CN110373210A - A kind of liquid-crystal compounds and combinations thereof containing difluoroethoxy - Google Patents
A kind of liquid-crystal compounds and combinations thereof containing difluoroethoxy Download PDFInfo
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Abstract
The invention discloses a kind of fluorinated liquid crystal compounds with big average dielectric constant, it is characterised in that shown in structure such as general formula (1):Wherein R is the straight chained alkyl of carbon number 1~9 or the alkenyl of alkoxy, carbon number 2-7；Ring A is trans-cyclohexane, cyclohexenyl group, phenyl ring, and hydrogen atom can be replaced one or more fluorine atoms on phenyl ring；N, m=0,1,2；X1、X2For hydrogen atom or fluorine atom；And the liquid-crystal composition comprising general formula (1).Liquid-crystal composition of the invention has the characteristics that mesophase range is wide, average dielectric constant is higher, rotary viscosity is lower, is suitable for the liquid crystal display modes such as TFT liquid crystal display, especially IPS and FFS.
Description
Technical field
The invention belongs to liquid crystal material technical fields, and in particular to a kind of fluorinated liquid crystal compound and include the LCD compound
The composition of object, is mainly used for liquid crystal display.
Background technique
Liquid crystal display has many advantages, such as panelized, low in energy consumption, light-weight, radiationless, develops in field of information display fast
Speed.Liquid crystal display realizes display function using the optical anisotropy of liquid crystal material and the characteristic of dielectric anisotropy.It presses
Classify according to display pattern, there is twisted-nematic formula (TN), super twisted nematic formula (STN), dynamic scattering mode (DSP), film crystal
Pipe drive mode (TFT) etc..Full color, high-resolution, wide viewing angle, quick response etc. may be implemented in TFT liquid crystal display, has obtained
It is most important display technology currently on the market to extensive use.
Liquid crystal material used in liquid crystal display is in use environment temperature range, usually at -20 DEG C~+70 DEG C or more
There is nematic phase within the scope of wide temperature；Must have the chemical stability with height, lower viscosity and suitable purposes simultaneously
The physics of liquid crystals property such as birefringence, dielectric anisotropy, resistivity.It is unable to satisfy with a kind of liquid-crystal compounds whole
Use condition, it is necessary to several, even ten several above liquid-crystal compounds are subjected to compounding and form mixed liquid crystal material, can be met
The actual operation requirements of display device.
It is different according to liquid crystal arrangement method in TFT LCD technology, and twisted-nematic (TN) can be divided into, in face
Switch the several modes such as (IPS) and fringe field (FFS), vertical orientation VA.TN mode using dielectric anisotropy Δ ε (Δ ε=
ε∥- ε⊥) be positive value liquid crystal material；VA mode is the liquid crystal material of negative value using dielectric anisotropy Δ ε；IPS and FFS mould
The liquid crystal material that dielectric anisotropy Δ ε is positive value had both can be used in formula, and it is negative value that liquid crystal anisotropy Δ ε, which also can be used,
Liquid crystal material.It is the liquid crystal material of positive value compared with Δ ε using the liquid crystal material that anisotropy Δ ε is negative value for FFS mode, it can
To obtain higher light transmittance；But since negative liquid crystal viscosity is larger, cause the response time slack-off, and be easy to generate image retention
Etc. bad phenomenons.With the continuous promotion of display panel resolution ratio, liquid crystal device light transmittance decline, it is therefore desirable to have high transparency
Liquid crystal material；Meanwhile the optimization of liquid crystal display device response speed is also a technical problem, needing to develop has low rotation
The liquid crystal material of viscosity.
Patent US20130207038A1, which is proposed, discloses the liquid-crystal composition with high transparency characteristic.The composition
It is to add the LCD compound that a certain amount of dielectric anisotropy is negative value in the liquid-crystal composition that dielectric anisotropy is positive value
Object, is characterized in the dielectric anisotropy Δ ε > 0 of the composition, and possesses the biggish dielectric constant perpendicular to liquid crystal director
(ε⊥) and biggish average dielectric constant (εave).Dielectric anisotropy disclosed in it is that the liquid-crystal compounds of negative value has 2,
The fluoro- 4- alkoxy benzene unit of 3- bis-, Typical molecular structure are as follows:
Although this liquid-crystal compounds based on the fluoro- 4- ethoxybenzene of 2,3- bis- has biggish ε⊥Value, however its ε∥Value
It is smaller；And rotary viscosity value (γ1) relatively large, adverse effect is brought to response speed.
