TWI881211B - A self-aligned polymerizable compound and its application - Google Patents

Abstract

The present invention provides a self-aligned polymerizable compound and its application, wherein the self-aligned polymerizable compound has a structure as shown in the general formula (I). The terminal group of the compound of the present invention introduces a ring structure, the rigidity of the molecular terminal group is increased, the molecule is not easily deformed, the elastic constant of the liquid crystal compound is increased, and there is a certain advantage in angular stability. On the other hand, the molecular terminal group changes from a linear structure to a ring structure, the viscous resistance of the molecule increases, that is, its rotational viscosity increases, and at the same time, it has good solubility, faster polymerization rate, more complete polymerization, lower residue, so that the overall structure has a better alignment effect, thereby greatly improving the problems of poor display, residual image, etc., and can be widely used in the field of liquid crystal display, with important application value.

Description

A self-aligned polymerizable compound and its application

The present invention relates to the field of liquid crystal material technology, and in particular to a self-aligned polymerizable compound and its application.

In recent years, liquid crystal display devices have been widely used in various electronic devices, such as smart phones, tablet computers, car navigation systems, and televisions. Representative liquid crystal display modes include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), edge field switching (FFS), and vertical alignment (VA). Among them, the VA mode has received 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 display elements of active matrix addressing methods such as VA mode has its own shortcomings, such as the level of afterimage is significantly worse than that of display elements with positive dielectric anisotropy, slow response time, and high driving voltage. 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 a wide viewing angle display mode similar to MVA/PVA, but also simplifies the CF process, reduces the cost of CF, improves the aperture rate, and can also obtain higher brightness, thereby obtaining higher contrast. In addition, since the entire surface of the 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 level of afterimages will not be affected.

The prior art has found that LC mixtures and RMs still have some disadvantages in terms of their application in PSVA displays. Firstly, not every desired soluble RM is suitable for use in PSA displays so far, and if it is desired to polymerize with the aid of UV light without adding photoinitiators (which may be advantageous for some applications), the choice becomes smaller; in addition, the "material system" formed by the combination of 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, which is used to increase the "voltage holding ratio" (VHR) to achieve the effect. In the case of PSVA, a high VHR after (UV) light irradiation is very important, otherwise it will lead to problems such as afterimages in the final display. So far, not all combinations of LC blends and polymerizable components are suitable for PSVA displays because the polymerizable units have too short a UV-sensitive wavelength, or no or insufficient tilt after illumination, or the polymerizable components have poor uniformity after illumination.

Therefore, the synthesis of polymerizable compounds with novel structures and excellent performance and the study of structure-performance relationships have become an important task in the field of liquid crystals.

The first purpose of the present invention is to provide a self-aligned polymerizable compound. The polymerizable liquid crystal compound of the present invention introduces a ring structure into the end group, the rigidity of the molecular end group is increased, the molecule is not easily deformed, the elastic constant of the liquid crystal compound is increased, and there is a certain advantage in angular stability. On the other hand, the molecular end group changes from a linear structure to a ring structure, the viscous resistance of the molecule increases, that is, its rotational viscosity increases, and at the same time it has good solubility, faster polymerization rate, more complete polymerization, lower residue, so that the overall structure has a better alignment effect, thereby greatly improving the problems of poor display and residual images, and can be widely used in the field of liquid crystal display, with important application value.

Specifically, the self-aligned polymerizable compound has a structure as shown in general formula (I):

