CN109679666A - Liquid-crystal compounds and preparation method thereof, liquid-crystal composition and microwave communication device - Google Patents
Liquid-crystal compounds and preparation method thereof, liquid-crystal composition and microwave communication device Download PDFInfo
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- CN109679666A CN109679666A CN201910088480.4A CN201910088480A CN109679666A CN 109679666 A CN109679666 A CN 109679666A CN 201910088480 A CN201910088480 A CN 201910088480A CN 109679666 A CN109679666 A CN 109679666A
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- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
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- 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
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Abstract
The present invention discloses a kind of liquid-crystal compounds and preparation method thereof, liquid-crystal composition and microwave communication device, and the liquid-crystal compounds has the structure as shown in structural formula (I).There is quaterphenyl structure in the structure of the liquid-crystal compounds provided by the invention, thus have the advantages that optical anisotropy greatly and stable structure, when it is applied in high dielectric anisotropic liquid crystals material, the dielectric loss of liquid crystal microwave device is advantageously reduced, phase-modulation ability is improved and increases the quality factor of liquid crystal material.
Description
Technical field
The present invention relates to technical field of organic synthesis, in particular to a kind of liquid-crystal compounds and preparation method thereof, liquid crystal group
Close object and microwave communication device.
Background technique
Currently, liquid crystal has been widely used in display field, however, in some researchs, liquid crystal media also by
It is proposed to be used in the component of microwave technology.Liquid crystal starts from the end of last century for microwave device research, and high speed development is in this century
Just；Global extensive concern had especially been obtained in recent years, had been quickly grown, and research finds that it can be used for tunable filter, can weigh
The key areas such as structure antenna, adjustable frequency selector and adjustable phase shifter, for example, Lim K.C. in 1993 et al. is using commercial liquid
Brilliant K15 applies 16V bias-voltage according to electro-optic birefringent effect, and 20 ° of phase shift is obtained in 10.5GHz frequency, is realized micro-
Wave phase is adjustable；Germany in 2002 reports a kind of Planar integration liquid crystal tunable phase shifter, obtains near 18GHz frequency 53 °
Phase shift, by world's colleague's most attention etc..
Nevertheless, but in related key technical, such as liquid crystal material, orientation, encapsulation, wiring, device design and menu
Sign etc. is many-sided all to have basic problem anxious to be resolved, and the research report especially in terms of liquid crystal material is less.For convenient for
Understand, be described below to the correlation performance parameters of liquid crystal material: Δ ε indicates dielectric anisotropy；△ n indicates optics respectively to different
Property, i.e. refractive index (589nm, 25 DEG C)；It Iso. is the clearing point temperature (DEG C) of the phase of liquid-crystal composition；In microwave range
Dielectric anisotropy is defined as: △ εr≡(εr||-εr⊥)；Tunability (τ) is defined as: τ ≡ (Δ ε r/ ε r | |)；Material product
Matter (η) is defined as: η ≡ (τ/tan δ ε r max.), maximum dielectric loss are as follows: tan δ ε r max. ≡ max. { tan δ ε r ⊥, tan δ
εr||}.Wherein, the wave frequency that dielectric loss refers to that microwave (4~40GHZ) irradiation or across liquid crystal material when generate absorbs and causes
The loss of microwave wave frequency, be usually microwave Insertion Loss；Dielectric constant " Δ ε is shown as in liquid crystal materialr", dielectric constant is divided into flat
Component " the ε of row liquid crystal long axisr∥ " and vertical component " εr⊥ ", dielectric constant values are Δ εr=εr∥-εr⊥；Physically to microwave
The quantitative expression of " dielectric loss " is: tangent value (the tan δ ε of dielectric lossr⊥ or tan δ εr max), it is that reflecting liquid crystal material exists
Main performance index parameter in microwave field generally requires tan δ εr⊥ (or tan δ εr max) value≤0.03 or so, tan δ εr∥
Value≤0.006 or so.Birefringence is liquid-crystal compounds and the anisotropic expression of mixed liquid crystal materials optical, refers to that light is logical
After crossing liquid crystal material, by liquid crystalline refractive and scattering, ordinary light and extraordinary ray are formed, ordinary refraction index indicates " no " is non-
Ordinary refraction index indicates " ne", birefringence is indicated with " Δ n ", " Δ n=no-ne", microwave high-frequency requirement on devices Δ n value >=
The 0.30 or more, Δ n value the high more is conducive to improve microwave amount of phase shift." high Jie's low consumption " liquid crystal material refers to high dielectric respectively to different
The liquid crystal material of property, high optical anisotropy, low-dielectric loss；Microwave is after liquid crystal material irradiation, dielectric loss very little,
tanδεr⊥ (or tan δ εr max) value be lower than 0.008 or so, tan δ εr| | value is lower than 0.004." the phase of microwave liquid crystal phase shifter
The index of modulation " is expressed as " τ ", parameter of the reflecting liquid crystal material to the phase-modulation ability of microwave frequency, 0.15≤τ≤0.5.
" quality factor " (η or the FOM) of liquid crystal refers to the microwave performance synthesis evaluation result later by liquid crystal, reflects liquid crystal material
The performance and quality of material, generally require η >=15 or more.
The liquid crystal used earliest is German Merck Products K15, E7, and Δ n value is lower than 0.2, Δ ε r in high frequency
It is worth very little, dielectric loss is larger, and LC box is blocked up (d=254 μm), and the response time is more than 350ms；Later using Merck company
GT3-23001 liquid crystal, Δ n value 0.3 or so, Δ ε r reaches 0.8 under high frequency, and dielectric loss is obviously reduced, and phase shift amount is increased
Add；Recent years, Germany Merck company reported the high Δ n value mixed liquid crystal material of the polycyclic fragrant acetylene base class of isothiocyano-, Δ
N value reaches 0.25~0.30 or so, makes moderate progress to the dielectric properties of microwave device, but dielectric loss is still larger.Herman
Et al. J. reported respectively at 2013 and 2015 four benzene diethyl alkynes liquid crystal compounds of the lateral ethyl of isothiocyano-(Δ n >=
0.6), microwave phase-shift phase obviously increases, but dielectric loss is bigger than normal, and material melting point is high.Reuter M. in 2013 et al. reports height
Frequently the different end groups such as p- F ,-CN ,-NCS inhale the influence of wave.Dziaduszek J in 2017 et al. report end group be NCS, CN,
F、OCF3Etc. the △ n=0.45 liquid-crystal composition that lateral fluorodiphenyl acetylene class series compound is prepared, analysis compares these
Influence of the end group to GHz and THz wave band dielectric anisotropy.Kowerdziej R. in 2018 et al. reports fluorine-containing two
Phenylacetylene isosulfocyanate liquid-crystal composition finds this kind of liquid in the optic tunable variation with temperature situation of 6GHz frequency range
Crystalline substance varies with temperature arranging property of microwave phase (τ) and dielectric properties (△ n) unobvious, shows isothiocyano and acetenyl etc.
