CN110452202A - A kind of novel benzofurans polymerizability compound and its application - Google Patents

Abstract

The invention relates to a novel benzofuran polymerizable compound and its application. The compound has the structure shown in general formula I. Compared with the prior art, the compound of the present 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 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.

Description

A novel benzofuran polymerizable compound and its application

technical field

The invention belongs to the technical field of liquid crystal materials, and relates to a novel benzofuran 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, and 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 R ₁ represents -Z ₁ -P ₁ or

R ₂ means -Z ₅ -P ₅ or (in, can be with same or different);

The P ₁ , P ₂ , P ₃ , P ₅ , P ₇ , and P ₈ independently represent acrylate, methacrylate, fluoroacrylate, chloroacrylate, vinyloxy, oxygen Heterobutanyl or epoxy;

The Z ₁ , Z ₄ , Z ₅ , and Z ₆ 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 One or more hydrogen atoms in -C ₁₂ alkylene or C ₂ -C ₁₂ alkenyl can be independently substituted by F, Cl, or CN, and one or more non-adjacent -CH ₂ - The groups can be independent of each other by -O-, -S-, -NH-, -CO-, COO-, -OCO-, -OCOO-, -SCO-, -COS- or ethylenic bonds that are not directly connected to each other way instead;

The Z ₂ , Z ₃ , Z ₇ , and Z ₈ 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 - One or more hydrogen atoms in C ₁₂ alkylene or C ₂ -C ₁₂ alkenyl can be independently substituted by F, Cl, or CN, and one or more non-adjacent -CH ₂ - groups Groups can be independent of each other by -O-, -S-, -NH-, -CO-, COO-, -OCO-, -OCOO-, -SCO- or -COS- or olefinic bonds in a manner that is not directly connected to each other replace;

The ring A and ring B independently represent 1,4-cyclohexylene or 1,4-phenylene;

The L ₁ , L ₂ , and L ₃ 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 r ₁ and r ₂ independently represent 0, 1, 2, 3 or 4; r ₃ represents 0, 1, 2 or 3;

The m and n independently represent 0 or 1, and m and n are not 0 at the same time.

The compound of the present invention, in the general formula I, about P ₁ , P ₂ , P ₃ , P ₅ , P ₇ , P ₈ : preferably, P ₁ , P ₂ , P ₃ , P ₅ , P ₇ , P ₈ independently represent a methacrylate group or an acrylate group.

About Z ₁ , Z ₄ , Z ₅ , Z ₆ : preferably, said Z ₁ , Z ₄ , Z ₅ , Z ₆ independently represent a single bond, -O-, C ₁ -C ₈ alkyl or alkane Oxygen; more preferably, said Z ₁ , Z ₄ , Z ₅ , and Z ₆ independently represent a single bond, -O-, C ₁ -C ₅ alkyl or alkoxy.

About Z ₂ , Z ₃ , Z ₇ , Z ₈ : preferably, said Z ₂ , Z ₃ , Z ₇ , Z ₈ independently represent a single bond or -(CH ₂ ) _k -, k represents 1-8; More preferably, said Z ₂ , Z ₃ , Z ₇ , and Z ₈ independently represent a single bond or -(CH ₂ ) _k -, k represents 1, 2, 3, 4 or 5; further, said Z ₂ , Z ₃ , Z ₇ , and Z ₈ independently represent a single bond or -(CH ₂ ) _k -, and k represents 1, 2 or 3.

About L ₁ , L ₂ , L ₃ : preferably, said L ₁ , L ₂ , L ₃ independently represent -F, -Cl, -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 , -CF ₃ , -OCF ₃ , -OCHF ₂ or -OC ₂ F ₅ ; More preferably, L ₁ , L ₂ , and L ₃ independently represent -F, -Cl, -CH ₃ , -OCH ₃ , -C ₂ H ₅ or -OC ₂ H ₅ ; further, L ₃ represents F or Cl.

Regarding r ₁ , r ₂ , r ₃ : preferably, said r ₁ , r ₂ , r ₃ represent 0, 1, 2 or 3 independently of each other.

