CN110343082A - A kind of dibenzofurans class can poly- property compound and its application - Google Patents

Abstract

The invention belongs to the technical field of liquid crystal materials, and in particular relates to a dibenzofuran polymerizable compound and an application thereof. The liquid crystal compound described in the present invention has the structure shown in general formula I. Compared with the prior art, the polymerizable liquid crystal compound of the invention has good solubility, better alignment effect, faster polymerization rate, more complete polymerization, and lower residue, thereby greatly improving the problem of poor display. The liquid crystal composition containing the compound has better alignment effect, more complete polymerization and lower residue. Moreover, the compound has low price and stable performance, can be widely used in the field of liquid crystal display, and has important application value.

Description

A kind of dibenzofuran polymerizable compound and its application

technical field

The invention belongs to the technical field of liquid crystal materials, and relates to a dibenzofuran polymerizable compound and an application thereof.

Background technique

In recent years, liquid crystal display devices have been widely used in various electronic devices such as smartphones, tablet computers, car navigation systems, televisions, and the like. Representative liquid crystal display modes include twisted nematic (TN) type, super twisted nematic (STN) type, in-plane switching (IPS) type, fringe field switching (FFS) type and vertical alignment (VA) type. Among them, the VA mode has attracted more and more attention due to its fast fall time, high contrast, wide viewing angle, and high-quality images.

However, the liquid crystal medium used in the display elements of the active matrix addressing mode such as VA mode has its own shortcomings, such as the afterimage level is obviously worse than that of the display elements with positive dielectric anisotropy, the response time is relatively slow, and the driving voltage is relatively low. higher. In order to solve the above problems, some new VA display technologies have emerged. Such as MVA technology, PVA technology, PSVA technology. Among them, PSVA technology not only realizes the wide viewing angle display mode similar to MVA/PVA, but also simplifies the CF process, realizes the reduction of CF cost, improves the aperture ratio, and can obtain higher brightness, and then obtain 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.

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 PSVA, it is very important to use high VHR after (UV) light irradiation, otherwise it will cause problems such as afterimage in the final display. So far, due to the problem that the UV sensitive wavelength of the polymerizable unit is too short, or there is no or insufficient tilt angle after irradiation, or the uniformity of the polymerizable component is poor after irradiation. Not all combinations of LC mixtures and polymerizable components are suitable for PSVA displays.

Therefore, the synthesis of polymeric compounds with novel structures and the study of their structure-property relationship has become an important task in the field of liquid crystals.

Contents of the invention

The first object of the present invention is to provide a polymerizable compound useful in polymer stabilization technology. The liquid crystal composition containing the compound has better alignment effect, more complete polymerization and lower residue. Moreover, the compound has low price and stable performance, can be widely used in the field of liquid crystal display, and has important application value.

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

Wherein, the ring A and ring B independently represent 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene, or 1-4 hydrogen atoms are independently 1,4-phenylene substituted by F or Cl;

The P ₁ , P ₂ , and P ₃ independently represent an acrylate group, a methacrylate group, a fluoroacrylate group, a chloroacrylate group, an ethyleneoxy group, an oxetane group or an epoxy group ;

The Z ₁ and Z ₄ independently represent a single bond, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CH=N -, -N=CH-, -N=N-, -C≡C-, C ₁ -C ₁₂ alkylene or alkenyl, wherein the C ₁ -C ₁₂ alkylene or alkenyl One or more hydrogen atoms can be independently replaced by F, Cl, or CN, and one or more non-adjacent _-CH2- groups can be independently replaced by -O-, -S-, -NH- , -CO-, COO-, -OCO-, -OCOO-, -SCO-, -COS- or olefinic bonds are replaced in a manner that is not directly connected to each other;

The Z ₂ and Z ₃ independently represent a single bond, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CH=N -, -N=CH-, -N=N-, -C≡C-, C ₁ -C ₁₂ alkylene or alkenyl, one of the C ₁ -C ₁₂ alkylene or alkenyl One or more hydrogen atoms can be independently replaced by F, Cl, or CN, and one or more non-adjacent _-CH2- groups can be independently replaced by -O-, -S-, -NH-, -CO-, COO-, -OCO-, -OCOO-, -SCO- or -COS- are substituted in such a way that they are not directly connected to each other;

L ₁ and L ₂ independently represent -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 , - _OCHF2 or _{-OC2F5 ;}

r, s represent 0, 1, 2 or 3 independently of each other;

m and n represent 0 or 1 independently of each other.

