CN110358547A - A kind of novel polymerizable compound and its application - Google Patents

Abstract

The invention belongs to the technical field of liquid crystal materials, and relates to a novel polymerizable compound and its application. The compound is shown in general formula I. The compound provided by the present invention has extremely high negative dielectric anisotropy, and at the same time significantly improves the clearing point, relatively high optical anisotropy, moderate rotational viscosity and liquid crystal mutual solubility, excellent low temperature working effect, and good thermal stability properties such as chemical stability, optical stability, and mechanics; thereby effectively reducing the driving voltage and improving the response speed of the liquid crystal display device; meanwhile, it has the characteristics of moderate optical anisotropy and high charge retention rate.

Description

A Novel Polymerizable Compound and Its Application

technical field

The invention belongs to the technical field of liquid crystal materials, and relates to a novel polymerizable compound and its application.

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 P ₁ , P ₂ , and P ₃ independently represent an acrylate group, a methacrylate group, a fluoroacrylate group, a chloroacrylate group, a vinyloxy group, an oxetanyl group or a ring Oxygen;

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 C ₂ -C ₁₂ alkenyl, wherein the C ₁ -C ₁₂ alkylene One or more hydrogen atoms in the C ₂ -C ₁₂ alkenyl group can be independently substituted 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-, or -COS- in a manner not directly connected to each other;

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

The 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 , -OCHF ₂ or -OC ₂ F ₅ ;

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 C ₂ -C ₁₂ alkenyl, said C ₁ -C ₁₂ alkylene Or one or more hydrogen atoms in the C ₂ -C ₁₂ alkenyl 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- or -COS- are substituted in a manner that is not directly connected to each other;

r and s independently represent 0, 1, 2 or 3; m and n represent 0 or 1 independently of each other.

As a preferred technical solution of the present invention, in general formula I:

Regarding the P ₁ , P ₂ , and P ₃ : preferably, the P ₁ , P ₂ , and P ₃ represent methacrylate groups or acrylate groups.

Regarding the Z ₁ and Z ₄ : preferably, the Z ₁ and Z ₄ independently represent a single bond, -O-, C ₁ -C ₅ alkyl or alkoxy.

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

Regarding the ring A and ring B: preferably, the ring A and ring B independently represent 1,4-phenylene, 1,4-cyclohexylene, 1-4 hydrogen atoms replaced by F atoms 1,4-phenylene; more preferably, the ring A and ring B independently represent 1,4-phenylene, 1-4 hydrogen atoms replaced by F atoms 1,4-phenylene.

Regarding the L ₁ and L ₂ : preferably, the L ₁ and L ₂ are the same or different, independently representing -F, -Cl, -CN, C ₁ -C ₃ alkyl or alkoxy; more Preferably, L ₁ and L ₂ are the same or different, and independently represent -F, -Cl.

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

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

Or, in the general formula I described in the present invention:

Preferably, in the general formula I, P ₁ , P ₂ , P ₃ represent methacrylate groups or acrylate groups; Z ₁ , Z ₄ independently represent single bonds, -O-, -S-, -CO -, -CO-O-, -O-CO-, -O-CO-O-, -CH=N-, -N=CH-, -N=N-, -C≡C-, C ₁ -C ₁₂ alkylene or C ₂ -C ₁₂ alkenyl, wherein one or more hydrogen atoms in the C ₁ -C ₁₂ alkylene or C ₂ -C ₁₂ alkenyl can be independently replaced by F , Cl or CN, and one or more non-adjacent -CH ₂ - groups may be independently of each other by -O-, -S-, -NH-, -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COS- are replaced in a manner that is not directly connected to each other; ring A and ring B independently represent 1,4-phenylene, 1,4-cyclohexylene, 1-4 hydrogens 1,4-phenylene whose atoms are replaced by F atoms; L ₁ and L ₂ independently represent -F, -Cl, -CN, C ₁ -C ₃ alkyl or alkoxy; said Z ₂ , Z ₃ independently represents a single bond or -(CH ₂ ) _k -, k represents 1 to 8, specifically, 1, 2, 3, 4, 5, 6, 7 or 8; r and s independently represent 0, 1, 2 or 3; m and n independently represent 0 or 1, and m+n≦1.

