Polymerizable compound and use thereof

Abstract

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

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of liquid crystal materials, and particularly relates to a polymerizable compound and application thereof. BACKGROUND

[0002] In recent years, liquid crystal display devices are widely used in various electronic devices, such as smart phones, tablet computers, car navigation devices, televisions and the like. Representative liquid crystal display modes include twisted nematic (TN) mode, super twisted nematic (STN) mode, in-plane switching (IPS) mode, fringe field switching (FFS) mode and vertical alignment (VA) mode. Among them, the VA mode has attracted more and more attention due to its fast falling time, high contrast, wide viewing angle and high quality image.

[0003] However, the liquid crystal medium used in the display element of the active matrix addressing mode such as the VA mode has some deficiencies itself, such as a significantly lower image retention level than the positive dielectric anisotropy display element, a relatively slow response time, a relatively high driving voltage and the like. In order to solve the above problems, some new VA display technologies have appeared. For example, MVA technology, PVA technology and PSVA technology. Among them, the PSVA technology not only realizes the similar wide viewing angle display mode of MVA / PVA, but also simplifies the CF process, realizes the reduction of CF cost, improves the aperture ratio, can obtain higher brightness, and further obtains higher contrast. In addition, since the whole surface of the liquid crystal has a pre-tilt angle, there is no domino delay phenomenon, and under the same driving voltage, a faster response time can be obtained, and the image retention level will not be affected.

[0004] It has been found that the application of LC mixtures and RMs in PSA displays still has some disadvantages. First, not every desired soluble RM is suitable for PSA displays so far: the selection becomes even smaller if polymerization by means of UV light without the addition of photoinitiators is desired (which can be advantageous for some applications): in addition, the "material system" formed by the LC mixture (in the following also referred to as "LC host mixture") in combination with the selected polymerizable component should have the lowest rotational viscosity and the best electro-optical properties for increasing the "voltage holding ratio" (VHR) to be effective. In the case of PSVA, a high VHR after (UV) light irradiation is very important, otherwise problems such as image retention in the final display can occur. So far, there have been problems such as too short UV sensitivity wavelength of the polymerizable unit, insufficient tilt angle after irradiation or no tilt angle, or poor uniformity of the polymerizable component after irradiation. Not every combination of LC mixture and polymerizable component is suitable for PSVA displays.

[0005] Therefore, the synthesis of new type of polymerizable compound with excellent performance and the structure-performance relationship research become an important work in the field of liquid crystal. SUMMARY

[0006] The first object of the present application is to provide a polymerizable compound for polymer stabilization technology. The liquid crystal composition containing the compound has better alignment effect, more complete polymerization, lower residual, and the compound is low in price, stable in performance, can be widely used in the field of liquid crystal display, and has important application value.

[0007] The liquid crystal compound described in the present application has the following structure:

[0008]

[0009] L1, L2 are the same or different, and independently represent H, -F, -Cl, -CN, -CH3, -C2H5, -OCH3, -OC2H5, -CF3, -OCF3, -OCHF2 or -OC2F5;

[0010] Q represents -CH2-, -CF2-, -C(CH3)-, -CH2CH2-, -CH2O-, -CH2S- or -CHFCHF-.

[0011] Further, L1, L2 are the same or different, and independently represent H, -F, -Cl, -CN, -CH3, -OCH3, -CF3, -OCF3 or -OCHF2;

[0012] Further, L1, L2 are the same or different, and independently represent H, -F or -Cl.

[0013] As a further preferred technical solution of the present application, the compound is selected from one of the following compounds:

[0014]

[0015]

[0016]

[0017]

[0018] The second object of the present application is to protect the liquid crystal composition containing the polymerizable compound. The mass percentage of the polymerizable compound in the liquid crystal composition is 0.01-10%, preferably 0.01-5%, and further preferably 0.1-3%.

