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WO2016082511A1 - 一种含有二氟甲氧基桥键的液晶化合物、组合物及其应用 - Google Patents

一种含有二氟甲氧基桥键的液晶化合物、组合物及其应用 Download PDF

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WO2016082511A1
WO2016082511A1 PCT/CN2015/080517 CN2015080517W WO2016082511A1 WO 2016082511 A1 WO2016082511 A1 WO 2016082511A1 CN 2015080517 W CN2015080517 W CN 2015080517W WO 2016082511 A1 WO2016082511 A1 WO 2016082511A1
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compound
liquid crystal
single bond
phenyl group
crystal compound
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PCT/CN2015/080517
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English (en)
French (fr)
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蒋战英
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北京八亿时空液晶科技股份有限公司
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Priority to JP2017531934A priority Critical patent/JP6306271B2/ja
Priority to KR1020177017605A priority patent/KR102347009B1/ko
Priority to US15/521,219 priority patent/US10494570B2/en
Priority to DE112015005357.3T priority patent/DE112015005357T5/de
Publication of WO2016082511A1 publication Critical patent/WO2016082511A1/zh

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    • C07D307/04—Heterocyclic compounds containing five-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
    • C07D307/10—Heterocyclic compounds containing five-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 substituted hydrocarbon radicals attached to ring carbon atoms
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    • 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
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    • 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
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    • 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
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    • 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
    • C09K19/3001—Cyclohexane rings
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    • 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
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    • 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
    • C09K19/3001—Cyclohexane rings
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    • 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 present invention relates to the field of liquid crystal display materials, and in particular to a liquid crystal compound containing a difluoromethoxy bridge, a composition, and use thereof.
  • liquid crystal As an environmentally friendly material, liquid crystal has become more and more popular in high-tech fields and has been favored by researchers.
  • the application of liquid crystal materials in the fields of information display materials and organic optoelectronic materials has great research value and ideal. 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 display information, no electromagnetic radiation, etc., and can be adapted to various information display requirements.
  • TFT-LCD has been widely used in direct-view TVs, large-screen projection TVs, computer terminal displays and some military instrument displays. It is believed that TFT-LCD technology has a broader application prospect. However, due to the limitation of the liquid crystal material itself, the TFT-LCD still has many defects such as insufficient response, low voltage, and insufficient charge retention. Therefore, it is particularly important to find a single crystal compound having a low viscosity and a high dielectric anisotropy. In order to improve the properties of materials to meet new requirements, the synthesis of new liquid crystal compounds and the study of structure-performance relationships have become an important task in the field of liquid crystals.
  • liquid crystal compounds there are also mentioned liquid crystal compounds containing a difluoromethoxy bridge.
  • liquid crystal compound monomer in 2003, Merck & Co., Germany, in the patent CN171748A, contains a difluoromethoxy bridge and a tetrahydropyridyl group.
  • the liquid crystal compound monomer has been disclosed and elaborated, but the compounds involved still do not have the desired application properties.
  • the present invention provides a novel liquid crystal compound having a difluoromethoxy bridge unit structure.
  • the compound has the characteristics of low rotational viscosity, large dielectric anisotropy, good mutual solubility and stable performance, and has the structure I as shown in the formula:
  • R is selected from H and unsubstituted or alkyl or alkoxy having 1 to 12 carbon atoms in which one or more H is substituted by halogen;
  • a 1 is selected from a single bond or a 1,4-phenyl group, wherein each of H in the 1,4-phenyl group may be independently substituted with one or more halogens;
  • L 1 and L 2 are each independently selected from H or halogen
  • Z 1 is selected from a single bond or -(CH 2 ) 2 -.
  • liquid crystal compound of the present invention preferably:
  • R is selected from H and an unsubstituted or alkyl or alkoxy group having 1 to 5 carbon atoms in which one or more H is substituted by a fluorine element;
  • a 1 is selected from a single bond or a 1,4-phenyl group, wherein each of H in the 1,4-phenyl group may be independently substituted with one or more fluorine elements;
  • L 1 and L 2 are each independently selected from H or F;
  • Z 1 is a single bond.
