CN110343531A - A kind of dibenzothiophenes class can poly- property compound and its application - Google Patents

Abstract

The invention relates to a dibenzothiophene polymerizable compound and its application. The compound has a structure as shown in general formula I. Compared with the prior art, the polymerizable liquid crystal compound of the invention has good solubility The property and alignment effect are better, the polymerization rate is faster, the polymerization is more complete, and the residue is lower, thus greatly improving the problem of poor display. Further, the liquid crystal composition containing the compound has a lower viscosity, can realize rapid response, and has moderate dielectric anisotropy △∆ at the same time, and the liquid crystal display element or liquid crystal display containing the liquid crystal composition has a wider orientation Phase temperature range, suitable or higher birefringence anisotropy △n, higher resistivity, good UV resistance, high charge retention and low vapor pressure.

Description

A kind of dibenzothiophene polymerizable compound and its application

technical field

The invention belongs to the field of liquid crystal compounds and applications thereof, and relates to a dibenzothiophene polymerizable compound and applications thereof.

Background technique

In recent years, liquid crystal display devices have developed more and more rapidly. The application of liquid crystal materials as environmental materials in information display materials, organic optoelectronic materials and other fields has great research value and bright application prospects, and different types have also been developed, such as vehicle-mounted small Liquid crystal display devices, portable liquid crystal display devices, ultra-thin liquid crystal display devices, etc., are making progress in the development of this field. Taking TV as an example, it is characterized by light weight, small space occupation, and easy movement. There are also notebook-type personal computers, Pocket PCs, mobile phones, etc., commercial TFT-LCD products basically adopt the TN display mode, and the biggest problem is the narrow viewing angle. With the increase of product size, especially in the application of TV field, IPS display mode and VA display mode with wide viewing angle have been developed and applied in turn, especially based on the improvement of VA display mode, they have been successively introduced in major The company has achieved a breakthrough development, which mainly depends on the advantages of the VA mode itself, such as wide viewing angle, high contrast and no need for rubbing alignment. In addition, the contrast displayed by the VA mode has a great influence on the optical anisotropy (Dn) of the liquid crystal. , The thickness (d) of the liquid crystal cell and the wavelength (λ) of the incident light depend on a small degree, which will make the VA mode a very promising display technology.

However, the liquid crystal media used in active matrix addressing display elements such as VA mode are not perfect. High disadvantage. At this time, some new VA display technologies emerged quietly: PSVA technology realizes a display mode with a wide viewing angle similar to MVA/PVA, and also simplifies the CF process, thereby reducing the cost of CF and increasing the aperture ratio. Get higher brightness, which in turn gets higher contrast. In addition, since the entire liquid crystal has a pre-tilt angle, there is no domino delay phenomenon, and a faster response time can be obtained while maintaining the same driving voltage, and the afterimage level will not be affected. However, due to the dense distribution of Fine Slit electrodes in the pixel , so if the electrode width cannot be evenly distributed, it is easy to appear the problem of uneven display. Like UVVA technology, on the basis of maintaining the advantages of PSVA technology, since there is no Slit structure on the TFT side, the problem of uneven display caused by uneven pixel electrode width has also been improved. Although the display devices are constantly developing, people still have to devote themselves to the research of new liquid crystal compounds, so that the performance of liquid crystal media and their applications in display devices can be continuously developed.

It has been found in the prior art that LC mixtures and RMs still have some disadvantages for their application in PSA displays. Firstly, not every soluble RM desired so far is suitable for use in PSA displays: at the same time, if one wishes to polymerize by means of UV light without adding photoinitiators (which may be advantageous for some applications) , the selection becomes even smaller: In addition, the "material system" formed by combining the LC mixture (hereinafter also referred to as "LC host mixture") with the selected polymerizable components should have the lowest rotational viscosity and the best optoelectronic properties , used to increase the "Voltage Hold Ratio" (VHR) to achieve the effect. In terms of PSAVA, it is very important to use a high VHR after (UV) light irradiation, otherwise it will cause problems such as afterimages in the final display. So far, not all combinations of LC mixtures with polymerizable components are suitable for PSA displays. This is mainly due to the fact that the polymerizable unit is too short for the UV sensitive wavelength, or there is no or insufficient tilt angle after illumination, or the uniformity of the polymerizable component is poor after illumination, or because the VHR after UV is not suitable for TFT display applications. In other words, it is a lower impact.

Therefore, there is a need for polymerizable compounds that can be applied in optically anisotropic bodies and polymer-stabilized liquid crystal display elements.

Contents of the invention

The first object of the present invention is to provide a dibenzothiophene polymerizable compound. Compared with the prior art, the polymerizable liquid crystal compound of the present invention has good solubility, better alignment effect, and faster polymerization rate. Faster, more complete polymerization and lower residue, thus greatly improving the problem of poor display.

The liquid crystal composition containing this compound has lower viscosity, can realize fast response, has moderate dielectric anisotropy A at the same time, the liquid crystal display element or liquid crystal display that comprises this liquid crystal composition has wider nematic phase temperature range, suitable or higher birefringence anisotropy An, higher resistivity, good UV resistance, high charge retention and low vapor pressure.

The liquid crystal compound described in the present invention has the following structure:

Wherein, said P ₁ , P ₂ and P ₃ are the same or different, and each independently represents ethyleneoxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate or oxetane Alkyl or epoxy;

The L ₁ and L ₂ are the same or different, each independently representing -F, -Cl, -CN, -NO ₂ , -CH ₃ , -C ₂ H ₅ , -C(CH ₃ ) ₃ , -CH(CH ₃ ) ₂ , -CH ₂ CH(CH ₃ )C ₂ H ₅ , -OCH ₃ , -OC ₂ H ₅ , -COCH ₃ , -COC ₂ H ₅ , -COOCH ₃ , -COOC ₂ H ₅ , -CF ₃ , -OCF ₃ , -OCHF ₂ or -OC ₂ F ₅ ;

