WO2022142821A1 - 一种液晶化合物及其制备方法与应用 - Google Patents

一种液晶化合物及其制备方法与应用 Download PDF

Info

Publication number
WO2022142821A1
WO2022142821A1 PCT/CN2021/131193 CN2021131193W WO2022142821A1 WO 2022142821 A1 WO2022142821 A1 WO 2022142821A1 CN 2021131193 W CN2021131193 W CN 2021131193W WO 2022142821 A1 WO2022142821 A1 WO 2022142821A1
Authority
WO
WIPO (PCT)
Prior art keywords
liquid crystal
carbon atoms
crystal compound
crystal display
alkenyloxy group
Prior art date
Application number
PCT/CN2021/131193
Other languages
English (en)
French (fr)
Inventor
戴雄
姜坤
边坤
刘殿君
王美艳
赵佳
王庆一
Original Assignee
北京八亿时空液晶科技股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 北京八亿时空液晶科技股份有限公司 filed Critical 北京八亿时空液晶科技股份有限公司
Publication of WO2022142821A1 publication Critical patent/WO2022142821A1/zh

Links

Classifications

    • 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
    • C09K19/3491—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur as hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes
    • 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
    • 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
    • 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
    • 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
    • C09K2019/0448—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 end chain group being a polymerizable end group, e.g. -Sp-P or acrylate

