CN104662125B - Liquid-crystal compounds and preparation method thereof, liquid-crystal composition and display panels - Google Patents
Liquid-crystal compounds and preparation method thereof, liquid-crystal composition and display panels Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 219
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 194
- 239000000203 mixture Substances 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title abstract description 14
- -1 (4,4 difluoro 3 cyclobutenyl) benzene class Chemical class 0.000 claims abstract description 7
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 58
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 20
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- VGDJCNVLJDUYPK-UHFFFAOYSA-N 2-chloro-2,2-difluoroacetic acid;sodium Chemical compound [Na].OC(=O)C(F)(F)Cl VGDJCNVLJDUYPK-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 claims description 9
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- 239000005711 Benzoic acid Substances 0.000 claims description 7
- 125000000304 alkynyl group Chemical group 0.000 claims description 7
- 235000010233 benzoic acid Nutrition 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 4
- 238000006473 carboxylation reaction Methods 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 230000032050 esterification Effects 0.000 claims description 3
- 238000005886 esterification reaction Methods 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- 238000003747 Grignard reaction Methods 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 20
- 230000003287 optical effect Effects 0.000 description 18
- 239000002904 solvent Substances 0.000 description 14
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 11
- 239000008346 aqueous phase Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 9
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
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- 239000000463 material Substances 0.000 description 4
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- 239000007787 solid Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001555 benzenes Chemical class 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- 0 CC(C)(C)PC(C)(C)NC(C)(C)*C(C)(C)*C=* Chemical compound CC(C)(C)PC(C)(C)NC(C)(C)*C(C)(C)*C=* 0.000 description 2
- YEJCHVFCLNKZPU-UHFFFAOYSA-N CC1COC(C)CC1 Chemical compound CC1COC(C)CC1 YEJCHVFCLNKZPU-UHFFFAOYSA-N 0.000 description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000010813 municipal solid waste Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
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- 238000010992 reflux Methods 0.000 description 2
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- 238000010998 test method Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- DQXKOHDUMJLXKH-PHEQNACWSA-N (e)-n-[2-[2-[[(e)-oct-2-enoyl]amino]ethyldisulfanyl]ethyl]oct-2-enamide Chemical compound CCCCC\C=C\C(=O)NCCSSCCNC(=O)\C=C\CCCCC DQXKOHDUMJLXKH-PHEQNACWSA-N 0.000 description 1
- QPTKCXWLRPZBKE-UHFFFAOYSA-N C#C.C1(=CC=CC=C1)OCC Chemical group C#C.C1(=CC=CC=C1)OCC QPTKCXWLRPZBKE-UHFFFAOYSA-N 0.000 description 1
- UEGTWSDWQJHWHL-UHFFFAOYSA-N CC(C1)=CC(F)=C(C)C1F Chemical compound CC(C1)=CC(F)=C(C)C1F UEGTWSDWQJHWHL-UHFFFAOYSA-N 0.000 description 1
- LPYXMXJLRHUESC-UHFFFAOYSA-N CC(C1F)=CC=C(C)C1F Chemical compound CC(C1F)=CC=C(C)C1F LPYXMXJLRHUESC-UHFFFAOYSA-N 0.000 description 1
- UBBQQHQQJDKFHU-UHFFFAOYSA-N CC(CC1C2)=CC=C1C(F)=C(C)C2F Chemical compound CC(CC1C2)=CC=C1C(F)=C(C)C2F UBBQQHQQJDKFHU-UHFFFAOYSA-N 0.000 description 1
- LDCFEAFMWBVWHO-UHFFFAOYSA-N CC1(CC2)CCC2(C)CC1 Chemical compound CC1(CC2)CCC2(C)CC1 LDCFEAFMWBVWHO-UHFFFAOYSA-N 0.000 description 1
- RPMUDXVQHUECRE-UHFFFAOYSA-N CC1COC(C)OC1 Chemical compound CC1COC(C)OC1 RPMUDXVQHUECRE-UHFFFAOYSA-N 0.000 description 1
- CFFHCMKGIPEENO-UHFFFAOYSA-N CC1Cc2cc(F)c(C)c(F)c2CC1 Chemical compound CC1Cc2cc(F)c(C)c(F)c2CC1 CFFHCMKGIPEENO-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YGYNBBAUIYTWBF-UHFFFAOYSA-N Cc(cc1)cc2c1cc(C)cc2 Chemical compound Cc(cc1)cc2c1cc(C)cc2 YGYNBBAUIYTWBF-UHFFFAOYSA-N 0.000 description 1
- WNQQYDVWIURCMA-UHFFFAOYSA-N Cc(ccc(cc1C)c2c(F)c1F)c2F Chemical compound Cc(ccc(cc1C)c2c(F)c1F)c2F WNQQYDVWIURCMA-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
- C09K19/18—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon triple bonds, e.g. tolans
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nonlinear Science (AREA)
- Mathematical Physics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Liquid Crystal Substances (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to technical field of liquid crystal display, disclose a kind of liquid-crystal compounds and preparation method thereof, a kind of liquid-crystal composition and a kind of display panels.Shown in formula I, this liquid-crystal compounds is the compound of 4 (4,4 difluoro 3 cyclobutenyl) benzene class to the structural formula of described liquid-crystal compounds, by adding different abutment Z1And Z2, ring A and ring B and end group R1, improve the clearing point of the liquid-crystal composition comprising this liquid-crystal compounds, and reduce the viscosity of liquid-crystal composition, and then widen the range of application of display panels.
Description
Technical field
The present invention relates to technical field of liquid crystal display, particularly relate to a kind of liquid-crystal compounds and preparation method thereof, one
Liquid-crystal composition and a kind of display panels.
Background technology
In panel display apparatus, Thin Film Transistor-LCD (Thin Film Transistor Liquid
Crystal Display, is called for short TFT-LCD) there is the features such as volume is little, low in energy consumption, manufacturing cost is relatively low and radiationless,
Leading position is occupied in current flat panel display market.