Further preferably, in the general formula I, P ₁ , P ₂ , P ₃ represent methacrylate groups or acrylate groups; Z ₁ , Z ₄ independently represent single bonds, -O-, C ₁ -C ₅ Alkyl or alkoxy; ring A and ring B independently represent 1,4-phenylene, 1,4-phenylene in which 1-4 hydrogen atoms are replaced by F atoms; L ₁ and L ₂ are the same Or different, independently represent -F, -Cl; Z ₂ , Z ₃ independently represent a single bond or -(CH ₂ ) _k -, k represent 1-3; r, s independently represent 0 or 1; m and n independently represent 0 and 1, and m+n≦1.

As a further preferred technical solution of the present invention, in the general formula I, P ₁ , P ₂ , and P ₃ independently represent a methacrylate group or an acrylate group; Z ₁ , Z ₄ independently represent a C ₁ - C ₅ alkyl or alkoxy; Z ₂ and Z ₃ independently represent a single bond or -(CH ₂ ) _k -, k represents 1, 2 or 3, L ₁ and L ₂ are the same or different, independently of each other Represents -F, -Cl, r and s independently represent 0 or 1;

Wherein, m=n=0; or, m=1, ring A is 1,4-cyclohexylene; or, n=1, ring B is 1,4-cyclohexylene; or, m=1, ring A 1,4-phenylene or 1,4-phenylene with 1 to 2 hydrogen atoms replaced by F atoms; or, n=1, ring B is 1,4-phenylene or 1 to 2 hydrogens 1,4-phenylene whose atoms are replaced by F atoms; in the above technical scheme, r=s=0, or r=s=1, or r+s=1.

More preferably, 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; Z ₁ , Z ₄ independently represent a single bond, -O-, C ₁ -C ₅ alkane group or alkoxy group; 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:

A second object of the present invention is to protect compositions containing said liquid crystal compounds. 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:

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

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 27.4 g of a white solid (compound BYLC-01-1), GC: 99.7%, yield: 88.8%.

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

Under nitrogen protection, 27.4g of compound BYLC-01-1, 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 29.2 g of white solid (compound BYLC-01-2), GC: 99.7%, yield: 92.1%.

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

Under nitrogen protection, 29.2g of compound BYLC-01-2 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. Conventional post-treatment, extraction with ethyl acetate, and column chromatography gave 24.9 g of a white solid (compound BYLC-01-3), GC: 99.8%, yield: 92.1%.

(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 24.9g of the ether solution of compound BYLC-01-3 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-01-4) 17.9g, GC : 99.8%, yield: 89.2%.

(5) Synthesis of compound BYLC-01:

Under the protection of nitrogen, add 17.9g of compound BYLC-01-4, 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 24.8 g of a white solid (compound BYLC-01), GC: 99.9%, yield: 84.2%.

The obtained white solid BYLC-01 was analyzed by GC-MS, and the m/z of the product was 496.1 (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,3H),7.15-7.65 (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 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 36.9 g of a white solid (compound BYLC-02), LC : 99.6%, yield: 81.3%.

The obtained white solid BYLC-02 was analyzed by GC-MS, and the m/z of the product was 454.1 (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, 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 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 32.3 g of a light yellow solid (compound BYLC-03-1), LC: 98.5%, yield 87.1%;

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

Add 32.3g 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): 32.8g, LC: 99.6%, yield: 82.8% 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: 572.1 (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, 6H), 7.15-7.75 (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 528.1 (M+).

