CN102888225A - Conjugated separate liquid crystal compound, and preparation method and application thereof - Google Patents
Conjugated separate liquid crystal compound, and preparation method and application thereof Download PDFInfo
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- CN102888225A CN102888225A CN 201210388466 CN201210388466A CN102888225A CN 102888225 A CN102888225 A CN 102888225A CN 201210388466 CN201210388466 CN 201210388466 CN 201210388466 A CN201210388466 A CN 201210388466A CN 102888225 A CN102888225 A CN 102888225A
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- 0 *c(ccc(OCC(CC1)CCC1c(cc1)ccc1I)c1[I-]=*)c1I Chemical compound *c(ccc(OCC(CC1)CCC1c(cc1)ccc1I)c1[I-]=*)c1I 0.000 description 10
Abstract
The invention provides a conjugated separate liquid crystal compound disclosed as a general formula I, and a preparation method and application thereof. In the general formula I, m is a whole number ranging from 1 to 4. Independent conjugated structures are respectively used at the two ends of the molecule to change the design of the past single conjugated system of liquid crystal molecules. Compared with other liquid crystal compounds in the prior art, the liquid crystal compound provided by the invention has large optical anisotropy and clear bright spots. In the liquid crystal compound preparation process, the raw materials are accessible, the synthetic route is simple and easy to implement, and thus, the preparation method is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to the liquid crystal material field, a kind of conjugation divergence type liquid crystalline cpd and its preparation method and application is provided.
Background technology
Liquid crystal display device can the home-use various electrical equipment take clock and watch, electronic calculator as representative, measure machine, automobile with panel, word processing agent, computer, printer, TV etc. in use.As the night scene display mode, in its representational mode, can enumerate PC(phase change, phase transformation), TN(twist nematic, twisted-nematic), STN (super twisted nematic, supertwist is to row), ECB(electrically controlled birefringence, electrically conerolled birefringence), OCB(optically compensated bend, optical compensation curved), IPS(in-plane switching, coplanar transformation), VA(vertical alignment, vertical orientation), CSH(color super homeotropic, colored super vertical plane) type such as.Type of drive according to element is divided into PM(passive matrix, passive-matrix) type and AM(active matrix, active-matrix) type.PM is divided into the types such as static state (static) and multichannel (multiplex).AM is divided into TFT(thin filmtransistor, thin film transistor), MIM(metal insulator metal, metal-insulator-metal) etc. type.The type of TFT has non-crystalline silicon (amorphous silicon) and polysilicon (polycrystal silicon).The latter is divided into high temperature modification and low temperature modification according to manufacturing process.Liquid crystal display device is divided into the reflection-type of utilizing natural light, utilizes infiltration type backlight and utilize natural light and the semi-transmission type of two kinds of light sources backlight according to the type of light source.
In these display modes, IPS type, ECB type, VA type or CSH type etc. are from TN type now commonly used or the STN type is different is, the former uses the liquid crystal material with negative dielectric anisotropic.In these display modes, the VA type that especially drives by AM shows, requiring at a high speed and the application in the display element at wide visual angle, wherein, Worth Expecting be application in the liquid crystal cells such as TV.
The liquid crystal material of using in VA type and other display mode requires it to have low driving voltage, high response speed, and wide operating temperature range, the absolute value of negative dielectric anisotropic is larger, and phase inversion temperature is high, viscosity is low.Wherein, in order to realize high-speed response, need to reduce the cell gap of display element.Yet the delay (retardation) that represents for the product (△ n*d) with specific refractory power anisotropy (△ n) and unit interval (d) is set as the best, specific refractory power anisotropy and the unit interval of liquid crystal material must be adjusted to optimum range.Therefore, in narrow unit interval, there is the border.For under the prerequisite that does not change unit interval, improve response speed, it is effective using the low liquid-crystal composition of viscosity.In the liquid crystal display device such as TV, high response speed need to be arranged, therefore require the low especially liquid-crystal composition of exploitation viscosity.