Liquid crystal display has been widely used the various aspects in social life, and lcd technology is developed so far, various respectively
The liquid-crystal compounds of sample is on the actual application.Some general requirements to liquid-crystal compounds, including the phase of liquid-crystal compounds
Temperature, optical anisotropy, dielectric anisotropy, viscosity, resistivity etc., all have the biggest to the application that liquid crystal material is final
Impact.The exploitation of new liquid-crystal compounds and the compositions of its composition, improve the various character of liquid crystal, improve liquid crystal
The application effect shown is of crucial importance.And liquid-crystal composition is to use various of monomer liquid-crystal compounds according to the electric light thing of liquid crystal display
The technology requirements such as rationality energy are compounded into.The liquid-crystal composition of excellent properties to be obtained must be by the monomer liquid crystallization of function admirable
Compound, people need the synthesis compound containing different liquid crystal structures to realize the different electric light physical properties of mixed liquid crystal.
According to its display mode, LCD can be divided into the type that dynamically shines, distortion type (TN), supertwist type (STN) and plane conversion
Type (IPS), although the liquid-crystal composition display characteristic used by these LCD is different, but have following general character: driving voltage
Low, liquid crystal operating temperature range width, suitable photoanisotropy and good heat stability, light stability and chemical stability.
In the allocation process of mixed liquid crystal compositions, often add some monomer liquid crystal compounds with a certain property,
Improve the clearing point of liquid-crystal composition or reduce the viscosity of liquid-crystal composition, or improving the optics of liquid-crystal composition respectively to different
Property, it is desired that the monomer liquid crystal compound of this property is always researcher.
Summary of the invention
The invention provides a kind of liquid-crystal compounds and preparation method thereof, a kind of liquid-crystal composition and a kind of LCD
Plate, in order to improve the optical anisotropy of liquid-crystal composition, and reduces the viscosity of liquid-crystal composition, and then widens liquid crystal display
The range of application of panel.
First the embodiment of the present invention provides a kind of liquid-crystal compounds, the structural formula of described liquid-crystal compounds shown in formula I:
Wherein, L1And L2Separately selected from hydrogen or fluorine；
Abutment Z1And Z2Separately selected from singly-bound ,-HC=N-N=CH-,-CH2-、-CH2-CH2-、-(CH2)3-、-
(CH2)4-,-CH=CH-,-C ≡ C-,-COO-,-OOC-,-CF2O-、-OCF2-、-OCH2-、-CH2O-、-CF2CH2-、-
CH2CF2-、-C2F4-or-CF=CF-；
Ring A and ring B is separately selected from
End group R1Selected from fluorine ,-OCF3, cyano group, the alkyl of C1-C5 or the alkoxyl of C1-C5；
M and n is separately selected from 0,1,2 or 3, and m+n >=1.
In this technical scheme, this liquid-crystal compounds is the compound of 4-(4,4-bis-fluoro-3-cyclobutenyl) benzene class, by adding
Enter different abutment Z1And Z2, ring A and ring B and end group R1So that the compositions containing this LCD compound has higher
Clearing point, and the viscosity of liquid-crystal composition can be reduced, improve response speed, expand the range of application of display panels.
Preferably, m+n=1 or 2.
Inventor it has furthermore been found that described liquid-crystal compounds particularly as follows:
The present invention also provides for a kind of method preparing above-mentioned liquid-crystal compounds, when the abutment of the liquid-crystal compounds shown in Formulas I
Z1During for alkynyl, described method includes: under the catalytic action of triphenylphosphine, will be anti-with chloro difluoro acetic acid sodium to bromobenzene propionic aldehyde
Should, generate 4-(4,4-bis-fluoro-3-cyclobutenyl) bromobenzene；By 4-(4,4-bis-fluoro-3-cyclobutenyl) bromobenzene and iodine generation iodide reaction,
Generate 4-(4,4-bis-fluoro-3-cyclobutenyl) iodobenzene；4-(4,4-bis-fluoro-3-cyclobutenyl) iodobenzene is reacted with compound HC ≡ C-R,
Generate abutment Z1For the liquid-crystal compounds shown in the Formulas I of alkynyl, wherein R and the liquid-crystal compounds shown in above-mentioned Formulas IIdentical；
Abutment Z when the liquid-crystal compounds shown in Formulas I1During for carboxyl, described method includes: the catalysis at triphenylphosphine is made
Under with, bromobenzene propionic aldehyde will be reacted with chloro difluoro acetic acid sodium, generate 4-(4,4-bis-fluoro-3-cyclobutenyl) bromobenzene；By 4-(4,4-
Two fluoro-3-cyclobutenyls) bromobenzene and carbon dioxide generation carboxylation reaction, generate 4-(4,4-bis-fluoro-3-cyclobutenyl) benzoic acid；Will
4-(4,4-bis-fluoro-3-cyclobutenyl) benzoic acid and compound generation esterification, generate abutment Z1For the liquid shown in the Formulas I of carboxyl
Crystallization compound, wherein R and the liquid-crystal compounds shown in above-mentioned Formulas IIdentical.
The present invention also provides for a kind of liquid-crystal composition, including the liquid-crystal compounds shown in the Formulas I that at least one is above-mentioned.
In this technical scheme, owing to have employed the liquid-crystal compounds shown in Formulas I in liquid-crystal composition, therefore, it is beneficial to
Improve the clearing point of liquid-crystal composition, there is suitable optical anisotropy, relatively low rotary viscosity and faster response speed,
The cryogenic property of liquid-crystal composition is the most preferable.In liquid-crystal composition the liquid-crystal compounds shown in Formulas I can add one, two
Kind, three kinds the most multiple.
Inventor finds, it is preferred that in described liquid-crystal composition, the mass fraction of the liquid-crystal compounds shown in Formulas I is
0.5%～30%, preferably 8%～16%.Such as mass fraction is 0.5%, 2%, 5%, 8%, 10%, 12%, 15%,
16%, 20%, 25% or 30%.