wherein ring A represents a C ₃ -C ₇ cycloalkyl or a C ₃ -C ₇ cycloalkane group; or, at least one hydrogen atom in the C ₃ -C ₇ cycloalkyl or C ₃ -C ₇ cycloalkane group is substituted by F; or, one -CH ₂ - or at least two non-adjacent -CH ₂ - in the C ₃ -C ₇ cycloalkyl or C ₃ -C ₇ cycloalkane group is substituted by -O- or -S- in a manner that they are not directly connected to each other; A ₁ , A ₂ , A ₃ each independently represents 1,4-cyclohexylene, 1,4-cyclohexenylene or 1,4-phenylene; or, at least one hydrogen atom in the 1,4-cyclohexylene, 1,4-cyclohexenylene or 1,4-phenylene is substituted by L or -ZP; or, at least one ring carbon atom in the 1,4-phenylene is substituted by a nitrogen atom; L represents H, -F, -Cl, -CN, -NO ₂ , -NCS, an optionally substituted silyl group, a C ₃ -C ₇ cycloalkyl group or a C ₁ -C ₁₂ straight or branched alkyl group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkoxycarbonyloxy group; or, the C ₃ -C ₇ cycloalkyl group or C ₁ -C at least one hydrogen atom in a C1- _C12 straight or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy group is substituted by F or Cl; P represents an acrylate group, a methacrylate group, a fluoroacrylate group, a chloroacrylate group, an vinyloxy group, an oxacyclobutane group or an epoxide group; Z, _Z1 , _Z2 , _Z3 , _Z4 and _Z5 each independently represent a single bond, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CH=N-, -N=CH-, -N=N-, a _C1 - _C12 alkylene group or a _C2 - _C12 alkenyl group; or, the _C1 - _C12 alkylene group or C2- _C12 alkenyl group at least one hydrogen atom in the C ₁ -C ₁₂ alkylene group or C 2 -C 12 alkenyl group is substituted by F, Cl, or CN; or, one -CH ₂ - or at least two non-adjacent -CH ₂ - in the C 1 -C ₁₂ alkylene group or C ₂ -C ₁₂ alkenyl group is substituted by -O-, -S-, -NH-, -CO-, -COO-, -OCO-, -OCOO-, -SCO-, or -COS- in a manner not directly linked to each other; R ₁ and R ₂ each independently represent H, a C ₁ -C ₁₂ alkyl or alkoxy group, or a C ₂ -C ₁₂ alkylenyl or alkoxyenyl group; or, at least one hydrogen atom in the C ₁ -C ₁₂ alkyl or alkoxy group, C ₂ -C ₁₂ alkylenyl or alkoxyenyl group is substituted by F; or, the C ₁ -C ₁₂ alkyl or alkoxy group, C ₂ -C 12 alkylenyl or alkoxyenyl group is substituted by F; One -CH ₂ - or at least two non-adjacent -CH ₂ - in the alkene or alkoxyalkenyl group of ₁₂ is substituted by -O- in a manner that they are not directly linked to each other; X represents -OH, -SH, or -NH ₂ ; m and n each independently represent 0, 1 or 2 and are not 0 at the same time.

Further, the general formula (I) is selected from one or more of the following structures:

wherein _A1 and _A2 represent 1,4-cyclohexylene, 1,4-cyclohexenylene or 1,4-phenylene; or, at least one hydrogen atom H in the 1,4-cyclohexylene, 1,4-cyclohexenylene or 1,4-phenylene is substituted by L or -ZP; L represents H, -F, -Cl, a _C3 - _C7 cycloalkyl group or a _C1 - _C6 straight or branched alkyl group; or, at least one hydrogen atom in the _C3 - _C7 cycloalkyl group or a _C1 - _C6 straight or branched alkyl group is substituted by F or Cl; P represents an acrylate group, a methacrylate group or a fluoroacrylate group; Z, _Z1 , _Z2 , _Z3 , _Z4 and _Z5 each independently represent a single bond, -O-, _C1 -C or, at least one hydrogen atom in _the C ₁ -C ₆ alkylene or C ₂ -C ₆ alkenyl is substituted by F; or, one -CH ₂ - or at least two non-adjacent -CH _{2 -} in the C _{1 -C 6} alkylene or C ₂ -C ₆ alkenyl is substituted by -O- in a manner that they are not directly connected to each other; R ₂ represents H, C ₁ -C ₆ alkyl or alkoxy, C 2 -C ₆ alkylenyl or alkoxyalkenyl; or, at least one hydrogen atom in the C _{1 -C 6} alkylene or C 2 -C 6 alkenyl is substituted by F; or, one -CH 2 - in the C ₁ -C ₆ alkylene or C ₂ -C ₆ alkenyl is substituted by -O- in a manner that they are not directly connected to each other; R ₂ represents H, C ₁ -C ₆ alkyl or alkoxy, C ₂ -C ₆ alkylenyl or alkoxyalkenyl; - or at least two non-adjacent -CH ₂ - are substituted by -O- in a manner that they are not directly connected to each other; X represents -OH; m and n each independently represent 0, 1 or 2 and are not 0 at the same time.

Further, one or more selected from the following compounds:

The second object of the present invention is to provide a liquid crystal composition comprising the self-aligned polymerizable compound, wherein the weight percentage of the self-aligned polymerizable compound in the liquid crystal composition is 0.01-10%, preferably 0.01-5%, and more preferably 0.1-3%.

The third purpose of the present invention is to provide the application of the above-mentioned self-aligned polymerizable compound and the above-mentioned liquid crystal composition in the display field. Furthermore, the application in the liquid crystal display field is the application in a liquid crystal display device. Furthermore, the liquid crystal display device is selected from one of TN, ADS, VA, PSVA, FFS or IPS liquid crystal displays, preferably VA, PSVA liquid crystal displays.