As a preferred solution of the present invention, in general formula I, with respect to ring A and ring B:

Preferably, said ring A and ring B independently represent 1,4-phenylene, 1,4-cyclohexylene or 1,4-phenylene in which 1-4 hydrogen atoms are replaced by F or Cl atoms ;

More preferably, said ring A and ring B independently represent 1,4-phenylene, 1,4-cyclohexylene, 2-fluoro-1,4-phenylene, 2-fluoro-1,4 - phenylene.

Regarding the P ₁ , P ₂ , and P ₃ : preferably, the P ₁ , P ₂ , and P ₃ independently represent a methacrylate group or an acrylate group.

Regarding the Z ₁ and Z ₄ : preferably, the Z ₁ and Z ₄ independently represent single bonds, -O- or C ₁ -C ₅ alkylene and alkoxy groups.

Regarding Z ₂ and Z ₃ : preferably, said Z ₂ and Z ₃ independently represent a single bond or -(CH ₂ ) _k -, k represents 1-8, specifically, K is 1, 2, 3, 4 , 5, 6, 7 or 8; more preferably, said Z ₂ , Z ₃ independently represent a single bond or -(CH ₂ ) _k -, k represents 1, 2, 3, 4 or 5; further , said Z ₂ and Z ₃ independently represent a single bond or -(CH ₂ ) _k -, wherein k represents 1, 2 or 3.

Regarding L ₁ , L ₂ : preferably, said L ₁ , L ₂ independently represent -F, -Cl, -CN, C ₁ -C ₃ alkyl or alkoxy; more preferably, said L ₁ and L ₂ are the same or different, independently representing -F, -Cl, -CN, -CH ₃ , -OCH ₃ , -CF ₃ , -OCF ₃ or -OCHF ₂ ; furthermore, said L ₁ , L ₂ are the same or different, and independently represent -F, -Cl.

Regarding r, s: preferably, said r, s represent 0 or 1 independently of each other.

Regarding m and n: preferably, m and n independently represent 0 or 1, and m+n≤1.

In the compound formula I of the present invention:

Preferably, in the general formula I, the ring A and ring B independently represent 1,4-phenylene, 1,4-cyclohexylene or 1 in which 1-4 hydrogen atoms are replaced by F or Cl atoms , 4-phenylene; said P ₁ , P ₂ , and P ₃ independently represent a methacrylate group or an acrylate group; said Z ₁ , Z ₄ each independently represent a single bond, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CH=N-, -N=CH-, -N=N-, -C≡C -, C ₁ -C ₁₂ alkylene or alkenyl, wherein one or more hydrogen atoms of the C ₁ -C ₁₂ alkylene or alkenyl species can be independently replaced by F, Cl, or CN, and One or more non-adjacent -CH ₂ - groups may each independently be replaced by -O-, -S-, -NH-, -CO-, -COO-, -OCO-, -OCOO-, -SCO -, -COS- or ethylenic bonds are replaced in a manner that is not directly connected to each other; said Z ₂ and Z ₃ independently represent a single bond or -(CH ₂ ) _k -, k represents 1, 2, 3, 4 or 5 ; said L ₁ and L ₂ are the same or different, and independently represent -F, -Cl, -CH ₃ , -OCH ₃ , -CF ₃ , -OCF ₃ or -OCHF ₂ ; r, s independently represent 0 , 1, 2 or 3; said m and n independently represent 0 or 1, and m+n≤1.

Further preferably, in the general formula I, the ring A and ring B independently represent 1,4-phenylene, 1,4-cyclohexylene, 2-fluoro-1,4-phenylene, 2 -Fluoro-1,4-phenylene; said P ₁ , P ₂ , and P ₃ independently represent a methacrylate group or an acrylate group; said Z ₁ , Z ₄ independently represent a single bond,- O- or C ₁ -C ₅ alkylene and alkoxy groups; said Z ₂ and Z ₃ independently represent a single bond or -(CH ₂ ) _k -, wherein k represents 1, 2 or 3; said L ₁ and L ₂ are the same or different, and independently represent -F, -Cl, -CN, -CH ₃ , -OCH ₃ , -CF ₃ , -OCF ₃ or -OCHF ₂ ; further, L ₁ , L ₂ The same or different, independently represent -F, -Cl; said r, s independently represent 0 or 1; said m, n independently represent 0 or 1, and m+n≤1.