Structural unit is more stable to microwave.Nearest Lapanik V. et al. is on the basis of Kowerdziej R. work, using different sulphur
The more aromatic ring class mixed liquid crystal materials of cyano-, not only reduce dielectric loss, also increase microwave amount of phase shift, disclose molecule knot
Group in structure, bridged bond stability to the influence of dielectric loss, but its material melting point is not also able to satisfy still at 0 DEG C or more
Outdoor requirement.And there is not been reported for the research in terms of influencing on the low temperature photoelectric properties of microwave liquid crystal.
It is further found during existing numerous studies, microwave current is primarily present in practical applications with liquid crystal material
Following problem: 1. Δ n value is less than normal, causes amount of phase shift insufficient；2. due to the suction wave of building stone and can in liquid crystal molecule
Polarization causes the dielectric loss of liquid crystal material bigger than normal；3. lacking high Δ n value, the liquid crystal solvent of low melting point and nematic phase
Liquid crystal components lead to the cryogenic property for influencing liquid crystal material.It would therefore be highly desirable to propose a kind of novel high-stability, Δ n >=0.35,
Low melting point, high Jie's low consumption nematic liquid crystal compound.
Summary of the invention
The main object of the present invention is to propose that a kind of liquid-crystal compounds and preparation method thereof, liquid-crystal composition and microwave are logical
Interrogate device, it is intended to reduce the dielectric loss of liquid crystal microwave device.
To achieve the above object, the present invention proposes that a kind of liquid-crystal compounds, the liquid-crystal compounds have the following structure formula
(I) structure shown in:
Wherein, R1And R2It is each independently selected from H atom or the unsubstituted alkyl containing 1~7 carbon atom, X1、X2、
X3、X4And X5It is each independently selected from H atom, F atom or Cl atom.
Preferably, the liquid-crystal compounds is the chemical combination of structure shown in the formula that has following structure (I -1) to structural formula (I -6)
At least one of object:
Wherein, R of the structural formula (I -1) into structural formula (I -6)1And R2It is each independently selected from containing 2~5 carbon atoms
Alkyl.
Preferably, the liquid-crystal compounds be in the compound of structure shown in the formula that has the following structure (I -3-1) at least
It is a kind of:
Wherein, 2,3,4 or 5 m.
To achieve the above object, the present invention also proposes a kind of preparation method of liquid-crystal compounds as described above, including with
Lower step:
Step S10, under nitrogen protection, by the first reactant, 2- ethyl -4- Iodoaniline, palladium catalyst, K2CO3, ethyl alcohol,
Toluene and water carry out Suzuki 3.5~4.5h of coupling reaction under condition of heating and stirring, then by separation, washing, it is dry and
Purification process obtains the first intermediate；
Step S20, it after mixing first intermediate, the concentrated sulfuric acid and tetrahydrofuran, then is added dropwise at a temperature of 0~10 DEG C
NaNO2Aqueous solution after 50~70min of insulated and stirred, continue at a temperature of 0~10 DEG C be added dropwise KI aqueous solution, after being added dropwise
Room temperature is warmed naturally to, sodium thiosulfate solution is added, then by extraction liquid separation, extraction drying and purification process, is obtained
To the second intermediate；
Step S30, under nitrogen protection, by second intermediate, the second reactant, palladium catalyst, K2CO3, ethyl alcohol,
Toluene and water carry out Suzuki 3.5~4.5h of coupling reaction under condition of heating and stirring, then by separation, washing, it is dry and
Purification process obtains target compound, obtains liquid-crystal compounds；
Wherein, first reactant in step S10 is the compound for having the following structure structure shown in formula (II), step
Second reactant in rapid S30 is the compound for having the following structure structure shown in formula (III):
Wherein, the R in structural formula (II)1With the R in structural formula (III)2It is each independently selected from H atom or unsubstituted contains
There are the alkyl of 1~7 carbon atom, the X in structural formula (III)1、X2、X3、X4And X5It is each independently selected from H atom, F atom or Cl
Atom.
Preferably, in step slo, first reactant, 2- ethyl -4- Iodoaniline, palladium catalyst and K2CO3Rub
You are than being (1~1.5): 1:(0.01~0.3): (2~5)；And/or
In step S20, first intermediate, the concentrated sulfuric acid, NaNO2Molar ratio with KI is 1:(1~4): (1~2):
(1~3)；And/or
In step s 30, second intermediate, the second reactant, palladium catalyst and K2CO3Molar ratio be 1:(1~
2): (0.1~3): (2~5)；And/or.
The palladium catalyst is tetra-triphenylphosphine palladium；And/or
The reaction temperature of the Suzuki coupling reaction is 40~80 DEG C.
Preferably, in step slo, compound E, 2- ethyl -4- Iodoaniline, palladium catalyst and K2CO3Molar ratio
For (1~1.2): 1:(0.1~0.3): (2~4)；And/or
In step S20, the intermediate I, the concentrated sulfuric acid, NaNO2Molar ratio with KI is 1:(1.2~2): (1~
1.5): (1~2)；And/or
In step s 30, the intermediate II, compound F, palladium catalyst and K2CO3Molar ratio be 1:(1~1.2):
(0.5~1.5): (2~4).
The present invention is it is further proposed that a kind of liquid-crystal composition, the liquid-crystal composition includes first kind compound, described
First kind compound is liquid-crystal compounds as described above.