Especially, described liquid-crystal composition includes:
Mass fraction is the compound of 18%:
Mass fraction is the compound of 10%:
Mass fraction is the compound of 7%:
Mass fraction is the compound of 9%:
Mass fraction is the compound of 7%:
Mass fraction is the compound of 8%:
Mass fraction is the compound of 4%:
Mass fraction is the compound of 4%:
Mass fraction is the compound of 10%:
Mass fraction is the compound of 4%:
Mass fraction is the compound of 5%:
Mass fraction is the compound of 5%:
Mass fraction is the compound of 5%:
Mass fraction is the compound of 4%:
Especially, described liquid-crystal composition includes:
Mass fraction is the compound of 24%:
Mass fraction is the compound of 5%:
Mass fraction is the compound of 12%:
Mass fraction is the compound of 8%:
Mass fraction is the compound of 4%:
Mass fraction is the compound of 4%:
Mass fraction is the compound of 8%:
Mass fraction is the compound of 8%:
Mass fraction is the compound of 15%:
Mass fraction is the compound of 8%:
Mass fraction is the compound of 4%:
Especially, described liquid-crystal composition includes:
Mass fraction is the compound of 20%:
Mass fraction is the compound of 10%:
Mass fraction is the compound of 6%:
Mass fraction is the compound of 5%:
Mass fraction is the compound of 4%:
Mass fraction is the compound of 6%:
Mass fraction is the compound of 7%:
Mass fraction is the compound of 7%:
Mass fraction is the compound of 7%:
Mass fraction is the compound of 8%:
Mass fraction is the compound of 4%:
Mass fraction is the compound of 4%:
Mass fraction is the compound of 6%:
Mass fraction is the compound of 6%:
The embodiment of the present invention also provides for the preparation method of a kind of any of the above-described kind of described liquid-crystal composition, described preparation method
Including: each component in liquid-crystal composition is mixed to get.
The embodiment of the present invention also provides for a kind of display panels, including the first substrate that box is put and second substrate,
And the liquid crystal layer between described first substrate and second substrate, described liquid crystal layer uses any of the above-described kind of liquid crystal combination
Thing obtains.
In this technical scheme, owing to liquid-crystal composition has higher optical anisotropy, suitable optics respectively to different
Property, low rotary viscosity and response speed faster, therefore, use this liquid-crystal composition as liquid crystal layer, be conducive to improving
The display performance of display panels.
Detailed description of the invention
In order to improve the performance of liquid-crystal composition, embodiments provide a kind of liquid-crystal compounds and preparation side thereof
Method, a kind of liquid-crystal composition and a kind of display panels.In this technical scheme, this liquid-crystal compounds is 4-(4,4-bis-fluoro-3-
Cyclobutenyl) compound of benzene class, by adding different abutment Z1And Z2, ring A and ring B and end group R1So that containing being somebody's turn to do
The compositions of LCD compound has a higher optical anisotropy, and can reduce the viscosity of liquid-crystal composition, improves response speed
Degree, expands the range of application of display panels.For making the object, technical solutions and advantages of the present invention clearer, below lift
The present invention is described in further detail by specific embodiment.
First the embodiment of the present invention provides a kind of liquid-crystal compounds, the structural formula of described liquid-crystal compounds shown in formula I:
Wherein, L1And L2Separately selected from hydrogen or fluorine；
Abutment Z1And Z2Separately selected from singly-bound ,-HC=N-N=CH-,-CH2-、-CH2-CH2-、-(CH2)3-、-
(CH2)4-,-CH=CH-,-C ≡ C-,-COO-,-OOC-,-CF2O-、-OCF2-、-OCH2-、-CH2O-、-CF2CH2-、-
CH2CF2-、-C2F4-or-CF=CF-；
Ring A and ring B is separately selected from
End group R1Selected from fluorine ,-OCF3, cyano group, the alkyl of C1-C5 or the alkoxyl of C1-C5；
M and n is separately selected from 0,1,2 or 3, and m+n >=1.
In this technical scheme, this liquid-crystal compounds is the compound of 4-(4,4-bis-fluoro-3-cyclobutenyl) benzene class, by adding
Enter different abutment Z1And Z2, ring A and ring B and end group R1So that the compositions containing this LCD compound has higher
Optical anisotropy, and the viscosity of liquid-crystal composition can be reduced, improve response speed, expand the application model of display panels
Enclose.
Wherein, C1-C4 is to include a group to four carbon atom, and in like manner, C1-C5 is former for including one to five carbon
The group of son, is the most all such, repeats the most one by one.The alkyl of C1-C4 can be straight or branched C1-C4
Alkyl, such as methyl, ethyl, n-pro-pyl, 1-Methylethyl, normal-butyl, 1-methyl-propyl, 2-methyl-propyl, 1,1-diformazan
Base propyl group etc..
Here it should be noted that as m=0, then abutment Z1And Z2It is joined directly together, as n=0, then abutment Z2With end
End group group R1It is joined directly together.
Preferably, m+n=1 or 2.I.e. m=0 and n=1；Or, m=1 and n=0；Or, m=1 and n=1.
Inventor it has furthermore been found that described liquid-crystal compounds particularly as follows:
The present invention also provides for a kind of method preparing above-mentioned liquid-crystal compounds, when the abutment of the liquid-crystal compounds shown in Formulas I
Z1During for alkynyl, described method includes: under the catalytic action of triphenylphosphine, will be anti-with chloro difluoro acetic acid sodium to bromobenzene propionic aldehyde
Should, generate 4-(4,4-bis-fluoro-3-cyclobutenyl) bromobenzene；By 4-(4,4-bis-fluoro-3-cyclobutenyl) bromobenzene and iodine generation iodide reaction,
Generate 4-(4,4-bis-fluoro-3-cyclobutenyl) iodobenzene；4-(4,4-bis-fluoro-3-cyclobutenyl) iodobenzene is reacted with compound HC ≡ C-R,
Generate abutment Z1For the liquid-crystal compounds shown in the Formulas I of alkynyl, the wherein R phase of R and the liquid-crystal compounds shown in above-mentioned Formulas I
With；
Abutment Z when the liquid-crystal compounds shown in Formulas I1During for carboxyl, described method includes: the catalysis at triphenylphosphine is made
Under with, bromobenzene propionic aldehyde will be reacted with chloro difluoro acetic acid sodium, generate 4-(4,4-bis-fluoro-3-cyclobutenyl) bromobenzene；By 4-(4,4-
Two fluoro-3-cyclobutenyls) bromobenzene and carbon dioxide generation carboxylation reaction, generate 4-(4,4-bis-fluoro-3-cyclobutenyl) benzoic acid；Will
4-(4,4-bis-fluoro-3-cyclobutenyl) benzoic acid and compound generation esterification, generate abutment Z1For the liquid shown in the Formulas I of carboxyl
Crystallization compound, wherein R is identical with the R of the liquid-crystal compounds shown in above-mentioned Formulas I；
Abutment Z when the liquid-crystal compounds shown in Formulas I1During for-HC=N-N=CH-, described method includes:
Under the catalytic action of triphenylphosphine, bromobenzene propionic aldehyde will be reacted with chloro difluoro acetic acid sodium, generate 4-(4,4-bis-
Fluoro-3-cyclobutenyl) bromobenzene；By 4-(4,4-bis-fluoro-3-cyclobutenyl) bromobenzene and magnesium generation grignard reaction again with dimethylformamide
React, generate 4-(4,4-bis-fluoro-3-cyclobutenyl) benzaldehyde；By 4-(4,4-bis-fluoro-3-cyclobutenyl) benzaldehyde and hydration
Hydrazine generation condensation reaction, generates abutment Z1For the liquid-crystal compounds shown in the Formulas I of-HC=N-N=CH-.