As a further preferred technical solution of the present invention:

In the general formula I, the P ₁ , P ₂ , and P ₃ independently represent a methacrylate group or an acrylate group; the Z ₁ , Z ₄ independently represent a single bond, -O- or C ₁ -C ₅ alkylene and alkoxy groups; Z ₂ and Z ₃ independently represent a single bond, -F or -(CH ₂ ) _k -, k represents 1, 2 or 3;

in,

m=n=0, L ₁ and L ₂ both represent-F, r and s are independently selected from 0 or 1;

Or, m=1, n=0, L ₁ and L ₂ both represent -F, ring A is selected from 1,4-phenylene, 1,4-cyclohexylene or 1-2 hydrogen atoms replaced by F or Cl In one or more substituted 1,4-phenylene atoms, r and s are independently selected from 0 or 1;

Or, m=0, n=1, L ₁ and L ₂ both represent -F, ring B is selected from 1,4-phenylene, 1,4-cyclohexylene or 1-2 hydrogen atoms replaced by F or Cl In one or more substituted 1,4-phenylene atoms, r and s are 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 a further preferred technical solution of the present invention, the compound is selected from one of the following compounds:

In the above formulas, P ₁ , P ₂ , and P ₃ independently represent a methacrylate group or an acrylate group; the Z ₁ , Z ₄ independently represent a single bond, -O- or C ₁ -C ₅ The alkylene and alkoxy groups; Z ₂ and Z ₃ independently represent a single bond or -(CH ₂ ) _k -, and k represents 1, 2 or 3.

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. The mass percentage of the compound in the composition is 0.01-10%, preferably 0.01-5%, 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 negative dielectric anisotropy of the liquid crystal compound is extremely high, and at the same time, the clearing point is significantly improved, relatively high optical anisotropy, moderate rotational viscosity and liquid crystal mutual solubility, excellent performance at low temperature, good thermal stability, Chemical stability, optical stability, and mechanical properties; thereby effectively reducing the driving voltage, improving the response speed of the liquid crystal display device, and having the characteristics of moderate optical anisotropy and high charge retention rate.

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:

100ml N,N-dimethylformamide, 30g (0.087mol) was added to a 500ml reaction flask, 4.2g of sodium hydroxide was slowly added, the temperature was controlled to 45-55°C, and the reaction was carried out for 1h. Continue to control the temperature at 45-55° C., add 14.8 g of methyl iodide dropwise, and react at the temperature for 6 hours. The reaction solution was poured into water, filtered, washed until neutral, and dried to obtain 28.4 g of a white solid (compound BYLC-01-1, 0.079 mol), GC: 99.8%, yield: 90.8%.

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

Under nitrogen protection, add 28.4g (0.079mol) compound BYLC-01-1, 25.2g diethyl malonate, 74.1g cesium carbonate, 1g cuprous iodide, 500ml tetrahydrofuran into a 1000ml reaction flask, and react at room temperature for 48h . The reaction solution was poured into water, and the pH was adjusted to neutral with dilute hydrochloric acid. After conventional post-treatment, extraction with ethyl acetate, chromatographic purification, eluting with n-hexane, and recrystallization from ethanol gave 28.2 g of white solid (compound BYLC-01-2, 0.072 mol), GC: 99.7%, yield: 91.1%.

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

Under the protection of nitrogen, add 28.2g (0.072mol) of compound BYLC-01-2 and 250ml of dichloromethane to a 500ml reaction flask, control the temperature to -15℃～-20℃, add 6g of boron tribromide dropwise, and react at room temperature 2h. After conventional post-treatment, extraction with ethyl acetate and column chromatography gave 25.7 g of a white solid (compound BYLC-01-3, 0.068 mol), GC: 99.8%, yield: 94.4%.