[0019] A third object of the present application is to protect the use of the polymerizable compound and the liquid crystal composition containing the polymerizable compound in the field of liquid crystal display, preferably in a liquid crystal display device. The liquid crystal display device includes but is not limited to TN, ADS, VA, PSVA, FFS or IPS liquid crystal display. DETAILED DESCRIPTION

[0020] The following examples are intended to illustrate the present application but not to limit the scope of the present application, and any equivalent changes or modifications made without departing from the spirit of the present application should be included in the scope of the claims.

[0021] In the following examples, each liquid crystal compound, if not otherwise specified, can be synthesized by known methods or obtained from public commercial channels. The synthesis techniques are conventional, and each liquid crystal compound obtained is tested to meet the standard of electronic compounds.

[0022] According to the conventional detection method in the art, each performance parameter of the liquid crystal compound is obtained by linear fitting, wherein the specific meaning of each performance parameter is as follows:

[0023] Δn represents optical anisotropy (25℃); Δε represents dielectric anisotropy (25℃, 1000 Hz); γ1 represents rotational viscosity (mPa.s, 25℃); and Cp represents clearing point.

[0024] Example 1

[0025] The structural formula of the polymerizable compound is as follows:

[0026]

[0027] The synthetic route for preparing the compound BYLC-01 is as follows:

[0028]

[0029] The specific steps are as follows:

[0030] (1) Synthesis of compound BYLC-01-1:

[0031] Into 100 ml of carbon disulfide, 39.2 g (0.2 mol) of 2-methoxyfluorene, 29.37 g (0.22 mol) of aluminum trichloride were added, and the temperature was lowered to 0°C. Then, 35.1 g (0.3 mol) of 1,1-dichloromethyl ether was slowly added dropwise while the temperature was controlled to 0-10°C. After the dropwise addition, the temperature was raised to 50°C, and the reaction was allowed to proceed for 6 hours while the temperature was controlled to 45-55°C. The reaction mixture was cooled to 0-10°C using an ice water bath, and 80 g of water was added dropwise thereto. After stirring for 1 hour, the mixture was separated, and the aqueous phase was extracted with dichloromethane once. The combined organic phase was dried over anhydrous magnesium sulfate, filtered, and concentrated. The resulting crude 7-methoxyfluorene-2-carboxaldehyde was purified by column chromatography to obtain a pure product, BYLC-01-1, 40.7 g (0.18 mol), GC: 99.0%, yield: 90%.

[0032] (2) Synthesis of compound BYLC-01-2

[0033] Into a 1000 ml reaction flask, 116.1 g (0.27 mol) of isopropyl triphenylphosphonium iodide and 300 ml of tetrahydrofuran were added, and the temperature was lowered to 10°C. Then, 30.2 g (0.24 mol) of potassium tert-butoxide was added thereto, and stirred for 1 hour. After that, a solution of 40.7 g (0.18 mol) of 7-methoxyfluorene-2-carboxaldehyde and 200 ml of tetrahydrofuran was added dropwise at the maximum temperature of 10°C. After stirring for 1 hour, the mixture was neutralized with 2M hydrochloric acid, and the mixture was extracted with n-heptane three times. The combined organic phase was dried over anhydrous sodium sulfate, filtered to remove triphenylphosphine oxide, and evaporated to dryness. The resulting white solid (compound BYLC-01-2, 0.144 mol) was recrystallized from 5-fold ethanol to obtain 36 g, GC: 99.7%, yield: 80%.

[0034] (3) Synthesis of compound BYLC-01-3

[0035] Into a 500 ml three-necked flask, 36 g (0.144 mol) of BYLC-01-2 and 27.4 g of 4-methylmorpholine-4-oxide were added, and 700 ml of acetone and 50 ml of distilled water were further added. Then, 18 ml of 4% osmium tetroxide aqueous solution was added dropwise. After stirring for 48 hours at room temperature, 250 ml of water was added, and the mixture was neutralized with 2M hydrochloric acid. The aqueous phase was extracted with ethyl acetate, and the combined organic phase was dried and evaporated to dryness. The resulting product BYLC-01-3 was crystallized from ethyl acetate to obtain 36.8 g (0.13 mol), GC 99.5%, yield 90%.