Definitions

  • the invention belongs to the technical field of liquid crystal compounds, and particularly relates to a liquid crystal compound and a preparation method and application thereof.
  • liquid crystal materials as environmental materials in information display materials, organic optoelectronic materials and other fields has great research value and bright application prospects.
  • 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 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 driving voltage of the liquid crystal needs to be as low as possible, so it is required to increase the dielectric anisotropy ⁇ of the liquid crystal.
  • liquid crystal materials are required to have a wide range of performance parameters in order to meet the requirements of various performance parameters of liquid crystal display devices and adapt to the technological requirements of liquid crystal display devices.
  • dielectric anisotropy ⁇ of the liquid crystal it is also necessary to have a suitable optical anisotropy and a higher cooling point.
  • the synthesis of new liquid crystal compounds and the study of structure-property relationship have become an important work in the field of liquid crystals.
  • the first object of the present invention is to provide a new type of liquid crystal compound 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):
  • R 1 represents H, an alkenyl group having 2-12 carbon atoms or an alkenyloxy group having 2-12 carbon atoms; wherein, the alkene having 2-12 carbon atoms
  • Z represents a single bond, -O- or -OCH 2 -;
  • A stands for single bond, cyclobutyl, cyclopropyl, cyclohexyl
  • R 2 represents H, represents an alkyl group having 1-12 carbon atoms, an alkenyl group having 2-12 carbon atoms or an alkenyloxy group having 2-12 carbon atoms.
  • the R 1 represents an alkenyloxy group having 2-7 carbon atoms
  • R 2 represents H, represents an alkyl group having 1-7 carbon atoms, an alkenyl group having 2-7 carbon atoms or an alkenyloxy group having 2-7 carbon atoms;
  • the R 1 represents an alkenyloxy group having 2-7 carbon atoms, and the oxygen in the alkenyloxy group is connected to the carbon atom on the benzene ring in the general formula (I).
  • the liquid crystal compound that meets the technological requirements of the liquid crystal display device in the present invention is for the purpose of research and development.
  • the left side is further supplemented with alkenyloxy end groups
  • the right side is supplemented with other groups, which not only has a proper negative dielectric anisotropy ⁇ and a proper clearing point Cp, but also reduces the rotational viscosity ⁇ 1.
  • the response time of the liquid crystal display device is effectively shortened.
  • 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 , Z, and A are as described above.
  • the third object of the present invention is to provide a liquid crystal composition comprising the liquid crystal compound of the present invention.
  • the mass percentage of the liquid crystal compound in the liquid crystal composition is 1-60%, preferably 3-50%, more preferably 5-25%.
  • the fourth object of the present invention is to protect the application of the above-mentioned liquid crystal compound and the composition containing the above-mentioned liquid crystal compound in the field of liquid crystal display, preferably in the application of liquid crystal display device, and the liquid crystal display device is more preferably TN, ADS, VA , PSVA, FFS or IPS LCD monitor.
  • the liquid crystal compound of the present invention has larger optical anisotropy ⁇ n, lower rotational viscosity ⁇ 1 and better mutual solubility while maintaining proper negative dielectric anisotropy ⁇ and proper clearing point Cp can improve the mutual solubility of the liquid crystal composition, widen the liquid crystal phase range of the liquid crystal composition, increase the working temperature range of the liquid crystal display, and effectively shorten the response time of the liquid crystal display device.
  • the raw materials can be obtained from open commercial channels unless otherwise specified.
  • Example 1 the following liquid crystal compounds can be synthesized by simply replacing the corresponding raw materials without changing any substantive operation.
  • the resulting white solid BYLC-06 was analyzed by GC-MS and the product had m/z of 402.49 (M+).
  • This experimental example involves the determination of the relevant properties of the compounds described in the examples and comparative examples.
  • ⁇ is detected by INSTEC liquid crystal detection instrument
  • ⁇ 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 maintain a proper negative dielectric anisotropy.
  • ⁇ and appropriate clearing point Cp it has larger optical anisotropy ⁇ n, lower rotational viscosity ⁇ 1, and better mutual solubility, which can improve the mutual solubility of liquid crystal compositions and broaden the liquid crystal composition of liquid crystal compositions.
  • the phase range is increased, the operating temperature range of the liquid crystal display is increased, and the response time of the liquid crystal display device is effectively shortened.
  • the present invention provides a liquid crystal compound and its preparation method and application.
  • the liquid crystal compound has a structure represented by the general formula (I).
  • the liquid crystal compound of the present invention has larger optical anisotropy ⁇ n and lower rotational viscosity ⁇ 1 while maintaining proper negative dielectric anisotropy ⁇ and proper clearing point Cp, which can improve the liquid crystal composition.
  • the mutual solubility of the liquid crystal composition broadens the liquid crystal phase range of the liquid crystal composition, increases the working temperature range of the liquid crystal display, and effectively shortens the response time of the liquid crystal display device, which has good economic value and application prospect.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mathematical Physics (AREA)
  • Liquid Crystal Substances (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明属于液晶化合物技术领域，具体涉及一种液晶化合物及其制备方法与应用。所述液晶化合物具有通式(I)所示结构。本发明所述液晶化合物在保持适当的负介电各向异性△ε及适当的清亮点Cp的同时，更具有大的光学各向异性△n，较低的旋转粘度γ1，可改善液晶组合物的互溶性，拓宽液晶组合物的液晶相范围，增加液晶显示器的工作温度范围，且有效缩短了液晶显示装置的响应时间。