(4) Synthesis of compound BYLC-01-4:

Under the protection of nitrogen, add 10g of lithium aluminum hydride and 1000ml of diethyl ether to a 2000ml reaction flask, control the temperature at -10°C to -15°C, add 25.7g of the ether solution of compound BYLC-01-3 (0.068mol) dropwise, and continue to control the temperature -10℃～-15℃, react for 1h; then react at room temperature for 6h. Ethyl acetate was added to the reaction solution, and the pH was adjusted to weak acidity with dilute hydrochloric acid. Then carry out conventional post-processing operations, extract with ethyl acetate, chromatographically purify, and recrystallize a mixed solution with a volume ratio of n-heptane and toluene of 3:1 to obtain a white solid (compound BYLC-01-4, 0.062mol) 18.2 g, GC: 99.8%, yield: 91.2%.

(5) Synthesis of compound BYLC-01:

Under the protection of nitrogen, add 18.2g (0.062mol) compound BYLC-01-4, 30g triethylamine, 500ml dichloromethane into a 1000ml reaction flask, control the temperature at -10℃～-15℃, add 28g methacrylic acid dropwise Acyl chloride, continue to control the temperature at -10°C to -15°C, react for 1h; then react at room temperature for 6h. The reaction solution was poured into water and neutralized with sodium bicarbonate until neutral. After conventional post-treatment, petroleum ether was recrystallized to obtain 26.9 g of a white solid (compound BYLC-01, 0.054 mol), GC: 99.9%, yield: 87.1%.

The obtained white solid BYLC-01 was analyzed by GC-MS, and the m/z of the product was 498.1 (M+).

¹ H-NMR (300 MHz, CDCl ₃ ): 0.75-1.25 (m, 3H), 1.95-2.65 (m, 3H), 4.75-5.05 (m, 2H), 6.55-7.45 (m, 8H).

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 the protection of nitrogen, add 30.0g of compound BYLC-01-3, 37.6g 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 39.4 g of a white solid (compound BYLC-02), LC : 99.6%, yield: 84.3%.

The obtained white solid BYLC-02 was analyzed by GC-MS, and the m/z of the product was 456.1 (M+).

¹ H-NMR (300 MHz, CDCl ₃ ): 3.35-4.55 (m, 5H), 4.65-5.85 (m, 3H), 5.95-6.45 (m, 6H), 5.65-7.25 (m, 4H).

Example 3

The structural formula of the liquid crystal compound is:

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 40g of 3-benzyloxy-7-bromo-4,6-difluorodibenzofuran and 300ml of tetrahydrofuran into the reaction flask, cool down to -70℃～-80℃, add dropwise 0.13mol of n-butyl Lithium, temperature control -70℃～-80℃, react for 1h, add 18.0g trimethyl borate dropwise, naturally return to -30℃, acidify with dilute hydrochloric acid to adjust the pH value to less than 2, carry out conventional post-treatment, and recrystallize to obtain light yellow Solid (compound BYLC-03-1) 31.2g, LC: 98.5%, yield 86.7%;

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

Add 31.2g of compound BYLC-03-1, 17.5g of p-chlorobromobenzene, 18.0g of anhydrous potassium carbonate, 200ml of toluene, 150ml of ethanol, 150ml of water, 0.3 tetrakistriphenylphosphine palladium, and heat to reflux for 8h. After conventional post-processing, an off-white solid (compound BYLC-03-2): 33.4g, LC: 99.6%, yield: 83.2% was obtained;

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: 576.1 (M+).

¹ H-NMR(300MHz, CDCl ₃ ):1.35-2.20(m,9H),3.63-4.45(m,3H),4.55-5.65(m,2H),5.75-7.25(m,6H),7.25-8.25 (m,4H).

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 532.1 (M+).

¹ H-NMR (300 MHz, CDCl ₃ ): 3.35-4.55 (m, 5H), 5.65-6.45 (m, 9H), 6.45-7.45 (m, 8H).

Example 5

The structural formula of the liquid crystal compound is:

The synthetic route for preparing compound BYLC-05 is as follows:

Replace 3-benzyloxy-7-bromo-4,6-difluorodibenzofuran with 3-benzyloxy-7-bromomethyl-4,6-difluorodibenzofuran, others

Condition is the same as embodiment 1.

The obtained white solid BYLC-05 was analyzed by GC-MS, and the m/z of the product was 512.1 (M+).

¹ H-NMR (300 MHz, CDCl ₃ ): 1.55-2.55 (m, 8H), 3.05-4.25 (m, 5H), 5.45-6.25 (m, 6H), 6.65-7.25 (m, 4H).