At present, as the liquid crystal material of dielectric anisotropy for bearing, at the liquid crystalline cpd of the following structure of patent documentation US4637897.
In the formula, R
1, R
2The alkyl of expression 1-12 carbon atom, X, Y are F, Z is-C
2H
4-,-OCH
2-,-COO-,-OCO-.
In patent documentation CN101128566A, the composition that contains following structural compounds is disclosed
In the formula, R
1The alkenyl of expression 2-10 carbon atom, R
2The alkenyl of expression 2-10 carbon atom or the alkenyloxy of 3-10 carbon atom, m is 0,1 or 2.
Use above-mentioned dielectric anisotropy to be negative liquid-crystal composition, require in the liquid-crystal composition of high response speed in LCD TV etc., can't realize enough low viscosity, isotropy attitude transition point (clearing point) is not high enough, can not satisfy the liquid crystal display device development to the needs of liquid crystal material.
Summary of the invention
The invention provides a kind of conjugation divergence type liquid crystalline cpd and preparation method thereof and application.
One aspect of the present invention provides a kind of conjugation divergence type liquid crystalline cpd, and this compound has the structure shown in the logical formula I:
Wherein,
R
1And R
2Identical or different, be selected from independently of one another by H, halogen, the halo with 1-15 carbon atom or unsubstituted alkyl or alkoxyl group and have the halo of 2-15 carbon atom or group that unsubstituted alkenyl or alkenyloxy group form, wherein, at described R
1And R
2In one or more-CH
2-group can be independently of one another by-CH=CH-,-O-,-CH=CF-,-CF=CH-,-CF=CF-,-CO-O-or-O-CO-substitutes, its prerequisite is that Sauerstoffatom directly is not connected to each other;
L
1, L
2Identical or different, be selected from independently of one another by F, Cl, CN, CF
3And OCF
3The group that forms;
M is 1,2,3 or 4.
In some embodiments, R
1And R
2Be selected from independently of one another by H, F, the halo with 1-10 carbon atom or unsubstituted alkyl or alkoxyl group and have the halo of 2-10 carbon atom or group that unsubstituted alkenyl or alkenyloxy form, wherein, at described R
1And R
2In one or more-CH
2-group can be independently of one another by-CH=CH-,-O-,-CH=CF-,-CF=CH-,-CF=CF-,-CO-O-or-O-CO-substitutes, its prerequisite is that Sauerstoffatom directly is not connected to each other.
In some embodiments, R
2Be selected from halo or the unsubstituted alkoxyl group with 1-10 carbon atom and halo or the unsubstituted alkenyloxy with 2-10 carbon atom.
In some embodiments, L
1, L
2Be selected from independently of one another the group that F, Cl and CN form.
In some embodiments, m is 1 or 2.
Preferably, compound of the present invention is selected from the group that is comprised of following compound:
More preferably, compound of the present invention is selected from the group that is comprised of following compound:
Wherein, R
1Be selected from halo or unsubstituted alkyl or the alkoxyl group with 1-7 carbon atom and halo or unsubstituted alkenyl or the alkenyloxy with 2-7 carbon atom.
Another aspect of the present invention provides a kind of method for preparing compound of the present invention, comprises the steps:
Step 1) is carried out substitution reaction with the compound of formula I a, obtains the compound of general formula II a, and wherein the MG group is selected from the group that forms by iodine atom, bromine atoms, to Methyl benzenesulfonyl oxygen base and sulfonyloxy methyl oxygen base;
Step 2) behind the compound and alkali reaction with general formula III a, the compound with the general formula II a of step 1) gained reacts again, obtains the described compound of formula I;
In the described step 1), described MG group is iodine atom or to Methyl benzenesulfonyl oxygen base; Described step 2) in, described alkali is selected from least a in the group that is comprised of sodium hydroxide, potassium hydroxide, salt of wormwood and yellow soda ash.
