CN114149812B - Negative liquid crystal composition and application thereof - Google Patents
Negative liquid crystal composition and application thereof Download PDFInfo
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- CN114149812B CN114149812B CN202111614893.5A CN202111614893A CN114149812B CN 114149812 B CN114149812 B CN 114149812B CN 202111614893 A CN202111614893 A CN 202111614893A CN 114149812 B CN114149812 B CN 114149812B
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 111
- 239000000203 mixture Substances 0.000 title claims abstract description 68
- 150000001875 compounds Chemical class 0.000 claims abstract description 93
- RGOVYLWUIBMPGK-UHFFFAOYSA-N nonivamide Chemical compound CCCCCCCCC(=O)NCC1=CC=C(O)C(OC)=C1 RGOVYLWUIBMPGK-UHFFFAOYSA-N 0.000 claims description 10
- -1 3-substituted-4-methyleneoxy cyclohexyl compound Chemical class 0.000 abstract description 4
- 230000000704 physical effect Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- XBYJCVDSFWJBSM-OAHLLOKOSA-N n-[(2r)-5-(aminosulfonyl)-2,3-dihydro-1h-inden-2-yl]-2-propylpentanamide Chemical compound C1=C(S(N)(=O)=O)C=C2C[C@H](NC(=O)C(CCC)CCC)CC2=C1 XBYJCVDSFWJBSM-OAHLLOKOSA-N 0.000 description 16
- 125000004432 carbon atom Chemical group C* 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 10
- 239000003381 stabilizer Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 239000012043 crude product Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- PKIYFPSPIFCDDB-UHFFFAOYSA-N 4-ethoxy-2,3-difluorophenol Chemical compound CCOC1=CC=C(O)C(F)=C1F PKIYFPSPIFCDDB-UHFFFAOYSA-N 0.000 description 2
- WNJSZOGOYJDJMP-UHFFFAOYSA-N ClCOCCl.C1=CC=C(C=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound ClCOCCl.C1=CC=C(C=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 WNJSZOGOYJDJMP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- GOYDNIKZWGIXJT-UHFFFAOYSA-N 1,2-difluorobenzene Chemical compound FC1=CC=CC=C1F GOYDNIKZWGIXJT-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 101100208473 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) lcm-2 gene Proteins 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- 239000007875 V-40 Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003098 cholesteric effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000007704 transition 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
- C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
- C09K19/44—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing compounds with benzene rings directly linked
-
- 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
- C09K19/063—Non-steroidal liquid crystal compounds containing one non-condensed saturated non-aromatic ring, e.g. cyclohexane ring
-
- 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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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Nonlinear Science (AREA)
- Mathematical Physics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Liquid Crystal Substances (AREA)
Abstract
The invention relates to a negative liquid crystal composition and application thereof, and belongs to the field of liquid crystal materials. The negative liquid crystal composition comprises at least one 3-substituted-4-methyleneoxy cyclohexyl compound, the structure of which is shown as a general formula I,at least one compound of formula II:and at least one compound of formula III:
Description
Technical Field
The invention relates to a negative liquid crystal composition and application thereof, in particular to a negative liquid crystal composition containing at least one 3-substituted-4-methylenecyclohexyl compound and application thereof, and belongs to the field of liquid crystal materials.
Background
Liquid crystal display elements using a liquid crystal composition are widely used in displays for watches, calculators, word processors, and the like. These liquid crystal display elements use refractive index anisotropy, dielectric anisotropy, and the like of liquid crystal compounds.
The liquid crystal display element includes a liquid crystal composition having appropriate physical properties. General physical properties required for the liquid crystal compound as a component of the liquid crystal composition are as follows:
(1) Chemically and physically stable;
(2) Has a high clearing point (phase transfer temperature of liquid crystal phase-isotropic phase);
(3) The lower limit temperature of the liquid crystal phase (nematic phase, cholesteric phase, smectic phase, blue phase, etc. of the optically isotropic liquid crystal is low);
(4) Excellent compatibility with other liquid crystal compounds;
(5) A dielectric anisotropy of a suitable magnitude;
(6) Having a refractive index anisotropy of a suitable magnitude.
