CN106635052A - Liquid crystal compound having negative dielectric anisotropy and application thereof - Google Patents
Liquid crystal compound having negative dielectric anisotropy and application thereof Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 83
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 78
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- RGOVYLWUIBMPGK-UHFFFAOYSA-N nonivamide Chemical compound CCCCCCCCC(=O)NCC1=CC=C(O)C(OC)=C1 RGOVYLWUIBMPGK-UHFFFAOYSA-N 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000013213 extrapolation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 2
- RKWWASUTWAFKHA-UHFFFAOYSA-N 1-bromo-2,3-difluorobenzene Chemical compound FC1=CC=CC(Br)=C1F RKWWASUTWAFKHA-UHFFFAOYSA-N 0.000 description 1
- VTNFFMYGXVMSND-UHFFFAOYSA-N CC(CC1)COC1c(c(C)cc(C1=CCC(C)C(F)=C1F)c1F)c1F Chemical compound CC(CC1)COC1c(c(C)cc(C1=CCC(C)C(F)=C1F)c1F)c1F VTNFFMYGXVMSND-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- -1 I-A-9 Chemical class 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- ANUZKYYBDVLEEI-UHFFFAOYSA-N butane;hexane;lithium Chemical compound [Li]CCCC.CCCCCC ANUZKYYBDVLEEI-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/04—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- 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
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- 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
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
-
- 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
-
- 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
- G02F1/137—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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Liquid Crystal Substances (AREA)
Abstract
The invention provides a liquid crystal compound having negative dielectric anisotropy, which is shown in a general formula I. The liquid crystal compound has large dielectric anisotropy absolute value, high voltage conservation rate, good intersolubility and good light stability and low-temperature stability, and the invention also provides a preparation process of the liquid crystal compound has the advantages of easy acquisition and simple synthesis route, and is suitable for large-scale industrial production. The invention also provides a liquid crystal composition containing the liquid crystal compound, and the liquid crystal composition has good liquid crystal performance.
Description
Technical Field
The invention relates to a liquid crystal compound, in particular to a liquid crystal compound with negative dielectric anisotropy and a synthesis method and application thereof.
Background
Liquid crystal display elements are used in various household electric appliances such as watches and calculators, measuring instruments, automobile panels, word processors, computers, printers, televisions, and the like. Typical examples of the night view display mode include PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), IPS (in-plane switching), VA (vertical alignment), CSH (color super homeotropic), and the like. The driving method of the element is classified into a PM (passive matrix) type and an AM (active matrix) type. PM is classified into static (static) and multiplex (multiplex) types. AM is classified into a TFT (thin film transistor), an MIM (metal insulator metal), and the like. The types of TFTs are amorphous silicon (amorphous silicon) and polycrystalline silicon (polysilicon). The latter is classified into a high temperature type and a low temperature type according to a manufacturing process. Liquid crystal display elements are classified into a reflection type using natural light, a transmission type using backlight, and a semi-transmission type using both light sources of natural light and backlight, depending on the type of light source.
Among these display modes, IPS mode, ECB mode, VA mode, CSH mode, and the like are different from TN mode or STN mode which are currently used in general in that the former uses a liquid crystal material having negative dielectric anisotropy. Among these display systems, VA display by AM driving is particularly applied to display elements requiring high speed and wide viewing angle, and among them, liquid crystal elements such as televisions are most expected.
The liquid crystal material used in any display mode is required to have a low driving voltage, a high response speed, a wide operating temperature range, a large absolute value of negative dielectric anisotropy, a high phase transition temperature, and good miscibility. However, the conventional liquid crystal composition has a highly conjugated molecular structure and tends to have poor compatibility with other liquid crystal materials, and thus it is difficult to use the liquid crystal composition as a component of a liquid crystal composition having good electrical characteristics. In addition, a liquid crystalline compound used as a component of a liquid crystal composition which requires light stability, such as a thin film transistor liquid crystal display device, is required to have high stability. In contrast, a liquid crystal display element containing a liquid crystal composition having a large absolute value of dielectric anisotropy can reduce the base voltage value, reduce the driving voltage, and further reduce the power consumption.
For a long time, a large number of liquid crystal compounds in which hydrogen on the benzene ring is substituted have been studied as a component of a liquid crystal composition having negative dielectric anisotropy which can be used for a liquid crystal display element.
Osman, m.a. at molec. crystals liq. crystals,82,295. negative dielectric anisotropy compounds of ref.1 structure are disclosed:
the compound Ref.1 has a large negative dielectric anisotropy due to the two cyano groups on the side of the molecule (literature value-20). This document also indicates that such lateral dicyano-based negative dielectric anisotropy compounds have the following disadvantages: 1) the viscosity is high; 2) the miscibility with the liquid crystal monomer is poor; 3) the light stability is poor. Due to the above disadvantages, the use of such negative compounds is limited.
