CN110776396B - Side ethyl quaterphenyl liquid crystal compound, preparation method thereof, liquid crystal composition and microwave device - Google Patents
Side ethyl quaterphenyl liquid crystal compound, preparation method thereof, liquid crystal composition and microwave device Download PDFInfo
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 153
- 150000001875 compounds Chemical class 0.000 title claims abstract description 135
- 239000000203 mixture Substances 0.000 title claims abstract description 76
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- 229910052731 fluorine Inorganic materials 0.000 claims description 13
- 238000000746 purification Methods 0.000 claims description 10
- 230000005684 electric field Effects 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 239000012264 purified product Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 32
- 239000004988 Nematic liquid crystal Substances 0.000 abstract description 9
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 81
- 238000006243 chemical reaction Methods 0.000 description 80
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 50
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 48
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 46
- 238000003756 stirring Methods 0.000 description 46
- 239000000243 solution Substances 0.000 description 43
- 238000010992 reflux Methods 0.000 description 41
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 36
- 238000001035 drying Methods 0.000 description 35
- 238000001914 filtration Methods 0.000 description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 30
- 239000007788 liquid Substances 0.000 description 30
- 239000000376 reactant Substances 0.000 description 30
- 238000010438 heat treatment Methods 0.000 description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 28
- OJLYTHOKCYLPMA-UHFFFAOYSA-N 5-pentyl-2-phenoxyphenol Chemical compound OC1=CC(CCCCC)=CC=C1OC1=CC=CC=C1 OJLYTHOKCYLPMA-UHFFFAOYSA-N 0.000 description 27
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 27
- 229910052757 nitrogen Inorganic materials 0.000 description 27
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 24
- 238000005406 washing Methods 0.000 description 24
- 238000001704 evaporation Methods 0.000 description 23
- 239000003208 petroleum Substances 0.000 description 23
- 239000002904 solvent Substances 0.000 description 23
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 22
- 238000001816 cooling Methods 0.000 description 19
- 239000000706 filtrate Substances 0.000 description 19
- 238000004809 thin layer chromatography Methods 0.000 description 19
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 18
- 229910000027 potassium carbonate Inorganic materials 0.000 description 16
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 16
- 239000000126 substance Substances 0.000 description 16
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 15
- 230000008569 process Effects 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- 229910052763 palladium Inorganic materials 0.000 description 13
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 238000000605 extraction Methods 0.000 description 11
- 238000002390 rotary evaporation Methods 0.000 description 11
- 238000000926 separation method Methods 0.000 description 11
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 238000004440 column chromatography Methods 0.000 description 9
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 230000003472 neutralizing effect Effects 0.000 description 8
- 235000010288 sodium nitrite Nutrition 0.000 description 8
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- KTADSLDAUJLZGL-UHFFFAOYSA-N 1-bromo-2-phenylbenzene Chemical group BrC1=CC=CC=C1C1=CC=CC=C1 KTADSLDAUJLZGL-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000010363 phase shift Effects 0.000 description 5
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 5
- 235000019345 sodium thiosulphate Nutrition 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- UZRMPSOGFATLJE-UHFFFAOYSA-N (4-pentylphenyl)boronic acid Chemical compound CCCCCC1=CC=C(B(O)O)C=C1 UZRMPSOGFATLJE-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- -1 pentylbiphenyl boronic acid Chemical compound 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- NGHPTBRVHDZITR-UHFFFAOYSA-N 3-ethyl-4-iodoaniline Chemical group CCC1=CC(N)=CC=C1I NGHPTBRVHDZITR-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000003989 dielectric material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 238000004293 19F NMR spectroscopy Methods 0.000 description 2
- PLKZGDYLTZBAEH-UHFFFAOYSA-N 2-ethyl-4-iodoaniline Chemical compound CCC1=CC(I)=CC=C1N PLKZGDYLTZBAEH-UHFFFAOYSA-N 0.000 description 2
- NVTHEIAQKUQRTM-UHFFFAOYSA-N B(O)(O)O.C(CCCC)C1=C(C=CC=C1)C1=CC=CC=C1 Chemical compound B(O)(O)O.C(CCCC)C1=C(C=CC=C1)C1=CC=CC=C1 NVTHEIAQKUQRTM-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical compound ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- ZYCMDWDFIQDPLP-UHFFFAOYSA-N hbr bromine Chemical compound Br.Br ZYCMDWDFIQDPLP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 230000009022 nonlinear effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- ZWZVWGITAAIFPS-UHFFFAOYSA-N thiophosgene Chemical compound ClC(Cl)=S ZWZVWGITAAIFPS-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
- C07C25/18—Polycyclic aromatic halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
- C07C331/16—Isothiocyanates
- C07C331/28—Isothiocyanates having isothiocyanate groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—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
- C09K19/126—Compounds containing at least one asymmetric carbon atom
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/42—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01P—WAVEGUIDES; RESONATORS, LINES, OR OTHER DEVICES OF THE WAVEGUIDE TYPE
- H01P1/00—Auxiliary devices
- H01P1/18—Phase-shifters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a side ethyl quaterphenyl liquid crystal compound and a preparation method thereof, a liquid crystal composition and a microwave device, and relates to the technical field of liquid crystal materials. The side ethyl tetrabiphenyl liquid crystal compound has a structure shown as a structural formula (I). The invention aims to provide a side ethyl quaterphenyl nematic liquid crystal compound which has a high delta n value, a stable structure, a small microwave absorption coefficient and low dielectric loss. And then the side ethyl quaterphenyl liquid crystal compound is mixed with other four wide-temperature nematic liquid crystal compounds to prepare the high-medium low-consumption nematic liquid crystal composition which can meet the use requirement of a microwave K wave band, so that the microwave dielectric loss is reduced, and the microwave phase modulation amount and device quality factors are improved.
Description
Technical Field
The invention relates to the technical field of liquid crystal materials, in particular to a side ethyl quaterphenyl liquid crystal compound and a preparation method thereof, a liquid crystal composition and a microwave device.
Background
The microwave phase shifter is a key device in the technical field of microwave K-band (millimeter wave, 0.3-40 GHz) communication, and has wide application in a plurality of aviation, military and civil fields such as radar systems, satellite antennas, communication systems, electronic countermeasure systems and the like. Nematic liquid crystal is an organic matter which has liquidity of liquid, orderliness of crystal and anisotropy, and molecules of the nematic liquid crystal can generate continuous deformation and flowing under the action of external fields such as light, electricity, magnetism and the like, so that dielectric constant and refractive index are induced to generate periodic continuous change, and a strong optical nonlinear effect is formed. The microwave liquid crystal phase shifter can be manufactured by taking nematic liquid crystal material as a microwave signal transmission medium.
The dielectric loss refers to microwave frequency loss caused by the absorption of the frequency generated when microwave (4-40 GHz) irradiates or passes through the liquid crystal material, namely microwave insertion loss, and the dielectric loss is generally expressed as dielectric constant (delta epsilon) in the liquid crystal material r )，Δε r The larger the microwave phase shift quantity, the more beneficial the microwave phase shift quantity is; meanwhile, after passing through the liquid crystal material, light is refracted and scattered through the liquid crystal to form ordinary light and white lightThe refractive index of the extraordinary ray indicates "no", and the refractive index of the extraordinary ray indicates "n e ", the birefringence is represented by" Δ n ", and" Δ n ═ n o -n e ", the birefringence index" delta n "can reflect the optical anisotropy of liquid crystal compounds and liquid crystal materials, the delta n value required by microwave high-frequency devices is more than or equal to 0.30, and the higher the delta n is, the more beneficial to improving the microwave phase shift quantity is.
The liquid crystal materials used first were products K15, E7 from Merck, germany, with Δ n values below 0.2, small Δ ∈ r values at high frequencies, large dielectric losses, excessively thick LC cells (d ═ 254 μm), response times exceeding 350 ms; in 2013, Reuter M. et al report the influence of high frequency on wave absorption of different end groups such as-F, -CN, -NCS and the like. In recent years, German Merck company reports that an isothiocyanato-polycyclic aromatic acetylene type high-delta n mixed liquid crystal material has a delta n value of about 0.25-0.30, improves the dielectric property of a microwave device, and still has large dielectric loss. Herman J. et al respectively report in 2013 and 2015 that isothiocyanato-lateral ethyl tetraphenyl diacetylene liquid crystal compounds (delta n is more than or equal to 0.6) have obviously increased microwave phase shift amount, but have large dielectric loss and high material melting point, and cannot meet the requirements of extreme low-temperature environment use. However, no study on the influence of the low-temperature photoelectric properties of the liquid crystal for the microwave has been reported.