Preferably, the liquid-crystal composition further includes the second class that at least one has the following structure structure shown in formula (IV)
Compound, at least one, which have the following structure the third class compound of structure shown in formula (V) and at least one, has following knot
4th class compound of structure shown in structure formula (VI):
Wherein, the n in structural formula (IV), (V) and (VI) is respectively independent is selected from 3,4,5 or 6 certainly, structural formula (IV), (V)
(VI) m in is each independently selected from 2,3,4 or 5.
Preferably, the first kind compound, dioxins, third class compound and the 4th class compound are described
Mass fraction in liquid-crystal composition corresponds to 1~40%, 1~80%, 1~50% and 1~50%.
Preferably, first compound, dioxins, third class compound and the 4th class compound are in the liquid
Mass fraction in brilliant composition corresponds to 3~30%, 10~80%, 5~40% and 3~40%.
Preferably, the first kind compound, dioxins, third class compound and the 4th class compound are described
Mass fraction in liquid-crystal composition corresponds to 5~20%, 20~70%, 5~30% and 5~30%.
The present invention also proposes that a kind of microwave communication device, the microwave communication device include liquid crystal combination as described above
Object.
Preferably, the microwave communication device is microwave liquid crystal phase shifter, tunable optic filter or phased array antenna.
In technical solution provided by the invention, there is quaterphenyl structure in the structure of the liquid-crystal compounds, thus has
The advantages of optical anisotropy is big and stable structure, when being applied in high dielectric anisotropic liquid crystals material, advantageously reduces
The dielectric loss of liquid crystal microwave device improves phase-modulation ability and increases the quality factor of liquid crystal material.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
Other relevant attached drawings are obtained according to these attached drawings.
Fig. 1 is the flow diagram of an embodiment of the preparation method of liquid-crystal compounds provided by the invention.
The embodiments will be further described with reference to the accompanying drawings for the realization, the function and the advantages of the object of the present invention.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
The present invention is quasi- to influence the dielectric properties of microwave K frequency range by research liquid crystal molecule structure, especially dielectric loss
Effect, develops the liquid crystal material of molecular structure small to microwave absorption coefficient, that polarizability is small；Develop " high Δ n value liquid crystal
The molecular compound of solvent " and " low-melting point liquid crystal component ", the high Δ n value of design synthesizing new, low melting point, low-dielectric loss, height
The nematic liquid crystal molecule of rock-steady structure；And these liquid-crystal compounds are hybridly prepared into meet microwave device requirement height be situated between it is low
The stable Nematic phase liquid crystal material of consumption, cryogenic property.
The present invention proposes that one kind has the following structure the liquid-crystal compounds of structure shown in formula (I):
Wherein, R1And R2It is each independently selected from H atom or the unsubstituted alkyl containing 1~7 carbon atom, X1、X2、
X3、X4And X5It is each independently selected from H atom, F atom or Cl atom.
There is quaterphenyl structure in the structure of the liquid-crystal compounds provided by the invention, thus there is optical anisotropy
The advantages of big and stable structure, when being applied in high dielectric anisotropic liquid crystals material, advantageously reduce liquid crystal microwave device
Dielectric loss, improve phase-modulation ability and increase liquid crystal material quality factor.Wherein, the side group X in structural formula (I)1、
X2、X3、X4And X5More preferably at least one of them is F atom, in this way, the side chain of the liquid-crystal compounds contains ethyl simultaneously
And fluorine atom, the quaterphenyl structure having in addition, so that the optical anisotropy of the liquid-crystal compounds is bigger, structural stability
More preferably, the quality factor for being conducive to the dielectric loss for further decreasing liquid crystal material and further increasing liquid crystal material.
As the preferred embodiment of the present invention, the liquid-crystal compounds is to have following structure formula (I -1) to structural formula (I -
6) at least one of the compound of structure shown in:
Wherein, R of the structural formula (I -1) into structural formula (I -6)1And R2It is each independently selected from containing 2~5 carbon atoms
Alkyl.
As highly preferred embodiment of the invention, the liquid-crystal compounds is to have the following structure knot shown in formula (I -3-1)
At least one of compound of structure:
Wherein, 2,3,4 or 5 m.Structural formula (I -3-1) compound represented is with bigger optical anisotropy and more
Good stability, when being applied in liquid crystal material, the improvement of optical anisotropy and quality factor to liquid crystal material
It is more significant.
Further, the present invention also proposes a kind of preparation method of liquid-crystal compounds as described above, and synthetic route is such as
Under:
Fig. 1 show an embodiment of the preparation method of liquid-crystal compounds provided by the invention.Referring to Fig. 1, in this reality
Apply in example, the preparation method of the liquid-crystal compounds the following steps are included:
Step S10, under nitrogen protection, by the first reactant, 2- ethyl -4- Iodoaniline, palladium catalyst, K2CO3, ethyl alcohol,
Toluene and water carry out Suzuki 3.5~4.5h of coupling reaction under condition of heating and stirring, then by separation, washing, it is dry and
Purification process obtains the first intermediate；
The separation, washing, drying and purification process in step S10 can be according to the conventional methods of organic synthesis field
It carries out, such as by being centrifuged or being separated by filtration reaction product, is washed with water after then being extracted using organic solvent, reuses drying
Agent is dried, and finally by processing such as chromatography, elutions, obtains product after purification.In the present embodiment, step S10 is having
Following manner progress can be used in body when implementing: under nitrogen protection, the first reactant, 2- ethyl-are sequentially added into reaction flask
4- Iodoaniline, palladium catalyst, K2CO3, ethyl alcohol, toluene and water, stop stirring after 3.5~4.5h of back flow reaction under heating stirring,
Make reaction solution cooled to room temperature, filtering removal insoluble matter after hydrochloric acid neutralizes then is added, after adding toluene extraction and separation
It is washed to and is in neutrality, using being filtered after anhydrous sodium sulfate drying, will be fitted into chromatographic column after filtrate revolving drying, using petroleum ether
Elution, then by the solvent in revolving removing eluent, obtain first intermediate.Wherein, the reaction flask can be selected
The containers such as conical flask, three-necked flask or organic synthesis kettle, depending on the dosage or reaction product of reaction raw materials when specific operation
Depending on throughput requirements.
First reactant is the compound for having the following structure structure shown in formula (II):
Wherein, the R in structural formula (II)1For H atom or the unsubstituted alkyl containing 1~7 carbon atom.