The present invention also provides for a kind of liquid-crystal composition, including the liquid-crystal compounds shown in the Formulas I that at least one is above-mentioned.
In this technical scheme, owing to have employed the liquid-crystal compounds shown in Formulas I in liquid-crystal composition, therefore, it is beneficial to
Improve the optical anisotropy of liquid-crystal composition, relatively low rotary viscosity and faster response speed, the low temperature of liquid-crystal composition
Performance is the most preferable.In liquid-crystal composition the liquid-crystal compounds shown in Formulas I can add one, two kinds, three kinds the most multiple.
Inventor finds, it is preferred that in described liquid-crystal composition, the mass fraction of the liquid-crystal compounds shown in Formulas I is
0.5%～30%, preferably 8%～16%.Such as mass fraction is 0.5%, 2%, 5%, 8%, 10%, 12%, 15%,
16%, 20%, 25% or 30%.
When in liquid-crystal composition the mass fraction of the liquid-crystal compounds shown in Formulas I less than 0.5% time, can cause optics respectively to
The opposite sex diminishes；When the mass fraction of the liquid-crystal compounds shown in Formulas I is more than 30% in liquid-crystal composition, it is easily caused product and dissolves
Degree is deteriorated, and component is insoluble, and therefore in the liquid-crystal composition of the present invention, the mass fraction of the liquid-crystal compounds shown in Formulas I is
0.5%～30%.
In liquid-crystal composition, other component can be determined according to the requirement of liquid-crystal composition.To other component
Content is not particularly limited, and according to the principle of similar compatibility, similar structure to be added, it is ensured that liquid-crystal composition
(i.e. mixed crystal) good mixing, will not separate out, and usually, can use the material of several analog structure in liquid-crystal composition.
Especially, described liquid-crystal composition includes:
Mass fraction is the compound of 18%:
Mass fraction is the compound of 10%:
Mass fraction is the compound of 7%:
Mass fraction is the compound of 9%:
Mass fraction is the compound of 7%:
Mass fraction is the compound of 8%:
Mass fraction is the compound of 4%:
Mass fraction is the compound of 4%:
Mass fraction is the compound of 10%:
Mass fraction is the compound of 4%:
Mass fraction is the compound of 5%:
Mass fraction is the compound of 5%:
Mass fraction is the compound of 5%:
Mass fraction is the compound of 4%:
Especially, described liquid-crystal composition includes:
Mass fraction is the compound of 24%:
Mass fraction is the compound of 5%:
Mass fraction is the compound of 12%:
Mass fraction is the compound of 8%:
Mass fraction is the compound of 4%:
Mass fraction is the compound of 4%:
Mass fraction is the compound of 8%:
Mass fraction is the compound of 8%:
Mass fraction is the compound of 15%:
Mass fraction is the compound of 8%:
Mass fraction is the compound of 4%:
Especially, described liquid-crystal composition includes:
Mass fraction is the compound of 20%:
Mass fraction is the compound of 10%:
Mass fraction is the compound of 6%:
Mass fraction is the compound of 5%:
Mass fraction is the compound of 4%:
Mass fraction is the compound of 6%:
Mass fraction is the compound of 7%:
Mass fraction is the compound of 7%:
Mass fraction is the compound of 7%:
Mass fraction is the compound of 8%:
Mass fraction is the compound of 4%:
Mass fraction is the compound of 4%:
Mass fraction is the compound of 6%:
Mass fraction is the compound of 6%:
The embodiment of the present invention also provides for the preparation method of a kind of any of the above-described kind of described liquid-crystal composition, described preparation method
Including: each component in liquid-crystal composition is mixed to get.
The embodiment of the present invention also provides for a kind of display panels, including the first substrate that box is put and second substrate,
And the liquid crystal layer between described first substrate and second substrate, described liquid crystal layer uses any of the above-described kind of liquid crystal combination
Thing obtains.
In this technical scheme, owing to liquid-crystal composition has higher optical anisotropy, suitable optics respectively to different
Property, low rotary viscosity and response speed faster, therefore, use this liquid-crystal composition as liquid crystal layer, be conducive to improving
The display performance of display panels.
Several specific embodiment is set forth below, but the present invention is not limited by these embodiments.
One, the preparation of the liquid-crystal compounds shown in Formulas I
Enumerating the preparation process of the liquid-crystal compounds shown in several specific embodiment formula I, the present invention is not limited to
Following embodiment, specifically, the preparation process of this liquid-crystal compounds is as follows:
Embodiment 1: the abutment Z of the liquid-crystal compounds shown in Formulas I1For alkynyl
Synthetic route is as follows:
The synthesis of step 1:4-(4,4-bis-fluoro-3-cyclobutenyl) bromobenzene (I-1-a)
In 2000ml there-necked flask, add 1200ml oxolane, open stirring, logical nitrogen emptying air, add 85.2g
To bromobenzene propionic aldehyde and 115.3g triphenylphosphine.Dropping 91.5g chloro difluoro acetic acid sodium, drips rear return stirring 2 hours.To
To reactant liquor carry out post processing, in reactant liquor, add 90g concentrated hydrochloric acid, 300ml water, stirring hydrolysis was carried out point after 10 minutes
Liquid, obtains aqueous phase and organic facies.Aqueous phase methylbenzene extraction, merges organic facies, and the organic facies after merging is washed to neutrality, is dried,
Being spin-dried for, under the conditions of 105-108 DEG C/20mmhg, decompression distillation is collected, and obtains product 69.2g, yield 70%, high performance liquid chromatography
(GC) detection purity is 95.2%.
