CN110373210B - Difluoroethoxy-containing liquid crystal compound and composition thereof - Google Patents

Difluoroethoxy-containing liquid crystal compound and composition thereof Download PDF

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CN110373210B
CN110373210B CN201910724327.6A CN201910724327A CN110373210B CN 110373210 B CN110373210 B CN 110373210B CN 201910724327 A CN201910724327 A CN 201910724327A CN 110373210 B CN110373210 B CN 110373210B
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liquid crystal
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difluoroethoxy
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CN110373210A (en
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李建
高嫒嫒
万丹阳
车昭毅
李娟利
杜渭松
邓登
杨晓哲
莫玲超
胡明刚
杨诚
张璐
甘宁
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XI'AN CAIJING OPTO-ELECTRICAL SCIENCE & TECHNOLOGY Co.,Ltd.
Xian Modern Chemistry Research Institute
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Xi'an Caijing Opto Electrical Science & Technology Co ltd
Xian Modern Chemistry Research Institute
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Abstract

The invention discloses a fluorine-containing liquid crystal compound with large average dielectric constant, which is characterized in that the structure is shown as a general formula (1):
Figure DDA0002158384920000011
wherein R is a linear alkyl or alkoxy group with a carbon number of 1-9 or an alkenyl group with a carbon number of 2-7; ring A is trans-cyclohexane, cyclohexenyl and benzene ring, and hydrogen atoms on the benzene ring can be substituted by 1 or more fluorine atoms; n, m is 0, 1, 2; x1、X2Is a hydrogen atom or a fluorine atom; and a liquid crystal composition comprising the general formula (1). The liquid crystal composition has the characteristics of wide liquid crystal phase region, higher average dielectric constant and lower rotational viscosity, and is suitable for TFT liquid crystal display, particularly liquid crystal display modes such as IPS (in-plane switching) mode, FFS (fringe field switching) mode and the like.

Description

Difluoroethoxy-containing liquid crystal compound and composition thereof
Technical Field
The invention belongs to the technical field of liquid crystal materials, and particularly relates to a fluorine-containing liquid crystal compound and a composition containing the liquid crystal compound, which are mainly used for a liquid crystal display.
Background
The liquid crystal display has the advantages of flat panel, low power consumption, light weight, no radiation and the like, and is rapidly developed in the field of information display. The liquid crystal display uses the characteristics of optical anisotropy and dielectric anisotropy of a liquid crystal material to realize a display function. The display modes are classified into Twisted Nematic (TN), Super Twisted Nematic (STN), dynamic scattering mode (DSP), thin film transistor driving mode (TFT), and the like. The TFT liquid crystal display can realize full color, high resolution, wide viewing angle, fast response, etc., has been widely used, and is the most important display technology in the current market.
The liquid crystal material for liquid crystal display has a nematic phase within a temperature range of the use environment, generally within a temperature range of-20 ℃ to +70 ℃ or more; meanwhile, the liquid crystal material must have high chemical stability, low viscosity, and suitable application of liquid crystal physical properties such as birefringence, dielectric anisotropy, resistivity and the like. One liquid crystal compound cannot meet all use conditions, and several or even more than ten liquid crystal compounds are compounded to form a mixed liquid crystal material, so that the practical use requirements of a display device can be met.
In the TFT liquid crystal display technology, depending on the liquid crystal alignment method, the liquid crystal display technology can be divided into several modes such as Twisted Nematic (TN), in-plane switching (IPS), Fringe Field Switching (FFS), and vertical alignment VA. The TN mode uses a dielectric anisotropy Δ ε (Δ ε ═ ε)∥－ε⊥) A liquid crystal material that is positive; the VA mode uses a liquid crystal material whose dielectric anisotropy Δ ∈ is a negative value; in the IPS and FFS modes, a liquid crystal material having a positive dielectric anisotropy Δ ∈ or a liquid crystal material having a negative dielectric anisotropy Δ ∈ may be used. For FFS mode, a liquid crystal material having a negative anisotropy Δ ε is usedThe liquid crystal material with the positive value of delta epsilon can obtain higher light transmittance; however, the negative liquid crystal has a large viscosity, and thus the response time is slow and a problem such as an afterimage is likely to occur. With the continuous improvement of the resolution of the display panel, the light transmittance of the liquid crystal device is reduced, so that a liquid crystal material with high light transmittance is required; meanwhile, the optimization of the response speed of the liquid crystal display device is also a technical problem, and the development of a liquid crystal material having low rotational viscosity is required.