Further, in the present embodiment, first reactant in step S10,2- ethyl -4- Iodoaniline, palladium are urged
Agent and K2CO3Molar ratio be (1~1.5): 1:(0.01~0.3): (2~5), more preferably (1~1.2): 1:(0.1~
0.3): (2~4).
Step S20, it after mixing first intermediate, the concentrated sulfuric acid and tetrahydrofuran, then is added dropwise at a temperature of 0~10 DEG C
NaNO2Aqueous solution after 50~70min of insulated and stirred, continue at a temperature of 0~10 DEG C be added dropwise KI aqueous solution, after being added dropwise
Room temperature is warmed naturally to, sodium thiosulfate solution is added, then by extraction liquid separation, extraction drying and purification process, is obtained
To the second intermediate；
The common method of technical field of organic synthesis equally can be used in the extraction liquid separation, purification drying and purification process etc.
It carries out, further, provides a specific implementation step of step S20 in the present embodiment: being sequentially added into reaction vessel
It after first intermediate, the concentrated sulfuric acid and tetrahydrofuran, is placed in ice salt bath, starts after temperature of charge is reduced to 0 DEG C or less
NaNO is added dropwise into material2Aqueous solution, guarantee to be added dropwise in 1h and keep temperature of charge not during entire be added dropwise
More than 10 DEG C (that is, it is 0~10 DEG C that temperature of charge is kept during being added dropwise), rear insulated and stirred 1h is added dropwise, then KI is added dropwise
Aqueous solution and temperature of charge is no more than 10 DEG C during keeping entire and being added dropwise, room temperature is warmed naturally to after being added dropwise, is added
The aqueous solution of sodium thiosulfate extracts liquid separation after being stirred, and reuses dry with anhydrous sodium sulfate after ethyl acetate extracts, rotation
It boils off except solvent, is finally fitted into chromatographic column, second intermediate is obtained after being eluted using petroleum ether.
In the present embodiment, first intermediate, the concentrated sulfuric acid, NaNO in step S202Molar ratio with KI is 1:(1
~4): (1~2): (1~3), more preferably 1:(1.2~2): (1~1.5): (1~2).
Step S30, under nitrogen protection, by second intermediate, the second reactant, palladium catalyst, K2CO3, ethyl alcohol,
Toluene and water carry out Suzuki 3.5~4.5h of coupling reaction under condition of heating and stirring, then by separation, washing, it is dry and
Purification process obtains target compound, obtains liquid-crystal compounds；
Similarly, the separation, washing, drying and the purification process in step S30 can also use organic synthesis field
Conventional method carry out, provide a specific embodiment of step S30 in the present embodiment: under nitrogen protection, Xiang Fanying
The second intermediate, the second reactant, palladium catalyst, K are sequentially added in bottle2CO3, ethyl alcohol, toluene and water, heating stirring next time
Stopping stirring after 3.5~4.5h of stream reaction, makes reaction solution cooled to room temperature, and filtering after hydrochloric acid neutralizes then is added and removes not
Molten object, adds after toluene extraction and separation to be washed to and is in neutrality, using anhydrous sodium sulfate it is dry after filter, filtrate is rotated into drying
It is fitted into chromatographic column, is eluted using petroleum ether afterwards, obtain the target compound, the as described liquid-crystal compounds.
Second reactant is the compound for having the following structure structure shown in formula (III):
Wherein, the R in structural formula (III)1For H atom or the unsubstituted alkyl containing 1~7 carbon atom, structural formula
(III) X in1、X2、X3、X4And X5It is each independently selected from H atom, F atom or Cl atom.
Further, in the present embodiment, second intermediate in step S30, the second reactant, palladium catalyst and
K2CO3Molar ratio be 1:(1~2): (0.1~3): (2~5), more preferably 1:1:(1~1.2): (0.5~1.5): (2~
4)。
Suzuki coupling reaction is also known as suzuki reaction, refers under zeroth order palladium complex catalyst, aryl or ene boric acid or
Cross-coupling occurs for borate and chlorine, bromine, iodo aromatic hydrocarbon or alkene, is usually used in synthesizing the derivative of polyene, styrene and biphenyl
Object.The catalyst of Suzuki coupling reaction mainly has two major classes: palladium catalyst and Raney nickel, wherein palladium catalyst can be used for
Aquo System, be resistant to many functional groups, and Raney nickel necessarily anhydrous and oxygen-free in the reaction.It selects in the present embodiment
Contain catalyst of the palladium catalyst of organophosphor ligand as the Suzuki coupling reaction, more preferably tetra-triphenylphosphine palladium,
Using more extensive, and stability more preferably, catalytic effect it is more preferable.In other embodiments of the invention, the palladium catalyst
Such as Ph can be selected3P、n-Bu3P or (MeO)3P etc..Further, in the present embodiment, the Suzuki coupling reaction
Reaction temperature be 40~80 DEG C.
Using the preparation method of liquid-crystal compounds provided by the invention, pass through boric acid containing alkyl biphenyl and ethyl biphenyl containing side
Bromo-derivative occur coupling reaction can mass, steadily be made side chain containing ethyl and with quaterphenyl structure LCD compound
Object, the liquid-crystal compounds have optical anisotropy big and the advantage of stable structure, can reduce when applied in liquid crystal material
The dielectric loss and raising tunability of liquid crystal material, provide performance more preferably liquid crystal material to develop microwave microwave communication device
Material.It is understood that corresponding selection has substituent group when needing to prepare the liquid-crystal compounds for having different substituents
First reactant and the second reactant can be realized, such as R in the target product of liquid-crystal compounds1For the alkane of 5 carbon atoms
Base, R2For the alkyl of 3 carbon atoms, X3For F atom, remaining X1To X5When for H atom, corresponding selection 4- n-amylbenzene boric acid
As first reactant, select fluoro- 4 ' the alkyl biphenylboronic acid of 3- as second reactant, and so on i.e.
The liquid crystal polymer with different substituents can be made, be further illustrated below in conjunction with specific embodiment.
The present invention also proposes that a kind of liquid-crystal composition, the liquid-crystal composition include first kind compound, the first kind
Compound is liquid-crystal compounds as described above, i.e., the liquid-crystalization with structure shown in structural formula (I) of above-mentioned offer of the invention
Object is closed, which can be combined to obtain the liquid-crystal composition with any existing liquid-crystal compounds, all had by institute
State the design feature of liquid-crystal compounds and bring dielectric loss is lower, the higher advantage of quality factor.
