CN112851562A - Aromatic ring liquid crystal compound, liquid crystal composition and application thereof - Google Patents

Aromatic ring liquid crystal compound, liquid crystal composition and application thereof Download PDF

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CN112851562A
CN112851562A CN202110088315.6A CN202110088315A CN112851562A CN 112851562 A CN112851562 A CN 112851562A CN 202110088315 A CN202110088315 A CN 202110088315A CN 112851562 A CN112851562 A CN 112851562A
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liquid crystal
halogenated
crystal composition
carbon atoms
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彭少磊
王艳伟
国新涛
崔建海
房凤梅
孙云峰
吕军
史子谦
丰佩川
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Yantai Xianhua Chem Tech Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
    • C09K19/3477—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a five-membered aromatic ring containing at least one nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3491—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur as hetero atom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • C09K19/44—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing compounds with benzene rings directly linked

Abstract

The present invention relates to an aromatic ring liquid crystal compound, a liquid crystal composition, and components suitable for use in the microwave region and the millimeter wave region of high frequency technology or the electromagnetic spectrum, particularly phase shifters and microwave array antennas. The liquid crystal composition provided by the invention at least comprises one compound represented by the general formula I, and has the advantages of good stability, high response speed and wide liquid crystal phase temperature range.

Description

Aromatic ring liquid crystal compound, liquid crystal composition and application thereof
Technical Field
The invention relates to the field of liquid crystal materials, relates to liquid crystal media of components in a microwave region and a millimeter wave region of a high-frequency technology or an electromagnetic spectrum, in particular to a phase shifter and a microwave array antenna, and specifically relates to an aromatic ring liquid crystal compound, a liquid crystal composition and application thereof.
Background
Information is the basis of the development of the society nowadays, and a huge amount of information is generated, stored and transmitted every moment, and a communication technology is an important technology in the information era and plays a vital role in the development of the society nowadays. Modern communication technologies are mainly divided into wired and wireless communication, and with the development and application of technologies such as internet, internet of things, mobile communication and the like, people have higher and higher requirements on wireless communication technologies, and the required functions of a microwave millimeter wave system which is an important hardware component in a wireless communication system are more and more complex. However, in the prior art, in order to meet the demand, the number of modules constituting the system is increasing, which results in higher and higher building cost of the wireless communication system and lower efficiency of the system.
The unique physical properties and optical properties of the liquid crystal material lead the liquid crystal material to be developed rapidly in the optical fields of display, light modulation and the like, and the liquid crystal is applied to the optical technology relatively mature. In recent years, the application of liquid crystal materials in the field of high frequency technology has received extensive attention of researchers, and compared with other materials, the liquid crystal materials have the characteristics of wider use frequency (from microwave frequency band to optical frequency band), lower bias voltage and power consumption, lower insertion loss, more stable performance, electric control and the like, so that the application of the liquid crystal materials in the high frequency technology and microwave millimeter wave devices becomes a hot research problem of the academic world.
However, most of the liquid crystal materials commonly used in the display field at present cannot meet the design of functional devices in the microwave and millimeter wave frequency band, and in the visible light band, the liquid crystal has large dielectric anisotropy, but due to the dielectric relaxation effect, the dielectric anisotropy of the liquid crystal in the microwave frequency band can be reduced sharply; in addition, its tangent angle dielectric loss is also high. The dielectric loss of the liquid crystal material is an important factor influencing the insertion loss of the microwave device, and the smaller the dielectric loss of the liquid crystal material is, the lower the insertion loss of the microwave functional device is, so that the lower the dielectric loss of the liquid crystal is required to be, the better the insertion loss of the microwave functional device is. In addition, it is also the main direction of the development of the high frequency liquid crystal technology to improve the quality parameter factors (FoM, η) of the liquid crystal and improve the low temperature storage performance of the liquid crystal.
Therefore, the research on novel liquid crystal materials correspondingly meeting the application of microwave and millimeter wave frequency bands is an important guarantee for promoting the development of high-frequency liquid crystal technology. However, liquid-crystalline compounds which have been used in the visible range have to date frequently been deficient, for example, in disadvantageously high losses, insufficient phase shifts or excessively small material quality parameters. For applications in high-frequency technology, there is a particular need for compounds with better properties for modifying existing liquid-crystalline media.
Disclosure of Invention
In order to meet the development requirement of high-frequency liquid crystal materials and overcome the defect of the liquid crystal materials in the microwave and millimeter wave frequency band in the existing display field, the invention provides an aromatic ring liquid crystal compound, a liquid crystal composition and application thereof.
The compound has the advantages of wide nematic phase range, larger delta n and delta epsilon, lower rotational viscosity, large dielectric tunable capability, small tangent angle loss, high quality parameter factor and good high-temperature and low-temperature storage performance in a high-frequency stage, particularly in a microwave and millimeter wave frequency range.
