POLYMERIZABLE COMPOUND AND USE THEREOF

Abstract

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

##STR00001##

Claims

1. A polymerizable compound, having a structure as shown in general formula I: ##STR00021## wherein L.sub.1 and L.sub.2 are the same or different and represent, independently of each other, H, F, Cl, CN, CH.sub.3, C.sub.2H.sub.5, OCH.sub.3, OC.sub.2H.sub.5, CF.sub.3, OCF.sub.3, OCHF.sub.2, or OC.sub.2F.sub.5; and Q represents CH.sub.2, CF.sub.2, C(CH.sub.3).sub.2, CH.sub.2CH.sub.2, CH.sub.2O, CH.sub.2S, or CHFCHF.

2. The polymerizable compound according to claim 1, wherein L.sub.1 and L.sub.2 are the same or different and represent, independently of each other, H, F, Cl, CN, CH.sub.3, OCH.sub.3, CF.sub.3, OCF.sub.3, or OCHF.sub.2.

3. The polymerizable compound according to claim 2, wherein L.sub.1 and L.sub.2 are the same or different and represent, independently of each other, H, F, or Cl.

4. The polymerizable compound according to claim 1, wherein the polymerizable compound is selected from one of the following compounds: ##STR00022## ##STR00023## ##STR00024## ##STR00025##

5. A liquid crystal composition, comprising the polymerizable compound according to claim 1.

6. The liquid crystal composition according to claim 5, wherein the mass percentage of the polymerizable compound in the liquid crystal composition is 0.01-10%.

7. The liquid crystal composition according to claim 6, wherein the mass percentage of the polymerizable compound in the liquid crystal composition is 0.01-5%.

8. The liquid crystal composition according to claim 7, wherein the mass percentage of the polymerizable compound in the liquid crystal composition is 0.1-3%.

9. The use of the polymerizable compound according to claim 1 in the field of liquid crystal display, preferably in a liquid crystal display device.

10. The use according to claim 9, wherein the liquid crystal display device comprises a TN, ADS, VA, PSVA, FFS, or IPS liquid crystal display.

11. The liquid crystal composition according to claim 5 in the field of liquid crystal display, preferably in a liquid crystal display device.

Description

DETAILED DESCRIPTION OF EMBODIMENTS

[0015] The following examples are intended to illustrate the present disclosure, but not to limit the scope of the present disclosure, and other equivalent alternations or modifications made without departing from the spirit disclosed in the present disclosure shall fall within the scope of the claims.

[0016] Unless otherwise specified, the liquid crystal compounds used in the following examples can be synthesized by well-known methods or obtained from public commercial sources. These synthesis techniques are conventional, and the obtained liquid crystal compounds meet the standards of electronic compounds after test.

[0017] According to the conventional detection methods in the art, the performance parameters of the liquid crystal compounds are obtained by linear fitting, wherein the specific meanings of the performance parameters are as follows:

[0018] n represents the optical anisotropy (25 C.); represents the dielectric anisotropy (25 C., 1000 Hz); 1 represents the rotational viscosity (mPa.Math.s, 25 C.); and Cp represents the clearing point.

Example 1

[0019] The polymerizable compound had a structural formula of:

##STR00007##

[0020] The synthetic route to prepare compound BYLC-01 was shown below:

##STR00008##

[0021] The specific steps were as follows:

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

[0022] 39.2 g (0.2 mol) of 2-methoxyfluorene and 29.37 g (0.22 mol) of aluminum trichloride were added to 100 ml of carbon disulfide, and cooled to 0 C.; 35.1 g (0.3 mol) of 1,1-dichloromethyl ether was slowly added dropwise, during which the temperature was controlled at 0-10 C.; and after the dropwise addition was completed, the system was heated to 50 C. and allowed to react for 6 hours with the temperature being controlled at 45-55 C. The reaction solution was cooled to 0-10 C. in an ice water bath, and 80 g of water was added dropwise thereto and stirred for 1 hour, followed by liquid separation; and the aqueous phase was extracted once with dichloromethane, and the organic phases were combined, dried over anhydrous magnesium sulfate, filtered and concentrated to obtain crude 7-methoxyfluorene-2-carboxaldehyde, followed by column chromatography to obtain 40.7 g of the pure product (BYLC-01-1, 0.18 mol), GC: 99.0%, yield: 90%.