The Z ₁ and Z ₄ are the same or different, each independently representing a single bond, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, One of -CH=N-, -N=CH-, -N=N-, -C≡C-, C ₁ -C ₁₂ alkylene or alkenyl, the C ₁ -C ₁₂ alkylene One or more hydrogen atoms in C ₂ -C ₁₂ alkenyl groups can be independently replaced by -F, -Cl, or -CN, and one or more non-adjacent -CH ₂ -groups Can be independently replaced by -O-, -S-, -NH-, -CO, -COO-, -OCO-, -OCOO-, -SCO-, -COS- in a manner that is not directly connected to each other;

The Z ₂ and Z ₃ are the same or different, and each independently represents a single bond, -O-, C ₁ -C ₁₂ alkylene or C ₂ -C ₁₂ alkenyl, and in the C ₁ -C ₁₂ One or more hydrogen atoms may each be independently replaced by -F, -Cl, or -CN, and one or more non-adjacent _-CH2- groups may each independently be replaced by -O-, -S-, -NH-, -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COS- are replaced in a manner that is not directly connected to each other;

The ring A and ring B are the same or different, and each independently represents 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene or 1-4 hydrogen atoms are replaced by F m and n each independently represent 0 or 1; r ₁ and r ₂ each independently represent 0, 1, 2 or 3.

As preferred technical scheme of the present invention:

In general formula I, with respect to said P ₁ , P ₂ and P ₃ :

Preferably, the P ₁ , P ₂ and P ₃ are the same or different, and each independently represents an ethyleneoxy group, an acrylate group, a methacrylate group, a fluoroacrylate group or a chloroacrylate group;

More preferably, the P ₁ , P ₂ and P ₃ are the same or different, and each independently represents an acrylate group, a methacrylate group, a fluoroacrylate group or a chloroacrylate group.

In general formula I, regarding the L ₁ and L ₂ : preferably, the L ₁ and L ₂ are the same or different, each independently representing -F, -Cl, -CN, -NO ₂ , -CH ₃ , -C ₂ H ₅ , -OCH ₃ , -OC ₂ H ₅ , -CF ₃ , -OCF ₃ , -OCHF ₂ or -OC ₂ F ₅ ; more preferably, said L ₁ and L ₂ are the same or different, each independently represents -F, -Cl, -CN, -CH ₃ , -OCH ₃ , -CF ₃ , -OCF ₃ or -OCHF ₂ ; further preferably, said L ₁ and L ₂ are the same or different, each independently Indicates -F, -Cl.

In general formula I, regarding Z ₁ and Z ₄ : preferably, said Z ₁ and Z ₄ are the same or different, each independently representing a single bond, -O-, -S-, -COO-, -C≡C -, C ₁ -C ₁₂ alkylene or alkenyl, one or more hydrogen atoms in the C ₁ -C ₁₂ alkylene or C ₂ -C ₁₂ alkenyl can be independently represented by - F, -Cl, or -CN substituted, and one or more non-adjacent _CH2 groups can each be independently replaced by -O-, -S-, -NH-, -CO-, -COO-, -OCO -, -OCOO-, -SCO-, -COS- are replaced in a manner that is not directly connected to each other; more preferably, the Z ₁ and Z ₄ are the same or different, and each independently represents a single bond, -O- or C ₁ -C ₈ alkylene or C ₂ -C ₈ alkenyl, one or more hydrogen atoms in the C ₁ -C ₈ alkylene or C ₂ -C ₈ alkenyl can be independently is substituted by F, Cl, or CN; further preferably, said Z ₁ and Z ₄ are the same or different, each independently representing a single bond, -O- or a C ₁ -C ₅ alkylene group.

In general formula I, regarding Z ₂ and Z ₃ : preferably, said Z ₂ and Z ₃ are the same or different, each independently representing a single bond, -O-, C ₁ -C ₆ alkylene or C ₂ -C ₆ alkenyl, one or more hydrogen atoms in the C ₁ -C ₆ alkylene or C ₂ -C ₆ alkenyl can be independently replaced by -F, -Cl, or - CN substitution, and one or more non-adjacent _CH2 groups can be independently replaced by -O-, -S-, -CO, -COO in a manner that is not directly connected to each other; more preferably, the Z _2. Z ₃ are the same or different, and each independently represents a single bond, -O-, a C ₁ -C ₅ alkylene group or a C ₂ -C ₅ alkenyl group, and the C ₁ -C ₅ alkylene group Or one or more hydrogen atoms in the C ₂ -C ₅ alkenyl group can be independently replaced by -F, -Cl, or -CN; further preferably, the Z ₂ and Z ₃ are the same or different, each Independently represent a single bond and a C ₁ -C ₃ alkylene group.

In general formula I, regarding ring A and ring B: preferably, the ring A and ring B are the same or different, each independently representing 1,4-phenylene, 1,4-cyclohexylene, or 1- 1,4-phenylene in which 4 hydrogen atoms are replaced by fluorine atoms.

In general formula I, regarding m and n: preferably, said m and n each independently represent 0 or 1, and m+n≤1.

In general formula I, regarding r ₁ and r ₂ : preferably, said r ₁ and r ₂ are each independently selected from 0, 1, 2 or 3; more preferably selected from 0, 1 or 2.

Or, preferably, in the general formula I, the P ₁ , P ₂ and P ₃ are the same or different, and each independently represents an ethyleneoxy group, an acrylate group, a methacrylate group, a fluoroacrylate group or a chlorine substituted acrylate group; said L ₁ and L ₂ are the same or different, each independently representing -F, -Cl, -CN, -NO ₂ , -CH ₃ , -C ₂ H ₅ , -OCH ₃ , -OC ₂ H ₅ , -CF ₃ , -OCF ₃ , -OCHF ₂ or -OC ₂ F ₅ ; said Z ₁ and Z ₄ are the same or different, each independently representing a single bond, -O-, -S-, -COO- , -C≡C-, C ₁ -C ₁₂ alkylene or C ₂ -C ₁₂ alkenyl, in the C ₁ -C ₁₂ alkylene or C ₂ -C ₁₂ alkenyl One or more hydrogen atoms may each be independently replaced by -F, -Cl, or -CN, and one or more non-adjacent _-CH2- groups may each independently be replaced by -O-, -S-, -NH-, -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COS- are replaced in a manner that is not directly connected to each other; the Z ₂ and Z ₃ are the same or different, each independently Represents a single bond, -O-, C ₁ -C ₆ alkylene or C ₂ -C ₆ alkenyl, in the C ₁ -C ₆ alkylene or C ₂ -C ₆ alkenyl One or more hydrogen atoms in can be independently replaced by -F, -Cl, or -CN, and one or more non-adjacent -CH ₂ - groups can be independently replaced by -O-, -S -, -CO-, -COO- are replaced in a manner that is not directly connected to each other; the ring A and ring B are the same or different, and each independently represents 1,4-phenylene, 1,4-cyclohexylene, or 1,4-phenylene in which 1-4 hydrogen atoms are replaced by fluorine atoms; m and n each independently represent 0 or 1, and m+n≤1; r ₁ and r ₂ each independently represent 0, 1, 2 or 3.