In summary, in the course of extensive research, it has been found that there is still a need to develop a liquid crystal material for microwave with "high dielectric constant, low consumption" and low melting point.
Disclosure of Invention
The invention mainly aims to provide a side ethyl quaterphenyl liquid crystal compound, a preparation method thereof, a liquid crystal composition and a microwave device, and aims to provide a liquid crystal material with high dielectric constant, low consumption and low melting point.
In order to achieve the above object, the present invention provides a pendant ethyl quaterphenyl liquid crystal compound, which has a structure represented by the following structural formula (i):
wherein R is 1 Is an alkyl group having 1 to 7 carbon atoms or an alkenyl-containing alkyl group having 3 to 7 carbon atoms; x 1 、X 2 And X 3 Each independently selected from-H, -F or-Cl; y is-NCS or-F.
The invention also provides a preparation method of the side ethyl quaterphenyl liquid crystal compound, which is used for synthesizing the side ethyl quaterphenyl liquid crystal compound, and the preparation method of the side ethyl quaterphenyl liquid crystal compound comprises the following steps:
step S10: under the protection of nitrogen, mixing a first reactant, a second reactant, palladium tetratriphenylphosphine, potassium carbonate, ethanol, toluene and water, carrying out reflux reaction for 4-8 hours at 65-85 ℃ under the stirring condition, detecting and tracking the reaction by using TLC (thin layer chromatography), and after the reaction is finished, carrying out separation, washing, drying and purification treatment to obtain a first intermediate;
step S20: under the condition of ice salt bath, adding hydrobromic acid and tetrahydrofuran into the first intermediate, after the temperature of the solution is reduced to be below 0 ℃, dropwise adding an aqueous solution of sodium nitrite, then keeping the temperature at 5-10 ℃, stirring for 50-70 min to obtain a reaction solution, mixing hydrobromic acid and cuprous bromide, heating to reflux, dropwise adding the reaction solution, and carrying out separation, drying and purification treatment to obtain a second intermediate;
step S30: under the protection of nitrogen and at a temperature not higher than-75 ℃, dropwise adding n-butyllithium into the mixed solution of the second intermediate and tetrahydrofuran, reacting at a constant temperature for 1-1.5 h, dropwise adding trimethyl borate, continuing to react at a constant temperature for 2-4 h, and separating, washing, drying and purifying to obtain a third intermediate;
step S40: under the protection of nitrogen, sequentially adding a third reactant, palladium tetratriphenylphosphine, potassium carbonate, ethanol, toluene and water into the third intermediate, performing reflux reaction for 4-6 hours at the temperature of 65-80 ℃ under the stirring condition, and performing separation, washing, drying and purification treatment to obtain a target compound;
wherein the first reactant in step S10 is a compound having a structure represented by the following structural formula (ii), the second reactant in step S10 is a compound having a structure represented by the following structural formula (iii), and the third reactant in step S40 is a compound having a structure represented by the following structural formula (iv):
wherein M is-NH 2 or-F.
In addition, the invention also provides a liquid crystal composition which comprises a first component, wherein the first component is one or more of the side ethyl quaterphenyl liquid crystal compounds.
Optionally, each compound component in the liquid crystal composition is a refined product purified by an electric field adsorption method.
Optionally, the first component is composed of one to five of side ethyl tetrabiphenyl liquid crystal compounds shown in a structural formula (I), and the weight percentage of each side ethyl tetrabiphenyl liquid crystal compound in the liquid crystal composition is 1-15%.
Optionally, the liquid crystal composition further comprises a second component, a third component and a fourth component;
wherein, the second component comprises at least one of a compound shown as a structural formula (V) and a compound shown as a structural formula (VI);
the third component comprises at least one of the compounds shown in the following structural formula (VII);
the fourth component comprises at least one of a compound shown in a structural formula (VIII) and a compound shown in a structural formula (IX);
therein, the structureIn the formula (V), R 2 Is a saturated alkyl group or an unsaturated alkyl group having 2 to 7 carbon atoms; x 4 、X 5 、X 6 Each independently selected from-H or-F, Y 1 is-NCS or-F;
in the structural formula (VI), R 3 Is a saturated alkyl group or an unsaturated alkyl group having 2 to 7 carbon atoms; x 7 is-H, -F or-Cl, X 8 And X 9 Each independently selected from-H or-F, Y 2 is-NCS or-F;
in the formula (VII), R 4 And R 5 Each independently selected from saturated alkyl or unsaturated alkyl containing 2-7 carbon atoms;
in the structural formula (VIII), R 6 Is a saturated or unsaturated alkyl group having 2 to 7 carbon atoms, X 10 And X 11 Each independently selected from-H or-F, Y 3 is-NCS or-F;
in the structural formula (IX), R 7 Is a saturated alkyl group or an unsaturated alkyl group having 2 to 7 carbon atoms; x 12 And X 13 Each independently selected from-H or-F, Y 4 is-NCS or-F.
Optionally, the weight percentage of each compound in the second component in the liquid crystal composition is 1-15%;
each compound in the third component accounts for 1-20% of the liquid crystal composition in percentage by weight;
each compound in the fourth component accounts for 1-15% of the liquid crystal composition in percentage by weight.
Optionally, the liquid crystal composition further comprises a fifth component comprising at least one of the compounds represented by the following structural formula (X):
wherein R is 8 And R 9 Each independently selected from saturated alkyl or unsaturated alkyl containing 2-7 carbon atoms, R 10 is-CH 3 or-C 2 H 5 。
Optionally, each compound in the fifth component accounts for 1-15% of the weight of the liquid crystal composition.
In addition, the invention also provides a microwave device, which comprises the liquid crystal composition.
In the technical scheme provided by the invention, the tetrabiphenyl liquid crystal compound containing a side ethyl branched chain is designed and synthesized, and fluorine or an isothiocyanic group is introduced into the molecular structure of the tetrabiphenyl liquid crystal compound, so that the nematic liquid crystal compound with a high delta n value, a stable structure, a small microwave absorption coefficient and low dielectric loss is obtained. And then the side ethyl quaterphenyl liquid crystal compound is mixed with other wide-temperature nematic liquid crystal compounds (II-IV) to prepare the nematic liquid crystal composition which has low co-freezing point and can meet the requirements of high medium and low consumption used in a microwave K wave band, thereby reducing the microwave dielectric loss and improving the microwave phase modulation amount and device quality factors.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments.
It should be noted that those whose specific conditions are not specified in the examples were performed according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. In addition, the meaning of "and/or" appearing throughout includes three juxtapositions, exemplified by "A and/or B", including either A or B or both A and B. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention relates to the relevant professional knowledge in the field of liquid crystal materials, and for the convenience of understanding, the relevant performance parameters of the liquid crystal materials are introduced as follows:
Δ ∈ represents dielectric anisotropy; Δ n represents the optical anisotropy, i.e., birefringence (589nm, 25 ℃); iso, clearing point temperature (deg.c) which is the phase state of the liquid crystal composition;
the dielectric anisotropy in the microwave range is defined as:
△ε r ≡(ε r,|| -ε r,⊥ ) Wherein the component "ε parallel to the long axis of the liquid crystal r,|| ", vertical liquid crystal major axis component". epsilon r,⊥ ”；
Tunability (τ) is defined as: τ ≡ (Δ ε) r /ε r|| )；
The material quality (η) is defined as: eta.ident (tau/tan delta epsilon) r max .)；
The maximum dielectric loss is: tan delta epsilon r max .≡max.{tanδε r⊥ ，tanδε r|| }。
Wherein the dielectric loss is expressed as a dielectric constant 'Delta epsilon' in the liquid crystal material r ", the quantitative representation of the physical" dielectric loss "of microwaves is: tangent value of dielectric loss (tan. delta. epsilon.) r⊥ Or tan delta epsilon r max ) Is a main performance index parameter reflecting the liquid crystal material in a microwave field and generally requires tan delta epsilon r⊥ (or tan. delta. epsilon.) r max ) A value of less than or equal to about 0.03 and tan delta epsilon r，∥ The value is less than or equal to about 0.005.
The term "high dielectric constant and low loss" liquid crystal material refers to a liquid crystal material with high dielectric anisotropy, high optical anisotropy and low dielectric loss; after the microwave is irradiated by the liquid crystal material, the dielectric loss is small, and tan delta epsilon r ⊥ (or tan. delta. epsilon.) r max ) The value is lower than about 0.008, and the tan delta epsilon r | | | value is lower than 0.004.