Summary of the invention
Demand for LCD technology to high transparency characteristic liquid crystal material, the object of the present invention is to provide one
Kind has the compound of liquid crystal containing fluorine of larger average dielectric anisotropy and low rotary viscosity.
In order to realize that above-mentioned task, the present invention take following technical solution:
A kind of liquid-crystal compounds, structure feature such as general formula is such as shown in (1):
Wherein R is the straight chained alkyl of carbon number 1~9 or the alkenyl of alkoxy, carbon number 2-7；Ring A is trans-cyclohexane, hexamethylene
Alkenyl, and hydrogen atom can be replaced one or more fluorine atoms on phenyl ring；N, m=0,1,2；X1、X2It is former for hydrogen atom or fluorine
Son.
Liquid-crystal compounds of the invention constructs liquid crystal molecule bone using the fluoro- 4- of 2,3- bis- (2,2-difluoroethoxy) benzene
Frame not only has high ε⊥Value, higher ε∥And εave, and with lower rotary viscosity, wider mesophase range it is excellent
Point.
The synthetic route of the compounds of this invention is as follows:
Specifically it is prepared according to the following steps:
(1) to contain the compound or 2 of the fluoro- 4- methoxybenzene class of 2,3- bis-, the chemical combination of the fluoro- 4- ethoxybenzene class of 3- bis-
Object is that (preparation method of such compound is shown in document to starting material: Angew.Chem.Int.Ed., 2000,39,4216-
4235) alkyl (R, is eliminated under the action of demethylation/ethyl reagent1Group)；Demethylation/ethyl reagent is for example
Boron tribromide, in low temperature or room temperature reaction；Or hydrobromic acid/acetum using 40% or more mass concentration, it is heated to reflux
Reaction, obtains phenols intermediate.
(2) obtained phenols intermediate and trifluoroethanol methanesulfonates perhaps trifluoroethanol p-methyl benzenesulfonic acid value or
Trifluoroethanol triflate, reacts into ether under alkaline condition, obtains target product；The alkali can be hydroxide
Sodium, potassium hydroxide, sodium carbonate, potassium carbonate etc..
The present invention can also be prepared according to following route:
I.e. by acquired phenol intermediate and trifluoroethanol, diethyl azodiformate (DEAD) or azoformic acid diisopropyl
Ester (DIAD), triphenylphosphine are reacted by Mitsunobu to be prepared.
General formula (1) liquid-crystal compounds of the present invention, preferably is selected from flowering structure:
It is a further object of the present invention to provide a kind of liquid-crystal composition, feature the composition is selected from comprising at least one
For liquid-crystal compounds shown in general structure (1) as the first component, mass ratio is 1%~70%wt, preferably 3%-40%
Wt, more preferable 5%-30%wt.
The second feature of liquid-crystal composition of the present invention is that the composition includes at least one selected from general structure (2) institute
The liquid-crystal compounds shown is as the second component:
Wherein R1, R2For straight chained alkyl, alkoxy, alkenyl or alkyl, F, Cl containing ethylene linkage, ring B, ring C, ring D are benzene
Ring or hexamethylene, oxinane, dioxanes etc., wherein phenyl ring can be replaced by one or more fluorine atoms, n=0, and 1,2.This hair
Second component of bright composition is that a kind of Δ ε is smaller or liquid-crystal compounds close to 0, mass ratio 5-80%, preferably
15%-75%, more preferable 30%~70%wt.
The preferred specific structure of its formula of (2) is as follows:
Wherein (2) -1 more preferably with flowering structure:
Wherein (2) -2 more preferable compounds in detail below:
Wherein (2) -3 more preferable compounds in detail below:
Its
In (2) -4 more preferable compounds in detail below:
Wherein (2) -5 more preferable compounds in detail below:
Wherein (2) -6 more preferable compounds in detail below:
Wherein (2) -7 preferred compound:
Wherein (2) -8 preferred compound:
Liquid-crystal composition of the present invention, which is characterized in that the composition includes at least one is selected from shown in general structure (3)
Liquid-crystal compounds is as third component:
Wherein R is straight chained alkyl, alkenyl or the alkyl containing ethylene linkage, and ring B, ring C, ring D are phenyl ring, hexamethylene, tetrahydro pyrrole
It mutters ring, dioxanes ring, wherein phenyl ring can be replaced by one or more fluorine atoms；X1, X2=H, F；Y=F, Cl, OCF3, OCF2H,
Straight chained alkyl or the alkyl containing ethylene linkage etc.；Z=CF2O, CH2CH2, COO, singly-bound etc.；N=0,1.The spy of third component of the present invention
Putting is a kind of liquid-crystal compounds with biggish Δ ε value, mass ratio 1-50%, preferably 5%~45%wt, more preferably
10%-40%.