Description

一种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12月28日提交的专利名称为“一种液晶化合物及其制备方法与应用”的第202011581201.7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，具体涉及一种液晶化合物及其制备方法与应用。
背景技术
液晶材料作为环境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。对于动态画面显示应用，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。另外，为了降低液晶显示器件的能耗，需要液晶的驱动电压尽量低，因此要求提高液晶的介电各向异性△ε。
液晶材料作为液晶显示器件的核心功能材料，为满足液晶显示器件的各种性能参数的要求，适应液晶显示器件的工艺要求，需要液晶材料具有广泛的多种性能参数，在降低液晶材料旋转粘度γ1，提高液晶的介电各向异性△ε的基础上还需要具有合适的光学各向异性，较高的清凉点。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，本发明所述液晶化合物具有通式(I)所示的结构：
Figure PCTCN2021131193-appb-000001
所述通式(I)中，R 1表示H、具有2-12个碳原子的烯基或具有2-12个碳原子的烯氧基；其中，所述具有2-12个碳原子的烯基或具有2-12个碳原子的烯氧基中的一个或多个氢可任选地被卤素取代，且一个或多个-CH 2-可以各自独立地被-C≡C-、-CH＝CH-、-CF＝CF-、-CF＝CH-、-COO-、-OCO-或-O-取代；
Z表示单键、-O-或-OCH 2-；
A代表单键，环丁基，环丙基，环己基
R 2表示H、代表具有1-12个碳原子的烷基，2-12个碳原子的烯基或具有2-12个碳原子的烯氧基。
优选的，通式(I)中，所述R 1表示具有2-7个碳原子的烯氧基；
R 2表示H、代表具有1-7个碳原子的烷基，2-7个碳原子的烯基或具有2-7个碳原子的烯氧基；
进一步优选的，所述R 1表示具有2-7个碳原子的烯氧基，所述烯氧基中的氧与通式(I)中苯环上的碳原子相连。
本发明以满足液晶显示器件工艺要求的液晶化合物为研发目的，经大量实验发现，采用
Figure PCTCN2021131193-appb-000002
为主体结构的基础上，进一步左侧辅以烯氧基端基，右侧辅以其他基团，不仅具有适当的负介电各向异性△ε及适当的清亮点Cp，旋转粘度γ1降低，使得液晶显示装置的响应时间有效缩短。
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 PCTCN2021131193-appb-000003
Figure PCTCN2021131193-appb-000004
Figure PCTCN2021131193-appb-000005
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 PCTCN2021131193-appb-000006
具体包括以下步骤：
(1)以
Figure PCTCN2021131193-appb-000007
与
Figure PCTCN2021131193-appb-000008
通过suzuki反应，得到
Figure PCTCN2021131193-appb-000009
(2)
Figure PCTCN2021131193-appb-000010
通过有机锂试剂，与溴素反应，得到
Figure PCTCN2021131193-appb-000011
(3)
Figure PCTCN2021131193-appb-000012
与巯基丙酸乙酯反应，得到
Figure PCTCN2021131193-appb-000013
(4)
Figure PCTCN2021131193-appb-000014
经催化合环，得到
Figure PCTCN2021131193-appb-000015
其中，R 1、R 2、Z、A的指代如前所述。
上述中间体均可以通过公开商业途径或者文献中本身已知的方法合成得到。
本发明的第三目的是提供包括本发明所述的液晶化合物的液晶组合物。
优选的，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％。
