CN110498743A - A kind of biphenyl polymerizable compound and its application - Google Patents

Abstract

The invention belongs to liquid crystal material technical fields, and in particular to a kind of biphenyl class can poly- property compound and its application.The compound has structure shown in general formula I.The compound has good application performance, and the compound or composition containing the compound has been used to have the performances such as wider nematic temperature range, suitable or higher birefringence anisotropy △ n, higher resistivity, good anti-ultraviolet property, high charge retention rate and low-steam pressure.And the compound is cheap, performance is stablized, and can be widely used for field of liquid crystal display, has important application value.

Description

A kind of biphenyl polymerizable compound and its application

technical field

The invention belongs to the technical field of liquid crystal materials, and particularly relates to a 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 navigators, televisions, and the like. Representative liquid crystal display modes are 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 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 the display elements of the active matrix addressing mode such as VA mode has its own shortcomings. For example, the level of afterimage is significantly 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 appeared, such as MVA technology, PVA technology, 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. It reduces the cost of CF, improves the aperture ratio, and can obtain higher brightness, thereby obtaining higher contrast. In addition, because 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 afterimage level will not be affected.

The prior art has found that the use of LC mixtures and RMs in PSA displays still has some disadvantages. First, not every soluble RM desired so far is suitable for use in PSA displays: at the same time, if it is desired to polymerize by means of UV light without adding a photoinitiator (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 the "LC host mixture") with the selected polymerizable components should have the lowest rotational viscosity and the best optoelectronic properties , used to increase the "Voltage Holding Ratio" (VHR) to achieve the effect. In terms of PSVA, high VHR after irradiation with (UV) light is very important, otherwise it will cause problems such as afterimages in the final display. So far, because the polymerizable unit is too short for UV-sensitive wavelength, or there is no or insufficient tilt angle after irradiation, or the homogeneity of the polymerizable component after irradiation is poor. Not all combinations of LC mixture and polymerizable components are suitable for PSVA displays.

Therefore, the synthesis of polymerizable compounds with novel structures with excellent properties and the study of structure-property relationship have become an important work in the field of liquid crystals.

SUMMARY OF THE INVENTION

The first object of the present invention is to provide a polymerizable compound for polymer stabilization technology. The liquid crystal composition containing the compound has better alignment effect, more complete polymerization and lower residue. In addition, 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 of the present invention has the following structure:

Wherein, the L ₁ and L ₂ independently represent H, F, Cl or an alkyl or alkoxy group of C ₁ -C ₁₂ , and L ₁ and L ₂ are not H at the same time;

Said X ₁ , X ₂ and X ₃ independently represent H or CH ₃ .

The compound of the present invention, in the general formula I, about L ₁ , L ₂ :

Preferably, the L ₁ and L ₂ independently represent H, F or a C ₁ -C ₆ alkyl or alkoxy group, and L ₁ and L ₂ are not H at the same time;

More preferably, the L ₁ and L ₂ independently represent H, F, CH ₃ , OCH ₃ , C ₂ H ₅ or OC ₂ H ₅ , and L ₁ and L ₂ are not H at the same time.

In the compound of the present invention, preferably, in the general formula I, the L ₁ and L ₂ independently represent H, F or a C ₁ -C ₆ alkyl or alkoxy group, and L ₁ and L ₂ are not at the same time is H;

The X ₁ , X ₂ , and X ₃ independently represent H or CH ₃ ;

Further preferably, in the general formula I, the L ₁ and L ₂ independently represent H, F, CH ₃ , OCH ₃ , C ₂ H ₅ or OC ₂ H ₅ , and L ₁ and L ₂ are not simultaneously H;

Said X ₁ , X ₂ and X ₃ independently represent H or CH ₃ .

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

When X ₁ represents H, X ₂ and/or X ₃ represent H;

When X ₂ represents H, X ₁ and/or X ₃ represent H;

When X ₃ represents H, X ₁ and/or X ₂ represent H;

When X ₁ represents CH ₃ , X ₂ and/or X ₃ represent CH ₃ ;

When X ₂ represents CH ₃ , X ₁ and/or X ₃ represent CH ₃ ;

When X ₃ represents CH ₃ , X ₁ and/or X ₂ represent CH ₃ ;

When L ₁ is a C ₁ -C ₁₂ alkyl or alkoxy group, L ₂ represents H;

When L ₂ is a C ₁ -C ₁₂ alkyl or alkoxy group, L ₁ represents H.

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

The second object of the present invention is to protect the composition containing the liquid crystal compound. Preferably, the mass percentage of the compound in the composition is 0.01-10%, more preferably 0.01-5%, further 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 the application of the liquid crystal display device. Said liquid crystal display device includes but is not limited to TN, ADS, VA, PSVA, FFS or IPS liquid crystal display. Using the liquid crystal compound or the composition containing the liquid crystal compound has a wide temperature range of nematic phase, suitable or high birefringence anisotropy Δn, high resistivity, good UV resistance performance, high charge retention, and low vapor pressure.