Further preferably, in the general formula I, P ₁ , P ₂ and P ₃ are the same or different, each independently representing an acrylate group, a methacrylate group, a fluoroacrylate group or a chloroacrylate group; the L ₁ and L ₂ are the same or different, each independently representing -F, -Cl, -CN, -CH ₃ , -OCH ₃ , -CF ₃ , -OCF ₃ or -OCHF ₂ ; said Z ₁ and Z ₄ are the same Or different, each independently represents a single bond, -O- or C ₁ -C ₈ alkylene or C ₂ -C ₈ alkenyl, the C ₁ -C ₈ alkylene or C ₂ -C One or more hydrogen atoms in the alkenyl group of ₈ can be independently replaced by F, Cl, or CN, and one or more non-adjacent -CH ₂ - groups can be independently replaced by -O-, -S-, -COO- are replaced in a manner that is not directly connected to each other; said Z ₂ and Z ₃ are the same or different, and each independently represents a single bond, -O-, C ₁ -C ₅ alkylene or C ₂ -C ₅ alkenyl, one or more hydrogen atoms in the C ₁ -C ₅ alkylene or C ₂ -C ₅ alkenyl can be independently replaced by -F, -Cl, or - CN substitution; ring A and ring B are the same or different, each independently represents 1,4-phenylene, 1,4-cyclohexylene, or 1,4-phenylene in which 1-4 hydrogen atoms are replaced by fluorine atoms one of the bases; m and n each independently represent 0 or 1, and m+n≤1; r ₁ and r ₂ each independently represent 0, 1 or 2.

More preferably, in the general formula I, P ₁ , P ₂ and P ₃ are the same or different, each independently representing an acrylate group, a methacrylate group, a fluoroacrylate group or a chloroacrylate group; L ₁ , L ₂ are the same or different, each independently represents -F, -Cl; said Z ₁ , Z ₄ are the same or different, each independently represent a single bond, -O- or C ₁ -C ₅ alkylene; The Z ₂ and Z ₃ are the same or different, each independently representing a single bond, C ₁ -C ₃ alkylene; the ring A, ring B are the same or different, each independently representing 1,4-phenylene , 1,4-cyclohexylene, or 1,4-phenylene in which 1-2 hydrogen atoms are replaced by fluorine atoms; said m and n each independently represent 0 or 1, and m+n≤1; Said r ₁ and r ₂ each independently represent 0, 1 or 2.

As a further preferred technical solution of the present invention:

In the general formula I, wherein said P ₁ , P ₂ and P ₃ are the same or different, each independently represents an acrylate group, a methacrylate group or a fluoroacrylate group; said Z ₁ , Z ₄ are the same or Different, each independently represents a single bond, -O-, C ₁ -C ₅ alkylene; said Z ₂ , Z ₃ are the same or different, each independently represents a single bond or a C ₁ -C ₃ alkylene ,

Wherein, in general formula I, m+n=1, ring A and ring B are 1,4-phenylene, L ₁ and L ₂ represent F, and r ₁ and r ₂ are each independently selected from 0 or 1; Or, in general formula I, m+n=1, ring A and ring B are one of 1,4-phenylene or 1,4-phenylene in which 1-2 hydrogen atoms are replaced by fluorine atoms , L ₁ and L ₂ represent F, r ₁ +r ₂ =1; or, in general formula I, m+n=1, ring A and ring B are 1,4-phenylene or 1-2 hydrogen One of the 1,4-phenylene atoms whose atoms are substituted by fluorine atoms, r ₁ and r ₂ are both 0; or, in general formula I, m+n=1, ring A and ring B are 1,4 - one of phenylene or 1,4-phenylene in which 1-2 hydrogen atoms are replaced by fluorine atoms, r ₁ and r ₂ are both 1; or, in general formula I, m=1, n =0, ring A is 1,4-cyclohexylene, L ₁ and L ₂ represent F, r ₁ and r ₂ are each independently selected from 0 or 1; or, in general formula I, m=0, n= 1. Ring B is 1,4-cyclohexylene, L ₁ and L ₂ represent F, r ₁ and r ₂ are each independently selected from 0 or 1; or, in general formula I, m=n=0, L ₁ and L ₂ represent F, and r ₁ and r ₂ are each independently selected from 0 or 1.

r and s described in the above technical solution are independently selected from 0 or 1 means that r=s=1, or r=s=0, or r is 0 and s is 1, or r is 1 and s is 0 One of four situations.

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

Wherein P ₁ , P ₂ and P ₃ are the same or different, each independently representing an acrylate group, a methacrylate group, a fluoroacrylate group; Z ₁ , Z ₄ are the same or different, each independently representing a single bond, - O-, C ₁ -C ₅ alkylene; Z ₂ , Z ₃ are the same or different, each independently represents a single bond, C ₁ -C ₃ alkylene;

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

The second object of the invention is to protect the composition containing said liquid crystal compound. Preferably, the mass percentage of the compound in the composition is 0.01-10%, more preferably 0.01-5%, even more preferably 0.1-3%.

The third object of the present invention is to protect the application of the liquid crystal compound and the composition containing the liquid crystal compound in the field of liquid crystal display, preferably in liquid crystal display devices. The liquid crystal display devices include but are not limited to TN, ADS, VA, PSVA, FFS or IPS liquid crystal displays. The composition using the liquid crystal compound or containing the liquid crystal compound has a wide nematic phase temperature range, suitable or high birefringence anisotropy Δn, high resistivity, and good UV resistance performance, high charge retention, and low vapor pressure.

