CN103087723B - Fluorine-containing dibenzothiophene sulfone single liquid crystal and preparation method and applications thereof - Google Patents
Fluorine-containing dibenzothiophene sulfone single liquid crystal and preparation method and applications thereof Download PDFInfo
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Abstract
The invention relates to the field of liquid crystals, and in particular relates to fluorine-containing dibenzothiophene sulfone single liquid crystal applied in a liquid crystal composition and a liquid crystal display, and a preparation method thereof. The fluorine-containing dibenzothiophene sulfone single liquid crystal has the structure formula shown in the specification, wherein in the formula, X is H or F, Y is H or F, W is linear-chain alkyl or linear-chain alkoxyl of C1-C10; and at least one substituent group of X and Y is F. According to the fluorine-containing dibenzothiophene sulfone single liquid crystal and the preparation method and applications thereof, not only is the synthesis method simple, but also the fluorine-containing dibenzothiophene sulfone single liquid crystal contains the two polar groups of fluorine and dibenzothiophene sulfone, so that the polarity of molecules can be enhanced, and the product has wider nematic phase temperature range, as well as larger anisotropicity and higher resistivity; and the fluorine-containing dibenzothiophene sulfone single liquid crystal can be liquid crystal components to improve the property of the liquid crystal material, and can also be used for producing the liquid crystal display.
Description
Technical field
The present invention relates to field of liquid crystals, particularly a kind of fluorine-containing dibenzothiophene sulfone monomer liquid crystal in liquid-crystal composition and liquid-crystal display and preparation method thereof that is applied to.
Background technology
Dibenzothiophene sulfuryl group is as a polar group with aromaticity, and many compounds that contain this group all have larger application at numerous areas, such as disclosing oil-source rock correlation in patent CN101955491
wherein R
1, R
2represent H or F, set it as novel inducing layer material, be applicable to the weak epitaxial growth of induction on-plane surface metal phthalocyanine, have good application prospect at semiconductor applications.In patent patent JP6228555, disclose XCCYCCZ, wherein in the time that Y represents dibenzothiophene sulfone, shown good luminous efficiency and fluorescence intensity.We introduce this group in liquid crystal molecule, find that the liquid crystal molecule that contains this group has good liquid crystal property, thereby can improve the performance of liquid crystal components.
Liquid-crystal display (LCDS), as the display device of counter and counting clock table, appears at 20 century 70s the earliest, and through the development of more than 40 years, LCDS spread among our daily life.Simultaneously in the demand that meets the growing technical elements of Thin Film Transistor-LCD (TFT-LCD), it has been proposed to more and more higher requirement, such as its sharpness, high brightness, high response speed, wide operating temperature range, reduce power consumption, the low driving voltage of animation, wherein liquid crystal material is most important.
As the liquid crystal material that is applied to LCD, except requiring to possess good materialization stability, wider operating temperature range, TFT-LCD also must possess lower viscosity with liquid crystal material, higher voltage retention, lower threshold voltage, and the optical anisotropy matching with TFT-LCD.
The fluorinated liquid crystal material of early development is because specific inductivity is large not, so threshold voltage is higher.So introduce polarity aromatic group and improve the dielectric anisotropy of molecule in fluorinated liquid crystal molecule, by increasing molecular polarity, thereby effectively increase macromolecular dielectric anisotropy, thereby improve the performance of liquid crystal components.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of clearing point that has wider nematic phase temperature, can improve liquid crystal components, there is larger anisotropy and specific inductivity, can improve liquid crystal components performance be applied to fluorine-containing dibenzothiophene sulfone monomer liquid crystal in liquid-crystal composition and liquid-crystal display and preparation method thereof.
The technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of fluorine-containing dibenzothiophene sulfone monomer liquid crystal, and the structural formula of described fluorine-containing dibenzothiophene sulfone monomer is as follows:
In formula, X is H or F, and Y is H or F, and W is C
1～C
10straight chained alkyl or straight chain alkoxyl group; Wherein, to have a substituting group at least be F for X or Y.
The invention has the beneficial effects as follows: fluorine-containing dibenzothiophene sulfone monomer liquid crystal of the present invention has wider nematic phase temperature, can improve the clearing point of liquid crystal components, has larger anisotropy and specific inductivity, can improve the performance of liquid crystal components.
The present invention also provides a kind of preparation method of fluorine-containing dibenzothiophene sulfone monomer, be that mix 2～3:1:0.0001～0.01:2～8 by chemical compounds I, compound ii, catalyzer in molar ratio with basic cpd, the organic solvent that to add with compound ii mass ratio be 3～10:1, at 60～80 DEG C of temperature, carry out Suzuki coupling, react 1～5 hour, obtain described fluorine-containing dibenzothiophene sulfone monomer liquid crystal; Wherein,
The structural formula of described chemical compounds I is:
The structural formula of described compound ii is:
The structural formula of described fluorine-containing dibenzothiophene sulfone monomer is:
In formula, X is H or F, and Y is H or F, and W is C
1～C
10straight chained alkyl or straight chain alkoxyl group; Wherein, to have a substituting group at least be F for X or Y.