In the compound of the present invention, preferably, in the general formula I, the P ₁ , P ₂ , P ₃ , P ₅ , P ₇ , and P ₈ independently represent a methacrylate group or an acrylate group; the Z ₁ , Z ₄ , Z ₅ , and Z ₆ 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 C ₂ -C ₁₂ alkenyl , wherein one or more hydrogen atoms in the C ₁ -C ₁₂ alkylene group or C ₂ -C ₁₂ alkenyl group can be independently substituted by F, Cl, or CN, and one or more hydrogen atoms are not in phase The adjacent -CH ₂ - groups can independently of each other be replaced by -O-, -S-, -NH-, -CO-, COO-, -OCO-, -OCOO-, -SCO-, -COS- or olefinic bonds are not directly connected to each other; said Z ₂ , Z ₃ , Z ₇ , and Z ₈ independently represent a single bond or -(CH ₂ ) _k -, k represents 1-8; said ring A and ring B independently represent 1,4-cyclohexylene or 1,4-phenylene; said L ₁ , L ₂ , and L ₃ independently represent -F, -Cl, -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 , -CF ₃ , -OCF ₃ , -OCHF ₂ or -OC ₂ F ₅ ; said r ₁ , r ₂ , and r ₃ independently represent 0, 1, 2 or 3; said m and n independently represent 0 or 1, and m and n are not 0 at the same time ;

Further preferably, in the general formula I, said P ₁ , P ₂ , P ₃ , P ₅ , P ₇ , and P ₈ independently represent a methacrylate group or an acrylate group; said Z ₁ , Z ₄ , Z ₅ , Z ₆ independently represent a single bond, -O-, C ₁ -C ₈ alkyl or alkoxy; said Z ₂ , Z ₃ , Z ₇ , Z ₈ independently represent a single bond or -(CH ₂ ) _k -, k represents 1 to 5; said ring A and ring B independently represent 1,4-cyclohexylene or 1,4-phenylene; said L ₁ , L ₂ , L ₃ represents -F, -Cl, -CH ₃ , -OCH ₃ , -C ₂ H ₅ or -OC ₂ H ₅ ; said r ₁ , r ₂ , r ₃ independently represent 0, 1 or 2; said m and n independently represent 0 or 1, and m and n are not 0 at the same time;

More preferably, in the general formula I, the P ₁ , P ₂ , P ₃ , P ₅ , P ₇ , and P ₈ independently represent a methacrylate group or an acrylate group; the Z ₁ , Z ₄ , Z ₅ , Z ₆ independently represent a single bond, -O-, C ₁ -C ₅ alkyl or alkoxy; said Z ₂ , Z ₃ , Z ₇ , Z ₈ independently represent a single bond or -(CH ₂ ) _k -, k represents 1 to 3; the ring A and ring B independently represent 1,4-cyclohexylene or 1,4-phenylene; the L ₁ and L ₂ are mutually independently represents -F, -Cl, -CH ₃ , -OCH ₃ , -C ₂ H ₅ , -OC ₂ H ₅ ; L ₃ represents F or Cl; r ₁ , r ₂ , r ₃ independently represent 0, 1 or 2; m and n independently represent 0 or 1, and m and n are not 0 at the same time;

As a further preferred technical solution of the present invention, in the compound, in general formula I, r ₁ +r ₂ +r ₃ ≤ 4;

Further, when r ₃ is not 0, r ₁ and/or r ₂ is 0;

or, when r ₁ and/or r ₂ is 2, r ₃ is 0;

Or, when m=n=1, L ₁ represents -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 , and When r ₁ is not 0, r ₃ is 0;

Or, when m=n=1, L ₂ represents -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 , and When r ₂ is not 0, r ₃ is 0;

Or, when m=n=1, ring A and ring B both represent 1,4-cyclohexylene, r ₁ and/or r ₂ are 0;

Or, when m=n=1, ring A represents 1,4-cyclohexylene, and ring B represents 1,4-phenylene, r ₃ is 0;

or, when _R1 represents and _R2 represents , r ₁ +r ₂ +r ₃ ≤2, and/or, L ₁ , L ₂ , L ₃ independently represent F or Cl;

Or, when m=n=1, and R ₂ represents When r ₁ is not 0, L ₁ is not -CH ₃ , -OCH ₃ , -C ₂ H ₅ or -OC ₂ H ₅ ; or, when m=n=1, and R ₂ represents When r ₂ is not 0, L ₂ is not -CH ₃ , -OCH ₃ , -C ₂ H ₅ or -OC ₂ H ₅ .