Ref.2, Ref.3 fluorine-containing negative compounds were proposed by Reiffenrath et al in liquid crystals, 1989, Vol.5, No.1,159-170 to avoid the disadvantages of dicyano-negative compounds:
although side fluorine-containing negative compounds such as Ref.2 and Ref.3 avoid the disadvantages of dicyano negative compounds, they cause the problem that the negative dielectric anisotropy value is too small (Ref.2 dielectric anisotropy value is-4.1, Ref.3 dielectric anisotropy value is-6.0). Therefore, lateral fluorine-containing compounds with large negative dielectrics are still sought.
Therefore, in order to meet the increasing application demands, there is a continuing need in the art for improved liquid crystal compounds of negative dielectric anisotropy.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a liquid crystal compound which has a large absolute value of dielectric anisotropy, low viscosity, higher voltage holding ratio, good intersolubility and good light stability and low-temperature stability, so that a composition containing the liquid crystal compound has the advantages of large dielectric anisotropy, low threshold voltage, high response speed, high contrast, good intersolubility and good light stability and low-temperature stability.
Another object of the present invention is to provide a method for synthesizing the above liquid crystal composition.
The invention also aims to provide the liquid crystal composition prepared from the liquid crystal compound and an application of the liquid crystal composition in a display.
The technical scheme is as follows: in order to accomplish the above object of the present invention, the present invention provides a compound having negative dielectric anisotropy, the compound having a structure of general formula i:
wherein,
R1and R2The same or different, each independently represents an alkyl group of 1 to 10 carbon atoms;
X1and X2Each independently represents-O-or-CH2-；
Z represents a single bond, -CH2O-、-CH2CH2-, -COO-or-CH ═ CH-.
In some embodiments of the invention, R is1And R2The same or different, each independently represents an alkyl group of 1 to 6 carbon atoms.
In some embodiments of the invention, Z represents a single bond, -CH2O-or-CH2CH2-。
In some embodiments of the invention, Z represents a single bond or-CH2CH2-。
In some embodiments of the invention, the compound of formula I is selected from the group consisting of one or more of the following formulae I-A to I-F:
and
wherein,
the R1 and R2 are the same or different and each independently represents an alkyl group of 1 to 6 carbon atoms.
In some embodiments of the invention, the compound of formula i is preferably selected from the group consisting of one or more of the following formulae:
and
wherein,
the R1 and R2 are the same or different and each independently represents an alkyl group of 1 to 6 carbon atoms.
In some embodiments of the invention, the compounds of formula I-A are preferably selected from the group consisting of one or more of the following structures:
and
in some embodiments of the invention, the compounds of formula I-B are preferably selected from the group consisting of one or more of the following structures:
and
in some embodiments of the invention, the compounds of formulae I-C are preferably selected from the group consisting of one or more of the following structures:
and
in some embodiments of the invention, the compounds of formulae I-D are preferably selected from the group consisting of one or more of the following structures:
and
in some embodiments of the invention, the compounds of formulae I-E are preferably selected from the group consisting of one or more of the following structures:
and
in some embodiments of the invention, the compounds of formulae I-F are preferably selected from the group consisting of one or more of the following structures:
and
in another aspect of the present invention, there is provided a liquid crystal composition comprising the liquid crystal compound of formula I of the present invention.
In some embodiments of the present invention, the liquid crystal composition further comprises one or more of the group consisting of formulas II, III, and/or IV:
and
wherein,
the R is3、R4、R5、R6、R7And R8The same or different, each independently represents a substituted or unsubstituted, linear or branched alkyl or alkoxy group of 1 to 10 carbon atoms, a substituted or unsubstituted, linear or branched alkenyl or alkenyloxy group of 2 to 10 carbon atoms, wherein one or more-CH2-may be substituted by-O-, with the proviso that the oxygen atoms are not directly attached;
m and n are the same or different and each independently represents 0 or 1.
Another aspect of the present invention provides a display device comprising the liquid crystal composition of the present invention.
The invention also provides application of the liquid crystal composition in VA, FFS, IPS and PSVA display modes.
Has the advantages that: compared with other negative liquid crystal compounds in the prior art, the liquid crystal compound with the general formula I has larger absolute value of dielectric anisotropy, low viscosity and high voltage holding ratio, and the composition containing the liquid crystal compound has large dielectric anisotropy, low threshold voltage, high response speed, high contrast, good intersolubility, good light stability and low-temperature stability; in addition, the preparation process of the liquid crystal compound with the general formula I has the advantages of easily obtained raw materials, simple and feasible synthetic route and suitability for large-scale industrial production.