Detailed ways

The following examples are used to illustrate the present invention, but not to limit the scope of the present invention. All other equivalent changes or modifications that do not deviate from the spirit disclosed in the present invention should be included in the scope of the claims.

The liquid crystal compounds used in the following examples, unless otherwise specified, can be synthesized by known methods or obtained from public commercial sources. These synthesis techniques are conventional, and the obtained liquid crystal compounds are tested to be in line with electronic compounds. standard.

According to conventional detection methods in this field, various performance parameters of the liquid crystal compound are obtained by linear fitting, wherein, the specific meanings of each performance parameter are as follows:

Δn represents optical anisotropy (25°C); Δε represents dielectric anisotropy (25°C, 1000Hz); γ1 represents rotational viscosity (mPa.s, 25°C); Cp represents clearing point.

Example 1

The structural formula of the liquid crystal compound is:

The synthetic route for preparing compound BYLC-01 is as follows:

Specific steps are as follows:

(1) Synthesis of compound BYLC-01-1:

Add 40.5g of 3-benzyloxy-7-bromo-4,6-difluorodibenzothiophene, 20g of diethyl malonate, 14g of potassium tert-butoxide, and 300ml of tetrahydrofuran into the reaction flask, and control the temperature at 50°C to 60°C React at ℃ for 6 hours, lower to room temperature, adjust the pH value to neutral with dilute hydrochloric acid, perform conventional post-treatment, and recrystallize to obtain 43.5 g of light yellow solid (compound BYLC-01-1), HPLC: 99.4%, yield 85.0%;

(2) Synthesis of compound BYLC-01-2:

Add 10.0g of aluminum hydride and 500mL of tetrahydrofuran into the reaction flask, cool down to 0°C, control the temperature at 0°C to 10°C, add dropwise a solution composed of 43.5g of compound BYLC-01-1 and 100ml of tetrahydrofuran, and then keep it at 0°C to 10°C for reaction After 1 h, it was raised to room temperature and reacted for 8 h. The reaction was quenched with ethyl acetate, and the pH value was adjusted to weak acidity with dilute hydrochloric acid. After conventional post-treatment, an off-white solid (compound BYLC-01-2) was obtained: 30.0 g, LC: 99.2 %, yield: 88.2%;

(2) Synthesis of compound BYLC-01-3:

Add 30.0g of compound BYLC-01-2, 90ml of toluene, 60ml of ethanol, 1.5g of palladium carbon into the reaction flask, replace with hydrogen three times, control the temperature at 30°C to 35°C for 6h, and perform conventional post-treatment to obtain a white solid ( Compound BYLC-01-3): 21.5g, LC: 99.6%, yield: 92.7%;

(3) Synthesis of compound BYLC-01:

Under the protection of nitrogen, add 21.5g of compound BYLC-01-3, 25.5g of triethylamine and 200mL of dichloromethane into the reaction flask, lower the temperature to -10°C, control the temperature from -10°C to 0°C, and add 25.2g of methacrylate dropwise Acyl chloride, rise to room temperature and react for 6 hours, pour the reaction liquid into water, neutralize with uranium bicarbonate aqueous solution, perform conventional post-treatment, purify by chromatography, elute with n-hexane, and recrystallize from ethanol to obtain 27.3g of white solid (compound BYLC-01) , LC: 99.5%, Yield: 76.8%.

The obtained white solid BYLC-01 was analyzed by GC-MS, and the m/z of the product was 514.1 (M+).

¹ H-NMR (300 MHz, CDCl ₃ ): 1.35-2.20 (m, 9H), 3.63-4.45 (m, 5H), 5.35-6.45 (m, 6H), 6.65-7.65 (m, 4H).

Example 2

The structural formula of the liquid crystal compound is:

The synthetic route for preparing compound BYLC-02 is as follows:

Specific steps are as follows:

Synthesis of compound BYLC-02:

Under nitrogen protection, add 31.0g of compound BYLC-01-3, 38.4g of triethylamine and 250mL of dichloromethane into the reaction flask, cool down to -10°C, control the temperature from -10°C to 0°C, and add 32.0g of acryloyl chloride dropwise, Rise to room temperature and react for 6 hours. Pour the reaction solution into water, neutralize it with aqueous uranium bicarbonate solution, perform conventional post-treatment, purify by chromatography, elute with n-hexane, and recrystallize from ethanol to obtain 38.9 g of a white solid (compound BYLC-02), LC : 99.6%, yield: 82.5%.

The obtained white solid BYLC-02 was analyzed by GC-MS, and the m/z of the product was 472.1 (M+).

¹ H-NMR (300 MHz, CDCl ₃ ): 2.75-4.45 (m, 5H), 5.63-6.45 (m, 9H), 7.05-7.55 (m, 4H).

Example 3

The synthetic route for preparing compound BYLC-03 is as follows:

Specific steps are as follows:

(1) Synthesis of compound BYLC-03-1:

Under the protection of nitrogen, add 40.5g 3-benzyloxy-7-bromo-4,6-difluorodibenzothiophene and 300ml tetrahydrofuran into the reaction flask, cool down to -70℃～-80℃, add dropwise 0.13mol n-butyl Lithium base, temperature control -70℃～-80℃, react for 1h, add 18.0g trimethyl borate dropwise, return to -30℃ naturally, acidify with dilute hydrochloric acid to adjust the pH value to less than 2, carry out conventional post-treatment, and recrystallize to obtain shallow Yellow solid (compound BYLC-03-1) 32.3g, LC: 98.5%, yield 87.3%;

(2) Synthesis of compound BYLC-03-2:

Add 32.3g of compound BYLC-03-1, 18.5g of p-bromoiodobenzene, 18.0g of anhydrous potassium carbonate, 200ml of toluene, 150ml of ethanol, 150ml of water, 0.3g of tetrakistriphenylphosphine palladium into the reaction flask, and heat to reflux for 8h , carried out conventional post-processing to obtain off-white solid (compound BYLC-03-2): 34.5g, LC: 99.3%, yield: 82.6%;

Other steps are with embodiment 1.

