WO2019242095A1 - 一种含有二氟甲氧基桥键的液晶化合物及其制备方法和应用 - Google Patents

一种含有二氟甲氧基桥键的液晶化合物及其制备方法和应用 Download PDF

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WO2019242095A1
WO2019242095A1 PCT/CN2018/102613 CN2018102613W WO2019242095A1 WO 2019242095 A1 WO2019242095 A1 WO 2019242095A1 CN 2018102613 W CN2018102613 W CN 2018102613W WO 2019242095 A1 WO2019242095 A1 WO 2019242095A1
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liquid crystal
carbon atoms
compound
atom
alkyl group
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PCT/CN2018/102613
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French (fr)
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栾兆昌
丰佩川
史子谦
蔡宗佑
董向波
张伟
朱翠英
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烟台显华化工科技有限公司
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    • 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
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • 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
    • C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
    • 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
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • 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
    • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
    • C09K2019/0466—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the linking chain being a -CF2O- chain
    • 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
    • C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
    • C09K2019/3422—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a six-membered ring

Definitions

  • the invention relates to a liquid crystal compound containing a difluoromethoxy bridge bond, a preparation method and application thereof, and belongs to the field of liquid crystal display materials.
  • Liquid crystal has been widely used in computers, notebook computers, LCD TVs, and so on.
  • the basic principle of using liquid crystal as a display material is: as the electric field intensity changes, the liquid crystal molecules will rotate regularly 90 degrees, which changes the light transmittance, and the liquid crystal will change from disorderly transparent to orderly non-transparent, which will produce light According to this principle, the brightness of each pixel in the image can be controlled according to this principle, so as to form the required image.
  • Liquid crystal display methods are not the same, and can be roughly divided into thin film transistor liquid crystal display (TFT-LCD), cholesteric nematic liquid crystal display (CH-N), super twisted nematic liquid crystal display (STN-LCD), guest-host type Liquid crystal display (GH-LCD), twisted nematic liquid crystal display (TN-LCD), polymer scattering liquid crystal display (PDLC), ferroelectric liquid crystal display (FLCD).
  • TFT-LCD thin film transistor liquid crystal display
  • CH-N cholesteric nematic liquid crystal display
  • STN-LCD super twisted nematic liquid crystal display
  • GH-LCD guest-host type Liquid crystal display
  • TN-LCD twisted nematic liquid crystal display
  • PDLC polymer scattering liquid crystal display
  • FLCD ferroelectric liquid crystal display
  • TFT is equipped with a thin film transistor on its back. Its role is to control the individual pixels on the screen. This control will significantly improve the smoothness of the image display, and the contrast will be more obvious. At the same time, it has a higher voltage retention rate. , Low refractive index, low viscosity and other characteristics, even under strong light conditions still display clearly, usually called true color, so TFT-LCD is a common display on the market.
  • IPS in-plane switching
  • FFS fringe-field switching
  • VA vertical alignment
  • other display modes both in-plane switching (IPS) and fringe field switching (FFS) have a wide viewing angle.
  • IPS in-plane switching
  • FFS fringe field switching
  • the positive liquid crystal is used in the IPS / FFS display mode, it can obtain a fast response and has good reliability; while the negative liquid crystal is used in the IPS / FFS display mode, it can obtain a higher transmittance, but due to the negative liquid crystal The viscosity is relatively large, so the response speed is slow.
  • IPS in-plane switching IPS in-plane switching
  • FFS fringe-field switching
  • the positive and negative liquid crystals have light transmittance. The difference is mainly reflected in the transmittance efficiency of the liquid crystal at the center of the pixel electrode interval. Because, at the center of the pixel electrode gap, the elastic force of the positive liquid crystal molecules is weaker than that of the negative liquid crystal. If the positive liquid crystal is to obtain the same light utilization efficiency, the ⁇ nd value is larger than that of the negative liquid crystal. Therefore, for the above two modes, the previous solution is to increase the transmittance from the perspective of the liquid crystal, and a negative component can be added to the positive liquid crystal.
