WO2022105790A1 - 一种含环己烯结构的液晶化合物及其制备方法与应用 - Google Patents

一种含环己烯结构的液晶化合物及其制备方法与应用 Download PDF

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WO2022105790A1
WO2022105790A1 PCT/CN2021/131188 CN2021131188W WO2022105790A1 WO 2022105790 A1 WO2022105790 A1 WO 2022105790A1 CN 2021131188 W CN2021131188 W CN 2021131188W WO 2022105790 A1 WO2022105790 A1 WO 2022105790A1
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liquid crystal
crystal compound
compound containing
alkyl
cyclohexene structure
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PCT/CN2021/131188
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French (fr)
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戴雄
姜坤
刘殿君
孙建波
边坤
王美艳
赵佳
王庆一
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北京八亿时空液晶科技股份有限公司
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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
    • C09K19/34—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
    • 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
    • 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
    • C07D309/06—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
    • C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
    • 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
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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
    • 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
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    • 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 belongs to the technical field of liquid crystal compounds, and particularly relates to a liquid crystal compound containing a cyclohexene structure and a preparation method and application thereof.
  • Liquid crystal materials have many advantages as new display materials, such as extremely low power consumption and low driving voltage. At the same time, compared with other materials, it also has the advantages of small size, light weight, long life, large amount of displayed information, no electromagnetic radiation, etc. It can almost meet the requirements of various information display, especially in TFT-LCD (Thin Film Transistor Technology) products aspect.
  • TFT-LCD Thin Film Transistor Technology
  • TFT active matrix system there are mainly TN (Twisted Nematic, twisted nematic structure) mode, IPS (In-Plane Switching, plane switching) mode, FFS (Fringe Field Switching, fringe field switching technology) mode and VA ( Vertical Alignment, vertical orientation) mode and other main display modes.
  • TN Transmission Nematic, twisted nematic structure
  • IPS In-Plane Switching, plane switching
  • FFS Frringe Field Switching, fringe field switching technology
  • VA Vertical Alignment, vertical orientation
  • TFT-LCD product technology has gradually matured, successfully solving technical problems such as viewing angle, resolution, color saturation and brightness.
  • Large- and small-sized TFT-LCD displays have gradually occupied the mainstream position of flat-panel displays in their respective fields. .
  • the liquid crystal material is required to have a fast response speed, so the liquid crystal material is required to have as low a rotational viscosity ⁇ 1 as possible.
  • the first objective of the present invention is to provide a novel liquid crystal compound containing a cyclohexene structure, so as to improve the deficiencies of existing liquid crystal materials and enhance the application value of such liquid crystal compounds.
  • the liquid crystal compound of the present invention has the structure represented by the general formula (I):
  • a 1 is selected from a single bond or one of the following groups:
  • R 1 and R 2 are the same or different, and each is independently selected from -H, C 1 -C 7 alkyl or C 1 -C 7 alkoxy, wherein the C One or more -CH2- in a 1 - C7 alkyl group or a C1 - C7 alkoxy group can be optionally replaced by cyclopentyl, cyclopropyl or cyclobutyl.
  • R 1 is selected from a C 1 -C 7 alkyl group or a C 1 -C 7 alkoxy group
  • R 2 is selected from a C 1 -C 7 alkoxy group
  • one or more -CH 2 - in the C 1 -C 7 alkyl or C 1 -C 7 alkoxy group may be optionally replaced by cyclopentyl, cyclopropyl or cyclobutyl.
  • the A 1 is selected from one of the following groups:
  • liquid crystal compound of the present invention is selected from one or more of the following compounds:
  • the second object of the present invention is to provide the preparation method of above-mentioned liquid crystal compound, and its synthetic route is as follows:
  • R 1 , R 2 and A 1 are the same as above.
  • the method of the present invention may involve conventional post-processing if necessary, and the conventional post-processing is specifically as follows: extraction with dichloromethane, ethyl acetate or toluene, liquid separation, washing with water, drying, and evaporation on a vacuum rotary evaporator, the obtained
  • the product can be purified by vacuum distillation or recrystallization and/or chromatographic separation.
