CN109762576B - Liquid crystal compound and liquid crystal composition and application thereof - Google Patents
Liquid crystal compound and liquid crystal composition and application thereof Download PDFInfo
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Abstract
本发明公开了一种二氟乙烯基苯类液晶化合物和液晶组合物及其应用。该液晶化合物的结构如式I所示；其中，n为1‑8的整数，X1和X2各自独立地选自H原子、F原子或Cl原子；本发明的液晶组合物为满足微波器件要求的高介低耗、低温性能稳定的向列相液晶材料，其能降低微波器件的介电损耗，能够作为微波移相器组件用液晶材料，适用于微波移相器元件。 The invention discloses a difluorovinylbenzene liquid crystal compound, a liquid crystal composition and its application. The structure of the liquid crystal compound is shown in formula I; wherein, n is an integer of 1-8, and X 1 and X 2 are each independently selected from H atom, F atom or Cl atom; the liquid crystal composition of the present invention meets the requirements of microwave devices. The required nematic liquid crystal material with high dielectric and low consumption and stable low temperature performance can reduce the dielectric loss of microwave devices, can be used as a liquid crystal material for microwave phase shifter components, and is suitable for microwave phase shifter components. 
Description
Technical Field
The invention belongs to the technical field of microwave device liquid crystal materials, and particularly relates to a liquid crystal compound, a liquid crystal composition and application thereof.
Background
The research of the liquid crystal used for the microwave device starts at the end of the 20 th century and develops at a high speed in the beginning of the century; especially in recent years, have gained widespread attention throughout the world. The research of the university of Darmstadt in germany in the field is in the lead of the world, and the research work covers important fields such as a tunable filter, a reconfigurable antenna, a tunable frequency selector, a tunable phase shifter and the like. The current liquid crystal material for display can not meet the requirement of a microwave device because the delta n value is less than about 0.22. The research on the microwave liquid crystal device has just started in China.
The main problems of the liquid crystal material for the microwave device at present are as follows: (1) insufficient microwave phase shift quantity due to insufficient delta n value and low dielectric constant (delta epsilon r) under a high-frequency K wave band; (2) the microwave dielectric loss is increased due to the stability of the liquid crystal molecular structure, the wave absorption effect of the groups and the polarizability effect of the groups; (3) the low temperature performance and outdoor low temperature operation are affected by the lack of high delta n value low melting point liquid crystal solvent and nematic liquid crystal component. Meanwhile, the data of the liquid crystal material for the microwave device, which is currently reported in foreign research, is mainly concentrated in the range of less than or equal to 19GHz, and the research report on the frequency of more than or equal to 20GHz is few; the dielectric property research of the microwave k wave band, especially the microwave frequency band above 25GHz, is more significant.
Therefore, there is a need to develop a liquid crystal material for microwave devices that can overcome the above-mentioned drawbacks.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a liquid crystal compound and a liquid crystal composition, so that the prepared liquid crystal composition can be used as a nematic phase liquid crystal material which meets the requirements of microwave devices and has high dielectric loss, low consumption and stable low-temperature performance.
In order to achieve the above object, a first aspect of the present invention provides a liquid crystal compound, wherein the structure of the liquid crystal compound is shown as formula I;
wherein n is an integer of 1 to 8, X1And X2Each independently selected from a H atom, a F atom or a Cl atom.
A second aspect of the present invention provides a liquid crystal composition comprising: a first, second, third, fourth and fifth component composition;
wherein the first component composition is at least one of the liquid crystal compounds of claim 1 or 2, the second component composition is at least one of the liquid crystal compounds represented by formulas IIa to IIc, the third component composition is at least one of the liquid crystal compounds represented by formulas IIIa to IIIc, the fourth component composition is at least one of the liquid crystal compounds represented by formulas IVa and IVb, and the fifth component composition is at least one of the liquid crystal compounds represented by formula V;
wherein in the above formulas, n is an integer of 1 to 8, m is an integer of 1 to 8, and q is 0 or 1.
The third aspect of the present invention provides the use of the above liquid crystal composition as a liquid crystal material for a microwave phase shifter element.
The technical scheme of the invention has the following beneficial effects:
(1) the compound shown in the formula I is a wide-temperature nematic liquid crystal compound with high stability and large delta n value (not less than 0.58) through structural design, synthesis and purification refining.