  • the negative liquid crystal compound is different from the positive liquid crystal in the synthesis method and processing process. Generally, after the negative liquid crystal molecules are subjected to UV irradiation, the voltage retention and resistivity will be greatly reduced, that is, the negative liquid crystal. Molecules have inferior UV stability compared to positive liquid crystal molecules. In addition, negative liquid crystal molecules usually have a larger rotational viscosity than positive molecules, which is not conducive to improving the response time.
  • the present invention addresses the above-mentioned shortcomings of the prior art, and provides a liquid crystal compound containing a difluoromethoxy bridge.
  • the liquid crystal compound not only improves the transmittance, but also has fast response time and good ultraviolet stability, thereby improving the contrast of the liquid crystal display.
  • a liquid crystal compound containing a difluoromethoxy bridge the compound has the general structure I:
  • R 1 independently represents an H atom, an alkyl group containing 1 to 7 carbon atoms or any H atom substituted with an F atom, an alkyl group containing 1 to 7 carbon atoms, or an alkoxy group containing 1 to 6 carbon atoms or An alkoxy group having 1 to 6 carbon atoms substituted with any H atom by an F atom, an alkenyl group containing 2 to 6 carbon atoms, or an alkenyl group containing 2 to 6 carbon atoms where any H atom is replaced with an F atom
  • L 1 and L 2 each independently represent an H or F atom
  • X 1 independently represents F, Cl, an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, an olefin group having 2 to 6 carbon atoms, and 2 to 6 carbon atoms Any one of a halogenated alkenyl group, a halogenated alkoxy group having 1 to 6 carbon atoms, or a halogenated alkenyl group having 2 to 6 carbon atoms;
  • n 0 or 1.
  • R 1 represents an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms;
  • X 1 independently represents any of F, a halogenated alkyl group having 1 to 6 carbon atoms, a halogenated alkoxy group having 2 to 5 carbon atoms, or a halogenated alkenyl group having 2 to 5 carbon atoms.
  • the compound of the general formula I is selected from one of the following general formulas I-1 to I-12:
  • R 1 represents an alkyl group containing 1 to 5 carbon atoms.
  • the present invention introduces a negative polar group into the positive liquid crystal molecular structure, which not only improves the transmittance, but also has a fast response time and good ultraviolet stability, thereby improving the contrast of the liquid crystal display.
  • the present invention also provides a method for preparing a liquid crystal compound having the general structure I as described above, including the following steps:
  • Compound b is obtained by taking hydrogen from a strong base and reacting with difluorodibromide to obtain compound c;
  • the strong base is butyllithium, LDA, potassium tert-butoxide, HMDSLi or sodium hydrogen.
  • the present invention also provides a liquid crystal composition including the liquid crystal compound containing a difluoromethoxy bridge bond according to any one of the above.
  • the mass of the liquid crystal compound accounts for 1-70% of the total mass of the liquid crystal composition.
  • the mass of the liquid crystal compound accounts for 3-50% of the total mass of the liquid crystal composition.
  • the invention also provides an application of the liquid crystal composition as described above in the field of liquid crystal displays.
  • step 2 the reaction solution was cooled to -78 ° C, 40 ml of butyllithium was added dropwise at -78 ° C, and stirred for 1 h.
  • step 2 20 g of difluorodibromomethane was added dropwise, naturally allowed to rise to room temperature, and stirred for 6 h.
  • Add 150 ml of toluene and 150 ml of water containing 7.5 ml of concentrated hydrochloric acid stir for 0.5 h, and separate the layers to obtain an organic layer.
  • the organic phase was spin-dried to give 31 g of compound 8.
  • step 2 the reaction solution was cooled to -78 ° C, 36 ml of butyllithium was added dropwise at -78 ° C, and stirred for 1 h. At -78 ° C, 19 g of difluorodibromomethane was added dropwise, naturally allowed to rise to room temperature, and stirred for 6 h. Add 150 ml of toluene and 150 ml of water, stir for 0.5 h, and separate the layers to obtain an organic layer. The organic phase was spin-dried to give 37 g of compound 15.