Compound BYLC-03: The obtained white solid BYLC-03 was analyzed by GC-MS, and the m/z of the product was: 592.1 (M+).

¹ H-NMR (300 MHz, CDCl ₃ ): 1.35-2.20 (m, 9H), 3.63-4.45 (m, 5H), 5.65-6.45 (m, 4H), 7.05-8.10 (m, 8H)).

Example 4

The structural formula of the liquid crystal compound is:

Reaction condition is with embodiment 1,2.

The obtained white solid BYLC-04 was analyzed by GC-MS, and the m/z of the product was 548.1 (M+).

¹ H-NMR (300 MHz, CDCl ₃ ): 3.35-4.45 (m, 5H), 5.63-6.45 (m, 9H), 7.05-7.65 (m, 8H).

Example 5

Replace 3-benzyloxy-7-bromo-4,6-difluorodibenzothiophene with 3-benzyloxy-7-bromomethyl-4,6-difluorodibenzothiophene, and other conditions are the same as in the examples 1 The obtained white solid BYLC-05 was analyzed by GC-MS, and the m/z of the product was 528.1 (M+).

¹ H-NMR (300 MHz, CDCl ₃ ): 1.35-2.55 (m, 8H), 3.03-4.25 (m, 5H), 5.35-6.45 (m, 6H), 7.05-7.50 (m, 4H).

Example 6

The synthetic route for preparing compound BYLC-06 is as follows:

Specific steps are as follows:

(1) Synthesis of compound BYLC-06-1:

Add 34.2g of 3-benzyloxy-7-hydroxyl-4,6-difluorodibenzothiophene, 20.7g of anhydrous potassium carbonate, 300ml of N,N-dimethylformamide in the reaction flask, and heat the reaction mixture to 60 ℃, 20.7g of 3-bromo-1-propanol was added dropwise thereto, and the temperature was controlled at 100°C to 110°C for 6h, then cooled down to room temperature, followed by conventional post-treatment, and recrystallized to obtain an off-white solid (compound BYLC-06-1 )31.4g, LC: 99.2%, yield 78.5%;

(2) Synthesis of compound BYLC-06-2:

Under the protection of nitrogen, add 31.4g of compound BYLC-06-1, 30.8g of triphenylphosphine, and 200ml of tetrahydrofuran into the reaction flask, cool down to -10°C to 0°C, add dropwise a solution consisting of 18.8g of bromine and 30ml of tetrahydrofuran, and control React at 5°C to 10°C for 3 hours, the aqueous solution of sodium bisulfite destroys the hydrolysis, conducts conventional post-treatment, and recrystallizes to obtain 30.0 g of a light yellow solid (compound BYLC-06-2), LC: 97.6%, yield 82.5%;

Other steps are with embodiment 1.

Compound BYLC-06: The obtained white solid BYLC-06 was analyzed by GC-MS, and the m/z of the product was: 572.1 (M+).

¹ H-NMR(300MHz, CDCl ₃ ):1.15-2.70(m,11H), 3.63-4.25(m,6H),4.95-5.65(m,3H),5.75-6.85(m,4H),7.05-7.75 (m,3H).

According to the technical solutions of the above examples 1-6, the following liquid crystal compounds can be synthesized only by simply replacing the corresponding raw materials without changing any substantive operations.

Example 7

The structural formula of the liquid crystal compound is:

The synthetic route for preparing compound BYLC-07 is as follows:

Specific steps are as follows:

(1) Synthesis of compound BYLC-07-1:

Add 36.7g of 3-benzyloxy-7-bromo-dibenzothiophene, 19.8g of diethyl malonate, 13.9g of potassium tert-butoxide, and 300ml of tetrahydrofuran into the reaction flask, and react at a temperature of 50°C to 60°C for 6 hours. Cool down to room temperature, adjust the pH value to neutral with dilute hydrochloric acid, perform conventional post-treatment, and recrystallize to obtain 36.8 g of light yellow solid (compound BYLC-07-1-1), HPLC: 99.5%, yield 86.2%;

(2) Synthesis of compound BYLC-07-2-2:

Add 11.2g of aluminum hydride and 500mL of tetrahydrofuran into the reaction flask, lower the temperature to 0°C, control the temperature at 0°C to 10°C, add dropwise a solution consisting of 36.8g of compound BYLC-07-1 and 100ml of tetrahydrofuran, and then keep the reaction at 0°C to 10°C After 1 h, it was raised to room temperature and reacted for 8 h. The reaction was quenched with ethyl acetate, and the pH value was adjusted to weak acidity with dilute hydrochloric acid. After conventional post-treatment, an off-white solid (compound BYLC-07-2) was obtained: 25.8 g, LC: 99.4 %, yield: 86.4%;

(2) Synthesis of compound BYLC-07-3:

Add 25.8g of compound BYLC-07-2, 90ml of toluene, 60ml of ethanol, 1.2g of palladium on carbon to the reaction flask, replace with hydrogen three times, control the temperature at 30°C to 35°C for 6h, and perform conventional post-treatment to obtain a white solid ( Compound BYLC-01-3): 18.2g, LC: 99.5%, yield: 93.5%;

(3) Synthesis of compound BYLC-07:

Under the protection of nitrogen, add 18.2g of compound BYLC-07-3, 23.4g of triethylamine and 200mL of dichloromethane into the reaction flask, cool down to -10°C, control the temperature from -10°C to 0°C, and add 24.2g of methpropylene dropwise Acyl chloride, rise to room temperature and react for 6 hours, pour the reaction solution into water, neutralize with uranium bicarbonate aqueous solution, perform conventional post-treatment, purify by chromatography, elute with n-hexane, and recrystallize from ethanol to obtain 23.5 g of white solid (compound BYLC-07) , LC: 99.6%, Yield: 75.2%.

The obtained white solid BYLC-07 was analyzed by GC-MS, and the m/z of the product was 478.1 (M+).

¹ H-NMR (300 MHz, CDCl ₃ ): 1.35-2.20 (m, 9H), 3.63-4.45 (m, 5H), 5.35-6.45 (m, 6H), 6.65-7.65 (m, 6H).