Patent US20130207038a1 proposes to disclose liquid crystal compositions having high light transmittance characteristics. The composition is prepared by adding a certain amount of liquid crystal compound with negative dielectric anisotropy into a liquid crystal composition with positive dielectric anisotropy, and is characterized in that the dielectric anisotropy delta epsilon of the composition is more than 0, and the composition has a larger dielectric constant (epsilon) vertical to a liquid crystal director⊥) And a larger average dielectric constant (. epsilon.)ave). The liquid crystal compound disclosed therein, which has a negative dielectric anisotropy, has a 2, 3-difluoro-4-alkoxybenzene unit, and a typical molecular structure is as follows:
Figure BDA0002158384910000021
although the liquid crystal compound based on 2, 3-difluoro-4-ethoxybenzene has a large epsilon⊥Value, however ε∥The value is small; and rotational viscosity value (. gamma.)1) Relatively large, adversely affecting the response speed.
Disclosure of Invention
Aiming at the requirement of liquid crystal display technology on a liquid crystal material with high light transmittance characteristic, the invention aims to provide a novel fluorine-containing liquid crystal compound with larger average dielectric anisotropy and low rotational viscosity.
In order to realize the task, the invention adopts the following technical solution:
a liquid crystal compound is characterized by the structural formula (1):
Figure BDA0002158384910000022
wherein R is a linear alkyl or alkoxy group with a carbon number of 1-9 or an alkenyl group with a carbon number of 2-7; ring A is trans-cyclohexane, cyclohexenyl, and the hydrogen atoms on the phenyl ring may be substituted by 1 or more fluorine atoms; n, m is 0, 1, 2; x1、X2Is a hydrogen atom or a fluorine atom.
The liquid crystal compound of the invention adopts 2, 3-difluoro-4- (2, 2-difluoroethoxy) benzene to construct a liquid crystal molecular framework, and not only has high epsilon⊥Value, higher epsilon∥And εaveAnd has the advantages of lower rotational viscosity and wider liquid crystal phase region.
The synthetic route for the compounds of the invention is shown below:
Figure BDA0002158384910000023
the preparation method specifically comprises the following steps:
(1) the compound containing 2, 3-difluoro-4-methoxybenzene or 2, 3-difluoro-4-ethoxybenzene is used as the starting material (the preparation method of the compound is shown in the literature: Angew. chem. int. Ed.,2000,39, 4216-substituted benzene 4235), and alkyl is eliminated under the action of a demethylating/ethyl reagent (R is1A group); said demethylating/ethyl reagent, such as boron tribromide, is reacted at low or room temperature; or heating and refluxing a hydrobromic acid/acetic acid solution with the mass concentration of more than 40% to react to obtain a phenol intermediate.
(2) Reacting the obtained phenol intermediate with trifluoroethanol methane sulfonate, or trifluoroethanol p-toluene sulfonic acid value, or trifluoroethanol trifluoromethane sulfonate to form ether under an alkaline condition to obtain a target product; the alkali can be sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc.
The invention can also be prepared according to the following route:
Figure BDA0002158384910000031
the phenol intermediate obtained is reacted with trifluoroethanol, diethyl azodicarboxylate (DEAD) or diisopropyl azodicarboxylate (DIAD), triphenylphosphine to prepare the compound by Mitsunobu reaction.
The liquid crystal compounds of the general formula (1) according to the invention are preferably selected from the following structures:
Figure BDA0002158384910000032
Figure BDA0002158384910000041
Figure BDA0002158384910000051
Figure BDA0002158384910000061
another object of the present invention is to provide a liquid crystal composition characterized in that the composition comprises at least one liquid crystal compound selected from the group consisting of the liquid crystal compounds represented by the general structural formula (1) as a first component in a mass ratio of 1 to 70% by weight, preferably 3 to 40% by weight, more preferably 5 to 30% by weight.