The invention provides an aromatic ring liquid crystal compound, which has a structure shown in a general formula I:
Figure BDA0002911776640000021
wherein, ring A1–A4Each independently represents:
a)
Figure BDA0002911776640000022
Figure BDA0002911776640000023
wherein X may represent NH, O or S;
b)1, 4-phenylene, 1, 4-naphthylene, 2, 6-naphthylene, 1, 4-anthracenylene, 2, 6-anthracenylene, 9, 10-anthracenylene, wherein one or more CH may be substituted by N;
c) trans-1, 4-cyclohexylene or cyclohexenylene, in which one or two non-adjacent CH' s2The radicals may be replaced by-O-and/or-S-, and where H may be replaced by F;
d) thiophene-2, 5-diyl, thiophene-2, 4-diyl, furan-2, 5-diyl, furan-2, 4-diyl;
preferably, ring A1、A4Is selected from
Figure BDA0002911776640000024
And A2、A3At least one of which represents a); preferably, ring A2、A3One of the groups is selected from the groups defined under a) above, more preferably
Figure BDA0002911776640000025
Particularly preferred
Figure BDA0002911776640000026
X can represent NH, O, S; another group is selected from
Figure BDA0002911776640000027
Figure BDA0002911776640000028
And in a), b), c) and d), one or more H atoms may also be replaced by Br, Cl, F, CN, -NCS, -SCN, SF5Halogenated or non-halogenated alkyl of 1 to 10 carbon atoms, alkoxy, halogenated or non-halogenated alkenyl of 2 to 10 carbon atoms, alkenyloxy, cycloalkyl of less than 6 carbons, cycloalkenyl;
R1、R2each independently represents:
1)F、Cl、Br、CN、CF3、OCF3SCN, NCS or SF5；
2) Halogenated or unhalogenated alkyl groups having 1 to 10 carbon atoms, in which one or more CH groups are present in these radicals2The radicals may also be replaced, independently of one another, by-C.ident.C-, -CH-, -CF-, -CF-CH-, -CH-CF-, - (CO) O-, -O (CO) -, -O-or-S-in such a way that the O or S atoms are not directly linked to one another;
preferably, R1、R2Each independently represents:
1)F、CN、NCS；
2) halogenated or unhalogenated alkyl having 1 to 10 carbon atoms, wherein in these radicals one or more CH2 radicals may also be replaced, independently of one another, by-C ≡ C-, -CH ═ CH-, -CF ═ CF-, -CF ═ CH-, -CH ═ CF-, - (CO) O-, -O (CO) -, -O-or-S-in such a way that the O or S atoms are not directly connected to one another;
more preferably, R1、R2Each independently represents an alkyl or alkoxy group of 1 to 7 carbon atoms, an alkenyl or alkenyloxy group of 2 to 7 carbon atoms;
more preferably, R1、R2One represents the group of 1) above and the other represents an alkyl group or an alkoxy group of 1 to 7 carbon atoms, an alkenyl group or an alkenyloxy group of 2 to 10 carbon atoms;
Z1、Z2、Z3each independently represents: single bond, -CH-, -CF-CH-, -C.ident.C-, -CF2O-、-CH2O-、-CH2-CH2-、-CF2CF2-、-CH2CF2-, - (CO) O-; preferably, the linking group Z1、Z2、Z3A single bond, -CH ═ CH-, -CF ═ CF-, -CF ≡ CH-, -C ≡ C-, particularly preferred single bond, -C ≡ C-;
n and m each independently represent 0 or 1, and m + n is particularly preferably 1.
Further, the general formula I has a specific structure as follows:
Figure BDA0002911776640000031
Figure BDA0002911776640000041
wherein X can represent NH, O, S, NH, S being particularly preferred.
The invention also provides a liquid crystal composition, which comprises the compound shown in the general formula I; the proportion of the general formula I is 10-80 weight percent, more preferably 10-60 weight percent, and still more preferably 20-60 weight percent, relative to the total weight of the liquid crystal composition.
The invention also provides a synthesis path of the related compound:
general formula (VII)
Figure BDA0002911776640000051
The compound of (1), scheme is as follows:
Figure BDA0002911776640000052
general formula (VII)
Figure BDA0002911776640000053
The compound of (1), scheme is as follows:
Figure BDA0002911776640000054
general formula (VII)
Figure BDA0002911776640000055
The compound of (1), scheme is as follows:
Figure BDA0002911776640000056
further, the liquid crystal composition also comprises a compound shown in a general formula II;
Figure BDA0002911776640000057
wherein
Ring A5、A6Each independently represents:
Figure BDA0002911776640000058
wherein one or more H atoms may also be replaced by Br, Cl, F, CN, NCS, SCN, SF5Halogenated or non-halogenated alkyl of 1 to 10 carbon atoms, alkoxy, halogenated or non-halogenated alkenyl of 2 to 10 carbon atoms, alkenyloxy, cycloalkyl of less than 6 carbons, cycloalkenyl; particularly preferred
Figure BDA0002911776640000061
Wherein, when ring A5、A6When represents phenylene, one or more CH on the benzene ring may be substituted by N;
R3、R4each independently represents:
1)F、Cl、Br、CN、CF3、OCF3SCN, NCS or SF5；
2) Halogenated or non-halogenated, alkyl or alkoxy of 1 to 10 carbon atoms, alkenyl or alkenyloxy of 2 to 10 carbon atoms;
preferably, R3、R4Each independently represent
1)F、CN、NCS；
2) Halogenated or non-halogenated, alkyl or alkoxy of 1 to 10 carbon atoms, alkenyl or alkenyloxy of 2 to 10 carbon atoms;
more preferably, R3、R4Each independently represents an alkyl or alkoxy group of 1 to 7 carbon atoms, an alkenyl or alkenyloxy group of 2 to 10 carbon atoms;
more preferably, R3、R4One of them represents a group of 1) above and the other represents an alkyl or alkoxy group of 1 to 7 carbon atoms, 2-alkenyl or alkenyloxy of 10 carbon atoms;
Z4represents a single bond, -CH-, -CF-, -CF-CH-, -C.ident.C-, -CF2O-、
-CH2O-、-CH2-CH2-、-CF2CF2-、-CH2CF2-, - (CO) O-; preferably, the linking group Z4A single bond, -CH ═ CH-, -CF ═ CF-, -CF ≡ CH-, -C ≡ C-, particularly preferred, a single bond, -C ≡ C-.
Further, the proportion of the general formula II is 5 to 60 weight percent, preferably 5 to 50 weight percent, and more preferably 10 to 50 weight percent, relative to the total weight of the liquid crystal composition.