Its formula of (3) preferably structure in detail below:
Wherein (3) -1 preferred compound:
Wherein (3) -2 preferred compound:
Wherein (3) -3 preferred compound:
Wherein (3) -4 preferred compound:
Wherein (3) -5 preferred compound:
Wherein (3) -6 preferred compound:
Wherein (3) -7 preferred compound:
Wherein (3) -8 preferred compound:
Wherein (3) -9 preferred compound:
Wherein (3) -10 preferred compound:
Wherein (3) -11 preferred compound:
Wherein (3) -12 preferred compound:
Wherein (3) -13 preferred compound:
Wherein (3) -14 preferred compound:
Liquid-crystal composition of the present invention, which is characterized in that the composition can also be selected from general structure comprising one or more
(4) liquid-crystal compounds shown in is as the 4th component:
Wherein R1、R2For the straight chained alkyl or alkoxy of carbon number 1~7, the straight-chain alkenyl or alkenyloxy group of carbon number 2~7, ring B,
Ring C, ring D are phenyl ring, hexamethylene, amylene oxide ring, and wherein phenyl ring can be replaced by one or more fluorine atoms；X1, X2=H, F；Z
=singly-bound, CH2CH2, CH2O；N=0,1.4th component of the invention is the liquid crystal material that a kind of Δ ε is negative value, and mass ratio is
0-30%, preferably 2%~20%wt, more preferable 3%-15%.
Its formula of (4) preferably structure in detail below:
Wherein (4) -1 preferred compound:
Wherein (4) -2 preferred compound:
Wherein (4) -3 preferred compound:
Wherein (4) -4 preferred compound:
Wherein (4) -5 preferred following compound:
Liquid-crystal composition of the present invention also may include one or more chiral additives, content 0.01%-1%；It is preferred that
0.1%-0.5%.The chiral additives preferably are selected from flowering structure:
Liquid-crystal composition of the present invention also includes one kind of multiple hindered phenols as antioxidative stabilizer, content 1ppm-
10000ppm；It is preferred that 10ppm-1000ppm.The antioxidative stabilizer preferably is selected from flowering structure:
Liquid-crystal composition of the present invention also includes one or more UV light stabilizing agents, content 1ppm-10000ppm；It is preferred that
10ppm-1000ppm.The UV light stabilizing agent preferably is selected from flowering structure:
The present invention also may include one or more liquid crystal components with polymerizable groups, content 1ppm-10000ppm；It is excellent
Select 100ppm-1000ppm.The polymerisable liquid crystal component preferably is selected from flowering structure:
Above-mentioned liquid-crystal composition has biggish average dielectric constant, lower rotary viscosity and faster response speed
Degree, is suitable for TFT LCD technology, especially FFS and IPS mode.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail.
Dispensing liquid crystal preparation method: heat of solution method is used.The monomer of different weight ratio is weighed with precision balance first
Liquid crystal is heated to 60 DEG C~100 DEG C, and being stirred 1~2 hour is uniformly dissolved each component.It is filtered after cooling, filters institute
Liquid is obtained in high vacuum (≤100Pa) degassing process, is finally encapsulated with high pure nitrogen, obtains target mixed liquid crystal.
Unless otherwise specified, liquid-crystal composition of the present invention is prepared in this way.
The liquid crystal mixed carries out physical property and photoelectric properties test.The present invention relates to physical property and photo electric
Energy detailed test method is as follows:
(1) clearing point (Tni):
Polarisation thermal station method: liquid crystalline sample being coated on glass slide and is placed in cross-polarized light microscopic heating stand, setting heating speed
Rate is 2 DEG C/min.The temperature of liquid crystalline sample blackening by illuminated state, as clearing point are observed in petrographic microscope.
Or use differential scanning calorimetry: under nitrogen atmosphere, setting heating rate is 2 DEG C/min.