The term "phase modulation coefficient" is expressed as "tau", and reflects the parameter of the phase modulation capability of the liquid crystal material to the microwave frequency, wherein tau is more than or equal to 0.15 and less than or equal to 0.5;
the term "quality factor" (eta, or FOM) refers to the comprehensive evaluation result of the performance after microwave passes through the liquid crystal, which reflects the performance and quality of the liquid crystal material, and generally requires eta to be more than or equal to 15.
The liquid crystal materials used first were products K15, E7 from Merck, germany, with Δ n values below 0.2, small Δ ∈ r values at high frequencies, large dielectric losses, excessively thick LC cells (d ═ 254 μm), response times exceeding 350 ms; in 2013, Reuter M. et al report the influence of high frequency on wave absorption of different end groups such as-F, -CN, -NCS and the like. In recent years, the German Merck company reports that an isothiocyanato-polycyclic aromatic acetylene type high delta n mixed liquid crystal material has a delta n value of about 0.25-0.30, improves the dielectric property of a microwave device, and still has large dielectric loss. Herman J. et al respectively report in 2013 and 2015 that isothiocyano-lateral ethyl tetraphenyl diacetylene side ethyl quaterphenyl liquid crystal compounds (delta n is more than or equal to 0.6), the microwave phase shift amount is obviously increased, but the dielectric loss is large, the melting point of the material is high, and the requirement of use in a limit low-temperature environment cannot be met. However, no report has been found on the influence of low-temperature photoelectric properties of microwave liquid crystals.
In summary, in the course of extensive research, it has been found that there is still a need to develop a liquid crystal material for microwave with "high dielectric constant, low consumption" and low melting point.
In view of the above, the present invention provides a pendant ethyl quaterphenyl liquid crystal compound, which has a structure represented by the following structural formula (i):
wherein R is 1 Is an alkyl group having 1 to 7 carbon atoms or an alkenyl-containing alkyl group having 3 to 6 carbon atoms; x 1 、X 2 And X 3 Each independently selected from-H, -F or-Cl; y is-NCS or-F.
The side ethyl quaterphenyl liquid crystal compound has a quaterphenyl structure with stable structure and small polarizability, and terminal groups such as-NCS or-F and the like which are stable to microwaves are introduced into the quaterphenyl structure, so that the side ethyl quaterphenyl liquid crystal compound has the advantages of large optical anisotropy and stable structure, and when the side ethyl quaterphenyl liquid crystal compound is applied to a high dielectric anisotropy liquid crystal material, the side ethyl quaterphenyl liquid crystal compound is beneficial to reducing the dielectric loss of a liquid crystal microwave device, improving the phase modulation capability and increasing the quality factor of the liquid crystal material; meanwhile, the side ethyl quaterphenyl liquid crystal compound in the embodiment is a quaterphenyl rod-shaped liquid crystal compound containing a side ethyl branched chain, has a lower melting point, and is beneficial to reducing the co-freezing point of the composition when being applied to the liquid crystal composition, so that the liquid crystal composition can adapt to a limit low-temperature environment.
The side ethyl quaterphenyl liquid crystal compound in the embodiment can be any compound with a structure shown in a structural formula (I). In the structure of the compound, R 1 May be-CH 3 、-C 2 H 5 、-C 3 H 8 、-C 4 H 9 、-C 5 H 11 or-C 6 H 13 It may be an alkyl chain in which one H atom is replaced by an alkenyl group and which is-CH 3 、-C 2 H 5 、-C 3 H 8 、-C 4 H 9 E.g., -CH 2 CH＝CH 2 、-CH 2 CH(CH＝CH 2 )CH 3 or-CH (CH ═ CH) 2 )CH 3 Etc.; x 1 Can be-H, -F or-Cl; x 2 Can be-H, -F or-Cl; x 3 Can be-H, -F or-Cl; y may be-NCS or-F. R 1 、X 1 、X 2 、X 3 And the group selection of Y does not interfere with each other.
Pendant group X in formula (I) 1 、X 2 、X 3 Preferably at least one of them is a F atom. The introduced ethyl and fluorine atoms and the tetra-biphenyl structure can make the lateral ethyl tetra-biphenyl liquid crystal compound have larger optical anisotropy and better structural stability, and are favorable for further reducing the dielectric loss of the liquid crystal material and further increasing the quality factor of the liquid crystal material.
For ease of expression, the structures of the compounds appearing hereinafter are represented by the structural codes in Table 1 below.
Table 1 radical structure code
In the table R n Represents an alkyl group having n carbon atoms, n being an integer; e (n) represents an alkenyl-containing alkyl group having a total number of carbon atoms of n, n being an integer; the Arabic numerals in the compound codes are the carbon atoms of alkyl chains.
For the sake of understanding, a preferred example I-1 of the pendant ethyl quaterphenyl liquid crystal compound having a structure represented by the following structural formula (I-1) and corresponding to the general structural formula represented by the structural formula (I) will be described. According to the codes shown in Table 1, the structural formula (I-1) can be named as liquid crystal compound 3PPI (2) GUF.
As a preferred embodiment, the structural formula of the side ethyl quaterphenyl liquid crystal compound in the invention is as follows: 5PP (2) PUF, 3PPI (2) PUS, 5PP (2) PUS, 5PPI (2) PUS, 4PP (2) GGS, 3PPI (2) PUS, 4PPI (2) GUS, 4PPI (2) GUF, 4PP (2) GUS, 3PP (2) JIUF, 4PP (2) PUS, 5PPI (2) GJIS, E (5) PP (2) PUF, E (5) PP (2) PGS, E (5) PPI (2) JUF.
The invention also provides a preparation method of the side ethyl quaterphenyl liquid crystal compound, which is used for synthesizing a target compound product with a structure shown in a structural formula (I), namely the side ethyl quaterphenyl liquid crystal compound.
The synthetic route is as follows:
in this embodiment, the preparation method of the pendant ethyl quaterphenyl liquid crystal compound includes the following steps:
step S10: under the protection of nitrogen, mixing a first reactant, a second reactant, palladium tetratriphenylphosphine, potassium carbonate, ethanol, toluene and water, carrying out reflux reaction for 4-8 h at 65-85 ℃ under a stirring condition, detecting and tracking the reaction by TLC, and after the reaction is finished, carrying out separation, washing, drying and purification treatment to obtain a first intermediate.
The first, second and third reactants are selected to have different structures depending on the specific structure (formula (I)) of the target compound. Specifically, in this embodiment, the first reactant is a compound having a structure represented by the following structural formula (ii); the second reactant is a compound having a structure represented by the following structural formula (III).
It is understood that R in the first reactant formula 1 With R of the target compound product 1 The same; the substitution position of the ethyl group in the second reactant is the same as the substitution position of the pendant ethyl group in the target compound product. For example, when the target compound is 3PPI (2) GUF, R in the first reactant 1 is-C 3 H 9 (ii) a The second reactant is 3-ethyl-4-iodoaniline.
In step S10, the separation, washing, drying and purification processes may be performed according to a conventional method in the field of organic synthesis, for example, the reaction product is separated by centrifugation or filtration, then extracted with an organic solvent, washed with water, dried with a drying agent, and finally subjected to chromatography, elution, etc. to obtain a purified product. In this embodiment, step S10 can be implemented in the following manner: under the protection of nitrogen, a first reactant, a second reactant and palladium tetratriphenylphosphine (catalyst, Pd (PPh) are added into a reaction bottle in sequence 3 ) 4 ) Potassium carbonate (K) 2 CO 3 ) Heating and stirring ethanol (EtOH), toluene and water until reflux, wherein the reflux temperature is 65-85 ℃, after reflux reaction is 4-8 hours, detecting and tracking reaction by adopting TLC (thin layer chromatography), and stopping stirring after the reaction is finished; after the reaction solution is naturally cooled to room temperature, adding hydrochloric acid for neutralization and filtering insoluble substances, and then addingAnd (3) extracting and separating the toluene, washing a toluene layer to be neutral, drying and filtering by using anhydrous sodium sulfate, drying the filtrate by rotary evaporation, loading the dried filtrate into a chromatographic column, eluting by using petroleum ether, and removing the solvent in the eluent by rotary evaporation to obtain the first intermediate.
Wherein the molar ratio of the first reactant to the second reactant to the tetrakistriphenylphosphine palladium to the potassium carbonate is 1: (1-1.05): (0.001-0.003): (2-2.5).