The synthesis of step 2:4-(4,4-bis-fluoro-3-cyclobutenyl) iodobenzene (I-1-b)
In 1L there-necked flask, add 8g magnesium chips, 100ml oxolane, open stirring, logical nitrogen emptying air, be heated to back
Stream, first instills the tetrahydrofuran solution of 20ml 4-(4,4-bis-fluoro-3-cyclobutenyl) bromobenzene (by 74.1g 4-(4,4-bis-fluoro-3-
Cyclobutenyl) bromobenzene and the mixing of 100ml oxolane prepare) cause, to be triggered after keep instilling remaining 4-under micro-reflux state
The tetrahydrofuran solution of (4,4-bis-fluoro-3-cyclobutenyl) bromobenzene, drips off back flow reaction 1 hour.Cooling, temperature control-10～0 DEG C of instillation
The solution that 83.8g iodine is made into 250ml oxolane, drip off temperature control-10～0 DEG C continue to stir 0.5 hour.Addition 42g concentrated hydrochloric acid,
200ml water, stirring hydrolysis 10 minutes, separatory obtains aqueous phase and organic facies.Aqueous phase methylbenzene extraction, merges organic facies, by organic
Being washed to neutrality mutually, be dried, be spin-dried for, obtain product 83g, yield 94%, high performance liquid chromatography (GC) detection purity is 96.8%.
The synthesis of step 3:I-1
88.2g, 4-(4,4-bis-fluoro-3-cyclobutenyl) iodobenzene, 0.5g Hydro-Giene (Water Science)., 0.8g it is sequentially added in 1L there-necked flask
Triphenyl phosphorus, 1.5g tetra-(triphenyl phosphorus) palladium, 76g triethylamine, 300ml toluene, open stirring, logical nitrogen emptying air.Temperature control
43.8g ethoxybenzene acetylene is dripped between 20～25 DEG C.Temperature control 50-60 DEG C reacts 3 hours.React in backward reactant liquor and added
500ml water, separatory obtains aqueous phase and organic facies.Aqueous phase methylbenzene extraction, merges organic facies, organic facies is washed to neutrality, rotation
Dry.Adding in product and cross silicon gel column after petroleum ether dissolution, post liquid is spin-dried for, twice of dehydrated alcohol recrystallization of product, obtains product
65.5g, yield 70%, high performance liquid chromatography detection purity is 99.9%.
Detect through nuclear magnetic resonance analyser, mass spectrograph etc., determine shown in the structural formula as I-1 of this liquid-crystal compounds, mass spectrometric data
As follows: MS:m/s%312 (49.6), 284 (2.3), 235 (100), 207 (57.4)；
Nuclear magnetic data is as follows:1H-NMR: δ (ppm) 1.32 (t, 3H), 2.29 (m, 2H), 2.56 (t, 2H), 4.09 (m,
2H), 4.28 (t, 1H), 6.95 (d, 2H), 7.25 (d, 2H), 7.48 (d, 2H), 7.54 (d, 2H).
The character of compound I-1 is as follows:
MP:40.8 DEG C of clearing point of fusing point CP:58 DEG C
Dielectric coefficient Δ ε: 8.6 (20 DEG C, 589nm)
Optical anisotropy Δ n:0.25 (20 DEG C, 1000Hz)
Embodiment 2
Synthetic route is as follows:
Step:
88.2g, 4-(the 4,4-bis-fluoro-3-cyclobutenyl) iodobenzene (step 1 by embodiment 1 it is sequentially added in 1L there-necked flask
Obtain), 0.5g Hydro-Giene (Water Science)., 0.8g triphenyl phosphorus, 1.5g tetra-(triphenyl phosphorus) palladium, 76g triethylamine, 300ml toluene, unlatching is stirred
Mix, logical nitrogen emptying air.It is passed through acetylene gas between temperature control 20～25 DEG C.It is passed through acetylene gas to react 2 hours.After having reacted
Adding 500ml water in reactant liquor, separatory obtains aqueous phase and organic facies.Aqueous phase methylbenzene extraction, merges organic facies, by organic facies
It is washed to neutrality, is spin-dried for.Crossing silicon gel column after adding petroleum ether dissolution in product, post liquid is spin-dried for, and product dehydrated alcohol is heavily tied
Brilliant twice, obtaining product 75.2g, yield 70%, high performance liquid chromatography (GC) detection purity is 99.9%.
Detect through nuclear magnetic resonance analyser, mass spectrograph etc., determine shown in the structural formula as I-2 of this liquid-crystal compounds, mass spectrometric data
As follows: MS:m/s%358 (36.2), 281 (100), 204 (45.4)；
Nuclear magnetic data is as follows:1H-NMR: δ (ppm) 2.29 (m, 4H), 2.56 (t, 4H), 4.28 (t, 2H), 7.25 (d,
4H), 7.54 (d, 4H).
The character of compound I-2 is as follows:
Fusing point MP:43 DEG C
Dielectric coefficient Δ ε: 10 (20 DEG C, 589nm)
Optical anisotropy Δ n:0.26 (20 DEG C, 1000Hz)
Embodiment 3: the abutment Z of the liquid-crystal compounds shown in Formulas I1For carboxyl
The synthesis of step 1:I-3-a
Adding 8g magnesium chips (reactant), oxolane (solvent) dried for 100g at 500ml there-necked flask, nitrogen is protected,
It is heated to backflow, first dropping 5ml 74g (0.3mol) 4-(4,4-bis-fluoro-3-cyclobutenyl) bromobenzene (reactant) and 50g tetrahydrochysene furan
Mutter the mixed-liquor return 20 minutes of (solvent), initiation reaction, drip remaining mixed liquor the most again, drip complete, backflow half is little
Time, it being cooled to 10 DEG C, logical carbon dioxide (reactant), about half an hour, reaction no longer heats up, and keeps malleation about 10 DEG C to stir 10 points
Clock, after terminating, pours in 200g trash ice and 30ml hydrochloric acid and hydrolyzes, hydrolyze 20 minutes, and separatory takes upper organic phase, 200ml × 2 second
Acetoacetic ester (solvent) extracts aqueous phase, merges organic facies, and rotation boils off solvent, adds 25g sodium hydroxide and 300ml water, stirs 30 points
After clock, solid dissolves, the water washing filter cake of 100ml × 2, discards, under aqueous phase stirring after 20ml × 2 toluene (solvent) wash filtrate
Dropping 40ml hydrochloric acid, separates out white solid, filters, and washes filter cake with water the most neutral, drains, and dries, and 50ml re crystallization from toluene obtains
To white crystal 44.5g, yield 70%.
