阅读说明：本技术 一种自配向剂化合物及应用 (Self-aligning agent compound and application thereof ) 是由 孙新战 梁志安 王一平 姜军 鲍永锋 李明 孟劲松 于 2020-04-29 设计创作，主要内容包括：本发明涉及自配向剂化合物、液晶组合物、液晶显示元件及液晶显示器。本发明的自配向剂化合物结构如下式Ⅰ所示,包含该自配向剂化合物的液晶组合物具有良好的配向能力及高的电压保持率,应用于液晶显示器件中时,能够降低残像,从而提高显示品质。(The present invention relates to a self-aligning agent compound, a liquid crystal composition, a liquid crystal display element and a liquid crystal display. The structure of the self-alignment agent compound is shown in the formula I, and the liquid crystal composition containing the self-alignment agent compound has good alignment capability and high voltage holding ratio, and can reduce afterimages when being applied to a liquid crystal display device, so that the display quality is improved.)

1. A self-aligning compound, a compound of formula I,

wherein the content of the first and second substances,

A、B、C、D、A₁、B₁、C₁、D₁each independently represents an aromatic, heteroaromatic, aliphatic or fused ring wherein at least one H atom is optionally substituted by L;

l represents-Sp₁-P₁F atoms, Cl atoms, -CN, straight chain alkyl groups having from 1 to 25 carbon atoms, branched alkyl groups having from 3 to 25 carbon atoms, cyclic alkyl groups having from 3 to 25 carbon atoms, alkenyl groups having from 2 to 25 carbon atoms or alkynyl groups having from 2 to 25 carbon atoms, where one or more non-adjacent-CH groups₂-the group is optionally substituted by-O-, -S-, -NH-, -CO-O-, -O-CO-O-, and wherein one or more H atoms are optionally substituted by halogen atoms;

P₁represents a polymerizable group;

R¹、R²、R³、R⁴each independently represents an H atom, -Sp₂-X₁、 And wherein at least one group does not represent a H atom;

to represento represents 1,2 or 3;

X₁、X₂、X₃each independently represents-OH, -OR_a、-NH₂、-NHR_a、-COOH、-SH、-SR_a、 Or a cyclic sulfone group;

R_arepresents an alkyl group having 1 to 5 carbon atoms;

Sp、Sp₁、Sp₂、Sp₃、Sp₄、Sp₅、Z¹、Z²、Z³、Z⁴、Z⁵、Z⁶each independently represents a single bond, a linear alkylene group having 1 to 25 carbon atoms, a branched alkylene group having 3 to 25 carbon atoms, a cyclic alkylene group having 3 to 25 carbon atoms, an alkenylene group having 2 to 25 carbon atoms, or an alkynylene group having 2 to 25C atoms, and wherein one or more non-adjacent-CH groups₂The radical-is optionally substituted by-O-, -S-, -CO-O-,-O-CO-, -O-CO-O-substituted, wherein one or more H atoms are optionally substituted by F atoms or Cl atoms;

m, m ', n' each independently represent 0, 1,2, 3 or 4.

2. The self-coordinator compound of claim 1, wherein the compound of formula I is selected from the group consisting of compounds of formulae I-1 through I-10,

wherein the content of the first and second substances,

L₁、L₂、L₃、L₄、L₅、L₆、L₇、L₈each independently represents-Sp₁-P₁H atom, alkyl group having 1 to 5 carbon atoms, fluorine-substituted alkyl group having 1 to 5 carbon atoms, alkenyl group having 2 to 5 carbon atoms, alkoxy group having 1 to 5 carbon atoms, fluorine-substituted alkoxy group having 1 to 5 carbon atoms or halogen atom, wherein at least one group represents-Sp₁-P₁；

r₁、r₂、r₃、r₄、r₅、r₆、r₇、r₈Each independently represents 0, 1 or 2;

P₁representation of

R¹、R²、R³、R⁴Each independently represents a H atom、-Sp₂-X₁、 And wherein at least one group does not represent a H atom;

to represento represents 1,2 or 3;

X₁、X₂、X₃each independently represents-OH, -OR_a、-NH₂、-NHR_a、-COOH、-SH、-SR_a、 Or a cyclic sulfone group;

R_arepresents an alkyl group having 1 to 5 carbon atoms;

Sp、Sp₁、Sp₂、Sp₃、Sp₄、Sp₅each independently represents a single bond, a linear alkylene group having 1 to 25 carbon atoms, a branched alkylene group having 3 to 25 carbon atoms, a cyclic alkylene group having 3 to 25 carbon atoms, an alkenylene group having 2 to 25 carbon atoms, or an alkynylene group having 2 to 25 carbon atoms, and wherein one or more non-adjacent-CH groups₂-the group is optionally substituted by-O-, -S-, -CO-O-, -O-CO-O-, wherein one or more H atoms are optionally substituted by F atoms or Cl atoms.

3. The self-coordinator compound of claim 2, wherein the compound of formula I is selected from the group consisting of compounds of formulae I-1-1 through formulae I-9-8,

4. a liquid crystal composition comprising one or more self-aligning agent compounds according to any one of claims 1 to 3.

5. The liquid crystal composition according to claim 4, further comprising one or more polymerizable compounds represented by the following formula VII,

wherein the content of the first and second substances,

R⁵、R⁶each independently represents H atom, C1-5 linear alkyl group, C3-6 cycloalkyl group or-CF₃；

Sp₆、Sp₇Each independently represents a single bond, a linear alkyl group having 1 to 6 carbon atoms, and one or more-CH groups₂-optionally substituted by-O-, -COO-or-C ═ C-;

L₉represents a F atom, a Cl atom, an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkenyloxy group having 2 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms;

w represents 1,2, 3, 4 or 5;

q represents 0, 1,2, 3 or 4.

6. The liquid crystal composition according to any one of claims 4 or 5, further comprising one or more compounds represented by the following formula II and one or more compounds represented by the following formula III,

in the formula II, R₁、R₂Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms;

each independently represent

In the formula III, R₃、R₄Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, and R₃、R₄Any one or more non-adjacent-CH₂-optionally substituted with cyclopentylene, cyclobutyl or cyclopropylene;

Z₁、Z₂each independently represents a single bond, -CH₂CH₂-、-CH₂O-or-OCH₂-；

Each independently represent

m₁Represents 1 or 2, when m₁When the expression is shown in the figure 2,the same or different;

n₁represents 0, 1 or 2, when n₁When the expression is shown in the figure 2,the same or different.