  • R is selected from H and unsubstituted alkyl groups having 1 to 5 carbon atoms
  • a 1 is selected from a single bond or a 1,4-phenyl group, wherein each of H in the 1,4-phenyl group may be independently substituted with one or more fluorine elements;
  • L 1 and L 2 are both H;
  • Z 1 is a single bond.
  • liquid crystal compound is selected from the group consisting of the following structural compounds:
  • R is selected from an alkyl group having 1 to 5 carbon atoms
  • the liquid crystal compound is:
  • the above compounds have a high dielectric anisotropy and can be applied to the composition to lower the driving voltage of the device.
  • a second object of the present invention is to provide a preparation method of a liquid crystal compound containing a difluoromethoxy bridge, and the synthesis route of the preparation method is as follows:
  • the method specifically includes the following steps:
  • R, A 1 , Z 1 , L 1 and L 2 are as defined above.
  • the present invention also claims a liquid crystal composition containing a liquid crystal compound of a difluoromethoxy bridge.
  • the liquid crystal compound containing a difluoromethoxy bridge is added in a reasonable manner, and the amount is preferably from 1 to 80%, more preferably from 3 to 50%. It is expected by those skilled in the art that based on the addition of the above liquid crystal compound, the dielectric anisotropy of the conventional liquid crystal composition can be further improved, and the technical effect of lowering the driving voltage of the device can be obtained.
  • Still another object of the present invention is to protect the above liquid crystal compound containing a difluoromethoxy bridge and a composition thereof in the field of liquid crystal display.
  • the use of the above compound or composition in a liquid crystal display device includes, but is not limited to, a TN, ADS, FFS or IPS liquid crystal display.
  • a liquid crystal display device When the liquid crystal composition is applied to a liquid crystal display device, there is an advantage that the driving voltage is lowered.
  • ⁇ represents dielectric anisotropy at 25 ° C and 1 kHz
  • ⁇ 1 represents the rotational viscosity (mPa ⁇ s) at 25 °C.
  • ⁇ n optical anisotropy, and no is refractive index (589 nm, 25 ° C);
  • C.p is the clearing point (°C) of the liquid crystal composition
  • VHR charge retention rate (%) The mixed liquid crystal is injected into the liquid crystal cell and placed in the incubator. After the temperature is stabilized, the test procedure is entered, and the charge retention rate value is obtained manually. The measurement voltage is 5V, the power-on time is 5ms, and the holding time is 500ms.
  • the organic phase was combined, and the organic phase was washed twice with 100 ml of 2 aqueous sodium chloride solution, dried over 30 g of anhydrous sodium sulfate for 30 min, filtered, and the filtrate was dried.
  • the ethanol was crystallized to give a white solid.
  • Theoretical yield 102 g, actual yield: 64 g, yield: 62.7%, white solid, GC: 99.6%, m.p.: 67.65.
  • reaction solution was suction filtered, and the filter cake was extracted once with 400 ml of toluene, filtered again, and the filter cake was rinsed with toluene.
  • the filtrate was combined, washed four times with sodium chloride aqueous solution, and the solvent was evaporated to dryness. Recrystallization of ethanol. It was recrystallized three times with 2 times ethanol and 1x toluene, and filtered to dry a white solid. Theoretical yield: 234.7 g, actual yield: 89.1 g, yield 38.0%.
  • ⁇ n 0.135
  • ⁇ 1 is 203 mPa ⁇ s.
  • Mass spectrometry fragmentation 239, 252, 267, 365, 526 (molecular ion peak);
  • reaction solution was suction filtered, and the filter cake was extracted once with 400 ml of toluene, filtered again, and the filter cake was rinsed with toluene.
  • the filtrate was combined, washed four times with sodium chloride aqueous solution, and the solvent was evaporated to dryness. Recrystallization of ethanol. It was recrystallized three times with 2 times ethanol and 1x toluene, and filtered to dry a white solid. Theoretical yield: 228.5 g, actual yield: 91.8 g, yield 40.2%.
  • ⁇ n 0.135
  • ⁇ 1 is 184 mPa ⁇ s.
  • Mass spectrometry fragmentation 239, 252, 267, 365, 526 (molecular ion peak),
  • liquid crystal monomers used in the following compositions were all supplied by Beijing 800 Million Time Liquid Crystal Technology Co., Ltd.