Further, the structure of the general formula II is specifically as follows:
Figure BDA0002911776640000062
Figure BDA0002911776640000071
further, the liquid crystal composition also comprises a compound shown in a general formula III;
Figure BDA0002911776640000072
wherein
Ring A7–A9Each independently represents:
Figure BDA0002911776640000073
wherein one or more H atoms may also be replaced by Br, Cl, F, CN, -NCS, -SCN, SF5Halogenated or non-halogenated alkyl of 1 to 10 carbon atoms, alkoxy, halogenated or non-halogenated alkenyl of 2 to 10 carbon atoms, alkenyloxy, cycloalkyl of less than 6 carbons, cycloalkenyl; preferably, ring A7–A9Is selected from
Figure BDA0002911776640000074
Wherein, when ring A7–A9When representing phenylene, one or more CH on the phenyl ring may be substituted by N;
R5、R6each independently represents:
1)F、Cl、Br、CN、CF3、OCF3SCN, NCS or SF5；
2) Halogenated or non-halogenated, alkyl or alkoxy of 1 to 10 carbon atoms, alkenyl or alkenyloxy of 2 to 10 carbon atoms;
preferably, R5、R6Each independently represent
1)F、CN、NCS；
2) Halogenated or non-halogenated, alkyl or alkoxy of 1 to 10 carbon atoms, alkenyl or alkenyloxy of 2 to 10 carbon atoms;
more preferably, R5、R6Each independently represents an alkyl or alkoxy group of 1 to 7 carbon atoms, an alkenyl or alkenyloxy group of 2 to 10 carbon atoms;
particularly preferably, R5、R6One of them represents the group of 1) above, and the other represents an alkyl group or an alkoxy group of 1 to 7 carbon atoms, an alkenyl group or an alkenyloxy group of 2 to 10 carbon atoms;
Z5、Z6each independently represents: single bond, -CH-, -CF-CH-, -C.ident.C-, -CF2O-、-CH2O-、-CH2-CH2-、-CF2CF2-、-CH2CF2-, - (CO) O-; particularly preferred is a single bond, -C.ident.C-.
Furthermore, the proportion of the general formula III is 1 to 40 weight percent, preferably 1 to 30 weight percent, and more preferably 10 to 30 weight percent relative to the total weight of the liquid crystal composition.
Further, the structure of the general formula III is specifically as follows:
Figure BDA0002911776640000081
Figure BDA0002911776640000091
the invention also provides the use of a liquid crystal composition for components in the microwave and millimeter wave regions of the high-frequency technology or electromagnetic spectrum. Further, the liquid crystal composition is used for phase shifters and microwave array antennas.
The preparation method of the liquid crystal composition provided by the invention has no special requirements, and the liquid crystal composition can be prepared by mixing two or more compounds at a proper temperature by adopting a conventional preparation method; or dissolving the components in an organic solvent such as acetone, chloroform, methanol, etc., and removing the solvent by distillation.
The liquid crystal composition provided by the invention can also be added with proper additives, such as an anti-ultraviolet agent, an antistatic agent, an antioxidant, a defoaming agent and the like.
Has the advantages that: the compound has wide nematic phase temperature range, extremely high optical anisotropy (delta n), low dielectric loss and higher tuning capacity, and can effectively improve the low-temperature storage performance by forming a mixed liquid crystal material with other compounds. These properties make them particularly suitable for use in components used in high frequency technology, especially in liquid crystal phase shifters.
Detailed Description
The following specific embodiments are intended to illustrate, but not limit, the invention. Other combinations and various modifications within the spirit or scope of the present invention may be made without departing from the spirit or scope of the present invention.
The liquid crystal compositions in the following examples were prepared by a conventional method.
The liquid crystal compositions in the following examples were tested for various performance parameters by conventional methods.
The percentages in the examples represent percentages by weight, unless otherwise specified.
T(N,I)(. degree. C.) represents clearing point.
DELTA.n represents the optical anisotropy at 20 ℃ of 589 nm.
DELTA ε represents the dielectric anisotropy at 25 ℃.
γ 1 (mPas) represents the rotational viscosity at 20 ℃.
Vo (V) represents the threshold voltage at 20 ℃.
Dielectric anisotropy in the microwave range is defined as Δ ∈r≡(εr,||-εr,⊥)。
The modulation capability or controllability (tunability τ) is defined as τ ≡ (Δ ∈) (Δ ≡)r/εr，||)。
A material quality parameter (η), defined as η ≡ (τ/tan δ)εr，max)。
Wherein tan deltaεr，maxIs the maximum dielectric loss factor tan deltaεr，max.≡Max.{tanδεr，⊥；tanδεr，||}。
For convenience of expression, in the following examples, the structures of liquid crystal compounds are represented by abbreviations. Table A lists the codes for the ring structures, Table B lists the codes for the linking groups, and Table C lists the codes for the terminal groups.
Structure of the watch ring
Figure BDA0002911776640000101
TABLE B linking groups
Figure BDA0002911776640000102
Figure BDA0002911776640000111
TABLE C end groups
Figure BDA0002911776640000112
The following table shows exemplary structures and their respective abbreviations. These are presented to illustrate the meaning of the abbreviation rules. They furthermore represent the compounds which are preferably used.
Exemplary Structure of Table D
The following exemplary structures are particularly preferred with
Figure BDA0002911776640000113
A compound of the group:
Figure BDA0002911776640000114
Figure BDA0002911776640000121
Figure BDA0002911776640000131
Figure BDA0002911776640000141
the following exemplary structures are auxiliary compounds having two six-membered rings, which are optionally used:
Figure BDA0002911776640000142
Figure BDA0002911776640000151
the following exemplary structures are auxiliary compounds having three six-membered rings, which are optionally used:
Figure BDA0002911776640000152
Figure BDA0002911776640000161
the following examples illustrate the invention without limiting it in any way. However, from a physical point of view, the skilled person is clear what properties can be obtained and within what ranges they can be varied. In particular, the combination of different properties which can preferably be achieved is also well defined for the skilled person.
Compound example 1: 4-propyl-7- (4-propylphenyl) -1H-indole PYn-3
The intermediate Ki-1 was synthesized as follows:
Figure BDA0002911776640000162
the synthesis route of the final product is as follows:
Figure BDA0002911776640000163
step 1 preparation of I-1
168g of 4-propylacetanilide was charged in a three-necked flask. Starting mechanical stirring, and dripping a prepared mixed acid solution (formed by mixing 300g of concentrated sulfuric acid and 200g of 68% concentrated nitric acid) under ice water, wherein the temperature is controlled to be below 15 ℃ in the dripping process. After the dropwise addition was completed for about 2 hours, the temperature was maintained for 30 minutes after the dropwise addition was completed, and after completion of the reaction of the starting materials was detected, the reaction mixture was poured into ice water, the organic layer was extracted with toluene, washed with a saturated aqueous sodium bicarbonate solution, washed with a saturated saline solution to neutrality, and dried over anhydrous sodium sulfate. Vacuum desolventizing and crystallizing with petroleum ether gave 150g I-1 for the next run.