7. The liquid crystal composition of claim 6, wherein the compound of formula II is selected from the group consisting of compounds of formulae II-1 to II-17,

the compound shown in the formula III is selected from the group consisting of compounds shown in formulas III-1 to III-15,

wherein R is₃₁、R₄₁Each independently represents an alkyl group having 1 to 10 carbon atoms or fluorineA substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, and any one or more non-adjacent-CH₂-optionally substituted with cyclopentylene, cyclobutyl or cyclopropylene.

8. The liquid crystal composition of any one of claims 4 or 5, further comprising one or more compounds of formula IV,

wherein R is₅、R₆Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, and any one or more of them is not adjacent-CH₂-optionally substituted by cyclopentylene, cyclobutyl or cyclopropylene; w represents-O-, -S-or-CH₂O-。

9. The liquid crystal composition of any one of claims 4 or 5, further comprising one or more compounds of formula V,

wherein R is₇、R₈Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to cAn alkyl group having 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms;

each independently represent

10. The liquid crystal composition according to any one of claims 4 or 5, further comprising one or more compounds of formula VI,

wherein R is₉、R₁₀Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms;

to represent

F₁、F₂、F₃Each independently represents a H atom or a F atom, and F₂、F₃Not simultaneously being F atoms.

11. A liquid crystal display element or a liquid crystal display comprising the self-alignment agent compound according to any one of claims 1 to 3 or the liquid crystal composition according to any one of claims 4 to 10, the display element or display being an active matrix display element or display or a passive matrix display element or display.

Technical Field

The invention belongs to the technical field of liquid crystal display, and particularly relates to a self-aligning agent, a liquid crystal composition containing the self-aligning agent, and a liquid crystal display element or a liquid crystal display containing the self-aligning agent or the liquid crystal composition.

Background

With the development of Display technology, flat panel Display devices such as Liquid Crystal Display (LCD) devices have advantages of high image quality, power saving, thin body, and wide application range, and thus are widely used in various consumer electronics products such as mobile phones, televisions, personal digital assistants, digital cameras, notebook computers, and desktop computers, and are becoming the mainstream of Display devices.

Currently, alignment of liquid crystal molecules can be achieved using a specific Polyimide (PI) alignment film. As an alignment treatment method for imparting alignment controllability to a liquid crystal alignment film, a brushing method has been conventionally used in many cases. However, the brush polishing method of rubbing the surface of a liquid crystal alignment film made of polyimide or the like has a problem of generating dust and static electricity. In addition, in recent years, the resolution of liquid crystal display elements has been increased, and the unevenness due to the electrode on the substrate or the switching active element for driving the liquid crystal has been increased. Therefore, the surface of the liquid crystal alignment film cannot be uniformly rubbed with cloth, and uniform liquid crystal alignment cannot be achieved.

On the other hand, the polymerizable compound (RMs) is currently a very popular and important topic in the display industry, and the possible application fields include Polymer Sustained Alignment (PSA) liquid crystal display, polymer sustained blue phase (PS-BP) liquid crystal display, patterned Retarder Film (Pattern Retarder Film), and the like. In a liquid crystal display element of a polymer stabilized alignment type, the alignment of liquid crystal molecules can be controlled by using a polymer.

In the liquid crystal display element without PI alignment film disclosed in the prior art, a liquid crystal composition containing a polymerizable compound having an anchor group and a liquid crystal compound is used to control the alignment of liquid crystal molecules, i.e., the vertical self alignment (SAVA) technique, but it has been found that it still has some disadvantages in application. For example, the types of polymerizable compounds containing an anchor group that can be practically used are rare, and most of them have weak anchoring ability to a substrate and liquid crystal molecules, and their applications are limited by their material properties. In addition, the liquid crystal display element has problems of poor pretilt angle stability, low VHR, afterimage, low contrast, and the like.

Disclosure of Invention

The present inventors have conducted extensive studies to obtain a novel anchoring group-containing self-alignment agent compound which, when applied to a PI-free alignment film, can overcome the disadvantage of weak substrate anchoring ability and thus weak vertical alignment ability, and at the same time solve the problems of low VHR and image sticking when applied to a liquid crystal display element or a liquid crystal display, and have found that at least one of the above problems can be solved when applied by containing the compound of the present invention in a liquid crystal composition, thereby completing the present invention.

Specifically, the present invention comprises the following:

in a first aspect of the invention, there is provided a self-aligning agent compound, such as a compound of formula I,

wherein the content of the first and second substances,

A、B、C、D、A₁、B₁、C₁、D₁each independently represents an aromatic, heteroaromatic, aliphatic or fused ring wherein at least one H atom is optionally substituted by L;

l represents-Sp₁-P₁F atoms, Cl atoms, -CN, straight chain alkyl groups having from 1 to 25 carbon atoms, branched alkyl groups having from 3 to 25 carbon atoms, cyclic alkyl groups having from 3 to 25 carbon atoms, alkenyl groups having from 2 to 25 carbon atoms or alkynyl groups having from 2 to 25 carbon atoms, where one or more non-adjacent-CH groups₂-the group is optionally substituted by-O-, -S-, -NH-, -CO-O-, -O-CO-O-, and wherein one or more H atoms are optionally substituted by halogen atoms;

P₁represents a polymerizable group;

R¹、R²、R³、R⁴each independently represents an H atom, -Sp₂-X₁、 And wherein at least one group does not represent a H atom;

to represento represents 1,2 or 3;

X₁、X₂、X₃each independently represents-OH, -OR_a、-NH₂、-NHR_a、-COOH、-SH、-SR_a、 Or a cyclic sulfone group;

R_arepresents an alkyl group having 1 to 5 carbon atoms;

Sp、Sp₁、Sp₂、Sp₃、Sp₄、Sp₅、Z¹、Z²、Z³、Z⁴、Z⁵、Z⁶each independently represents a single bond, a linear alkylene group having 1 to 25 carbon atoms, a branched alkylene group having 3 to 25 carbon atoms, a cyclic alkylene group having 3 to 25 carbon atoms, an alkenylene group having 2 to 25 carbon atoms, or an alkynylene group having 2 to 25 carbon atoms, and wherein one or more non-adjacent-CH groups₂-the group is optionally substituted by-O-, -S-, -CO-O-, -O-CO-O-, wherein one or more H atoms are optionally substituted by F atoms or Cl atoms;

m, m ', n' each independently represent 0, 1,2, 3 or 4.