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

In the above formulas, Z ₁ , Z ₄ , Z ₅ , Z ₆ independently represent a single bond, -O-, C ₁ -C ₅ alkyl or alkoxy; Z ₂ , Z ₃ , Z ₇ , Z ₈ independently represent a single bond or -(CH ₂ ) _k -, k represents 1 to 3; P ₁ , P ₂ , P ₃ , P ₅ , P ₇ , P ₈ independently represent methacrylate, acrylic acid Ester group.

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. 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 the conventional detection method 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 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:

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 30.5 g of a light yellow solid (compound BYLC-01-1), LC: 99.5%, yield 88.1%;

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

Add 30.5g of compound BYLC-01-1, 17.5g of p-iodobromobenzene, 18.0g of anhydrous potassium carbonate, 200ml of toluene, 150ml of ethanol, 150ml of water, 0.3 tetrakistriphenylphosphine palladium in the reaction flask, heat and reflux for 8h, After conventional post-processing, an off-white solid (compound BYLC-01-2): 47.2g, LC: 99.6%, yield: 83.8% was obtained;

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

Under nitrogen protection, 47.2g of compound BYLC-01-2, 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 52.6 g of white solid (compound BYLC-01-3), GC: 99.7%, yield: 93.2%.

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

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 52.6g 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, and 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) 38.8g, GC : 99.8%, yield: 89.2%.

(5) Synthesis of compound BYLC-01-5:

Add 38.8g of compound BYLC-01-4, 6g of NaOH, and 400ml of deionized water into the reaction flask, and stir at room temperature for 2h. After acidification with hydrochloric acid, conventional post-treatment was carried out to obtain a white solid (compound BYLC-01-5), 32.6g, HPLC: 99.8%, yield 95.3%

(6) Synthesis of compound BYLC-01:

Under the protection of nitrogen, add 32.6g of compound BYLC-01-5, 28.5g of triethylamine and 200mL of dichloromethane into the reaction flask, cool down to -10°C, and add 29.5g of methpropylene dropwise at -10°C to 0°C Acyl chloride, rise to room temperature and react for 6 hours. Pour the reaction liquid 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 42.6 g of white solid (compound BYLC-01) , LC: 99.8%, Yield: 83.5%.

The obtained white solid BYLC-01 was analyzed by GC-MS, and the m/z of the product was 564.1 (M+).

1H-NMR (300MHz, CDCl3): 1.55-2.15 (m, 9H), 3.35-4.55 (m, 5H), 5.35-6.55 (m, 6H), 6.65-7.95 (m, 12H).

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 45.0g of compound BYLC-01-5, 32.5g 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 28.0g of acryloyl chloride dropwise, Rise to room temperature and react for 6 hours. Pour the reaction liquid into water, neutralize it with aqueous uranium bicarbonate solution, perform conventional post-treatment, and purify by chromatography, eluting with n-hexane, and recrystallizing from ethanol to obtain 56.44 g of a white solid (compound BYLC-02), LC : 99.8%, yield: 86.5%.

The obtained white solid BYLC-02 was analyzed by GC-MS, and the m/z of the product was 522.1 (M+).

1H-NMR(300MHz, CDCl3):3.15-4.75(m,5H),5.15-6.75(m,10H),7.25-7.95(m,11H)

Example 3

The structural formula of the liquid crystal compound is:

by replace Other reaction conditions are with embodiment 1;

The obtained white solid BYLC-03 was analyzed by GC-MS, and the m/z of the product was 578.1 (M+).