In an embodiment of the liquid crystal combination provided by the invention, the liquid-crystal composition further includes at least one tool
Dioxins, at least one just like structure shown in flowering structure formula (IV) have the following structure of structure shown in formula (V)
Three classes compound and at least one have the following structure the 4th class compound of structure shown in formula (VI):
Wherein, the n in structural formula (IV), (V) and (VI) is respectively independent is selected from 3,4,5 or 6 certainly, structural formula (IV), (V)
(VI) m in is each independently selected from 2,3,4 or 5.
It is understood that the first kind compound can be selected from such as structural formula in the liquid-crystal composition
(I) at least one of the compound of structure shown in, the dioxins can be selected from as shown in structural formula (IV)
At least one of compound of structure, the third class compound can be selected from the changes with the structure as shown in structural formula (V)
At least one of object is closed, the 4th class compound can be in the compound with the structure as shown in structural formula (VI)
It is at least one.Preferably, the first kind compound, dioxins, third class compound and the 4th class compound select
2~5 kinds of the mixture from the compound with structure shown in its counter structure formula, the liquid-crystal composition combined are being answered
The optical anisotropy of used time is larger, dielectric loss is lower, quality factor are larger.
Further, in the present embodiment, the first kind compound, dioxins, third class compound and
Mass fraction of the four class compounds in the liquid-crystal composition corresponds to 1~40%, 1~80%, 1~50% and 1~50%,
Combine the application performance of obtained liquid-crystal composition more preferably.
As a preferred embodiment of the liquid-crystal composition provided by the invention, the first kind compound, the second class
The mass fraction of compound, third class compound and the 4th class compound in the liquid-crystal composition corresponds to 3~30%, 10
~80%, 5~40% and 3~40%, the application performance of the liquid-crystal composition combined is further improved.
As another more preferably embodiment of the liquid-crystal composition provided by the invention, the first kind compound, second
The mass fraction of class compound, third class compound and the 4th class compound in the liquid-crystal composition corresponds to 5~20%,
20~70%, 5~30% and 5~30%, the application performance of the liquid-crystal composition combined it is further preferred that.
The liquid-crystal composition provided by the invention can further improve the optics of existing customary liquid-crystal composition respectively to different
Property and the stability under microwave, have the effect of that dielectric loss can be reduced, can be applied to microwave communication device field.
Further, the present invention also proposes that a kind of microwave communication device, the microwave communication device include as described above
Liquid-crystal composition.The microwave communication device can be tunable filter, reconfigurable antenna, adjustable frequency selector or adjustable
The component or device that phase shifter etc. etc. can be tuned by application magnetic field and/or electric field, provided by the invention described
In one embodiment of microwave communication device, the microwave communication device is microwave liquid crystal phase shifter, tunable optic filter or phased
Array antenna, the liquid-crystal composition provided by the invention when applying in above-mentioned three kinds of microwave communication devices, liquid crystal material
Dielectric loss is lower, quality factor are higher.
Technical solution of the present invention is described in further detail below in conjunction with specific embodiments and the drawings, it should be understood that
Following embodiment is only used to explain the present invention, is not intended to limit the present invention.
For convenient for the first kind compound (liquid crystal with structure shown in structural formula (I) in differentiation liquid-crystal composition
Compound), dioxins (compound with structure shown in structural formula (IV)), third class compound (have structural formula
(V) compound of structure shown in) and the 4th class compound (compound with structure shown in structural formula (VI)) structure, press
It is named according to the element category rule in following table 1, is liquid-crystal compounds nPP (2) by the first kind Compound nomenclature
The second class Compound nomenclature is compound nPTP (2) TPm by GIPm, is compound by the third class Compound nomenclature
The 4th class Compound nomenclature is compound nUTGTPm, combines done with the abbreviation of above-mentioned name below by nUTP (1) TPm
It further illustrates.
1 element category of table
The synthesis of embodiment 1 liquid-crystal compounds 5PP (2) GIP4, structural formula are as follows:
Preparation process are as follows:
(1) 4- n-amylbenzene boric acid (0.04mol, 7.68g), 2- ethyl -4- iodine are sequentially added into the four-hole bottle of 250mL
Aniline (0.04mol, 9.88g), K2CO3(0.10mol, 13.8g), ethyl alcohol 80mL, toluene 60mL and water 30mL, nitrogen are replaced 4 times
Catalyst tetra-triphenylphosphine palladium (0.01mol, 0.46g) is added afterwards, carry out heating stirring and liquidus temperature is made to remain 70 DEG C, returns
Stream stops stirring after reacting 4h, and reaction solution is naturally cooling to room temperature, is then added after hydrochloric acid neutralizes to filter and removes insoluble matter, then plus
It is washed to neutrality after entering toluene (3 × 50mL) extraction liquid separation, product anhydrous Na will be washed2SO4It is filtered after drying, filtrate revolving
It is fitted into chromatographic column after dry, is eluted with petroleum ether, finally revolving obtains intermediate 5PP (2) NH after removing solvent2, obtain brown liquid
Body 8.5g, yield 80.3%.
(2) intermediate 5PP (2) NH is sequentially added into the three-necked flask of 250mL2(0.035mol, 9.3g), the concentrated sulfuric acid
(98%, 0.044mol, 4.4g) and tetrahydrofuran (THF) 100mL, is placed into after ice salt bath to temperature drops to 0 DEG C and 20mL is added dropwise
NaNO2(2.4g, 0.035mol) aqueous solution is added dropwise in 1 hour and keeps reacting liquid temperature during being added dropwise that cannot surpass
10 DEG C are crossed, rear insulated and stirred 1h is added dropwise, KI (0.042mol, 6.9g) aqueous solution of 50mL is then added dropwise again, process is added dropwise
Middle holding temperature is no more than 10 DEG C, is warmed to room temperature naturally after being added dropwise, and the sodium thiosulfate of 50mL is then added
(0.042mol, 6.6g) aqueous solution extracts liquid separation, then uses anhydrous sodium sulfate after ethyl acetate (3 × 50mL) extraction after stirring
Dry, revolving removal solvent obtains rufous liquid 8.3g, is then charged into chromatographic column and is eluted with petroleum ether, obtains intermediate 5PP (2)
I obtains yellow liquid 7.6g, yield 57.6%.