  • the contents of the respective components in the examples represent the mass percentages unless otherwise specified.
  • liquid crystal compound The following parts by weight of the liquid crystal compound were taken and a liquid crystal composition was prepared.
  • the specific ratios and the performance parameters of the obtained liquid crystal composition are shown in the following table.
  • liquid crystal compound having a difluoromethyl ether bridge structure in the TN, IPS, FFS, and ADS-TFT modes are shown in Tables 1 and 2. Meanwhile, in order to verify the properties of the liquid crystal compound of the present invention, a liquid crystal composition formed by not adding the above compound and adding a conventional dielectric anisotropic compound was further introduced for performance comparison, and the results are shown in Tables 1 to 4.
  • a liquid crystal composition in which a compound of the present invention is directly added or a compound of the present invention is used in place of a conventional dielectric anisotropic compound has a moderate rotational viscosity, a moderate ⁇ n value, and a high charge retention ratio. In particular, it has a large dielectric anisotropy.
  • liquid crystal compositions to which other liquid crystal compounds having a difluoromethyl ether bridge structure provided by the present invention are added can obtain the same excellent optical and electrical properties.
  • the present invention provides a liquid crystal compound and a liquid crystal composition containing the same, which has the characteristics of low rotational viscosity, large dielectric anisotropy, good mutual solubility, and stable performance, and can be applied to a composition to lower the liquid crystal display device. Drive voltage.
  • the liquid crystal display device of the present invention includes, but is not limited to, a TN, ADS, FFS or IPS liquid crystal display.
  • the liquid crystal compound/liquid crystal composition of the present invention has broad application prospects and good industrial applicability in the field of liquid crystal display.