The synthesis of step 2:I-3
100g dichloromethane (solvent), 15.5g (0.1mol) 3,5-bis-fluoro-4-cyano group benzene is added in 500ml there-necked flask
Phenol (reactant), 30.9g (0.15mol) N, N '-dicyclohexylcarbodiimide, 2g N, N-dimethylamino naphthyridine, the lower dropping of stirring
The solution of 20g (0.095mol) 4-(4,4-bis-fluoro-3-cyclobutenyl) benzoic acid 100ml dichloromethane, is stirred at room temperature 12 hours.Cross
Filtering solid, filtrate is washed to neutral solvent evaporated again with the dilute hydrochloric acid solution of 100ml 5% after washing, add normal heptane post
Chromatography, solvent evaporated obtains white crystal 25.9g, yield 78%, high-efficient liquid phase color 2 times with 2 times of dehydrated alcohol (solvent) recrystallization
Spectrum (GC) detection purity is 99.8%.
Detect through nuclear magnetic resonance analyser, mass spectrograph etc., determine shown in the structural formula as I-3 of this liquid-crystal compounds, mass spectrometric data
As follows: MS:m/s%349 (2.1), 195 (100), 118 (15.3), 90 (2.6)；
Nuclear magnetic data is as follows:1H-NMR: δ (ppm) 2.29 (m, 2H), 2.56 (t, 2H), 4.28 (t, 1H), 6.97 (d,
2H), 7.47 (d, 2H), 8.17 (d, 2H).
The character of compound I-3 is as follows:
Fusing point MP:36 DEG C
Dielectric coefficient Δ ε: 19 (20 DEG C, 589nm)
Optical anisotropy Δ n:0.15 (20 DEG C, 1000Hz)
Can be by the similar method following compound of synthesis by changing different reactants:
Wherein,Synthetic method can be such that
Synthetic route:
The synthesis of step 1:I-4-a
Adding 8g magnesium chips (reactant), oxolane (solvent) dried for 100g at 500ml there-necked flask, nitrogen is protected,
It is heated to backflow, by (molten with the oxolane of 50g for 4-(4, the 4-bis-fluoro-3-cyclobutenyl) bromobenzene (reactant) of 74g (0.3mol)
Agent) mixing forms mixed liquor, and first drip the mixed-liquor return 20 minutes of 5ml, initiation reaction, drip remaining mixing the most again
Liquid, after dropping, refluxes half an hour, is cooled to 10 DEG C, drips dimethylformamide (reactant) 33g, about half an hour, reaction
No longer heat up, keep stirring 10 minutes at malleation about 10 DEG C, after reaction terminates, the liquid in there-necked flask is poured into 200g trash ice and
30ml hydrochloric acid is hydrolyzed, hydrolyzes 20 minutes, the liquid after hydrolysis is carried out separatory, takes upper organic phase, 200ml × 2 second
Acetoacetic ester (solvent) extracts aqueous phase, merges organic facies, and rotation boils off solvent, obtains light yellow liquid 53g, yield 90%.
The synthesis of step 2:I-4
Addition 100g methanol (solvent) in 500ml there-necked flask, 12.5g (0.2mol) 80% hydrazine hydrate (reactant),
19.6g (0.1mol) 4-(4,4-bis-fluoro-3-cyclobutenyl) benzaldehyde, is stirred at room temperature 12 hours.It is refrigerated to 0 DEG C and is filtered to remove solid
Body, then obtain white crystal 13.5g, yield 70% for 2 times with 2 times of dehydrated alcohol (solvent) recrystallization, high performance liquid chromatography (GC) is examined
Surveying purity is 99.90%.
Detect through nuclear magnetic resonance analyser, mass spectrograph etc., determine shown in the structural formula as I-3 of this liquid-crystal compounds, mass spectrometric data
As follows: MS:m/s%386 (2.1), 309 (100), 232 (15.3), 100 (2.6)；
Nuclear magnetic data is as follows:1H-NMR: δ (ppm) 2.29 (m, 2H), 2.56 (t, 2H), 4.28 (t, 2H), 7.34 (d,
4H), 7.78 (d, 4H), 8.40 (d, 2H).
The character of compound I-4 is as follows:
Fusing point MP:46 DEG C
Dielectric coefficient Δ ε: 19 (20 DEG C, 589nm)
Optical anisotropy Δ n:0.20 (20 DEG C, 1000Hz)
Two, the preparation of the liquid-crystal composition of above-mentioned liquid-crystal compounds is included
Only choose several preferred embodiment at this and illustrate that the compositions comprising above-mentioned liquid-crystal compounds has preferably
Performance, the present invention is not limited to these embodiments restrictions.
In the liquid-crystal composition of following embodiment, in addition to the liquid-crystal compounds shown in Formulas I, other each component by
Commercially available.
The liquid-crystal composition of embodiment 4～6 is prepared by each component being mixed to get.
Embodiment 4
Each component of liquid-crystal composition A and content (weight fraction wt.%) thereof are as shown in table 1:
Each component of table 1 liquid-crystal composition A and weight fraction table thereof
The physical property values of liquid-crystal composition A is as shown in table 2, and physical property values therein is for measuring initial value.
Method of testing
One, the method for testing of clearing point (Cp), the liquid crystal material performance issued by The Ministry of Information Industry of the People's Republic of China, MOII
In method of testing (SJ 20746-1999), the method for testing of liquid crystal material clearing point is measured.
Two, the method for testing of optical anisotropy (measuring at 25 DEG C) is as follows: measure at 25 DEG C, with wavelength 589nm's
Light, uses Abbe refractometer to be measured Δ n.Specifically, the surface of headprism (Pr I 3m) is rubbed in a direction
After, sample is added drop-wise on headprism.Refractive index n‖It is to measure institute's value, refraction when polarization direction is parallel with frictional direction
Rate n⊥Being to measure institute's value when polarization direction is vertical with frictional direction, the value of optical anisotropy Δ n is by Δ n=n‖-n⊥
Calculate.