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

[0023] Under the protection of nitrogen, 116.1 g (0.27 mol) of isopropyltriphenylphosphonium iodide and 300 ml of tetrahydrofuran were added to a 1000 ml reaction flask; the system was cooled to 10 C., and 30.2 g (0.24 mol) of potassium tert-butoxide was added and stirred for 1 hour, and a solution of 40.7 g (0.18 ml) of 7-methoxyfluorene-2-carboxaldehyde and 200 ml of tetrahydrofuran was then added with the temperature controlled at a maximum of 10 C.; after stirring for 1 hour, the system was neutralized with 2 M hydrochloric acid, and the mixture was extracted three times with n-heptane; the organic phases were combined, dried over anhydrous sodium sulfate, and filtered to remove triphenylphosphine oxide; and the solvent was evaporated to dryness, and the system was recrystallized with 5-fold volume of ethanol to obtain 36 g of a white solid (compound BYLC-01-2, 0.144 mol), GC: 99.7%, yield: 80%.

(3) Synthesis of Compound BYLC-01-3

[0024] 36 g (0.144 mol) of BYLC-01-2 and 27.4 g of 4-methylmorpholine-4-oxide were added to a 500 ml three-necked flask at room temperature, followed by 700 ml of acetone and 50 ml of distilled water; 18 ml of a 4% aqueous osmium tetroxide solution was added dropwise and stirred at room temperature for 48 hours; then 250 ml of water was added, and the mixture was neutralized with 2 M hydrochloric acid, followed by liquid separation; the aqueous phase was extracted with ethyl acetate, and the organic phases were combined and dried; and the solvent was evaporated to dryness, followed by crystallization with ethyl acetate to obtain the product BYLC-01-3, 36.8 g (0.13 mol), GC: 99.5%, yield: 90%.

(4) Synthesis of Compound BYLC-01-4

[0025] 36.8 g of BYLC-01-3 and 500 ml of dichloromethane were added to a 1000 ml three-necked flask, the system was cooled to 0 C., 42.2 g of boron tribromide diethyl etherate was added dropwise, and after the addition was completed, the mixture was stirred at 0 C. for 2 hours; and 100 ml of water was slowly added dropwise, and the mixture was stirred for 0.5 hours, followed by liquid separation, washing with water, drying, and recrystallization with acetonitrile to obtain BYLC-01-4, 31.6 g (0.117 mol), GC: 99.5%, yield: 90%.

(5) Synthesis of Compound BYLC-01

[0026] Under the protection of nitrogen, 31.6 g (0.117 mol) of compound BYLC-01-4, 60 g of triethylamine, 10 g of 4-dimethylaminopyridine, and 500 ml of dichloromethane were added to a 1000 ml reaction flask; and with the temperature being controlled at 10 C. to 15 C., 27 g of methacryloyl chloride was added dropwise, and the system was allowed to react for 1 h with the temperature maintained at 10 C. to 15 C., and then react at room temperature for 6 hours. The reaction solution was poured into water and neutralized with sodium bicarbonate until neutral. Following conventional post-treatments, the resulting product was recrystallized with petroleum ether to obtain 40.9 g of a white solid (compound BYLC-01, 0.1 mol), GC: 99.9%, yield: 86%.

[0027] The resulting white solid BYLC-01 was analyzed by means of GC-MS, and the m/z of the product was 406.1 (M+).

[0028] 1H-NMR (300 MHz, CDCl.sub.3): 1.24-2.01 (s, 12H), 3.65-5.31 (s, 4H), 6.18-6.43 (m, 4H), 7.25-8.25 (m, 6H).

Example 2

[0029] The polymerizable compound had a structural formula of:

##STR00009##

[0030] Following the method in Example 1, BYLC-02 was synthesized.

[0031] The resulting white solid BYLC-02 was analyzed by means of GC-MS, and the m/z of the product was 442.1 (M+).

[0032] 1H-NMR (300 MHz, CDCl.sub.3): 1.24-2.01 (s, 12H), 3.65-5.31 (s, 4H), 6.18-6.43 (m, 4H), 7.25-8.25 (m, 4H).

Example 3

[0033] The polymerizable compound had a structural formula of:

##STR00010##

[0034] Following the method in Example 1, BYLC-03 was synthesized.

[0035] The resulting white solid BYLC-03 was analyzed by means of GC-MS, and the m/z of the product was 420.2 (M+).

[0036] 1H-NMR (300 MHz, CDCl.sub.3): 1.24-2.01 (s, 12H), 2.99-5.31 (s, 6H), 6.18-6.43 (m, 4H), 7.25-8.25 (m, 6H).

Example 4

[0037] The polymerizable compound had a structural formula of:

##STR00011##

[0038] Following the method in Example 1, BYLC-04 was synthesized.