Step S20: under the condition of ice salt bath, adding hydrobromic acid and tetrahydrofuran into the first intermediate, after the temperature of the solution is reduced to be below 0 ℃, dropwise adding an aqueous solution of sodium nitrite, then keeping the temperature at 5-10 ℃, stirring for 50-70 min to obtain a reaction solution, mixing hydrobromic acid and cuprous bromide, heating to reflux, dropwise adding the reaction solution, and carrying out separation, drying and purification treatment to obtain a second intermediate.
In this example, the first intermediate, hydrobromic acid (HBr) and Tetrahydrofuran (THF) were added sequentially to a three-necked flask in an ice salt bath, and sodium nitrite (NaNO) was added dropwise after the temperature of the solution decreased to below 0 ℃ 2 ) The reaction solution is kept at the temperature of 5-10 ℃ for 50-70 min under stirring (after the dropwise addition is finished within 1 hour, and the temperature of the solution cannot exceed 10 ℃ in the dropwise addition process). And (3) adding hydrobromic acid and cuprous bromide (CuBr) into the other three-neck flask in sequence, heating to reflux, dropwise adding the reaction solution, and keeping the reflux all the time in the dropwise adding process. And after the dropwise addition, naturally heating to room temperature, adding an aqueous solution of sodium thiosulfate, stirring, extracting, separating liquid, extracting with ethyl acetate, drying with anhydrous sodium sulfate, removing the solvent by rotary evaporation, finally loading into a chromatographic column, and eluting with petroleum ether to obtain the second intermediate.
Wherein the molar ratio of the first intermediate, the hydrobromic acid added for the first time, the hydrobromic acid added for the second time, the sodium nitrite and the cuprous bromide is 1: (1-4): (2.5-4): (1-2): (0.6-3).
Step S30: under the protection of nitrogen and at the temperature of not higher than-75 ℃, dropwise adding n-butyllithium into the mixed solution of the second intermediate and tetrahydrofuran, reacting at constant temperature for 1-1.5 h, dropwise adding trimethyl borate, continuing to react at constant temperature for 2-4 h, and separating, washing, drying and purifying to obtain a third intermediate.
In this example, under the protection of nitrogen, the second intermediate and Tetrahydrofuran (THF) were sequentially added into a reaction flask, the reaction flask was placed in a cryotank, n-butyllithium (n-BuLi) was added dropwise after the cryotank was cooled to-78 ℃, the temperature was maintained at not higher than-75 ℃ throughout the entire 1 hour period. Reacting at constant temperature for 1-1.5 h, and then dropwise adding trimethyl borate (B (OCH) 3 ) 3 ) And the temperature is always kept not higher than-75 ℃ in the dropping process. After reacting for 2-4 h at constant temperature, detecting and tracking the reaction by adopting TLC (thin layer chromatography), and stopping stirring after the reaction is finished; and after the reaction liquid is naturally cooled to room temperature, adding hydrochloric acid for neutralization, filtering out insoluble substances, then adding ethyl acetate for extraction and liquid separation, washing with water to be neutral, drying and filtering by using anhydrous sodium sulfate, and recrystallizing by using petroleum ether after rotary evaporation and drying of filtrate to obtain a third intermediate.
Wherein the molar ratio of the second intermediate to n-butyllithium to trimethyl borate is 1: (1.0-1.5): (1.5-2).
Step S40: under the protection of nitrogen, sequentially adding a third reactant, palladium tetratriphenylphosphine, potassium carbonate, ethanol, toluene and water into the third intermediate, carrying out reflux reaction for 4-6 h at the temperature of 65-80 ℃ under the stirring condition, and carrying out separation, washing, drying and purification treatment to obtain the target compound.
Similarly, depending on the specific structure of the target compound (see formula (I)), a third reactant of a different structure, namely bromobiphenyl containing different substituent groups, is selected. Specifically, in this embodiment, the third reactant is a compound having a structure represented by the following structural formula (iv).
Wherein M may be-F or-NH 2 . It is to be understood that X in the third reactant formula 1 、X 2 、X 3 And MWhether the selected group structure or the substitution position is the same as X in the structural formula of the target compound product 1 、X 2 、X 3 And Y corresponds one to one. For example, where the target compound is 3PPI (2) GUF, the structural formula of the third reactant is as follows. However, in view of the fact that when Y in the formula (I) is-NCS, bromobiphenyl containing a-NCS substituent is less likely to react, and M is selected to be-NH in order to promote the reaction to proceed smoothly 2 A third reactant of (1).
A third reactant:
wherein the molar ratio of the third intermediate to the third reactant to the tetrakistriphenylphosphine palladium to the potassium carbonate is 1: (1-1.05): (0.001-0.003): (2-4).
In specific implementation, step S40 may be performed by: under the protection of nitrogen, sequentially adding a third intermediate, a third reactant, palladium tetratriphenylphosphine, potassium carbonate, ethanol, toluene and water into a reaction bottle, heating and stirring until reflux is achieved, wherein the reflux temperature is 65-80 ℃, the reflux reaction is carried out for 4-6 hours, then detecting and tracking reaction by adopting TLC (thin layer chromatography), and stopping stirring after the reaction is finished; and (2) after the reaction liquid is naturally cooled to room temperature, adding toluene for extraction and liquid separation, washing with water to be neutral, drying and filtering by using anhydrous sodium sulfate, drying the filtrate by rotary evaporation, then loading the dried filtrate into a chromatographic column, eluting by using petroleum ether, removing the solvent by rotary evaporation, and then recrystallizing by using the petroleum ether to obtain a target compound, namely a crude product of the side ethyl quaterphenyl liquid crystal compound with the structure shown in the structural formula (I).
In another embodiment of the preparation process according to the invention, when Y is in the formula (I) of the target compound 1 When it is-NCS, Y is selected to be-NH 2 As a third reactant, of course, X of the third reactant 1 、M 1 、N 1 Remain all with X in the structural formula of the target compound product 1 、M 1 、N 1 And (4) corresponding to each other. In the embodiment, the product obtained in the step S40, calcium carbonate, water and dichloromethane are mixed at 0-5 ℃ and then drippedAdding dichlorocarbon sulfide, reacting at 0-5 deg.C for 1.5h, naturally heating to room temperature for 0.5h, heating under reflux for 0.5h, separating, and purifying to obtain Y 1 Is a target compound of NCS.
In order to further increase the resistivity of the side ethyl quaterphenyl liquid crystal compound, the obtained crude side ethyl quaterphenyl liquid crystal compound product can be subjected to power plant adsorption purification and trace ion removal after the step S40. Specifically, an electric field adsorption method may be employed: dissolving the crude product in toluene to prepare a solution to be treated; and (2) correspondingly adding toluene, the solution to be treated and nano silicon dioxide into a cathode solvent chamber, a sample chamber and an anode solvent chamber of a three-tank ionic membrane purifier respectively, adopting oxide film electrodes, setting the electrode spacing to be 6-15 mm, setting the electric field intensity to be 1.0-4 kV/cm, and purifying for 30min to obtain a refined product.
In addition, the invention also provides a liquid crystal composition which comprises a first component, wherein the first component comprises one or more of the side ethyl quaterphenyl liquid crystal compounds as described above, namely the first component comprises at least one of the side ethyl quaterphenyl liquid crystal compounds provided by the invention and having the structure shown in the structural formula (I), for example, the liquid crystal composition of the embodiment can comprise a 5PP (2) PUF, a 5PP (2) PUF and a 5PPI (2) PUF, and can also comprise three or more side ethyl quaterphenyl liquid crystal compounds having the structure shown in the structural formula (I). The liquid crystal composition can also be obtained by combining the side ethyl quaterphenyl liquid crystal compound with any existing liquid crystal compound, and has the advantages of lower dielectric loss and higher quality factor caused by the structural characteristics of the side ethyl quaterphenyl liquid crystal compound.
Further, in this embodiment, each of the compound components in the liquid crystal composition is a purified product obtained by purifying the liquid crystal composition by an electric field adsorption method, so that a composition having a lower dielectric loss and a higher quality factor can be obtained. The purification process by electric field adsorption is described above and will not be described herein.
As a more preferable embodiment of the liquid crystal composition of the present invention, the liquid crystal composition of this embodiment includes a first component, and the first component may be composed of one to five compounds represented by structural formula (I), and the weight percentage of each of the compounds in the liquid crystal composition is 1 to 15%, preferably 5 to 10%. For example, if the liquid crystal composition comprises a first component and other existing liquid crystal compounds, and the first component comprises 5PP (2) PUF and 5PPI (2) PUF, the weight percentage content of the 5PP (2) PUF is 1-15% and the weight percentage content of the 5PPI (2) PUF is 1-15% in the liquid crystal composition of this embodiment.