[0036] (4) Synthesis of compound BYLC-01-4

[0037] In a 1000ml three-necked flask, add 36.8g of BYLC-01-3, 500ml of dichloromethane, cool to 0 degree, drop 42.2g of boron tribromide ethyl ether, stir for 2 hours at 0 degree after dropping, slowly drop 100ml of water, stir for 0.5 hours, separate, wash with water, dry, recrystallize with acetonitrile to obtain 31.6g (0.117mol) of BYLC-01-4, GC 99.5%, yield 90%

[0038] (5) Synthesis of compound BYLC-01

[0039] Under nitrogen protection, add 31.6g (0.117mol) of compound BYLC-01-4, 60g of triethylamine, 10g of 4-dimethylamino pyridine, 500ml of dichloromethane into a 1000ml reaction flask, control temperature at -10℃ to -15℃, drop 27g of methacryloyl chloride, continue to control temperature at -10℃ to -15℃, react for 1h; then react for 6 hours at room temperature. Pour the reaction liquid into water, neutralize to neutral with sodium bicarbonate. Perform routine post-treatment, recrystallize with petroleum ether to obtain white solid (compound BYLC-01, 0.1mol) 40.9g, GC: 99.9%, yield: 86%.

[0040] Use GC-MS to analyze the obtained white solid BYLC-01, the m / z of the product is 406.1 (M+).

[0041] 1H-NMR (300MHz, CDCl3): 1.24-2.01 (s, 12H), 3.65-5.31 (s, 4H), 6.18-6.43 (m, 4H), 7.25-8.25 (m, 6H).

[0042] Example 2

[0043] The structural formula of the polymerizable compound is:

[0044]

[0045] Refer to the method of Example 1 to synthesize BYLC-02.

[0046] Use GC-MS to analyze the obtained white solid BYLC-02, the m / z of the product is 442.1 (M+).

[0047] 1H-NMR (300MHz, CDCl3): 1.24-2.01 (s, 12H), 3.65-5.31 (s, 4H), 6.18-6.43 (m, 4H), 7.25-8.25 (m, 6H).

[0048] Example 3

[0049] The structure of the polymerizable compound is:

[0050]

[0051] BYLC-03 was synthesized according to the method of Example 1.

[0052] The white solid BYLC-03 was analyzed by GC-MS, and the m / z of the product was 420.2 (M+).

[0053] 1H-NMR (300 MHz, CDC13): 1.24-2.01 (s, 12H), 2.99-5.31 (s, 6H), 6.18-6.43 (m, 4H), 7.25-8.25 (m, 6H).

[0054] Example 4

[0055] The structure of the polymerizable compound is:

[0056]

[0057] BYLC-04 was synthesized according to the method of Example 1.

[0058] The white solid BYLC-04 was analyzed by GC-MS, and the m / z of the product was 456.1 (M+).

[0059] 1H-NMR (300 MHz, CDC13): 1.24-2.01 (s, 12H), 2.99-5.31 (s, 6H), 6.18-6.43 (m, 4H), 7.25-8.25 (m, 4H).

[0060] Example 5

[0061] The structure of the polymerizable compound is:

[0062]

[0063] BYLC-05 was synthesized according to the method of Example 1.

[0064] The white solid BYLC-05 was analyzed by GC-MS, and the m / z of the product was 422.1 (M+).

[0065] 1H-NMR (300 MHz, CDC13): 1.24-2.01 (s, 12H), 2.99-5.31 (s, 6H), 6.18-6.43 (m, 4H), 7.25-8.25 (m, 6H).

[0066] Example 6

[0067] The structure of the polymerizable compound is:

[0068]

[0069] BYLC-06 was synthesized according to the method of Example 1.

[0070] The white solid BYLC-05 was analyzed by GC-MS, and the m / z of the product was 438.1 (M+).

[0071] 1H-NMR (300 MHz, CDC13): 1.24-2.01 (s, 12H), 3.65-5.31 (s, 4H), 6.18-6.43 (m, 4H), 7.25-8.25 (m, 6H).