  • the liquid crystal compound of the present invention can be obtained stably and efficiently.
  • the third object of the present invention is to protect the composition containing the liquid crystal compound.
  • the addition amount of the above-mentioned liquid crystal compound is preferably 1-60%, more preferably 3-50%, and further preferably 5-25%.
  • the fourth object of the present invention is to protect the application of the liquid crystal compound and the composition containing the liquid crystal compound in the field of liquid crystal display, preferably in the liquid crystal display device, and the liquid crystal display device is more preferably a VA or PSVA display.
  • the liquid crystal display device is more preferably a VA or PSVA display.
  • the liquid crystal compound of the present invention has higher clearing point, relatively high optical anisotropy, low rotational viscosity, good thermal stability, chemical stability, optical stability and mechanical properties, and improves the liquid crystal
  • the response speed of the display device has the characteristics of better charge retention rate and the like.
  • the raw materials can be obtained from open commercial sources (for example, provided by Beijing Bayi Shikong).
  • a mixed solution of 44.8 g of propyltetrahydropyrancyclohexanone (BYLC-01-2) and 150 L of tetrahydrofuran was added dropwise, and the reaction temperature was maintained at -70 to -80°C. After the dropwise addition was completed, sampling and tracking were performed after the incubation for another 3 hours. When the remaining raw material was less than 0.5%, the reaction was stopped.
  • the filtrate was poured into a silica gel column packed with 100 g of silica gel, and the column was passed through the column at atmospheric pressure. After passing through the column, the light yellow column liquid was concentrated under reduced pressure.
  • the obtained column liquid was heated to 60.0 ⁇ 70.0°C, the degree of vacuum was -0.08 ⁇ -0.09MPa, concentrated, and recrystallized twice with absolute ethanol to obtain 54.6g of white solid, BYLC-01.
  • the purity is 99.9%, and the yield is 75%.
  • Example 1 Compared with Example 1, its synthetic route only carries out the simple replacement of raw material;
  • Example 3 Compared with Example 3, its synthetic route only carries out the simple replacement of raw material;
  • Example 3 Compared with Example 3, its synthetic route only carries out the simple replacement of raw material;
  • ⁇ 1 is detected by viscometer
  • ⁇ n is detected by Abbe refractometer
  • Cp is detected by differential calorimeter.
  • the liquid crystal compounds provided by the present invention have lower rotational viscosity ⁇ 1, larger optical anisotropy ⁇ n, and higher clarity than traditional compounds with similar chemical structures.
  • the bright spot Cp can improve the response time and increase the working temperature of the liquid crystal composition.
  • the invention provides a liquid crystal compound containing a cyclohexene structure and a preparation method and application thereof.
  • the cyclohexene structure-containing liquid crystal compound has a structure represented by the general formula (I).
  • the liquid crystal compound of the present invention has higher clearing point, relatively high optical anisotropy, low rotational viscosity, good thermal stability, chemical stability, optical stability and mechanical properties, etc., and can improve the liquid crystal
  • the response speed of the display device has the characteristics of good charge retention rate and the like, and has good economic value and application prospect.