(2) low temperature storage temperature (LTS): the mixed liquid crystal of 1mL or so is fitted into transparent vial, is placed in Low-temperature Ice
In case.- 20 DEG C of temperature setting, -30 DEG C, -40 DEG C store 10 days respectively, and observation is precipitated whether there is or not crystal or smectic phase.If -30
DEG C without crystal be precipitated, LTS≤- 30 DEG C.
(3) (Δ n): using abbe's refractometer to birefringence, under 25 DEG C of constant temperatures, measures ordinary light (n respectivelyo) and it is non-
Ordinary light (ne) refractive index, birefringence Δ n=ne- no。
(4) it under dielectric constant (Δ ε): 25 DEG C of constant temperatures, is tested using LCR table.Δ ε=ε∥-ε⊥, i.e. molecular long axis side
To dielectric constant (ε∥) and molecular short-axis direction dielectric constant (ε⊥) difference.
(5) elastic constant (K11, K33): under 25 DEG C of constant temperatures, by testing liquid crystal capacitance-voltage (C-V) curve, intend
Conjunction obtains K11And K33。
(6) rotary viscosity (γ1): under 25 DEG C of constant temperatures, by applying voltage to liquid crystal test box, test liquid crystal molecule
With the transient current value Ip of electric field movement deflection, rotary viscosity γ is calculated1。
The performance test of monomer liquid crystal is to be dissolved into following basic components (Host) to be tested.The property of monomer
Energy parameter, such as clearing point, Δ ε, Δ n, γ1It is calculated by extrapolation.Basic components (Host) are by following three kinds of LCD compounds
Object is formulated according to mass ratio 1:1:1.
Code name and explanation:
(1) physical parameter
| Code name | Explanation | Unit |
| Tni | Clearing point | ℃ |
| TCN | Low temperature storage temperature | ℃ |
| ε⊥ | Perpendicular to the dielectric constant of director | |
| ε∥ | It is parallel to the dielectric constant of director | |
| εave | Average dielectric constant | |
| Δε | Dielectric anisotropy | |
| Δn | Birefringence | |
| γ1 | Rotary viscosity | mPa·s |
| K11 | Splay elastic constant | pN |
| K33 | Bend elastic constant | pN |
(2) structure is abridged
Such as:
Liquid-crystal phase-transition temperature: C represents fusing point, and S represents smectic phase, and N represents nematic phase, and Iso represents liquid.
Embodiment 1:
The synthesis of the fluoro- 1- of 2,3- bis- (trans- -4- pentylcyclohexyl) -4- (2,2- difluoroethoxy) benzene
Reaction equation is as follows:
Specific synthesis step is as follows:
(1) synthesis of the fluoro- 1- of 2,3- bis- (trans- -4- pentylcyclohexyl)-phenol
In 500mL three-necked flask, the fluoro- 1- of 2,3- bis- (trans- -4- pentylcyclohexyl) -4- ethoxybenzene is added
(31.0g, 0.1mol), 100mL methylene chloride is cooled to -10 DEG C, and BBr is added dropwise3Dichloromethane solution (2mol/L, 50ml),
Room temperature is warmed naturally to after dripping off, and after reacting 3h, water quenching reaction is slowly added dropwise.Liquid separation is stood, organic phase is washed to neutrality, nothing
Aqueous sodium persulfate is spin-dried for obtaining faint yellow solid after drying, filtering.It is recrystallized with normal heptane according to 1g:2ml, it is brilliant to obtain 26.2g white
Body.G/C content 99.9%, yield 93%.
(2) synthesis of the fluoro- 1- of 2,3- bis- (trans- -4- pentylcyclohexyl) -4- (2,2- difluoroethoxy) benzene
In 250mL three-necked flask, the addition fluoro- 1- of 2,3- bis- (trans- -4- pentylcyclohexyl)-phenol (14.1g,
0.05mol), Anhydrous potassium carbonate (13.8g, 0.10mol), CF2HCH2OSO2CH3(8.0g, 0.05mol), DMF (50mL), stirring
Under be heated to 130 DEG C of reaction 8h.It is down to room temperature, water 100ml, toluene 50ml × 2 is added and extracts.Organic phase washing is secondary, anhydrous
Sodium sulphate dries, filters rear filtrate and is spin-dried for, and obtains pale yellow oily liquid.Crude product is dissolved with normal heptane, crosses silicagel column, normal heptane leaching
It washes, is spin-dried for obtaining colourless oil liquid.Ethyl alcohol recrystallization is added, obtains 14.0g white crystal product.G/C content 99.9%, yield
81%.