Preparation method's of the present invention beneficial effect is: the present invention not only synthetic method is simple, and contain fluorine and two polar groups of dibenzothiophene sulfone, strengthen the polarity of molecule, make product there is wider nematic temperature range, there is larger anisotropic simultaneously, may there is higher resistivity, can be used as liquid crystal components, the character of liquid crystal material is improved, also can be used for preparing liquid-crystal display.
On the basis of technique scheme, the present invention can also do following improvement.
Further, the mol ratio of the organic solvent of described chemical compounds I, compound ii, catalyzer and alkali is 2.2:1:0.005:5.
Further, the mass ratio of described organic solvent and compound ii is 5:1.
Further, the described Suzuki linked reaction time is 2 hours.
Further, described basic cpd be salt of wormwood, potassium hydroxide, sodium hydroxide, sodium carbonate,
Any one in saleratus, cesium carbonate or potassiumphosphate.
Further, described organic solvent is any one or a few in tetrahydrofuran (THF), toluene, benzene, sherwood oil, normal hexane or ethanol.
Further, described catalyzer is any one in tetrakis triphenylphosphine palladium, palladium or dichloro diphenylphosphine palladium.
The application of fluorine-containing dibenzothiophene sulfone monomer liquid crystal of the present invention in liquid-crystal composition.
The application of fluorine-containing dibenzothiophene sulfone monomer liquid crystal of the present invention in liquid-crystal display.
Embodiment
Below principle of the present invention and feature are described, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Embodiment 13, two (the fluoro-4-amyl group-phenyl of 2, the 3-bis-)-dibenzothiophene sulfones of 7-synthetic
In the tri-mouthfuls of round-bottomed flasks of 500ml that have nitrogen protection, add 5.6g (0.015mol) 3, the bromo-dibenzothiophene sulfone of 7-bis-, 7.5g (0.033nol) 2, the fluoro-4-amyl group-phenylo boric acid of 3-bis-, 10.4g (0.075mol) salt of wormwood, 112g tetrahydrofuran (THF), 31.2g water, 0.087g (0.000075mol) four (triphenyl phosphorus) palladium, reflux 2 hours, obtain yellow solution, cooling, add 200g toluene to stir 0.5 hour, layering, organic phase is washed with clear water, anhydrous sodium sulfate drying, remove siccative, the de-solvent to the greatest extent of Rotary Evaporators decompression obtains the yellowish solid of 9g, product obtains 7.9g white crystal with toluene recrystallization, Y:90.8%.Be 99.9% through gas-chromatography test purity, through testing transformation temperature through differential scanning calorimeter (DSC) and microscope: crystal phase (Cr) arrives smectic phase (S): 150.9～152.9 DEG C, smectic phase (S) arrives smectic phase (S): 203.6～204.5 DEG C, smectic phase (S) arrives nematic phase (N): 222.9～223.8 DEG C, nematic phase (N) arrives isotropic phase (Iso): 228.2～228.7 DEG C.Through GC-MS (GC-MS) test feature ion, M/Z+ is: 580,548,523,491,466,434,403.
Embodiment 23, two (the fluoro-4-propyl group-phenyl of the 2-)-dibenzothiophene sulfones of 7-synthetic
In the tri-mouthfuls of round-bottomed flasks of 500ml that have nitrogen protection, add 5.6g (0.015mol) 3, the bromo-dibenzothiophene sulfone of 7-bis-, the fluoro-4-propyl group-phenylo boric acid of 6.3g (0.030nol) 2-, 1.2g (0.030mol) sodium hydroxide, 16.8g toluene, 25.6g water, 0.000336g (0.0000015mol) four (triphenyl phosphorus) palladium, reflux 1 hour, obtain yellow solution, cooling, add 200g toluene to stir 0.5 hour, layering, organic phase is washed with clear water, anhydrous sodium sulfate drying, remove siccative, the de-solvent to the greatest extent of Rotary Evaporators decompression obtains the yellowish solid of 8g, product obtains 6.1g white crystal with toluene recrystallization, Y:90.5%.Be 99.7% through gas-chromatography test purity, through testing transformation temperature through differential scanning calorimeter (DSC) and microscope: crystal phase (Cr) is to 198.5～199.6 DEG C of nematic phases (N), and nematic phase (N) is to 233.2～234.1 DEG C of isotropic phases.
