Polymerizable compound and application thereof

Abstract

The present invention provides a polymerizable compound with a structure of general formula I, which exhibits none or few of the problems existing in the prior art. A polymerizable liquid crystal composition comprising the polymerizable compound has good stability and higher reliability, and is embodied by having a smaller pretilt angle change and higher voltage holding ratio. Also, there is little or no image sticking effect in a liquid crystal display device comprising the polymerizable liquid crystal composition. The present invention also provides a method of synthesizing a polymerizable compound with a structure of general formula I. The present invention further provides a polymerizable liquid crystal composition comprising the polymerizable compound and a liquid crystal display device comprising the polymerizable liquid crystal composition. ##STR00001##

Claims

1. A polymerizable compound comprising one or more compounds selected from compounds of general formula I-1 to I-3: ##STR00128## in which, X.sub.1 and X.sub.2 are same or different and each independently represents —H or —CH.sub.3; L.sub.1-L.sub.16 are same or different and each independently represents —H, —F or —CH.sub.3; Z represents —CH.sub.2O—, —OCH.sub.2—, —CH.sub.2CH.sub.2—, —COO— or —OCO—; wherein at least one of L.sub.5-L.sub.8 and/or L.sub.13-L.sub.16 in the general formula I-1 is —F or —CH.sub.3; and wherein in general formulas I-1 and I-3 Z represents —CH.sub.2O—, —OCH.sub.2—, —CH.sub.2CH.sub.2—.

2. The polymerizable compound according to claim 1, wherein in the general formula I-2 Z represents —CH.sub.2O—, —OCH.sub.2— or —CH.sub.2CH.sub.2—.

3. The polymerizable compound according to claim 1 wherein polymerizable compound includes at least one compound represented by formula I-1, and the compound of general formula I-1 is one or more compounds selected from the following compounds: ##STR00129## ##STR00130## in which, X.sub.1 and X.sub.2 are same or different and each independently represents —H or —CH.sub.3; Z represents —CH.sub.2O—, —OCH.sub.2— or —CH.sub.2CH.sub.2—.

4. The polymerizable compound according to claim 1 wherein polymerizable compound includes at least one compound represented by formula I-2, and the compound of general formula I-2 is one or more compounds selected form the following compounds: ##STR00131## in which, X.sub.1 and X.sub.2 are same or different and each independently represents —H or —CH.sub.3, and Z represents —CH.sub.2O—, —OCH.sub.2—, —CH.sub.2CH.sub.2—, —COO—, or —OCO—.

5. The polymerizable compound according to claim 1 wherein polymerizable compound includes at least one compound represented by formula I-3, and the compound of general formula I-3 is one or more compounds selected form the following compounds: ##STR00132## ##STR00133## in which, X.sub.1 and X.sub.2 are same or different and each independently represents —H or —CH.sub.3; Z represents —CH.sub.2O—, —OCH.sub.2— or —CH.sub.2CH.sub.2—.

6. A polymerizable liquid crystal composition comprising the polymerizable compound of claim 1.

7. A liquid crystal display device comprising the polymerizable liquid crystal composition of claim 6.

8. A polymerizable compound comprising one or more compounds selected form the following compounds: ##STR00134## in which, X.sub.1 and X.sub.2 are same or different and each independently represents —H or —CH.sub.3, and Z represents —CH.sub.2O—, —OCH.sub.2—, —CH.sub.2CH.sub.2—, —COO—, —OCO—, —CF.sub.2O— or —OCF.sub.2—.

9. A polymerizable compound comprising one or more compounds selected from the following compounds: ##STR00135## ##STR00136## in which, X.sub.1 and X.sub.2 are same or different and each independently represents —H or —CH.sub.3; Z represents —CH.sub.2O—, —OCH.sub.2— or —CH.sub.2CH.sub.2—.

Description

DETAILED EMBODIMENTS

(1) The present invention will be illustrated by combining the detailed embodiments below. It should be noted that, the following examples are exemplary embodiments of the present invention, which are only used to illustrate the present invention, not to limit it. Other combinations and various modifications within the conception of the present invention are possible without departing from the subject matter and scope of the present invention.