Example 8

The structural formula of the liquid crystal compound is:

The synthetic route for preparing compound BYLC-08 is as follows:

Specific steps are as follows:

Synthesis of compound BYLC-08:

Under the protection of nitrogen, add 35.0g of compound BYLC-07-3, 42.0g of triethylamine and 250mL of dichloromethane into the reaction flask, cool down to -10°C, control the temperature from -10°C to 0°C, and add 35.2g of acryloyl chloride dropwise, Rise to room temperature and react for 6 hours. Pour the reaction solution into water, neutralize it with aqueous uranium bicarbonate solution, perform conventional post-treatment, purify by chromatography, elute with n-hexane, and recrystallize from ethanol to obtain 47.6 g of a white solid (compound BYLC-08), LC : 99.7%, yield: 85.5%.

The resulting white solid BYLC-08 was analyzed by GC-MS, and the m/z of the product was 436.1 (M+).

¹ H-NMR (300 MHz, CDCl ₃ ): 2.75-4.45 (m, 5H), 5.63-6.45 (m, 9H), 7.05-7.55 (m, 6H).

Example 9

The synthetic route for preparing compound BYLC-09 is as follows:

Specific steps are as follows:

(1) Synthesis of compound BYLC-09-1:

Under the protection of nitrogen, add 37.0g 3-benzyloxy-7-bromo-dibenzothiophene and 300ml tetrahydrofuran to the reaction flask, cool down to -70℃～-80℃, add 0.13mol n-butyllithium dropwise, and control the temperature- React at 70°C to -80°C for 1 hour, add 18.5g of trimethyl borate dropwise, return to -30°C naturally, acidify with dilute hydrochloric acid to adjust the pH value to less than 2, perform conventional post-treatment, and recrystallize to obtain a light yellow solid (compound BYLC- 09-1) 28.9g, LC: 97.3%, yield 86.5%;

(2) Synthesis of compound BYLC-09-2:

Add 28.9g of compound BYLC-09-1, 16.4g of p-bromoiodobenzene, 17.8g of anhydrous potassium carbonate, 200ml of toluene, 150ml of ethanol, 150ml of water, 0.25g of tetrakistriphenylphosphine palladium into the reaction flask, and heat to reflux for 8h , carried out conventional post-processing to obtain off-white solid (compound BYLC-09-2): 32.0g, LC: 99.5%, yield: 83.5%;

Other steps are with embodiment 1.

Compound BYLC-09: The obtained white solid BYLC-09 was analyzed by GC-MS, and the m/z of the product was: 556.1 (M+).

¹ H-NMR (300 MHz, CDCl ₃ ): 1.35-2.20 (m, 9H), 3.63-4.45 (m, 5H), 5.65-6.45 (m, 4H), 7.05-8.10 (m, 10H)).

Example 10

The structural formula of the liquid crystal compound is:

Reaction condition is with embodiment 1,2.

The resulting white solid BYLC-10 was analyzed by GC-MS, and the m/z of the product was 512.1 (M+).

¹ H-NMR (300 MHz, CDCl ₃ ): 3.35-4.45 (m, 5H), 5.63-6.45 (m, 9H), 7.05-7.65 (m, 10H).

Example 11

Replace 3-benzyloxy-7-bromo-dibenzothiophene with 3-benzyloxy-7-bromomethyl-dibenzothiophene, and other conditions are the same as in Example 1. Use GC-MS to analyze the resulting white solid BYLC-11 Analysis gave the product a m/z of 492.1 (M+).

¹ H-NMR (300 MHz, CDCl ₃ ): 1.35-2.55 (m, 8H), 3.03-4.25 (m, 5H), 5.35-6.45 (m, 6H), 7.05-7.50 (m, 6H).

Example 12

The synthetic route for preparing compound BYLC-12 is as follows:

Specific steps are as follows:

(1) Synthesis of compound BYLC-12-1:

Add 36.5g of 3-benzyloxy-7-hydroxy-dibenzothiophene, 21.2g of anhydrous potassium carbonate, 300ml of N,N-dimethylformamide into the reaction flask, heat the reaction mixture to 60°C, and add dropwise 22.3g of 3-bromo-1-propanol was reacted at a temperature of 100°C to 110°C for 6h, cooled down to room temperature, followed by conventional post-treatment, and recrystallized to obtain 31.8g of an off-white solid (compound BYLC-12-1), LC: 99.3%, yield 79.6%;

(2) Synthesis of compound BYLC-12-2:

Under nitrogen protection, add 31.8g of compound BYLC-12-1, 29.4g of triphenylphosphine, and 200ml of tetrahydrofuran into the reaction flask, cool down to -10°C to 0°C, add dropwise a solution consisting of 17.5g of bromine and 30ml of tetrahydrofuran, and control Reaction at 5°C-10°C for 3 hours, aqueous solution of sodium bisulfite destroys hydrolysis, conventional post-treatment, recrystallization to obtain 31.0 g of light yellow solid (compound BYLC-12-2), LC: 98.2%, yield 83.6%;

Other steps are with embodiment 1.

Compound BYLC-12: The obtained white solid BYLC-12 was analyzed by GC-MS, and the m/z of the product was: 536.1 (M+).

¹ H-NMR(300MHz, CDCl ₃ ):1.15-2.70(m,11H),3.63-4.25(m,6H),4.95-5.65(m,3H),5.75-6.85(m,6H),7.05-7.75 (m,3H).

Example 13

Reaction condition is with embodiment 1,2.

Compound BYLC-13: The obtained white solid BYLC-13 was analyzed by GC-MS, and the m/z of the product was: 496.1 (M+).

¹ H-NMR (300 MHz, CDCl ₃ ): 1.35-2.20 (m, 9H), 3.63-4.45 (m, 5H), 5.35-6.45 (m, 6H), 6.65-7.65 (m, 5H).

Example 14

Reaction condition is with embodiment 1,2.

Compound BYLC-14: The obtained white solid BYLC-08 was analyzed by GC-MS, and the m/z of the product was: 454.1 (M+).

¹ H-NMR (300 MHz, CDCl ₃ ): 2.75-4.45 (m, 5H), 5.63-6.45 (m, 9H), 7.05-7.55 (m, 5H).

Example 15

Reaction condition is with embodiment 1,2.