(2) The liquid crystal composition is prepared by mixing five types of liquid crystal compounds, so that the prepared liquid crystal composition has the birefringence value of 0.38-0.45, the microwave phase modulation amount of 0.20-0.40 and the maximum microwave insertion loss of less than or equal to 0.015; the prepared liquid crystal composition has the characteristics of high dielectric constant and low consumption, has low dielectric loss to the microwave K frequency band, and can be used as a liquid crystal material for microwave devices.
(3) In the invention, each component compound in the liquid crystal composition is a compound purified by an electric field adsorption method, and has high resistivity.
(4) The liquid crystal composition is a nematic liquid crystal material which meets the requirements of microwave devices, has high dielectric loss, low consumption and stable low-temperature performance, can reduce the dielectric loss of the microwave devices, can be used as a liquid crystal material for microwave phase shifter components, and is suitable for microwave phase shifter elements.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
The first aspect of the invention provides a liquid crystal compound, the structure of which is shown as formula I;
wherein n is an integer of 1 to 8, X1And X2Each independently selected from a H atom, a F atom or a Cl atom.
In the invention, in order to prolong the conjugated length of pi-pi electrons in liquid crystal molecules, improve the birefringence of liquid crystal and obtain a liquid crystal compound with an ultrahigh delta n value, double bonds, triple bonds and unsaturated six-membered rings are added in the molecules, and an isothiocyanato (NCS) is introduced at the tail end as a polar end group of the liquid crystal molecules so as to increase the molecular polarity and the conjugated degree of the pi electrons; the 1, 2-difluorovinyl is introduced into a molecular structure as a bridge bond, so that the conjugation degree can be increased, the birefringence of the liquid crystal compound is improved, the molecular viscosity can be reduced, and the response speed of liquid crystal is improved, so that the quick response liquid crystal compound with high birefringence (delta n is more than or equal to 0.45) and low viscosity is obtained. In summary, the present invention improves the birefringence (Δ n) of the liquid crystal compound represented by formula I by the following ways: (1) the number of benzene rings is increased, and the structure of three benzene rings is taken as the basis; (2) unsaturated bonds are added as bridges, such as 1, 2-difluorovinyl and acetylenic bonds; (3) introducing a radical isothiocyanate with unsaturated characteristic into a terminal group position in a molecule; (4) fluorine substituent groups are introduced at the side positions of the molecules to reduce the acting force among liquid crystal molecules and the like to reduce the rotational viscosity of the liquid crystal and improve the response speed.
The compound represented by formula I of the present invention can be obtained according to any synthetic method capable of obtaining the compound represented by formula I of the present invention, preferably, according to the synthetic route shown in the following formula (1);
according to the present invention, preferably, the compound represented by formula I is selected from at least one of formula Ia, formula Ib and formula Ic;
wherein n is an integer of 1 to 8.
In a second aspect, the present invention provides a liquid crystal composition comprising: a first, second, third, fourth and fifth component composition;
wherein the first component composition is at least one of the liquid crystal compounds of claim 1 or 2, the second component composition is at least one of the liquid crystal compounds represented by formulas IIa to IIc, the third component composition is at least one of the liquid crystal compounds represented by formulas IIIa to IIIc, the fourth component composition is at least one of the liquid crystal compounds represented by formulas IVa and IVb, and the fifth component composition is at least one of the liquid crystal compounds represented by formula V;
wherein in the above formulas, n is an integer of 1 to 8, m is an integer of 1 to 8, and q is 0 or 1.
In the liquid crystal composition, a multi-component low-melting-point liquid crystal compound is used for reducing the eutectic point of the liquid crystal composition, an acetylene bond and a difluoroethylene bond are used for increasing the molecular conjugation property and the rigidity and reducing the viscosity of the liquid crystal compound, the liquid crystal composition is prepared by taking the compounds as main components, the freezing point of the nematic phase liquid crystal material with the high delta n value reaches about-30 ℃, and the clearing point reaches over 125 ℃; the optical anisotropy (birefringence) delta n is more than or equal to 0.380, and the phase modulation amount (tau) of the liquid crystal composition applied to the microwave phase shifter reaches 0.25-0.40.
According to the present invention, preferably, the liquid crystal composition comprises, based on the total weight of the liquid crystal composition: 5-15 wt% of a first component compound, 25-55 wt% of a second component compound, 5-15 wt% of a third component compound, 5-30 wt% of a fourth component compound and 5-25 wt% of a fifth component compound; wherein, the content of the second component compound is preferably 30-55 wt%, and the content of the fifth component compound is preferably 5-15 wt%.