Above-mentioned preparation method's reaction process is as follows:
Formula III a (I)
Another aspect of the present invention provides a kind of liquid-crystal composition that comprises the described compound of one or more of logical formula I.
Another aspect of the present invention provides and a kind ofly comprises that described liquid-crystal composition is as the liquid crystal display device of integrant.
The present invention uses respectively independently conjugated structure by handle at the molecule two ends, changed the in the past design of the single conjugated system of liquid crystal molecule, other liquid crystalline cpds of the liquid crystalline cpd of the logical formula I that provides and prior art are compared, and have large optical anisotropy and clearing point; In the liquid crystalline cpd preparation process of logical formula I, raw material is easy to get, and synthetic route is simple, is fit to large-scale industrial production.
In following examples test event to write a Chinese character in simplified form code name as follows:
Tni: clearing point (to row-isotropic phase transition temperature)
η: volume viscosity (mPa.s, 20 ℃, except as otherwise noted)
Δ n: optical anisotropy (589nm, 20 ℃)
Embodiment
Below with reference to specific embodiments the present invention is described.Need to prove, the following examples are example of the present invention, only are used for illustrating the present invention, and are not used for limiting the present invention.In the situation that do not depart from purport of the present invention or scope, can carry out the present invention and conceive interior other combination and various improvement.
Following embodiment prepares liquid crystalline cpd shown in the formula I of gained and all carries out as follows the test of optical anisotropy and clearing point and the mensuration of extrapolation parameter:
Choose the commodity liquid crystal that is numbered TS023-102 of Jiangsu Hecheng Display Technology Co., Ltd.'s production as parent, be dissolved in the parent leading to the part by weight of liquid crystalline cpd shown in the formula I with 10%, the optical anisotropy of test mixing thing, clearing point and volume viscosity η (20 ℃), and according to institute's adding proportion in the parent according to n(20 ℃ of the optical anisotropy Δ of liquid crystalline cpd shown in the extrapolated logical formula I of linear relationship, 589nm) and clearing point Tni.
Embodiment 1 compound I-1-2-1 (R
1=C
3H7, R
2=C
2H
5) preparation
Step 1:
Add 27.2g (4-(4-propyl group phenyl) cyclohexyl) methyl alcohol, 23.7g triethylamine and 400ml methylene dichloride in the 1000ml there-necked flask.After being cooled to 0 ℃, add the 26.7g p-methyl benzene sulfonic chloride at the solution of 150ml methylene dichloride, subsequently room temperature reaction 3h.Reaction solution is poured into water, use dichloromethane extraction, wash again organic layer with water to neutral, with rotary evaporation desolventizing behind the anhydrous sodium sulfate drying, use again ethyl alcohol recrystallization, obtain 29g (4-(4-propyl group phenyl) cyclohexyl) methyl 4-toluene sulfonic acide ester.
Step 2:
Add 8.4g4-oxyethyl group-2 in the 500ml there-necked flask, the 3-difluorophenol, 60ml N, dinethylformamide is cooled to 0 ℃, adds 1.4g sodium hydroxide in batches, rise to again 60 ℃, drip 15.6g (4-(4-propyl group phenyl) cyclohexyl) methyl 4-toluene sulfonic acide ester at the solution of 90ml DMF, then under this temperature, react 3h.Reaction solution is poured in the frozen water, used ethyl acetate extraction, washing, drying is spin-dried for to get product.Use the normal hexane column chromatography, and the normal hexane recrystallization obtains 5g target compound I-1-2-1 (R
1=C
3H
7, R
2=C
2H
5).MS?m/z：388(M
+)。
Liquid crystalline cpd I-1-2-1 (the R that test is synthesized
1=C
3H
7, R
2=C
2H
5) optical anisotropy and dielectric constant anisotropy, obtain volume of mixture viscosities il=52.1, the parameter of extrapolation: Δ n=0.140, η=52.1mPa.s, Tni=171.2 ℃
Embodiment 2 compound I-5-2-1 (R
1=C
3H
7, R
2=C
2H
5) preparation
Step 1:
Add 8g (4'-(4-propyl group phenyl)-[1,1'-bicyclohexane]-4-yl) methyl alcohol, 7.1g triethylamine and 200ml methylene dichloride in the 1000ml there-necked flask.After being cooled to 0 ℃, add the 5.7g p-methyl benzene sulfonic chloride at the solution of 50ml methylene dichloride, subsequently room temperature reaction 3h.Reaction solution is poured into water, use ethyl acetate extraction, wash again organic layer with water to neutral, with rotary evaporation desolventizing behind the anhydrous sodium sulfate drying, use again ethyl alcohol recrystallization, obtain 10g (4'-(4-propyl group phenyl)-[1,1'-bicyclohexane]-4-yl) methyl 4-toluene sulfonic acide ester.
