阅读说明：本技术 一种高性能液晶化合物及其制备方法与应用 (High-performance liquid crystal compound and preparation method and application thereof ) 是由 苏学辉 于海龙 王迎运 刘俊 田会强 储士红 姜天孟 陈海光 于 2018-06-22 设计创作，主要内容包括：本发明属于液晶材料技术领域,涉及一种高性能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所示的结构,使用了所述液晶化合物或含有所述液晶化合物的组合物具有较宽的向列相温度范围、合适的或较高的双折射率各向异性△n、具有较低的旋转粘度、较大的Δε<Sub>⊥</Sub>、较高的电阻率、良好的抗紫外线性能、高电荷保持率以及低蒸汽压等性能。且该化合物价格低廉、性能稳定,可广泛用于液晶显示领域,具有重要的应用价值。<Image he="241" wi="700" file="DDA0001704703530000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention belongs to the technical field of liquid crystal materials, and relates to a high-performance liquid crystal compound, and a preparation method and application thereof. The liquid crystal compound has a structure shown in a general formula I, and the liquid crystal compound or the composition containing the liquid crystal compound has a wider nematic phase temperature range, proper or higher birefringence anisotropy Deltan, lower rotational viscosity and larger Deltaepsilon ⊥ Higher resistivity, good ultraviolet resistance, high charge retention rate, low vapor pressure and the like. The compound has low price and stable performance, and can be widely used inThe liquid crystal display has important application value.)

1. A liquid crystal compound having a structure represented by formula I:

r represents C₁～C₁₅Alkyl, alkoxy or C₂～C₁₅Wherein any one or more H atoms may be independently substituted with F or Cl, any one or more CH₂May each independently be replaced by cyclopentyl, cyclobutyl or cyclopropyl;

z represents C₁～C₁₅Wherein any one or more H atoms may each independently be substituted by F or Cl;

each independently represent

L represents H, CH₃Or OCH₃；

m and n independently represent 0 or 1.

2. The liquid crystal compound according to claim 1, wherein R represents C₁～C₁₀Alkyl, alkoxy, C₂～C₁₀Wherein any one or more H atoms may be independently substituted with F or Cl, any one or more CH₂May each independently be replaced by cyclopentyl, cyclobutyl or cyclopropyl;

preferably, R represents C₁～C₁₀Alkyl, alkoxy, C₂～C₁₀Wherein any one or more H atoms may be substituted by F, any one or more CH₂Each independently may be replaced by cyclopentyl, cyclobutyl or cyclopropyl.

3. The liquid crystal compound according to claim 1 or 2, wherein Z represents C₁～C₁₀Wherein any one or more H atoms may each independently be substituted by F or Cl;

preferably, Z represents C₁～C₁₀Alkylene or alkenylene groups of (a).

4. According to claims 1-3Any of the liquid crystal compounds described in the general formula I, wherein when m ═ n ═ 1, ring a and ring B are not simultaneously the same

Or, when m ═ n ═ 1, ring a or ring B isWhen ring B or ring A is selected from

5. The liquid crystal compound according to any one of claims 1 to 4, wherein the compound is one selected from the group consisting of:

6. the liquid crystal compound according to any one of claims 1 to 5, wherein the compound is one selected from the group consisting of:

R₁is represented by C₁～C₁₀Wherein any one or more H atoms may be substituted by F;

7. a method for preparing the liquid crystal compound according to any one of claims 1 to 6, wherein the synthetic route is as follows:

r, L, Z, m and n in the compounds involved in the reactions in the steps correspond to R, L, Z, m and n in the obtained liquid crystal compound product;

preferably, the method comprises the following steps:

(1)firstly carrying out metalation reaction with n-butyl lithium, and then reacting with difluorodibromomethane to synthesize the compound

(2)Firstly reacting with magnesium chips to form a Grignard reagent, and then reacting with trimethyl borate to obtain the compound

(3) Obtained by the step (2)By reaction with hydrogen peroxide to give

(4) Obtained by the step (1)And the one obtained by the step (3)Reactive synthesis of compounds by Williamson synthesis

8. The method according to claim 7, wherein, in step (1),the feeding molar ratio of n-butyllithium to dibromodifluoromethane is 1: 1.0-1.5: 1.6-2.0, the reaction temperature is-80-0 ℃, and the reaction time is 1-6 h;

and/or the presence of a gas in the gas,

in the step (2),the feeding molar ratio of the magnesium chips to the trimethyl borate is as follows: 1: 1.5-2.5: 1.6-2.5; the temperature for dropping trimethyl borate is-20 ℃ to 0 ℃;

and/or the presence of a gas in the gas,

in the step (3), the step (c),the feeding molar ratio of the hydrogen peroxide to the hydrogen peroxide is as follows: 1: 2.5 to 3.5; the reaction time is 2 h;

and/or the presence of a gas in the gas,

in the step (4), the step (c),the feeding molar ratio of (A) to (B) is 1: 1.0-2.0, the reaction temperature is 50-120 ℃, and the reaction time is 3-8 h.