Step 2 preparation of I-2
Under the protection of nitrogen, 110g of the I-1 intermediate prepared in the step 1 is added into a three-neck bottle1500ml of propanol, 100g of sodium hydroxide and 500g of deionized water. And heating and refluxing for 16 hours under stirring, and detecting to show that the reaction of the raw materials is finished. Cooling to room temperature, and cooling with 6mol.L-1The pH of the reaction solution was adjusted to about 10, then the solvent was distilled off at normal pressure, when the internal temperature reached 84 ℃, heating was stopped, 2000ml of toluene was added for extraction, anhydrous sodium sulfate was dried, and vacuum desolventization was carried out to obtain 85g I-2 for direct next operation.
Step 3 preparation of I-3
To a three-necked flask A were added 272 g of the intermediate I prepared in step 2, 400ml of dioxane, 750ml of water, followed by 214ml of 48% hydrobromic acid. Cooling to 0 deg.C, adding dropwise sodium nitrite solution (28g sodium nitrite dissolved in 250ml water), and controlling temperature below 7 deg.C during dropwise addition. After the dropwise addition is finished, controlling the temperature to be 0 ℃ and keeping the temperature for 2 hours to prepare the diazonium salt intermediate. And adding 65g of cuprous bromide and 75ml of 48% hydrobromic acid solution into the other three-necked flask B, vigorously stirring, controlling the temperature to be about 40 ℃, dropwise adding the diazonium salt intermediate prepared by the three-necked flask A into the three-necked flask B, discharging gas in the dropwise adding process, and carefully controlling the dropwise adding speed and temperature. After the dropwise addition, the temperature is gradually raised to 60 ℃, the temperature is kept for 6 hours, and the detection shows that the reaction is finished. The reaction mixture was cooled to room temperature, 400ml of water was added to the reaction mixture, and the mixture was extracted with ethyl acetate, washed with water, saturated sodium bicarbonate, saturated brine, dried over anhydrous sodium sulfate, filtered and vacuum-desolventized. The crude product was passed through a silica gel column to obtain 76g of the objective product I-3 for the next reaction.
Step 4 preparation of Ki-1
Under the protection of nitrogen, I-348 g of tetrahydrofuran 600ml is added into a three-neck flask. After stirring to dissolve completely, the temperature was reduced to-55 ℃ and 40ml of vinylmagnesium bromide (1M in THF) was added dropwise over about 1 hour, followed by 1 hour of incubation. Detection shows that the reaction of the raw materials is finished. And cooling to room temperature, slowly pouring the reaction solution into a saturated ammonium chloride solution, extracting with dichloromethane, washing with water, drying with sodium sulfate, and performing vacuum desolventization to obtain 35g of Ki-1 crude product. The crude product was subjected to gradient elution (5% ethyl acetate/95% n-hexane) through a chromatographic column to give pure Ki-1 (25 g) for the next reaction.
Preparation of PYn-3-3 of step 5
Deionized water 9 is added into the three-mouth bottle in sequence0g of tetrabutylammonium bromide, 5.2g of potassium phosphate and 56.8g of potassium phosphate are stirred for 30 min. DMF 209g, intermediate Ki-1: 22.5g of p-propylphenylboronic acid and 20g of p-propylphenylboronic acid, heating to 60-70 ℃, stirring, introducing nitrogen, and deoxidizing for 1 hour. After deoxidation, quickly adding 0.024g of palladium acetate and 0.06g of tricyclohexylphosphine into a reaction bottle, stirring and heating to 90-100 ℃, keeping the temperature for reaction for 1h, sending a sample to detect that no Ki-1 remains, adding water and toluene into the reaction bottle, stirring and layering, extracting a water layer with toluene, combining organic layers, washing with saturated saline once, drying with anhydrous sodium sulfate, and performing vacuum desolventization. 23g of crude product are obtained. Crude product is SiO filtered2And (5) carrying out chromatography column, and crystallizing to obtain 15g of a target product.
1H NMR(400MHz,DMSO-d6)9.90(s,1H),8.01(d,J＝8,1H),7.50(d,J＝8,1H),7.20-7.32(m,4H),7.01(d,J＝7,1H),6.52(d,J＝7,1H),2.62(q,J＝6,4H),1.61(m,4H),0.91(t,J＝8,1H)。MS(EI):m/z＝277.18。
Δε:10.5；Δn:0.253；Cp:50.6℃；γ1:282mPa·s。
Compound example 2: 4-propyl-7- (4-propylphenyl) -thianaphthene PYs-3
Figure BDA0002911776640000181
Step 1 preparation of II-1
Under the protection of nitrogen, 131g of diisopropylamine and 537ml of tetrahydrofuran are added in sequence, and stirring is turned on. Introducing liquid nitrogen to cool under the protection of nitrogen, when the temperature is reduced to-35 ℃, beginning to drop 525ml of butyl lithium (2.5M), controlling the temperature to be-25 to-30 ℃, and preserving the temperature for 1 hour after dropping. After heat preservation, continuing to introduce liquid nitrogen for cooling, when the temperature is reduced to-70 ℃, dropwise adding a prepared THF solution of 3-fluoro-4-bromopropylbenzene (260g of 3-fluoro-4-bromopropylbenzene and 520ml of THF), controlling the internal temperature to be-70 to-60 ℃ during dropwise adding, after about 1 hour of dropwise adding, preserving heat for 30 minutes after the dropwise adding, dropwise adding 255g N-formylpiperidine, and finishing dropwise adding for about 2 to 3 hours. After the dripping is finished, the temperature is kept for 1 hour at minus 70 to minus 60 ℃. And then naturally heating to about-30 ℃, adding the reaction solution into prepared dilute hydrochloric acid for hydrolysis, layering, extracting a water layer with toluene, combining organic phases, and washing with saturated brine. Rotary evaporation is carried out for desolventizing, 245g of intermediate II-1 is obtained after desolventizing, and the next reaction is directly carried out.