In a second aspect of the invention, there is provided a liquid crystal composition comprising one or more self-director compounds of formula i.

In a third aspect of the present invention, there is provided a liquid crystal display element or a liquid crystal display comprising one or more self-alignment agent compounds represented by formula i or a liquid crystal composition comprising one or more self-alignment agent compounds represented by formula i.

Effects of the invention

The invention provides a novel self-alignment agent compound containing an anchoring group, which has stronger anchoring force through the interaction of the anchoring group and the surface of a substrate, and can realize the vertical alignment of liquid crystal molecules under the condition of not containing a PI alignment film. When the liquid crystal composition containing the polymerizable compound containing the anchor group is applied to liquid crystal display, VHR (very high frequency response) and afterimage can be improved when the liquid crystal composition is prepared into a display device, so that the product quality is improved.

Drawings

FIG. 1 shows a process for producing a compound represented by the formula I-1-1¹H-NMR spectrum.

Detailed Description

The invention discloses a self-alignment agent compound shown in the formula I.

The invention discloses a self-aligning agent compound shown in a formula I, preferably, the compound shown in the formula I is selected from the group consisting of compounds shown in the following formulas I-1 to I-10,

wherein the content of the first and second substances,

L₁、L₂、L₃、L₄、L₅、L₆、L₇、L₈each independently represents-Sp₁-P₁H atom, C1-5 alkaneA fluorine-substituted alkyl group having 1 to 5 carbon atoms, a carbon-2 to 5 alkenyl group, a carbon-1 to 5 alkoxy group, a fluorine-substituted alkoxy group having 1 to 5 carbon atoms or a halogen atom, wherein at least one group represents-Sp₁-P₁；

r₁、r₂、r₃、r₄、r₅、r₆、r₇、r₈Each independently represents 0, 1 or 2;

P₁representation of

R¹、R²、R³、R⁴Each independently represents an H atom, -Sp₂-X₁、 And wherein at least one group does not represent a H atom;

to represento represents 1,2 or 3;

X₁、X₂、X₃each independently represents-OH, -OR_a、-NH₂、-NHR_a、-COOH、-SH、-SR_a、 Or a cyclic sulfone group;

R_arepresents an alkyl group having 1 to 5 carbon atoms;

Sp、Sp₁、Sp₂、Sp₃、Sp₄、Sp₅each independently represents a single bond, a linear alkylene group having 1 to 25 carbon atoms, a branched alkylene group having 3 to 25 carbon atoms, a cyclic alkylene group having 3 to 25 carbon atoms, an alkenylene group having 2 to 25 carbon atoms, or an alkynylene group having 2 to 25 carbon atoms, and wherein one or more non-adjacent-CH groups₂-the group is optionally substituted by-O-, -S-, -CO-O-, -O-CO-O-, wherein one or more H atoms are optionally substituted by F atoms or Cl atoms.

The self-aligning agent compounds of formula I disclosed herein are more preferably selected from the group consisting of compounds of formula I-1-1 through formula I-9-8,

the present invention also provides a liquid crystal composition comprising one or more of the foregoing self-alignment agent compounds of the present invention.

A liquid crystal composition according to one embodiment of the present invention comprises the compound represented by the formula I. The liquid crystal composition may contain a liquid crystal compound other than the compound represented by the formula I and other additive materials in addition to the compound represented by the formula I.

In the liquid crystal composition disclosed by the invention, optionally, the liquid crystal composition further comprises one or more polymerizable compounds shown in the following formula VII,

wherein the content of the first and second substances,

R⁵、R⁶each independently represents H atom, C1-5 linear alkyl group, C3-6 cycloalkyl group or-CF₃；

Sp₆、Sp₇Each independently represents a single bond, a linear alkyl group having 1 to 6 carbon atoms, and one or more-CH groups₂-optionally substituted by-O-, -COO-or-C ═ C-;

L₉represents a F atom, a Cl atom, an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkenyloxy group having 2 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms;

w represents 1,2, 3, 4 or 5;

q represents 0, 1,2, 3 or 4.

In the liquid crystal composition disclosed in the present invention, preferably, the above-mentioned compound represented by the formula VII is selected from the group consisting of compounds represented by the following formulae VII-1 to VII-4,

wherein the content of the first and second substances,

R⁵¹、R⁶¹each independently represents a H atom, -CH₃or-CF₃；

Sp₆₁、Sp₇₁Each independently represents a linear alkyl group having 1 to 6 carbon atoms, wherein any one or more-CH₂-optionally substituted by-O-, -COO-or-C ═ C-;

L₉₁、L₉₂each independently represents a F atom, a Cl atom, an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkenyloxy group having 2 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms;

q', q "each independently represent 0, 1,2, 3 or 4.

In the liquid crystal composition disclosed in the present invention, more preferably, the above-mentioned compound represented by the formula VII is selected from the group consisting of the compounds represented by the following formulae VII-1-1 to VII-4-2,

in the liquid crystal composition disclosed by the invention, optionally, the liquid crystal composition also comprises one or more compounds shown in a formula II and one or more compounds shown in a formula III,

in the formula II, R₁、R₂Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms;

each independently represent

In the formula III, R₃、R₄Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, and R₃、R₄Any one or more non-adjacent-CH₂-optionally substituted with cyclopentylene, cyclobutyl or cyclopropylene;

Z₁、Z₂each independently represents a single bond, -CH₂CH₂-、-CH₂O-or-OCH₂-；

Each is independentExpress it in elevation

m₁Represents 1 or 2, when m₁When the expression is shown in the figure 2,the same or different;

n₁represents 0, 1 or 2, when n₁When the expression is shown in the figure 2,the same or different.