1H-NMR(300MHz, CDCl3):1.55-2.15(m,9H),3.35-4.55(m,7H),5.35-6.55(m,6H),6.65-7.95(m,12H)

Example 4

The structural formula of the liquid crystal compound is:

by replace Other conditions are with embodiment 1;

The obtained white solid BYLC-04 was analyzed by GC-MS, and the m/z of the product was 600.1 (M+).

1H-NMR(300MHz, CDCl3):1.55-2.15(m,7H),3.35-4.55(m,5H),5.35-6.55(m,6H),6.65-7.95(m,12H)

Example 5

The structural formula of the liquid crystal compound is:

by replace Other reaction conditions are with embodiment 1;

The obtained white solid BYLC-05 was analyzed by GC-MS, and the m/z of the product was 578.1 (M+).

1H-NMR(300MHz, CDCl3):1.55-2.15(m,7H),3.35-4.55(m,7H),5.35-6.55(m,8H),6.65-7.95(m,12H)

Example 6

The structural formula of the liquid crystal compound is:

by replace Other reaction conditions are with embodiment 1;

The obtained white solid BYLC-06 was analyzed by GC-MS, and the m/z of the product was 488.1 (M+).

1H-NMR(300MHz, CDCl3):1.55-2.15(m,7H),3.35-4.55(m,5H),5.35-6.55(m,6H),6.65-7.95(m,8H)

Example 7

The structural formula of the liquid crystal compound is:

The resulting white solid BYLC-07 was analyzed by GC-MS, and the m/z of the product was 564.1 (M+).

1H-NMR (300MHz, CDCl3): 1.55-2.15 (m, 8H), 3.35-4.55 (m, 5H), 5.35-6.55 (m, 7H), 6.65-7.95 (m, 12H).

Example 8

The structural formula of the liquid crystal compound is:

The resulting white solid BYLC-08 was analyzed by GC-MS, and the m/z of the product was 488.1 (M+).

1H-NMR(300MHz, CDCl3):1.55-2.15(m,8H),3.35-4.55(m,5H),5.35-6.55(m,7H),6.65-7.95(m,8H)

Example 9

The structural formula of the liquid crystal compound is:

by replace Other reaction conditions are with embodiment 1;

The obtained white solid BYLC-09 was analyzed by GC-MS, and the m/z of the product was 582.1 (M+).

1H-NMR (300MHz, CDCl3): 1.55-2.15 (m, 9H), 3.35-4.55 (m, 5H), 5.35-6.55 (m, 6H), 6.65-7.95 (m, 11H).

Example 10

The structural formula of the liquid crystal compound is:

The obtained white solid BYLC-10 was analyzed by GC-MS, and the m/z of the product was 690.1 (M+).

1H-NMR (300MHz, CDCl3): 1.55-2.15 (m, 12H), 3.35-4.55 (m, 6H), 5.35-6.55 (m, 9H), 6.65-7.95 (m, 11H).

Example 11

The structural formula of the liquid crystal compound is:

The obtained white solid BYLC-10 was analyzed by GC-MS, and the m/z of the product was 438.1 (M+).

1H-NMR (300MHz, CDCl3): 1.55-2.15 (m, 6H), 5.35-6.75 (m, 5H), 6.95-7.95 (m, 11H).