Three, the method for testing of dielectric constant anisotropy (Δ ε measures at 25 DEG C) is as follows: by Hewlett-Packard HP4284a
LCR test set is measured.Measure the liquid crystal molecule DIELECTRIC CONSTANT ε at long axis direction‖, measure liquid crystal molecule in short axle side
To dielectric constant (ε⊥), dielectric constant anisotropy Δ ε passes through Δ ε=ε‖-ε⊥Calculate.
Four, rotary viscosity (γ1) detection method is as follows: rotary viscosity γ1Measuring at 20 DEG C, unit is cPa, uses
ToYo6254 liquid crystal comprehensive tester measures.
The detection method of the liquid-crystal composition of following embodiment, with this embodiment, follow-up repeats the most one by one.
The physical property values table of table 2 liquid-crystal composition A
| Performance parameter | Test initial value |
| Cp | 85℃ |
| Δn | 0.109 |
| Δε | 7.8 |
| γ1 | 75 |
As shown in Table 2, this liquid-crystal composition A has high clearing point, suitable optical anisotropy；Due to its viscous system
Number is less, therefore has relatively low rotary viscosity, owing to the coefficient of viscosity is less and dielectric coefficient is relatively big, therefore has and rings faster
Answer speed, be applicable in display panels.
Embodiment 5
Each component of liquid-crystal composition B and content (weight fraction wt.%) thereof are as shown in table 3:
Each component of table 3 liquid-crystal composition B and weight fraction table thereof
The physical property values of liquid-crystal composition B is as shown in table 4, and physical property values therein is for measuring initial value.
The physical property values table of table 4 liquid-crystal composition B
| Performance parameter | Test initial value |
| Cp | 94℃ |
| Δn | 0.125 |
| Δε | -5.6 |
| γ1 | 65 |
As shown in Table 4, this liquid-crystal composition B has high clearing point, suitable optical anisotropy；Due to its viscous system
Number is less, therefore has relatively low rotary viscosity, owing to the coefficient of viscosity is less and dielectric coefficient is relatively big, therefore has and rings faster
Answer speed, be applicable in display panels.
Embodiment 6
Each component of liquid-crystal composition C and content (weight fraction wt.%) thereof are as shown in table 5:
Each component of table 5 liquid-crystal composition C and weight fraction table thereof
The physical property values of liquid-crystal composition C is as shown in table 6, and physical property values therein is for measuring initial value.
The physical property values table of table 6 liquid-crystal composition C
| Performance parameter | Test initial value |
| Cp | 97℃ |
| Δn | 0.179 |
| Δε | 7.9 |
| γ1 | 76 |
As shown in Table 4, this liquid-crystal composition B has high clearing point, suitable optical anisotropy；Due to its viscous system
Number is less, therefore has relatively low rotary viscosity, owing to the coefficient of viscosity is less and dielectric coefficient is relatively big, therefore has and rings faster
Answer speed, be applicable in display panels.
Each component of liquid-crystal composition D and content (weight fraction wt.%) thereof are as shown in table 5:
Each component of table 7 liquid-crystal composition D and weight fraction table thereof
The physical property values of liquid-crystal composition D is as shown in table 8, and physical property values therein is for measuring initial value.
The physical property values table of table 8 liquid-crystal composition D
| Performance parameter | Test initial value |
| Cp | 87℃ |
| Δn | 0.112 |
| Δε | 7.8 |
| γ1 | 120 |
As shown in Table 8, the liquid-crystal composition D in comparative example does not comprise 4-(4, the 4-bis-fluoro-3-cyclobutenyl) benzene of the present invention
The compound of class, it has a relatively low clearing point, the bigger coefficient of viscosity and have relatively low optical anisotropy.
Obviously, those skilled in the art can carry out various change and the modification essence without deviating from the present invention to the present invention
God and scope.So, if these amendments of the present invention and modification belong to the scope of the claims in the present invention and equivalent technologies thereof
Within, then the present invention is also intended to comprise these change and modification.
Claims (10)
1. a liquid-crystal compounds, it is characterised in that the structural formula of described liquid-crystal compounds shown in formula I:
Wherein, L1And L2Separately selected from hydrogen or fluorine；
Abutment Z1Selected from-HC=N-N=CH-,-C ≡ C-or-COO-；
Abutment Z2Selected from-HC=N-N=CH-,-C ≡ C-or-COO-；
Ring A and ring B is separately selected from
End group R1Selected from fluorine ,-OCF3, cyano group, the alkyl of C1-C5 or the alkoxyl of C1-C5；
M and n is separately selected from 0,1,2 or 3, and m+n >=1.
2. liquid-crystal compounds as claimed in claim 1, it is characterised in that m+n=1 or 2.
3. liquid-crystal compounds as claimed in claim 1, it is characterised in that described liquid-crystal compounds particularly as follows:
4. the method preparing liquid-crystal compounds, it is characterised in that described liquid-crystal compounds shown in formula I:
Wherein, L1And L2Separately selected from hydrogen or fluorine；
Abutment Z1Selected from-C ≡ C-,-COO-or-HC=N-N=CH-；
Abutment Z2Selected from-HC=N-N=CH-,-C ≡ C-or-COO-；
Ring A and ring B is separately selected from
End group R1Selected from fluorine ,-OCF3, cyano group, the alkyl of C1-C5 or the alkoxyl of C1-C5；
M and n is separately selected from 0,1,2 or 3, and m+n >=1；
Abutment Z when the liquid-crystal compounds shown in Formulas I1During for alkynyl, described method includes: under the catalytic action of triphenylphosphine,
Bromobenzene propionic aldehyde will be reacted with chloro difluoro acetic acid sodium, generate 4-(4,4-bis-fluoro-3-cyclobutenyl) bromobenzene；By 4-, (4,4-bis-is fluoro-
3-cyclobutenyl) bromobenzene and iodine generation iodide reaction, generate 4-(4,4-bis-fluoro-3-cyclobutenyl) iodobenzene；By 4-(the fluoro-3-of 4,4-bis-
Cyclobutenyl) iodobenzene reacts with compound HC ≡ C-R, generates abutment Z1For the liquid-crystal compounds shown in the Formulas I of alkynyl, wherein R with
Liquid-crystal compounds shown in Formulas IIdentical；
Abutment Z when the liquid-crystal compounds shown in Formulas I1During for-COO, described method includes: under the catalytic action of triphenylphosphine,
Bromobenzene propionic aldehyde will be reacted with chloro difluoro acetic acid sodium, generate 4-(4,4-bis-fluoro-3-cyclobutenyl) bromobenzene；By 4-, (4,4-bis-is fluoro-
3-cyclobutenyl) bromobenzene and carbon dioxide generation carboxylation reaction, generate 4-(4,4-bis-fluoro-3-cyclobutenyl) benzoic acid；By 4-(4,
4-bis-fluoro-3-cyclobutenyl) there is esterification in benzoic acid and compound HO-R, generates abutment Z1For the liquid shown in the Formulas I of-COO
Crystallization compound, wherein R and the liquid-crystal compounds shown in Formulas IIdentical；
Abutment Z when the liquid-crystal compounds shown in Formulas I1During for-HC=N-N=CH-, described method includes: urging at triphenylphosphine
Under change effect, bromobenzene propionic aldehyde will be reacted with chloro difluoro acetic acid sodium, generate 4-(4,4-bis-fluoro-3-cyclobutenyl) bromobenzene；By 4-
(4,4-bis-fluoro-3-cyclobutenyl) bromobenzene reacts with dimethylformamide with magnesium generation grignard reaction again, generates 4-(4,4-bis-
Fluoro-3-cyclobutenyl) benzaldehyde；By 4-(4,4-bis-fluoro-3-cyclobutenyl) benzaldehyde and hydrazine hydrate generation condensation reaction, generate abutment
Z1For the liquid-crystal compounds shown in the Formulas I of-HC=N-N=CH-.