9. A liquid crystal composition comprising the liquid crystal compound according to any one of claims 1 to 6; preferably, the mass percentage of the compound in the composition is 0.01-99%, more preferably 0.01-60%, and even more preferably 0.1-40%.

10. Use of the liquid crystal compound according to any one of claims 1 to 6 and/or the liquid crystal composition according to claim 9 in the field of liquid crystal displays; preferably in liquid crystal display devices; more preferably, the liquid crystal display device comprises a TN, ADS, VA, PSVA, FFS or IPS liquid crystal display.

Technical Field

The invention belongs to the technical field of liquid crystal materials, and relates to a high-performance liquid crystal compound, and a preparation method and application thereof.

Background

In recent years, liquid crystal display devices have been developed more and more rapidly, and various types such as a small liquid crystal display device for vehicles, a portable liquid crystal display device, an ultra-thin liquid crystal display device, and the like have been developed. Developments in the field are progressing, and in the case of a television, for example, it is characterized by light weight, small space occupation, convenience in movement, and also a notebook-type personal computer, a mobile phone, and the like.

The liquid crystal material is used as an environmental material and has great research value and good application prospect in the fields of information display materials, organic optoelectronic materials and the like. At present, the TFT-LCD product technology has matured, and successfully solves the technical problems of viewing angle, resolution, color saturation, brightness, etc., and large-size and medium-and small-size TFT-LCD displays have gradually occupied the mainstream status of flat panel displays in respective fields. However, the requirements for display technology are continuously increasing, and liquid crystal displays are required to achieve faster response, reduce driving voltage to reduce power consumption, and the like, and liquid crystal materials are also required to have low voltage driving, fast response, wide temperature range and good low temperature stability.

The liquid crystal material plays an important role in improving the performance of the liquid crystal display, especially reducing the rotational viscosity of the liquid crystal material and improving the dielectric anisotropy delta epsilon of the liquid crystal material. In order to improve the properties of materials and enable the materials to meet new requirements, the synthesis of novel structure liquid crystal compounds and the research of structure-property relationship become important work in the field of liquid crystal.

Disclosure of Invention

The first object of the present invention is to provide a novel liquid crystal compound. The liquid crystal composition containing the compound has lower rotary viscosity and larger delta epsilon_⊥. And the compound has low price and stable performance, can be widely applied to the field of liquid crystal display and has important application value.

Wherein, in the general formula I, R represents C₁～C₁₅Alkyl, alkoxy, C₂～C₁₅Wherein any one or more H atoms may be independently substituted with F or Cl, any one or more CH₂May each independently be replaced by cyclopentyl, cyclobutyl or cyclopropyl;

z represents C₁～C₁₅Wherein any one or more H atoms may each independently be substituted by F or Cl;

each independently represent

L represents H, CH₃Or OCH₃；

m and n independently represent 0 or 1.

The liquid crystal compound of the invention has the general formula I, wherein R:

preferably, R represents C₁～C₁₀Alkyl, alkoxy, C₂～C₁₀Wherein any one or more H atoms may be independently substituted with F or Cl, any one or more CH₂May each independently be replaced by cyclopentyl, cyclobutyl or cyclopropyl; more preferably, R represents C₁～C₁₀Alkyl, alkoxy, C₂～C₁₀Wherein any one or more H atoms may be substituted by F, any one or more CH₂Each independently may be replaced by cyclopentyl, cyclobutyl or cyclopropyl.

Regarding Z:

preferably, Z represents C₁～C₁₀Wherein any one or more H atoms may each independently be substituted by F or Cl; more preferably, Z represents C₁～C₁₀Alkylene or alkenylene groups of (a).