[0039] The resulting white solid BYLC-04 was analyzed by means of GC-MS, and the m/z of the product was 456.1 (M+).

[0040] 1H-NMR (300 MHz, CDCl.sub.3): 1.24-2.01 (s, 12H), 2.99-5.31 (s, 6H), 6.18-6.43 (m, 4H), 7.25-8.25 (m, 4H).

Example 5

[0041] The polymerizable compound had a structural formula of:

##STR00012##

[0042] Following the method in Example 1, BYLC-05 was synthesized.

[0043] The resulting white solid BYLC-05 was analyzed by means of GC-MS, and the m/z of the product was 422.1 (M+).

[0044] 1H-NMR (300 MHz, CDCl.sub.3): 1.24-2.01 (s, 12H), 3.65-5.31 (s, 4H), 6.18-6.43 (m, 4H), 7.25-8.25 (m, 6H).

Example 6

[0045] The polymerizable compound had a structural formula of:

##STR00013##

[0046] Following the method in Example 1, BYLC-06 was synthesized.

[0047] The resulting white solid BYLC-05 was analyzed by means of GC-MS, and the m/z of the product was 438.1 (M+).

[0048] 1H-NMR (300 MHz, CDCl.sub.3): 1.24-2.01 (s, 12H), 3.65-5.31 (s, 4H), 6.18-6.43 (m, 4H), 7.25-8.25 (m, 6H).

Example 7

[0049] The polymerizable compound had a structural formula of:

##STR00014##

[0050] Following the method in Example 1, BYLC-07 was synthesized.

[0051] The resulting white solid BYLC-07 was analyzed by means of GC-MS, and the m/z of the product was 442.1 (M+).

[0052] 1H-NMR (300 MHz, CDCl.sub.3): 1.24-2.01 (s, 12H), 3.65-5.31 (s, 2H), 6.18-6.43 (m, 4H), 7.19-7.84 (m, 6H).

Example 8

[0053] The polymerizable compound had a structural formula of:

##STR00015##

[0054] Following the method in Example 1, BYLC-08 was synthesized.

[0055] The resulting white solid BYLC-08 was analyzed by means of GC-MS, and the m/z of the product was 478.1 (M+).

[0056] 1H-NMR (300 MHz, CDCl.sub.3): 1.24-2.01 (s, 12H), 3.65-5.31 (s, 2H), 6.18-6.43 (m, 4H), 7.19-7.84 (m, 4H).

Example 9

[0057] The polymerizable compound had a structural formula of:

##STR00016##

[0058] Following the method in Example 1, BYLC-09 was synthesized.

[0059] The resulting white solid BYLC-09 was analyzed by means of GC-MS, and the m/z of the product was 434.5 (M+).

[0060] 1H-NMR (300 MHz, CDCl.sub.3): 1.24-2.01 (s, 18H), 3.65-5.31 (s, 2H), 6.18-6.43 (m, 4H), 7.25-8.25 (m, 6H).

Example 10

[0061] The polymerizable compound had a structural formula of:

##STR00017##

[0062] Following the method in Example 1, BYLC-10 was synthesized.

[0063] The resulting white solid BYLC-10 was analyzed by means of GC-MS, and the m/z of the product was 470.1 (M+).

[0064] 1H-NMR (300 MHz, CDCl.sub.3): 1.24-2.01 (s, 18H), 3.65-5.31 (s, 2H), 6.18-6.43 (m, 4H), 7.25-8.25 (m, 4H).

Example 11

[0065] The polymerizable compound had a structural formula of:

##STR00018##

[0066] Following the method in Example 1, BYLC-11 was synthesized.

[0067] The resulting white solid BYLC-11 was analyzed by means of GC-MS, and the m/z of the product was 456.1 (M+).

[0068] 1H-NMR (300 MHz, CDCl.sub.3): 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, 6H).

Example 12

[0069] The polymerizable compound had a structural formula of:

##STR00019##

[0070] Following the method in Example 1, BYLC-12 was synthesized.

[0071] The resulting white solid BYLC-12 was analyzed by means of GC-MS, and the m/z of the product was 492.1 (M+)

[0072] 1H-NMR (300 MHz, CDCl.sub.3): 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).