The second feature of the liquid crystal composition of the present invention is that the composition contains at least one liquid crystal compound selected from the group consisting of liquid crystal compounds represented by the general structural formula (2) as a second component:
Figure BDA0002158384910000062
wherein R is1，R2F, Cl, ring B, ring C, and ring D are benzene rings or cyclohexane, tetrahydropyran, dioxane, etc., wherein the benzene rings may be substituted with 1 or more fluorine atoms, and n is 0, 1, 2. Second component of the composition of the inventionIs a liquid crystal compound with smaller delta epsilon or close to 0, and the mass proportion of the liquid crystal compound is 5-80%, preferably 15-75%, and more preferably 30-70%.
Wherein the preferred specific structure of formula (2) is as follows:
Figure BDA0002158384910000063
wherein (2) -1 is more preferably of the structure:
Figure BDA0002158384910000071
among them, (2) -2 are more preferably the following specific compounds:
Figure BDA0002158384910000072
among them, (2) -3 are more preferably the following specific compounds:
Figure BDA0002158384910000073
Figure BDA0002158384910000074
among them, (2) to 4 are more preferably the following specific compounds:
Figure BDA0002158384910000075
among them, (2) to 5 are more preferably the following specific compounds:
Figure BDA0002158384910000081
among them, (2) to 6 are more preferably the following specific compounds:
Figure BDA0002158384910000082
among them, (2) -7 are preferred compounds:
Figure BDA0002158384910000083
among them, (2) to 8 are preferred compounds:
Figure BDA0002158384910000084
the liquid crystal composition of the present invention is characterized in that the composition comprises at least one liquid crystal compound selected from the group consisting of liquid crystal compounds represented by the general structural formula (3) as a third component:
Figure BDA0002158384910000091
wherein R is a straight-chain alkyl group, an alkenyl group, or an alkyl group containing an ethylenic bond, and ring B, ring C, and ring D are a benzene ring, a cyclohexane ring, a tetrahydropyran ring, a dioxane ring, wherein the benzene ring may be substituted with 1 or more fluorine atoms; x1，X2＝H，F；Y＝F，Cl，OCF3，OCF2H, straight-chain alkyl groups or alkyl groups containing an ethylenic bond, etc.; z ═ CF2O，CH2CH2COO, single bond, etc.; n is 0, 1. The third component of the invention is characterized in that the liquid crystal compound with a larger delta epsilon value has a mass proportion of 1-50%, preferably 5-45% by weight, more preferably 10-40%.
Wherein the general formula (3) is preferably of the following specific structure:
Figure BDA0002158384910000092
Figure BDA0002158384910000101
among them, (3) -1 is preferably a compound:
Figure BDA0002158384910000102
Figure BDA0002158384910000111
among them, (3) -2 is preferably a compound:
Figure BDA0002158384910000112
Figure BDA0002158384910000121
among them, (3) -3 are preferably compounds:
Figure BDA0002158384910000122
among them, (3) -4 are preferred compounds:
Figure BDA0002158384910000131
among them, (3) -5 are preferred compounds:
Figure BDA0002158384910000132
among them, (3) -6 are preferred compounds:
Figure BDA0002158384910000133
among them, (3) -7 are preferred compounds:
Figure BDA0002158384910000141
among them, (3) -8 are preferred compounds:
Figure BDA0002158384910000142
among them, (3) to 9 are preferred compounds:
Figure BDA0002158384910000143
among them, (3) -10 are preferred compounds:
Figure BDA0002158384910000144
among them, (3) -11 are preferred compounds:
Figure BDA0002158384910000151
among them, (3) -12 are preferred compounds:
Figure BDA0002158384910000152
among them, (3) -13 are preferred compounds:
Figure BDA0002158384910000153
among them, (3) to 14 are preferred compounds:
Figure BDA0002158384910000154
the liquid crystal composition is characterized by also comprising one or more liquid crystal compounds selected from the liquid crystal compounds shown in the structural general formula (4) as a fourth component:
Figure BDA0002158384910000155
wherein R is1、R2Is a C1-7 linear alkyl or alkoxy group, a C2-7 linear alkenyl or alkenyloxy group, and the ring B, the ring C and the ring D are benzene rings, cyclohexane and tetrahydropyrane rings, wherein the benzene rings can be substituted by 1 or more fluorine atoms; x1，X2H, F; z being a single bond, CH2CH2，CH2O; n is 0, 1. The fourth component of the invention is a liquid crystal material with negative delta epsilon, and the mass proportion of the liquid crystal material is 0-30%, preferably 2-20% by weight, and more preferably 3-15%.
