
VHR(初始)是使用TOY06254型液晶物性评价系统测试得；脉冲电压：5V 6HZ，测试温度为60℃，测试单位周期为166.7ms；
下述实施例制备所得的通式Ⅰ所示液晶化合物均按照如下方法进行光学各向异性和清亮点的测试以及外推参数的测定：
选取江苏和成显示科技股份有限公司生产的编号为TS023的商品液晶作为母体，将通式Ⅰ所示液晶化合物以10％的重量比例溶解于母体液晶(host)中，测试混合物的光学各向异性、清亮点和介电各向异性，并根据母体中所添加比例依照线性关系外推出通式Ⅰ所示液晶化合物的液晶性能数据。
母体液晶(host)为下述化合物按照20％：40％：40％的比例混合所得：
Figure PCTCN2016103328-appb-000040
Figure PCTCN2016103328-appb-000041
以及
Figure PCTCN2016103328-appb-000042
母体液晶其性能参数测试结果如下：
Cp：112 Δn：0.08 Δε：5.0 VHR：98.1％。
实施例1
化合物Ⅰ-A-9合成路线如下所示：
Figure PCTCN2016103328-appb-000043
1)合成化合物B
500ml三口瓶中，加入8.6g化合物A，9.7g 2,3-二氟溴苯，100ml甲苯，50ml乙醇，50ml水，21.2g碳酸钠，氮气保护下，加入0.3g Pd(PPh3)4，加热回流6h后，分液，水洗，柱层析得白色固体化合物B 10.1g，GC>97％,收率：84.2％
2)合成化合物D
250ml三口瓶中，加入6g化合物B，100ml无水四氢呋喃，氮气保护下，降温至-78℃，滴加10.5ml正丁基锂的正己烷溶液(2.4mol/L)，保温搅拌2h，滴加2.6g化合物C和10ml无水四氢呋喃的混合溶液，并控温至-65～-70℃之间，滴加完毕后，保温搅拌1h，然后将反应液倒入冰水混合物中，甲基叔丁基醚提取，分液，水洗，蒸除溶剂后得到化合物D 8g(0.02mol)，不用提纯，直接用于下一步反应。
3)合成化合物Ⅰ-A-9
250ml三口瓶中，加入上步所得8g(0.02mol)化合物D，100ml二氯甲烷，降温至-75℃，加入5.8g三乙基硅烷和10ml二氯甲烷的混合溶液，然后，滴加0.05mol的三氟化硼乙醚，保温搅拌3h，自然升温至-10℃，将反应液倒入碳酸氢钠和冰水的混合物中，分液，水洗，柱层析提纯，得到白色化合物3.2g，即为Ⅰ-A-9，GC>99％,收率：43.7％。
化合物Ⅰ-A-9的表征数据：
MS:M+366(41％)267(100％)240(55％)。
依据上述合成方法，可以利用下表1所示化合物通过化合物C和化合物A的变换，从而得到其它目标化合物：
表1
Figure PCTCN2016103328-appb-000044
Figure PCTCN2016103328-appb-000045
上述目标化合物的液晶性能如下所示：
Figure PCTCN2016103328-appb-000046
实施例1中提供了通式Ⅰ-A、Ⅰ-B、Ⅰ-C和Ⅰ-D中具有代表性的化合物数据，通过实施例1中液晶化合物Ⅰ-A-9、Ⅰ-A-11、Ⅰ-B-9、Ⅰ-B-10、Ⅰ-C-19和Ⅰ-D-19的数据可以看出，通式Ⅰ-A、Ⅰ-B、Ⅰ-C和Ⅰ-D中包含的液晶化合物均具有大的介电各向异性绝对值。
实施例2
将化合物Ⅰ-A-9、化合物Ⅰ-A-11、化合物Ⅰ-B-9、化合物Ⅴ与母体液晶(host)按照10:90比例混合，外推法测试各化合物的液晶参数如下表2所示：
Figure PCTCN2016103328-appb-000047
表2
  Cp(℃) Δn Δε VHR(％) T-10℃
Ⅰ-A-9 75.2 0.126 -8.2 97.0 >144h
Ⅰ-A-11 71.6 0.12 -8.0 97.1 >144h
Ⅰ-B-9 62.6 0.124 -8.5 97.0 >144h
Ⅴ 183 0.18 -5.7 94.0 <72h
host 112 0.08 5.0 98.1 -