Example 6

The structural formula of the liquid crystal compound is:

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

Specific steps are as follows:

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

Add 34.5g 3-benzyloxy-7-hydroxyl-4,6-difluorodibenzofuran, 20.5g anhydrous potassium carbonate, 300ml N,N-dimethylformamide to the reaction flask, and heat the reaction mixture to 60 ℃, 20.4g 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 recrystallization to obtain an off-white solid (compound BYLC-06-1 )33.5g, LC: 99.7%, yield 81.5%;

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

Under nitrogen protection, add 33.5g of compound BYLC-06-1, 31.5g 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 Reaction at 5°C-10°C for 3 hours, aqueous solution of sodium bisulfite destroyed hydrolysis, conventional post-treatment, recrystallization to obtain light yellow solid (compound BYLC-06-2) 32.1g, LC: 98.8%, yield 83.4%;

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: 556.1 (M+).

¹ H-NMR(300MHz, CDCl ₃ ):1.15-2.25(m,10H),2.65-4.25(m,5H),4.35-5.65(m,3H),5.65-6.65(m,4H),6.75-7.75 (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:

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

100ml N,N-dimethylformamide, 30g Add it to a 500ml reaction bottle, slowly add 4.2g of sodium hydroxide, control the temperature to 45-55°C, and react for 1h. Continue to control the temperature at 45-55° C., add 14.8 g of methyl iodide dropwise, and react at the temperature for 6 hours. The reaction solution was poured into water, filtered, washed until neutral, and dried to obtain 28.4 g of a white solid (compound BYLC-07-1), GC: 99.7%, yield: 89.2%.

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

Under nitrogen protection, 28.4g of compound BYLC-07-1, 25.2g of diethyl malonate, 74.1g of cesium carbonate, 1g of cuprous iodide, and 500ml of tetrahydrofuran were added to a 1000ml reaction flask, and reacted at room temperature for 48h. The reaction solution was poured into water, and the pH was adjusted to neutral with dilute hydrochloric acid. After conventional post-treatment, extraction with ethyl acetate, chromatographic purification, eluting with n-hexane, and recrystallization from ethanol gave 29.3 g of white solid (compound BYLC-07-2), GC: 99.7%, yield: 93.1%.

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

Under nitrogen protection, 29.3g of compound BYLC-07-2 and 250ml of dichloromethane were added to a 500ml reaction flask, the temperature was controlled to -15°C to -20°C, 6g of boron tribromide was added dropwise, and the reaction was carried out at room temperature for 2h. After conventional post-treatment, extraction with ethyl acetate and column chromatography gave 24.3 g of a white solid (compound BYLC-07-3), GC: 99.8%, yield: 91.1%.

(4) Synthesis of compound BYLC-07-4:

Under the protection of nitrogen, add 10g of lithium aluminum hydride and 1000ml of diethyl ether to a 2000ml reaction flask, control the temperature at -10°C to -15°C, add 24.3g of the ether solution of compound BYLC-07-3 dropwise, and continue to control the temperature at -10°C to -15°C -15°C, react for 1h; then react at room temperature for 6h. Ethyl acetate was added to the reaction solution, and the pH was adjusted to weak acidity with dilute hydrochloric acid. Then carry out conventional post-processing operations, extract through ethyl acetate, chromatographically purify, the mixed solution that the volume ratio of n-heptane and toluene is 3:1 carries out recrystallization, obtains white solid (compound BYLC-07-4) 17.1g, GC : 99.8%, yield: 87.2%.

(5) Synthesis of compound BYLC-07:

Under the protection of nitrogen, add 17.1g of compound BYLC-07-4, 30g of triethylamine, 500ml of dichloromethane into a 1000ml reaction flask, control the temperature at -10℃～-15℃, add 28g of methacryloyl chloride dropwise, and continue to control Temperature -10℃～-15℃, react for 1h; then react at room temperature for 6h. The reaction solution was poured into water and neutralized with sodium bicarbonate until neutral. After conventional post-processing, petroleum ether was recrystallized to obtain 24.3 g of a white solid (compound BYLC-07), GC: 99.9%, yield: 83.4%.

The obtained white solid BYLC-07 was analyzed by GC-MS, and the m/z of the product was 462.1 (M+).