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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)
  • Mathematical Physics (AREA)
  • General Physics & Mathematics (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Liquid Crystal (AREA)

Abstract

本发明涉及一种如式I所示结构的液晶化合物，其中，R选自H和未取代或其中一个或多个H由卤素取代的含有1-12个碳原子的烷基或烷氧基；A1选自单键或1，4-苯基，其中1，4-苯基中的H各自独立地可被一个或多个卤素取代；L1和L2各自独立地选自H或卤素；Z1选自单键或-(CH2)2-。本发明所述化合物具有旋转粘度低、介电各向异性大、互溶性好和性能稳定的特点应用至组合物后可降低器件的驱动电压，具有广阔的应用前景。

Description

一种含有二氟甲氧基桥键的液晶化合物、组合物及其应用 技术领域
本发明涉及液晶显示材料领域，具体涉及一种含有二氟甲氧基桥键的液晶化合物、组合物及其应用。
背景技术
液晶作为环境友好材料，在高新技术领域显示出越来越广阔的应用前景因而倍受研究者的青睐，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理想的应用前景。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。
近几年，液晶化合物的应用领域已经显著拓宽到各类显示器件、电光器件、电子元件、传感器等。为此，已经提出许多不同的结构，特别是在向列型液晶领域，向列型液晶化合物迄今已经在平板显示器中得到最为广泛的应用。特别是用于TFT有源矩阵的系统中。
彩色显示大多采用有源矩阵显示方式。TFT-LCD已经广泛用于直视型电视、大屏幕投影电视、计算机终端显示和某些军用仪表显示，相信TFT-LCD技术具有更为广阔的应用前景。但是因受液晶材料本身的限制，TFT-LCD仍然存在着响应不够快，电压不够低，电荷保持率不够高等诸多缺陷。因此寻找低粘度、高介电各向异性的单晶化合物尤为重要。为了改善材料的性能使其适应新的要求，新型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。
现有技术公开了多种液晶化合物，其中也有提到含二氟甲氧基桥键的液晶化合物，如2003年德国默克公司在专利CN171748A中对含有二氟甲氧基桥键和四氢吡喃的液晶化合物单体进行了公开及阐述阐述，但其所涉及的化合物依然不具备理想的应用性能。
发明内容
针对上述背景，本发明提供一种新型的液晶化合物，该化合物具有二氟甲氧基桥键单元结构。该化合物具有旋转粘度低、介电各向异性大、互溶性好和性能稳定的特点，具有如式所示的结构I：
Figure PCTCN2015080517-appb-000001
其中，R选自H和未取代或其中一个或多个H由卤素取代的含有1-12个碳原子的烷基或烷氧基；
A1选自单键或1，4-苯基，其中1，4-苯基中的H各自独立地可被一个或多个卤素取代；
L1和L2各自独立地选自H或卤素；
Z1选自单键或-(CH2)2-。
其中，本发明所述的液晶化合物优选：
R选自H和未取代或其中一个或多个H由氟元素取代的含有1-5个碳原子的烷基或烷氧基；
A1选自单键或1，4-苯基，其中1，4-苯基中的H各自独立地可被一个或多个氟元素取代；
L1和L2各自独立地选自H或F；
Z1为单键。
进一步优选：
R选自H和未取代含有1-5个碳原子的烷基；
A1选自单键或1，4-苯基，其中1，4-苯基中的H各自独立地可被一个或多个氟元素取代；
L1和L2均为H；
Z1为单键。
以及更优选所述液晶化合物选自如下通式结构化合物：
Figure PCTCN2015080517-appb-000002
R选自含有1-5个碳原子的烷基；
作为本发明最佳实施方式，所述液晶化合物为：
Figure PCTCN2015080517-appb-000003
上述化合物具有较高的介电各向异性，应用至组合物后可降低器件的驱动电压。
本发明的第二目的在于提供一种含有二氟甲氧基桥键液晶化合物的制备方法，所述制备方法的合成路线如下：
Figure PCTCN2015080517-appb-000004
Figure PCTCN2015080517-appb-000005