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Abstract

本发明属于液晶化合物技术领域，具体涉及一种含环己烯结构的液晶化合物及其制备方法与应用。所述含环己烯结构的液晶化合物具有通式(I)所示结构。本发明所述液晶化合物具有更高的清亮点，比较高的光学各向异性，低的旋转粘度，具有良好的热稳定性、化学稳定性、光学稳定性及力学等方面的性能，可提高液晶显示装置的响应速度，同时具有较好电荷保持率等特点。

Description

一种含环己烯结构的液晶化合物及其制备方法与应用
交叉引用
本申请要求2020年11月20日提交的专利名称为“一种含环己烯结构的液晶化合物及其制备方法与应用”的第202011308752.6号中国专利申请的优先权，其全部公开内容通过引用整体并入本文。
技术领域
本发明属于液晶化合物技术领域，具体涉及一种含环己烯结构的液晶化合物及其制备方法与应用。
背景技术
自30年前发现可商业化的液晶材料以来。液晶材料在信息显示材料、有机光电子材料等领域中的应用具有极大的研究价值和美好的应用前景。液晶材料作为新型显示材料有许多优势，如功耗极低，驱动电压低。同时与其他材料相比，还具有体积小、重量轻、长寿命、显示信息量大、无电磁辐射等优点，几乎可以适应各种信息显示的要求，尤其在TFT-LCD(薄膜晶体管技术)产品方面。
在TFT有源矩阵的系统中，主要有TN(Twisted Nematic，扭曲向列结构)模式，IPS(In-Plane Switching，平面转换)模式，FFS(Fringe Field Switching，边缘场开关技术)模式和VA(Vertical Alignment，垂直取向)模式等主要显示模式。
目前，TFT-LCD产品技术已经逐渐成熟，成功地解决了视角、分辨率、色饱和度和亮度等技术难题，大尺寸和中小尺寸TFT-LCD显示器在各自的领域已逐渐占据平板显示器的主流地位。但是对于动态画面显示应用，如手机、电视，为了实现高品质显示，消除显示画面残影和拖尾，要求液晶材料具有很快的响应速度，因此要求液晶材料具有尽量低的旋转粘度γ1。
为了改善材料的性能使其适应新的要求，新型结构液晶化合物的合成及结构-性能关系的研究成为液晶领域的一项重要工作。
发明内容
本发明的第一目的是提供一种新型的含环己烯结构的液晶化合物，以改善现有液晶材料的不足，提升此类液晶化合物的应用价值。
本发明所述的液晶化合物，具有通式(I)所示结构：
Figure PCTCN2021131188-appb-000001
所述通式(I)中，R 1和R 2相同或不同，各自独立地选自-H、-Cl、-F、-CN、-OCN、-OCF 3、-CF 3、-CHF 2、-CH 2F、-OCHF 2、-SCN、-NCS、-SF 5、C 1-C 12的烷基或C 1-12的烷氧基，其中所述C 1-C 12的烷基或C 1-12的烷氧基中的一个或多个氢可任选地被氟或氯取代，且一个或多个-CH 2-可任选地被环戊基、环丙基或环丁基替代；
A 1选自单键或下列基团中的一种：
Figure PCTCN2021131188-appb-000002
优选的，通式(I)中，R 1和R 2相同或不同，各自独立地选自-H、C 1-C 7的烷基或C 1-C 7的烷氧基，其中所述C 1-C 7的烷基或C 1-C 7的烷氧基中的一个或多个-CH 2-可任选地被环戊基、环丙基或环丁基替代。
进一步优选的，通式(I)中，R 1选自C 1-C 7的烷基或C 1-C 7的烷氧基；R 2选自C 1-C 7的烷氧基；
其中所述C 1-C 7的烷基或C 1-C 7的烷氧基中的一个或多个-CH 2-可任选地被环戊基、环丙基或环丁基替代。
优选的，通式(I)中，所述A 1选自下列基团中的一种：
Figure PCTCN2021131188-appb-000003
优选地，本发明所述液晶化合物选自如下化合物的一种或几种：
Figure PCTCN2021131188-appb-000004
Figure PCTCN2021131188-appb-000005
Figure PCTCN2021131188-appb-000006
Figure PCTCN2021131188-appb-000007
Figure PCTCN2021131188-appb-000008
Figure PCTCN2021131188-appb-000009