By containing the combination of the compound represented by the formula II and the compound represented by the formula III in the liquid crystal composition, the obtained liquid crystal composition has low rotational viscosity, is favorable for improving the response speed of the liquid crystal composition, has negative dielectric anisotropy, and can adjust the driving voltage of the composition.

In the present invention, the total mass of the compounds other than the compounds represented by the formulae I and VII is taken as 100%, and the percentage of the ratio between the mass of the compounds represented by the formulae I and VII and the total mass of the other compounds is taken as the mass fraction of the compounds represented by the formulae I and VII in the liquid crystal composition. For example, in the case where the liquid crystal composition contains only the compounds represented by the formulae I, II and III, the total content of the compounds represented by the formulae II and III is taken as 100%, and the percentage of the ratio of the amount of the compound represented by the formula I added to the total mass of the compounds represented by the formulae II and III is taken as the mass fraction of the compound represented by the formula I.

In the liquid crystal composition of the present invention, preferably, the compound represented by the aforementioned formula II is selected from the group consisting of compounds represented by the formulae II-1 to II-17,

preferably, the aforementioned compound represented by the formula III is selected from the group consisting of compounds represented by the formulae III-1 to III-15,

wherein R is₃₁、R₄₁Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, and R₃、R₄Any one or more non-adjacent-CH in the group₂-optionally substituted with cyclopentylene, cyclobutyl or cyclopropylene.

The liquid crystal composition disclosed by the invention optionally further comprises one or more compounds shown as a formula IV,

wherein R is₅、R₆Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atomsAnd R is₅、R₆Any one or more non-adjacent-CH₂-optionally substituted by cyclopentylene, cyclobutyl or cyclopropylene; w represents-O-, -S-or-CH₂O-。

By containing the compound shown in the formula IV in the liquid crystal composition, the liquid crystal composition has larger negative dielectric anisotropy, and is favorable for reducing the driving voltage of a device.

Further, the compound represented by the formula IV is selected from compounds represented by formulas IV-1 to IV-10,

wherein R is₅₁、R₆₁Represents an alkyl group having 1 to 6 carbon atoms;

the liquid crystal composition disclosed by the invention optionally further comprises one or more compounds shown as a formula V,

wherein R is₇、R₈Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms;

each independently represent

Further, the compound represented by the above formula V is preferably selected from the group consisting of compounds represented by the formulae V-1 to V-4,

wherein R is₇₁、R₈₁Each independently represents an alkyl group having 2 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms; examples of the alkenyl group having 2 to 6 carbon atoms include a vinyl group, a 2-propenyl group, or a 3-pentenyl group; r₈₂Represents an alkoxy group having 1 to 5 carbon atoms;

by including the compound represented by the formula V in the liquid crystal composition of the present invention, a high clearing point and a high elastic constant, particularly a splay elastic constant K can be obtained₃₃And is beneficial to improving the parameter performance of the liquid crystal composition.

The liquid crystal composition disclosed by the invention optionally further comprises one or more compounds shown as a formula VI,

wherein R is₉、R₁₀Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms;

to represent

Further, the aforementioned compound represented by the formula VI is preferably selected from the group consisting of compounds represented by the formulae VI-1 to VI-3,

wherein R is₉₁、R₁₀₁Each independently preferably represents an alkyl group having 2 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms.

The clearing point of the liquid crystal composition can be improved by containing the compound selected from the compounds shown in formulas VI-1 to VI-3 in the liquid crystal composition.

In the liquid crystal composition disclosed by the invention, preferably, the liquid crystal composition comprises the following components in percentage by mass: 0.01-1% of a compound shown as a formula I, 0-1% of a compound shown as a formula VII, 30-60% of a compound shown as a formula II, 30-60% of a compound shown as a formula III and 1-10% of a compound shown as a formula VI;

preferably, the liquid crystal composition of the present invention comprises, in mass percent: 0.01-1% of a compound shown as a formula I, 0-0.5% of a compound shown as a formula VII, 15-60% of a compound shown as a formula II, 20-60% of a compound shown as a formula III, 1-15% of a compound shown as a formula IV and 1-10% of a compound shown as a formula VI;

preferably, the liquid crystal composition of the present invention comprises, in mass percent: 0.03-0.2% of a compound shown as a formula I, 0-0.5% of a compound shown as a formula VII, 35-45% of a compound shown as a formula II, 45-50% of a compound shown as a formula III, 2-10% of a compound shown as a formula IV and 2-5% of a compound shown as a formula VI.

Preferably, the liquid crystal composition of the present invention comprises, in mass percent: 0.01-1% of a compound shown as a formula I, 0-0.5% of a compound shown as a formula VII, 15-60% of a compound shown as a formula II, 20-60% of a compound shown as a formula III, 1-30% of a compound shown as a formula V and 1-10% of a compound shown as a formula VI;

preferably, the liquid crystal composition of the present invention comprises, in mass percent: 0.03-0.2% of a compound shown as a formula I, 0-0.5% of a compound shown as a formula VII, 25-40% of a compound shown as a formula II, 35-50% of a compound shown as a formula III, 5-20% of a compound shown as a formula V and 2-5% of a compound shown as a formula VI.

Preferably, the liquid crystal composition of the present invention comprises, in mass percent: 0.01-1% of a compound shown as a formula I, 0-0.5% of a compound shown as a formula VII, 15-60% of a compound shown as a formula II, 20-60% of a compound shown as a formula III, 1-15% of a compound shown as a formula IV, 1-30% of a compound shown as a formula V and 1-10% of a compound shown as a formula VI;

preferably, the liquid crystal composition of the present invention comprises, in mass percent: 0.03-0.2% of a compound shown as a formula I, 0-0.5% of a compound shown as a formula VII, 20-40% of a compound shown as a formula II, 30-50% of a compound shown as a formula III, 2-10% of a compound shown as a formula IV, 5-20% of a compound shown as a formula V and 2-5% of a compound shown as a formula VI.