Preferably, in the liquid crystal composition: the content of each third component compound is 1-20 wt%, preferably 3-10 wt%; the content of each fourth component compound is 1-20 wt%, preferably 5-10 wt%; the content of each of the fifth component compounds is 1-20 wt%, preferably 3-15 wt%.
Preferably, when the fifth group of compounds is represented by formula Va, each compound represented by formula Va is contained in an amount of 1 to 20 wt%, preferably 5 to 15 wt%; when the fifth group of compounds is represented by formula Vb, the content of each compound represented by formula Vb is 1 to 10% by weight, preferably 3 to 5% by weight; wherein, the compound shown in the formula Va is npTGS, and the compound shown in the formula Vb is npTUS; (codes representing formula Va and formula Vb are explained in Table 1 below).
According to the present invention, preferably, each component compound in the liquid crystal composition is a compound purified by an electric field adsorption method.
According to the invention, each component compound in the liquid crystal composition is purified, refined and deionized by an electric field adsorption method to improve the resistivity and charge retention rate of the liquid crystal compound, and then the liquid crystal compound is mixed and prepared to obtain the high-medium and low-consumption nematic phase liquid crystal composition which can meet the requirements of microwave K wave band use.
In the invention, the electric field adsorption method is as follows: the method comprises the following steps of utilizing a high-activity adsorption material as an adsorbent and assisting an external electric field to deeply purify and refine the liquid crystal material, wherein the adsorbent is nano silicon dioxide, nano alumina, an MCM-41 mesoporous molecular sieve, an SBA-15 mesoporous molecular sieve, activated carbon fiber or activated silica gel or a composition of the nano silicon dioxide, the nano alumina, the MCM-41 mesoporous molecular sieve, the SBA-15 mesoporous molecular sieve and the activated carbon fiber; preferred adsorbents are nano-silica, nano-alumina, MCM-41 mesoporous molecular sieves, or combinations thereof. Wherein the pore diameter of the adsorbent is 2-20nm, preferably 2-10 nm; the specific surface area of the adsorbent is 500-1500m2Per g, preferably 1000-1200m2(ii) in terms of/g. The dosage of the adsorbent is 0.5 wt% -20 wt% of the mass of the liquid crystal material, and the preferred dosage is 2 wt% -5 wt% of the mass of the liquid crystal material. Under the action of the adsorbent, the purification time of the liquid crystal material in the electric field is 30-210min, and the preferred purification time is 60-90 min. The electric field strength is 0.2-20kV/cm, preferably l-4 kV/cm.
In the invention, the liquid crystal compound is purified by an electric field adsorption method, so that the resistivity rho of the purified liquid crystal compound is more than or equal to 5 multiplied by 1011Ω.cm3。
The Liquid crystal compounds of the present invention, the Liquid crystal compounds of the formulae IIa to IIc, the Liquid crystal compounds of the formulae IIIa to IIIc, the Liquid crystal compounds of the formulae IVa and IVb and the Liquid crystal compounds of the formula V can be synthesized according to conventional synthesis methods in the art, and preferably, the Liquid crystal compounds of the formulae IIa to IIc are synthesized by the preparation method described in Hsu C S, Shyu K F, Chuang Y, et al.Synthesis of laterally substitated biostolane Liquid Crystals [ J ]. Liquid Crystals,2000,27(2): 283-287; the liquid crystal compounds shown in formulas IIIa to IIIc are synthesized according to the preparation method of Liu Chong Shuoshi paper (Liu Chong, ultra-high birefringence liquid crystal synthesis and performance research thereof [ D ], Wuhan university, 2014); the liquid crystal compounds represented by the formulae IVa and IVb are synthesized according to the preparation method of Gauza, S.A., Li, J., Wu, S.T., Spadlo, A., Dabrowski, R.A., Tzeng, Y.N., & Cheng, K.L. (August 2005). High birefringence and High resistance isoflavone-based liquid crystal mixture. liq.Cryst.,32, 1077-membered 1085; the liquid crystal compound shown in formula V is synthesized according to the preparation method of Master thesis of Wuhan university of light industry [ D ], Wuhan university of light industry [ 2013 ], synthetic research on fluorine-containing isothiocyanate high-delta n liquid crystal [ D ].