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TN、ADS、VA、PSVA、FFS或IPS液晶显示器。
本发明具有如下有益效果：
本发明所述液晶化合物在保持适当的负介电各向异性△ε及适当的清亮点Cp的同时，更具有大的光学各向异性△n，较低的旋转粘度γ1，更加优异的互溶性，可改善液晶组合物的互溶性，拓宽液晶组合物的液晶相范围，增加液晶显示器的工作温度范围，且有效缩短了液晶显示装置的响应时间。
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
实施例1
本实施例涉及一种液晶化合物，其结构式为：
Figure PCTCN2021131193-appb-000016
制备化合物BYLC-01的合成线路如下所示：
Figure PCTCN2021131193-appb-000017
具体步骤如下：
(1)化合物BYLC-01-1的合成：
氮气保护下，向反应瓶中加入32.0g(0.15mol)4-丙烯氧基-2,3-二氟苯硼酸，36.8g(0.15mol)4-溴-1-环戊甲氧基-2-氟苯，180ml甲苯，90ml去离子水，75ml乙醇，16.0g无水碳酸钠，0.6g四三苯基膦合钯，加热回流反应3小时。进行常规后处理，经色谱纯化，正己烷洗脱，乙醇重结晶得到白色固体(化合物BYLC-01-1)40g，GC：99.7％，收率：80％。
(2)化合物BYLC-01-2的合成：
氮气保护下，反应瓶中加入40.0g(0.12mol)BYLC-01-1，500ml四氢呋喃，控温-70～-80℃滴加0.14mol叔丁基锂的正己烷溶液，滴毕保温反应1小时，控温-70～-80℃滴加22g溴素，然后自然回温至-30℃。加入500ml饱和亚硫酸钠水溶液进行水解破坏，进行常规后处理，乙醇重结晶得到浅黄色固体(化合物BYLC-01-2)41.3g，GC：99.2％，收率83.3％。
(3)化合物BYLC-01-3的合成：
氮气保护下，向反应瓶中加入41.3g(0.1mol)化合物BYLC-01-2，18g 巯基丙酸乙酯，24g N,N-二异丙基乙胺，0.5g 2-二环己基膦-2,4,6-三异丙基联苯，0.4g三(二亚苄基丙酮)二钯，250ml二氧六环，控温90℃～100℃反应6小时。进行常规后处理，经色谱纯化，正己烷洗脱，得到浅黄色液体(化合物BYLC-01-3)39.6g，GC：97.5％，收率：85％。
(4)化合物BYLC-01的合成：
氮气保护下，向反应瓶中加入39.6g(0.85mol)化合物BYLC-01-3，10g叔丁醇钾，300ml四氢呋喃，65℃～70℃反应6小时。进行常规后处理，经色谱纯化，正己烷洗脱，乙醇结晶得到白色固体(化合物BYLC-01)22g，GC：99.8％，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346.4(M+)。
元素分析：C，65.88；H，4.66；O，9.24；F，10.97，S，9.26。
实施例2
本实施例涉及一种液晶化合物，其结构式为：
Figure PCTCN2021131193-appb-000018
制备化合物BYLC-02的合成线路如下所示：
Figure PCTCN2021131193-appb-000019
具体步骤如下：
(1)化合物BYLC-02-1的合成：
氮气保护下，向反应瓶中加入45.6g(0.2mol)4-丁烯氧基-2,3-二氟苯硼酸，51.8g 4-溴-1-环丁甲氧基-2-氟苯，220ml甲苯，130ml去离子水， 90ml乙醇，23.3g无水碳酸钠，0.8g四三苯基膦合钯，加热回流反应3小时。进行常规后处理，经色谱纯化，正己烷洗脱，乙醇重结晶得到白色固体(化合物BYLC-02-1)60.16g，GC：99.5％，收率：83％。
(2)化合物BYLC-02-2的合成：
氮气保护下，反应瓶中加入54.4g(0.15mol)BYLC-02-1，500ml四氢呋喃，控温-70～-80℃滴加0.16mol叔丁基锂的正己烷溶液，滴毕保温反应1小时，控温-70～-80℃滴加26.4g溴素，然后自然回温至-30℃。加入600ml饱和亚硫酸钠水溶液进行水解破坏，进行常规后处理，乙醇重结晶得到浅黄色固体(化合物BYLC-02-2)53g，GC：99.5％，收率80％。
(3)化合物BYLC-02-3的合成：