Step 2:
Add 4.5g4-oxyethyl group-2 in the 500ml there-necked flask, the 3-difluorophenol, the 60ml DMF is cooled to 0 ℃, add 1.4g sodium hydroxide in batches, rise to again 60 ℃, drip 10g (4'-(4-propyl group phenyl)-[1,1'-bicyclohexane]-4-yl) methyl 4-toluene sulfonic acide ester at 90ml N, then the solution of dinethylformamide react 3h under this temperature.Reaction solution is poured in the frozen water, used ethyl acetate extraction, washing, drying is spin-dried for to get product.Use the normal hexane column chromatography, and the normal hexane recrystallization obtains 5.1g target compound I-5-2-1 (R
1=C
3H
7, R
2=C
2H
5).MS?m/z：470(M
+)。
Liquid crystalline cpd I-5-2-1 (the R that test is synthesized
1=C
3H
7, R
2=C
2H
5) optical anisotropy and dielectric constant anisotropy, obtain volume of mixture viscosities il=55.1, the parameter of extrapolation: Δ n=0.151, η=55.1mPa.s, Tni=214 ℃
Comparative Examples 1
Press document Liquid Crystals (1989), 5 (1), the method described in the 159-70 synthesizes the compound of following structure and tests.
Above several compounds are contrasted, and the result lists following table in.
Table 1
| Compound | η（mPa.s） | Δn | Tni（℃） |
| I-1-2-1(R 1=C 3H 7,R 2=C 2H 5) | 52.1 | 0.140 | 172 |
| I-5-2-1(R 1=C 3H 7,R 2=C 2H 5) | 55.1 | 0.151 | 214 |
| C-1 | 52.5 | 0.095 | 127 |
| C-2 | 51.4 | 0.107 | 160 |
As can be seen from the above table, liquid crystalline cpd shown in the formula I is under the condition of equal viscosities il, has larger optical anisotropy Δ n, and higher clearing point Tni, this will bring great convenience to the modulation of liquid-crystal composition, can make liquid-crystal composition possess simultaneously the characteristic of low viscosity, large optical anisotropy, high clearing point, thereby expand the performance of liquid crystal display device.
Claims (11)
1. the compound shown in the formula I:
Wherein,
R
1And R
2Identical or different, be selected from independently of one another H, halogen, have halo or unsubstituted alkyl or the alkoxyl group of 1-15 carbon atom and have the group of halo or unsubstituted alkenyl or the alkenyloxy composition of 2-15 carbon atom, wherein, at described R
1And R
2In one or more-CH
2-group can be independently of one another by-CH=CH-,-O-,-CH=CF-,-CF=CH-,-CF=CF-,-CO-O-or-O-CO-substitutes, its prerequisite is that Sauerstoffatom directly is not connected to each other;
L
1, L
2Identical or different, be selected from independently of one another by F, Cl, CN, CF
3And OCF
3The group that forms;
M is 1,2,3 or 4.