Further, in an embodiment of the liquid crystal composition provided by the present invention, the liquid crystal composition further includes a second component, a third component and a fourth component.
Wherein the second component comprises at least one of a compound shown in a structural formula (V) and a compound shown in a structural formula (VI). Namely, the second component can select one or more compounds with the structure shown in the structural formula (V); one or more compounds with the structure shown in the structural formula (VI) can also be selected; at least one compound having a structure represented by formula (V) and at least one compound having a structure represented by formula (VI) may also be selected.
In the formula (V), R 2 Is a saturated or unsaturated alkyl group having 2 to 7 carbon atoms, X 4 、X 5 、X 6 Each independently selected from-H or-F, Y 1 is-NCS or-F; in the structural formula (VI), R 3 Is a saturated or unsaturated alkyl group having 2 to 7 carbon atoms, X 7 is-H, -F or-Cl, X 8 And X 9 Each independently selected from-H or-F, Y 2 is-NCS or-F.
The third component comprises at least one of the compounds shown in the following structural formula (VII).
In the formula (VII), R 4 And R 5 Each independently selected from saturated alkyl or unsaturated alkyl containing 2-7 carbon atoms.
The fourth component comprises at least one of a compound represented by the following structural formula (VIII) and a compound represented by the following structural formula (IX).
In the structural formula (VIII), R 6 Is a saturated or unsaturated alkyl group having 2 to 7 carbon atoms, X 10 And X 11 Each independently selected from-H or-F, Y 3 is-NCS or-F; in the formula (IX), R 7 Is a saturated alkyl group or an unsaturated alkyl group having 2 to 7 carbon atoms; x 12 And X 13 Each independently selected from-H or-F, Y 4 is-NCS or-F.
It is understood that, in the present embodiment, the liquid crystal composition includes a first component, a second component, a third component, and a fourth component; wherein, the first component can be selected from at least one of the compounds with the structure shown in the structural formula (I), the second component can be selected from at least one of the compounds with the structures shown in the structural formula (V) and the structural formula (VI), the third component can be selected from at least one of the compounds with the structural formula (VII), the fourth component can be selected from at least one of the compounds with the structural formula (VIII) and the structural formula (IX), and the fifth component can be selected from at least one of the compounds with the structural formula (X). In the liquid crystal composition of the embodiment, the weight percentage of each compound in the second component is 1-15%, preferably 5-10%; the weight percentage of each compound in the third component is 1-20%, preferably 5-15%; the weight percentage of each compound in the fourth component is 1-15%, preferably 2-8%.
As a preferred embodiment of the present invention, the liquid crystal composition further comprises a fifth component, i.e. the liquid crystal composition of the present embodiment comprises a first component, a second component, a third component, a fourth component and a fifth component. Wherein the fifth component comprises at least one of the compounds represented by the following structural formula (X):
wherein R is 8 And R 9 Each independently selected from saturated alkyl or unsaturated alkyl containing 2-7 carbon atoms, R 10 is-CH 3 or-C 2 H 5 。
In the liquid crystal composition of the embodiment, each compound in the fifth component is 1 to 15% by weight, preferably 2 to 5% by weight of the liquid crystal composition.
In addition, the invention also provides a microwave device, which comprises the liquid crystal composition.
The liquid crystal composition provided by the invention can further improve the optical anisotropy and the stability of the conventional liquid crystal composition under microwave, has the effect of reducing dielectric loss, can be applied to the field of microwave devices, and is used for preparing microwave devices.
The technical solutions of the present invention are further described in detail with reference to the following specific examples, which should be understood as merely illustrative and not limitative.
Examples of preparation methods
Example 1 Synthesis of 5PP (2) PUF, a liquid crystalline compound of the pendant ethyl quaterphenyl type
The molecular structure of the 5PP (2) PUF is as follows:
the synthetic route is as follows:
(1) in a 250mL four-necked flask were added 7.6g (0.04mol) of 4-n-pentylphenylboronic acid, 9.88g (0.04mol) of 2-ethyl-4-iodoaniline, 13.8g (0.10mol) of potassium carbonate, 80mL of ethanol, 60mL of toluene and 30mL of water in this order; after 6 times of nitrogen replacement, 0.46g (1% mol) of catalyst palladium tetrakistriphenylphosphine is added under the protection of nitrogen; heating and stirring, controlling the temperature at 70 ℃, carrying out reflux reaction for 4 hours, tracking and detecting by using TLC (thin layer chromatography), and stopping stirring after the reaction is completed; cooling to room temperature, neutralizing with 5% hydrochloric acid, filtering off insoluble substances, adding toluene for extraction, separating liquid, washing with water to neutrality, drying with anhydrous sodium sulfate, filtering, evaporating filtrate, loading into chromatographic column, eluting with petroleum ether, and evaporating to remove solvent to obtain 8.7g intermediate 4- (4' -n-pentyl) -2-ethylaniline [5PP (2) NH ] 2 ]In 82.2% yield.
(2) Into a 250mL three-necked flask, 8g (0.03mol) of Compound 5PP (2) NH was sequentially added 2 24.3g (40%, 0.12mol) of hydrobromic acid and 100mL of Tetrahydrofuran (THF), carrying out ice salt bath, dropping 20mL of sodium nitrite (2.4g,0.035mol) aqueous solution after the temperature is reduced to 0 ℃, completing dropping within 1 hour, keeping the temperature of the solution not more than 10 ℃ in the dropping process, keeping the temperature and stirring at 5 ℃ for 60min, and storing at low temperature for standby; 15.2g (40%, 0.075mol) of hydrobromic acid and 2.88g (0.02mol) of cuprous bromide are added into another three-neck flask in sequence, heated to reflux, and then the reaction solution obtained in the previous step is added dropwise, and the reflux is kept all the time during the dropwise addition. After the dropwise addition, naturally heating to room temperature, adding an aqueous solution of sodium thiosulfate, stirring, extracting, separating liquid, extracting with ethyl acetate, drying with anhydrous sodium sulfate, removing the solvent by rotary evaporation, finally loading into a chromatographic column, and leaching with petroleum ether (60-90 ℃); after removal of the solvent, 6.9g of intermediate 5PP (2) Br (yellow liquid) were obtained in 70.0% yield.
(3) 5.6g (0.016mol) of 5PP (2) Br and 100ml of Tetrahydrofuran (THF) are sequentially added into a 250ml four-mouth bottle, the reaction bottle is placed into a low-temperature tank, 1.1g (0.02mol) of n-butyllithium is dropwise added after the temperature of the low-temperature tank is reduced to-78 ℃, and the temperature of the reaction solution is kept to be not higher than-75 ℃ all the time after 1h of dropwise addition. After reacting for 1h at constant temperature, 2.5g (0.024mol) trimethyl borate is added dropwise (the temperature of the reaction solution can not exceed-75 ℃ in the process). After reacting for 2 hours at constant temperature, tracking the reaction process by TLC, stopping stirring after the reaction is completed, naturally cooling the reaction solution to room temperature, adding 5% hydrochloric acid for neutralization, filtering out insoluble substances, adding ethyl acetate for extraction and liquid separation, washing with water to be neutral, drying and filtering by using anhydrous sodium sulfate, carrying out recrystallization by using petroleum ether after carrying out rotary evaporation and drying on the filtrate, and obtaining 3.1g of white solid pentylbiphenyl boric acid with the yield of 65.2%.
(4) 2.9g (0.01mol) of intermediate pentylbiphenyl boronic acid, 2.86g (0.01mol) of bromobiphenyl, 5.5g (0.04mol) of solid potassium carbonate powder, 60mL of ethanol, 50mL of toluene and 15mL of water were successively charged into a 250mL four-necked flask under nitrogen atmosphere, the mixture was replaced with nitrogen 6 times, and 0.12g (1% mol) of tetrakistriphenylphosphine palladium as a catalyst was charged. Heating and stirring to reflux under the protection of nitrogen, wherein the reflux temperature is 70 ℃, performing tracking detection by TLC (thin layer chromatography) after refluxing reaction for 4 hours, and stopping stirring after complete reaction; naturally cooling the reaction solution to room temperature, neutralizing with hydrochloric acid, filtering out insoluble substances, adding toluene for extraction and liquid separation, washing with water to be neutral, drying with anhydrous sodium sulfate, filtering, evaporating the filtrate to dryness, separating by column chromatography, eluting with petroleum ether (60-90 ℃), evaporating to remove most of solvent, cooling and crystallizing to obtain 3.4g of a white solid target compound 5PP (2) PUF, wherein the yield is 75.2%, and the phase state transition temperature is Cr 72 ℃ and N185 ℃ Iso.