Figure PCTCN2021131188-appb-000010
Figure PCTCN2021131188-appb-000011
Figure PCTCN2021131188-appb-000012
Figure PCTCN2021131188-appb-000013
Figure PCTCN2021131188-appb-000014
Figure PCTCN2021131188-appb-000015
Figure PCTCN2021131188-appb-000016
Figure PCTCN2021131188-appb-000017
Figure PCTCN2021131188-appb-000018
Figure PCTCN2021131188-appb-000019
本发明的第二目的是提供上述液晶化合物的制备方法，其合成路线如下：
Figure PCTCN2021131188-appb-000020
具体包括以下步骤：
1)
Figure PCTCN2021131188-appb-000021
与丁基锂制备锂试剂，锂试剂与
Figure PCTCN2021131188-appb-000022
反应，制得
Figure PCTCN2021131188-appb-000023
2)
Figure PCTCN2021131188-appb-000024
与对甲苯磺酸反应脱水，得
Figure PCTCN2021131188-appb-000025
其中，R 1、R 2、A 1的定义同上。
本发明所述的方法，在必要时会涉及常规后处理，所述常规后处理具体如：用二氯甲烷、乙酸乙酯或甲苯萃取，分液，水洗，干燥，真空旋转蒸发仪蒸发，所得产物用减压蒸馏或重结晶和/或色谱分离法提纯，即可。
采用上述制备方法能够稳定、高效地得到本发明所述的液晶化合物。
本发明的第三目的是保护含有所述液晶化合物的组合物。其中，上述液晶化合物的加入量以1～60％为宜，更优选3-50％，进一步优选为5～25％。本领域技术人员可以预见，基于上述液晶化合物的加入，能够进一步提高已有惯用液晶组合物的光学各向异性，具有缩短响应时间的技术效果。
本发明的第四目的是保护上述液晶化合物以及含有上述液晶化合物的组合物在液晶显示领域的应用，优选为在液晶显示装置中的应用，所述的液晶显示装置进一步优选为VA或PSVA显示器。将上述液晶组合物应用至液晶显示装置后，具有缩短响应时间的优点。
本发明具有如下有益效果：
本发明所述液晶化合物具有更高的清亮点，比较高的光学各向异性，低的旋转粘度，具有良好的热稳定性、化学稳定性、光学稳定性及力学等方面的性能，提高了液晶显示装置的响应速度，同时具有较好电荷保持率等特点。
具体实施方式
以下实施例用于说明本发明，但不用来限制本发明的范围。
所述原材料如无特别说明，均能从公开商业途径获得(如北京八亿时空提供)。
实施例1
本实施例涉及一种液晶化合物，其结构式如下：
Figure PCTCN2021131188-appb-000026
其合成路线如下：
Figure PCTCN2021131188-appb-000027
具体合成步骤如下：
1、BYLC-01的合成
向1L四口瓶中加入0.2L无水四氢呋喃，2,3-二氟苯乙醚(BYLC-01-1)31.6g(0.2mol)氮气置换排空3次。降温到-70度。滴加丁基锂2.5M 80ml控制滴加速度，控制温度在-70～-80℃。滴加完毕后，继续保温1h。
滴加44.8g丙基四氢吡喃环己酮(BYLC-01-2)与150L四氢呋喃的混合溶液，保持反应温度在-70～-80℃。滴加完毕，再保温3h后取样跟踪，当原料剩余＜0.5％时，停止反应。
向反应液中加入200mL甲苯，在80～90℃常压蒸馏四氢呋喃，蒸馏出大部分四氢呋喃，将反应液冷却至室温(20～30℃)，将反应液慢慢倒入0.2L盐酸与0.5L冰水配好的稀盐酸溶液中水解，外部用冷冻液冷却，控制温度在15～25℃。倒完后搅拌、静置、分液。水相用1L*2甲苯萃取两次，合并有机层，有机层用1L*2饱和食盐水洗两遍至中性。
将有机相进行(常压)浓缩，升温至110℃，所得浓缩液，GC主产物纯度88％，直接用于下一步脱水反应。
向51L四口瓶中加入浓缩液、10g对甲苯磺酸、1.5g BHT、100mL乙二醇，升温至110℃，反应液回流，用分水器分水。控制回流速度，3h后开始取样，约分出50g水。停止加热、搅拌至温度降到室温。