[0072] Example 7

[0073] The structure of the polymerizable compound is:

[0074]

[0075] BYLC-07 was synthesized according to the method of Example 1.

[0076] The white solid BYLC-07 was analyzed by GC-MS, and the m / z of the product was 442.1 (M+).

[0077] 1H-NMR (300 MHz, CDC13): 1.24-2.01 (s, 12H), 3.65-5.31 (s, 2H), 6.18-6.43 (m, 4H), 7.19-7.84 (m, 6H).

[0078] Example 8

[0079] The structure of the polymerizable compound is:

[0080]

[0081] BYLC-08 was synthesized according to the method of Example 1.

[0082] The white solid BYLC-08 was analyzed by GC-MS, and the m / z of the product was 478.1 (M+).

[0083] 1H-NMR (300 MHz, CDC13): 1.24-2.01 (s, 12H), 3.65-5.31 (s, 2H), 6.18-6.43 (m, 4H), 7.19-7.84 (m, 4H).

[0084] Example 9

[0085] The structure of the polymerizable compound is:

[0086]

[0087] BYLC-09 was synthesized according to the method of Example 1.

[0088] The white solid BYLC-09 was analyzed by GC-MS, and the m / z of the product was 434.5 (M+).

[0089] 1H-NMR (300 MHz, CDC13): 1.24-2.01 (s, 18H), 3.65-5.31 (s, 2H), 6.18-6.43 (m, 4H), 7.25-8.25 (m, 6H).

[0090] Example 10

[0091] The structure of the polymerizable compound is:

[0092]

[0093] BYLC-10 was synthesized according to the method of Example 1.

[0094] The white solid BYLC-10 was analyzed by GC-MS, and the m / z of the product was 470.1 (M+).

[0095] 1H-NMR (300 MHz, CDC13): 1.24-2.01 (s, 18H), 3.65-5.31 (s, 2H), 6.18-6.43 (m, 4H), 7.25-8.25 (m, 4H).

[0096] Example 11

[0097] The structure of the polymerizable compound is:

[0098]

[0099] BYLC-11 was synthesized according to the method of Example 1.

[0100] The white solid BYLC-11 was analyzed by GC-MS, and the m / z of the product was 456.1 (M+).

[0101] 1H-NMR (300 MHz, CDC13): 1.24-2.01 (s, 18H), 3.65-5.31 (s, 2H), 6.18-6.43 (m, 4H), 7.25-8.25 (m, 6H).

[0102] Example 12

[0103] The structure of the polymerizable compound is:

[0104]

[0105] BYLC-12 was synthesized according to the method of Example 1.

[0106] The white solid BYLC-12 was analyzed by GC-MS, and the m / z of the product was 492.1 (M+)

[0107] 1H-NMR (300 MHz, CDC13): 1.24-2.01 (s, 12H), 3.65-5.31 (s, 2H) 5.26 (m, 2H), 6.18-6.43 (m, 4H), 7.25-8.25 (m, 4H).

[0108] Test Example 1

[0109] The properties of the mixed crystal BHR87800 are listed in Table 1:

[0110] Table 1 Summary of the properties of the mixed crystal BHR87800

[0111]

[0112] The mixture BHR87800 was purchased from the Eight Billion Space Liquid Crystal Technology Co., Ltd. 0.3% of the polymerizable compounds BYLC-01 to BYLC-12 provided in Examples 1 to 12 were added to 99.7% of the liquid crystal composition BHR87800, respectively, and uniformly dissolved to obtain mixtures PM-1 to PM-12. The properties of PM-1 to PM-12 were almost the same as those of the mixture BHR87800.