The molecular structure identification data are as follows:
1 H-NMR(CDCl 3 ,400MHz)δ(ppm):7.31～7.68(m,13H),2.65～2.68(t,4H),2.51～2.54(m,2H),1.68～1.82(m,4H),1.45～1.49(m,6H),0.99～1.26(t,9H)；
13 C-NMR(100MHz，CDCl 3 )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，CDCl 3 )δ(ppm)：-114.34。
example 2 Synthesis of 5PPI (2) PUF as a pendant Ethyl Tetrabiphenyl liquid Crystal Compound
The molecular structure of the 5PPI (2) PUF is as follows:
(1) in a 250mL four-necked flask were added 7.6g (0.04mol) of 4-n-pentylphenylboronic acid, 9.88g (0.04mol) of 3-ethyl-4-iodoaniline, 13.8g (0.10mol) of potassium carbonate, 80mL of ethanol, 60mL of toluene and 30mL of water in this order; after 6 times of nitrogen replacement, 0.46g (0.1 mol percent) of catalyst tetratriphenylphosphine palladium is added under the protection of nitrogen; heating and stirring, controlling the temperature at 85 ℃, carrying out reflux reaction for 4 hours, tracking and detecting by using TLC (thin layer chromatography), and stopping stirring after the reaction is completed; cooling to room temperature, neutralizing with 5% hydrochloric acid, filtering off insoluble substances, adding toluene for extraction, separating liquid, washing with water to neutrality, drying with anhydrous sodium sulfate, filtering, evaporating filtrate, purifying with column chromatography, eluting with petroleum ether (60-90 deg.C), evaporating solvent to obtain 7.8g intermediate 4- (4' -n-amyl) -2-ethylaniline [5PPI (2) NH 2 ]In 74.5% yield.
(2) Into a 250mL three-necked flask, 8g (0.03mol) of Compound 5PPI (2) NH was sequentially added 2 24.3g (40%, 0.12mol) of hydrobromic acid and 100mL of Tetrahydrofuran (THF), carrying out ice salt bath, dropping 20mL of sodium nitrite (2.4g,0.035mol) aqueous solution after the temperature is reduced to 0 ℃, completing dropping within 1 hour, keeping the temperature of the solution not higher than 10 ℃ in the dropping process, keeping the temperature at 7 ℃ and stirring for 70min, and storing at low temperature for standby; adding 15.2g (40%, 0.075mol) of hydrobromic acid and 2.88g (0.02mol) of cuprous bromide into another three-neck flask, heating to reflux, dropwise adding the reaction solution in the previous step, keeping reflux all the time during the dropwise adding process, naturally heating to room temperature after the dropwise adding is finished, adding an aqueous solution of sodium thiosulfate, stirring, extracting, separating liquid, extracting with ethyl acetate, drying with anhydrous sodium sulfate, performing rotary evaporation to remove the solvent, finally filling into a chromatographic column, and leaching with petroleum ether (60-90 ℃); after removal of the solvent, 6.7g of intermediate 5PPI (2) Br (yellow liquid) were obtained in 69.5% yield.
(3) 5.6g (0.016mol) of 5PPI (2) Br and 100ml of Tetrahydrofuran (THF) are added into a 250ml four-mouth bottle, the reaction bottle is placed into a low-temperature tank, 1.1g (0.02mol) of n-butyllithium is added dropwise after the temperature of the low-temperature tank is reduced to-78 ℃, and the temperature of the reaction solution is kept to be not higher than-75 ℃ all the time after 1h of dropwise addition. After reacting for 1.5h at constant temperature, 2.5g (0.024mol) of trimethyl borate is added dropwise (the temperature of the reaction solution can not exceed-75 ℃ in the process). After reacting for 2.2h at constant temperature, tracking the reaction process by TLC, stopping stirring after the reaction is completed, naturally cooling the reaction solution to room temperature, adding 5% hydrochloric acid for neutralization, filtering out insoluble substances, adding ethyl acetate for separating liquid, washing with water to neutrality, drying with anhydrous sodium sulfate, filtering, evaporating the filtrate to dryness, and recrystallizing with petroleum ether to obtain 3.7g of white solid pentylbiphenyl boric acid with a yield of 68.2%.
(4) 2.9g (0.01mol) of intermediate pentylbiphenyl boronic acid, 2.86g (0.01mol) of bromobiphenyl, 5.5g (0.04mol) of solid potassium carbonate powder, 60mL of ethanol, 50mL of toluene and 15mL of water were successively charged into a 250mL four-necked flask under nitrogen atmosphere, the mixture was replaced with nitrogen 6 times, and 0.12g (0.1 mol%) of palladium tetrakistriphenylphosphine as a catalyst was charged. Heating and stirring to reflux under the protection of nitrogen, wherein the reflux temperature is 65 ℃, performing reaction reflux for 6 hours, tracking and detecting by using TLC (thin layer chromatography), and stopping stirring after the reaction is completed; naturally cooling the reaction solution to room temperature, neutralizing with hydrochloric acid, filtering out insoluble substances, adding toluene for extraction, separating liquid, washing with water to neutrality, drying with anhydrous sodium sulfate, filtering, evaporating the filtrate to dryness, separating by column chromatography, eluting with petroleum ether (60-90 ℃), evaporating to remove most of the solvent, cooling and crystallizing to obtain 3.6g of a white solid target compound 5PPI (2) PUF, wherein the yield is 80.3%, and the phase state transition temperature is Cr 65 ℃ and N180 ℃ Iso; Δ n is 0.385.
The molecular structure identification data are as follows:
1 H-NMR(CDCl 3 ,400MHz)δ(ppm):7.25～7.88(m,13H),2.71～2.73(t,2H),2.64～2.67(t,2H),2.53～2.56(m,2H),1.61～0.65(m,4H),1.45～1.54(m,6H),0.98～1.25(m,9H)；
13 C-NMR(100MHz，CDCl 3 )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；
19 F-NMR(376.29MHz，CDCl 3 )δ(ppm)：-115.45。
example 3 Synthesis of 5PP (2) PUS which is a pendant ethyl quaterphenyl liquid Crystal Compound
The molecular structure of 5PP (2) PUS is as follows:
(1) 7.6g (0.04mol) of 4-n-pentylphenylboronic acid, 9.88g (0.04mol) of 2-ethyl-4-iodoaniline, 13.8g (0.10mol) of potassium carbonate, 80mL of ethanol, 60mL of toluene and 30mL of water are successively introduced into a 250mL four-necked flask; after 6 times of nitrogen replacement, 0.46g (0.1 mol percent) of catalyst tetratriphenylphosphine palladium is added under the protection of nitrogen; heating and stirring, controlling the temperature at about 65 ℃, carrying out reflux reaction for 8 hours, tracking and detecting by TLC, and stopping stirring after the reaction is completed; cooling to room temperature, neutralizing with 5% hydrochloric acid, filtering off insoluble substances, adding toluene for extraction, separating liquid, washing with water to neutrality, drying with anhydrous sodium sulfate, filtering, evaporating filtrate, purifying with column chromatography, eluting with petroleum ether (60-90 deg.C), and evaporating to remove solvent to obtain 8.7g intermediate 4- (4' -n-amyl) -2-ethylaniline [5PP (2) NH 2 ]Brown liquid of (2), yield 82.2%.
(2) Into a 250mL three-necked flask, 8g (0.03mol) of Compound 5PP (2) NH was sequentially added 2 24.3g (40%, 0.12mol) of hydrobromic acid and 100mL of Tetrahydrofuran (THF), carrying out ice salt bath, dropping 20mL of sodium nitrite (2.4g,0.035mol) aqueous solution after the temperature is reduced to 0 ℃, completing dropping within 1 hour, keeping the temperature of the solution not higher than 10 ℃ in the dropping process, keeping the temperature at 10 ℃ and stirring for 50min, and storing at low temperature for standby; 15.2g (40%, 0.075mol) of hydrobromic acid and 2.88g (0.02mol) of cuprous bromide are added into another three-neck flask in sequence, heated to reflux, and then the reaction solution obtained in the previous step is added dropwise, and the reflux is kept all the time during the dropwise addition. After the dropwise addition, naturally heating to room temperature, adding an aqueous solution of sodium thiosulfate, stirring, extracting, separating liquid, extracting with ethyl acetate, drying with anhydrous sodium sulfate, removing the solvent by rotary evaporation, finally loading into a chromatographic column, and leaching with petroleum ether (60-90 ℃); after removal of the solvent, 6.9g of intermediate 5PP (2) Br (yellow liquid) were obtained in 70.0% yield.