Embodiment 33, two (the fluoro-4-butyl-phenyl of the 2-)-dibenzothiophene sulfones of 7-synthetic
In the tri-mouthfuls of round-bottomed flasks of 500ml that have nitrogen protection, add 5.6g (0.015mol) 3, the bromo-dibenzothiophene sulfone of 7-bis-, 10.26g (0.045nol) 2, the fluoro-4-amyl group-phenylo boric acid of 3-bis-, 12g (0.12mol) saleratus, 56g sherwood oil, 45g water, 0.05895g (0.00015mol) dichloro diphenylphosphine palladium, reflux 5 hours, obtain yellow solution, cooling, add 300g toluene to stir 1.5 hours, layering, organic phase is washed with clear water, anhydrous sodium sulfate drying, remove siccative, the de-solvent to the greatest extent of Rotary Evaporators decompression obtains the yellowish solid of 12g, product obtains 10.8g white crystal with toluene recrystallization, Y:90.9%.Be 99.7% through gas-chromatography test purity, test transformation temperature through differential scanning calorimeter (DSC) and microscope: crystal phase (Cr) is to 179.5～180.6 DEG C of nematic phases (N), and nematic phase (N) is to 214.8～215.3 DEG C of isotropic phases.
Embodiment 43, two (the fluoro-4-amyl group-phenyl of the 2-)-dibenzothiophene sulfones of 7-synthetic
In the tri-mouthfuls of round-bottomed flasks of 500ml that have nitrogen protection, add 5.6g (0.015mol) 3, the bromo-dibenzothiophene sulfone of 7-bis-, the fluoro-4-amyl group-phenylo boric acid of 7.5g (0.033nol) 2-, 15.225g (0.075mol) potassiumphosphate, 112g normal hexane, 31.2g water, 0.087g (0.000075mol) four (triphenyl phosphorus) palladium, reflux 2 hours, obtain yellow solution, cooling, add 200g toluene to stir 0.5 hour, layering, organic phase is washed with clear water, anhydrous sodium sulfate drying, remove siccative, the de-solvent to the greatest extent of Rotary Evaporators decompression obtains the yellowish solid of 10.1g, product obtains 8.4g white crystal with toluene recrystallization, Y:90.7%.Be 99.9% through gas-chromatography test purity, test transformation temperature through differential scanning calorimeter (DSC) and microscope: crystal phase (Cr) is to 163.0～164.0 DEG C of nematic phases (N), and nematic phase (N) is to 212.8～213.3 DEG C of isotropic phases.
Embodiment 53, two (the fluoro-4-propoxy--phenyl of 2, the 3-bis-)-dibenzothiophene sulfones of 7-synthetic
In the tri-mouthfuls of round-bottomed flasks of 500ml that have nitrogen protection, add 5.6g (0.015mol) 3, the bromo-dibenzothiophene sulfone of 7-bis-, 7.128g (0.033nol) 2, the fluoro-4-propoxy--phenylo boric acid of 3-bis-, 7.95g (0.075mol) sodium carbonate, 112g ethanol, 31.2g water, 0.087g (0.000075mol) four (triphenyl phosphorus) palladium, reflux 2 hours, obtain yellow solution, cooling, add 200g toluene to stir 0.5 hour, layering, organic phase is washed with clear water, anhydrous sodium sulfate drying, remove siccative, the de-solvent to the greatest extent of Rotary Evaporators decompression obtains the yellowish solid of 9.1g, product obtains 7.9g white crystal with toluene recrystallization, Y:90.8%.Be 99.8% through gas-chromatography test purity, through testing transformation temperature through differential scanning calorimeter (DSC) and microscope: crystal phase (Cr) is to 256.2～257.5 DEG C of nematic phases (N), and nematic phase (N) is to 393.5～395.0 DEG C of isotropic phases.
Application example
Preparation parent liquid crystal M, fills a prescription as follows:
| Title | Ratio |
| PCH501 | 0.30 |
| PCH502 | 0.30 |
| VHHP1 | 0.20 |
| V2HP1 | 0.20 |
M is parent liquid crystal, and M-1～M-4 is 94% parent liquid crystal M and 6% monocrystalline is obtained by mixing, and parameter is as follows:
Table 1M-1～M-4 parameter
| Mixed crystal | T N-Iso(℃) | Δε |
| M | 70.0 | 0.3 |
| M-1(3GBSO2G3) | 73.2 | -0.5 |
| M-2(5GBSO2G5) | 72.1 | -0.6 |
| M-3(4GBSO2G4) | 72.5 | -0.6 |
| M-3(5GBSO2M5) | 73.9 | -0.8 |
Can find out and add this series monocrystal by data in table 1, can effectively improve clearing point.Novel liquid crystal monomer has negative dielectric anisotropy (Δ ε) as can be seen from the above table simultaneously.