¹ H-NMR(300MHz, CDCl ₃ ):0.95-1.95(m,6H),3.05-4.05(m,3H),4.35-5.65(m,7H),5.75-6.45(m,4H),7.15-7.65 (m,5H).

Example 8

The structural formula of the liquid crystal compound is:

raw material becomes Other reaction conditions are with embodiment 1.

The obtained white solid BYLC-08 was analyzed by GC-MS, and the m/z of the product was 480.1 (M+).

¹ H-NMR(300MHz, CDCl ₃ ):0.95-1.95(m,6H),3.05-4.05(m,3H),4.35-5.65(m,7H),5.75-6.45(m,4H),7.15-7.65 (m,4H).

Example 9

The structural formula of the liquid crystal compound is:

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

Specific steps are as follows:

Synthesis of compound BYLC-09:

Under the protection of nitrogen, add 30.0g of compound BYLC-07-3, 37.6g of triethylamine and 250mL of dichloromethane to the reaction flask, cool down to -10°C, and add 32.0g of acryloyl chloride dropwise at -10°C to 0°C. Rise to room temperature and react for 6 hours. Pour the reaction liquid into water, neutralize it with uranium bicarbonate aqueous solution, perform conventional post-treatment, purify by chromatography, elute with n-hexane, and recrystallize from ethanol to obtain 36.4 g of white solid (Compound BYLC-09), LC : 99.6%, yield: 81.1%.

The obtained white solid BYLC-09 was analyzed by GC-MS, and the m/z of the product was 420.1 (M+).

¹ H-NMR (300 MHz, CDCl ₃ ): 3.35-4.55 (m, 7H), 4.65-5.85 (m, 3H), 5.95-6.45 (m, 8H), 5.65-7.25 (m, 4H).

Example 10

The structural formula of the liquid crystal compound is:

The synthetic route for preparing compound BYLC-10 is as follows:

Specific steps are as follows:

(1) Synthesis of compound BYLC-10-1:

Under nitrogen protection, add 40g 300ml tetrahydrofuran, cool down to -70°C~-80°C, add 0.13mol n-butyllithium dropwise, control the temperature at -70°C~-80°C for 1 hour, add 18.0g trimethyl borate dropwise, and naturally return to -30°C , acidified with dilute hydrochloric acid to adjust the pH value to less than 2, performed conventional post-treatment, and recrystallized to obtain 31.4 g of a light yellow solid (compound BYLC-10-1), LC: 98.7%, yield 86.2%;

(2) Synthesis of compound BYLC-10-2:

Add 31.4g of compound BYLC-10-1, 17.5g of p-chlorobromobenzene, 18.0g of anhydrous potassium carbonate, 200ml of toluene, 150ml of ethanol, 150ml of water, and 0.3 tetrakistriphenylphosphine palladium into the reaction flask, and heat to reflux for 8h. After conventional post-treatment, an off-white solid (compound BYLC-10-2): 32.1 g, LC: 99.6%, yield: 81.7% was obtained;

Other steps are with embodiment 1

Compound BYLC-10: The obtained white solid BYLC-10 was analyzed by GC-MS, and the m/z of the product was: 538.1 (M+).

¹ H-NMR (300 MHz, CDCl ₃ ): 1.35-2.20 (m, 6H), 3.63-4.45 (m, 6H), 5.45-6.25 (m, 8H), 7.15-7.75 (m, 8H).

Example 11

The structural formula of the liquid crystal compound is:

raw material from becomes Other conditions are the same

Example 4.

The obtained white solid BYLC-11 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, 6H), 3.63-4.45 (m, 6H), 5.45-6.25 (m, 7H), 7.15-7.75 (m, 8H).

Example 12

The structural formula of the liquid crystal compound is:

Reaction condition is with embodiment 1,3.

The obtained white solid BYLC-12 was analyzed by GC-MS, and the m/z of the product was 496.1 (M+).

¹ H-NMR (300 MHz, CDCl ₃ ): 3.35-4.55 (m, 7H), 5.65-6.45 (m, 11H), 6.45-7.65 (m, 8H).

Example 13

The structural formula of the liquid crystal compound is:

The synthetic route for preparing compound BYLC-13 is as follows:

by replace Other conditions are with embodiment 1.