(3) 5.6g (0.016mol) of 5PP (2) Br and 100ml of Tetrahydrofuran (THF) are added into a 250ml four-mouth bottle, the reaction bottle is placed into a low-temperature tank, 1.1g (0.02mol) of n-butyllithium is added dropwise after the temperature of the low-temperature tank is reduced to-78 ℃, and the temperature of the reaction solution is kept to be not higher than-75 ℃ all the time after 1h of dropwise addition. After reacting for 1.2h at constant temperature, 2.5g (0.024mol) of trimethyl borate is added dropwise (the temperature of the reaction solution can not exceed-75 ℃ in the process). After reacting for 3 hours at constant temperature, tracking the reaction process by TLC, stopping stirring after the reaction is completed, naturally cooling the reaction solution to room temperature, adding 5% hydrochloric acid for neutralization, filtering out insoluble substances, adding ethyl acetate for separating liquid, washing with water to be neutral, drying with anhydrous sodium sulfate, filtering, evaporating the filtrate by rotation, and recrystallizing with petroleum ether to obtain 3.1g of white solid with a yield of 65.2%.
(4) 2.9g (0.01mol) of intermediate pentylbiphenyl boronic acid, 2.86g (0.01mol) of bromobiphenyl, 5.5g (0.04mol) of potassium carbonate powder solid, 60mL of ethanol, 50mL of toluene and 15mL of water were successively charged into a 250mL four-necked flask under nitrogen protection, replaced with nitrogen 6 times, and 0.12g (0.1 mol%) of palladium tetrakistriphenylphosphine was added as a catalyst. Heating and stirring to reflux under the protection of nitrogen, wherein the reflux temperature is 80 ℃, carrying out tracking detection by TLC (thin layer chromatography) after refluxing for 6h, and stopping stirring after complete reaction; naturally cooling the reaction solution to room temperature, neutralizing with hydrochloric acid, filtering out insoluble substances, adding toluene for extraction, separating liquid, washing with water to neutrality, drying with anhydrous sodium sulfate, filtering, evaporating filtrate to dryness, separating by column chromatography, eluting with petroleum ether (60-90 deg.C), evaporating to remove most of solvent, cooling, and crystallizing to obtain 3.4g pale yellow solid 5PP (2) PUNH 2 The yield was 75.2%.
(5) 3.6g of the product 5PP (2) PUNH from the previous step was added to a 250ml three-necked flask 2 ，2g CaCO 3 Powder, 5ml water and 50ml CH 2 Cl 2 . Controlling the temperature to be about 0-5 ℃, then injecting 2ml of carbon dichloride into a constant pressure dropping funnel, slowly dropping and controlling the temperature not to exceed 5 ℃, reacting for 1.5h at constant temperature, naturally heating to room temperature for reacting for 0.5h, and heating for reflux reaction for 0.5 h. Tracking and detecting by TLC, and stopping stirring after the reaction is completed; naturally cooling the reaction solution to room temperature, filtering out insoluble substances, and adding ethyl acetate for extractionSeparating liquid, washing to neutrality with water, drying with anhydrous sodium sulfate, filtering, evaporating filtrate to dryness, separating by column chromatography, eluting with petroleum ether (60-90 deg.C), evaporating most solvent, cooling and crystallizing to obtain 3.4g white solid 5PP (2) PUS with yield of about 78%. The phase transition temperature is Cr 108 ℃ N185 ℃ Iso.
The molecular structure identification data are as follows:
1 H-NMR(CDCl 3 ,400MHz)δ(ppm):7.31～7.68(m,13H),2.65～2.68(t,4H),2.51～2.54(m,2H),1.68～1.82(m,4H),1.45～1.49(m,6H),0.99～1.26(t,9H)；
13 C-NMR(100MHz，CDCl 3 )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，CDCl 3 )δ(ppm)：-114.34。
example 4 Synthesis of 5PPI (2) PUS, a liquid crystalline compound of the side ethyl quaterphenyl type
5PPI (2) PUS has the following molecular structure:
(1) in a 250mL four-necked flask were added 7.6g (0.04 mol.) of 4-n-pentylphenylboronic acid, 9.88g (0.04 mol.) of 3-ethyl-4-iodoaniline, 13.8g (0.10 mol.) of potassium carbonate, 80mL of ethanol, 60mL of toluene and 30mL of water, in that order; after 6 times of nitrogen replacement, 0.46g (0.1 mol percent) of catalyst tetratriphenylphosphine palladium is added under the protection of nitrogen; heating and stirring, controlling the temperature at about 85 ℃, carrying out reflux reaction for 5 hours, tracking and detecting by TLC, and stopping stirring after the reaction is completed; cooling to room temperature, neutralizing with 5% hydrochloric acid, filtering off insoluble substances, adding toluene (3 × 50ml) for extraction, separating liquid, washing with water to neutrality, drying with anhydrous sodium sulfate, filtering, evaporating filtrate, purifying with column chromatography, eluting with petroleum ether (60 deg.C-90 deg.C), and evaporating to remove solvent to obtain 8.7g intermediate 4- (4' -n-pentyl) -2-ethylaniline [5PPI (2) NH 2 ]The brown liquid of (a) is,the yield was 82.2%.
(2) Into a 250mL three-necked flask, 8g (0.03mol) of Compound 5PPI (2) NH was sequentially added 2 24.3g (40%, 0.12mol) of hydrobromic acid and 100mL of Tetrahydrofuran (THF), carrying out ice salt bath, dropping 20mL of sodium nitrite (2.4g,0.035mol) aqueous solution after the temperature is reduced to 0 ℃, completing dropping within 1 hour, keeping the temperature of the solution not more than 10 ℃ in the dropping process, keeping the temperature at 5 ℃ and stirring for 70min, and storing at low temperature for standby; adding 15.2g (40%, 0.075mol) of hydrobromic acid and 2.88g (0.02mol) of cuprous bromide into the other three-neck flask, heating to reflux, dropwise adding the reaction solution in the previous step, keeping the reflux all the time in the dropwise adding process, naturally heating to room temperature after the dropwise adding is finished, adding an aqueous solution of sodium thiosulfate, stirring, extracting, separating liquid, extracting with ethyl acetate, drying with anhydrous sodium sulfate, removing the solvent by rotary evaporation, finally filling into a chromatographic column, and leaching with petroleum ether (60-90 ℃); after removal of the solvent, 6.9g of intermediate 5PPI (2) Br (yellow liquid) were obtained in 70.0% yield.
(3) 5.6g (0.016mol)5PPI (2) Br and 100ml Tetrahydrofuran (THF) are added into a 250ml four-neck flask, 1.1g (0.02mol) n-butyllithium is added into the flask after the temperature of the cryotank is reduced to-78 ℃, the dropwise addition is finished for 1h (the temperature of the reaction solution cannot exceed-75 ℃ in the process), and after the reaction is carried out for 1h at constant temperature, 2.5g (0.024mol) trimethyl borate is added into the flask again (the temperature of the reaction solution cannot exceed-75 ℃ in the process). After reacting for 4 hours at constant temperature, tracking the reaction process by TLC, stopping stirring after the reaction is completed, naturally cooling the reaction solution to room temperature, adding 5% hydrochloric acid for neutralization, filtering out insoluble substances, adding ethyl acetate for separating liquid, washing with water to be neutral, drying with anhydrous sodium sulfate, filtering, evaporating the filtrate by rotation, and recrystallizing with petroleum ether to obtain 3.1g of white solid with the yield of 65.2%.
(4) 2.9g (0.01mol) of intermediate pentylbiphenyl boronic acid, 2.86g (0.01mol) of bromobiphenyl, 5.5g (0.04mol) of potassium carbonate powder solid, 60mL of ethanol, 50mL of toluene and 15mL of water were successively charged into a 250mL four-necked flask under nitrogen protection, replaced with nitrogen 6 times, and 0.12g (0.1 mol%) of palladium tetrakistriphenylphosphine was added as a catalyst. Heating and stirring to reflux under the protection of nitrogen, wherein the reflux temperature is 70 ℃, carrying out tracking detection by TLC after refluxing reaction for 5h, and stopping stirring after complete reaction; reaction liquid is fromCooling to room temperature, neutralizing with hydrochloric acid, filtering off insoluble substances, adding toluene for extraction, separating liquid, washing with water to neutrality, drying with anhydrous sodium sulfate, filtering, evaporating filtrate to dryness, separating by column chromatography, eluting with petroleum ether (60-90 deg.C), evaporating to remove most of solvent, cooling, and crystallizing to obtain 3.4g pale yellow solid 5PPI (2) PUNH 2 The yield was 75.2%.