Wherein the general formula (4) is preferably of the following specific structure:
Figure BDA0002158384910000161
among them, (4) -1 is preferably a compound:
Figure BDA0002158384910000162
among them, (4) -2 are preferred compounds:
Figure BDA0002158384910000163
among them, (4) -3 are preferred compounds:
Figure BDA0002158384910000164
among them, (4) -4 are preferred compounds:
Figure BDA0002158384910000165
Figure BDA0002158384910000171
among them, (4) -5 are preferably the following compounds:
Figure BDA0002158384910000172
the liquid crystal composition can also comprise one or more chiral additives, and the content is 0.01-1%; preferably 0.1% to 0.5%. The chiral additive is preferably selected from the following structures:
Figure BDA0002158384910000173
the liquid crystal composition also comprises a plurality of hindered phenols as antioxidant stabilizers, and the content of the hindered phenols is 1ppm-10000 ppm; preferably from 10ppm to 1000 ppm. The antioxidant stabilizer is preferably selected from the following structures:
Figure BDA0002158384910000174
the liquid crystal composition also comprises one or more ultraviolet light stabilizers with the content of 1ppm to 10000 ppm; preferably from 10ppm to 1000 ppm. The ultraviolet light stabilizer is preferably selected from the following structures:
Figure BDA0002158384910000175
the invention may further comprise one or more liquid crystal components having a polymerizable group in an amount of 1ppm to 10000 ppm; preferably 100ppm to 1000 ppm. The polymerizable liquid crystal component is preferably selected from the following structures:
Figure BDA0002158384910000181
the liquid crystal composition has larger average dielectric constant, lower rotational viscosity and faster response speed, and is suitable for TFT liquid crystal display technology, especially FFS and IPS modes.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
The preparation method of the liquid crystal formula comprises the following steps: a thermal dissolution method is used. Firstly, weighing monomer liquid crystals with different weight proportions by using a precision balance, heating to 60-100 ℃, and stirring and mixing for 1-2 hours to uniformly dissolve all components. Cooling, filtering, degassing the filtered liquid in high vacuum (less than or equal to 100Pa), and packaging with high-purity nitrogen to obtain the target mixed liquid crystal.
Unless otherwise specified, the liquid crystal compositions according to the invention are prepared according to this process.
And testing the physical property and the photoelectric property of the mixed liquid crystal. The detailed test method of the physical property and the photoelectric property comprises the following steps:
(1) clearing point (Tni):
the polarizing hot stage method: the liquid crystal sample was coated on a glass slide and placed in an orthogonal polarization microscope hot stage with a temperature rise rate of 2 ℃/min. And observing the temperature at which the liquid crystal sample turns black from a bright state in a polarizing microscope, namely the clearing point.
Or by differential scanning calorimetry: the heating rate was set at 2 ℃/min under nitrogen atmosphere.
(2) Low temperature storage temperature (LTS): about 1mL of the mixed liquid crystal was put into a transparent glass bottle and placed in a low-temperature refrigerator. The temperature is set to-20 ℃, 30 ℃ and 40 ℃, and the mixture is stored for 10 days respectively, and whether crystal precipitation or smectic phase exists is observed. If no crystal is precipitated at the temperature of minus 30 ℃, LTS is less than or equal to minus 30 ℃.