(2) The abbreviated codes of the test items in the following Examples are as follows:

(3) Y1: pretilt angle 1, the pretilt angle data tested after irradiation of test cell with UV lamp 1 for 3 minutes;

(4) Y2: pretilt angle 2, the pretilt angle data tested after irradiation of test cell with UV lamp 1 for 3 minutes and the subsequent continuous illuminating of test cell with alternating current (16 V, 60 Hz) for 24 hours;

(5) Y: the amount of pretilt angle change=pretilt angle 2−pretilt angle 1;

(6) VHR1: the data of voltage holding ratio tested after irradiation of test cell with UV lamp 2 for 20 minutes;

(7) VHR2: the data of voltage holding ratio tested after irradiation of test cell with UV lamp 1 for 3 minutes and the subsequent irradiation of test cell with UV lamp 2 for 60 minutes;

(8) In which, the pretilt angle refers to the angle at which the alignment of the liquid crystal offsets by 90° (the initial pretilt angle of the vertically aligned test cell for testing is 1°);

(9) The light intensity of UV lamp 1 is 50 mw/cm.sup.2;

(10) The light intensity of UV lamp 2 is 5 mw/cm.sup.2.

(11) The polymerizable compounds with the structure of general formula I prepared by the following Examples are tested for pretilt angle and voltage holding ratio according to the following methods:

(12) selecting the commercial liquid crystal with No. HCMM-02 produced by Jiangsu Hecheng Display Technology Co., Ltd. as a host, dissolving the polymerizable compound with the structure of general formula I in the host liquid crystal in a percent of 0.1 wt %-0.3 wt %, and testing the polymerizable liquid crystal composition for pretilt angle and voltage holding ratio.

Example 1

(13) The synthetic route of compound I-1-1-1 is shown as follows:

(14) ##STR00012##

(15) 1) Synthesis of Compound A3

(16) To a 500 ml three-necked flask was added 19.1 g A1, 200 ml ethanol, and 10 g sodium hydroxide. 25 g A2 was added in portions (5 g, 8 g, 12 g, in three portions) with stirring. The reaction mixture was heated to reflux for 3 hours. After post-treatment, 33 g compound A3 was obtained, GC>97%, yield: 92%.

(17) 2) Synthesis of Compound A5

(18) To a 500 ml three-necked flask was added 18 g compound A3, 14 g A4, 21.2 g anhydrous sodium carbonate, 150 ml toluene, 75 ml ethanol, and 75 ml water. 0.5 g tetrakis(triphenylphosphine)palladium was added under nitrogen, and the reaction mixture was heated to reflux for 6 hours. After post-treatment, 5.2 g compound A5 was obtained, HPLC>95%, yield: 27%.

(19) 3) Synthesis of Compound I-1-1-1

(20) To a 500 ml three-necked flask was added 2 g compound A5, 150 ml toluene, 50 ml triethylamine, and a trace amount of 2,6-di-tert-butyl-p-cresol. 1.2 g A6 was added dropwise under nitrogen. After the addition was completed, the reaction mixture was stirred for 6 hours at a controlled temperature of 40° C. After post-treatment, 1 g compound I-1-1-1 was obtained, HPLC>99%, yield: 38%.

(21) The mass spectrum data of compound I-1-1-1 is as follows:

(22) Ms: 522 (2.8%) 251 (100%) 69 (45%).

(23) According to the above synthesis methods, target compounds can be obtained by substituting the compounds shown in Table 1 for compounds A1, A2, A4 and A6:

(24) TABLE-US-00001 TABLE 1 Alternative Alternative Alternative Alternative Target compound of A1 compound of A2 compound of A4 compound of A6 compound I-1-2-1 0 I-1-3-1 I-1-4-1 I-1-5-1 0 I-1-6-1 I-1-7-1 0 I-1-8-1 I-1-9-1 I-1-10-1 0 I-1-11-1 I-1-12-1 0 I-1-13-1 I-1-14-1

(25) The specific structures of the target compounds in Table 1 are shown as follows:

(26) ##STR00065## ##STR00066##

Example 2

(27) The synthetic route of compound I-2-1-1 is shown as follows:

(28) ##STR00067##

(29) 1) Synthesis of Compound B3

(30) To a 500 ml three-necked flask was added 28.2 g B2, 250 ml anhydrous tetrahydrofuran. The temperature was cooled to 0° C. under nitrogen, and 5.6 g potassium tert-butoxide was added in portions during which the temperature was kept below 10° C. The stirring was then continued for 30 minutes, and 12.3 g of a solution of compound B1 (trans-acetoxyphenyl cyclohexylcarbaldehyde) and 50 ml anhydrous tetrahydrofuran was added dropwise. The reaction mixture was then naturally warmed to room temperature and stirred for 12 hours. After post-treatment, 13 g compound B3 was obtained, GC (containing isomers)>95%, yield: 65%.

(31) 2) Synthesis of Compound B4

(32) To a 1 L hydrogenated kettle was added 10 g compound B3, 100 ml toluene, 100 ml ethyl acetate, and 0.5 g of 5% Pd/C. The air in the hydrogenated kettle was first discharged with nitrogen, and then the nitrogen was replaced with hydrogen. The hydrogen pressure was adjusted to 0.3 MPa, and catalytic hydrogenation was carried out at room temperature for 8 hours. After completion of the reaction and post-treatment, 10 g compound B4 was obtained, GC>95%, yield: 100%.

(33) 3) Synthesis of Compound B5

(34) To a 500 ml three-necked flask was added 10 g compound B4, 8.5 g A4, 100 ml toluene, 50 ml ethanol, 50 ml water and 10.6 g anhydrous sodium carbonate. 0.25 g tetrakis(triphenylphosphine)palladium was added under nitrogen, and the reaction mixture was heated to reflux for 6 hours. After completion of the reaction and post-treatment, 3.6 g compound B5 was obtained, HPLC>95%, yield: 39%.

(35) 4) Synthesis of Compound I-2-1-1

(36) To a 500 ml three-necked flask was added 3.6 g compound B5, 100 ml toluene, 50 ml triethylamine, and a trace amount of 2,6-di-tert-butyl-p-cresol. 2.5 g A6 was added dropwise under nitrogen. The reaction mixture was then kept at 40° C. and stirred for 6 hours. After post-treatment, 2.3 g compound I-2-1-1 was obtained, HPLC>99%, yield: 47%.

(37) The mass spectrometry data of compound I-2-1-1 is as follows:

(38) Ms: 508 (1.1%) 277 (100%) 264 (83%) 251 (34%) 200 (75%) 187 (62%) 174 (21%) 69 (36%).

(39) According to the above synthesis methods, target compounds can be obtained by substituting the compounds shown in Table 2 for compounds B1, B2, A4 and A6:

(40) TABLE-US-00002 TABLE 2 Alternative Alternative compound Alternative Alternative compound target of B1 compound of B2 compound of A4 of A6 compound 0 I-2-2-1 I-2-3-1 I-2-4-1 0 I-2-5-1 I-2-6-1

(41) The specific structures of the target compounds in Table 2 are shown as follows:

(42) ##STR00088##

Example 3

(43) The synthetic route of compound I-3-1-1 is shown as follows:

(44) ##STR00089##

(45) 1) Synthesis of Compound C3

(46) To a 500 ml three-necked flask was added 11.5 g C1, 8.7 g C2, 200 ml anhydrous dimethylacetamide, and 13.8 g anhydrous potassium carbonate. The reaction mixture was stirred for 3 hours at a controlled temperature of 90° C. After post-treatment, 14.5 g compound C3 was obtained, GC>97%, yield: 90%.

(47) 2) Synthesis of Compound C4

(48) To a 500 ml three-necked flask was added 9.6 g compound C3, 4.9 g A4, 120 ml toluene, 60 ml water, 60 ml ethanol, and 12.7 g anhydrous sodium carbonate. 0.2 g tetrakis(triphenylphosphine)palladium was added under nitrogen, and the reaction mixture was heated to reflux for 6 hours. After post-treatment, 4.8 g compound C4 was obtained, GC>97%, yield: 55%.