Example 12

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 12

The properties of the liquid crystal 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 3 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-03 provided in Example 4 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-05 provided in Example 6 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, adjust the irradiation intensity on the surface of the box to 30mW/cm2, and irradiate for 600s to obtain a vertically aligned liquid crystal display after polymerization For 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 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 ultraviolet rays to the test box, adjust the irradiation intensity on the surface of the box to 30mW/cm2, and irradiate for 600s to obtain a vertically aligned liquid crystal display after polymerization For 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 benzofuran polymerizable compound, characterized in that it has a structure shown in general formula I: has the following structure: Wherein, the R ₁ represents -Z ₁ -P ₁ or The R ₂ represents -Z ₅ -P ₅ or The P ₁ , P ₂ , P ₃ , P ₅ , P ₇ , and P ₈ independently represent acrylate, methacrylate, fluoroacrylate, chloroacrylate, vinyloxy, oxygen Heterobutanyl or epoxy; The Z ₁ , Z ₄ , Z ₅ , and Z ₆ 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 One or more hydrogen atoms in -C ₁₂ alkylene or C ₂ -C ₁₂ alkenyl can be independently substituted by F, Cl, or CN, and one or more non-adjacent -CH ₂ - The groups can be independent of each other by -O-, -S-, -NH-, -CO-, COO-, -OCO-, -OCOO-, -SCO-, -COS- or ethylenic bonds that are not directly connected to each other way instead; The Z ₂ , Z ₃ , Z ₇ , and Z ₈ 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 - One or more hydrogen atoms in C ₁₂ alkylene or C ₂ -C ₁₂ alkenyl can be independently substituted by F, Cl, or CN, and one or more non-adjacent -CH ₂ - groups Groups can be independent of each other by -O-, -S-, -NH-, -CO-, COO-, -OCO-, -OCOO-, -SCO- or -COS- or olefinic bonds in a manner that is not directly connected to each other replace; The ring A and ring B independently represent 1,4-cyclohexylene or 1,4-phenylene; The L ₁ , L ₂ , and L ₃ 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 ; r ₁ , r ₂ represent 0, 1, 2, 3 or 4 independently of each other; r ₃ means 0, 1, 2 or 3; m and n independently represent 0 or 1, and m and n are not 0 at the same time. 2. The compound according to claim 1, characterized in that, said P ₁ , P ₂ , P ₃ , P ₅ , P ₇ , and P ₈ independently represent a methacrylate group or an acrylate group. 3. The compound according to claim 1 or 2, wherein said Z ₁ , Z ₄ , Z ₅ , and Z ₆ independently represent a single bond, -O-, C ₁ -C ₈ alkyl or alkoxy; Preferably, said Z ₁ , Z ₄ , Z ₅ and Z ₆ 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 , Z ₃ , Z ₇ , and Z ₈ independently represent a single bond or -(CH ₂ ) _k -, k represents 1～8; Preferably, said k represents 1, 2, 3, 4 or 5; More preferably, said k represents 1, 2 or 3. 5. The compound according to any one of claims 1-4, wherein said L ₁ , L ₂ , and L ₃ independently represent -F, -Cl, -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 , -CF ₃ , -OCF ₃ , -OCHF ₂ or -OC ₂ F ₅ ; Preferably, L ₁ , L ₂ , and L ₃ independently represent -F, -Cl, -CH ₃ , -OCH ₃ , -C ₂ H ₅ or -OC ₂ H ₅ ; More preferably, L3 represents F or _Cl . 6. The compound according to any one of claims 1-5, wherein said r ₁ , r ₂ , r ₃ independently represent 0, 1, 2 or 3. 7. The compound according to any one of claims 1-6, wherein r ₁ +r ₂ +r ₃ ≤ 4; Preferably, when r ₃ is not 0, r ₁ and/or r ₂ are 0; or, when r ₁ and/or r ₂ is 2, r ₃ is 0; Or, when m=n=1, L ₁ represents -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 , and When r ₁ is not 0, r ₃ is 0; Or, when m=n=1, L ₂ represents -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 , and When r ₂ is not 0, r ₃ is 0; Or, when m=n=1, ring A and ring B both represent 1,4-cyclohexylene, r ₁ and/or r ₂ are 0; Or, when m=n=1, ring A represents 1,4-cyclohexylene, and ring B represents 1,4-phenylene, r ₃ is 0; or, when _R1 represents and _R2 represents When , r ₁ +r ₂ +r ₃ ≤2, and/or, L ₁ , L ₂ , and L ₃ independently represent F or Cl. 8. The compound according to any one of claims 1-7, characterized in that, it is selected from one of the following compounds: Preferably, one selected from 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 composition described in claim 9 in the liquid crystal display field, preferably the application in the liquid crystal display device; More preferably described liquid crystal display device Including TN, ADS, VA, PSVA, FFS or IPS LCD.