Detailed Description
The invention will be illustrated below with reference to specific embodiments. It should be noted that the following examples are illustrative of the present invention, and are not intended to limit the present invention. Other combinations and various modifications within the spirit or scope of the present invention may be made without departing from the spirit or scope of the present invention.
For convenience of expression, in the following examples, the group structures of the liquid crystal compounds are represented by the codes listed in Table 1:
TABLE 1 radical structural code of liquid crystal compounds
The abbreviated codes of the test items in the following examples are as follows:
cp: clearing Point (nematic-isotropic phase transition temperature, degree C.)
Δ n refractive index anisotropy (589nm, 20 ℃ C.)
Delta dielectric anisotropy (1KHz, 25 ℃ C.)
VHR initial Voltage holding ratio (%)
Wherein, the refractive index anisotropy is obtained by testing an Abbe refractometer under a sodium lamp (589nm) light source at 25 ℃; the dielectric test cell was of the type TN90, the cell thickness being 7 μm.
Δ ═ j, where | is the dielectric constant parallel to the molecular axis, | is the dielectric constant perpendicular to the molecular axis, test conditions: the test box is TN90 type at 25 deg.C and 1KHz, and has a thickness of 7 μm.
VHR (initial) was tested using the TOY06254 type liquid crystal physical property evaluation system; pulse voltage: 5V 6HZ, the testing temperature is 60 ℃, and the testing unit period is 166.7 ms;
the liquid-crystalline compounds of the formula I prepared in the examples below were tested for optical anisotropy and clearing point and for extrapolation parameters as follows:
a commercial liquid crystal with a serial number of TS023, produced by Jiangsu Hecheng display science and technology Limited is selected as a matrix, a liquid crystal compound shown as a general formula I is dissolved in the matrix liquid crystal (host) according to the weight proportion of 10 percent, the optical anisotropy, clearing point and dielectric anisotropy of the mixture are tested, and liquid crystal performance data of the liquid crystal compound shown as the general formula I are externally obtained according to the linear relation according to the adding proportion of the matrix.
The parent liquid crystal (host) is 20% of the following compound: 40%: mixing the following components in a ratio of 40%:
and
the test results of the performance parameters of the mother liquid crystal are as follows:
Cp：112Δn：0.08Δ：5.0VHR：98.1％。
example 1
The synthetic route of compound I-A-9 is shown below:
1) synthesis of Compound B
Adding 8.6g of compound A, 9.7g of 2, 3-difluorobromobenzene, 100ml of toluene, 50ml of ethanol, 50ml of water and 21.2g of sodium carbonate into a 500ml three-necked bottle, adding 0.3g of Pd (PPh3)4 under the protection of nitrogen, heating and refluxing for 6 hours, separating liquid, washing with water, and carrying out column chromatography to obtain a white solid compound B10.1 g, wherein GC content is more than 97%, and yield is as follows: 84.2 percent of
2) Synthesis of Compound D
Adding 6g of compound B and 100ml of anhydrous tetrahydrofuran into a 250ml three-neck flask, cooling to-78 ℃ under the protection of nitrogen, dropwise adding 10.5ml of n-butyl lithium n-hexane solution (2.4mol/L), stirring for 2h under heat preservation, dropwise adding a mixed solution of 2.6g of compound C and 10ml of anhydrous tetrahydrofuran, controlling the temperature to-65-70 ℃, stirring for 1h under heat preservation after dropwise adding is finished, then pouring a reaction solution into an ice-water mixture, extracting by using methyl tert-butyl ether, separating liquid, washing with water, and evaporating the solvent to obtain 8g of compound D (0.02mol), wherein the compound D is directly used for the next reaction without purification.
3) Synthesis of Compound I-A-9
Adding 8g (0.02mol) of the compound D obtained in the previous step and 100ml of dichloromethane into a 250ml three-necked flask, cooling to-75 ℃, adding a mixed solution of 5.8g of triethylsilane and 10ml of dichloromethane, then dropwise adding 0.05mol of boron trifluoride diethyl etherate, keeping the temperature and stirring for 3 hours, naturally heating to-10 ℃, pouring the reaction solution into a mixture of sodium bicarbonate and ice water, separating, washing with water, and purifying by column chromatography to obtain 3.2g of a white compound, namely I-A-9, GC is more than 99%, and the yield is as follows: 43.7 percent.