  • the liquid crystal compound of the invention has the characteristics of low rotational viscosity, high clearing point, good stability and UV resistance, and good mutual solubility. Because the H atom is replaced by the F atom at the 2-position of the benzene ring in front of the difluoromethoxy bridge, the dielectric perpendicular to the long axis of the liquid crystal is increased. In the IPS-TFT, FFS-TFT display mode, The transmittance is greatly improved, and because the system does not need to specifically add a single crystal with negative dielectric anisotropy, the stability of the system and the UV resistance are also greatly improved.

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  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Nonlinear Science (AREA)
  • Engineering & Computer Science (AREA)
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  • Organic Chemistry (AREA)
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Abstract

提供一种含有二氟甲氧基桥键的液晶化合物及其制备方法和应用。该液晶化合物具有如通式Ⅰ的结构。通过在正性液晶分子结构上引入负性极性基团，既提高了穿透率，同时又具备快的响应时间，紫外稳定性良好，从而提高了液晶显示器的对比度。

Description

一种含有二氟甲氧基桥键的液晶化合物及其制备方法和应用 技术领域
本发明涉及一种含有二氟甲氧基桥键的液晶化合物及其制备方法和应用，属于液晶显示材料领域。
背景技术
液晶现在已经被广泛地应用到计算机、笔记本电脑的显示屏、液晶电视等。用液晶做显示材料的基本原理是：随着电场强度的变化液晶分子会做有规律的90度旋转，从而改变了透光度，液晶会从无序透明变为有序非透明，会产生明暗的变化，可以依据此原理控制图像上每个像素的明暗，从而构成所需的图像。
液晶的显示方式并不相同，大概可分为薄膜晶体管液晶显示(TFT-LCD)、胆甾向列相变液晶显示(CH-N)、超扭曲向列液晶显示(STN-LCD)、宾主型液晶显示(GH-LCD)、扭曲向列液晶显示(TN-LCD)、聚合物散射型液晶显示(PDLC)、铁电液晶显示(FLCD)。如果单单用TN型液晶，则显示器只有黑白两种颜色，STN显示器主要是以橘黄色和淡绿色为主，为此需要给它加一层带有彩色的滤光片，当通过滤光片时会显示出三原色，三原色经过一定的比例显示就能显示出彩色图像。TFT则在其背部设置了薄膜晶体管，它的作用是控制屏幕上各个独立的像素，这种控制会显著提高图像显示的流畅度，对比度也会更加的明显同时因为它具备较高的电压保持率、低折射率、低黏度等特征，即使在光线较强的条件下依然显示清晰，通常称为真彩色，所以TFT-LCD是市场上常见的显示器。