Test Example 1

[0073] The properties of mixed crystal BHR87800 are listed in Table 1:

TABLE-US-00001 TABLE 1 Summary of properties of mixed crystal BHR87800 Properties Cp n .sub.| K.sub.3/K.sub.1 Numerical +70 C. 0.095 3.5 3.3 0.97 value

[0074] The mixture BHR87800 was purchased from Bayi Space LCD Technology Co., Ltd. 0.3% of polymerizable compounds BYLC-01 to BYLC-12 provided in Examples 1-12 were added to 99.7% of a liquid crystal composition BHR87800, respectively, and dissolved until uniform to obtain mixtures PM-1 to PM-12. The physical properties of PM-1 to PM-12 were almost the same as those of the mixture BHR87800 described above.

[0075] PM-1 to PM-12 were injected into a test cassette with a gap of 4.0 m and vertical alignment using a vacuum infusion process. One side of the test cassette was applied with square waves having a frequency of 60 HZ and a driving voltage of 24 V, and the other side was irradiated with ultraviolet by using a high pressure mercury UV lamp, where the irradiation intensity on the surface of the cassette was adjusted to 100 mW/cm.sup.2 and the irradiation lasted for 600 s, so as to obtain a polymerized vertically aligned liquid crystal display element. The pretilt angle was measured using an LCT-5016E liquid crystal photoelectric parameter tester. The test cassette was then decomposed, and the residual polymerizable compound in the liquid crystal composition was determined by high performance liquid chromatography (HPLC). The results are summarized in Tables 2 and 3.

Comparative Example

##STR00020##

[0076] 0.3% of polymerizable compounds RM-13 and RM-14 were added to 99.7% of mixture BHR87800, respectively, and dissolved until uniform to obtain mixtures PM-13 and PM-14. The physical properties of PM-13 and PM-14 were almost the same as those of the mixture BHR87800 described above. PM-13 and PM-14 were injected into a test cassette with a gap of 4.0 m and vertical alignment using a vacuum infusion process. One side of the test cassette was applied with square waves having a frequency of 60 HZ and a driving voltage of 24 V, and the other side was irradiated with ultraviolet by using a high pressure mercury UV lamp, where the irradiation intensity on the surface of the cassette was adjusted to 100 mW/cm.sup.2 and the irradiation lasted for 600 s, so as to obtain a polymerized vertically aligned liquid crystal display element. The pretilt angle was measured using an LCT-5016E liquid crystal photoelectric parameter tester. The test cassette was then decomposed, and the residual polymerizable compound in the liquid crystal composition was determined by high performance liquid chromatography (HPLC). The results are summarized in Tables 2 and 3.

TABLE-US-00002 TABLE 2 Summary of pretilt angle before and after UV irradiation Before UV After UV irradiation irradiation () (360 s) () PM-1 89.7 75.1 PM-3 89.8 76.3 PM-5 89.7 74.1 PM-7 89.7 75.3 PM-9 89.7 76.2 PM-11 89.7 77.1 PM-13 89.6 77.5 PM-14 89.6 77.8

TABLE-US-00003 TABLE 3 Summary of polymer residue data UV PM-1 PM-3 PM-5 PM-7 PM-9 PM-11 PM-13 PM-14 polymer- polymer polymer polymer polymer polymer polymer polymer polymer ization residue residue residue residue residue residue residue residue time (s) (%) (%) (%) (%) (%) (%) (%) (%) 0 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 120 0.24 0.25 0.23 0.22 0.24 0.23 0.26 0.25 240 0.18 0.20 0.19 0.19 0.19 0.20 0.23 0.22 360 0.15 0.16 0.16 0.16 0.16 0.16 0.20 0.19 480 0.13 0.14 0.13 0.14 0.13 0.13 0.18 0.17 600 0.11 0.12 0.10 0.11 0.10 0.12 0.16 0.15

[0077] As can be seen from the comparative data in Tables 2 and 3, the polymerizable compound of the present disclosure exhibits a better alignment effect, a higher polymerization rate, more complete polymerization, and lower residues than the polymerizable liquid crystal compounds RM-13 and RM-14, thereby significantly improving the problem of poor display.

[0078] Although the present disclosure has been described in detail with general explanations, specific embodiments and tests, it is obvious to a person skilled in the art that some modifications or improvements can be made thereto based on the present disclosure. Therefore, all the modifications and improvements which can be made without departing from the spirit of the present disclosure belong to the scope of protection of the present disclosure.

INDUSTRIAL APPLICABILITY

[0079] Compared with the prior art, the polymerizable compound of the present disclosure has good solubility, a better alignment effect, a higher polymerization rate, more complete polymerization, and lower residues, thereby greatly improving the problem of poor display; a liquid crystal composition containing the polymerizable compound has a better alignment effect, more complete polymerization, and lower residue; and the polymerizable compound has a low price and stable performance, can be widely applied to the field of liquid crystal display, and has an important application value.