Characterization data for compounds I-A-9:
MS:M+366(41％)267(100％)240(55％)。
according to the above synthesis method, the compounds shown in the following table 1 can be used for transformation of the compound C and the compound a, so as to obtain other target compounds:
TABLE 1
The liquid crystal properties of the above target compounds are as follows:
Ⅰ-A-9 Δn：0.126 Δ：-8.2；
Ⅰ-A-11 Δn：0.12 Δ：-8.0；
Ⅰ-B-9 Δn：0.124 Δ：-8.5；
Ⅰ-B-10 Δn：0.122 Δ：-8.3；
Ⅰ-C-19 Δn：0.119 Δ：-7.9；
Ⅰ-D-19 Δn：0.119 Δ：-8.1。
data for representative compounds of formulae I-A, I-B, I-C and I-D are provided in example 1, and it can be seen from the data for liquid crystal compounds I-A-9, I-A-11, I-B-9, I-B-10, I-C-19 and I-D-19 of example 1 that the liquid crystal compounds contained in formulae I-A, I-B, I-C and I-D all have large absolute values of dielectric anisotropy.
Example 2
Compounds I-A-9, I-A-11, I-B-9, V were mixed with the parent liquid crystal (host) in a 10:90 ratio, and the liquid crystal parameters of each compound were determined by extrapolation as shown in Table 2 below:
TABLE 2
| Cp(℃) | Δn | Δε | VHR(％) | T-10℃ | |
| Ⅰ-A-9 | 75.2 | 0.126 | -8.2 | 97.0 | >144h |
| Ⅰ-A-11 | 71.6 | 0.12 | -8.0 | 97.1 | >144h |
| Ⅰ-B-9 | 62.6 | 0.124 | -8.5 | 97.0 | >144h |
| Ⅴ | 183 | 0.18 | -5.7 | 94.0 | <72h |
| host | 112 | 0.08 | 5.0 | 98.1 | - |
Note: t is-10℃It shows the storage stability at-10 ℃ of a mixture of compounds I-A-9, I-A-11, I-B-9, V and the parent liquid crystal host in a ratio of 10: 90.
Compared with the compound V in the prior art, the compound has larger absolute value of dielectric anisotropy, higher voltage holding ratio and stable low-temperature stability.
Example 3
The liquid crystal composition of example 3 was prepared according to the compounds and weight percentages listed in table 3, and filled between two substrates of a liquid crystal display for performance testing, and the test data are shown in the following table:
TABLE 3 liquid crystal composition formula and its test performance
Example 4
The liquid crystal composition of example 4 was prepared according to the compounds and weight percentages listed in table 4, and filled between two substrates of a liquid crystal display for performance testing, and the test data are shown in the following table:
TABLE 4 liquid crystal composition formula and its test performance
Example 5
The liquid crystal composition of example 5 was prepared according to the compounds and weight percentages listed in table 5, and filled between two substrates of a liquid crystal display for performance testing, and the test data are shown in the following table:
TABLE 5 liquid crystal composition formulations and their test properties
As can be seen from the data of examples 3, 4 and 5, when the compound of the present invention is applied to a liquid crystal composition, the liquid crystal composition has good liquid crystal performance, and the compound of the present invention achieves very good technical effects.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. A compound having negative dielectric anisotropy, the compound having the general structure i:
wherein,
R1and R2The same or different, each independently represents an alkyl group of 1 to 10 carbon atoms;
X1and X2Are different from each other and independently represent-O-or-CH2-；
Z represents a single bond, -CH2O-、-CH2CH2-, -COO-or-CH ═ CH-.
2. The compound having negative dielectric anisotropy according to claim 1, wherein Z represents a single bond, -CH2O-or-CH2CH2-。
3. The compound having negative dielectric anisotropy according to claim 1, wherein Z represents a single bond or-CH2CH2-。
4. The compound having negative dielectric anisotropy according to claim 1, wherein R is1And R2The same or different, each independently represents an alkyl group of 1 to 6 carbon atoms.
5. The compound having negative dielectric anisotropy according to claim 1, wherein the compound of formula i is selected from the group consisting of one or more of the following formulae i-a to i-F:
wherein,
the R is1And R2The same or different, each independently represents an alkyl group of 1 to 6 carbon atoms.
6. A liquid crystal composition comprising the compound having negative dielectric anisotropy according to any one of claims 1 to 5.
7. The liquid crystal composition of claim 6, wherein the liquid crystal composition further comprises one or more compounds of formulae II, III, and/or IV:
wherein,
the R is3、R4、R5、R6、R7And R8The same or different, each independently represents a substituted or unsubstituted, linear or branched alkyl or alkoxy group of 1 to 10 carbon atoms, a substituted or unsubstituted, linear or branched alkenyl or alkenyloxy group of 2 to 10 carbon atoms, wherein one or more-CH2-may be substituted by-O-, with the proviso that the oxygen atoms are not directly attached;
m and n are the same or different and each independently represents 0 or 1.
8. A display device comprising a liquid crystal composition of the compound having negative dielectric anisotropy of claim 6.
9. Use of a liquid crystal composition of the compound having negative dielectric anisotropy of claim 6 in VA, FFS, IPS, PSVA display modes.
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