目前市场上有各种不同的显示模式，比较具有竞争力的显示模式主要有，面内切换(in-plane switching,IPS)边缘场切换(fringe-field switching,FFS)，和垂直排列(vertical alignment,VA)等显示模式。在这些显示模式中，面内切换(IPS)和边缘场切换(FFS)都具有宽视角的特点。当正性液晶用于IPS/FFS显示模式时可以获得快速响应，并且有良好的可靠性；而负性液晶用于IPS/FFS显示模式时可以获得更高的透过率，但是由于负性液晶黏度比较大，所以响应速度较慢。
针对目前的宽视角显示模式IPS面内切换(in-pline switching,IPS),边缘场切换(fringe-field switching,FFS),这两种模式中，正性液晶和负性液晶在光透过率上的差异，主要体现在像素电极间隔中心的液晶的透过率效率上。因为，在像素电极间隔中心，正性液晶分子转动的弹性力量比负性液晶的要弱。如果正性液晶要获得相同的光利用效率，△nd值要比负性液晶的大。所以针对以上两种模式，之前的解决方案是从液晶角度提高穿透率可以在正性液晶中添加负性组分。
而负性液晶化合物由于在合成方法和处理工艺上于正性液晶的区别，通常负性液晶分子在经过UV照射后，电压保持率和电阻率均会有较大幅度的降低，即负性液晶分子相较于正性液晶分子而言具有较差的紫外稳定性。除此之外，负性液晶分子通常较正性分子具有较大的旋转黏度，不利于响应时间的提高。
发明内容
本发明针对上述现有技术的不足，提供一种含有二氟甲氧基桥键的液晶化合物。该液晶化合物既提高了穿透率，同时具备快的响应时间，紫外稳定性良好，从而提高液晶显示器的对比度。
本发明解决上述技术问题的技术方案如下：
一种含有二氟甲氧基桥键的液晶化合物，所述化合物具有通式Ⅰ结构：
Figure PCTCN2018102613-appb-000001
其中，R 1独立的表示H原子、含有1～7个碳原子的或任意H原子被F原子取代的含有1～7个碳原子的烷基、含有1～6个碳原子的烷氧基或任意H原子被F原子取代的含有1～6个碳原子的烷氧基、含有2～6个碳原子的链烯基或任意H原子被F原子取代的含有2～6个碳原子的链烯基、和含有3～5个碳原子的链烯氧基或任意H原子被F原子取代的含有3～5个碳原子的链烯氧基中的一种；
Figure PCTCN2018102613-appb-000002
独立的表示
Figure PCTCN2018102613-appb-000003
Figure PCTCN2018102613-appb-000004
表示下列基团中的一种或多种:
Figure PCTCN2018102613-appb-000005
L 1、L 2各自独立的分别表示H或F原子；
X 1独立的表示F、Cl、碳原子数为1-6的烷基、碳原子数为1-6的卤代烷基、碳原子数为2-6的烯烃基、碳原子数为2-6的卤代烯烃基、碳原子数为1-6的卤代烷氧基或碳原子数为2-6的卤代烯氧基中的任意一种；
m表示0或1。
进一步的，所述R 1表示含有1～6个碳原子的烷基、或含有1～5个碳原子的烷氧基；
X 1独立的表示F、碳原子数为1-6的卤代烷基、碳原子数为2-5的卤代烷氧基或碳原子数为2-5的卤代烯氧基中的任一种。
进一步的，所述通式Ⅰ的化合物选自如下通式Ⅰ-1至Ⅰ-12中的一种：
Figure PCTCN2018102613-appb-000006
Figure PCTCN2018102613-appb-000007
R 1表示含有1～5个碳原子的烷基。
有益效果：本发明在正性液晶分子结构上引入负性极性基团，既提高了穿透率，同时具备快的响应时间，紫外稳定性良好，从而提高液晶显示器的对比度。
本发明还提供一种制备如上述的具有通式Ⅰ结构的液晶化合物的方法，包括如下步骤：
(1)化合物a通过格氏、suzuki偶联合成化合物b；
Figure PCTCN2018102613-appb-000008
(2)所述化合物b通过强碱夺氢后，与二氟二溴反应后得化合物c；
(3)所述化合物c与酚在碱性条件下得最终化合物。