(3) Birefringence (Δ n): respectively measuring ordinary rays (n) by using Abbe refractometer at constant temperature of 25 DEG Co) And extraordinary ray (n)e) Refractive index of (1), birefringence (Δ n) being equal to ne－no。
(4) Dielectric constant (Δ ∈): and (3) testing by using an LCR (liquid crystal resistance) meter at the constant temperature of 25 ℃. Δ ε ═ ε∥-ε⊥I.e. the dielectric constant (. epsilon.) in the direction of the molecular long axis∥) Dielectric constant (. epsilon.) with respect to the minor axis of the molecule⊥) The difference of (a).
(5) Spring constant (K)11，K33): under the constant temperature condition of 25 ℃, K is obtained by testing a liquid crystal capacitance-voltage (C-V) curve and fitting11And K33。
(6) Rotational viscosity (. gamma.)1): under the constant temperature condition of 25 ℃, the transient current value Ip of the liquid crystal molecules deflected along with the movement of the electric field is tested by applying voltage to the liquid crystal test box, and the rotational viscosity gamma is calculated1。
The performance of the monomer liquid crystal was tested by dissolving it in the following basic formulation (Host). The property parameters of the monomers, e.g. clearing point, Δ ε, Δ n, γ1Calculated by extrapolation. The basic formula (Host) is prepared from the following three liquid crystal compounds according to the mass ratio of 1:1: 1.
Figure BDA0002158384910000191
Code number and description:
(1) physical parameters
(Code) Description of the invention Unit of
Tni Clearing points ℃
TCN Low temperature storage temperature ℃
ε⊥ Dielectric constant perpendicular to director
ε∥ Dielectric constant parallel to the director
εave Average dielectric constant
Δε Dielectric anisotropy
Δn Double refractive index
γ1 Rotational viscosity mPa·s
K11 Elasticity constant of splay pN
K33 Flexural elastic constant pN
(2) Structural abbreviations
Figure BDA0002158384910000192
Figure BDA0002158384910000201
For example:
Figure BDA0002158384910000202
liquid crystal phase transition temperature: c represents melting point, S represents smectic phase, N represents nematic phase, and Iso represents liquid state.
Example 1:
synthesis of 2, 3-difluoro-1- (trans-4-pentylcyclohexyl) -4- (2, 2-difluoroethoxy) benzene
The reaction equation is as follows:
Figure BDA0002158384910000203
the specific synthesis steps are as follows:
(1) synthesis of 2, 3-difluoro-1- (trans-4-pentylcyclohexyl) -phenol
In a 500mL three-necked flask, 2, 3-difluoro-1- (trans-4-pentylcyclohexyl) -4-ethoxybenzene (31.0g, 0.1mol) and 100mL of methylene chloride were added, the temperature was lowered to-10 ℃ and BBr was added dropwise3After the solution is dripped, the temperature is naturally raised to the room temperature, and after the reaction is carried out for 3 hours, water is slowly dripped to quench the reaction. Standing, separating, washing the organic phase to neutrality, drying with anhydrous sodium sulfate, filtering, and spin-drying to obtain light yellow solid. 1g of n-heptane: 2ml of the mixture was recrystallized to obtain 26.2g of white crystals. GC content 99.9% and yield 93%.
(2) Synthesis of 2, 3-difluoro-1- (trans-4-pentylcyclohexyl) -4- (2, 2-difluoroethoxy) benzene
Into a 250mL three-necked flask, 2, 3-difluoro-1- (trans-4-pentylcyclohexyl) -phenol (14.1g, 0.05mol), anhydrous potassium carbonate (13.8g, 0.10mol), CF were added2HCH2OSO2CH3(8.0g, 0.05mol) and DMF (50mL) were heated to 130 ℃ with stirring for 8 h. The temperature was lowered to room temperature, and 100ml of water and 50ml of toluene were added thereto, followed by extraction with 2. Washing the organic phase twice, drying the organic phase by anhydrous sodium sulfate, filtering the organic phase, and spin-drying the filtrate to obtain light yellow oily liquid. Dissolving the crude product with n-heptane, passing through silica gel column, eluting with n-heptane, and spin drying to obtain colorless oily liquid. Ethanol was added for recrystallization to give 14.0g of a white crystalline product. GC content 99.9% and yield 81%.