The liquid crystal composition comprising the chemically and physically stable liquid crystal compound according to (1) can improve the voltage holding ratio when used in a liquid crystal display element. In addition, if the liquid crystal composition is a liquid crystal composition comprising a liquid crystal compound having a low lower limit temperature of a high clearing point or a liquid crystal phase as described in (2) and (3), the temperature range of a nematic phase or an optically isotropic liquid crystal phase can be widened, and the liquid crystal composition can be used as a display element in a wide temperature range. In order to exhibit characteristics that are difficult to be exhibited by a single liquid crystal compound, a liquid crystal compound is generally used as a liquid crystal composition prepared by mixing a liquid crystal compound with a large number of other liquid crystal compounds. Therefore, the liquid crystal compound used in the liquid crystal display element is preferably excellent in compatibility with other liquid crystal compounds and the like as described in (4). In recent years, liquid crystal display elements having higher display performance, such as contrast, display capacity, response time characteristics, and the like, have been particularly demanded. Further, a liquid crystal composition having a low rotational viscosity and a low driving voltage is required for the liquid crystal material to be used.
The negative liquid crystal is mainly used for VA mode, and the response time of VA type liquid crystal display depends on the rotational viscosity and elastic constant of the liquid crystal composition. The lower the rotational viscosity, the faster the response time, the greater the elastic constant, and the faster the response time.
In the case of negative liquid crystals, the larger the absolute value of dielectric anisotropy of the liquid crystals, the lower the threshold voltage, and the display power consumption can be effectively reduced by using a liquid crystal display element made of a liquid crystal composition having a lower threshold voltage. By adding polymerizable compounds to the negative system, a mixture called PSVA is obtained, which, through appropriate UV light irradiation, can be pretilted to achieve a fast response, but it is well known that the negative liquid crystals generally have a smaller absolute value of dielectric negative than the positive liquid crystals and thus have a continuous negative liquid crystal requirement to obtain a larger absolute value of dielectric anisotropy.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a dielectric negative liquid crystal composition, which comprises a 3-substituted-4-methoxylidene cyclohexyl compound, a negative compound with methoxy connection groups, and a connection group with a single bond relative to C-C, wherein the negative compound has larger dielectric anisotropy, and the dielectric negativity of the compound can be further regulated by introducing substituent groups on adjacent cyclohexyl groups, so that the composition has larger dielectric absolute value, and the prepared liquid crystal display has lower threshold voltage and higher response speed.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a negative liquid crystal composition with negative dielectric anisotropy comprises at least one 3-substituted-4-methylenecyclohexyl compound with a structure shown in a general formula I,
at least one compound of formula II:
and at least one compound of formula III:
wherein, in the compound shown in the general formula I, R 1 、R 2 Respectively represents H, or alkyl, alkoxy or haloalkyl having 1 to 12 carbon atoms, wherein one or more-CH 2 Can be each independently bound by-O-, -CH=CH-, -C≡C-, -CO-O-or-O-CO-substitution, -CH 2 -the hydrogen on the group may be substituted by halogen; l represents an alkyl group or an alkoxy group having 1 to 5 carbon atoms; n represents 0 or 1.
Preferably, in the compound of formula I, R 1 、R 2 Respectively represents H, or alkyl, alkoxy or haloalkyl having 1 to 8 carbon atoms, wherein one or more-CH 2 Can be each independently bound by-O-, -CH=CH-, -C≡C-, -CO-O-or-O-CO-substitution, -CH 2 -groupThe hydrogen on may be substituted by halogen; l represents an alkyl group or an alkoxy group having 1 to 5 carbon atoms; n represents 0 or 1.
In the compounds of the formulae II-III, ring A represents
R A1 、R A2 、R B1 、R B2 Each independently of the others represents an alkyl group of 1 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, or an alkenyl group of 2 to 12 carbon atoms;
ring B1 represents
Ring B2 representsWherein one or more H on the benzene ring may be substituted with F or Cl;
a represents 0 or 1; b represents 1 or 2.
Preferably, the compound of formula I is selected from one or more of the group of compounds of formulas I-1 and I-2:
wherein R is 1 、R 2 And L has the same meaning as in formula I.
Further, the compound represented by the general formula I-1 is selected from the group of compounds represented by the structural formulas I-1-1 to I-1-30:
further, the compound represented by the general formula I-2 is selected from the group of compounds represented by the structural formulas I-2-1 to I-2-30:
in the liquid crystal composition of the present invention, the mass content of the compound represented by the general formula I is 0.01 to 60%, preferably 0.01 to 50%, more preferably 0.01 to 40%.