氮气保护下，向反应瓶中加入53.0g(0.12mol)化合物BYLC-02-2，26.8g巯基丙酸乙酯，28.5g N,N-二异丙基乙胺，0.7g 2-二环己基膦-2,4,6-三异丙基联苯，0.5g三(二亚苄基丙酮)二钯，300ml二氧六环，控温90℃～100℃反应6小时。进行常规后处理，经色谱纯化，正己烷洗脱，得到浅黄色液体(化合物BYLC-02-3)49.4g，GC：96.7％，收率：83.3％。
(4)化合物BYLC-02的合成：
氮气保护下，向反应瓶中加入49.4g(0.1mol)化合物BYLC-02-3，15.6g叔丁醇钾，400ml四氢呋喃，65℃～70℃反应6小时。进行常规后处理，经色谱纯化，正己烷洗脱，乙醇结晶得到白色固体(化合物BYLC-02)30g，GC：99.8％，收率：80％。
采用GC-MS对所得白色固体BYLC-02进行分析，产物的m/z为374.4(M+)。
元素分析：C，67.36；H，5.38；O，8.55；F，10.15，S，8.56。
依据实施例1、实施例2的技术方案，只需要简单替换对应的原料，不改变任何实质性操作，可以合成以下液晶化合物。
实施例3
Figure PCTCN2021131193-appb-000020
采用GC-MS对所得白色固体BYLC-03进行分析，产物的m/z为360.4(M+)。
实施例4
Figure PCTCN2021131193-appb-000021
采用GC-MS对所得白色固体BYLC-04进行分析，产物的m/z为360.4(M+)。
实施例5
Figure PCTCN2021131193-appb-000022
采用GC-MS对所得白色固体BYLC-05进行分析，产物的m/z为374.47(M+)。
实施例6
Figure PCTCN2021131193-appb-000023
采用GC-MS对所得白色固体BYLC-06进行分析，产物的m/z为402.49(M+)。
实施例7
Figure PCTCN2021131193-appb-000024
采用GC-MS对所得白色固体BYLC-07进行分析，产物的m/z为430.5(M+)。
实施例8
Figure PCTCN2021131193-appb-000025
采用GC-MS对所得白色固体BYLC-08进行分析，产物的m/z为360.4(M+)。
实施例9
Figure PCTCN2021131193-appb-000026
采用GC-MS对所得白色固体BYLC-09进行分析，产物的m/z为362.4(M+)。
对比例1
本对比例所涉及的化合物的结构为：
Figure PCTCN2021131193-appb-000027
实验例
本实验例涉及对实施例以及对比例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△ε的检测采用INSTEC液晶检测仪器测试，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℃)；△ε代表介电各向异性(25℃，1000Hz)；γ1代表旋转粘度(mPa.s，25℃)；Cp代表清亮点。
将实施例所制得的化合物与对比例的液晶化合物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 PCTCN2021131193-appb-000028
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的负介电各向异性化合物相比，本发明提供的液晶化合物在保持适当的负介电各向异性△ε及适当的清亮点Cp的同时，更具有大的光学各向异性△n，较低的旋转粘度γ1，更加优异的互溶性，可改善液晶组合物的互溶性，拓宽液晶组合物的液晶相范围，增加液晶显示器的工作温度范围，且有效的缩短了液晶显示装置的响应时间。
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液晶化合物及其制备方法与应用。所述液晶化合物具有通式(I)所示结构。本发明所述液晶化合物在保持适当的负介电各向异性△ε及适当的清亮点Cp的同时，更具有大的光学各向异性△n，较低的旋转粘度γ1，可改善液晶组合物的互溶性，拓宽液晶组合物的液晶相范围，增加液晶显示器的工作温度范围，且有效缩短了液晶显示装置的响应时间，具有较好的经济价值和应用前景。
Figure PCTCN2021131193-appb-000029