进一步的，所述强碱为丁基锂，LDA，叔丁醇钾，HMDSLi或钠氢。
本发明还提供一种液晶组合物，包括上述任一项所述的含有二氟甲氧基桥键的液晶化合物。
进一步的，所述液晶化合物的质量占所述液晶组合物总质量的1-70％。
进一步的，所述液晶化合物的质量占所述液晶组合物总质量的3-50％。
本发明还提供一种如上述的液晶组合物在液晶显示器领域中的应用。
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他组合和各种改良。
实施例1
Figure PCTCN2018102613-appb-000009
Scheme:
Figure PCTCN2018102613-appb-000010
1 40g对丙基溴苯，54g硼酸三丁酯，200ml THF混合；在60℃下将20ml混合液滴入到含有5.7g镁屑氮气保护的三口烧瓶中，4滴溴乙烷引发；反应引发后，将剩余混合液滴入，控制内温在65℃，滴加完后，68℃保温4h。冷却，加入20ml浓盐酸和200ml水搅拌0.5h，加入200mlEA，分层；有机相用饱和食盐水洗涤3次，干燥，旋干，用100ml石油醚在-10℃重结晶，得29.5g化合物1。
2 29.5g化合物1，38.2g 2,3,5-三氟溴苯，60g磷酸钾，0.5g四三苯基磷钯，300ml甲苯，在氮气保护下90℃搅拌8h。冷却，用饱和食盐水洗涤有机相3次，无水硫酸钠干燥，过滤，旋干，蒸馏得40g化合物2。
3 40g化合物2溶于200mlTHF中，冷却到-78℃，将84ml丁基锂在-78℃下滴入，搅拌1h。在-78℃下，将35g二氟二溴甲烷滴入，自然升 至室温，搅拌6h。加入300ml甲苯和300ml含有15ml浓盐酸的水，搅拌0.5h，分层，得有机层。有机相旋干，得60g化合物3。
4 60g化合物3，24g 3，4，5-三氟苯酚，17g碳酸钾在200mlTHF中50℃搅拌8h。旋干，加入200ml甲苯，用去离子水洗涤4次，干燥，旋干，用乙醇在0℃下重结晶2次得30gⅠ-1。Purity:99.9％。
实施例2
Figure PCTCN2018102613-appb-000011
Scheme:
Figure PCTCN2018102613-appb-000012
1 20.9g 2,6-二氟-4-溴苯酚，21g全氟代3-溴丙烯，13g碳酸钾在150ml THF中50℃搅拌8h。旋干，加入200ml甲苯，用去离子水洗涤4次，干燥，旋干，蒸馏得30g化合物4。
2 30g化合物4溶于200mlTHF中，冷却到-78℃，将40ml丁基锂在-78℃下滴入，搅拌1h。在-78℃下，将23g硼酸三丁酯滴入，自然升至室温，搅拌6h。加入200ml甲苯和100ml含有20ml浓盐酸的水，搅拌0.5h，分层，得有机层。有机相旋干，加入100mlTHF，120g双氧水，25℃下搅拌12h。旋干，用30g 1：1＝乙醇：水混合液重结晶，得19.3g化合物5。
3 19.3g化合物5，10.3g 3，4，5-三氟苯酚，8.2g碳酸钾在200mlTHF中50℃搅拌8h。旋干，加入200ml甲苯，用去离子水洗涤4次，干燥，旋干，用乙醇在10℃下重结晶2次得20gⅠ-2。Purity:99.9％。
实施例3
Figure PCTCN2018102613-appb-000013
Scheme:
Figure PCTCN2018102613-appb-000014
1 20.9g 2,3,5-三氟溴苯溶于150mlTHF中，冷却到-78℃，将44ml丁基锂在-78℃下滴入，搅拌1h。在-78℃下，将7.3g DMF滴入，自然升至室温，搅拌6h。加入200ml甲苯和100ml含有12ml浓盐酸的水，搅拌0.5h，分层；有机相干燥，旋干得14.4化合物6。
2 14.4g化合物6，11.8g 2-正丙基丙烷-1，3-二醇，0.02g对甲基苯磺酸，100ml甲苯回流除水8h。
3步骤2中反应液冷却到-78℃，将40ml丁基锂在-78℃下滴入，搅拌1h。在-78℃下，将20g二氟二溴甲烷滴入，自然升至室温，搅拌6h。加入150ml甲苯和150ml含有7.5ml浓盐酸的水，搅拌0.5h，分层，得有机层。有机相旋干，得31g化合物8。