搅拌下向反应液中加入1L纯水，搅拌，静置后分出下层水相，上层有机相再加入0.2L纯水搅拌，静置后分液，合并水相用100mL甲苯萃取一次，将两次所得有机相合并用0.2L*3饱和盐水洗3遍，弃去水相。将所得有机相加入50g无水硫酸钠干燥2小时，过滤，滤饼用100mL甲苯淋洗。
将滤液压入100g硅胶装成的硅胶柱，开始常压过柱，过柱后浅黄色过柱液进行减压浓缩。
所得过柱液，升温至60.0～70.0℃，真空度-0.08～-0.09MPa，浓缩，无水乙醇重结晶两次 得白色固体54.6g，BYLC-01。纯度99.9％，收率75％。
采用GC-MS对所得白色固体BYLC-01进行分析，产物的m/z为3364.2(M+)。
实施例2
本实施例涉及一种液晶化合物，其结构式如下：
Figure PCTCN2021131188-appb-000028
其合成路线与实施例1相比仅进行原料的简单替换；
采用GC-MS对所得白色固体BYLC-02进行分析，产物的m/z为366.2(M+)。
实施例3
本实施例涉及一种液晶化合物，其结构式如下：
Figure PCTCN2021131188-appb-000029
采用GC-MS对所得白色固体BYLC-03进行分析，产物的m/z为364.2(M+)。
实施例4
本实施例涉及一种液晶化合物，其结构式如下：
Figure PCTCN2021131188-appb-000030
其合成路线与实施例3相比仅进行原料的简单替换；
采用GC-MS对所得白色固体BYLC-04进行分析，产物的m/z为366.2(M+)。
实施例5
本实施例涉及一种液晶化合物，其结构式如下：
Figure PCTCN2021131188-appb-000031
其合成路线与实施例3相比仅进行原料的简单替换；
采用GC-MS对所得白色固体BYLC-05进行分析，产物的m/z为392.2(M+)。
实施例6
本实施例涉及一种液晶化合物，其结构式如下：
Figure PCTCN2021131188-appb-000032
采用GC-MS对所得白色固体BYLC-06进行分析，产物的m/z为418.2(M+)。
实验例
本实验例涉及对实施例1～6所述化合物的相关性能测定。
按照本领域的常规检测方法，如γ1的检测采用粘度计测试，△n的检测采用阿贝折射仪测试，Cp的检测采用差示热量扫描仪测试。
通过线性拟合得到液晶化合物的各项性能参数，其中，各性能参数的具体含义如下：
△n代表光学各向异性(25℃)；γ1代表旋转粘度(mPa.s，25℃)；Cp代表清亮点。
将实施例1～6所制得的液晶化合物和对比例1～3液晶化合物的性能参数数据进行对比整理，检测结果如表1所示：
表1：液晶化合物的性能检测结果
Figure PCTCN2021131188-appb-000033
由表1的检测结果可以明显看出，本发明提供的液晶化合物与传统的相似化学结构化合物相比，具有较低的旋转粘度γ1，较大的光学各向异性△n，和更高的清亮点Cp，可改善响应时间，提高液晶组合物的工作温度。
虽然，上文中已经用一般性说明、具体实施方式及试验，对本发明作了详尽的描述，但在本发明基础上，可以对之作一些修改或改进，这对本领域技术人员而言是显而易见的。因此，在不偏离本发明精神的基础上所做的这些修改或改进，均属于本发明要求保护的范围。
工业实用性
本发明提供一种一种含环己烯结构的液晶化合物及其制备方法与应用。所述含环己烯结构的液晶化合物具有通式(I)所示结构。本发明所述液晶化合物具有更高的清亮点，比较高的光学各向异性，低的旋转粘度，具有良好的热稳定性、化学稳定性、光学稳定性及力学等方面的性能，可提高液晶显示装置的响应速度，同时具有较好电荷保持率等特点，具有较好的经济价值和应用前景。
Figure PCTCN2021131188-appb-000034

Claims (10)

  1. 一种含环己烯结构的液晶化合物，其特征在于，具有通式(I)所示的结构：
    Figure PCTCN2021131188-appb-100001
    所述通式(I)中，R 1和R 2相同或不同，各自独立地选自-H、-Cl、-F、-CN、-OCN、-OCF 3、-CF 3、-CHF 2、-CH 2F、-OCHF 2、-SCN、-NCS、-SF 5、C 1-C 12的烷基或C 1- 12的烷氧基，其中所述C 1-C 12的烷基或C 1- 12的烷氧基中的一个或多个氢可任选地被氟或氯取代，且一个或多个-CH 2-可任选地被环戊基、环丙基或环丁基替代；