Conclusion: can find out that by above data the mixed liquid crystal that has added novel liquid crystal monomer has excellent physicals.
The structure that this example is related:
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any amendment of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. a fluorine-containing dibenzothiophene sulfone monomer liquid crystal, is characterized in that, the structural formula of described fluorine-containing dibenzothiophene sulfone monomer liquid crystal is as follows:
In formula, X is H or F, and Y is H or F, and W is C
1～C
10straight chained alkyl or straight chain alkoxyl group; Wherein, to have a substituting group at least be F for X or Y.
2. the preparation method of a fluorine-containing dibenzothiophene sulfone monomer liquid crystal, it is characterized in that, be that mix 2～3:1:0.0001～0.01:2～8 by chemical compounds I, compound ii, catalyzer in molar ratio with basic cpd, the organic solvent that to add with compound ii mass ratio be 3～10:1, at 60～80 DEG C of temperature, carry out Suzuki coupling, react 1～5 hour, obtain described fluorine-containing dibenzothiophene sulfone monomer liquid crystal; Wherein,
The structural formula of described chemical compounds I is:
The structural formula of described compound ii is:
The structural formula of described fluorine-containing dibenzothiophene sulfone monomer is:
In formula, X is H or F, and Y is H or F, and W is C
1～C
10straight chained alkyl or straight chain alkoxyl group; Wherein, to have a substituting group at least be F for X or Y.
3. the preparation method of fluorine-containing dibenzothiophene sulfone monomer liquid crystal according to claim 2, is characterized in that, the mol ratio of described chemical compounds I, compound ii, catalyzer and basic cpd is 2.2:1:0.005:5.
4. the preparation method of fluorine-containing dibenzothiophene sulfone monomer liquid crystal according to claim 2, is characterized in that, described organic solvent and the mass ratio of compound ii are 5:1.
5. the preparation method of fluorine-containing dibenzothiophene sulfone monomer liquid crystal according to claim 2, is characterized in that, the described Suzuki linked reaction time is 2 hours.
6. according to the preparation method of the arbitrary described fluorine-containing dibenzothiophene sulfone monomer liquid crystal of claim 2～5, it is characterized in that, described basic cpd is any one in salt of wormwood, potassium hydroxide, sodium hydroxide, sodium carbonate, saleratus, cesium carbonate or potassiumphosphate.
7. according to the preparation method of the arbitrary described fluorine-containing dibenzothiophene sulfone monomer liquid crystal of claim 2～5, it is characterized in that, described organic solvent is any one or a few in tetrahydrofuran (THF), toluene, benzene, sherwood oil, normal hexane or ethanol.
8. according to the preparation method of the arbitrary described fluorine-containing dibenzothiophene sulfone monomer liquid crystal of claim 2～5, it is characterized in that, described catalyzer is any one in tetrakis triphenylphosphine palladium, palladium or dichloro diphenylphosphine palladium.
9. the application of the fluorine-containing dibenzothiophene sulfone monomer liquid crystal as described in as arbitrary in claim 1～8 in liquid-crystal composition.
10. the application of the fluorine-containing dibenzothiophene sulfone monomer liquid crystal as described in as arbitrary in claim 1～8 in liquid-crystal display.
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| EP3228681B1 (en) * | 2016-04-07 | 2018-11-14 | Merck Patent GmbH | Liquid-crystalline medium and liquid-crystal display comprising the same |
| CN106699710B (en) * | 2016-12-12 | 2019-08-16 | 陕西中医药大学 | A kind of lateral tetrafluoro substituted biphenyl and heterocyclic compound and preparation method thereof |
| CN113684036B (en) * | 2020-05-19 | 2022-11-25 | 北京八亿时空液晶科技股份有限公司 | Dibenzothiophene sulfone liquid crystal compound and preparation method and application thereof |
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| CN1942461A (en) * | 2004-04-14 | 2007-04-04 | 默克专利股份有限公司 | Dibenzofuran-, dibenzothiophene- and fluorene derivatives |
| CN102838585A (en) * | 2011-06-22 | 2012-12-26 | 海洋王照明科技股份有限公司 | Organic semiconductor material containing dibenzothiophene sulfone, and preparation method and application thereof |
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| CN1942461A (en) * | 2004-04-14 | 2007-04-04 | 默克专利股份有限公司 | Dibenzofuran-, dibenzothiophene- and fluorene derivatives |
| CN102838585A (en) * | 2011-06-22 | 2012-12-26 | 海洋王照明科技股份有限公司 | Organic semiconductor material containing dibenzothiophene sulfone, and preparation method and application thereof |
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