¹ H-NMR (300 MHz, CDCl ₃ ): 3.35-4.55 (m, 7H), 5.65-6.45 (m, 9H), 6.45-7.65 (m, 8H).

Example 5

The structural formula of the liquid crystal compound is:

by replace Other conditions are with embodiment 1.

The obtained white solid BYLC-05 was analyzed by GC-MS, and the m/z of the product was 508.1 (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, 6H), 6.65-7.65 (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 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-06-1) 38.5, LC: 99.7%, yield 84.2%;

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

Under the protection of nitrogen, add 38.5g BYLC-06-1, 31.5g triphenylphosphine, 200ml tetrahydrofuran to the reaction flask, cool down to -10℃～0℃, add dropwise a solution composed 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 35.1 g of light yellow solid (compound BYLC-06-2), LC: 98.8%, yield 82.4%;

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: 552.1 (M+).

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

Example 7

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 8

The structural formula of the liquid crystal compound is:

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

(1) Synthesis of compound BYLC-08-1:

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 29.4 g of a white solid (compound BYLC-08-1), GC: 99.7%, yield: 90.3%.

(2) Synthesis of compound BYLC-08-2:

Under nitrogen protection, 29.4g of compound BYLC-08-1, 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 27.9 g of white solid (compound BYLC-08-2), GC: 99.7%, yield: 92.1%.

(3) Synthesis of compound BYLC-08-3:

Under nitrogen protection, 27.9g of compound BYLC-08-2 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. Conventional post-treatment, extraction with ethyl acetate, and column chromatography gave 24.5 g of a white solid (compound BYLC-08-3), GC: 99.8%, yield: 91.6%.

(4) Synthesis of compound BYLC-08-4:

Under nitrogen protection, add 10g of lithium aluminum hydride and 1000ml of ether to a 2000ml reaction flask, control the temperature at -10°C to -15°C, add 24.5g of the ether solution of compound BYLC-08-3 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 operation, extract through ethyl acetate, chromatographic purification, the mixed solution that the volume ratio of n-heptane and toluene is 3:1 carries out recrystallization, obtains white solid (compound BYLC-08-4) 16.9g, GC : 99.8%, yield: 87.4%.

(5) Synthesis of compound BYLC-08:

Under the protection of nitrogen, add 16.9g of compound BYLC-08-4, 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-treatment, petroleum ether was recrystallized to obtain 14.1 g of a white solid (compound BYLC-08), GC: 99.9%, yield: 85.4%.

The obtained white solid BYLC-08 was analyzed by GC-MS, and the m/z of the product was 460.1 (M+).

¹ H-NMR(300MHz, CDCl ₃ ):0.95-1.95(m,6H),3.05-4.05(m,3H),4.35-5.65(m,9H),5.75-6.45(m,4H),

7.15-7.65 (m, 5H).

Example 9

The structural formula of the liquid crystal compound is:

raw material becomes Other reaction conditions are with embodiment 8.

The obtained white solid BYLC-09 was analyzed by GC-MS, and the m/z of the product was 478.1 (M+).

¹ H-NMR(300MHz, CDCl ₃ ):0.95-1.95(m,6H),3.05-4.05(m,3H),4.35-5.65(m,9H),5.75-6.45(m,4H),7.15-7.65 (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:

Synthesis of compound BYLC-10:

Under nitrogen protection, add 30.0g of compound BYLC-08-3, 37.6g of triethylamine and 250mL of dichloromethane into 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 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 35.9 g of a white solid (compound BYLC-10), LC : 99.6%, yield: 80.9%.

The obtained white solid BYLC-10 was analyzed by GC-MS, and the m/z of the product was 418.1 (M+).

¹ H-NMR (300 MHz, CDCl ₃ ): 3.35-4.55 (m, 7H), 4.65-5.85 (m, 5H), 5.95-6.45 (m, 8H), 5.65-7.25 (m, 4H).