As another embodiment of the present invention, the liquid crystal compound of the present invention preferably has a structure in which R represents C in the formula I₁～C₁₀Alkyl, alkoxy, C₂～C₁₀Wherein any one or more H atoms may be independently substituted with F or Cl, any one or more CH₂May each independently be replaced by cyclopentyl, cyclobutyl or cyclopropyl;

z represents C₁～C₁₀Wherein any one or more H atoms may each independently be substituted by F or Cl;

each independently represent

L denotes H, CH₃Or OCH₃；

m and n independently represent 0 or 1.

Further preferably, in formula I, R represents C₁～C₁₀Alkyl, alkoxy, C₂～C₁₀Wherein any one or more H atoms may be substituted by F, any one or more CH₂May each independently be replaced by cyclopentyl, cyclobutyl or cyclopropyl;

z represents C₁～C₁₀Alkylene or alkenylene groups of (a);

each independently represent

L denotes H, CH₃Or OCH₃；

m and n independently represent 0 or 1.

As a further preferred embodiment of the present invention, in formula I:

when m is 1, ring A and ring B are not simultaneously

When m ═ n ═ 1, ring A or ring B areWhen ring B or ring A is selected from

As the most preferable technical scheme of the present invention, the liquid crystal compound is selected from one of the following compounds:

as the best embodiment of the present invention, the compound is selected from one of the following compounds:

R₁is represented by C₁～C₁₀Wherein any one or more H atoms may be substituted by F;

the second object of the present invention is to provide a method for preparing the liquid crystal compound.

The synthetic route is as follows:

the method specifically comprises the following steps:

(1)firstly carrying out metalation reaction with n-butyl lithium, and then reacting with difluorodibromomethane to synthesize the compound

(2)Firstly reacting with magnesium chips to form a Grignard reagent, and then reacting with trimethyl borate to obtain the compound

(3) Obtained by the step (2)By reaction with hydrogen peroxide to give

(4) Obtained by the step (1)And the one obtained by the step (3)Williamson Synthesis (Williamson Synthesis) reaction for Synthesis of compounds

R, L, Z, m and n in the compounds involved in the reactions in the above steps correspond to R, L, Z, m and n in the obtained liquid crystal compound product (the same as above).

In the step (1) of the above method,the feeding molar ratio of n-butyllithium to dibromodifluoromethane is 1: 1.0-1.5: 1.6-2.0, the reaction temperature is-80-0 ℃, and the reaction time is 1-6 h.

In the step (2) of the above method,the feeding molar ratio of the magnesium chips to the trimethyl borate is as follows: 1: 1.5-2.5: 1.6-2.5; the temperature for dropping trimethyl borate is-20 to 0 ℃.

In the step (3) of the above method,the feeding molar ratio of the hydrogen peroxide to the hydrogen peroxide is as follows: 1: 2.5 to 3.5; the reaction time is 2 h.

In the step (4) of the above method,the feeding molar ratio of (A) to (B) is 1: 1.0-2.0, the reaction temperature is 50-120 ℃, and the reaction time is 3-8 h.

A third object of the present invention is to protect a composition containing the liquid crystal compound. Preferably, the mass percentage of the compound in the composition is 0.01-99%, more preferably 0.01-60%, and even more preferably 0.1-40%.

The fourth purpose of the invention is to protect the application of the liquid crystal compound and the composition containing the liquid crystal compound in the field of liquid crystal display, preferably in a liquid crystal display device. The liquid crystal display device includes, but is not limited to, TN, ADS, VA, PSVA, FFS or IPS liquid crystal display. The liquid crystal compound or the composition containing the liquid crystal compound has the properties of wide nematic phase temperature range, proper or high birefringence anisotropy delta n, high resistivity, good ultraviolet resistance, high charge retention rate, low vapor pressure and the like.

Detailed Description

The following examples are intended to illustrate the present invention, but are not intended to limit the scope of the invention, which is intended to include within the scope of the appended claims all such equivalent changes and modifications as may be made without departing from the spirit of the invention disclosed herein.

The liquid crystal compounds used in the following examples can be synthesized by a known method or obtained from a publicly available commercial source, unless otherwise specified, and these synthesis techniques are conventional, and the resulting liquid crystal compounds are tested to meet the standards for electronic compounds.

According to the conventional detection method in the field, various performance parameters of the liquid crystal compound are obtained through linear fitting, wherein the specific meanings of the performance parameters are as follows:

Δ n represents optical anisotropy (25 ℃); Δ ε represents the dielectric anisotropy (25 ℃, 1000 Hz); γ 1 represents rotational viscosity (mpa.s, 25 ℃); cp represents a clearing point; epsilon_⊥Representing the dielectric constant perpendicular to the director.