所述方法具体包括如下步骤：
(a)以化合物II-1为起始原料，以弱酸为催化剂(如盐酸)，二氯甲烷为溶剂，在室温与二氢吡喃反应，得到化合物II-2；
(b)化合物II-2以四氢呋喃为溶剂，氮气保护，在-75℃～-85℃，与丁基锂反应，形成锂试剂；再与碘甲烷反应，得到化合物II-3；
(c)化合物II-3以对甲苯磺酸吡啶鎓为催化剂，搅拌加热反应得到化合物II-4；
(d)化合物II-5以四氢呋喃为溶剂，氮气保护，在低温下，与丁基锂反应，形成锂试剂；再与二氟二溴甲烷反应，得到化合物II-6；
(e)化合物II-4与化合物II-6，以二甲基亚砜和水为溶剂，四丁基溴化铵为催化剂，碳酸钾为缚酸剂，反应得到目标化合物I；
其中，R、A1、Z1、L1及L2的指代同上。
采用上述制备方法能够批量化稳定得到含有二氟甲氧基桥键液晶化合物，具有介电各向异性大的优势。
此外，本发明还要求保护含有二氟甲氧基桥键液晶化合物的液晶组合物。其中含有二氟甲氧基桥键液晶化合物以合理的方式加入，加入量以1-80％为宜，更优选3-50％。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介电各向异性，具有降低器件的驱动电压的技术效果。
本发明的又一目的在于保护上述含有二氟甲氧基桥键的液晶化合物及其组合物在液晶显示领域的应用。
具体即上述化合物或组合物在液晶显示装置中的应用，所述的液晶显示装置包括但并不限于TN、ADS、FFS或IPS液晶显示器。将液晶组合物应用至液晶显示装置后，具有降低驱动电压的优点。
本发明中各性能测试参数缩写如下所示：
Δε表示在25℃和1kHz下的介电各向异性；
γ1表示在25℃下的旋转粘度(mPa·s)。
Δn为光学各向异性，no为折射率(589nm，25℃)；
C.p为液晶组合物的清亮点(℃)；
VHR电荷保持率(％)：将混合液晶注入液晶盒内，放入恒温箱中，待温度稳定后，进入测试程序，手动取点得到电荷保持率数值。测量电压为5V，加电时间为5ms，Holding Time为500ms。
具体实施方式
实施例1：
Figure PCTCN2015080517-appb-000006
2-{4’-[(3，4，5-三氟-2-甲基-苯氧基)-二氟甲基]-3’，5’-二氟联苯}-5-丙基四氢吡喃(化合物7)的合成
1)2-(3，4，5-三氟-苯氧基)-四氢吡喃(化合物2)的合成
Figure PCTCN2015080517-appb-000007
500ml干燥洁净的三口瓶中加入70g 3，4，5-三氟苯酚，72g 2，3-二氢吡喃，140ml二氯甲烷，搅拌，室温下缓慢滴加5滴浓盐酸，滴毕室温反应3小时。反应液用10％的氢氧化钠水溶液100ml×2洗涤两次，20g无水硫酸钠干燥30分钟，抽滤，滤液旋干待用。
2)2-(3，4，5-三氟-2-甲基-苯氧基)-四氢吡喃(化合物3)的合成
Figure PCTCN2015080517-appb-000008
1L干燥洁净的三口瓶中加入97g 2-(3，4，5-三氟-苯氧基)-四氢吡喃(化合物2)，500ml四氢呋喃，氮气保护，液氮降温至-75℃～-85℃，滴加200ml丁基锂，滴毕控温反应1h，滴加89g碘甲烷，滴毕，控温-75℃～-85℃反应30分钟后自然升温至-20℃，用氯化铵水溶液水解破坏。分液，水相用100ml×2乙酸乙酯提取两次，合并有机相，有机相用100ml×2氯化钠水溶液洗涤两次，30g无水硫酸钠干燥30min，抽滤，滤液旋干，1.5倍乙醇结晶，得白色固体。
理论产量：102g，实际产量：64g，收率：62.7％，白色固体，GC：99.6％，熔点：67.65℃。
3)3，4，5-三氟-2-甲基-苯酚(化合物4)的合成
Figure PCTCN2015080517-appb-000009
100ml干燥洁净的三口瓶中加入10g2-(3，4，5-三氟-2-甲基-苯氧基)-四氢吡喃(化合物3)，2g对甲苯磺酸吡啶鎓，50ml乙醇，搅拌加热至60℃～70℃，计时反应3小时。旋干反应液，加入20ml二氯甲烷，溶解产品，用10ml×2氯化钠水溶液洗涤两次，10g无水硫酸钠干燥分钟，旋干。
理论产量：6.5g，实际产量：6.5g，收率：100％(按理论计)，无色液体，GC：99.155％。
4)二氟甲基溴代物(化合物6)的合成
Figure PCTCN2015080517-appb-000010
2L三口瓶中加入141g 2-(3’，5’-二氟联苯)-5-丙基四氢吡喃(化合物5)，1L四氢呋喃，开动搅拌，至固体完全溶解，抽排氮气三次，降温至-70℃，控温-65～-75℃滴加232ml 2.5M丁基锂，滴毕，100ml四氢呋喃冲洗滴液漏斗，控温-65～-75℃反应1小时，控温-65～-75℃滴加含141g二氟二溴甲烷的四氢呋喃0.5L溶液，滴毕，自然升温至-20℃。