Structural Identification data are as follows:
1HNMR(CDCl3, 500MHz) and δ: 6.892~6.855 (m, 1H), 6.719~6.682 (m, 1H), 6.208~
5.971 (m, 1H), 4.256~4.196 (m, 2H), 2.787~2.726 (m, 1H), 1.870~1.829 (m, 4H), 1.472~
1.388 (m, 2H), 1.348~1.194 (m, 9H), 1.106~1.024 (m, 2H), 0.907~0.879 (t, 3H, J=
7.5Hz)。
MS (70eV) m/z (%): 220.1 (100), 346.3 (68.71, M+), 207.1 (44.43), 233.1 (40.8),
234.1 (21.74), 143 (15.98), 347.3 (15.13), 221.1 (13.55).
Quantitative measurement data are as follows:
DSC tests fusing point are as follows: C 49.19Iso.
The compound is dissolved into basic components with 10% mass ratio and carries out quantitative measurement, extrapolation obtains performance
Parameter are as follows: Tni=-39.4 DEG C；Δ n=0.0564；ε⊥=9.202, ε∥=9.142, εave=9.182, Δ ε=- 0.078；γ1
=-9mPas.
The conjunction of embodiment 2:4- (2,3- bis- fluoro- 4- (2,2- difluoroethoxy) phenyl)-trans- -4 '-propyl bis cyclohexane
At
Method same as Example 1 obtains 4- (2,3- bis- fluoro- 4- (2,2- difluoroethoxy) phenyl)-trans- -4 ' -
Propyl bis cyclohexane.
Structural Identification data are as follows:
1H NMR(CDCl3, 500MHz) and δ: 6.887~6.850 (m, 1H), 6.716~6.679 (m, 1H), 6.207~
5.970 (m, 1H), 4.254~4.194 (m, 2H), 2.762~2.708 (m, 1H), 1.876~1.823 (t, 4H, J=14Hz),
1.775~1.718 (t, 4H, J=13.5Hz), 1.444~1.377 (m, 2H), 1.346~1.273 (m, 2H), 1.205~
1.148 (m, 6H), 1.097~0.957 (m, 3H), 0.890~0.826 (m, 5H).
MS (70eV) m/z (%): 400.3 (M+, 100), 220.1 (71.98), 207.1 (56.58), 69.1 (29.08),
401.3 (27.32), 83.1 (22.33), 143 (13.24), 55.1 (12.03), 125.1 (10.14).
Quantitative measurement data are as follows:
DSC tests fusing point are as follows: C 96.96N 161.99Iso.
The compound is dissolved into basic components with 10% mass ratio and carries out quantitative measurement, extrapolation obtains performance
Parameter are as follows: Tni=144.3 DEG C；Δ n=0.098；ε⊥=8.298, ε∥=7.960, εave=8.185, Δ ε=- 0.338；γ1
=305mPas.
The synthesis of embodiment 3:4 '-(trans--propylcyclohexyl) -2,3- two fluoro- 4- (2,2- difluoroethoxy) biphenyl
Method same as Example 1 obtains 4 '-(trans--propylcyclohexyl) -2,3-, bis- fluoro- 4- (2,2- difluoro ethoxies
Base) biphenyl.
Structural Identification data are as follows:
1H NMR(CDCl3, 500MHz) and δ: 7.430~7.410 (m, 2H), 7.293~7.277 (m, 2H), 7.136~
7.098 (m, 1H), 6.836~6.799 (m, 1H), 6.249~6.013 (m, 1H), 4.323~4.263 (m, 2H), 2.541~
2.480 (m, 1H), 1.943~1.866 (m, 4H), 1.523~1.442 (m, 2H), 1.396~1.281 (m, 3H), 1.246~
1.201 (m, 2H), 1.101~1.026 (m, 2H), 0.924~0.895 (t, 3H, J=7.5Hz).
MS (70eV) m/z (%): 394.3 (M+, 100), 296.1 (42.59), 309.1 (38.11), 395.3 (27.91),
283.1 (25.51), 231.1 (17.38), 310.1 (13.05).