The structure identification data is as follows:
1HNMR(CDCl3，500MHz)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)。
physical property test data are as follows:
melting point by DSC: c49.19 Iso.
Dissolving the compound into a basic formula by the mass ratio of 10% for physical property test, and extrapolating to obtain the following performance parameters: t isni＝-39.4℃；Δn＝0.0564；ε⊥＝9.202，ε∥＝9.142，εave＝9.182，Δε＝-0.078；γ1＝-9mPa·s。
Example 2: synthesis of 4- (2, 3-difluoro-4- (2, 2-difluoroethoxy) phenyl) -trans-4' -propylbicyclohexane
Figure BDA0002158384910000211
In the same manner as in example 1, 4- (2, 3-difluoro-4- (2, 2-difluoroethoxy) phenyl) -trans-4' -propylbicyclohexane was obtained.
The structure identification data is as follows:
1H NMR(CDCl3，500MHz)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)。
physical property test data are as follows:
melting point by DSC: C96.96N 161.99 Iso.
Dissolving the compound into a basic formula by the mass ratio of 10% for physical property test, and extrapolating to obtain the following performance parameters: t isni＝144.3℃；Δn＝0.098；ε⊥＝8.298，ε∥＝7.960，εave＝8.185，Δε＝-0.338；γ1＝305mPa·s。
Example 3: synthesis of 4' - (trans-propylcyclohexyl) -2, 3-difluoro-4- (2, 2-difluoroethoxy) biphenyl
Figure BDA0002158384910000221
In the same manner as in example 1, 4' - (trans-propylcyclohexyl) -2, 3-difluoro-4- (2, 2-difluoroethoxy) biphenyl was obtained.
The structure identification data is as follows:
1H NMR(CDCl3，500MHz)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)。
physical property test data are as follows:
melting point by DSC: C85.67SA105.59N 145.6Iso。
Dissolving the compound into a basic formula by the mass ratio of 10% for physical property test, and extrapolating to obtain the following performance parameters: t isni＝123.2℃；Δn＝0.1382；ε⊥＝9.588，ε∥＝10.57，εave＝9.915，Δε＝0.992；γ1＝217mPa·s。
Example 4: synthesis of 4 '- (trans-4-propylcyclohexyl) -2, 2', 3-trifluoro-4- (2, 2-difluoroethoxy) biphenyl
Figure BDA0002158384910000231
In the same manner as in example 1, 4 '- (trans-4-propylcyclohexyl) -2, 2', 3-trifluoro-4- (2, 2-difluoroethoxy) biphenyl was obtained.
The structure identification data is as follows:
1H NMR(CDCl3，500MHz)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)。
physical property test data are as follows:
melting point by DSC: C71.81N 98.89 Iso.
Dissolving the compound into a basic formula by the mass ratio of 10% for physical property test, and extrapolating to obtain the following performance parameters: t isni＝90.0℃；Δn＝0.1452；ε⊥＝10.198，ε∥＝12.120，εave＝10.839，Δε＝1.922；γ1＝245mPa·s。
Example 5: synthesis of 2, 3-difluoro-1- (4- (trans-4-propylcyclohexyl) cyclohex-1-enyl) -4- (2, 2-difluoroethoxy) benzene
Figure BDA0002158384910000232
The intermediate 2, 3-difluoro-1- (4- (trans-4-propylcyclohexyl) cyclohex-1-enyl) -4-phenol was prepared by the same procedure as in example 1.
3.3g of 2, 3-difluoro-1- (4- (4-propylcyclohexyl) cyclohex-1-enyl) -4-phenol, 2.0g of diethyl azodicarboxylate and 3.5g of triphenylphosphine were dissolved in 30ml of tetrahydrofuran, and the temperature was reduced to 0 ℃ to drop-add a solution of 1.1g of difluoroethanol in 20ml of tetrahydrofuran. After the dropwise addition, the mixture was slowly warmed to room temperature and stirred for 4 hr. The reaction mixture was poured into water, and 50ml of toluene was added thereto for extraction. The organic phase was dried and the solvent was removed under reduced pressure. Dissolving the crude product with n-heptane, passing through silica gel column, eluting with n-heptane, and spin drying to obtain white solid. Ethanol was added thereto for recrystallization to obtain 3.1g of white crystals. GC content 99.9% and yield 78%.