Step 2 preparation of II-2
Adding 200g of II-1 and 2000ml of anhydrous DMF into a three-neck flask, stirring to dissolve completely, adding 114g of methyl thioglycolate and 400g of potassium carbonate, heating to 75 ℃ for reacting overnight, detecting that no raw material is left, removing 1000ml of DMF under reduced pressure, cooling to room temperature, adding water and ethyl acetate, layering, extracting a water layer again, combining organic layers, drying with anhydrous sodium sulfate, filtering, and performing vacuum desolventization to obtain 188g of II-2 crude product which is directly used in the next step without purification.
Step 3 preparation of II-3
150g of II-2 prepared in the previous step was added to a three-necked flask, 1000ml of dioxane and 20% potassium hydroxide solution (100g of potassium hydroxide and 400ml of deionized water) were added thereto, and the mixture was heated under reflux for 10 hours. Subsequently, the temperature is reduced to room temperature and the solution is adjusted to acidity by hydrochloric acid. After removing dioxane in vacuum, the water layer was extracted with dichloromethane, desolventized in vacuum, and crystallized with ethanol to obtain 100g of II-3 for the next reaction.
Step 4 preparation of Ki-2
Adding 90g of II-3 prepared in the previous step into a three-neck flask, adding acetic acid, silver carbonate and DMSO, heating to 120 ℃, and reacting for 18 hours. Subsequently, the temperature is reduced to room temperature and the solution is adjusted to acidity by hydrochloric acid. The aqueous layer was extracted with ethyl acetate and desolventized in vacuo to give 80g of Ki-2 for the next reaction.
Step 5 preparation of PYs-3-3
Adding deionized water into a three-mouth bottle under the protection of nitrogen: 384g, stirring was turned on, and potassium carbonate: 252g, stirred for about 15 minutes to dissolve completely, and ethanol: 72.8g, a toluene solution of propylphenylboronic acid (containing 72g of propylphenylboronic acid), Ki-2: 70 g. After the addition, nitrogen is introduced to replace the air in the kettle for 30 minutes, the temperature is raised to 55 ℃, and a catalyst of tetratriphenylphosphine palladium is added under the protection of nitrogen: 1g, heated to reflux.
And (5) after the reaction is finished, introducing circulating water, cooling to 30-40 ℃, standing and layering. The aqueous phase was separated off with toluene: 120g of the extract was extracted once. The organic phases were combined, each time with tap water: 140 g. Washing with water to 6-8. And (5) after the water washing is finished, carrying out vacuum desolventizing on the organic phase. And cooling to 30-40 ℃, and passing through a column for crystallization to obtain 72g of a target product.
Δε:13.3；Δn:0.286；Cp:45.6℃；γ1:375mPa·s。
Compound example 3: 4-propyl-7- (4-propylphenylethynyl) -1H-indole PTYn-3
Figure BDA0002911776640000191
Figure BDA0002911776640000201
Step 1 preparation of III-1
III-1 can be prepared by referring to the preparation method of I-1 in which 4-propylacetanilide is replaced with 4-methylacetanilide.
Step 2 preparation of III-2
With reference to the preparation process of I-2, wherein I-1 is replaced by III-1, III-2 can be prepared.
Step 3 preparation of III-3
With reference to the preparation process of III-2, wherein I-2 is replaced with III-2, III-3 can be prepared.
Step 4 preparation of Ki-3
Ki-3 can be prepared by reference to the preparation of Ki-1, in which I-3 is replaced by III-3.
Preparation of PTYn-3-3 in step 5
Under the protection of nitrogen, adding Ki-370 g prepared in the step 4, adding 150ml of triethylamine, 300ml of toluene, 54g of triphenylphosphine and 3.5g of cuprous iodide, heating to 60 ℃, adding 1.5g of palladium bis (triphenylphosphine) dichloride, then dropwise adding 50g of 4-propylphenylacetylene, after about 4 hours of dropwise addition, continuously heating and refluxing after the dropwise addition is finished, and reacting for 5 hours. Filtering, and leaching a filter cake with toluene. The filtrate was washed with water, saturated ammonium chloride, dried over anhydrous sodium sulfate, passed through a silica gel column and crystallized to obtain 75g of the target product III.
Δε:12.1；Δn:0.353；Cp:58.6℃；γ1:398mPa·s。
Compound example 4: 4-isothiocyanato-7- (2, 6-difluoro-4-propylphenylethynyl) -thianaphthene UTYs-3-S
Figure BDA0002911776640000202
Step 1 preparation of IV-1
Under the protection of nitrogen, 131g of diisopropylamine and 600ml of tetrahydrofuran are added in turn, and stirring is turned on. Introducing liquid nitrogen to cool under the protection of nitrogen, when the temperature is reduced to-35 ℃, beginning to drop 525ml of butyl lithium (2.5M), controlling the temperature to be-25 to-30 ℃, and preserving the temperature for 1 hour after dropping. After the heat preservation is finished, the liquid nitrogen is continuously introduced for cooling, when the temperature is reduced to-70 ℃, the prepared THF solution of the 3, 5-difluoropropylbenzene (156g of 3, 5-difluoropropylbenzene and 300ml of THF) is dripped, the internal temperature is controlled to be-70 to-60 ℃ during the dripping, the dripping is finished after about 1 hour, after the dripping is finished and the heat preservation is carried out for 1 hour, the THF solution of the iodine (300g of iodine is prepared by dissolving in 900ml of THF) is dripped, and the dripping is finished after about 2 to 3 hours. After the dripping is finished, the temperature is kept for 1 hour at minus 70 to minus 60 ℃. And then naturally heating to about-30 ℃, and adding the reaction solution into diluted hydrochloric acid prepared in advance for hydrolysis. Adding sodium bisulfite into the hydrolysate, and fading out the purple color inside. The layers were separated, the aqueous layer was extracted with toluene, the organic phases were combined and washed with saturated brine. And (4) performing rotary evaporation and desolventizing to obtain 278g of intermediate IV-1, and directly performing the next reaction.