In some embodiments of the present invention, it is preferred that the compound of formula II comprises 1 to 60%, more preferably 5 to 50% by weight of the total weight of the negative liquid crystal composition.
In some embodiments of the present invention, it is preferred that the compound represented by formula II is selected from one or more of the group consisting of the following compounds II-1 to II-32:
in some embodiments of the present invention, it is preferred that the compound of formula III comprises 1 to 59%, more preferably 4 to 49% by weight of the total weight of the negative liquid crystal composition.
In some embodiments of the present invention, preferably, the compound of formula III is selected from one or more of the group consisting of the following compounds III-1 to III-63:
the negative liquid crystal composition of the invention comprises one or more liquid crystal compounds shown in a general formula IV in addition to one or more compounds shown in general formulas I, II and III, wherein the general formula IV has the structure:
wherein, in the general formula IV, R 41 、R 42 Each independently represents an alkyl group of 1 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, or an alkenyl group of 2 to 12 carbon atoms.
In some embodiments of the present invention, the compound of formula IV preferably comprises 1-60%, more preferably 5-50% of the total weight of the negative liquid crystal composition.
In some embodiments of the present invention, preferably, the compound represented by the general formula IV is selected from one or more compounds from the group consisting of the following compounds IV-1 to IV-16:
in some embodiments of the present invention, a compound having a structure represented by the following formula V may be further added to the negative liquid crystal composition:
wherein R is 5 And R is 6 The same or different, each independently represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms;
rings D1, D2, D3, D4 are each independently representedWherein one or more H on the benzene ring may be substituted with F or Cl.
In some embodiments of the present invention, it is preferred that the compound of formula V comprises 0 to 15%, preferably 0 to 10%, more preferably 0 to 8%, even more preferably 2 to 8% by weight of the total weight of the negative liquid crystal composition.
In some embodiments of the present invention, preferably, the compound represented by general V is selected from one or more of the group consisting of the following compounds V-1 to V-40:
the negative liquid crystal composition of the invention comprises one or more polymerizable liquid crystal compounds shown in a general formula VI in addition to one or more compounds shown in a general formula I, II, III, IV, V, wherein the general formula VI has a structure as follows:
wherein, in the general formula VI, R 3 、R 4 Each independently represents an acrylate or methacrylate; l (L) 51 、L 52 、L 53 、L 54 、L 55 、L 56 Each independently represents H, F, methyl, methoxy or ethoxy; d represents 0 or 1.
Preferably, the compound of formula VI is selected from one or more of the compounds of formulas VI-1 to VI-7:
wherein R is 3 、R 4 The meaning of (C) is as in formula VI.
Further preferably, the compound of formula VI is selected from one or more of the group of compounds of formulae VI-1-1 to VI-7-1:
in the liquid crystal composition of the present invention, the polymerizable compound represented by the general formula VI is used in an amount of 0.1 to 3% by weight based on the total weight of the liquid crystal composition, preferably 0.2 to 0.5% by weight based on the total weight of the liquid crystal composition.
In another aspect, the present invention provides liquid crystal compositions having negative dielectric anisotropy, further comprising one or more additives known to those skilled in the art and described in the literature, such as stabilizers and the like.
For example, one or more of the stabilizers having the following structures may be added to the liquid crystal mixture of the present invention:
preferably, the stabilizer is selected from one or more of the stabilizers with the following structures:
in the stabilizer, n represents an integer of 1 to 8.
In an embodiment of the invention, the stabilizer comprises 0-5%, preferably 0.01-5% of the total weight of the liquid crystal composition; more preferably, the stabilizer comprises 0-1% of the total weight of the liquid crystal composition; as a particularly preferred embodiment, the stabilizer comprises 0.01 to 0.2% by weight of the total weight of the liquid crystal composition.
The application of the negative liquid crystal composition in preparing a liquid crystal display device comprises VA, MVA, PVA, PSVA, IPS and FFS mode liquid crystal display devices. The liquid crystal composition of the present invention is applicable to liquid crystal display devices, preferably VA-type liquid crystal display devices such as VA/MVA/PVA/PSVA and/or IPS and FFS mode liquid crystal display devices, more preferably MVA/PVA/PSVA mode liquid crystal displays, and even more preferably PSVA mode liquid crystal displays.