Quantitative measurement data are as follows:
DSC tests fusing point are as follows: C85.67SA105.59N 145.6Iso。
The compound is dissolved into basic components with 10% mass ratio and carries out quantitative measurement, extrapolation obtains performance
Parameter are as follows: Tni=123.2 DEG C；Δ n=0.1382；ε⊥=9.588, ε∥=10.57, εave=9.915, Δ ε=0.992；γ1
=217mPas.
Embodiment 4:4 '-(trans- -4- propylcyclohexyl) -2,2 ', the conjunction of 3- tri- fluoro- 4- (2,2- difluoroethoxy) biphenyl
At
Method same as Example 1 obtains 4 '-(trans- -4- propylcyclohexyls) -2,2 ', 3-, tri- fluoro- 4- (2,2- bis-
Fluorine ethyoxyl) biphenyl.
Structural Identification data are as follows:
1H NMR(CDCl3, 500MHz) and δ: 7.263~7.232 (m, 1H), 7.089~7.052 (m, 2H), 7.028~
7.002 (m, 1H), 6.843~6.807 (m, 1H), 6.257~6.021 (m, 1H), 4.332~4.272 (m, 2H), 2.541~
2.479 (m, 1H), 1.940~1.860 (m, 4H), 1.494~1.413 (m, 2H), 1.395~1.269 (m, 3H), 1.253~
1.201 (m, 2H), 1.099~1.019 (m, 2H), 0.923~0.894 (t, 3H, J=7.5Hz).
MS (70eV) m/z (%): 412.3 (M+, 100), 314.1 (47.71), 301.1 (26.09), 413.3 (25.98),
249.1 (15.9), 327.1 (13.47).
Quantitative measurement data are as follows:
DSC tests fusing point are as follows: C 71.81N 98.89Iso.
The compound is dissolved into basic components with 10% mass ratio and carries out quantitative measurement, extrapolation obtains performance
Parameter are as follows: Tni=90.0 DEG C；Δ n=0.1452；ε⊥=10.198, ε∥=12.120, εave=10.839, Δ ε=1.922；
γ1=245mPas.
The fluoro- 1- of embodiment 5:2,3- bis- (4- (trans- -4- propylcyclohexyl) hexamethylene -1- alkenyl) -4- (2,2- difluoro ethoxy
Base) benzene synthesis
The preparation method of the fluoro- 1- of intermediate 2,3- bis- (4- (trans- -4- propylcyclohexyl) hexamethylene -1- alkenyl) -4- phenol
It is same as Example 1.
By the fluoro- 1- of 2,3- bis- (4- (4- propylcyclohexyl) hexamethylene -1- alkenyl) -4- phenol 3.3g, azoformic acid diethyl
Ester 2.0g, triphenylphosphine 3.5g are dissolved in 30ml tetrahydrofuran, are cooled to 0 DEG C, and the 20ml tetra- dissolved with 1.1g difluoroethanol is added dropwise
Hydrogen tetrahydrofuran solution.After being added dropwise, it is to slowly warm up to that 4hr is stirred at room temperature.Reaction solution imports in water, and the extraction of 50ml toluene is added.
Organic phase is dry, and solvent is divided exactly in decompression.Crude product is dissolved with normal heptane, crosses silicagel column, and normal heptane elution is spin-dried for obtaining white admittedly
Body.Ethyl alcohol recrystallization is added, obtains 3.1g white crystal.G/C content 99.9%, yield 78%.
Structural Identification data are as follows:
1HNMR (δ, CDCl3): 6.92-6.87 (m, 1H), 6.71-6.67 (m, 1H), 6.21-6.09 (m, 1H), 5.92 (t,
J=2.5Hz, 1H), 4.24 (td, J=13.0Hz, J=4.0Hz, 2H), 2.40-2.22 (m, 3H), 1.95-1.89 (m, 2H),
1.83–1.75(m,4H),1.42–1.28(m,4H),1.20–1.11(m,4H),1.07–0.96(m,2H),0.91–0.84(m,
5H)。
MS (70eV) m/z (%): 398.2 (M+,69.3),259.0(100),220.0(95.5),206.9(68.5),
180.9(50.8),246.0(45.9),69.0(45.3),273.0(41.9)。
Quantitative measurement data are as follows:
DSC tests fusing point are as follows: C 89.46S 124.28N 155.72Iso.