According to the present invention, preferably, the liquid crystal composition has a birefringence value of 0.38 to 0.45; the phase modulation amount in the microwave band of 4-40GHz is 0.20-0.40, and the maximum microwave insertion loss is less than or equal to 0.015. Further, the microwave phase modulation amount is improved, and the microwave insertion loss (namely, the dielectric loss) is reduced.
The third aspect of the present invention provides the use of the above liquid crystal composition as a liquid crystal material for a microwave phase shifter element.
In the invention, the working temperature of the liquid crystal composition is-30-120 ℃.
The invention is further illustrated by the following examples:
in the following examples: compounds of formula Ia and formula Ib are the compounds prepared in example 1; processes for the preparation of compounds of formula IIa are described in Hsu C S, Shyu K F, Chuang Y Y, et al.Synthesis of synergistic biological Liquid Crystals [ J ]. Liquid Crystals,2000,27(2): 283-. The compounds shown in the formulas IIIa and IIIb are synthesized according to a preparation method of Liu Chong Shuoshi general paper (Liu Chong, synthesis of liquid crystal with ultrahigh birefringence and performance research thereof [ D ], Wuhan university of California, 2014); compounds of formula IVa are synthesized according to the preparation method of Gauza, S., Li, J., Wu, S.T., Spadlo, A., Dabrowski, R., Tzeng, Y.N., & Cheng, K.L. (August 2005. High birefringence and High-reactivity isoflavone-based liquid crystal systems. liq. Crystal., 32, 1077-1085.; the compound shown in the formula V is synthesized according to a preparation method of a Master thesis of Wuhan university (Wang Guohua, synthetic research on fluorine-containing isothiocyanate high-delta n liquid crystal [ D ], Wuhan university of light industry, 2013);
each of the compounds used for preparing the liquid crystal mixtures in the following examples 2 to 5 was a compound purified by an electric field adsorption method; wherein, the electric field adsorption method comprises the following steps: adding a toluene solution of the compound into a purification chamber in the middle of a purifier, and respectively adding 15m1 analytically pure toluene and 0.2 g of nano silicon dioxide into a cathode solvent chamber and an anode solvent chamber; adopting oxide film electrodes, wherein the inter-electrode distance is 30mm, and the electric field intensity is 4 kV/cm; the reaction mixture was kept for 60min, and toluene was distilled off.
The code descriptions of the liquid-crystalline compounds appearing in the following examples are given in Table 1:
TABLE 1
Compounds of the following formula are exemplified:
the structure shown in formula IIIa is represented by the code in Table 1: nUTP (1) TPm, wherein the code n represents the number of C atoms of the left-end alkyl group, and when n is 2, for example, the alkyl group is C2H5-; the code U represents 3, 5-difluoro-1, 4-phenylene; the code T represents an ethynyl group; in the code P (1), P represents 1,4 phenylene, and (1) represents that a side group is methyl attached to the 1,4 phenylene; the code P represents 1,4 phenylene; the code m represents the number of C atoms of the alkyl group at the right end, for example, when m is 2, it means that the alkyl group is-C2H5。
The abbreviated symbols for the test items in the following examples are as follows:
Δ n is the optical anisotropy, i.e. birefringence (589nm, 25 ℃);
delta epsilon is the dielectric constant of the liquid crystal driven at 25 ℃ and 1KHz at low frequency;
cr. is the melting point of the liquid crystal composition or the transition temperature from solid state to liquid crystal state; n is the liquid crystal nematic phase transition temperature; iso, clearing point temperature (deg.c) which is the phase state of the liquid crystal composition;
m.p. is the eutectic point of the mixed liquid crystal material; rho is the resistivity of the liquid crystal material; mu is the viscosity of the liquid crystal material;
epsilon r is a vertical component of the microwave high-frequency dielectric constant; ε r/is the microwave high frequency dielectric constant parallel component; delta epsilon r is the dielectric constant under microwave high frequency; tan delta epsilon r is a dielectric loss representation of the vertical component of the liquid crystal molecules at microwave high frequency; tan delta epsilon r/is a dielectric loss representation of the parallel component of the liquid crystal molecules at microwave high frequency; tau is the phase modulatable coefficient of the microwave frequency; eta is the medium quality factor of the microwave high-frequency device;
the dielectric anisotropy in the microwave range is defined as: Δ ε r ≡ (ε)r,||-εr,⊥)；
The phase modulatable factor (τ) of the microwave frequency is defined as: τ ≡ (Δ ε)r/εr,||)；
The medium quality factor (η) of a microwave high-frequency device is defined as: eta.ident (tau/tan delta epsilon)r,max.)；
Wherein the maximum dielectric loss is tan delta epsilonr,max.≡max.{tanδεr,⊥；tanδεr,||}；
Example 1
This example provides several methods for the preparation of compounds of formula I (see the synthetic route shown in formula (1)), as follows:
(1) synthesis of 4- (1,2, 2-trifluoro) vinyl bromobenzene
Preparation of Lithium Diisopropylamine (LDA) reagent[74]: in a 100mL three-necked flask equipped with a mechanical stirrer, a 100mL constant pressure dropping funnel and a low temperature thermometer, diisopropylamine (0.2mol, 20.4g) and anhydrous THF (110mL) were charged, and the temperature was lowered to-30 ℃ under N2Under protection, slowly dripping n-BuLi (0.2mol, 80mL), controlling the temperature at about-30 ℃, reacting for 1h after dripping, sealing and storing at low temperature for later use.