Step 2 preparation of IV-2
The flask was purged with nitrogen for 10 minutes, 110g of 3-methyl-2-butynol, 260g of potassium carbonate, 285g of triphenylphosphine, 560ml of toluene and 200ml of DMF were sequentially added to a three-necked flask, the mixture was stirred, and after warming to 60 ℃ 2g of bis (triphenylphosphine) palladium was added, with attention paid to nitrogen protection. And (3) continuously heating to 100 ℃, starting reflux, then starting to dropwise add an IV-1 DMF solution (prepared by dissolving 240g of IV-4 in 480ml of DMF), continuing to reflux and preserving heat for 3 hours after the dropwise addition is finished for 4 hours, sampling and checking until no IV-1 remains, and adding the reaction solution into diluted hydrochloric acid prepared in advance for hydrolysis. The layers were separated, the aqueous layer was extracted with toluene, the organic phases were combined and washed with saturated brine. Rotary evaporation to remove the solvent, obtaining 195g of intermediate IV-2 after the solvent is removed, and directly carrying out the next reaction.
Step 3 preparation of Ki-4
Under the protection of nitrogen, sequentially adding the intermediate IV-2190 g prepared in the previous step, 600ml of toluene and 10g of sodium hydroxide into a three-neck flask. And opening stirring, slowly heating, evaporating the solvent with a low boiling point, stopping distillation when the temperature in the reaction bottle is raised to about 108 ℃, and performing reflux reaction until no raw material IV-2 is left. Cooling to room temperature, and adding dilute hydrochloric acid into the three-necked bottle until the solution is neutral. The aqueous layer was separated, the organic layer washed with water, dried over sodium sulfate and desolventized in vacuo to give 140g of Ki-4 crude.
Dissolving the crude product with petroleum ether, passing through a chromatographic column with SiO2 as filler, eluting with petroleum ether, and vacuum spin-drying to obtain 125g Ki-4.
Step 4 preparation of IV-4
Under the protection of nitrogen, IV-345 g (IV-3 preparation refers to synthesis example 2, wherein the raw material 3-fluoro-4-bromopropylbenzene is replaced by 3-fluoro-4-bromoaniline), 120ml of triethylamine, 200ml of toluene, 45g of triphenylphosphine and 1.5g of cuprous iodide are added into a three-necked flask, the temperature is raised to 60 ℃, 2g of bis (triphenylphosphine) palladium dichloride is added, then a solution of Ki-436 g and 250ml of toluene is added dropwise, the dropwise addition is finished for about 4 hours, the temperature is raised and the reflux is continued after the dropwise addition is finished, and the reaction is carried out for 5 hours. Filtering, and leaching a filter cake with toluene. The filtrate was washed with water, saturated ammonium chloride and dried over anhydrous sodium sulfate. Vacuum desolventizing and crystallizing to obtain 55g of target product.
Step 5 preparation of UTYs-3-S
Under the protection of nitrogen, 40g N, N' -thiocarbonyldiimidazole and 240ml of anhydrous DMF are added into a three-neck flask and stirred to be dissolved completely. The temperature was reduced to-10 ℃ and a solution of intermediate 50g IV-4 and 200ml DMF was added dropwise. After the dropwise addition, the temperature is kept between minus 10 ℃ and 0 ℃ for 1 hour, then the temperature is naturally raised to the room temperature, and the mixture is stirred overnight. The temperature is reduced to 0 ℃ the next day, and sodium bicarbonate solution is slowly added into the reaction bottle. After the addition was completed, stirring was carried out for 30 minutes, and then ethyl acetate was added for extraction, followed by drying over anhydrous sodium sulfate, filtration and vacuum desolventization to obtain 52g of a crude product. The crude product was crystallized from toluene to obtain 38g of a pure product.
Δε:22.8；Δn:0.390；Cp:66.2℃；γ1:601mPa·s。
Compound example 5: 4-propyl-7- (4-pentylcyclohexylphenyl) -1H-indole CPYn-5-3
Figure BDA0002911776640000221
Adding deionized water into a three-mouth bottle under the protection of nitrogen: 384g, stirring was turned on, and potassium carbonate: 252g, stirred for about 15 minutes to dissolve completely, and THF was added: 200ml of a THF solution of 4-pentylcyclohexylphenylboronic acid (81 g of 4-pentylcyclohexylphenylboronic acid dissolved in 240ml of THF), Ki-1: 70 g. After the addition, nitrogen is introduced to replace the air in the kettle for 30 minutes, the temperature is raised to 55 ℃, and a catalyst of tetratriphenylphosphine palladium is added under the protection of nitrogen: 1g, heated to reflux. And after the reaction is finished, cooling to 30-40 ℃, and standing for layering. The aqueous phase was separated off with toluene: 400ml are extracted once. The organic phases are combined and washed by water, and the organic phases are vacuum desolventized. And cooling to 30-40 ℃, and passing through a column for crystallization to obtain 80g of the target product.
Δε:12.8；Δn:0.290；Cp:166.2℃；γ1:685mPa·s。
Compound example 6: 4-isothiocyanato-7- (4- (2, 6-difluoro-4-propylphenylethynyl) -2-fluorophenylacetylene Yl) -1H-indole UTGTYn-3-S
Figure BDA0002911776640000222
Step 1 preparation of VI-1
Under the protection of nitrogen, 345g of potassium carbonate, 1.5L of deionized water, a solution of 3-fluoro-4-bromoiodobenzene and toluene (containing 301g of 3-fluoro-4-bromoiodobenzene) were added to a three-necked flask, the temperature was raised to 50 ℃, and 3g of Pd (PPh3)4 as a catalyst was added. After the mixture was heated to reflux, a mixed solution of 193g of intermediate Ki-4 prepared in Synthesis example 4 and 500ml of toluene was added dropwise over about 6 hours. After the dropwise addition, the temperature was kept for 8 hours. Detecting and confirming that no 3-fluoro-4-bromoiodobenzene remains. Adding water into the reaction solution, layering, extracting the water layer with toluene, combining the organic layers, washing with brine, drying with anhydrous sodium sulfate, filtering, and vacuum desolventizing. 325g of crude intermediate VI-1 are obtained and directly subjected to the next reaction.