Claims (9)

  1. 一种液晶化合物，其特征在于，具有通式(I)所示的结构：
    Figure PCTCN2021131193-appb-100001
    所述通式(I)中，R 1表示H、具有2-12个碳原子的烯基或具有2-12个碳原子的烯氧基；其中，所述具有2-12个碳原子的烯基或具有2-12个碳原子的烯氧基中的一个或多个氢可任选地被卤素取代，且一个或多个-CH 2-可以各自独立地被-C≡C-、-CH＝CH-、-CF＝CF-、-CF＝CH-、-COO-、-OCO-或-O-取代；
    Z表示单键、-O-或-OCH 2-；
    A代表单键，环丁基，环丙基，环己基；
    R 2代表H、具有1-12个碳原子的烷基，2-12个碳原子的烯基或具有2-12个碳原子的烯氧基。
  2. 根据权利要求1所述的液晶化合物，其特征在于，所述R 1表示具有2-7个碳原子的烯氧基；
    R 2代表H、具有1-7个碳原子的烷基，2-7个碳原子的烯基或具有2-7个碳原子的烯氧基。
  3. 根据权利要求2所述的液晶化合物，其特征在于，所述R 1表示具有2-7个碳原子的烯氧基，所述烯氧基中的氧与通式(I)中苯环上的碳原子相连。
  4. 根据权利要求1所述的液晶化合物，其特征在于，所述液晶化合物选自以下结构中的一种或多种：
    Figure PCTCN2021131193-appb-100002
    Figure PCTCN2021131193-appb-100003
    Figure PCTCN2021131193-appb-100004
    Figure PCTCN2021131193-appb-100005
  5. 一种制备权利要求1～4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 PCTCN2021131193-appb-100006
    具体包括以下步骤：
    (1)以
    Figure PCTCN2021131193-appb-100007
    与
    Figure PCTCN2021131193-appb-100008
    通过suzuki反应，得到
    Figure PCTCN2021131193-appb-100009
    (2)
    Figure PCTCN2021131193-appb-100010
    通过有机锂试剂，与溴素反应，得到
    Figure PCTCN2021131193-appb-100011
    (3)
    Figure PCTCN2021131193-appb-100012
    与巯基丙酸乙酯反应，得到
    Figure PCTCN2021131193-appb-100013
    (4)
    Figure PCTCN2021131193-appb-100014
    经催化合环，得到
    Figure PCTCN2021131193-appb-100015
    其中，R 1、R 2、Z、A的指代同权利要求1～3任一项所述。
  6. 一种液晶组合物，其特征在于，包括权利要求1～4任一项所述的液 晶化合物。
  7. 根据权利要求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％。
  8. 权利要求1-4任一项所述液晶化合物或权利要求6或7所述液晶组合物在液晶显示领域中的应用。
  9. 根据权利要求8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TN、ADS、VA、PSVA、FFS或IPS液晶显示器。
PCT/CN2021/131193 2020-12-28 2021-11-17 一种液晶化合物及其制备方法与应用 WO2022142821A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202011581201.7 2020-12-28
CN202011581201.7A CN114686242B (zh) 2020-12-28 2020-12-28 一种液晶化合物及其制备方法与应用

Publications (1)

Publication Number Publication Date
WO2022142821A1 true WO2022142821A1 (zh) 2022-07-07

Family

ID=82129700

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/131193 WO2022142821A1 (zh) 2020-12-28 2021-11-17 一种液晶化合物及其制备方法与应用

Country Status (2)

Country Link
CN (1) CN114686242B (zh)
WO (1) WO2022142821A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116165819B (zh) * 2023-04-25 2023-06-27 北京大学 一种宽温域电控液晶调光膜及其制备方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002055463A1 (de) * 2001-01-11 2002-07-18 Clariant International Ltd. Fluorierte aromaten und ihre verwendung in flüssigkristallmischungen
US20040002576A1 (en) * 2002-03-15 2004-01-01 Sumitomo Chemical Company, Limited Polymer compound and polymer light emitting device using the same
JP2012206970A (ja) * 2011-03-29 2012-10-25 Canon Inc 新規有機化合物およびそれを有する有機発光素子
CN105153112A (zh) * 2014-04-22 2015-12-16 默克专利股份有限公司 4,6-二氟二苯并噻吩衍生物
CN109423296A (zh) * 2017-08-24 2019-03-05 北京八亿时空液晶科技股份有限公司 一种二苯并噻吩类负介电各向异性化合物及其制备方法和应用
CN109423297A (zh) * 2017-08-24 2019-03-05 北京八亿时空液晶科技股份有限公司 一种二苯并噻吩液晶化合物及其制备方法和应用
CN109628107A (zh) * 2018-12-13 2019-04-16 晶美晟光电材料（南京）有限公司 一种具有高光学各向异性的液晶化合物及其应用
TW201925435A (zh) * 2017-11-30 2019-07-01 日商捷恩智股份有限公司 具有二苯並噻吩環的化合物、液晶組成物及液晶顯示元件
CN110872521A (zh) * 2018-08-30 2020-03-10 捷恩智株式会社 液晶组合物、液晶显示元件及用于液晶显示元件的用途

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114573550A (zh) * 2020-12-01 2022-06-03 北京八亿时空液晶科技股份有限公司 一种液晶化合物及其制备方法与应用