(3) under nitrogen protection, sequentially added into the four-hole bottle of 250mL intermediate 5PP (2) I (0.0185mol,
7.0g), the fluoro- 4 '-normal-butyl biphenylboronic acid (0.0185mol, 5.03g) of 3-, K2CO3(0.0555mol, 7.6g), ethyl alcohol 60mL,
Toluene 50mL and water 15mL, nitrogen are added catalyst tetra-triphenylphosphine palladium (0.01mol, 0.21g) after replacing 4 times, are heated
It stirs and liquidus temperature is made to remain 70 DEG C, stop stirring after back flow reaction 4h, reaction solution is naturally cooling to room temperature, is then added
Insoluble matter is removed in filtering after hydrochloric acid neutralizes, and is washed to neutrality after adding toluene (3 × 50mL) extraction liquid separation, washing product is used
Anhydrous Na2SO4It is filtered after drying, is fitted into chromatographic column after filtrate revolving is dry, is eluted with petroleum ether, after revolving removes solvent, tied again
It is brilliant that target compound 5PP (2) GIP4, acquisition white solid 4.7g, yield 53.4%, phase transition temperature are 56.3 DEG C of Cr,
73.8 DEG C of Sm, N 110.3 DEG C of I, △ n (optical anisotropy, i.e. birefringence (589nm, 25 DEG C)) are 0.295.
Structure detection, test result are carried out through hydrogen-NMR spectrum and fluoro- NMR spectrum are as follows:
1H-NMR(CDCl3, 400MHz) and δ (ppm): 7.35~7.66 (m, 14H), 2.72~2.77 (m, 6H), 1.72~
1.77 (m, 4H), 1.45~1.49 (m, 6H), 0.99~1.26 (m, 9H)；
13C-NMR (100MHz, CDCl3) δ (ppm): 14.050,14.132,15.273,22.478,22.656,
26.490,31.267,31.663,33.665,35.390,35.690,113.73,122.36,124.33,126.88,127.35,
128.88,129.07,130.81,132.04,133.73,137.02,138.46,141.15,142.21,158.84,161.28；
19F-NMR (376.29MHz, CDCl3) δ (ppm): -114.34.
Illustrate that the structure of target compound obtained is consistent with structure shown in structure above.
The synthesis of embodiment 2 liquid-crystal compounds 5PP (2) GIP5, structural formula are as follows:
Preparation process are as follows:
(1) 4- n-amylbenzene boric acid (0.08mol, 15.36g), 2- ethyl -4- are sequentially added into the four-hole bottle of 250mL
Iodoaniline (0.08mol, 19.76g), K2CO3(0.24mol, 33.12g), ethyl alcohol 100mL, toluene 60mL and water 35mL, nitrogen are set
Catalyst tetra-triphenylphosphine palladium (0.01mol, 1.24g) is added after changing 4 times, carry out heating stirring and liquidus temperature is made to remain 70
DEG C, stop stirring after back flow reaction 4h, reaction solution is naturally cooling to room temperature, and filtering is removed insoluble after then addition hydrochloric acid neutralizes
Object is washed to neutrality after adding toluene (3 × 50mL) extraction liquid separation, will wash product anhydrous Na2SO4It filters, filters after drying
It is fitted into chromatographic column after liquid revolving is dry, is eluted with petroleum ether, finally revolving obtains intermediate 5PP (2) NH after removing solvent2, obtain
Brown liquid 16.94g, yield 79.3%.
(2) intermediate 5PP (2) NH is sequentially added into the three-necked flask of 250mL2(0.05mol, 13.35g), the concentrated sulfuric acid
(98%, 0.075mol, 7.5g) and tetrahydrofuran (THF) 150mL, is placed into ice salt bath after dropping to 0 DEG C to temperature and is added dropwise
The NaNO of 30mL2(4.14g, 0.06mol) aqueous solution, be added dropwise in 1 hour and keep be added dropwise during reacting liquid temperature not
It can exceed that 10 DEG C, rear insulated and stirred 1h be added dropwise, KI (0.10mol, 16.6g) aqueous solution of 50mL is then added dropwise again, be added dropwise
It keeps temperature to be no more than 10 DEG C in the process, is warmed to room temperature naturally after being added dropwise, the sodium thiosulfate of 50mL is then added
(0.10mol, 15.8g) aqueous solution extracts liquid separation, then uses anhydrous sodium sulfate after ethyl acetate (3 × 50mL) extraction after stirring
Dry, revolving removal solvent obtains rufous liquid, is then charged into chromatographic column and is eluted with petroleum ether, obtains intermediate 5PP (2) I, obtain
Obtain yellow liquid 9.26g, yield 49.0%.
(3) under nitrogen protection, sequentially added into the four-hole bottle of 250mL intermediate 5PP (2) I (0.0085mol,
3.2g), the fluoro- 4 '-normal-butyl biphenylboronic acid (0.0085mol, 2.4g) of 3-, K2CO3 (0.021mol, 2.9g), ethyl alcohol 60mL, first
Catalyst tetra-triphenylphosphine palladium (0.01mol, 0.098g) is added after replacing 4 times in benzene 40mL and water 15mL, nitrogen, carries out heating and stirs
It mixes and liquidus temperature is made to remain 70 DEG C, stop stirring after back flow reaction 4h, reaction solution is naturally cooling to room temperature, salt is then added
Insoluble matter is removed in filtering after acid neutralizes, and is washed to neutrality after adding toluene (3 × 50mL) extraction liquid separation, will wash product nothing
It is filtered after water Na2SO4 is dry, is fitted into chromatographic column after filtrate revolving is dry, is eluted with petroleum ether, after revolving removes solvent, tied again
It is brilliant that target compound 5PP (2) GIP5, acquisition white solid 1.9g, yield 45.4%, phase transition temperature are Cr75.8 DEG C of N
112.5 DEG C of I, △ n are 0.301.
Structure detection, test result are carried out through hydrogen-NMR spectrum and fluoro- NMR spectrum are as follows:
1H-NMR(CDCl3, 400MHz) and δ (ppm): 7.35~7.66 (m, 14H), 2.72~2.77 (m, 6H), 1.45~
1.79 (m, 10H), 0.99~1.26 (m, 9H)；
13C-NMR (100MHz, CDCl3) δ (ppm): 14.050,14.132,15.273,22.478,22.656,26.490,
31.267,31.663,32.452,33.665,35.390,35.690,113.73,122.36,124.33,126.88,127.35,
128.88,129.07,130.81,132.04,133.73,137.02,138.46,141.15,142.21,158.84,161.28；
19F-NMR (376.29MHz, CDCl3) δ (ppm): -114.34.