The present invention provides a self-aligned polymerizable compound having a structure as shown in the general formula (I):

wherein ring A represents a C ₃ -C ₇ cycloalkyl or a C ₃ -C ₇ cycloalkane group; or, at least one hydrogen atom in the C ₃ -C ₇ cycloalkyl or C ₃ -C ₇ cycloalkane group is substituted by F; or, one -CH ₂ - or at least two non-adjacent -CH ₂ - in the C ₃ -C ₇ cycloalkyl or C ₃ -C ₇ cycloalkane group is substituted by -O- or -S- in a manner that they are not directly connected to each other; A ₁ , A ₂ , A ₃ each independently represents 1,4-cyclohexylene, 1,4-cyclohexenylene or 1,4-phenylene; or, at least one hydrogen atom in the 1,4-cyclohexylene, 1,4-cyclohexenylene or 1,4-phenylene is substituted by L or -ZP; or, at least one ring carbon atom in the 1,4-phenylene is substituted by a nitrogen atom; L represents H, -F, -Cl, -CN, -NO ₂ , -NCS, an optionally substituted silyl group, a C ₃ -C ₇ cycloalkyl group or a C ₁ -C ₁₂ straight or branched alkyl group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkoxycarbonyloxy group; or, the C ₃ -C ₇ cycloalkyl group or C ₁ -C at least one hydrogen atom in a C1- _C12 straight or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy group is substituted by F or Cl; P represents an acrylate group, a methacrylate group, a fluoroacrylate group, a chloroacrylate group, an vinyloxy group, an oxacyclobutane group or an epoxide group; Z, _Z1 , _Z2 , _Z3 , _Z4 and _Z5 each independently represent a single bond, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CH=N-, -N=CH-, -N=N-, a _C1 - _C12 alkylene group or a _C2 - _C12 alkenyl group; or, the _C1 - _C12 alkylene group or C2- _C12 alkenyl group at least one hydrogen atom in the C ₁ -C ₁₂ alkylene group or C 2 -C 12 alkenyl group is substituted by F, Cl, or CN; or, one -CH ₂ - or at least two non-adjacent -CH ₂ - in the C 1 -C ₁₂ alkylene group or C ₂ -C ₁₂ alkenyl group is substituted by -O-, -S-, -NH-, -CO-, -COO-, -OCO-, -OCOO-, -SCO-, or -COS- in a manner not directly linked to each other; R ₁ and R ₂ each independently represent H, a C ₁ -C ₁₂ alkyl or alkoxy group, or a C ₂ -C ₁₂ alkylenyl or alkoxyenyl group; or, at least one hydrogen atom in the C ₁ -C ₁₂ alkyl or alkoxy group, C ₂ -C ₁₂ alkylenyl or alkoxyenyl group is substituted by F; or, the C ₁ -C ₁₂ alkyl or alkoxy group, C ₂ -C 12 alkylenyl or alkoxyenyl group is substituted by F; One -CH ₂ - or at least two non-adjacent -CH ₂ - in the alkene or alkoxyalkenyl group of ₁₂ is substituted by -O- in a manner that they are not directly linked to each other; X represents -OH, -SH, or -NH ₂ ; m and n each independently represent 0, 1 or 2 and are not 0 at the same time.

Further, the general formula (I) is selected from one or more of the following structures:

wherein _A1 and _A2 represent 1,4-cyclohexylene, 1,4-cyclohexenylene or 1,4-phenylene; or, at least one hydrogen atom H in the 1,4-cyclohexylene, 1,4-cyclohexenylene or 1,4-phenylene is substituted by L or -ZP; L represents H, -F, -Cl, a _C3 - _C7 cycloalkyl group or a _C1 - _C6 straight or branched alkyl group; or, at least one hydrogen atom in the _C3 - _C7 cycloalkyl group or a _C1 - _C6 straight or branched alkyl group is substituted by F or Cl; P represents an acrylate group, a methacrylate group or a fluoroacrylate group; Z, _Z1 , _Z2 , _Z3 , _Z4 and _Z5 each independently represent a single bond, -O-, _C1 -C or, at least one hydrogen atom in _the C ₁ -C ₆ alkylene or C ₂ -C ₆ alkenyl is substituted by F; or, one -CH ₂ - or at least two non-adjacent -CH _{2 -} in the C _{1 -C 6} alkylene or C ₂ -C ₆ alkenyl is substituted by -O- in a manner that they are not directly connected to each other; R ₂ represents H, C ₁ -C ₆ alkyl or alkoxy, C 2 -C ₆ alkylenyl or alkoxyalkenyl; or, at least one hydrogen atom in the C _{1 -C 6} alkylene or C 2 -C 6 alkenyl is substituted by F; or, one -CH 2 - in the C ₁ -C ₆ alkylene or C ₂ -C ₆ alkenyl is substituted by -O- in a manner that they are not directly connected to each other; R ₂ represents H, C ₁ -C ₆ alkyl or alkoxy, C ₂ -C ₆ alkylenyl or alkoxyalkenyl; - or at least two non-adjacent -CH ₂ - are substituted by -O- in a manner that they are not directly connected to each other; X represents -OH; m and n each independently represent 0, 1 or 2 and are not 0 at the same time.