The invention has the advantages that:
the compound adopted by the invention has stable chemical and physical properties, good low-temperature intersolubility, larger absolute value of dielectric anisotropy and moderate refractive index anisotropy, and has wide application.
The negative liquid crystal composition has good low-temperature intersolubility, large elastic constant and shortened response time.
Detailed Description
For convenience of expression, in the following examples, the group structures of the liquid crystal compositions are represented by codes listed in Table 1.
TABLE 1 group Structure codes for liquid Crystal Compounds
Take the following compounds as examples:
the code in Table 1 is used to represent 3CWO4,3 for cyclohexyl, C for cyclohexane, W for 2, 3-difluorobenzene and 4 for butyl.
The shorthand designations for the test items in the following examples are as follows:
cp (. Degree. C.): clearing point (nematic-isotropic phase transition temperature);
an: refractive index anisotropy (589 nm,25 ℃);
Δε: dielectric anisotropy (1 KHz,25 ℃);
γ 1 : represents the rotational viscosity [ mPa.s ] measured at 25 DEG C]；
Wherein Δε=ε || -ε ⊥ Wherein ε is || For dielectric constant parallel to the molecular axis ε ⊥ For dielectric constants perpendicular to the molecular axis, test conditions: 25 ℃ and 1KHz.
Example 1
The synthesis of compound 3C (1) 1OWO2 (I-1-18) is specifically prepared as follows:
(1) Synthesis of 3C (1) 1K
Adding 100ml of THF into a 500ml reaction bottle, adding 41.0g of chloromethyl ether triphenylphosphine salt, cooling to-10 to-20 ℃ under nitrogen, then heating to 0 ℃ and stirring for reacting for 1h, slowly dropwise adding 15.4g/50ml of THF solution of 3C (1) K, reacting for 4h at room temperature, filtering, adding 200ml of ethyl acetate and 100ml of water into filtrate for layering, extracting a water layer, merging organic layers, washing with water, drying, concentrating to obtain an intermediate, adding 200ml of toluene and 2.3g of formic acid into the obtained intermediate, stirring for 8h at room temperature, washing with water, washing with sodium bicarbonate solution, washing with water of the organic layers, drying, concentrating to obtain 13.4g of 3C (1) 1K, and obtaining 80% of yield.
(2) Synthesis of 3C (1) 1H
A500 ml reaction bottle is added with 16g of 3C (1) 1K, 100ml of methanol, cooled to 0 ℃, 1.1g of sodium borohydride is added in batches, then the temperature is kept for 1h at 0 ℃, the reaction is carried out for 1h at room temperature, 20ml of ammonium chloride aqueous solution is added into the reaction solution, the methanol is removed by rotary evaporation, 100ml of ethyl acetate is used for extraction, water washing and drying, the crude product is obtained by concentration, and the product 3C (1) 1H 13.6g is obtained by ethyl acetate/petroleum ether silica gel column chromatography, and the yield is 80%.
(3) Synthesis of 3C (1) 1OTs
250ml of dichloromethane and 19g of pyridine are added into a 500ml three-port bottle, 3CC (1) 1H 17.8g and p-toluenesulfonyl chloride 27.6g are sequentially added, the temperature is controlled between 20 ℃ and 25 ℃ for reaction for 8 hours, 90ml of water is added, standing and layering are carried out, 30ml of dichloromethane is used for extracting the water phase twice, 100ml of diluted hydrochloric acid is used for merging the organic layers, 100ml of water is used for washing to neutrality, a crude product 3C (1) 1OTs is obtained after solvent is removed by rotary evaporation, a proper amount of absolute ethyl alcohol is used for recrystallization, a white solid is obtained after recrystallization, a proper amount of dichloromethane and petroleum ether mixed solvent is used for obtaining 24.3g of 3C (1 OTs, HPLC is more than or equal to 98%, and the yield is 75%.