Illustrate that the structure of target compound obtained is consistent with structure shown in structure above.
The synthesis of embodiment 3 liquid-crystal compounds 5PP (2) GIP2, structural formula are as follows:
Step is same as Example 1, the difference is that, the fluoro- 4 '-normal-butyl biphenylboronic acid of 3- in step (3) is replaced
Change the fluoro- 4 '-ethyl biphenyl boric acid of 3- into.
Detected through hydrogen-NMR spectrum and fluoro- NMR spectrum, it was demonstrated that the structure of target compound obtained with it is upper
It is consistent to state structure shown in structural formula.
The synthesis of embodiment 4 liquid-crystal compounds 5PP (2) GIP3, structural formula are as follows:
Step is same as Example 1, the difference is that, the fluoro- 4 '-normal-butyl biphenylboronic acid of 3- in step (3) is replaced
Change the fluoro- 4 '-pentylbiphenyl boric acid of 3- into.
Detected through hydrogen-NMR spectrum and fluoro- NMR spectrum, it was demonstrated that the structure of target compound obtained with it is upper
It is consistent to state structure shown in structural formula.
Embodiment 5
Step is same as Example 1, the difference is that:
4- n-amylbenzene boric acid, 2- ethyl -4- Iodoaniline, tetra-triphenylphosphine palladium and K in step (1)2CO3Molar ratio
For 1.2:1:0.1:4；
Intermediate 5PP (2) NH in step (2)2, the concentrated sulfuric acid, NaNO2Mole ratio with KI is 1:2:1.5:1；
The fluoro- 4 '-normal-butyl biphenylboronic acid of intermediate 5PP (2) I, 3-, tetra-triphenylphosphine palladium and K in step (3)2CO3's
Molar ratio is 1:1.2:1.5:2.
It is detected through hydrogen-NMR spectrum and fluoro- NMR spectrum, it was demonstrated that the structure and reality of target compound obtained
It is consistent to apply structure shown in structural formula in example 1.
Embodiment 6
Step is same as Example 1, the difference is that:
4- n-amylbenzene boric acid, 2- ethyl -4- Iodoaniline, tetra-triphenylphosphine palladium and K in step (1)2CO3Molar ratio
For 1.1:1:0.3:2；
Intermediate 5PP (2) NH in step (2)2, the concentrated sulfuric acid, NaNO2Mole ratio with KI is 1:1.2:1.3:1.5；
The fluoro- 4 '-normal-butyl biphenylboronic acid of intermediate 5PP (2) I, 3-, tetra-triphenylphosphine palladium and K in step (3)2CO3's
Molar ratio is 1:1.1:0.8:4.
It is detected through hydrogen-NMR spectrum and fluoro- NMR spectrum, it was demonstrated that the structure and reality of target compound obtained
It is consistent to apply structure shown in structural formula in example 1.
Embodiment 7
Step is same as Example 1, the difference is that:
4- n-amylbenzene boric acid, 2- ethyl -4- Iodoaniline, tetra-triphenylphosphine palladium and K in step (1)2CO3Molar ratio
For 1.5:1:0.01:5；
Intermediate 5PP (2) NH in step (2)2, the concentrated sulfuric acid, NaNO2Mole ratio with KI is 1:3:1.8:3；
The fluoro- 4 '-normal-butyl biphenylboronic acid of intermediate 5PP (2) I, 3-, tetra-triphenylphosphine palladium and K in step (3)2CO3's
Molar ratio is 1:1.5:0.1:3.5.
It is detected through hydrogen-NMR spectrum and fluoro- NMR spectrum, it was demonstrated that the structure and reality of target compound obtained
It is consistent to apply structure shown in structural formula in example 1.
Embodiment 8
Step is same as Example 1, the difference is that:
4- n-amylbenzene boric acid, 2- ethyl -4- Iodoaniline, tetra-triphenylphosphine palladium and K in step (1)2CO3Molar ratio
For 1.3:1:0.05:3.5；
Intermediate 5PP (2) NH in step (2)2, the concentrated sulfuric acid, NaNO2Mole ratio with KI is 1:4:2:2.5；
The fluoro- 4 '-normal-butyl biphenylboronic acid of intermediate 5PP (2) I, 3-, tetra-triphenylphosphine palladium and K in step (3)2CO3's
Molar ratio is 1:2:3:5.
It is detected through hydrogen-NMR spectrum and fluoro- NMR spectrum, it was demonstrated that the structure and reality of target compound obtained
It is consistent to apply structure shown in structural formula in example 1.
Embodiment 9
Step is same as Example 1, the difference is that, the back flow reaction temperature in step (1) and step (3) is 80
℃。
It is detected through hydrogen-NMR spectrum and fluoro- NMR spectrum, it was demonstrated that the structure and reality of target compound obtained
It is consistent to apply structure shown in structural formula in example 1.
Embodiment 10
Step is same as Example 1, the difference is that, the back flow reaction temperature in step (1) and step (3) is 55
℃。
It is detected through hydrogen-NMR spectrum and fluoro- NMR spectrum, it was demonstrated that the structure and reality of target compound obtained
It is consistent to apply structure shown in structural formula in example 1.
Embodiment 11
Step is same as Example 1, the difference is that, the back flow reaction temperature in step (1) and step (3) is 40
℃。
It is detected through hydrogen-NMR spectrum and fluoro- NMR spectrum, it was demonstrated that the structure and reality of target compound obtained
It is consistent to apply structure shown in structural formula in example 1.
Embodiment 12
The each component mass fraction (Wt%) and performance parameter of liquid-crystal composition are as shown in table 2.
In 2 embodiment 12 of table in liquid-crystal composition each component mass fraction and performance parameter
Embodiment 13
The each component mass fraction (Wt%) and performance parameter of liquid-crystal composition are as shown in table 3.