Further, one or more selected from the following compounds:

The present invention provides a liquid crystal composition of the self-aligned polymerizable compound, wherein the weight percentage of the self-aligned polymerizable compound in the liquid crystal composition is 0.01-10%, preferably 0.01-5%, and more preferably 0.1-3%.

The present invention provides the application of the self-aligned polymerizable compound and the liquid crystal composition in the display field. Furthermore, the application in the liquid crystal display field is the application in a liquid crystal display device. Furthermore, the liquid crystal display device is selected from one of TN, ADS, VA, PSVA, FFS or IPS liquid crystal displays, preferably VA, PSVA liquid crystal displays.

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

Unless otherwise specified, the liquid crystal compounds used in the following examples can be synthesized by known methods or obtained from public commercial channels. These synthesis techniques are conventional, and the obtained liquid crystal compounds have been tested to meet the standards of electronic compounds.

According to the conventional detection method in this field, various performance parameters of liquid crystal compounds are obtained through linear fitting, among which the specific meanings of various performance parameters are as follows: △n represents optical anisotropy (25℃); △ε represents dielectric anisotropy (25℃, 1000Hz); γ1 represents rotational viscosity (mPa.s, 25℃); 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:

The specific steps are as follows:

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

Under nitrogen protection, 100 g of 2-ethyl-4-bromoiodobenzene, 45 g of p-hydroxyphenylboric acid, 86 g of sodium carbonate, 0.9 L of dioxane, and 0.3 L of water were added to the reaction bottle, and then stirring was started, 6.7 g of Pd(PPh ₃ ) ₂ Cl ₂ was added, and the mixture was heated to 85° C. and reacted for 10 h. After the reaction solution was cooled to room temperature, 0.9 L of water was added, extracted once with 0.9 L of EA, washed once with 3 L of water until neutral, dried with 50 g of anhydrous sodium sulfate, passed through a 50 g silica gel column, eluted with ethyl acetate, then mixed with 100 g of silica gel and purified by chromatography on 400 g of silica gel, n-heptane/EA=100:1 (v/v), and the column liquid was spun dry to obtain 77.7 g of a colorless liquid (compound BYLC-01-1), LC: 95.458%, yield: 87.3%.

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

Under nitrogen protection, add 72g of compound BYLC-01-1, 69.3g of cyclopentylbiphenylboronic acid, 56g of sodium carbonate, 430ml of toluene, 145ml of ethanol, and 145ml of water to the reaction bottle, start stirring, add 0.92g of Pd0132, heat to 73℃ and react for 10h, perform conventional post-treatment, and recrystallize from ethanol to obtain 93g of white solid (compound BYLC-01-2), LC: 97.4%, yield: 85.6%.

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

Add 93g of compound BYLC-01-2, 6.3g of diisopropylamine, and 1500ml of THF to the reaction bottle, start stirring, cool to -5℃, control the temperature at 0~-5℃, add 103.3g of NBS in batches, then naturally heat up, react for 6h, treat, add 1L of sodium sulfite aqueous solution to the reaction solution to neutralize to neutrality, separate the liquid, extract the aqueous phase with 500ml*2 dichloromethane twice, combine the organic phases, and wash with 1L*2 water twice, dry 50g of anhydrous sodium sulfate, pass through 50g of silica gel, elute with dichloromethane, recrystallize with n-heptane and ethanol to obtain 113g of white solid (compound BYLC-01-03), LC: 99.194%, yield: 88.2%.

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

Under nitrogen protection, add 25.8g of compound BYLC-01-3, 19.3g of Y-1, 14.2g of triphenylphosphine, and 200ml of tetrahydrofuran to the reaction bottle, start stirring, control the temperature at -5℃~5℃, and drop a solution composed of 13.6g of DIAD and 50ml of tetrahydrofuran. After dropping, control the temperature at -5℃~5℃ to react for 30 minutes, and naturally react at room temperature for 4 hours. After conventional post-treatment, column chromatography purification, n-heptane/ethyl acetate = 80:1 (v/v), obtain 33.2g of light yellow liquid (compound BYLC-01-4), LC: 98.8%, yield: 78%.