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002055463A1 (de) * 2001-01-11 2002-07-18 Clariant International Ltd. Fluorierte aromaten und ihre verwendung in flüssigkristallmischungen
US20040002576A1 (en) * 2002-03-15 2004-01-01 Sumitomo Chemical Company, Limited Polymer compound and polymer light emitting device using the same
JP2012206970A (ja) * 2011-03-29 2012-10-25 Canon Inc 新規有機化合物およびそれを有する有機発光素子
CN105153112A (zh) * 2014-04-22 2015-12-16 默克专利股份有限公司 4,6-二氟二苯并噻吩衍生物
CN109423296A (zh) * 2017-08-24 2019-03-05 北京八亿时空液晶科技股份有限公司 一种二苯并噻吩类负介电各向异性化合物及其制备方法和应用
CN109423297A (zh) * 2017-08-24 2019-03-05 北京八亿时空液晶科技股份有限公司 一种二苯并噻吩液晶化合物及其制备方法和应用
TW201925435A (zh) * 2017-11-30 2019-07-01 日商捷恩智股份有限公司 具有二苯並噻吩環的化合物、液晶組成物及液晶顯示元件
CN110872521A (zh) * 2018-08-30 2020-03-10 捷恩智株式会社 液晶组合物、液晶显示元件及用于液晶显示元件的用途
CN109628107A (zh) * 2018-12-13 2019-04-16 晶美晟光电材料（南京）有限公司 一种具有高光学各向异性的液晶化合物及其应用

Also Published As

Publication number Publication date
CN114686242A (zh) 2022-07-01
TW202225387A (zh) 2022-07-01
CN114686242B (zh) 2024-05-10

Similar Documents

Publication Publication Date Title
CN109206400B (zh) 一种含有二苯并噻吩结构的液晶化合物及其应用
CN106883862B (zh) 一种液晶化合物、组合物及其应用
CN109423296B (zh) 一种二苯并噻吩类负介电各向异性化合物及其制备方法和应用
CN106811208B (zh) 一种液晶化合物、组合物及其应用
CN109207160B (zh) 一种负介电各向异性的液晶化合物及其制备方法与应用
WO2016082511A1 (zh) 一种含有二氟甲氧基桥键的液晶化合物、组合物及其应用
CN106811209B (zh) 一种液晶化合物、组合物及其应用
WO2022105790A1 (zh) 一种含环己烯结构的液晶化合物及其制备方法与应用
WO2022142821A1 (zh) 一种液晶化合物及其制备方法与应用
CN114105941B (zh) 一种新型液晶化合物及其制备方法和应用
TWI792117B (zh) 一種負介電的液晶化合物及其製備和應用
WO2022116826A1 (zh) 一种液晶化合物及其制备方法与应用
WO2022000982A1 (zh) 一种含有二苯并噻吩结构的液晶化合物及其应用
CN106479514B (zh) 一种7,8-二氟-5-甲基-1，2，3，4－四氢萘类液晶化合物及其制备方法与应用
CN106398716B (zh) 一种4，5－二氟-7-甲基茚满类液晶化合物及其制备方法与应用
CN109082281B (zh) 一种负介电各向异性的液晶化合物及其制备方法与应用
TWI765464B (zh) 一種液晶化合物及其製備方法和應用
CN107400517B (zh) 一种环戊基类负介电各向异性液晶化合物及组合物与应用
CN107345141B (zh) 一种异戊基类负介电各向异性的液晶化合物及其应用
CN112980458B (zh) 一种含桥环烷烃液晶化合物及其制备方法与应用
CN109401758A (zh) 一种液晶化合物及液晶组合物
CN107286949B (zh) 一种环戊基类负介电各向异性的液晶化合物及其应用
CN107286953A (zh) 一种环戊基类负介电各向异性液晶化合物及其组合物与应用
CN114105919A (zh) 一种液晶化合物及其制备方法和应用
CN107286950A (zh) 一种环戊基液晶化合物、组合物及其应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21913564

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21913564

Country of ref document: EP

Kind code of ref document: A1