Detailed ways

The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention. All other equivalent changes or modifications accomplished without departing 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 can be synthesized by known methods or obtained from open commercial sources unless otherwise specified. These synthetic techniques are conventional, and the obtained liquid crystal compounds are tested to meet the electronic compounds. standard.

According to conventional detection methods in the art, 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 the preparation of compound BYLC-01 is shown below:

Specific steps are as follows:

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

Add 40g to the reaction flask (0.153mol), 40g 14.0g of anhydrous potassium carbonate, 200ml of toluene, 150ml of ethanol, 150ml of water, 0.3g of tetrakistriphenylphosphine palladium, heated under reflux for 8h, carried out conventional post-treatment to obtain an off-white solid (compound BYLC-01-1, 0.134mol ) 53.3g, HPLC: 99.7%, yield 87.5%;

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

53.3g of compound BYLC-01-1, 90ml of toluene, 60ml of ethanol, 1.5g of palladium-carbon were added to the reaction flask, hydrogen was replaced three times, and the temperature was controlled at 30°C to 35°C by hydrogenation and debenzylation for 6h, and conventional post-treatment was performed to obtain a white solid ( Compound BYLC-01-2, 0.127 mol): 39.2 g, LC: 99.6%, yield: 95.1%;

(3) Synthesis of compound BYLC-01:

Under nitrogen protection, 39.2g of compound BYLC-01-2, 28.5g of triethylamine and 200mL of dichloromethane were added to the reaction flask, cooled to -10°C, and 29.5g of methpropylene was added dropwise under temperature control -10°C to 0°C Acyl chloride, warmed to room temperature and reacted for 6h, poured the reaction solution into water, neutralized with uranium bicarbonate aqueous solution, carried out routine post-treatment, purified by chromatography, eluted with n-hexane, and recrystallized from ethanol to obtain a white solid (compound BYLC-01, 0.098mol ) 50.3 g, LC: 99.8%, yield: 77.4%.

The resulting white solid BYLC-01 was analyzed by GC-MS and the product had m/z of 512.1 (M+).

1H-NMR (300 MHz, CDCl3): 1.55-2.15 (m, 9H), 4.23-5.65 (m, 11H), 5.95-6.65 (m, 5H), 7.05-7.95 (m, 4H).

Example 2

The structural formula of the liquid crystal compound is:

by replace Other conditions are the same as in Example 1.

The resulting white solid BYLC-02 was analyzed by GC-MS and the product had m/z of 530.1 (M+).

1H-NMR (300 MHz, CDCl3): 1.55-2.15 (m, 9H), 4.23-5.65 (m, 10H), 5.95-6.65 (m, 5H), 7.05-7.95 (m, 4H).

Example 3

The structural formula of the liquid crystal compound is:

by replace Other reaction conditions are the same as in Example 1.

The resulting white solid BYLC-03 was analyzed by GC-MS and the product had m/z of 508.1 (M+).

1H-NMR (300 MHz, CDCl3): 1.55-2.15 (m, 11H), 4.23-5.65 (m, 12H), 5.95-6.65 (m, 5H), 7.05-7.95 (m, 4H).

Example 4

The structural formula of the liquid crystal compound is:

by replace Other reaction conditions are the same as in Example 1.

The resulting white solid BYLC-04 was analyzed by GC-MS and the product had m/z of 508.1 (M+).

1H-NMR (300 MHz, CDCl3): 1.55-2.15 (m, 10H), 4.23-5.65 (m, 13H), 5.95-6.65 (m, 5H), 7.05-7.95 (m, 4H).

Example 5

The structural formula of the liquid crystal compound is:

by replace Other reaction conditions are the same as in Example 1.

The resulting white solid BYLC-05 was analyzed by GC-MS and the product had m/z of 524.1 (M+).

1H-NMR (300 MHz, CDCl3): 1.55-2.15 (m, 11H), 4.23-5.65 (m, 12H), 5.95-6.65 (m, 5H), 7.05-7.95 (m, 4H).

Example 6

The structural formula of the liquid crystal compound is:

The synthetic route for the preparation of compound BYLC-06 is shown below:

Specific steps are as follows:

Synthesis of compound BYLC-06:

Under nitrogen protection, add 30.0 g of compound BYLC-01-2 (0.097 mol), 37.6 g of triethylamine and 250 mL of dichloromethane to the reaction flask, cool down to -10 °C, control the temperature from -10 °C to 0 °C, and add 32.0 g acryloyl chloride, warmed to room temperature and reacted for 6 h, poured the reaction solution into water, neutralized with uranium bicarbonate aqueous solution, carried out routine post-treatment, purified by chromatography, eluted with n-hexane, and recrystallized from ethanol to obtain a white solid (compound BYLC-06, 0.083 mol) 38.9 g, LC: 99.7%, yield: 85.4%.

The resulting white solid, BYLC-06, was analyzed by GC-MS, and the m/z of the product was 470.1 (M+).

1H-NMR (300MHz, CDCl3):

4.23-5.65 (m, 11H), 5.95-6.65 (m, 5H), 7.05-7.95 (m, 4H).

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 7

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. 0.3% of the polymerizable compound BYLC-01 provided in Example 1 was added to 99.7% of the liquid crystal composition BHR87800, and the mixture was uniformly dissolved to obtain a mixture PM-1.