In the liquid crystal composition disclosed by the present invention, a dopant having various functions may be added, and when the liquid crystal composition contains a dopant, the content of the dopant is preferably 0.01 to 1% by mass in the liquid crystal composition, and examples of the dopant include an antioxidant, an ultraviolet absorber, and a chiral agent.

Examples of the antioxidant and ultraviolet absorber include:

wherein t represents an integer of 1 to 10.

The liquid crystal display device of the present invention comprises the self-aligning agent compound of the present invention or the liquid crystal composition of the present invention, and the display device is an active matrix display device or a passive matrix display device.

Preferably, the liquid crystal display device of the present invention is preferably an active matrix liquid crystal display device.

The liquid crystal display device of the present invention is not limited in its structure as long as the compound represented by formula i of the present invention is contained in the liquid crystal composition used for the liquid crystal display device, and those skilled in the art can select an appropriate structure of the liquid crystal display device according to the desired performance.

As an embodiment of the liquid crystal display device of the present invention, for example, the following structures can be cited: the liquid crystal display device comprises a first substrate, a second substrate and a liquid crystal composition arranged between the first substrate and the second substrate, wherein the first substrate and the second substrate are oppositely arranged in parallel, the first substrate is provided with a common electrode, the second substrate is provided with a pixel electrode, and spacers are scattered between the first substrate and the second substrate.

Examples

In order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and the accompanying drawings. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.

In the invention, the preparation method is a conventional method if no special description is provided, the used raw materials can be obtained from a public commercial way if no special description is provided, the percentages refer to mass percentage, the temperature is centigrade (DEG C), the liquid crystal compound also becomes a liquid crystal monomer, and the specific meanings and test conditions of other symbols are as follows:

cp represents a liquid crystal clearing point (DEG C), and is measured by a DSC quantitative method;

Δ n represents optical anisotropy, and Δ n ═ n_e-n_oWherein n is_oRefractive index of ordinary light, n_eThe refractive index of the extraordinary ray is measured under the conditions of 25 +/-2 ℃ and 589nm, and the Abbe refractometer is used for testing;

Δ ε represents dielectric anisotropy, and Δ ε_∥-ε_⊥Wherein, epsilon_∥Is a dielectric constant parallel to the molecular axis,. epsilon_⊥Dielectric constant perpendicular to the molecular axis, at 25 + -0.5 deg.C, 20 μm vertical cell, INSTEC: ALCT-IR1 test;

VHR represents the voltage holding ratio (%), and the test conditions are 20 +/-2 ℃, voltage +/-5V, pulse width 10ms and voltage holding time 16.7 ms. The testing equipment is a TOYO Model6254 liquid crystal performance comprehensive tester;

γ₁expressed as rotational viscosity (mPas) at 25 + -0.5 deg.C, 20 micron vertical cell, INSTEC: ALCT-IR1 test;

afterimage: the residual image of the liquid crystal display device was evaluated by visually observing the residual level of the fixed pattern in the case of performing uniform display in the full screen, on a 4-scale basis as follows, after displaying the fixed pattern for 1000 hours in the display region:

excellent no residue;

a very small amount of residue was allowed;

the delta is remained and is not allowed to be increased;

x remained quite poor.

The preparation method of the liquid crystal composition comprises the following steps: weighing the polymerizable compounds according to a certain ratio, putting the polymerizable compounds into a stainless steel beaker, putting the stainless steel beaker filled with the polymerizable compounds on a magnetic stirring instrument for heating and melting, adding a magnetic rotor into the stainless steel beaker after the polymerizable compounds in the stainless steel beaker are melted, uniformly stirring the mixture, and cooling to room temperature to obtain the liquid crystal composition.

The liquid crystal monomer structure used in the embodiment of the invention is represented by codes, and the code representation methods of the liquid crystal ring structure, the end group and the connecting group are shown in the following tables 1 and 2.

Corresponding code of the ring structure of Table 1

TABLE 2 corresponding codes for end groups and linking groups

Examples are:

the code is CC-Cp-V1;

the code is PGP-Cpr 1-2;

the code is CPY-2-O2;

the code is CCY-3-O2;

the code is COY-3-O2;

the code is CCOY-3-O2;

the code is Sb-CpO-O4;

the code is Sc-CpO-O4;

the code is COYL-Cprl-O2;

the code is COYL-1-OV 1.

The invention is illustrated below with the following specific examples:

[ Compound ]

The compounds of formula i of the present invention can be synthesized according to the following scheme:

the key step of the compound shown in the formula I is-Sp-synthesis, and the compound can be synthesized according to the following scheme:

1. when the alkyl chain is an alkyl chain, the alkyl chain can be obtained by a wittig reaction and then hydrogenation reduction of an olefinic bond;

2. when the alkyl ether is an ether chain, the alkyl ether can be obtained through etherification reaction;

3. when it is an ester chain, it can be obtained by a dehydration condensation reaction.

The other steps are conventional reactions, and the specific steps are shown in the following examples.

The raw materials and reagents in the synthesis can be obtained by conventional synthesis or commercial purchase, and the methods such as the method principle, the operation process, the conventional post treatment, silica gel column passing, recrystallization purification and the like are well known by synthesizers in the field, so that the synthesis process can be completely realized to obtain the target product.

The reactions of all the steps of all the above processes are carried out in a solvent; the solvent is at least one selected from tetrahydrofuran, N-dimethylformamide, ethanol, methanol, dichloromethane, acetone, toluene and deionized water.

Example 1

The structural formula of the compound is shown as the following formula I-1-1:

the preparation route is as follows:

the specific operation flow of the preparation is as follows:

intermediate 1

Under nitrogen protection, 0.3mol of (3- (benzyloxy) -4- (3- ((tert-butyldimethylsilyl) oxy) propoxy) phenyl) phenylboronic acid, 0.3mol of 4-bromo-3-fluoro-4 '-pentyl [1, 1' -biphenyl ] -2-ol, 2.0L of toluene, 0.7L of water, 0.36mol of potassium carbonate, and 0.3g of a catalyst were charged in a 5L three-necked flask, and the mixture was heated under reflux for reaction for 3 hours. Standing, separating, performing column chromatography, and recrystallizing with toluene/ethanol to obtain compound 1 as light yellow solid. HPLC: 92%, yield Y75%.