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

Under nitrogen protection, add 28.5g of compound BYLC-01-4, 15.8g of heterocyclopentaborane, 0.56g of RuPhos, 12.8g of sodium carbonate, 200ml of tetrahydrofuran, 50ml of water, and 0.1g of palladium chloride to the reaction bottle, start stirring, heat to 75℃ and react for 12 hours, perform routine post-treatment, column chromatography purification, n-heptane/ethyl acetate = 30:1 (v/v), and obtain 20.3g of colorless viscous liquid (compound BYLC-01-5), LC: 97.8%, yield: 75%.

(6) Synthesis of compound BYLC-01-6:

Under nitrogen protection, add 20g of compound BYLC-01-5, 7.5g of methacrylic acid, 1.2g of DMAP, and 150ml of DCM to the reaction bottle, start stirring, and add a solution consisting of 18.1g of DCC and 50ml of DCM at a temperature of -5℃~5℃. After the addition, naturally return the temperature to room temperature for 12 hours, and perform conventional post-treatment to obtain 17.8g of colorless viscous liquid (compound BYLC-01-6), LC: 97.3%, yield: 78%.

(7) Synthesis of compound BYLC-01:

Under nitrogen protection, add 15.0g of compound BYLC-01-6 and 50ml of THF to the reaction bottle, start stirring, control the temperature at 0℃~5℃, and drop a solution composed of 11.2g of tetrabutylammonium fluoride and 20ml of THF. After dropping, naturally return to room temperature (20℃) and react for 10 hours. Destroy and hydrolyze with 100ml of saturated sodium bicarbonate aqueous solution, perform conventional post-treatment, purify by column chromatography, n-heptane/ethyl acetate = 10:1 (v/v), and recrystallize from n-heptane to obtain 7.8g of white solid (compound BYLC-01), LC: 99.5%, yield: 66.8%.

The obtained white solid BYLC-01 was analyzed by LC-MS, and the m/z of the product was 814.1 (M+).

Elemental analysis: C, 78.10; H, 8.16; O, 13.74.

¹ H-NMR (300MHz, CDCl ₃ ): 0.95-2.10(m,30H), 2.25-2.85(m,7H), 3.13-3.74(m,6H), 3.95-4.75(m,6H), 6.25-6.87(m,4H), 6.92-7.98(m,13H).

Example 2

The structural formula of the liquid crystal compound is:

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

The specific steps are as follows:

(1) Synthesis of compound BYLC-02-1:

Under nitrogen protection, add 69.8g of compound BYLC-01-1, 60.0g of cyclopropylbiphenylboronic acid, 26.7g of sodium carbonate, 500ml of toluene, 150ml of ethanol, and 150ml of water to the reaction bottle, start stirring, add 0.8g of Pd0132, heat to 73℃ and react for 10h, perform conventional post-treatment, and recrystallize from ethanol to obtain 80.9g of white solid (compound BYLC-02-01), LC: 98.2%, yield: 82.4%.

(2) Synthesis of compound BYLC-02-2:

Add 80g of compound BYLC-02-1, 4.15g of diisopropylamine, and 1800ml of THF to the reaction bottle, start stirring, cool to -5℃, control the temperature at 0~-5℃, add 94.9g of NBS in batches, then naturally heat up, react for 6h, treat, add 1L of sodium sulfite aqueous solution to the reaction solution to neutralize to neutrality, separate the liquids, extract the aqueous phase with 500ml*2 dichloromethane twice, combine the organic phases, and wash with 1L*2 water twice, dry 50g of anhydrous sodium sulfate, pass through 50g of silica gel, elute with dichloromethane, recrystallize with n-heptane and ethanol to obtain 95.0g of white solid (compound BYLC-02-2), LC: 99.3%, yield: 84.5%.

(3) Synthesis of compound BYLC-02-3:

Under nitrogen protection, add 50.0g of compound BYLC-02-2, 37.4g of Y-1, 27.5g of triphenylphosphine, and 500ml of tetrahydrofuran to the reaction bottle, start stirring, control the temperature at -5℃~5℃, and drop a solution composed of 31.2g of DIAD and 50ml of tetrahydrofuran. After dropping, control the temperature at -5℃~5℃ to react for 30 minutes, and naturally react at room temperature for 4 hours. After conventional post-treatment, column chromatography purification, n-heptane/ethyl acetate = 80:1 (v/v), obtain 63.2g of light yellow liquid (compound BYLC-02-3), LC: 99.1%, yield: 75.6%.