Preparation of VI-2 in step 2
Under nitrogen protection, 2g of cuprous iodide, 211g of intermediate IV-4 (prepared by Synthesis example 4), 850ml of toluene, 125g of trimethylsilylacetylene, 200ml of anhydrous triethylamine, and 3.5g of the catalyst bis (triphenylphosphine) palladium dichloride were added in succession to a three-necked flask, and the mixture was heated to 90 ℃ and refluxed overnight. Cooling, filtering, removing solvent from the filtrate in vacuum, adding toluene into the residue, washing with water, drying, removing solvent in vacuum, and passing through SiO2 chromatographic column to obtain 178 VI-2.
Step 3, preparation of VI-3
Introducing nitrogen to purge the flask for 10 minutes, adding 114g of VI-2,190g of potassium carbonate, 100ml of methanol and 280ml of dichloromethane into the three-neck flask in sequence, reacting for 4 hours at 30 ℃, sampling and checking that IV-2 is not left, adding saturated brine into a reaction solution, extracting a water layer by using dichloromethane, combining organic layers, washing with brine, drying with anhydrous sodium sulfate, performing vacuum desolventization to obtain 60g of an intermediate VI-3, and directly performing the next reaction.
Step 4, preparation of VI-4
70g of intermediate VI-1, 125ml of triethylamine, 400ml of toluene, 45g of triphenylphosphine and 1.3g of cuprous iodide are added into a three-necked bottle under the protection of nitrogen, the temperature is raised to 60 ℃, 2g of palladium bis (triphenylphosphine) dichloride is added, then a solution of VI-331 g and 150ml of toluene is added dropwise, the dropwise addition is finished within about 5 hours, the temperature is raised continuously and the reflux is carried out after the dropwise addition is finished, and the reaction is carried out for 5 hours. Filtering, and leaching a filter cake with toluene. The filtrate was washed with water, saturated ammonium chloride and dried over anhydrous sodium sulfate. Vacuum desolventizing and crystallizing to obtain 65g of target product
Step 5 preparation of UTGTYn-3-S
42g N, N' -thiocarbonyldiimidazole and 260ml anhydrous DMF were added to a three-necked flask under nitrogen protection, and stirred to dissolve completely. The temperature was reduced to-10 ℃ and a solution of intermediate 65g VI-4 and 250ml DMF was added dropwise. After the dropwise addition, the temperature is kept between minus 10 ℃ and 0 ℃ for 1 hour, then the temperature is naturally raised to the room temperature, and the mixture is stirred overnight. The temperature is reduced to 0 ℃ the next day, and sodium bicarbonate solution is slowly added into the reaction bottle. After the addition, stirring for 30 minutes, adding ethyl acetate for extraction, drying with anhydrous sodium sulfate, filtering, and vacuum desolventizing to obtain 72g of crude product. The crude product was crystallized from toluene to give 45g of pure product.
Δε:38.8；Δn:0.386；Cp:46.2℃；γ1:1299mPa·s。
Compound example 7: 4- (4-isothiocyanatophenylethynyl) -7- (4-propylphenylethynyl) -1H-indole PTYnTP-3-S
Figure BDA0002911776640000241
Step 1 preparation of VII-1
VII-1 may be prepared by reference to the preparation of I-1 wherein 4-propylacetanilide is replaced by p-dibromobenzene.
Step 2 preparation of Ki-7
With reference to the preparation of Ki-1, in which I-3 was replaced with VII-1, Ki-7 was prepared.
Step 3 preparation of VII-2
Reference is made to the preparation of VI-3, in which Ki-4 is replaced by 4-propylphenylacetylene and 3-fluoro-4-bromoiodobenzene is replaced by Ki-7.
Preparation of step 4 VII-2
According to the preparation method of VI-4, VI-1 is replaced by V11-2, and VI-3 is replaced by 4-aminophenylacetylene.
Step 5 preparation of PTYnTP-3-S
Referring to the preparation method of VI, VI-4 is prepared by replacing VII-3.
Δε:32.7；Δn:0.456；Cp:66.7℃；γ1:989mPa·s。
Comparative example:
the physical properties of the commonly used known liquid crystal compounds 5CB, PEP-3-5, PGU-3-F, were investigated at 20 ℃ especially in the microwave region:
physical Properties of different Compounds at 25GHz
Figure BDA0002911776640000251
As can be seen from the comparative examples, the commonly used compounds generally have the problems of low modulation efficiency τ and low quality parameter η, which seriously hampers the application in the microwave region, and the compounds in the examples can effectively solve the problems, and are very suitable for the application in the microwave region.
Composition example 1:
Figure BDA0002911776640000252
The composition has high tunability and quality parameters and is very suitable for applications in the microwave region, in particular for phase shifters.
Composition example 2:
Figure BDA0002911776640000253
Figure BDA0002911776640000261
The composition has high tunability and quality parameters and is very suitable for applications in the microwave region, in particular for phase shifters.
Composition example 3:
Figure BDA0002911776640000262
The composition has high tunability and quality parameters and is very suitable for applications in the microwave region, in particular for phase shifters.
Composition example 4::
Figure BDA0002911776640000263
Figure BDA0002911776640000271
The composition has high tunability and quality parameters and is very suitable for applications in the microwave region, in particular for phase shifters.
Composition example 5:
Figure BDA0002911776640000272
The composition has high tunability and quality parameters and is very suitable for applications in the microwave region, in particular for phase shifters.
Composition example 6:
Figure BDA0002911776640000273
Figure BDA0002911776640000281
The composition has high tunability and quality parameters and is very suitable for applications in the microwave region, in particular for phase shifters.
Composition example 7:
Figure BDA0002911776640000282
The composition has high tunability and quality parameters and is very suitable for applications in the microwave region, in particular for phase shifters.
Composition example 8:
Figure BDA0002911776640000283
Figure BDA0002911776640000291
The composition has high tunability and quality parameters and is very suitable for applications in the microwave region, in particular for phase shifters.
Composition example 9:
Figure BDA0002911776640000292
The composition has high tunability and quality parameters and is very suitable for applications in the microwave region, in particular for phase shifters.
Composition example 10:
Figure BDA0002911776640000293
The composition has high tunability and quality parameters and is very suitable for applications in the microwave region, in particular for phase shifters.