注：T-10℃表示化合物Ⅰ-A-9、Ⅰ-A-11、Ⅰ-B-9、Ⅴ与母体液晶host按照10:90比例混合组成的混合物在-10℃时存储稳定性。
与现有技术化合物Ⅴ相比，本发明所述化合物具有更大的介电各向异性绝对值及更高 的电压保持率和稳定的低温稳定性。
实施例3
按表3中所列的各化合物及重量百分数配制成实施例3的液晶组合物，其填充于液晶显示器两基板之间进行性能测试，测试数据如下表所示：
表3液晶组合物配方及其测试性能
Figure PCTCN2016103328-appb-000048
实施例4
按表4中所列的各化合物及重量百分数配制成实施例4的液晶组合物，其填充于液晶显示器两基板之间进行性能测试，测试数据如下表所示：
表4液晶组合物配方及其测试性能
Figure PCTCN2016103328-appb-000049
实施例5
按表5中所列的各化合物及重量百分数配制成实施例5的液晶组合物，其填充于液晶显示器两基板之间进行性能测试，测试数据如下表所示：
表5液晶组合物配方及其测试性能
Figure PCTCN2016103328-appb-000050
通过实施例3、4及5的数据可以看出，本发明化合物应用于液晶组合物时，液晶组合物具有良好的液晶性能，本发明的化合物取得了非常好的技术效果。
以上所述，仅是本发明的较佳实施例而已，并非对本发明作任何形式上的限制，虽然本发明已以较佳实施例揭露如上，然而并非用以限定本发明，任何熟悉本专业的技术人员，在不脱离本发明技术方案范围内，当可利用上述揭示的技术内容作出些许更动或修饰为等同变化的等效实施例，但凡是未脱离本发明技术方案内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均仍属于本发明技术方案的范围内。

Claims (9)

  1. 一种具有负介电各向异性的化合物，所述化合物具有通式Ⅰ结构：
    Figure PCTCN2016103328-appb-100001
    其中，
    R1和R2相同或不同，各自独立地表示1-10个碳原子的烷基；
    X1和X2各不相同，独立地表示-O-或-CH2-；
    Z表示单键、-CH2O-、-CH2CH2-、-COO-或-CH＝CH-。
  2. 根据权利要求1所述的具有负介电各向异性的化合物，其特征在于，所述Z表示单键、-CH2O-或-CH2CH2-。
  3. 根据权利要求1所述的具有负介电各向异性的化合物，其特征在于，所述Z表示单键或-CH2CH2-。
  4. 根据权利要求1所述的具有负介电各向异性的化合物，其特征在于，所述R1和R2相同或不同，各自独立地表示1-6个碳原子的烷基。
  5. 根据权利要求1所述的具有负介电各向异性的化合物，其特征在于，所述通式Ⅰ的化合物选自如下通式Ⅰ-A至Ⅰ-F中的一种或多种组成的组：
    Figure PCTCN2016103328-appb-100002
    其中，
    所述R1和R2相同或不同，各自独立地表示1-6个碳原子的烷基。
  6. 一种包含权利要求1～5中任一项所述具有负介电各向异性的化合物的液晶组合物。
  7. 根据权利要求6所述具有负介电各向异性的化合物的液晶组合物，其特征在于，所述液晶组合物还包含通式Ⅱ、Ⅲ和\或Ⅳ中的一种或多种组成的组：
    Figure PCTCN2016103328-appb-100003
    其中，
    所述R3、R4、R5、R6、R7和R8相同或不同，各自独立的表示1-10个碳原子的取代或未被取代的直链或支链烷基或烷氧基，2-10个碳原子的取代或未被取代的直链或支链烯基或烯氧基，其中，一个或多个-CH2-可以被-O-取代，其前提是氧原子不直接相连；
    所述m和n相同或不同，各自独立的表示0或1。
  8. 一种包含权利要求6所述具有负介电各向异性的化合物的液晶组合物的显示器件。
  9. 权利要求6所述具有负介电各向异性的化合物的液晶组合物在VA、FFS、IPS、PSVA显示模式中的应用。
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