(5) 2.5g of the product of the above step 5PPI (2) PUNH were added in sequence to a 250ml three-necked flask 2 ，1.4gCaCO 3 Powder, 5ml of water and 50ml of CH 2 Cl 2 . Controlling the temperature to be about 0-5 ℃, then injecting 2ml of carbon dichloride into a constant pressure dropping funnel, slowly dropping and controlling the temperature not to exceed 5 ℃, reacting for 1.5h at constant temperature, naturally heating to room temperature for reacting for 0.5h, and heating for reflux reaction for 0.5 h. Tracking and detecting by TLC, and stopping stirring after the reaction is completed; naturally cooling the reaction solution to room temperature, filtering out insoluble substances, adding ethyl acetate to extract and separate liquid, washing with water to neutrality, drying with anhydrous sodium sulfate, filtering, evaporating the filtrate to dryness, separating by column chromatography, eluting with petroleum ether (60-90 ℃), evaporating to remove most of the solvent, and cooling to crystallize to obtain 2.1g of 5PPI (2) PUS as a white solid with the yield of about 75%. The phase transition temperature is Cr 68 ℃ and N185 ℃ Iso; Δ n is 0.44.
1 H NMR(400MHz,CDCl 3 )δ7.78(d,J＝8.2Hz,2H),7.72–7.58(m,3H),7.58–7.46(m,2H),7.32(dt,J＝11.9,8.8Hz,6H),2.92–2.64(m,3H),1.70(dd,J＝35.6,28.2Hz,2H),1.52–1.33(m,4H),1.23(t,J＝7.5Hz,3H),0.98(t,J＝6.6Hz,3H).
13 C NMR(101MHz,CDCl 3 )δ159.54(s,1H),157.05(s,1H),144.95(s,1H),142.38(s,1H),141.73(d,J＝4.0Hz,2H),141.37(s,1H),140.66(s,1H),138.94(s,2H),138.64(s,1H),136.49(s,1H),130.81(s,3H),129.07(s,5H),128.18(s,5H),127.81(s,5H),127.24(d,J＝10.3Hz,8H),124.25(s,3H),110.29(s,3H),110.07(s,3H),35.74(s,2H),31.70(s,3H),31.22(s,2H),26.36(s,2H),22.64(s,2H),15.79(s,2H),14.12(s,2H).
19 F-NMR(376.29MHz，CDCl 3 )δ(ppm)：-116.41。
Liquid crystal composition examples
Example 5
Selecting different liquid crystal compounds of a first component, a second component, a third component, a fourth component and a fifth component, sampling and weighing according to a certain mass ratio, mixing, heating and stirring for 0.5 hour to prepare the liquid crystal composition (M-1). The microwave dielectric property of the microwave dielectric material is tested by the Dow microwave technology company Limited by adopting a rectangular resonant cavity perturbation method. The specific component contents (Wt%) and the high-frequency dielectric properties are shown in table 2 below:
TABLE 2 composition and dielectric Properties of the liquid Crystal composition Material (M-1)
Example 6
Selecting different liquid crystal compounds of a first component, a second component, a third component and a fourth component, sampling and weighing according to a certain mass ratio, mixing, heating and stirring for 0.5 hour to prepare the liquid crystal composition (M-2). The microwave dielectric property of the microwave dielectric material is tested by the Dow microwave technology company Limited by adopting a rectangular resonant cavity perturbation method. The specific component contents (Wt%) and high-frequency dielectric properties are shown in table 3 below:
TABLE 3 composition and dielectric Properties of the liquid Crystal composition Material (M-2)
Example 7
Mixing the first component, the second component, the third component, the fourth component and the fifth component to obtain a mixture, weighing the mixture according to a certain mass ratio, heating, and stirring for 0.5 hour to obtain a liquid crystal composition (M-3). The microwave dielectric property of the microwave dielectric material is tested by the Dow microwave technology company Limited by adopting a rectangular resonant cavity perturbation method. The specific component contents (Wt%) and high-frequency dielectric properties are shown in table 4 below:
TABLE 4 composition and dielectric Properties of the liquid Crystal composition Material (M-3)
Comparative example
The liquid crystal composition M6-2 was prepared as a comparative example by mixing the components shown in Table 5 below, and the specific component contents and high-frequency dielectric properties of the comparative example liquid crystal composition M6-2 are shown in Table 5:
TABLE 5 comparative examples composition and dielectric Properties of Mixed liquid Crystal Material (M6-2)
Comparative example composition M6-2 as a comparative example for dielectric properties was a liquid crystal composition to which the first component liquid crystal compound (I) was not added. Through microwave dielectric property tests, the compositions M-1, M-2 and M-3 in the embodiment of the invention are added with the first composition compound (I) under high frequency, so that the high frequency dielectric properties of the compositions are all better than those of M6-2, the dielectric loss under high frequency is all lower than those of M6-2, and the quality factor of the liquid crystal material is all better than that of M6-2.
The above is only a preferred embodiment of the present invention, and it is not intended to limit the scope of the invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall be included in the scope of the present invention.
Claims (7)
1. A liquid crystal composition is characterized by comprising a first component, wherein the first component is one or more of side ethyl quaterphenyl liquid crystal compounds, and the side ethyl quaterphenyl liquid crystal compounds have a structure shown in a structural formula (I):
wherein R is 1 Is an alkyl group having 1 to 7 carbon atoms or one of the H atoms is-CH ═ CH 2 Substituted C n H 2n+1 A chain, and n is 1-4; x 1 、X 2 And X 3 Each independently selected from-H, -F or-Cl; y is-NCS or-F;
the liquid crystal composition further comprises a second component, a third component and a fourth component;
wherein, the second component comprises at least one of a compound shown as a structural formula (V) and a compound shown as a structural formula (VI);
the third component comprises at least one compound shown in the following structural formula (VII);
the fourth component comprises at least one of a compound shown in a structural formula (VIII) and a compound shown in a structural formula (IX);
wherein in the structural formula (V), R 2 Is a saturated alkyl group having 2 to 7 carbon atoms; x 4 、X 5 、X 6 Each independently selected from-H or-F, Y 1 is-NCS or-F;
in the structural formula (VI), R 3 Is a saturated alkyl group having 2 to 7 carbon atoms; x 7 is-H, -F or-Cl, X 8 And X 9 Each independently selected from-H or-F, Y 2 is-NCS or-F;
in the structural formula (VII), R 4 And R 5 Each independently selected from saturated alkyl groups containing 2 to 7 carbon atoms;
in the structural formula (VIII), R 6 Is a saturated alkyl group having 2 to 7 carbon atoms; x 10 And X 11 Each independently selected from-H or-F, Y 3 is-NCS or-F;
in the formula (IX), R 7 Is a saturated alkyl group having 2 to 7 carbon atoms; x 12 And X 13 Each independently selected from-H or-F, Y 4 is-NCS or-F.
2. The liquid crystal composition according to claim 1, wherein each of the compound components in the liquid crystal composition is a purified product obtained by purification treatment by an electric field adsorption method.
3. The liquid crystal composition as claimed in claim 1, wherein the first component comprises one to five of the side ethyl quaterphenyl liquid crystal compounds represented by the structural formula (I), and the weight percentage of each side ethyl quaterphenyl liquid crystal compound in the liquid crystal composition is 1 to 15%.
4. The liquid crystal composition of claim 1, wherein each compound of the second component is present in an amount of 1 to 15% by weight of the liquid crystal composition;
each compound in the third component accounts for 1-20% of the liquid crystal composition in percentage by weight;
each compound in the fourth component accounts for 1-15% of the liquid crystal composition in percentage by weight.
5. The liquid crystal composition of claim 4, further comprising a fifth component comprising at least one of the compounds of formula (X):
wherein R is 8 And R 9 Each independently selected from saturated alkyl groups containing 2 to 7 carbon atoms, R 10 is-CH 3 or-C 2 H 5 。
6. The liquid crystal composition of claim 5, wherein each compound in the fifth component is present in an amount of 1 to 15% by weight of the liquid crystal composition.
7. A microwave device comprising a liquid crystal composition according to any one of claims 1 to 6.
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