In 3 embodiment 13 of table in liquid-crystal composition each component mass fraction and performance parameter
Embodiment 14
The each component mass fraction (Wt%) and performance parameter of liquid-crystal composition are as shown in table 4.
In 4 embodiment 14 of table in liquid-crystal composition each component mass fraction and performance parameter
Embodiment 15
The each component mass fraction (Wt%) and performance parameter of liquid-crystal composition are as shown in table 5.
In 5 embodiment 15 of table in liquid-crystal composition each component mass fraction and performance parameter
Embodiment 16
The each component mass fraction (Wt%) and performance parameter of liquid-crystal composition are as shown in table 6.
In 6 embodiment 16 of table in liquid-crystal composition each component mass fraction and performance parameter
Embodiment 17
The each component mass fraction (Wt%) and performance parameter of liquid-crystal composition are as shown in table 7.
In 7 embodiment 17 of table in liquid-crystal composition each component mass fraction and performance parameter
By the performance parameter result of liquid-crystal composition in the various embodiments described above it is found that liquid crystal group provided in an embodiment of the present invention
Close object has biggish optical anisotropy, lower dielectric loss and biggish quality factor under microwave, can be used as micro-
Liquid crystal material in wave microwave communication device uses, and especially can be used as microwave phase shifter nematic liquid crystal material, is a kind of high Δ n
Value, low melting point, low-dielectric loss, high stable structure Nematic phase liquid crystal material.
The above is only a preferred embodiment of the present invention, is not intended to limit the scope of the invention, for this field
For technical staff, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any
Modification, equivalent replacement, improvement etc. should all be included within the scope of the present invention.
Claims (10)
1. a kind of liquid-crystal compounds, which is characterized in that the liquid-crystal compounds has the following structure structure shown in formula (I):
Wherein, R1And R2It is each independently selected from H atom or the unsubstituted alkyl containing 1~7 carbon atom, X1、X2、X3、X4
And X5It is each independently selected from H atom, F atom or Cl atom.
2. liquid-crystal compounds as described in claim 1, which is characterized in that the liquid-crystal compounds is to have following structure formula
At least one of the compound of structure shown in (I -1) to structural formula (I -6):
Wherein, R of the structural formula (I -1) into structural formula (I -6)1And R2It is each independently selected from the alkane containing 2~5 carbon atoms
Base.
3. liquid-crystal compounds as claimed in claim 2, which is characterized in that the liquid-crystal compounds is to have the following structure formula
At least one of the compound of structure shown in (I -3-1):
Wherein, 2,3,4 or 5 m.
4. a kind of preparation method of the liquid-crystal compounds as described in claims 1 to 3 any one, which is characterized in that including with
Lower step:
Step S10, under nitrogen protection, by the first reactant, 2- ethyl -4- Iodoaniline, palladium catalyst, K2CO3, ethyl alcohol, toluene
Suzuki 3.5~4.5h of coupling reaction is carried out under condition of heating and stirring with water, then by separation, washing, dry and purifying
Processing, obtains the first intermediate；
Step S20, after mixing first intermediate, the concentrated sulfuric acid and tetrahydrofuran, then at a temperature of 0~10 DEG C NaNO is added dropwise2
Aqueous solution after 50~70min of insulated and stirred, continue the aqueous solution that KI is added dropwise at a temperature of 0~10 DEG C, it is natural after being added dropwise
Be warming up to room temperature, add sodium thiosulfate solution, then by extraction liquid separation, extract dry and purification process, obtain the
Two intermediates；
Step S30, under nitrogen protection, by second intermediate, the second reactant, palladium catalyst, K2CO3, ethyl alcohol, toluene
Suzuki 3.5~4.5h of coupling reaction is carried out under condition of heating and stirring with water, then by separation, washing, dry and purifying
Processing, obtains target compound, obtains liquid-crystal compounds；
Wherein, first reactant in step S10 is the compound for having the following structure structure shown in formula (II), step
Second reactant in S30 is the compound for having the following structure structure shown in formula (III):
Wherein, the R in structural formula (II)1With the R in structural formula (III)2It is each independently selected from H atom or unsubstituted containing 1
The alkyl of~7 carbon atoms, the X in structural formula (III)1、X2、X3、X4And X5It is former to be each independently selected from H atom, F atom or Cl
Son.
5. the preparation method of liquid-crystal compounds as claimed in claim 4, which is characterized in that in step slo, described first is anti-
Answer object, 2- ethyl -4- Iodoaniline, palladium catalyst and K2CO3Molar ratio be (1~1.5): 1:(0.01~0.3): (2~5)；
And/or
In step S20, first intermediate, the concentrated sulfuric acid, NaNO2Molar ratio with KI is 1:(1~4): (1~2): (1~
3)；And/or
In step s 30, second intermediate, the second reactant, palladium catalyst and K2CO3Molar ratio be 1:(1~2):
(0.1~3): (2~5)；And/or
The palladium catalyst is tetra-triphenylphosphine palladium；And/or
The reaction temperature of the Suzuki coupling reaction is 40~80 DEG C.
6. a kind of liquid-crystal composition, which is characterized in that the liquid-crystal composition includes first kind compound, the first kind chemical combination
Object is the liquid-crystal compounds as described in claims 1 to 3 any one.
7. liquid-crystal composition as claimed in claim 6, which is characterized in that the liquid-crystal composition further includes that at least one has
Dioxins, at least one of structure shown in following structural formula (IV) have the following structure the third of structure shown in formula (V)
Class compound and at least one have the following structure the 4th class compound of structure shown in formula (VI):
Wherein, the n in structural formula (IV), (V) and (VI) is each independently selected from 3,4,5 or 6, structural formula (IV), (V) and
(VI) m in is each independently selected from 2,3,4 or 5.
8. liquid-crystal composition as claimed in claim 7, which is characterized in that the first kind compound, dioxins,
The mass fraction of three classes compound and the 4th class compound in the liquid-crystal composition corresponds to 1~40%, 1~80%, 1~
50% and 1~50%.
9. a kind of microwave communication device, which is characterized in that the microwave communication device includes such as claim 6 to 8 any one
The liquid-crystal composition.
10. microwave communication device as claimed in claim 9, which is characterized in that the microwave communication device is the shifting of microwave liquid crystal
Phase device, tunable optic filter or phased array antenna.
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