(4) Synthesis of 3C (1) 1OWO2
32.4g of 3C (1) 1OTs,17.4g of 2, 3-difluoro 4-ethoxyphenol, 110ml of DMF and 11g of sodium hydroxide are added into a 500ml three-port bottle, stirred and heated to 80 ℃ for reaction for 4 hours, cooled to 0 ℃,100ml of water is added, ice salt water is cooled to 0 ℃, white solid is separated out, the 3C (1) 1OWO crude product is obtained after suction filtration and air drying, the crude product is subjected to silica gel and alumina column chromatography by using methylbenzene as eluent, and then a proper amount of absolute ethyl alcohol is used for recrystallization to obtain 22.8g of a product, and the yield is 70%. GC 99%, molecular formula: c (C) 19 H 28 F 2 O 2 。
The obtained product was analyzed by nuclear magnetic resonance hydrogen spectroscopy, and the result was: 1 H NMR(300MHz,CDCl 3 )δ7.35–6.35(m,2H),4.51–3.68(m,4H),2.21–1.11(m,18H),1.00–0.65(m,6H)。
example 2
The synthesis of the compound 3CC (1) 1OWO2 (I-2-18) comprises the following specific synthesis steps:
(1) Synthesis of 3CC (1) 1K
Adding 100ml of THF into a 500ml reaction bottle, adding 41.0g of chloromethyl ether triphenylphosphine salt, cooling to-10 to-20 ℃ under nitrogen, then heating to 0 ℃ and stirring for reacting for 1h, slowly dropwise adding 23.6g/50ml of THF solution of 3C (1) K, reacting for 4h at room temperature, filtering, adding 200ml of ethyl acetate and 100ml of water into filtrate for layering, extracting a water layer, merging organic layers, washing with water, drying, concentrating to obtain an intermediate, adding 200ml of toluene and 2.3g of formic acid into the obtained intermediate, stirring for 8h at room temperature, washing with water, washing with sodium bicarbonate solution, washing with water of the organic layers, drying, concentrating to obtain 20.5g of 3C (1) 1K, and obtaining 82% of yield.
(2) Synthesis of 3CC (1) 1H
Adding 12.5g of 1K 3CC (1) into a 500ml reaction bottle, cooling to 0 ℃ with 60ml of methanol, adding 0.6g of sodium borohydride in batches, then preserving the heat for 1h at 0 ℃, reacting for 1h at room temperature, adding 15ml of ammonium chloride aqueous solution into the reaction solution, removing methanol by rotary evaporation, extracting with 80ml of ethyl acetate, washing with water, drying, concentrating to obtain a crude product, and obtaining 10.1g of 3CC (1) 1H product by ethyl acetate/petroleum ether silica gel column chromatography with the yield of 80%.
(3) Synthesis of 3CC (1) 1OTs
250ml of dichloromethane and 27g of pyridine are added into a 500ml three-port bottle, 3CC (1) 1H 25.2g and p-toluenesulfonyl chloride 20.4g are sequentially added, the temperature is controlled at 20-25 ℃ for reaction for 8 hours, 90ml of water is added, standing and layering are carried out, 30ml of dichloromethane is used for extracting the water phase twice, 100ml of diluted hydrochloric acid is used for merging the organic layers, 100ml of 2 water is used for washing to neutrality, a proper amount of absolute ethyl alcohol is added for recrystallization after solvent is removed by rotary evaporation, 30.4g of 3CC (1 OTs) is obtained by recrystallization by adding a proper amount of mixed solvent of dichloromethane and petroleum ether, HPLC is more than or equal to 98%, and the yield is 75%.
(4) Synthesis of 3CC (1) 1OWO2
40.6g of 3CC (1) 1OTs,17.4g of 2, 3-difluoro 4-ethoxyphenol, 110ml of DMF and 11g of sodium hydroxide are added into a 500ml three-port bottle, stirred and heated to 80 ℃ for reaction for 4 hours, cooled to 0 ℃,100ml of water is added, ice salt water is cooled to 0 ℃, white solid is separated out, the 3C (1) 1OWO crude product is obtained after suction filtration and air drying, the crude product is subjected to silica gel and alumina column chromatography by using methylbenzene as eluent, and then a proper amount of absolute ethyl alcohol is used for recrystallization to obtain 30.6g of a product, and the yield is 75%. GC 99%, molecular formula: c (C) 25 H 38 F 2 O 2 。
The obtained product was analyzed by nuclear magnetic resonance hydrogen spectroscopy, and the result was: 1 H NMR(300MHz,CDCl 3 )δ7.19–6.34(m,2H),4.45–3.74(m,4H),2.24–1.07(m,32H),1.01–0.66(m,6H)。
comparative example 1: the compound LCM-D1 was prepared as a mixture according to the weight percentage of each compound listed in Table 2, and was filled between two substrates of a liquid crystal display for performance test, and the test data are shown in Table 2.