5. a liquid-crystal composition, it is characterised in that include at least one liquid-crystal compounds as described in claim 1
Liquid-crystal compounds shown in Formulas I.
6. liquid-crystal composition as claimed in claim 5, it is characterised in that in described liquid-crystal composition, the liquid crystal shown in Formulas I
The mass fraction of compound is 0.5%～30%.
7. liquid-crystal composition as claimed in claim 6, it is characterised in that described liquid-crystal composition includes:
Mass fraction is the compound of 18%:
Mass fraction is the compound of 10%:
Mass fraction is the compound of 7%:
Mass fraction is the compound of 9%:
Mass fraction is the compound of 7%:
Mass fraction is the compound of 8%:
Mass fraction is the compound of 4%:
Mass fraction is the compound of 4%:
Mass fraction is the compound of 10%:
Mass fraction is the compound of 4%:
Mass fraction is the compound of 5%:
Mass fraction is the compound of 5%:
Mass fraction is the compound of 5%:
Mass fraction is the compound of 4%:
8. liquid-crystal composition as claimed in claim 6, it is characterised in that described liquid-crystal composition includes:
Mass fraction is the compound of 24%:
Mass fraction is the compound of 5%:
Mass fraction is the compound of 12%:
Mass fraction is the compound of 8%:
Mass fraction is the compound of 4%:
Mass fraction is the compound of 4%:
Mass fraction is the compound of 8%:
Mass fraction is the compound of 8%:
Mass fraction is the compound of 15%:
Mass fraction is the compound of 8%:
Mass fraction is the compound of 4%:
9. liquid-crystal composition as claimed in claim 6, it is characterised in that described liquid-crystal composition includes:
Mass fraction is the compound of 20%:
Mass fraction is the compound of 10%:
Mass fraction is the compound of 6%:
Mass fraction is the compound of 5%:
Mass fraction is the compound of 4%:
Mass fraction is the compound of 6%:
Mass fraction is the compound of 7%:
Mass fraction is the compound of 7%:
Mass fraction is the compound of 7%:
Mass fraction is the compound of 8%:
Mass fraction is the compound of 4%:
Mass fraction is the compound of 4%:
Mass fraction is the compound of 6%:
Mass fraction is the compound of 6%:
10. a display panels, it is characterised in that include first substrate and the second substrate that box is put, and be positioned at
Liquid crystal layer between described first substrate and second substrate, described liquid crystal layer use as arbitrary in claim 5～9 as described in liquid
Crystal composite obtains.
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| CA1336441C (en) * | 1987-12-28 | 1995-07-25 | Manabu Uchida | Liquid crystal composition |
| JP2001328975A (en) * | 2000-05-22 | 2001-11-27 | Chisso Corp | Fluorinated alkenyl compound, liquid crystal composition and liquid crystal display element |
| JP5163635B2 (en) * | 2007-02-19 | 2013-03-13 | Ｊｎｃ株式会社 | Liquid crystal composition and liquid crystal display element |
| CN102399117A (en) * | 2010-09-16 | 2012-04-04 | 石家庄诚志永华显示材料有限公司 | Method for synthesis of 2'-fluoro terphenyl liquid crystal |
| CN102153441A (en) * | 2011-03-04 | 2011-08-17 | 石家庄诚志永华显示材料有限公司 | Fluorinated terphenyl liquid crystal compound containing two 3-butenyls and preparation method thereof |
| JP5961933B2 (en) * | 2011-06-24 | 2016-08-03 | Dic株式会社 | Liquid crystal composition having negative dielectric anisotropy, and liquid crystal display device using the liquid crystal composition |
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| CN103130649B (en) * | 2011-10-24 | 2014-10-22 | 财团法人工业技术研究院 | Liquid crystal compound and liquid crystal display |
| JP2012144732A (en) * | 2012-03-02 | 2012-08-02 | Dic Corp | Nematic liquid crystal composition and liquid crystal display element using the same |
| JP5962164B2 (en) * | 2012-04-17 | 2016-08-03 | Jnc株式会社 | Tricyclic compound having a plurality of CF2O bonding groups, liquid crystal composition, and liquid crystal display device |
| CN102675041B (en) * | 2012-05-15 | 2014-06-25 | 石家庄诚志永华显示材料有限公司 | Method for preparing trifluoromethyl-benzene-containing liquid crystals |
| CN103205262B (en) * | 2013-03-13 | 2014-11-05 | 江苏和成显示科技股份有限公司 | Liquid crystal composition and liquid crystal display device |
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| CN104513139A (en) * | 2013-09-30 | 2015-04-15 | 江苏和成新材料有限公司 | Liquid crystal compound with terminal position containing difluoroethylene group and difluoromethyleneoxyl group |
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