Intermediate 2

Under the protection of nitrogen, 0.22mol of 1, 0.1mol of 1, 2-dibromohexane, 0.22mol of anhydrous potassium carbonate, 1.2L of DMF, N are added into a 2L three-necked bottle₂The temperature is controlled at 120 ℃ for 4 hours under protection. After the reaction is finished, the temperature is reduced, ice water is poured into the mixture while stirring, 30 mIn is stirred, the mixture is filtered, 0.5L of petroleum ether is beaten, and the compound 2 can be obtained, wherein HPLC (high performance liquid chromatography) accounts for 90 percent, and the yield Y is 60 percent.

Intermediate 3

0.08mol of Compound 2, 6.6g of Pd/C, 0.3L of THF and 0.3L of EtOH are placed in a 1L three-necked flask, N₂Replacing three times by H2, removing benzyl by hydrogenation at 40 deg.C, reacting for 6 hours. After the reaction is finished, filtering by using kieselguhr, concentrating the filtrate, and mixing PE, EA and 10: pulping 1, stirring 10 mIn to obtain the compound 3, HPLC: 98% and yield Y: 75%.

Compound 4

In a 500ml three-necked flask are added 0.02mol of 3, 0.1mol of triethylamine, 0.2L of DCM, N₂Under the protection, the temperature is controlled at 0 ℃, and 0.1mol of methacrylic chloride is dripped. After dropping, the reaction was carried out at room temperature for 3 hours. After the reaction is finished, adding water for separating liquid, extracting a water phase by DCM, combining organic phases, washing the organic phases with saturated salt water once, drying the anhydrous sodium sulfate, filtering, concentrating the filtrate, dissolving the filtrate by 5 times of toluene at 45 ℃, passing through a 50g silica gel column, washing the column by 3 times of toluene, concentrating, heating and dissolving the filtrate by 3 times of toluene and ethanol by 3 times of toluene, freezing the filtrate for 4 hours in a refrigerator at the temperature of-20 ℃, filtering, airing to obtain a white solid compound 4,HPLC: 98%, yield Y60%.

Compound I-1

0.01mol of 4, 0.2L THF, N are introduced into a 500ml three-necked flask₂0.01mol TBAF (1mol/L) is added dropwise at the temperature of 0 ℃ under protection. After dropping, the reaction was carried out at room temperature for 1 hour. After the reaction is finished, water is added for separating liquid, the water phase is extracted twice by EA, the organic phases are combined, the saturated salt solution is washed once, anhydrous sodium sulfate is dried and filtered, the filtrate is concentrated, an EA/PE system passes through a silica gel separation column and is concentrated, 3 times of toluene and 3 times of alcohol are heated and dissolved, the mixture is frozen in a refrigerator at the temperature of-20 ℃ for 4 hours, the filtrate is sucked and filtered, the mixture is recrystallized for four times according to the same method and is dried, and a white solid compound I-1-1 is obtained, the HPLC (high performance liquid chromatography) ratio is 99.0%, and the yield Y is 45%.

Process for preparation of compound I-1-1¹The H-NMR spectrum is shown in FIG. 1.

Example 2

The structural formula of the compound is shown as the following formula I-2-1:

the preparation route is as follows:

the specific operation flow of the preparation is as follows:

intermediate 5

Under nitrogen protection, 0.3mol of (3- (benzyloxy) -4- (3- ((tert-butyldimethylsilyl) oxy) propoxy) phenyl) phenylboronic acid, 0.3mol of 3-bromo-2-fluoro-6- (4' -pentylcyclohexyl) phenol, 2.0L of toluene, 0.7L of water, 0.36mol of potassium carbonate, and 0.3g of a catalyst were charged in a 5L three-necked flask, and the mixture was heated under reflux for 3 hours. Standing, separating, performing column chromatography, and recrystallizing with toluene/ethanol to obtain compound 1 as light yellow solid. HPLC: 91%, yield Y: 69%.

Intermediate 6

Under the protection of nitrogen, 0.20mol of 5, 0.1mol of 1, 2-dibromohexane, 0.22mol of anhydrous potassium carbonate, 1.2L of DMF, N are added into a 2L three-necked bottle₂The temperature is controlled at 120 ℃ for 4 hours under protection. After the reaction, the temperature was reduced, the mixture was poured into ice water with stirring, stirred for 30 mn, filtered, and slurried with 0.5L of petroleum ether to obtain compound 6, which was 89% by HPLC, with a yield Y of 70%.

Intermediate 7

0.08mol of Compound 6, 6.6g of Pd/C, 0.3L of THF and 0.3L of EtOH are placed in a 1L three-necked flask, N₂Replacing three times by H2, removing benzyl by hydrogenation at 40 deg.C, reacting for 6 hours. After the reaction is finished, filtering by using kieselguhr, concentrating the filtrate, and mixing PE, EA and 10: slurry 1 and stir 10 ml of ln to give compound 7 in 92% HPLC yield Y75%.

Compound 8

In a 500ml three-necked flask are charged 0.02mol of 7, 0.1mol of triethylamine, 0.2L of DCM, N₂Under the protection, the temperature is controlled at 0 ℃, and 0.1mol of methacrylic chloride is dripped. After dropping, the reaction was carried out at room temperature for 3 hours. After the reaction is finished, water is added for separating liquid, the water phase is extracted by DCM, the organic phases are combined, saturated salt water is washed once, anhydrous sodium sulfate is dried, the filtrate is filtered, the filtrate is concentrated, 5 times of toluene is dissolved at 45 ℃, the filtrate passes through a 50g silica gel column, 3 times of toluene is washed by a column, the concentration is carried out, 3 times of toluene is dissolved by heating in 3 times of ethanol, the filtrate is frozen for 4 hours in a refrigerator at the temperature of-20 ℃, the filtrate is sucked, filtered and dried, and the white solid compound 8 is obtained, 95 percent of HPLC and 63 percent of yield Y.