Example 11

The structural formula of the liquid crystal compound is:

The synthetic route for preparing compound BYLC-11 is as follows:

Specific steps are as follows:

(1) Synthesis of compound BYLC-11-1:

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 32.1 g of a light yellow solid (compound BYLC-11-1), LC: 98.7%, yield 88.7%;

(2) Synthesis of compound BYLC-11-2:

Add 32.1g of compound BYLC-11-1, 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-11-2): 30.2g, LC: 99.6%, yield: 81.2% was obtained;

Other steps are the same as embodiment 8

The resulting white solid BYLC-11 was analyzed by GC-MS, and the m/z of the product was: 536.1 (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, 10H).

Example 12

The structural formula of the liquid crystal compound is:

raw material from becomes Other conditions are with embodiment 11.

The resulting white solid BYLC-12 was analyzed by GC-MS, and the m/z of the product was: 554.1 (M+).

¹ H-NMR (300 MHz, CDCl ₃ ): 1.35-2.20 (m, 6H), 3.63-4.45 (m, 8H), 5.45-6.25 (m, 7H), 7.15-7.75 (m, 8H).

Example 13

The structural formula of the liquid crystal compound is:

Reaction condition is the same as embodiment 8,10.

The obtained white solid BYLC-13 was analyzed by GC-MS, and the m/z of the product was 494.1 (M+).

¹ H-NMR (300 MHz, CDCl ₃ ): 3.35-4.55 (m, 7H), 5.65-6.45 (m, 13H), 6.45-7.65 (m, 8H).

Example 14

The structural formula of the liquid crystal compound is:

The synthetic route for preparing compound BYLC-14 is as follows:

by replace Other conditions are with embodiment 8.

The obtained white solid BYLC-14 was analyzed by GC-MS, and the m/z of the product was 474.1 (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, 10H), 6.65-7.65 (m, 4H).

Example 15

The structural formula of the liquid crystal compound is:

by replace Other conditions are with embodiment 14.

The obtained white solid BYLC-15 was analyzed by GC-MS, and the m/z of the product was 492.1 (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, 8H), 6.65-7.65 (m, 4H).

Example 16

The structural formula of the liquid crystal compound is:

The synthetic route for preparing compound BYLC-16 is as follows:

Specific steps are as follows:

(1) Synthesis of compound BYLC-16-1:

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-16-1) 33.4, LC: 99.7%, yield 81.2%;

(2) Synthesis of compound BYLC-16-2:

Under nitrogen protection, add 33.4g BYLC-16-1, 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 After reacting at 5°C-10°C for 3 hours, the aqueous solution of sodium bisulfite was hydrolyzed, followed by conventional post-treatment, and recrystallized to obtain 30.2 g of light yellow solid (compound BYLC-16-2), LC: 98.8%, yield 81.2%;

Other steps are with embodiment 8;

The resulting white solid BYLC-16 was analyzed by GC-MS, and the m/z of the product was: 518.1 (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,5H),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

Table 1 Summary of properties of mixed crystal BHR87800

0.3% of the polymerizable compound of BYLC-01 provided in Example 1 was added to 99.7% of the liquid crystal composition BHR87800, and dissolved uniformly to obtain a mixture PM-1. The physical properties of PM-1 were almost the same as those of the above-mentioned mixture BHR87800.

0.3% of the polymerizable compound of BYLC-03 provided in Example 3 was added to 99.7% of the liquid crystal composition BHR87800, and dissolved uniformly to obtain a mixture PM-2. The physical properties of PM-2 were almost the same as those of the above-mentioned mixture BHR87800.

Add 0.3% of the polymerizable compound of BYLC-08 provided in Example 8 to the 99.7% liquid crystal composition BHR87800, and dissolve it uniformly to obtain the mixture PM-3. The physical properties of PM-3 were almost the same as those of the above-mentioned mixture BHR87800.