TABLE 2 comparative example 1 composition (wt%) and test Properties of liquid crystal composition
| Component (A) | Percentage of | Performance of | |
| 3CC2 | 20 | Cp | 74.9.0 |
| 4CC3 | 6 | Δn | 0.1000 |
| 5CC3 | 5 | Δε | -2.6 |
| 5PP1 | 16 | γ 1 | 83 |
| 3CWO2 | 6 | Ts-N | -20 |
| 3CCWO2 | 5 | K11 | 15.2 |
| 2CPWO2 | 12 | K33 | 16.1 |
| 3CPWO2 | 9 | Low temperature storage | Crystallization at-20 ℃ for 168h |
| 3CPO2 | 4 | ||
| 2CCWO2 | 7 | ||
| 4CCWO2 | 10 | ||
| Totals to | 100 |
Application example 1
Liquid crystals were prepared using the compound 3C (1) 1OWO2 as a component to obtain a mixture LCM-1, which was filled between two substrates of a liquid crystal device for performance test, and test data are shown in table 3.
TABLE 3 composition (wt%) and test Properties of liquid Crystal composition of application example 1
Application example 2
The contents of the components were unchanged, and a mixture LCM-2 was obtained, which was filled between two substrates of a liquid crystal display for performance test, and the test data are shown in table 4.
TABLE 4 composition (wt%) and test Properties of liquid Crystal composition of application example 2
| Component (A) | Percentage of | Performance of | |
| 3CC2 | 20 | Cp | 75.0 |
| 4CC3 | 6 | Δn | 0.1000 |
| 5CC3 | 5 | Δε | -3.2 |
| 5PP1 | 16 | γ 1 | 82 |
| 3C(1)1OWO2 | 6 | ||
| 3CPWO4 | 5 | K11 | 15.3 |
| 2CPWO2 | 12 | K33 | 16.0 |
| 3CPWO2 | 9 | Low temperature storage | Non-crystallized at-30 ℃ for 240h |
| 3CPO2 | 4 | ||
| 2CC(1)1OWO2 | 7 | ||
| 3CC(1)1OWO2 | 10 | ||
| Totals to | 100 |
Application example 3
The components were the same and varied in content to obtain a mixture LCM-3, which was filled between two substrates of a liquid crystal display for performance testing, and the test data are shown in table 5.
TABLE 5 composition (wt%) and test Properties of liquid Crystal composition of application example 3
| Component (A) | Percentage of | Performance of | |
| 3CC2 | 20 | Cp | 75.0 |
| 4CC3 | 7 | Δn | 0.1000 |
| 5CC3 | 5 | Δε | -3.5 |
| 3PP1 | 16 | γ 1 | 82 |
| 2C(1)1OWO2 | 6 | ||
| 3C(1)1OWO2 | 3 | K11 | 15.4 |
| 2CPWO2 | 12 | K33 | 16.2 |
| 3CPWO2 | 9 | Low temperature storage | Non-crystallized at-30 ℃ for 240h |
| 3CPO2 | 5 | ||
| 2CC(1)1OWO2 | 7 | ||
| 3CC(1)1OWO2 | 10 | ||
| Totals to | 100 |
Application example 4
The liquid crystal composition LCM-1 of application example 1 was compounded with a polymerizable monomer selected from the group consisting of those represented by the general formula VI-1 in the proportions shown in Table 6 to give PSVA mixture PA-1.
TABLE 6 composition (wt%) of liquid crystal composition of application example 4
| LCM-1 | VI-1 | |
| PA-1 | 100 | 0.3 |
The formulated PSVA mixture PA-1 was filled into standard VA test cells and dried using UV (365 nm 60 mw/cm) 2 ) The threshold voltage and response time were measured by irradiation for two minutes at 20V applied voltage, and the test results are shown in table 7.
TABLE 7 test Properties of liquid Crystal compositions
The liquid crystal composition of the present invention may further comprise 0 to 5% of a stabilizer.