Compound BYLC-15: The obtained white solid BYLC-15 was analyzed by GC-MS, and the m/z of the product was: 574.1 (M+).

¹ H-NMR (300 MHz, CDCl ₃ ): 1.35-2.20 (m, 9H), 3.63-4.45 (m, 5H), 5.65-6.45 (m, 4H), 7.05-8.10 (m, 9H)).

Example 16

Reaction condition is with embodiment 1,2.

Compound BYLC-16: The obtained white solid BYLC-16 was analyzed by GC-MS, and the m/z of the product was: 532.1 (M+).

¹ H-NMR (300 MHz, CDCl ₃ ): 3.35-4.45 (m, 5H), 5.63-6.45 (m, 9H), 7.05-7.65 (m, 9H).

Example 17

According to the technical solutions of the above embodiments, the following liquid crystal compounds can be synthesized by simply replacing the corresponding raw materials without changing any substantive operations.

Example 18

The properties of the mixture BHR87800 are listed in Table 1:

Table 1 Summary of properties of mixed crystal BHR87800

Among them, the mixture BHR87800 was purchased from Bayi Space-Time Liquid Crystal Technology Co., Ltd. Add 0.3% of the polymerizable compound BYLC-01 provided in Example 1 to the 99.7% liquid crystal composition BHR87800, and dissolve it uniformly to obtain the mixture PM-1.

Add 0.3% of the polymerizable compound BYLC-02 provided in Example 2 to the 99.7% liquid crystal composition BHR87800, and dissolve it uniformly to obtain the mixture PM-2.

Add 0.3% of the polymerizable compound BYLC-07 provided in Example 7 to the 99.7% liquid crystal composition BHR87800, and dissolve it uniformly to obtain the mixture PM-3.

Add 0.3% of the polymerizable compound BYLC-08 provided in Example 8 to the 99.7% liquid crystal composition BHR87800, and dissolve it uniformly to obtain the mixture PM-4.

The physical properties of PM-1, PM-2, PM-3, and PM-4 were almost the same as those of the above-mentioned mixture BHR87800. PM-1, PM-2, PM-3, and PM-4 were injected into test cells with a gap of 4.0 μm and vertical alignment using a vacuum infusion method. While applying a square wave with a frequency of 60HZ and a driving voltage of 16V, a high-pressure mercury ultraviolet lamp is used to irradiate ultraviolet rays to the test box, and the irradiation intensity on the surface of the box is adjusted to 30mW/cm ² , and the irradiation is 600s to obtain a vertically aligned liquid crystal after polymerization. For display components, use LCT-5016E liquid crystal photoelectric parameter tester to measure the pretilt angle, then decompose the test box, and use high performance liquid chromatography (HPLC) to measure the residual polymeric compound in the liquid crystal composition. The results are summarized in Table 2 and Table 3.

Comparative example 1

0.3% of the polymerizable compound of CP was added to 99.7% liquid crystal composition BHR87800, and it was dissolved uniformly, and the mixture PM-5 was obtained. The physical properties of PM-5 were almost the same as those of the above-mentioned mixture BHR87800. PM-5 was injected into a test cell with a gap of 4.0 μm and a vertical alignment using a vacuum infusion method. While applying a square wave with a frequency of 60HZ and a driving voltage of 16V, a high-pressure mercury ultraviolet lamp is used to irradiate the test box with ultraviolet light, adjust the irradiation intensity on the surface of the box to 30mW/cm ² , and irradiate for 600s to obtain a vertically aligned liquid crystal after polymerization. For display components, use LCT-5016E liquid crystal photoelectric parameter tester to measure the pretilt angle, then decompose the test box, and use high performance liquid chromatography (HPLC) to measure the residual polymeric compound in the liquid crystal composition. The results are summarized in Table 2 and Table 3.

Table 2 Summary of UV front and rear pretilt angles

Table 3 Summary of polymer residue data

From the comparative data in Table 2 and Table 3, it can be seen that compared with the polymerizable liquid crystal compound CP, the polymeric compound of the present invention has a better alignment effect, faster polymerization rate, more complete polymerization, and lower residue, so that the larger The problem of bad display has been improved.

Although, the present invention has been described in detail with general description, specific implementation and test above, but on the basis of the present invention, some modifications or improvements can be made to it, which will be obvious to those skilled in the art . Therefore, the modifications or improvements made on the basis of not departing from the spirit of the present invention all belong to the protection scope of the present invention.

Claims (10)