The compound is dissolved into basic components with 10% mass ratio and carries out quantitative measurement, extrapolation obtains performance
Parameter are as follows: Tni=117.4 DEG C；Δ n=0.0732；ε⊥=9.458, ε∥=9.44, εave=9.452, Δ ε=- 0.018；γ1
=198mPas.
Embodiment 6 (composition)
Embodiment 7 (composition)
Embodiment 8 (composition)
Comparative example 1:
The liquid-crystal compounds for the fluoro- 4- ethoxybenzene containing 2,3- bis- being shown below:
It is added in basic components HOST according to 10% mass ratio, carries out quantitative measurement, obtaining property of extrapolating
Energy parameter are as follows: Tni=176.0 DEG C；Δ n=0.1683；ε⊥=9.991, ε∥=6.887, εave=8.956, Δ ε=- 2.935；
γ1=255.9mPas.
The embodiment of the present invention 3 has the ε significantly increased compared with comparative example 1∥, εaveIncrease；And γ1Significantly drop
It is low.
Comparative example 2:
Patent US6159393A discloses the liquid-crystal compounds such as flowering structure:
The liquid-crystal compounds is on phenyl ring that fluorine atom the position of substitution is different from difference of the invention.By it according to 10%
Mass ratio is added in basic components HOST, carries out quantitative measurement, and extrapolation obtains performance parameter are as follows: Tni=92.2 DEG C；Δn
=0.1402；ε⊥=6.168, ε∥=19.02, εave=10.452, Δ ε=12.852；γ1=229mPas.
The embodiment of the present invention 4 has the ε significantly increased compared with comparative example 2⊥And biggish εave。
Comparative example 3:
Comparative example 3 is by the monomer liquid crystal 5CYO2F in the embodiment of the present invention 72It is substituted for 5CYO2, other components and its correspondence
Mass ratio is unchanged.Compared with comparative example 4, the embodiment of the present invention 7 has the ε being close⊥Value and lower γ1, and
Biggish Δ ε promotes the response speed of device while being conducive to promote display device light transmittance.
Claims (7)
1. a kind of liquid-crystal compounds containing difluoroethoxy, which is characterized in that shown in structure such as general formula (1):
Wherein R is the straight chained alkyl of carbon number 1~9 or the alkenyl of alkoxy, carbon number 2-7；Ring A is trans-cyclohexane, cyclohexenyl group
Or phenyl ring, wherein hydrogen atom can be replaced one or more fluorine atoms on phenyl ring；N, m=0,1,2；X1、X2For hydrogen atom or
Fluorine atom.
2. liquid-crystal compounds according to claim 1, it is characterised in that n=1, m=0.
3. liquid-crystal compounds according to claim 1, it is characterised in that n=1, m=1.
4. a kind of nematic phase liquid crystal composition, which is characterized in that the composition includes general structure LCD compound as shown in (1)
Object is 1~70wt% as the first component, content:
Wherein R, the definition of ring A, n, m, X1, X2 are identical as claim 1.
5. liquid-crystal composition according to claim 4, which is characterized in that the composition includes that the structure of 5~80wt% is logical
Formula liquid-crystal compounds as shown in (2) is as the second component:
Wherein R1, R2For straight chained alkyl, alkoxy, alkenyl or alkyl, F, Cl containing ethylene linkage, ring B, ring C, ring D be phenyl ring or
Hexamethylene, wherein phenyl ring can be replaced by one or more fluorine atoms, n=0, and 1.
6. liquid-crystal composition according to claim 5, which is characterized in that the composition includes that the structure of 1~50wt% is logical
Formula liquid-crystal compounds as shown in (3) is as third component:
Wherein R is straight chained alkyl, alkenyl or the alkyl containing ethylene linkage, and ring B, ring C, ring D are phenyl ring or hexamethylene, wherein phenyl ring
It can be replaced by one or more fluorine atoms；X1, X2=H, F；Y=F, Cl, OCF3, OCF2H, straight chained alkyl or the alkane containing ethylene linkage
Base；Z=CF2O, CH2CH2, COO or singly-bound；N=0,1.