Compound I-2-1

0.01mol of 8, 0.2L THF, N are introduced into a 500ml three-necked flask₂0.01mol TBAF (1mol/L) is added dropwise at the temperature of 0 ℃ under protection. After dropping, the reaction was carried out at room temperature for 1 hour. After the reaction is finished, water is added for separating liquid, an aqueous phase is extracted twice by EA, organic phases are combined, the saturated salt solution is washed once, anhydrous sodium sulfate is dried and filtered, filtrate is concentrated, an EA/PE system passes through a silica gel separation column and is concentrated, 3 times of toluene and 3 times of alcohol are heated and dissolved, the mixture is frozen in a refrigerator at the temperature of-20 ℃ for 4 hours, suction filtration is carried out, recrystallization is carried out for four times according to the same method, and air drying is carried out to obtain a white solid compound I-2-1, HPLC (high performance liquid chromatography) is 98.9%, and the yield Y is 35%.

Example 3

The structural formula of the compound is shown as the following formula I-5-1:

the preparation route is as follows:

the specific operation flow of the preparation is as follows:

intermediate 9

Under the protection of nitrogen, 0.3mol of (3- (benzyloxy) -4- (3- ((tert-butyldimethylsilyl) oxy) propoxy) phenyl) phenylboronic acid, 0.3mol of 3-bromo-2-fluoro-6- (4' -pentylbiphenyl) phenol, 2.0L of toluene, 0.7L of water, 0.36mol of potassium carbonate, and 0.3g of a catalyst were charged into a 5L three-necked flask, and the mixture was heated under reflux for 3 hours. Standing, separating, performing column chromatography, and recrystallizing with toluene/ethanol to obtain compound 9 as light yellow solid. HPLC: 90% and yield Y: 77%.

Intermediate 10

Under the protection of nitrogen, 0.20mol of 9, 0.1mol of 1, 2-dibromohexane, 0.22mol of anhydrous potassium carbonate, 1.2L of DMF, N are added into a 2L three-necked bottle₂The temperature is controlled at 120 ℃ for 4 hours under protection. After the reaction, the temperature was reduced, the mixture was poured into ice water with stirring, stirred for 30 mn, filtered, and slurried with 0.5L of petroleum ether to obtain compound 10, which was 88% by HPLC, with a yield Y of 72%.

Intermediate 11

0.08mol of Compound 10, 6.6g of Pd/C, 0.3L of THF and 0.3L of EtOH are placed in a 1L three-necked flask, N₂Replacing three times by H2, removing benzyl by hydrogenation at 40 deg.C, reacting for 6 hours. After the reaction is finished, filtering by using kieselguhr, concentrating the filtrate, and mixing PE, EA and 10: slurry 1 and stir 10 ml of ln afforded compound 11 in 92% HPLC yield Y74%.

Intermediate 12

In a 500ml three-necked flask are charged 0.02mol of 11, 0.1mol of triethylamine, 0.2L of DCM, N₂Under the protection, the temperature is controlled at 0 ℃, and 0.1mol of methacrylic chloride is dripped. After dropping, the reaction was carried out at room temperature for 3 hours. After the reaction, adding water for separating liquid, extracting the water phase with DCM, combining the organic phases, washing with saturated salt water once, drying with anhydrous sodium sulfate, filtering, concentrating the filtrate, dissolving 5 times of toluene at 45 DEG CSeparating, passing through 50g silica gel column, washing with 3 times of toluene, concentrating, dissolving with 3 times of toluene and 3 times of ethanol under heating, freezing at-20 deg.C for 4 hr, filtering, and air drying to obtain white solid compound 12, HPLC 94%, and yield Y65%.

Compound I-2-1

0.01mol of 12, 0.2L THF, N are introduced into a 500ml three-necked flask₂0.01mol TBAF (1mol/L) is added dropwise at the temperature of 0 ℃ under protection. After dropping, the reaction was carried out at room temperature for 1 hour. After the reaction is finished, water is added for separating liquid, the water phase is extracted twice by EA, the organic phases are combined, the saturated salt solution is washed once, anhydrous sodium sulfate is dried and filtered, the filtrate is concentrated, an EA/PE system passes through a silica gel separation column and is concentrated, 3 times of toluene and 3 times of alcohol are heated and dissolved, the mixture is frozen in a refrigerator at the temperature of-20 ℃ for 4 hours, the filtrate is sucked and filtered, the mixture is recrystallized for four times according to the same method and is dried, and a white solid compound I-2-1 is obtained, the HPLC (high performance liquid chromatography) ratio is 98.5%, and the yield Y is 40%.

Example 4

The structural formula of the compound is shown as the following formula I-6-1:

the preparation route is as follows:

the specific operation flow of the preparation is as follows:

intermediate 13

Under nitrogen protection, 0.3mol of (3- (benzyloxy) -4- (3- ((tert-butyldimethylsilyl) oxy) propoxy) phenyl) phenylboronic acid, 0.3mol of 4-bromo-3-fluoro-4 '- (4-pentylcyclohexyl) - [1, 1' -biphenyl ] -2-ol, 2.0L of toluene, 0.7L of water, 0.36mol of potassium carbonate, and 0.3g of a catalyst were charged in a 5L three-necked flask, and the mixture was heated under reflux for 3 hours. Standing, separating, performing column chromatography, and recrystallizing with toluene/ethanol to obtain compound 13 as light yellow solid. HPLC: 85%, yield Y: 74%.

Intermediate 14

Under the protection of nitrogen, 0.20mol of the extract is added into a 2L three-necked bottle13. 0.1mol of 1, 2-dibromohexane, 0.22mol of anhydrous potassium carbonate, 1.2L of DMF, N₂The temperature is controlled at 120 ℃ for 4 hours under protection. After the reaction is finished, the temperature is reduced, ice water is poured into the mixture while stirring, 30 mIn is stirred, the mixture is filtered, 0.5L of petroleum ether is beaten, and the compound 14 can be obtained, wherein the HPLC (high performance liquid chromatography) content is 93%, and the yield Y is 76%.

Intermediate 15

0.08mol of Compound 14, 6.6g of Pd/C, 0.3L of THF and 0.3L of EtOH are placed in a 1L three-necked flask, N₂Replacing three times by H2, removing benzyl by hydrogenation at 40 deg.C, reacting for 6 hours. After the reaction is finished, filtering by using kieselguhr, concentrating the filtrate, and mixing PE, EA and 10: pulping 1, stirring 10 mIn to obtain 15, HPLC: 90%, yield Y: 85%.