The obtained white solid BYLC-13 was analyzed by GC-MS, and the m/z of the product was 476.1 (M+).

¹ H-NMR (300 MHz, CDCl ₃ ): 1.55-2.55 (m, 11H), 3.05-4.25 (m, 7H), 5.45-6.25 (m, 8H), 6.65-7.65 (m, 4H).

Example 14

The structural formula of the liquid crystal compound is:

by replace Other conditions are the same

Example 7.

The obtained white solid BYLC-14 was analyzed by GC-MS, and the m/z of the product was 494.1 (M+).

¹ H-NMR (300 MHz, CDCl ₃ ): 1.55-2.55 (m, 11H), 3.05-4.25 (m, 6H), 5.45-6.25 (m, 6H), 6.65-7.65 (m, 4H).

Example 15

The structural formula of the liquid crystal compound is:

The synthetic route for preparing compound BYLC-15 is as follows:

Specific steps are as follows:

(1) Synthesis of compound BYLC-15-1:

Add 40g to the reaction bottle 23.5g of anhydrous potassium carbonate, 300ml of N,N-dimethylformamide, heated the reaction mixture to 60°C, added dropwise 20.4g of 3-bromo-1-propanol, and reacted at a temperature of 100°C to 110°C for 6h. Cool down to room temperature, perform conventional post-treatment, and recrystallize to obtain an off-white solid (compound BYLC-15-1) 35.1, LC: 99.7%, yield 83.4%;

(2) Synthesis of compound BYLC-15-2:

Under nitrogen protection, add 35.1g BYLC-15-1, 31.5g triphenylphosphine, and 200ml tetrahydrofuran to the reaction flask, cool down to -10°C to 0°C, add dropwise a solution consisting of 18.8g bromine and 30ml tetrahydrofuran, and control the temperature for 5 After reacting at ℃～10℃ for 3 hours, the aqueous solution of sodium bisulfite was hydrolyzed, followed by conventional post-treatment, and recrystallized to obtain 32.1 g of light yellow solid (compound BYLC-15-2), LC: 98.8%, yield 81.4%;

Other steps are with embodiment 1

The obtained white solid BYLC-15 was analyzed by GC-MS, and the m/z of the product was: 520.1 (M+).

¹ H-NMR(300MHz, CDCl ₃ ):1.15-2.25(m,10H),2.65-4.25(m,9H),4.35-5.65(m,5H),5.65-6.65(m,3H),6.75-7.75 (m,4H).

Example 16

The structural formula of the liquid crystal compound is:

raw material replaced by Other conditions are the same

Example 9.

The obtained white solid BYLC-16 was analyzed by GC-MS, and the m/z of the product was: 520.1 (M+).

¹ H-NMR(300MHz, CDCl ₃ ):1.15-2.25(m,10H),2.65-4.25(m,9H),4.35-5.65(m,4H),5.65-6.65(m,3H),6.75-7.75 (m,4H).

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.

Test example 1

The properties of mixed crystal 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 99.7% liquid crystal composition BHR87800, and dissolve it uniformly to obtain a mixture PM-1. Add 0.3% of the polymerizable compound BYLC-03 provided in Example 3 to the 99.7% liquid crystal mixture 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 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.