0.3% of the polymerizable compound BYLC-02 provided in Example 2 was added to 99.7% of the liquid crystal composition BHR87800, and the mixture was uniformly dissolved to obtain a mixture PM-2.

0.3% of the polymerizable compound BYLC-03 provided in Example 3 was added to 99.7% of the liquid crystal composition BHR87800, and the mixture was uniformly dissolved to obtain a mixture PM-3.

0.3% of the polymerizable compound BYLC-05 provided in Example 5 was added to 99.7% of the liquid crystal composition BHR87800, and the mixture was uniformly dissolved to obtain a mixture PM-4.

The physical properties of PM-1, PM-2, PM-3, and PM-4 are almost the same as those of the above-mentioned mixture BHR87800. PM-1, PM-2, PM-3, 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, irradiate the test box with ultraviolet rays with a high-pressure mercury ultraviolet lamp, adjust the irradiation intensity to the surface of the box to be 30mW/cm2, and irradiate for 600s to obtain a vertical alignment liquid crystal display after polymerization. Components, use LCT-5016E liquid crystal optoelectronic parameter tester to measure the pretilt angle, then decompose the test box, use high performance liquid chromatography HPLC to measure the residual polymerizable compounds in the liquid crystal composition, the results are summarized in Table 2 and Table 3.

Comparative ratio

0.3% of the CP polymerizable compound was added to 99.7% of the liquid crystal composition BHR87800, and the mixture was uniformly dissolved to obtain a mixture PM-5. The physical properties of PM-5 are almost indistinguishable from those of the above-mentioned mixture BHR87800. PM-5 was injected into the test cell with a gap of 4.0 μm and vertical alignment using the vacuum infusion method. While applying a square wave with a frequency of 60HZ and a driving voltage of 16V, irradiate the test box with ultraviolet rays with a high-pressure mercury ultraviolet lamp, adjust the irradiation intensity to the surface of the box to be 30mW/cm2, and irradiate for 600s to obtain a vertical alignment liquid crystal display after polymerization. Components, use LCT-5016E liquid crystal optoelectronic parameter tester to measure the pretilt angle, then decompose the test box, use high performance liquid chromatography HPLC to measure the residual polymerizable compounds in the liquid crystal composition, the results are summarized in Table 2 and Table 3.

Table 2 Summary of pre-tilt angles before and after UV

Table 3 Summary of polymer residue data

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

Although the present invention has been described in detail above with general description, specific embodiments and tests, some modifications or improvements can be made on the basis of the present invention, which is obvious to those skilled in the art . Therefore, these modifications or improvements made without departing from the spirit of the present invention fall within the scope of the claimed protection of the present invention.

Claims (10)

1. a biphenyl polymerizable compound, is characterized in that, has the structure shown in general formula I: Wherein, the L ₁ and L ₂ independently represent H, F, Cl or an alkyl or alkoxy group of C ₁ -C ₁₂ , and L ₁ and L ₂ are not H at the same time; Said X ₁ , X ₂ and X ₃ independently represent H or CH ₃ . 2 . The compound according to claim 1 , wherein the L ₁ and L ₂ independently represent H, F or a C ₁ -C ₆ alkyl or alkoxy group, and L ₁ and L ₂ are not Also H. 3. The compound according to claim 2, wherein said L ₁ , L ₂ independently represent H, F, CH ₃ , OCH ₃ , C ₂ H ₅ or OC ₂ H ₅ , and L ₁ , _L2 is not H at the same time. 4. The compound according to any one of claims 1-3, wherein in general formula I: When X ₁ represents H, X ₂ and/or X ₃ represent H; When X ₂ represents H, X ₁ and/or X ₃ represent H; When X ₃ represents H, X ₁ and/or X ₂ represent H; When X ₁ represents CH ₃ , X ₂ and/or X ₃ represent CH ₃ ; When X ₂ represents CH ₃ , X ₁ and/or X ₃ represent CH ₃ ; When X ₃ represents CH ₃ , X ₁ and/or X ₂ represent CH ₃ ; When L ₁ is a C ₁ -C ₁₂ alkyl or alkoxy group, L ₂ represents H; When L ₂ is a C ₁ -C ₁₂ alkyl or alkoxy group, L ₁ represents H. 5. the compound according to any one of claim 1-4, is characterized in that, is selected from a kind of following compound: 6. A liquid crystal composition, characterized by comprising the compound according to any one of claims 1-5. 7 . The liquid crystal composition according to claim 6 , wherein the mass percentage of the compound in the composition is 0.01-10%, preferably 0.01-5%, and more preferably 0.1-3%. 8 . 8. The application of the compound according to any one of claims 1-5 in the field of liquid crystal display. 9. The application of the liquid crystal composition according to claim 6 or 7 in the field of liquid crystal display. 10. The application according to claim 8 or 9, wherein the application in the liquid crystal display field is an application in a liquid crystal display device; Preferably, the liquid crystal display device includes a TN, ADS, VA, PSVA, FFS or IPS liquid crystal display.