向反应液中滴入40ml浓盐酸和200ml水组成的溶液，搅拌30分钟后，静置分出水相，加入0.5L石油醚，1L×3水洗三次，旋干溶剂。产品为黄色液体，重189g，收率95％。
5)2-{4’-[(3，4，5-三氟-2-甲基-苯氧基)-二氟甲基]-3’，5’-二氟联苯}-5-丙基四氢吡喃(化合物7)
Figure PCTCN2015080517-appb-000011
2L三口瓶中加入189g二氟甲基溴代物(化合物6)，1L二甲基亚砜，0.2L水，开动搅拌，加入72g 3，4，5-三氟-2-甲基-苯酚(化合物4)，14g四丁基溴化铵，123g碳酸钾，抽排氮气三次，开加热升温，控温90～95℃反应5小时。
抽滤反应液，滤饼用400ml甲苯加热萃取一次，再次抽滤，甲苯淋洗滤饼，合并滤液，用氯化钠水溶液洗四次，旋干溶剂，加入1倍石油醚和2倍无水乙醇重结晶。再用2倍乙醇和1倍甲苯重结晶三次，抽滤晾干白色固体。理论产量：234.7g，实际产量：89.1g，收率38.0％。
产物分析：
气相纯度(GC)99.9％，
熔点：75.8℃，
清亮点：122.6℃，
Δn为0.135，
Δε为27.0，
γ1为203mPa·s。
质谱分析碎片：239、252、267、365、526(分子离子峰)；
H-NMR核磁谱图(CDCl3，300MHz)：δH：0.90-2.60(m，15H)，3.50-4.90(m，3H)，6.10-7.60(m，7H)。
实施例2：
Figure PCTCN2015080517-appb-000012
2-{4’-[(3，4，5-三氟-2-甲基-苯氧基)-二氟甲基]-3’，5’-二氟联苯}-5-乙基四氢吡喃(化合物10)的合成(本实施例中化合物8可参考实施例1公开的步骤1-3得到，在此不再赘述)
1)二氟甲基溴代物(化合物9)的合成
Figure PCTCN2015080517-appb-000013
2L三口瓶中加入135g 2-(3’，5’-二氟联苯)-5-乙基四氢吡喃(化合物5)，1L四氢呋喃，开动搅拌，至固体完全溶解，抽排氮气三次，降温至-70℃，控温-65～-75℃滴加232ml 2.5M丁基锂，滴毕，100ml四氢呋喃冲洗滴液漏斗，控温-65～-75℃反应1小时，控温-65～-75℃滴加含141g二氟二溴甲烷的四氢呋喃0.5L溶液，滴毕，自然升温至-20℃。
向反应液中滴入40ml浓盐酸和200ml水组成的溶液，搅拌30分钟后，静置分出水相，加入0.5L石油醚，1L×3水洗三次，旋干溶剂。产品为黄色液体，重180g，收率91％。
2)2-{4’-[(3，4，5-三氟-2-甲基-苯氧基)-二氟甲基]-3’，5’-二氟联苯}-5-乙基四氢吡喃(化合物10)的合成
Figure PCTCN2015080517-appb-000014
Figure PCTCN2015080517-appb-000015
2L三口瓶中加入180g二氟甲基溴代物(化合物6)，1L二甲基亚砜，0.2L水，开动搅拌，加入72g 3，4，5-三氟-2-甲基-苯酚(化合物4)，14g四丁基溴化铵，123g碳酸钾，抽排氮气三次，开加热升温，控温90～95℃反应5小时。
抽滤反应液，滤饼用400ml甲苯加热萃取一次，再次抽滤，甲苯淋洗滤饼，合并滤液，用氯化钠水溶液洗四次，旋干溶剂，加入1倍石油醚和2倍无水乙醇重结晶。再用2倍乙醇和1倍甲苯重结晶三次，抽滤晾干白色固体。理论产量：228.5g，实际产量：91.8g，收率40.2％。
产物分析：
气相纯度(GC)99.9％，
熔点：82.1℃，
Δn为0.135，
Δε为27.5，
γ1为184mPa·s。
质谱分析碎片：239、252、267、365、526(分子离子峰)，
H-NMR核磁谱图(CDCl3，300MHz)：δH：0.90-2.60(m，13H)，3.50-4.90(m，3H)，6.10-7.60(m，7H)。
实施例3-10：
依据实施例1-2的技术方案，简单更换含有相应基团的原料可合成以下化合物：
Figure PCTCN2015080517-appb-000016
Figure PCTCN2015080517-appb-000017
实施例11：混晶组合物
以下组合物中使用的液晶单体全部由北京八亿时空液晶科技股份有限公司提供。除特殊说明外，实施例中各组分的含量均表示质量百分比。
取以下重量份数的液晶化合物并配制液晶组合物，具体的配比及所得的液晶组合物的性能参数由下表所示。
具有二氟甲基醚桥键结构的液晶化合物在TN、IPS、FFS、ADS-TFT模式中的应用例见表1及表2。同时，为了验证本发明所述液晶化合物的性能，进一步引入了不加入上述化合物以及加入传统的介电各向异性化合物形成的液晶组合物进行性能对比，结果见表1-表4。