7. a kind of liquid crystal display element, which is characterized in that include the described in any item liquid-crystal compositions of claim 4-6.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111454729A (en) * | 2019-12-16 | 2020-07-28 | 西安近代化学研究所 | Liquid crystal compound containing difluoroethyleneoxy and composition |
| WO2022088916A1 (en) * | 2020-11-02 | 2022-05-05 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal composition containing pyran and terphenyl and use thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1903090A2 (en) * | 2006-09-06 | 2008-03-26 | Chisso Corporation | Cyclohexene derivative having alkenyl, liquid crystal composition and liquid crystal display device |
| CN104004527A (en) * | 2014-05-07 | 2014-08-27 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal compound and its preparation method and use |
| CN108659860A (en) * | 2017-03-31 | 2018-10-16 | 北京八亿时空液晶科技股份有限公司 | A kind of liquid-crystal composition containing fluoroethoxy compound and its application |
| CN108690636A (en) * | 2017-04-06 | 2018-10-23 | 北京八亿时空液晶科技股份有限公司 | A kind of liquid-crystal compounds of negative dielectric anisotropic and the preparation method and application thereof |
| CN108690637A (en) * | 2017-04-05 | 2018-10-23 | 北京八亿时空液晶科技股份有限公司 | A kind of liquid-crystal composition containing fluoroethoxy compound and its application |
| CN108728112A (en) * | 2017-04-19 | 2018-11-02 | 北京八亿时空液晶科技股份有限公司 | A kind of liquid-crystal compounds of negative dielectric anisotropic and the preparation method and application thereof |
| CN108728119A (en) * | 2017-04-20 | 2018-11-02 | 北京八亿时空液晶科技股份有限公司 | A kind of fast-response negative dielectric anisotropy liquid crystal composition and its application |
| CN108728114A (en) * | 2017-04-20 | 2018-11-02 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal media and its application |
| CN108949190A (en) * | 2017-05-17 | 2018-12-07 | 北京八亿时空液晶科技股份有限公司 | A kind of liquid-crystal composition containing cyclohexene compound and its application |
| CN109207159A (en) * | 2017-06-30 | 2019-01-15 | 北京八亿时空液晶科技股份有限公司 | A kind of liquid-crystal compounds of negative dielectric anisotropic and the preparation method and application thereof |
-
2019
- 2019-08-07 CN CN201910724327.6A patent/CN110373210B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1903090A2 (en) * | 2006-09-06 | 2008-03-26 | Chisso Corporation | Cyclohexene derivative having alkenyl, liquid crystal composition and liquid crystal display device |
| CN104004527A (en) * | 2014-05-07 | 2014-08-27 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal compound and its preparation method and use |
| CN108659860A (en) * | 2017-03-31 | 2018-10-16 | 北京八亿时空液晶科技股份有限公司 | A kind of liquid-crystal composition containing fluoroethoxy compound and its application |
| CN108690637A (en) * | 2017-04-05 | 2018-10-23 | 北京八亿时空液晶科技股份有限公司 | A kind of liquid-crystal composition containing fluoroethoxy compound and its application |
| CN108690636A (en) * | 2017-04-06 | 2018-10-23 | 北京八亿时空液晶科技股份有限公司 | A kind of liquid-crystal compounds of negative dielectric anisotropic and the preparation method and application thereof |
| CN108728112A (en) * | 2017-04-19 | 2018-11-02 | 北京八亿时空液晶科技股份有限公司 | A kind of liquid-crystal compounds of negative dielectric anisotropic and the preparation method and application thereof |
| CN108728119A (en) * | 2017-04-20 | 2018-11-02 | 北京八亿时空液晶科技股份有限公司 | A kind of fast-response negative dielectric anisotropy liquid crystal composition and its application |
| CN108728114A (en) * | 2017-04-20 | 2018-11-02 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal media and its application |
| CN108949190A (en) * | 2017-05-17 | 2018-12-07 | 北京八亿时空液晶科技股份有限公司 | A kind of liquid-crystal composition containing cyclohexene compound and its application |
| CN109207159A (en) * | 2017-06-30 | 2019-01-15 | 北京八亿时空液晶科技股份有限公司 | A kind of liquid-crystal compounds of negative dielectric anisotropic and the preparation method and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111454729A (en) * | 2019-12-16 | 2020-07-28 | 西安近代化学研究所 | Liquid crystal compound containing difluoroethyleneoxy and composition |
| CN111454729B (en) * | 2019-12-16 | 2023-03-21 | 西安近代化学研究所 | Liquid crystal compound containing difluoroethyleneoxy and composition |
| WO2022088916A1 (en) * | 2020-11-02 | 2022-05-05 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal composition containing pyran and terphenyl and use thereof |
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