Compound 16

In a 500ml three-necked flask are charged 0.02mol of 15, 0.1mol of triethylamine, 0.2L of DCM, N₂Under the protection, the temperature is controlled at 0 ℃, and 0.1mol of methacrylic chloride is dripped. After dropping, the reaction was carried out at room temperature for 3 hours. After the reaction is finished, water is added for separating liquid, the water phase is extracted by DCM, the organic phases are combined, saturated salt water is washed once, anhydrous sodium sulfate is dried, the filtrate is filtered, the filtrate is concentrated, 5 times of toluene is dissolved at 45 ℃, the filtrate passes through a 50g silica gel column, 3 times of toluene is washed by a column, the concentration is carried out, 3 times of toluene is dissolved by heating in 3 times of ethanol, the filtrate is frozen for 4 hours in a refrigerator at the temperature of-20 ℃, the filtrate is sucked, filtered and dried, and the white solid compound 16 is obtained, 94 percent of HPLC and 71 percent of yield Y.

Compound I-6-1

In a 500ml three-necked flask, 0.01mol of 16, 0.2L of THF, N are introduced₂0.01mol TBAF (1mol/L) is added dropwise at the temperature of 0 ℃ under protection. After dropping, the reaction was carried out at room temperature for 1 hour. After the reaction is finished, water is added for separating liquid, the water phase is extracted twice by EA, the organic phases are combined, the saturated salt solution is washed once, anhydrous sodium sulfate is dried and filtered, the filtrate is concentrated, an EA/PE system passes through a silica gel separation column and is concentrated, 3 times of toluene and 3 times of alcohol are heated and dissolved, the mixture is frozen in a refrigerator at the temperature of-20 ℃ for 4 hours, the filtrate is sucked and filtered, the mixture is recrystallized for four times according to the same method and is dried, and a white solid compound I-6-1 is obtained, the HPLC (high performance liquid chromatography) ratio is 99.2%, and the yield Y is 30%.

Mother liquid crystal composition:

mother liquid crystal composition 1

The formulation and corresponding properties of the liquid crystal compositions are shown in table 3 below.

Table 3: formulation and corresponding Properties of the mother liquid Crystal composition 1

Mother liquid crystal composition 2

The formulation and corresponding properties of the liquid crystal compositions are shown in table 4 below.

Table 4: formulation and corresponding Properties of mother liquid Crystal composition 2

Mother liquid Crystal composition 3

The formulation and corresponding properties of the liquid crystal compositions are shown in table 5 below.

Table 5: formulation and corresponding Properties of mother liquid Crystal composition 3

Mother liquid Crystal composition 4

The formulation and corresponding properties of the liquid crystal compositions are shown in table 6 below.

Table 6: formulation and corresponding Properties of mother liquid Crystal composition 4

Mother liquid Crystal composition 5

The formulation and corresponding properties of the liquid crystal compositions are shown in table 7 below.

Table 7: master liquid crystal composition 5 formulation and corresponding properties

Mother liquid crystal composition 6

The formulation and corresponding properties of the liquid crystal compositions are shown in Table 8 below.

Table 8: master liquid crystal composition 6 formulation and corresponding properties

Polymerizable compound (c):

comparative compound (c):

examples 5 to 10, comparative examples 1 to 3:

table 9: compositions and contents of examples and comparative examples

Examples 5 to 10 and comparative examples 1 to 3 were prepared, respectively, with the components and contents described in Table 9 above, with reference to the above-mentioned liquid crystal composition preparation method.

In examples 6, 8, 10, the resulting mixture was introduced into a test cell without polyimide alignment layer, layer thickness d ≈ 4.0 μm, ITO coated on both sides, structured ITO in the case of multi-domain switching, without passivation layer. The LC medium has a spontaneous homeotropic (vertical) alignment with respect to the substrate surface. The alignment remains stable up to the clearing point and the resulting test cell can be reversibly switched by applying a voltage.

In examples 5, 7, 9, the resulting mixture was introduced into a test cell without polyimide alignment layer, with a layer thickness d ≈ 4.0 μm, with ITO coated on both sides (structured ITO in the case of multi-domain switching), without passivation layer. The LC medium has a spontaneous homeotropic (vertical) alignment with respect to the substrate surface. The alignment remains stable up to the clearing point and the resulting test cell can be reversibly switched by applying a voltage. With a voltage greater than the optical threshold voltage (e.g. 14Vpp) at 20 deg.C, with a voltage of 100mW/cm²The box was irradiated with UV light at intensity for 12 minutes with a 340nm band pass filter. This causes polymerization of the polymerizable compound. Thus, the homeotropic alignment is further stabilized, and a 'pretilt' is established.

Test of reliability

The reliability of the liquid crystal mixture is tested by ultraviolet and high temperature aging tests and VHR tests, and the smaller the VHR data change before and after the ultraviolet and high temperature tests of the liquid crystal panel, the stronger the ultraviolet and high temperature resistance. Therefore, the ultraviolet and high temperature resistance can be judged by comparing the difference of VHR data of each example and comparative example before and after the test.

Ultraviolet aging test: the cell containing the liquid crystal mixture was placed under an ultraviolet lamp at 365nm to irradiate 5000mJ of energy.

High-temperature aging test: the test cell containing the liquid crystal mixture was placed in an oven at 100 ℃ for one hour.

The smaller the change of the VHR data after the aging test is relative to the initial VHR data, the stronger the ultraviolet resistance and the high temperature resistance of the liquid crystal mixture during application, so that the stronger the resistance to the damage of the external environment in the working process can be judged, and the higher the reliability is.

The VHR, afterimage and contrast data for the liquid crystal mixture examples and comparative examples are shown in table 10 below.

Table 10: VHR, afterimage data for liquid crystal mixture examples and comparative examples

As can be seen from table 10 above, compared with the comparative example, the liquid crystal mixture of the present invention has less VHR drop after uv and high temperature, and the improvement of the afterimage is more obvious.

It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.