The liquid crystal composition of the present invention has a larger absolute value of dielectric anisotropy, so that a lower threshold voltage can be obtained, and in addition, the liquid crystal composition has low viscosity, large elastic constant, suitable optical anisotropy, good low-temperature intersolubility, and can reduce the response time of a liquid crystal display, thereby solving the problem of slow response speed of the liquid crystal display. Therefore, the liquid crystal composition provided by the invention is suitable for VA display modes such as VA/MVA/PVA/PSVA and the like and IPS and FFS type TFT liquid crystal display devices; is especially suitable for MVA, PVA, PSVA and other liquid crystal display devices.
Claims (5)
1. A negative-working liquid crystal composition characterized in that: consists of the following compounds in percentage by mass: 20% of compound 3CC2:
6% of compound 4CC3:
5% of compound 5CC3:
16% of compound 5PP1:
16% of compound 3C (1) 1OWO2:
5% of Compound 3CCWO2:
12% of Compound 2CPWO2:
compound 3CPWO2 at 9%:
4% of Compound 3CPO2:
7% of compound 2C (1) 1OWO2:
2. a negative-working liquid crystal composition characterized in that: consists of the following compounds in percentage by mass: 20% of compound 3CC2:
6% of compound 4CC3:
5% of compound 5CC3:
16% of compound 5PP1:
6% of compound 3C (1) 1OWO2:
5% of Compound 3CPWO4:
12% of Compound 2CPWO2:
compound 3CPWO2 at 9%:
4% of Compound 3CPO2:
7% of compound 2CC (1) 1OWO2:
10% of compound 3CC (1) 1OWO2:
3. a negative-working liquid crystal composition characterized in that: consists of the following compounds in percentage by mass:
20% of compound 3CC2:
7% of compound 4CC3:
5% of compound 5CC3:
16% of compound 3PP1:
6% of compound 2C (1) 1OWO2:
3% of compound 3C (1) 1OWO2:
12% of Compound 2CPWO2:
compound 3CPWO2 at 9%:
5% of Compound 3CPO2:
7% of compound 2CC (1) 1OWO2:
10% of compound 3CC (1) 1OWO2:
4. use of the negative liquid crystal composition according to any one of claims 1 to 3 for the preparation of a liquid crystal display device.
5. The use according to claim 4, characterized in that: the liquid crystal display device includes VA, MVA, PVA, PSVA, IPS and FFS mode liquid crystal display devices.
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| CN105518105A (en) * | 2013-09-06 | 2016-04-20 | Dic株式会社 | Nematic liquid crystal composition and liquid crystal display element using same |
| CN105637065A (en) * | 2013-10-08 | 2016-06-01 | Dic株式会社 | Nematic liquid crystal composition and liquid crystal display element using same |
| CN108690641A (en) * | 2018-07-27 | 2018-10-23 | 烟台丰蓬液晶材料有限公司 | Liquid crystal composition containing bis-trifluoromethyl compound and negative dielectric anisotropy and application thereof |
| CN108822872A (en) * | 2018-06-08 | 2018-11-16 | 烟台丰蓬液晶材料有限公司 | Liquid crystal composition with extremely low negative dielectric anisotropy and application thereof |
| JP2020023592A (en) * | 2016-12-06 | 2020-02-13 | Dic株式会社 | Liquid crystal composition, liquid crystal display element and liquid crystal display |
| CN112143508A (en) * | 2020-10-09 | 2020-12-29 | 烟台显华化工科技有限公司 | Liquid crystal compound with negative dielectric anisotropy, liquid crystal composition and liquid crystal display device |
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| CN105518105A (en) * | 2013-09-06 | 2016-04-20 | Dic株式会社 | Nematic liquid crystal composition and liquid crystal display element using same |
| CN105637065A (en) * | 2013-10-08 | 2016-06-01 | Dic株式会社 | Nematic liquid crystal composition and liquid crystal display element using same |
| JP2020023592A (en) * | 2016-12-06 | 2020-02-13 | Dic株式会社 | Liquid crystal composition, liquid crystal display element and liquid crystal display |
| CN108822872A (en) * | 2018-06-08 | 2018-11-16 | 烟台丰蓬液晶材料有限公司 | Liquid crystal composition with extremely low negative dielectric anisotropy and application thereof |
| CN108690641A (en) * | 2018-07-27 | 2018-10-23 | 烟台丰蓬液晶材料有限公司 | Liquid crystal composition containing bis-trifluoromethyl compound and negative dielectric anisotropy and application thereof |
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