(49) 3) Synthesis of Compound I-3-1-1

(50) To a 500 ml three-necked flask was added 2.9 g compound C4, 100 ml toluene, 50 ml triethylamine, and a trace amount of 2,6-di-tert-butyl-p-cresol. 2.5 g A6 was added dropwise under nitrogen, and reaction mixture was stirred for 6 hours at a controlled temperature of 40° C. After post-treatment, 1.7 g compound I-3-1-1 was obtained, HPLC>99%, yield: 40%.

(51) The mass spectrum data of compound I-3-1-1 is as follows:

(52) Ms: 428 (3.3%) 175 (100%) 69 (49%)

(53) According to the above synthesis methods, target compounds can be obtained by substituting the compounds shown in Table 3 for compounds C1, C2, A4 and A6:

(54) TABLE-US-00003 TABLE 3 Alternative Alternative Alternative Alternative Target compound of C1 compound of C2 compound of A4 compound of A6 compound 0 I-3-2-1 I-3-3-1 00 01 I-3-4-1 02 03 04 05 I-3-5-1 06 07 08 09 I-3-6-1 0 I-3-7-1 I-3-8-1 0 I-3-9-1 I-3-10-1

(55) The specific structures of the target compounds in Table 3 are shown as follows:

(56) ##STR00126## ##STR00127##

Example 4

(57) Compounds I-1-1-1, I-1-2-1, I-1-3-1, I-1-14-1, I-2-1-1, I-2-5-1, I-3-1-1 and I-3-8-1 were added to the host liquid crystal HCMM-02 (Type: HCMM-02, Jiangsu Hecheng Display Technology Co., Ltd.) in a weight ratio of 0.3:100 of compounds to host liquid crystal respectively and heated to dissolve, thereby forming mixtures MI-1-1-1, MI-1-2-1, MI-1-3-1, MI-1-14-1, MI-2-1-1, MI-2-5-1, MI-3-1-1 and MI-3-8-1. They were naturally cooled to the laboratory ambient temperature, sampled and filled into a vertically aligned test cell to investigate the parameters of Table 4 below:

(58) TABLE-US-00004 TABLE 4 Dissolution Y1(°) VHR1(%) VHR2(%) Y2(°) Y(°) HCMM-02 — 0 95.1 93.6 0 0 MI-1-1-1 No crystallization 6.9 97.3 97.1 6.9 0 MI-1-2-1 (Annotation) Crystallization 2.4 96.6 95.7 2.6 0.2 MI-1-3-1 No crystallization 6.8 97.3 97 6.8 0 MI-1-14-1 No crystallization 7.5 97.2 97.1 7.5 0 MI-2-1-1 No crystallization 6.9 97.2 97.2 6.9 0 MI-2-5-1 No crystallization 6.6 97 97.1 6.7 0.1 MI-3-1-1 No crystallization 6.3 96.7 96.5 6.2 −0.1 MI-3-8-1 No crystallization 6.1 96.8 96.4 6.1 0
Annotation: Since there is crystallization in MI-1-2-1, the parameters in the table were obtained by testing a sample which has a weight ratio of 0.1:100 of I-1-2-1 to host liquid crystal.

(59) It can be seen from Examples 1-4 that the polymerizable liquid crystal compositions comprising the polymerizable compounds has good stability and higher reliability, and are embodied by having a smaller pretilt angle change and higher voltage holding ratio, such that there is little or no image sticking effect in the liquid crystal display device comprising the polymerizable liquid crystal composition.

(60) The foregoing descriptions are merely preferred examples of the present invention and are not intended to limit the present invention in any form. Although the present invention has been disclosed by the preferred examples as described above, it is not intended to be used to limit the present invention. Without departing from the scope of the technical solutions of the present invention, some changes may be made and equivalent examples can be modified through equivalent variations by those skilled in the art by means of the technical contents disclosed above. Without departing from the content of the technical solutions of the present invention, any simple amendment, equivalent change or modification of the above examples according to the technical essence of the present invention still falls within the scope of the technical solutions of the present invention.

INDUSTRIAL APPLICABILITY

(61) The compound related in the present invention can be applied to the field of liquid crystal.