The preparation method of the liquid crystal composition provided by the invention has no special requirements, and the liquid crystal composition can be prepared by mixing two or more compounds at a proper temperature by adopting a conventional preparation method; or dissolving the components in an organic solvent such as acetone, chloroform, methanol, etc., and removing the solvent by distillation.
The liquid crystal composition provided by the invention can also be added with proper additives, such as an anti-ultraviolet agent, an antistatic agent, an antioxidant, a defoaming agent and the like.

Claims (9)

1. An aromatic ring liquid crystal compound, characterized in that the compound has the general formula I:
Figure FDA0002911776630000011
wherein the content of the first and second substances,
ring A1–A4Each independently represents:
a)
Figure FDA0002911776630000012
Figure FDA0002911776630000013
wherein X may represent NH, O or S;
b)1, 4-phenylene, 1, 4-naphthylene, 2, 6-naphthylene, 1, 4-anthracenylene, 2, 6-anthracenylene, 9, 10-anthracenylene, wherein one or more CH may be substituted by N;
c) trans-1, 4-cyclohexylene or cyclohexenylene, in which one or two non-adjacent CH' s2The radicals may be replaced by-O-and/or-S-, and where H may be replaced by F;
d) thiophene-2, 5-diyl, thiophene-2, 4-diyl, furan-2, 5-diyl, furan-2, 4-diyl;
and A2、A3At least one of which represents a);
and in a), b), c) and d), one or more H atoms may also be replaced by Br, Cl, F, CN, -NCS, -SCN, SF5Halogenated or non-halogenated alkyl of 1 to 10 carbon atoms, alkoxy, halogenated or non-halogenated alkenyl of 2 to 10 carbon atoms, alkenyloxy, cycloalkyl of less than 6 carbons, cycloalkenyl;
R1、R2each independently represents:
1)F、Cl、Br、CN、CF3、OCF3SCN, NCS or SF5；
2) Halogenated or unhalogenated alkyl groups having 1 to 10 carbon atoms, in which one or more CH groups are present in these radicals2The radicals may also be replaced, independently of one another, by-C.ident.C-, -CH-, -CF-, -CF-CH-, -CH-CF-, - (CO) O-, -O (CO) -, -O-or-S-in such a way that the O or S atoms are not directly linked to one another;
Z1、Z2、Z3each independently represents: single bond, -CH-, -CF-CH-, -C.ident.C-, -CF2O-、-CH2O-、-CH2-CH2-、-CF2CF2-、-CH2CF2-、-(CO)O-；
n and m each independently represent 0 or 1.
2. The aromatic ring liquid crystal compound according to claim 1, wherein the structure of formula i is specifically as follows:
Figure FDA0002911776630000021
Figure FDA0002911776630000031
wherein X can represent NH, O, S, NH, S being particularly preferred.
3. A liquid crystal composition comprising a compound of formula I according to claim 1 or 2; the proportion of the general formula I is 10-80 weight percent relative to the total mass of the liquid crystal composition.
4. The liquid crystal composition of claim 3, wherein the liquid crystal composition further comprises a compound of formula II;
Figure FDA0002911776630000032
wherein
Ring A5、A6Each independently represents:
Figure FDA0002911776630000033
wherein one or more H atoms may also be replaced by Br, Cl, F, CN, -NCS, -SCN,SF5Halogenated or non-halogenated alkyl of 1 to 10 carbon atoms, alkoxy, halogenated or non-halogenated alkenyl of 2 to 10 carbon atoms, alkenyloxy, cycloalkyl of less than 6 carbons, cycloalkenyl;
wherein, when ring A5、A6When represents phenylene, one or more CH on the benzene ring may be substituted by N;
R3、R4each independently represents:
1)F、Cl、Br、CN、CF3、OCF3SCN, NCS or SF5；
2) Halogenated or non-halogenated, alkyl or alkoxy of 1 to 10 carbon atoms, alkenyl or alkenyloxy of 2 to 10 carbon atoms;
Z4represents a single bond, -CH-, -CF-, -CF-CH-, -C.ident.C-, -CF2O-、-CH2O-、-CH2-CH2-、-CF2CF2-、-CH2CF2-、-(CO)O-。
5. The liquid crystal composition of claim 3, wherein the ratio of the compound represented by formula II is 5 to 60 wt% based on the total weight of the liquid crystal composition.
6. The liquid crystal composition of claim 3, wherein the liquid crystal composition further comprises a compound of formula III;
Figure FDA0002911776630000041
wherein
Ring A7–A9Each independently represents:
Figure FDA0002911776630000042
wherein one or more H atoms may also be replaced by Br, Cl, F, CN, -NCS, -SCN, SF5A halogenated or unhalogenated alkyl group of 1 to 10 carbon atoms, an alkoxy group, a halogenated or unhalogenated alkenyl group of 2 to 10 carbon atoms,Alkenyloxy, cycloalkyl of less than 6 carbons, cycloalkenyl;
wherein, when ring A7–A9When representing phenylene, one or more CH on the phenyl ring may be substituted by N;
R5、R6each independently represents:
1)F、Cl、Br、CN、CF3、OCF3SCN, NCS or SF5；
2) Halogenated or non-halogenated, alkyl or alkoxy of 1 to 10 carbon atoms, alkenyl or alkenyloxy of 2 to 10 carbon atoms;
Z5、Z6each independently represents: single bond, -CH-, -CF-CH-, -C.ident.C-, -CF2O-、-CH2O-、-CH2-CH2-、-CF2CF2-、-CH2CF2-、-(CO)O-。。
7. The liquid crystal composition according to claim 6, wherein the proportion of the formula III is 1 to 40 wt% based on the total mass of the liquid crystal composition.
8. Use of a liquid crystal composition according to claims 3-7 for high frequency technology or components in the microwave and millimetre wave regions of the electromagnetic spectrum.
9. Use of the liquid crystal composition according to claim 8 for phase shifters and microwave array antennas.
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TWI796263B (en) * 2021-08-17 2023-03-11 大陸商江蘇和成顯示科技有限公司 A liquid crystal composition and a spatial light modulator comprising it

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