The structure identification data is 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)。
physical property test data are as follows:
melting point by DSC: C89.46S 124.28N 155.72 Iso.
Dissolving the compound into a basic formula by the mass ratio of 10% for physical property test, and extrapolating to obtain the following performance parameters: t isni＝117.4℃；Δn＝0.0732；ε⊥＝9.458，ε∥＝9.44，εave＝9.452，Δε＝-0.018；γ1＝198mPa·s。
Example 6 (composition)
Figure BDA0002158384910000241
Example 7 (composition)
Figure BDA0002158384910000251
Example 8 (composition)
Figure BDA0002158384910000252
Figure BDA0002158384910000261
Comparative example 1:
a 2, 3-difluoro-4-ethoxybenzene-containing liquid crystal compound represented by the following formula:
Figure BDA0002158384910000262
adding the mixture into a basic formula HOST according to the mass ratio of 10%, carrying out physical property test, and extrapolating to obtain the following performance parameters: t isni＝176.0℃；Δn＝0.1683；ε⊥＝9.991，ε∥＝6.887，εave＝8.956，Δε＝-2.935；γ1＝255.9mPa·s。
Example 3 of the present invention has a significantly increased ε compared to comparative example 1∥，εaveIncreasing; and gamma1And (4) greatly reducing.
Comparative example 2:
patent US6159393A discloses liquid crystal compounds of the following structure:
Figure BDA0002158384910000263
the liquid crystal compound is different from the present invention in the substitution position of fluorine atom on the benzene ring. Adding the mixture into a basic formula HOST according to the mass ratio of 10%, carrying out physical property test, and extrapolating to obtain the following performance parameters: t isni＝92.2℃；Δn＝0.1402；ε⊥＝6.168，ε∥＝19.02，εave＝10.452，Δε＝12.852；γ1＝229mPa·s。。
Example 4 of the present invention has a significantly increased ε compared to comparative example 2⊥And a larger epsilonave。
Comparative example 3:
Figure BDA0002158384910000264
Figure BDA0002158384910000271
comparative example 3 monomeric liquid crystal 5CYO2F from example 7 of the invention2The other components and the corresponding mass ratio are unchanged when the component is replaced by 5CYO 2. Example 7 of the present invention has a close ε compared to comparative example 4⊥Value, and lower gamma1And a larger delta epsilon is beneficial to improving the light transmittance of the display device and improving the response speed of the device.

Claims (5)

1. A difluoroethoxy group-containing liquid crystal compound is characterized in that the structure is shown as a general formula (1):
Figure FDA0003348110000000011
wherein R is a linear alkyl or alkoxy group with a carbon number of 1-9 or an alkenyl group with a carbon number of 2-7; ring a is a trans-cyclohexane, cyclohexenyl or phenyl ring, wherein the hydrogen atoms of the phenyl ring may be substituted by 1 or more fluorine atoms; n, m is 0, 1, 2; x1、X2Is a hydrogen atom or a fluorine atom; and when m is 0 and R is an alkenyl group having 2 to 7 carbon atoms, ring a is not a cyclohexenyl group.
2. The liquid crystal compound according to claim 1, wherein n is 1 and m is 0.
3. The liquid crystal compound according to claim 1, wherein n is 1 and m is 1.
4. A nematic phase liquid crystal composition is characterized by comprising a liquid crystal compound as a first component, wherein the liquid crystal compound has a structural general formula (1) and is contained in the first component in an amount of 1-70 wt%:
Figure FDA0003348110000000012
wherein R, ring A, n, m, X1、X2Is as defined in claim 1.
5. A liquid crystal display element comprising the liquid crystal composition according to claim 4.
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