2. compound according to claim 1 is characterized in that, described R
1And R
2Be selected from independently of one another H, F, have halo or unsubstituted alkyl or the alkoxyl group of 1-10 carbon atom and have the group of halo or unsubstituted alkenyl or the alkenyloxy composition of 2-10 carbon atom, wherein, at described R
1And R
2In one or more-CH
2-group can be independently of one another by-CH=CH-,-O-,-CH=CF-,-CF=CH-,-CF=CF-,-CO-O-or-O-CO-substitutes, its prerequisite is that Sauerstoffatom directly is not connected to each other.
3. compound according to claim 2 is characterized in that, described R
2Be selected from halo or the unsubstituted alkoxyl group with 1-10 carbon atom and halo or the unsubstituted alkenyloxy with 2-10 carbon atom.
4. compound according to claim 1 is characterized in that, described L
1, L
2Be selected from independently of one another the group that is formed by F, Cl and CN.
5. compound according to claim 1 is characterized in that, described m is 1 or 2.
6. the described compound of any one according to claim 1-5, wherein said compound is selected from the group that is comprised of following compound:
7. compound according to claim 6, wherein said compound is selected from the group that is comprised of following compound:
Wherein,
R
1Be selected from halo or unsubstituted alkyl or the alkoxyl group with 1-7 carbon atom and halo or unsubstituted alkenyl or the alkenyloxy with 2-7 carbon atom.
8. a method for preparing such as any one described compound in the claim 1 to 7 comprises the steps:
Step 1) is carried out substitution reaction with the compound of formula I a, obtains the compound of general formula II a, and wherein the MG group is selected from the group that forms by iodine atom, bromine atoms, to Methyl benzenesulfonyl oxygen base and sulfonyloxy methyl oxygen base;
Step 2) behind the compound and alkali reaction with general formula III a, the compound with the general formula II a of step 1) gained reacts again, obtains the described compound of formula I;
9. method according to claim 8 is characterized in that:
In the described step 1), described MG group is iodine atom or to Methyl benzenesulfonyl oxygen base;
Described step 2) in, described alkali is selected from least a in the group that is comprised of sodium hydroxide, potassium hydroxide, salt of wormwood and yellow soda ash.
10. the liquid-crystal composition that comprises any one described liquid crystalline cpd among the claim 1-7.
11. liquid crystal display device that comprises liquid-crystal composition as claimed in claim 10.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103880595A (en) * | 2014-04-10 | 2014-06-25 | 石家庄科润显示材料有限公司 | Flexible liquid crystal intermediate trans p-alkyl dicyclohexyl methanol benzene and preparation method thereof |
| CN110804005A (en) * | 2018-08-04 | 2020-02-18 | 石家庄诚志永华显示材料有限公司 | Compound, liquid crystal composition, liquid crystal display element and liquid crystal display |
| CN115894181A (en) * | 2022-09-30 | 2023-04-04 | 渭南高新区海泰新型电子材料有限责任公司 | Synthetic method of cyclohexenyl cyclohexyl difluorobenzene liquid crystal compound |
-
2012
- 2012-10-13 CN CN 201210388466 patent/CN102888225A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880595A (en) * | 2014-04-10 | 2014-06-25 | 石家庄科润显示材料有限公司 | Flexible liquid crystal intermediate trans p-alkyl dicyclohexyl methanol benzene and preparation method thereof |
| CN103880595B (en) * | 2014-04-10 | 2016-01-06 | 石家庄科润显示材料有限公司 | A kind of flexible liquid crystal intermediate trans is to alkylbenzene dicyclohexyl methyl alcohol and preparation method thereof |
| CN110804005A (en) * | 2018-08-04 | 2020-02-18 | 石家庄诚志永华显示材料有限公司 | Compound, liquid crystal composition, liquid crystal display element and liquid crystal display |
| CN115894181A (en) * | 2022-09-30 | 2023-04-04 | 渭南高新区海泰新型电子材料有限责任公司 | Synthetic method of cyclohexenyl cyclohexyl difluorobenzene liquid crystal compound |
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