1. A dibenzothiophene polymerizable compound, characterized in that it has the following structure: Wherein, said P ₁ , P ₂ and P ₃ are the same or different, and each independently represents ethyleneoxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate or oxetane Alkyl or epoxy; The L ₁ and L ₂ are the same or different, each independently representing -F, -Cl, -CN, -NO ₂ , -CH ₃ , -C ₂ H ₅ , -C(CH ₃ ) ₃ , -CH(CH ₃ ) ₂ , -CH ₂ CH(CH ₃ )C ₂ H ₅ , -OCH ₃ , -OC ₂ H ₅ , -COCH ₃ , -COC ₂ H ₅ , -COOCH ₃ , -COOC ₂ H ₅ , -CF ₃ , -OCF ₃ , -OCHF ₂ or -OC ₂ F ₅ ; The Z ₁ and Z ₄ are the same or different, each independently representing a single bond, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, One of -CH=N-, -N=CH-, -N=N-, -C≡C-, C ₁ -C ₁₂ alkylene or alkenyl, the C ₁ -C ₁₂ alkylene One or more hydrogen atoms in C ₂ -C ₁₂ alkenyl groups can be independently replaced by -F, -Cl, or -CN, and one or more non-adjacent -CH ₂ -groups Can be independently replaced by -O-, -S-, -NH-, -CO, -COO-, -OCO-, -OCOO-, -SCO-, -COS- in a manner that is not directly connected to each other; The Z ₂ and Z ₃ are the same or different, and each independently represents a single bond, -O-, C ₁ -C ₁₂ alkylene or C ₂ -C ₁₂ alkenyl, and in the C ₁ -C ₁₂ One or more hydrogen atoms may each be independently replaced by -F, -Cl, or -CN, and one or more non-adjacent _-CH2- groups may each independently be replaced by -O-, -S-, -NH-, -CO-, -COO-, -OCO-, -OCOO--SCO-, -COS- are replaced in a manner that is not directly connected to each other; The ring A and ring B are the same or different, and each independently represents 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene or 1-4 hydrogen atoms are replaced by F 1,4-phenylene; m and n each independently represent 0 or 1; r ₁ and r ₂ each independently represent 0, 1, 2 or 3. 2. The compound according to claim 1, characterized in that, said P ₁ , P ₂ and P ₃ are the same or different, each independently representing ethyleneoxy, acrylate, methacrylate, fluoroacrylic acid Ester or chloroacrylate groups; Preferably, the P ₁ , P ₂ and P ₃ are the same or different, and each independently represents an acrylate group, a methacrylate group, a fluoroacrylate group or a chloroacrylate group. 3. The compound according to claim 1 or 2, wherein said L ₁ and L ₂ are the same or different, each independently representing -F, -Cl, -CN, -NO ₂ , -CH ₃ , - _C2H5 , _-OCH3 , _-OC2H5 , _-CF3 , _-OCF3 , _{-OCHF2 , or -OC2F5 ;} Preferably, said L ₁ and L ₂ are the same or different, each independently representing -F, -Cl, -CN, -CH ₃ , -OCH ₃ , -CF ₃ , -OCF ₃ or -OCHF ₂ ; Further preferably, said L ₁ and L ₂ are the same or different, each independently representing -F, -Cl. 4. The compound according to any one of claims 1-3, characterized in that, The Z ₁ and Z ₄ are the same or different, and each independently represents a single bond, -O-, or a C ₁ -C ₈ alkylene group or a C ₂ -C ₈ alkenyl group, and the C ₁ -C ₈ One or more hydrogen atoms in the alkylene or C ₂ -C ₈ alkenyl can be independently replaced by F, Cl, or CN; Preferably, said Z ₁ and Z ₄ are the same or different, each independently representing a single bond, -O- or a C ₁ -C ₅ alkylene group. 5. The compound according to any one of claims 1-4, characterized in that, said Z ₂ and Z ₃ are the same or different, each independently representing a single bond, -O-, C ₁ -C ₆ alkylene C ₂ -C ₆ alkenyl group, one or more hydrogen atoms in the C ₁ -C ₆ alkylene group or C ₂ -C ₆ alkenyl group can be independently replaced by -F, - Cl, or -CN is substituted, and one or more non-adjacent -CH ₂ - groups can be independently replaced by -O-, -S-, -CO, -COO in a manner that is not directly connected to each other; Preferably, the Z ₂ and Z ₃ are the same or different, and each independently represents a single bond, -O-, C ₁ -C ₅ alkylene or alkenyl, and the C ₁ -C ₅ alkylene or One or more hydrogen atoms in the C ₂ -C ₅ alkenyl can be independently replaced by -F, -Cl, or -CN; Further preferably, said Z ₂ and Z ₃ are the same or different, and each independently represents a single bond or a C ₁ -C ₃ alkylene group. 6. The compound according to any one of claims 1-5, characterized in that, the ring A and ring B are the same or different, each independently representing 1,4-phenylene, 1,4-cyclohexylene , or 1,4-phenylene with 1-4 hydrogen atoms replaced by fluorine atoms; And/or, said m and n each independently represent 0 or 1, and m+n≤1; And/or, the r ₁ and r ₂ are each independently selected from 0, 1 or 2. 7. The compound according to any one of claims 1-6, characterized in that, in the general formula I, the P ₁ , P ₂ and P ₃ are the same or different, each independently representing an acrylate group, a methyl group Acrylate or fluoroacrylate; The Z ₁ and Z ₄ are the same or different, each independently representing a single bond, -O-, C ₁ -C ₅ alkylene; The Z ₂ and Z ₃ are the same or different, and each independently represents a single bond or a C ₁ -C ₃ alkylene group; Wherein, m+n=1, ring A and ring B are 1,4-phenylene, L ₁ and L ₂ represent F, r ₁ and r ₂ are each independently selected from 0 or 1; Or, m+n=1, ring A and ring B are 1,4-phenylene or 1,4-phenylene with 1-2 hydrogen atoms replaced by fluorine atoms, L ₁ , L ₂ Indicates F, r ₁ +r ₂ =1; Or, m+n=1, ring A and ring B are 1,4-phenylene or 1,4-phenylene with 1-2 hydrogen atoms replaced by fluorine atoms, r ₁ and r ₂ Both are 0; Or, m+n=1, ring A and ring B are 1,4-phenylene or 1,4-phenylene with 1-2 hydrogen atoms replaced by fluorine atoms, r ₁ and r ₂ Both are 1; Or, m=1, n=0, ring A is 1,4-cyclohexylene, L ₁ and L ₂ represent F, r ₁ and r ₂ are each independently selected from 0 or 1; Or, m=0, n=1, ring B is 1,4-cyclohexylene, L ₁ and L ₂ represent F, r ₁ and r ₂ are each independently selected from 0 or 1; Or, m=n=0, L ₁ and L ₂ represent F, and r ₁ and r ₂ are each independently selected from 0 or 1. 8. The compound according to claim 1, characterized in that it is selected from one of the following compounds: Wherein P ₁ , P ₂ and P ₃ are the same or different, each independently representing an acrylate group, a methacrylate group or a fluoroacrylate group; Z ₁ and Z ₄ are the same or different, each independently representing a single bond, -O-, C ₁ -C ₅ alkylene; Z ₂ and Z ₃ are the same or different, and each independently represents a single bond or a C ₁ -C ₃ alkylene group; Preferably, the compound is selected from one of the following compounds: 9. A liquid crystal composition, characterized in that it contains the compound according to any one of claims 1-8; Preferably, the mass percentage of the compound in the composition is 0.01-10%, more preferably 0.01-5%, even more preferably 0.1-3%. 10. The application of the compound described in any one of claims 1-8 and/or the liquid crystal composition described in claim 9 in the liquid crystal display field; preferably the application in a liquid crystal display device; more preferably, the liquid crystal Display devices include TN, ADS, VA, PSVA, FFS or IPS liquid crystal displays.