PM-1, PM-2, and PM-3 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 1

0.3% of the polymerizable compound of CP was added to the 99.7% liquid crystal composition BHR87800, and it was uniformly dissolved, and the mixture PM-4 was obtained. The physical properties of PM-4 were almost the same as those of the above-mentioned mixture BHR87800. PM-4 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 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.

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 novel polymerizable compound, characterized in that it has the following structure: Wherein, the P ₁ , P ₂ , and P ₃ independently represent an acrylate group, a methacrylate group, a fluoroacrylate group, a chloroacrylate group, a vinyloxy group, an oxetanyl group or a ring Oxygen; 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 C ₂ -C ₁₂ alkenyl, wherein the C ₁ -C ₁₂ alkylene One or more hydrogen atoms in the C ₂ -C ₁₂ alkenyl group can be independently substituted 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-, or -COS- in a manner not directly connected to each other; The ring A and ring B independently represent 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene, or 1-4 hydrogen atoms are independently replaced by F or 1,4-phenylene substituted by Cl atom; The 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 , -OCHF ₂ or -OC ₂ F ₅ ; 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 C ₂ -C ₁₂ alkenyl, said C ₁ -C ₁₂ alkylene Or one or more hydrogen atoms in the C ₂ -C ₁₂ alkenyl 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- or -COS- are substituted in a manner that is not directly connected to each other; 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, characterized in that, said P ₁ , P ₂ , P ₃ represent a methacrylate group or an acrylate group; And/or, said m and n independently represent 0,1, and m+n≤1; And/or, the r and s independently represent 0 or 1. 3. The compound according to claim 1 or 2, wherein said Z ₁ and Z ₄ independently represent a single bond, -O-, C ₁ -C ₅ alkyl or alkoxy. 4. The compound according to any one of claims 1-3, characterized in that, said Z ₂ and Z ₃ independently represent a single bond or -(CH ₂ ) _k -, k represents 1-8; Preferably, Z ₂ and Z ₃ independently represent a single bond or -(CH ₂ ) _k -, k represents 1, 2 or 3. 5. The compound according to any one of claims 1-4, wherein said ring A and ring B independently represent 1,4-phenylene, 1,4-cyclohexylene, 1-4 1,4-phenylene in which hydrogen atoms are replaced by F atoms; Preferably, the rings A and B independently represent 1,4-phenylene, 1,4-phenylene in which 1-4 hydrogen atoms are replaced by F atoms. 6. The compound according to any one of claims 1-5, characterized in that, said L ₁ and L ₂ are the same or different, independently representing -F, -Cl, -CN, C ₁ -C ₃ Alkyl or alkoxy; Preferably, 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, In the general formula I, P ₁ , P ₂ , and P ₃ independently represent a methacrylate group or an acrylate group; Z ₁ and Z ₄ independently represent a C ₁ -C ₅ alkyl or alkoxy group ; Z ₂ and Z ₃ independently represent a single bond or -(CH ₂ ) _k -, k represents 1, 2 or 3, L ₁ and L ₂ are the same or different, independently represent -F or -Cl, r, s represent 0 or 1 independently of each other; where m=n=0; Or, m=1, ring A is 1,4-cyclohexylene; Or, n=1, ring B is 1,4-cyclohexylene; Or, m=1, ring A is 1,4-phenylene or 1,4-phenylene in which 1 to 2 hydrogen atoms are replaced by F atoms; Or, n=1, and ring B is 1,4-phenylene or 1,4-phenylene in which 1 to 2 hydrogen atoms are replaced by F atoms. 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; Z ₁ , Z ₄ independently represent a single bond, -O-, C ₁ -C ₅ alkane or alkoxy; 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. Application of the compound according to any one of claims 1-8 and/or the liquid crystal composition according to claim 9 in the field of liquid crystal display; It is preferably used in liquid crystal display devices; More preferably, the liquid crystal display device includes a TN, ADS, VA, PSVA, FFS or IPS liquid crystal display.