(4) Synthesis of compound BYLC-02-4:

Under nitrogen protection, add 60.0g of compound BYLC-02-3, 34.2g of heterocyclopentaborane, 1.2g of RuPhos, 27.7g of sodium carbonate, 200ml of tetrahydrofuran, 50ml of water, and 0.18g of palladium chloride to the reaction bottle, start stirring, heat to 75℃ and react for 12 hours, perform routine post-treatment, column chromatography purification, n-heptane/ethyl acetate = 30:1 (v/v), and obtain 46.2g of colorless viscous liquid (compound BYLC-02-4), LC: 98.3%, yield: 81%.

(5) Synthesis of compound BYLC-02-5:

Under nitrogen protection, add 45g of compound BYLC-02-4, 17.6g of methacrylic acid, 3.0g of DMAP, and 150ml of DCM to the reaction bottle, start stirring, and add a solution consisting of 42.0g of DCC and 50ml of DCM at a temperature of -5℃~5℃. After the addition, naturally return the temperature to room temperature for 12 hours, and perform conventional post-treatment to obtain 41.6g of colorless viscous liquid (compound BYLC-02-5), LC: 98%, yield: 80.5%.

(6) Synthesis of compound BYLC-02:

Under nitrogen protection, add 40.0g of compound BYLC-02-5 and 200ml of THF to the reaction bottle, start stirring, control the temperature at 0℃~5℃, and drop 30.5g of tetrabutylammonium fluoride and 50ml of THF. After dropping, naturally return to room temperature (20℃) and react for 10 hours. Destroy and hydrolyze with 200ml of saturated sodium bicarbonate aqueous solution, perform conventional post-treatment, purify by column chromatography, n-heptane/ethyl acetate = 10:1 (v/v), and recrystallize from n-heptane to obtain 19.1g of white solid (compound BYLC-02), LC: 99.7%, yield: 62.4%.

The obtained white solid BYLC-02 was analyzed by LC-MS, and the m/z of the product was 786.1 (M+).

Elemental analysis: C, 77.83; H, 7.94; O, 14.23.

¹ H-NMR (300MHz, CDCl ₃ ): 0.85-2.15(m,27H), 2.25-2.95(m,6H), 3.16-3.73(m,6H), 3.95-4.78(m,6H), 6.25-6.89(m,4H), 6.96-7.95(m,13H).

Implementation Example 3

The structural formula of the liquid crystal compound is:

Simply replace the raw materials and the reaction conditions are the same as Example 1.

The obtained white solid BYLC-03 was analyzed by LC-MS, and the m/z of the product was 820.1 (M+).

Elemental analysis: C, 77.52; H, 8.84; O, 13.64.

¹ H-NMR (300MHz, CDCl ₃ ): 0.90-2.12(m,40H), 2.27-2.91(m,7H), 3.16-3.75(m,6H), 3.95-4.75(m,6H), 6.26-6.82(m,4H), 6.93-7.98(m,9H).

Example 4

The structural formula of the liquid crystal compound is:

Simply replace the raw materials and the reaction conditions are the same as Example 1.

The obtained white solid BYLC-04 was analyzed by LC-MS, and the m/z of the product was 792.1 (M+).

Elemental analysis: C, 77.24; H, 8.64; O, 14.12.

¹ H-NMR (300MHz, CDCl ₃ ): 0.92-2.15(m,36H), 2.28-2.95(m,7H), 3.13-3.77(m,6H), 3.94-4.78(m,6H), 6.25-6.87(m,4H), 6.95-7.99(m,9H).

Example 5

The structural formula of the liquid crystal compound is:

Simply replace the raw materials and the reaction conditions are the same as Example 1.

The obtained white solid BYLC-05 was analyzed by LC-MS, and the m/z of the product was 738.1 (M+).

Elemental analysis: C, 76.39; H, 8.46; O, 15.16.

¹ H-NMR (300MHz, CDCl ₃ ): 0.95-2.17(m,26H), 2.25-2.94(m,7H), 3.15-3.78(m,6H), 3.95-4.72(m,6H), 6.24-6.89(m,4H), 6.97-7.98(m,9H).

Example 6

The structural formula of the liquid crystal compound is:

Simply replace the raw materials and the reaction conditions are the same as Example 1.

The obtained white solid BYLC-06 was analyzed by LC-MS, and the m/z of the product was 746.1 (M+).

Elemental analysis: C, 72.36; H, 7.56; O, 14.99, F, 5.09.