comparative example

0.3% of the polymerizable compound of CP was added to the 99.7% mixture BHR87800, and it was uniformly dissolved, and the mixture PM-2 was obtained. The physical properties of PM-2 were almost the same as those of the above-mentioned mixture BHR87800. PM-2 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 poor 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 dibenzofuran polymerizable compound, characterized in that it has the following structure: Wherein, the ring A and ring B independently represent 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene, or 1-4 hydrogen atoms are independently 1,4-phenylene substituted by F or Cl; The P ₁ , P ₂ , and P ₃ independently represent an acrylate group, a methacrylate group, a fluoroacrylate group, a chloroacrylate group, an ethyleneoxy group, an oxetane group or an epoxy group ; The Z ₁ and Z ₄ independently represent a single bond, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CH=N -, -N=CH-, -N=N-, -C≡C-, C ₁ -C ₁₂ alkylene or alkenyl, wherein the C ₁ -C ₁₂ alkylene or alkenyl One or more hydrogen atoms can be independently replaced by F, Cl, or CN, and one or more non-adjacent _-CH2- groups can be independently replaced by -O-, -S-, -NH- , -CO-, COO-, -OCO-, -OCOO-, -SCO-, -COS- or olefinic bonds are replaced in a manner that is not directly connected to each other; The Z ₂ and Z ₃ independently represent a single bond, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CH=N -, -N=CH-, -N=N-, -C≡C-, C ₁ -C ₁₂ alkylene or alkenyl, one of the C ₁ -C ₁₂ alkylene or alkenyl One or more hydrogen atoms can be independently replaced by F, Cl, or CN, and one or more non-adjacent _-CH2- groups can be independently replaced by -O-, -S-, -NH-, -CO-, COO-, -OCO-, -OCOO-, -SCO- or -COS- are substituted in such a way that they are not directly connected to each other; L ₁ and L ₂ independently represent -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 , - _OCHF2 or _{-OC2F5 ;} r, s represent 0, 1, 2 or 3 independently of each other; m and n represent 0 or 1 independently of each other. 2. The compound according to claim 1, wherein said ring A and ring B independently represent 1,4-phenylene, 1,4-cyclohexylene or 1-4 hydrogen atoms replaced by F Or 1,4-phenylene substituted by Cl atom; Preferably, said ring A and ring B independently represent 1,4-phenylene, 1,4-cyclohexylene, 2-fluoro-1,4-phenylene, 2-fluoro-1,4- phenylene. 3. The compound according to claim 1 or 2, characterized in that, said P ₁ , P ₂ , and P ₃ independently represent a methacrylate group or an acrylate group; And/or, said r, s represent 0 or 1 independently of each other And/or, the m and n independently represent 0 or 1, and m+n≤1. 4. The compound according to any one of claims 1-3, characterized in that, said Z ₁ and Z ₄ independently represent a single bond, -O- or C ₁ -C ₅ alkylene and alkoxy base. 5. The compound according to any one of claims 1-4, characterized in that, said Z ₂ and Z ₃ independently represent a single bond or -(CH ₂ ) _k -, k represents 1-8; Preferably, k represents 1, 2, 3, 4 or 5; Further preferably, k represents 1, 2 or 3. 6. The compound according to any one of claims 1-5, wherein said L ₁ and L ₂ independently represent -F, -Cl, -CN, or C ₁ -C ₃ alkyl or alkoxy; Preferably, L ₁ and L ₂ are the same or different, independently representing -F, -Cl, -CN, -CH ₃ , -OCH ₃ , -CF ₃ , -OCF ₃ or -OCHF ₂ ; Further, said L ₁ and L ₂ are the same or different, and independently represent -F, -Cl. 7. The compound according to any one of claims 1-6, characterized in that, said P ₁ , P ₂ , P ₃ represent a methacrylate group or an acrylate group; The Z ₁ and Z ₄ independently represent single bonds, -O- or C ₁ -C ₅ alkylene and alkoxy groups; The Z ₂ and Z ₃ independently represent a single bond or -(CH ₂ ) _k -, k represents 1, 2 or 3; in, m=n=0, L ₁ and L ₂ both represent-F, r and s are independently selected from 0 or 1; Or, m=1, n=0, L ₁ and L ₂ both represent -F, ring A is selected from 1,4-phenylene, 1,4-cyclohexylene or 1-2 hydrogen atoms replaced by F or Cl In one or more substituted 1,4-phenylene atoms, r and s are independently selected from 0 or 1; Or, m=0, n=1, L ₁ and L ₂ both represent -F, ring B is selected from 1,4-phenylene, 1,4-cyclohexylene or 1-2 hydrogen atoms replaced by F or Cl In one or more substituted 1,4-phenylene atoms, r and s are independently selected from 0 or 1. 8. The compound according to any one of claims 1-7, wherein the compound is selected from one of the following compounds: In the above formulas, P ₁ , P ₂ , and P ₃ independently represent a methacrylate group or an acrylate group; The Z ₁ and Z ₄ independently represent single bonds, -O- or C ₁ -C ₅ alkylene and alkoxy groups; Z ₂ and Z ₃ independently represent a single bond or -(CH ₂ ) _k -, k represents 1, 2 or 3; Preferably, the compound is selected from one of the following compounds: 9. A liquid crystal composition, characterized in that it comprises 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.