[0113] PM-1 to PM-12 were injected into a test cell with a gap of 4.0 μm and vertical alignment using a vacuum infusion method. While applying a square wave with a frequency of 60 Hz and a driving voltage of 24 V, the test cell was irradiated with ultraviolet light using a high-pressure mercury ultraviolet lamp, and the irradiation intensity on the surface of the cell was adjusted to 100 mW / cm 2 After irradiation for 600 s, a polymerized vertically aligned liquid crystal display element was obtained, the pretilt angle was measured using an LCT-5016E liquid crystal photoelectric parameter tester, and then the test cell was disassembled, and the residual polymerizable compound in the liquid crystal composition was measured using high-performance liquid chromatography (HPLC). The results are summarized in Tables 2 and 3.

[0114] Comparative Example

[0115]

[0116] 0.3% of the polymerizable compounds of RM-13, RM-14 were added to 99.7% of the mixture BHR87800, and uniformly dissolved to obtain mixtures PM-13, PM-14. The physical properties of PM-13, PM-14 had little difference from those of the mixture BHR87800 described above. PM-13, PM-14 were injected into a test cell having a gap of 4.0 μm and vertical alignment using a vacuum injection method. While applying a square wave having a frequency of 60 Hz and a driving voltage of 24 V, the test cell was irradiated with ultraviolet rays from a high-pressure mercury ultraviolet lamp, and the irradiation intensity on the surface of the cell was adjusted to 100 mW / cm2. The cell was irradiated for 600 s to obtain a polymerized vertical alignment liquid crystal display element. The pretilt angle was measured using an LCT-5016E liquid crystal photoelectric parameter tester, and then the test cell was disassembled. The residual polymerizable compound in the liquid crystal composition was measured using high-performance liquid chromatography (HPLC). The results are summarized in Tables 2 and 3. 2 The test cell was irradiated for 600 s to obtain a polymerized vertical alignment liquid crystal display element. The pretilt angle was measured using an LCT-5016E liquid crystal photoelectric parameter tester, and then the test cell was disassembled. The residual polymerizable compound in the liquid crystal composition was measured using high-performance liquid chromatography (HPLC). The results are summarized in Tables 2 and 3.

[0117] Table 2 Summary of UV pre-tilt angle

[0118]

[0119] Table 3 Summary of polymer residue data

[0120]

[0121] From the comparative data in Tables 2 and 3, it can be seen that the alignment effect of the polymerizable compound of the present application is better, the polymerization rate is faster, the polymerization is more complete, and the residual is lower, compared to the polymerizable liquid crystal compounds RM-13, RM-14, thereby greatly improving the display problems.

[0122] Although the present application has been described in detail with general description, specific embodiments and experiments above, it is obvious to those skilled in the art that some modifications or improvements can be made on the basis of the present application. Therefore, these modifications or improvements made on the basis of not deviating from the spirit of the present application, are within the scope of the present application claimed.

Claims

1. A polymerizable compound, characterized by, having the general structure of Formula I: Formula I; wherein L1, L2 are the same or different and each independently represents H, -F or -Cl; Q represents -CH2-, -CF2-, -C(CH3)2-, -CH2CH2-, -CH2O-, -CH2S- or -CHFCHF-.

2. The polymerizable compound according to claim 1, characterized by selected from one of the following compounds: 。 3. A liquid crystal composition, characterized by comprising comprising the polymerizable compound according to claim 1 or 2.

4. The liquid crystal composition according to claim 3, characterized by The mass percentage of the polymerizable compound in the liquid crystal composition is 0.01-10%.

5. The liquid crystal composition according to claim 4, characterized by The mass percentage of the polymerizable compound in the liquid crystal composition is 0.01-5%.

6. The liquid crystal composition according to claim 5, characterized by The mass percentage of the polymerizable compound in the liquid crystal composition is 0.1-3%.

7. Use of the polymerizable compound according to claim 1 or 2 and / or the liquid crystal composition according to any one of claims 3-6 in the field of liquid crystal display.

8. Use according to claim 7, characterized in that, for use in a liquid crystal display device.

9. Use according to claim 8, characterized in that, The liquid crystal display device comprises a TN, ADS, VA, PSVA, FFS or IPS liquid crystal display. The liquid crystal display device comprises a TN, ADS, VA, PSVA, FFS or IPS liquid crystal display.

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