¹ H-NMR (300MHz, CDCl ₃ ): 0.95-2.17(m,27H), 2.25-2.94(m,5H), 3.15-3.78(m,6H), 3.95-4.72(m,6H), 6.24-6.89(m,4H), 6.97-7.98(m,9H).

Example 7

The structural formula of the liquid crystal compound is:

The obtained white solid BYLC-07 was analyzed by LC-MS, and the m/z of the product was 828.1 (M+).

Elemental analysis: C, 78.23; H, 8.27; O, 13.51.

¹ H-NMR (300MHz, CDCl ₃ ): 0.96-2.13(m,31H), 2.28-2.97(m,8H), 3.13-3.76(m,6H), 3.96-4.78(m,6H), 6.25-6.85(m,4H), 6.95-7.97(m,13H).

Example 8

The structural formula of the liquid crystal compound is:

Simply replace the raw materials and the reaction conditions are the same as Example 1.

The obtained white solid BYLC-08 was analyzed by LC-MS, and the m/z of the product was 800.1 (M+).

Elemental analysis: C, 77.97; H, 8.05; O, 13.98.

¹ H-NMR (300MHz, CDCl ₃ ): 0.95-2.16(m,27H), 2.24-2.95(m,8H), 3.14-3.78(m,6H), 3.95-4.76(m,6H), 6.26-6.88(m,4H), 6.98-7.96(m,13H).

Comparative Example 1

The structural formula of the liquid crystal compound is:

Comparative Example 2

The structural formula of the liquid crystal compound is:

Experimental example

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

Among them, the mixture BHR87800 was purchased from Bayi Spacetime Liquid Crystal Technology Co., Ltd.

The structural formula of RM monomer is:

Add 0.3% of the polymerizable compound BYLC-01 provided in Example 1 and 0.3% of the RM monomer RM-1 to 100% of the liquid crystal mixture BHR87800, and dissolve them uniformly to obtain a mixture PM-1.

Add 0.28% of the polymerizable compound BYLC-02 provided in Example 2 and 0.3% of the RM monomer RM-1 to 100% of the liquid crystal mixture BHR87800, and dissolve evenly to obtain a mixture PM-2.

Add 0.33% of the polymerizable compound BYLC-03 provided in Example 3 and 0.3% of the RM monomer RM-1 to 100% of the liquid crystal mixture BHR87800, and dissolve evenly to obtain a mixture PM-3.

Add 0.35% of the polymerizable compound BYLC-04 provided in Example 4 and 0.3% of the RM monomer RM-1 to 100% of the liquid crystal mixture BHR87800, and dissolve evenly to obtain a mixture PM-4.

Add 0.3% of the polymerizable compound represented by CP-1 and 0.3% of the RM monomer RM-1 to 100% of the liquid crystal mixture BHR87800, dissolve evenly, and obtain the mixture PM-5.

Add 0.3% of the polymerizable compound represented by CP-2 and 0.3% of the RM monomer RM-1 to 100% of the liquid crystal mixture BHR87800, dissolve evenly, and obtain the mixture PM-6.

The physical properties of PM-1, PM-2, PM-3, PM-4, PM-5, and PM-6 are almost the same as those of the above-mentioned mixture BHR87800. PM-1, PM-2, PM-3, PM-4, PM-5, and PM-6 were injected into a "non-aligned" test cell (cell thickness d~3.2μm, ITO coating on both sides (structured ITO in the case of multi-domain switching), no alignment layer and no passivation layer) using vacuum infusion.

Then, through a filter that filters out ultraviolet rays below 310nm, ultraviolet rays are irradiated to the liquid crystal cell using a fluorescent lamp. At this time, the illuminance measured at a central wavelength of 365nm is adjusted to 100mW/ ^cm2 , and the cumulative light quantity of ultraviolet rays is 30J/ ^cm2 (irradiation condition 1). Next, a fluorescent UV lamp is used, and the illuminance measured at a central wavelength of 313nm is adjusted to 3mW/ ^cm2 , and the cumulative light quantity of ultraviolet rays is 10J/ ^cm2 (ultraviolet irradiation condition 2). UV1 is the process of ultraviolet irradiation under irradiation condition 1, and UV2 is the process of ultraviolet irradiation under irradiation condition 1 and irradiation condition 2. A vertically aligned liquid crystal display element was obtained after polymerization. The pre-tilt angle was measured using an AXO-Step pre-tilt angle tester. The test cell was then decomposed and the residual polymerizable compound in the liquid crystal composition was measured using high performance liquid chromatography HPLC. The results are summarized in Table 2.