4 31g化合物8，11.8g 3，4，5-三氟苯酚，9.5g碳酸钾在200mlTHF中50℃搅拌8h。旋干，加入200ml甲苯，用去离子水洗涤4次，干燥，旋干，用乙醇在10℃下重结晶2次得15gⅠ-5。Purity:99.9％。
实施例4
Figure PCTCN2018102613-appb-000015
Scheme:
Figure PCTCN2018102613-appb-000016
1 31g实施例3所制备的化合物8，22g实施例2所制备的化合物5，9.5g碳酸钾在200mlTHF中50℃搅拌8h。旋干，加入200ml甲苯，用去离子水洗涤4次，干燥，旋干，用乙醇在-10℃下重结晶2次得18gⅠ-6。Purity:99.9％。
实施例5
Figure PCTCN2018102613-appb-000017
Scheme:
Figure PCTCN2018102613-appb-000018
1 27.5g对溴丙基联苯，25g硼酸三丁酯，200ml THF混合；在60℃下20ml混合液滴入到含有2.5g镁屑氮气保护的三口烧瓶中，4滴溴乙烷引发；反应引发后，将剩余混合液滴入，控制内温在65℃，滴加完后，68℃保温4h。冷却，加入10ml浓盐酸和200ml水搅拌0.5h，加入200mlEA，分层；有机相用饱和食盐水洗涤3次，干燥，旋干，用50ml石油醚在-10℃重结晶，得21.6g化合物9。
2 21.6g化合物9，19.1g 2,3,5-三氟溴苯，30g磷酸钾，0.3g四三苯基磷钯，200ml甲苯，在氮气保护下90℃搅拌8h。冷却，用饱和食盐水洗涤有机相3次，无水硫酸钠干燥，过滤，旋干，乙醇重结晶得22.8g化合物10。
3 22.8g化合物10溶于200mlTHF中，冷却到-78℃，将30ml丁基锂在-78℃下滴入，搅拌1h。在-78℃下，将17g二氟二溴甲烷滴入，自然升至室温，搅拌6h。加入150ml甲苯和150ml含有7.5ml浓盐酸的水，搅拌0.5h，分层，得有机层。有机相旋干，得31.7g化合物11。
4 31.7g化合物11，11g 3，4，5-三氟苯酚，7.5g碳酸钾在100mlTHF中50℃搅拌8h。旋干，加入100ml甲苯，用去离子水洗涤4次，干燥，旋干，用乙醇在0摄氏度下重结晶2次得15gⅠ-7。Purity:99.9％。
实施例6
Figure PCTCN2018102613-appb-000019
Scheme:
Figure PCTCN2018102613-appb-000020
1 21.1g 2,3,5-三氟溴苯，25g硼酸三丁酯，200ml THF混合；在60℃下20ml混合液滴入到含有2.5g镁屑氮气保护的三口烧瓶中，4滴溴乙烷引发；反应引发后，将剩余混合液滴入，控制内温在65℃，滴加完后，68℃保温4h。冷却，加入10ml浓盐酸和200ml水搅拌0.5h，加入200mlEA，分层；有机相用饱和食盐水洗涤3次，干燥，旋干，用50ml石油醚在-10℃重结晶，得15.8g化合物12。
2 15.8g化合物12，16.6g对溴苯甲醛，30g磷酸钾，0.3g四三苯基磷钯，200ml甲苯，在氮气保护下90℃搅拌8h。冷却，用饱和食盐水洗涤有机相3次，无水硫酸钠干燥，过滤，旋干，蒸馏得18.8g化合物13。
3 18.8g化合物13，9.4g 2-正丙基丙烷-1，3-二醇，0.02g对甲基苯磺酸，100ml甲苯回流除水8h。
4步骤2中反应液冷却到-78℃，将36ml丁基锂在-78℃下滴入，搅拌1h。在-78℃下，将19g二氟二溴甲烷滴入，自然升至室温，搅拌6h。加入150ml甲苯和150ml水，搅拌0.5h，分层，得有机层。有机相旋干，得37g化合物15。
5 37g化合物15，11.8g 3，4，5-三氟苯酚，8.5g碳酸钾在100mlTHF中50℃搅拌8h。旋干，加入100ml甲苯，用去离子水洗涤4次，干燥，旋干，用乙醇在0摄氏度下重结晶2次得25gⅠ-11。Purity:99.9％。