    A 1选自单键或下列基团中的一种：
    Figure PCTCN2021131188-appb-100002
  2. 根据权利要求1所述的含环己烯结构的液晶化合物，其特征在于，R 1和R 2相同或不同，各自独立地选自-H、C 1-C 7的烷基或C 1-C 7的烷氧基；
    其中所述C 1-C 7的烷基或C 1-C 7的烷氧基中的一个或多个-CH 2-可任选地被环戊基、环丙基或环丁基替代。
  3. 根据权利要求2所述的含环己烯结构的液晶化合物，其特征在于，R 1选自C 1-C 7的烷基或C 1-C 7的烷氧基；R 2选自C 1-C 7的烷氧基；
    其中所述C 1-C 7的烷基或C 1-C 7的烷氧基中的一个或多个-CH 2-可任选地被环戊基、环丙基或环丁基替代。
  4. 根据权利要求1-3任一项所述的含环己烯结构的液晶化合物，其特征在于，所述A 1选自下列基团中的一种：
    Figure PCTCN2021131188-appb-100003
  5. 根据权利要求1所述的含环己烯结构的液晶化合物，其特征在于，所述通式(I)代表的液晶化合物选自以下结构中的一种或多种：
    Figure PCTCN2021131188-appb-100004
    Figure PCTCN2021131188-appb-100005
    Figure PCTCN2021131188-appb-100006
    Figure PCTCN2021131188-appb-100007
    Figure PCTCN2021131188-appb-100008
    Figure PCTCN2021131188-appb-100009
    Figure PCTCN2021131188-appb-100010
    Figure PCTCN2021131188-appb-100011
    Figure PCTCN2021131188-appb-100012
    Figure PCTCN2021131188-appb-100013
    Figure PCTCN2021131188-appb-100014
    Figure PCTCN2021131188-appb-100015
    Figure PCTCN2021131188-appb-100016
    Figure PCTCN2021131188-appb-100017
    Figure PCTCN2021131188-appb-100018
    Figure PCTCN2021131188-appb-100019
  6. 一种制备权利要求1～5任一项所述液晶化合物的方法，其特征在于，合成路线如下：
    Figure PCTCN2021131188-appb-100020
    具体包括以下步骤：
    1)
    Figure PCTCN2021131188-appb-100021
    与丁基锂制备锂试剂，锂试剂与
    Figure PCTCN2021131188-appb-100022
    反应，制得
    Figure PCTCN2021131188-appb-100023
    2)
    Figure PCTCN2021131188-appb-100024
    与对甲苯磺酸反应脱水，得
    Figure PCTCN2021131188-appb-100025
    其中，R 1、R 2、A 1的指代同权利要求1～5任一项所述。
  7. 一种液晶组合物，其特征在于，包括权利要求1～5任一项所述的液晶化合物。
  8. 根据权利要求7所述的液晶组合物，其特征在于，所述液晶化合物在所述液晶组合物中的质量百分比为1～60％，优选为3～50％，进一步优选为5～25％。
  9. 权利要求1-5任一项所述液晶化合物或权利要求7或8所述液晶组合物在液晶显示领域中的应用。
  10. 根据权利要求9所述的应用，其特征在于，所述液晶显示领域为液晶显示装置，优选的，所述液晶显示装置为VA或PSVA显示器。
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