Effect test:

1. Change in pre-tilt angle

A mixture of various polymerizable compounds and liquid crystal compounds is injected into a test box. After the polymerizable compound is polymerized by irradiating ultraviolet rays, the pre-tilt angle of the test box after the UV1 and UV2 irradiation processes is measured respectively. It is preferred that the pre-tilt angle change after the UV1 and UV2 processes is small.

In different temperature ranges, there is no significant difference in the pre-tilt angles of different regions after the UV2 process, which can effectively improve the regional mura problem.

2. Conversion rate of polymerizable compounds

A polymerizable compound is added to the composition, and the polymerizable compound is consumed by polymerization to form a polymer. The conversion rate of this reaction is preferably a large conversion rate.

This is because: from the perspective of image residue, the residual amount of the polymer compound (the amount of the unreacted polymerizable compound) is preferably small.

3. LCD quality test VHR&ION

VHR is the charge retention rate. The higher the VHR, the longer the LCD panel can hold its charge. ION is the ion content in the liquid crystal. The lower the ION, the better the quality of the LCD panel. VHR and ION are LCD panel quality parameters. A high VHR value and a low ION value are preferred.

From the comparative data in Table 2, it can be seen that the polymerizable compound of the present invention has a better alignment effect, faster polymerization rate, more complete polymerization, and lower residue than the polymerizable liquid crystal compounds CP-1 and CP-2, thereby greatly improving the problem of poor display and improving the response time.

Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit them. Although the present invention has been described in detail with reference to the above embodiments, ordinary technicians in this field should understand that they can still modify the technical solutions described in the above embodiments, or replace some of the technical features therein with equivalent ones. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims (8)

A self-aligning polymerizable compound characterized by being selected from one or more of the following structures:

wherein _A1 and _A2 represent 1,4-cyclohexylene, 1,4-cyclohexenylene or 1,4-phenylene; or, at least one hydrogen atom H in the 1,4-cyclohexylene, 1,4-cyclohexenylene or 1,4-phenylene is substituted by L or -ZP; L represents H, -F, -Cl, a _C3 - _C7 cycloalkyl group or a _C1 - _C6 straight or branched alkyl group; or, at least one hydrogen atom in the _C3 - _C7 cycloalkyl group or a _C1 - _C6 straight or branched alkyl group is substituted by F or Cl; P represents an acrylate group, a methacrylate group or a fluoroacrylate group; Z, _Z1 , _Z2 , _Z3 , _Z4 and _Z5 each independently represent a single bond, -O-, _C1 -C or, at least one hydrogen atom in _the C ₁ -C ₆ alkylene or C ₂ -C ₆ alkenyl is substituted by F; or, one -CH ₂ - or at least two non-adjacent -CH _{2 -} in the C _{1 -C 6} alkylene or C ₂ -C ₆ alkenyl is substituted by -O- in a manner that they are not directly connected to each other; R ₂ represents H, C ₁ -C ₆ alkyl or alkoxy, C 2 -C ₆ alkylenyl or alkoxyalkenyl; or, at least one hydrogen atom in the C _{1 -C 6} alkylene or C 2 -C 6 alkenyl is substituted by F; or, one -CH 2 - in the C ₁ -C ₆ alkylene or C ₂ -C ₆ alkenyl is substituted by -O- in a manner that they are not directly connected to each other; R ₂ represents H, C ₁ -C ₆ alkyl or alkoxy, C ₂ -C ₆ alkylenyl or alkoxyalkenyl; - or at least two non-adjacent -CH ₂ - are substituted by -O- in a manner that they are not directly connected to each other; X represents -OH; m and n each independently represent 0, 1 or 2 and are not 0 at the same time. The self-aligned polymerizable compound as described in claim 1 is characterized in that it is selected from one or more of the following compounds:

A liquid crystal composition, characterized in that it contains the self-aligned polymerizable compound described in claim 1 or 2, and the weight percentage of the self-aligned polymerizable compound in the liquid crystal composition is 0.01~10%. The liquid crystal composition as described in claim 3 is characterized in that the weight percentage of the self-aligned polymerizable compound in the liquid crystal composition is 0.01~5%. The liquid crystal composition as described in claim 3 is characterized in that the weight percentage of the self-aligned polymerizable compound in the liquid crystal composition is 0.1~3%. An application of a self-aligned polymerizable compound and a liquid crystal combination in the field of liquid crystal display, such as the self-aligned polymerizable compound described in claim 1 or 2 or the liquid crystal combination described in any one of claims 3-5. The application as described in claim 6 is characterized in that the application in the field of liquid crystal display is an application in a liquid crystal display device. The application as described in claim 7 is characterized in that the liquid crystal display device includes a TN, ADS, VA, PSVA, FFS or IPS liquid crystal display.