本发明所述液晶化合物具有旋转粘度低，较高的清亮点，稳定性及抗UV能力好，互溶性好等特点。由于在二氟甲氧基桥键前面的苯环2位上用F原子取代了H原子，增大了垂直于液晶长轴方向的介电，在IPS-TFT,FFS-TFT显示模式中，较大幅度提高了透过率，且因为体系中不需要专门添加负的介电各项异性的单晶，因此体系稳定系及抗UV能力也有极大提高。
本发明可用其他的不违背本发明的精神或主要特征的具体形式来概述。 因此，无论从哪一点来看，本发明的上述实施方案都只能认为是对本发明的说明而不能限制本发明，权利要求书指出了本发明的范围，而上述的说明并未指出本发明的范围，因此，在与本发明的权利要求书相当的含义和范围内的任何改变，都应认为是包括在本发明的权利要求书的范围内。

Claims (9)

  1. 一种含有二氟甲氧基桥键的液晶化合物，其特征在于，所述化合物具有通式Ⅰ结构：
    Figure PCTCN2018102613-appb-100001
    其中，R 1独立的表示H原子、含有1～7个碳原子的或任意H原子被F原子取代的含有1～7个碳原子的烷基、含有1～6个碳原子的烷氧基或任意H原子被F原子取代的含有1～6个碳原子的烷氧基、含有2～6个碳原子的链烯基或任意H原子被F原子取代的含有2～6个碳原子的链烯基、和含有3～5个碳原子的链烯氧基或任意H原子被F原子取代的含有3～5个碳原子的链烯氧基中的一种；
    Figure PCTCN2018102613-appb-100002
    独立的表示
    Figure PCTCN2018102613-appb-100003
    Figure PCTCN2018102613-appb-100004
    表示下列基团中的一种或多种:
    Figure PCTCN2018102613-appb-100005
    L 1、L 2各自独立的分别表示H或F原子；
    X 1独立的表示F、Cl、碳原子数为1-6的烷基、碳原子数为1-6的卤代烷基、碳原子数为2-6的烯烃基、碳原子数为2-6的卤代烯烃基、碳原子数为1-6的卤代烷氧基或碳原子数为2-6的卤代烯氧基中的任意一种；
    m表示0或1。
  2. 根据权利要求1所述的含有二氟甲氧基桥键的液晶化合物，其特征在于，所述R 1表示含有1～6个碳原子的烷基、或含有1～5个碳原子的烷氧基；
    X 1独立的表示F、碳原子数为1-6的卤代烷基、碳原子数为2-5的卤代烷氧基或碳原子数为2-5的卤代烯氧基中的任一种。
  3. 根据权利要求2所述的含有二氟甲氧基桥键的液晶化合物，其特征在于，所述通式Ⅰ的化合物选自如下通式Ⅰ-1至Ⅰ-12中的一种：
    Figure PCTCN2018102613-appb-100006
    R 1表示含有1～5个碳原子的烷基。
  4. 一种制备具有通式Ⅰ结构的含有二氟甲氧基桥键的液晶化合物的方法，其特征在于，包括如下步骤：
    (1)化合物a通过格氏、suzuki偶联合成化合物b；
    Figure PCTCN2018102613-appb-100007
    (2)所述化合物b通过强碱夺氢后，与二氟二溴反应后得化合物c；
    (3)所述化合物c与酚在碱性条件下得最终化合物。
  5. 如权利要求4所述的方法，其特征在于，所述强碱为丁基锂，LDA， 叔丁醇钾，HMDSLi或钠氢。
  6. 一种液晶组合物，其特征在于，包括权利要求1～3任一项所述的含有二氟甲氧基桥键的液晶化合物。
  7. 如权利要求6所述的液晶组合物，其特征在于，所述液晶化合物的质量占所述液晶组合物总质量的1-70％。
  8. 如权利要求6所述的液晶组合物，其特征在于，所述液晶化合物的质量占所述液晶组合物总质量的3-50％。
  9. 一种如权利要求8所述的液晶组合物在液晶显示器领域中的应用。
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