表1 液晶组合物中各组分的重量份数及性能参数
Figure PCTCN2015080517-appb-000018
表2 液晶组合物中各组分的重量份数及性能参数
Figure PCTCN2015080517-appb-000019
Figure PCTCN2015080517-appb-000020
表3 未添加本发明化合物的液晶组合物的性能参数
Figure PCTCN2015080517-appb-000021
表4 对照液晶组合物中各组分的重量份数及性能参数
Figure PCTCN2015080517-appb-000022
由表1-4可以看出：直接加入了本发明化合物或使用本发明化合物替代传统的介电各向异性化合物(化合物11)的液晶组合物，旋转粘度适中、Δn数值适中、电荷保持率高，尤其具有很大的介电各向异性。同时，本发明所述液晶组合物，其中化合物的加入量以1-80％为宜，更优选3-50％。
除试验例所例举的组合物外，添加本发明提供的其它具有二氟甲基醚桥键结构的液晶化合物的其他液晶组合物能得到同样优良的光学和电学性能。
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
本发明提供了一种液晶化合物和含有该化合物的液晶组合物，该化合物具有旋转粘度低、介电各向异性大、互溶性好和性能稳定的特点，应用至组合物后可降低液晶显示装置的驱动电压。本发明所述的液晶显示装置包括但并不限于TN、ADS、FFS或IPS液晶显示器。本发明所述的液晶化合物/液晶组合物在液晶显示领域具有广阔的应用前景及良好的工业实用性。

Claims (10)

  1. 一种含有二氟甲氧基桥键液晶化合物，其特征在于：具有如式I所示结构：
    Figure PCTCN2015080517-appb-100001
    其中，R选自H和未取代或其中一个或多个H由卤素取代的含有1-12个碳原子的烷基或烷氧基；
    A1选自单键或1，4-苯基，其中1，4-苯基中的H各自独立地可被一个或多个卤素取代；
    L1和L2各自独立地选自H或卤素；
    Z1选自单键或-(CH2)2-。
  2. 根据权利要求1所述的化合物，其特征在于：R选自H和未取代或其中一个或多个H由氟元素取代的含有1-5个碳原子的烷基或烷氧基；
    A1选自单键或1，4-苯基，其中1，4-苯基中的H各自独立地可被一个或多个氟元素取代；
    L1和L2各自独立地选自H或F；
    Z1为单键。
  3. 根据权利要求1或2所述的化合物，其特征在于：R选自H和未取代含有1-5个碳原子的烷基；
    A1选自单键或1，4-苯基，其中1，4-苯基中的H各自独立地可被一个或多个氟元素取代；
    L1和L2均为H；
    Z1为单键。
  4. 根据权利要求1所述的化合物，其特征在于：所述液晶化合物选自如 下通式结构化合物：
    Figure PCTCN2015080517-appb-100002
    R选自含有1-5个碳原子的烷基。
  5. 根据权利要求1或4所述的化合物，其特征在于：所述液晶化合物为：
  6. 权利要求1-5任一项所述化合物的制备方法，其特征在于：合成路线如下：
    Figure PCTCN2015080517-appb-100004
    Figure PCTCN2015080517-appb-100005
    具体包括如下步骤：
    (a)以化合物II-1为起始原料，以弱酸为催化剂，二氯甲烷为溶剂，在室温与二氢吡喃反应，得到化合物II-2；
    (b)化合物II-2以四氢呋喃为溶剂，氮气保护，在-75℃～-85℃，与丁基锂反应，形成锂试剂；再与碘甲烷反应，得到化合物II-3；
    (c)化合物II-3以对甲苯磺酸吡啶鎓为催化剂，搅拌加热反应得到化合物II-4；
    (d)化合物II-5以四氢呋喃为溶剂，氮气保护，在低温下，与丁基锂反应，形成锂试剂；再与二氟二溴甲烷反应，得到化合物II-6；
    (e)化合物II-4与化合物II-6，以二甲基亚砜和水为溶剂，四丁基溴化铵为催化剂，碳酸钾为缚酸剂，反应得到目标化合物I；
    其中，R、A1、Z1、L1及L2的指代同上。
  7. 含有权利要求1-5任一项所述液晶化合物的液晶组合物。
  8. 根据权利要求7所述的组合物，其特征在于：所述液晶化合物的加入量为1-80％。
  9. 根据权利要求8所述的组合物，其特征在于：所述液晶化合物的加入量为3-50％。
  10. 权利要求1-5任一项所述液晶化合物或权利要求7-9任一项所述组合物在液晶显示领域的应用。
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