Adding anhydrous ZnCl into another three-mouth bottle2(0.1mol, 13.8g), 60mL of anhydrous THF, under the protection of nitrogen, cooling to-70 ℃, and introducing CF3CH2F (0.11mol, 12g), controlling the temperature at about-70 ℃, slowly adding the LDA reagent into a three-mouth bottle through a needle tube, and keeping a needle below the liquid level all the time. Stirring for 2 hours at-70 ℃ after the addition is finished, and naturally heating to room temperature to prepare the zinc trifluoroethylene reagent for later use.
To the above zinc trifluoroethylene reagent were added 4-bromoiodobenzene (0.07mol, 19.8g) and Pd (PPh)3)4(1.5 mol% and 1.2g) under the protection of N2, reacting at room temperature for 12h, adding 100mL of water to quench the reaction, adjusting the pH to about 6 with dilute hydrochloric acid, performing suction filtration, adding 100mL of ethyl acetate for separating liquid, extracting a water layer twice with ethyl acetate, combining organic layers, washing with water for three times, drying with anhydrous sodium sulfate, removing the solvent, and passing through a column (petroleum ether is an eluent) to obtain 8.8g of light yellow liquid with the yield of 80.7%; ir (kbr) v: 1757, 1593,1490, 1470, 1401, 1379, 982, 825; 1HNMR (400MHz, CDCl3) delta: 7.55(d, 2H), 7.27(d, 2H).
(2) Synthesis of (E) -1-bromo-4- (1, 2-difluoro-2- (4-alkylphenyl) vinyl) benzene (1a to 1c)
Adding 4-alkylbromobenzene (0.036mol) and 100mL of anhydrous THF into a three-neck flask with a nitrogen protection device, a constant-pressure dropping funnel and a low-temperature thermometer, adding n-BuLi solution (0.036mol and 14.4mL) into the constant-pressure dropping funnel under the protection of nitrogen, vacuumizing, replacing with nitrogen for 3 times, cooling to-60 ℃, slowly dropping the n-BuLi solution, stirring at-65 ℃ for 1h after dropping, adding trifluorovinyl bromobenzene (0.036mol and 8.8g) and 50mL of anhydrous THF into the constant-pressure dropping funnel under the protection of nitrogen, controlling the temperature at-60 ℃, slowly dropping, reacting at-78 ℃ for 2h after dropping, naturally heating to room temperature for 1h, cooling to 0 ℃, dilute acidifying with hydrochloric acid (pH about 6), adding 50mL of petroleum ether for extraction, separating, drying an organic layer through anhydrous sodium sulfate, removing the solvent to obtain a crude product, recrystallizing the ethanol to obtain a pure product.
(E) -1-bromo-4- (1, 2-difluoro-2- (4-propylphenyl) vinyl) benzene (1 a); 4.8g of white powdery solid, 39.6% of yield and 89-91 ℃ of melting point; ir (kbr) v: 2957, 2938, 2858, 1910, 1656, 1610, 1512, 1488, 1459, 901, 826. (when the above-mentioned 4-alkylbromobenzene added is 4-propylbromobenzene, 1a is obtained)
(E) -1-bromo-4- (1, 2-difluoro-2- (4-butylphenyl) vinyl) benzene (1 b); 5.4g of white powdery solid, 42.8 percent of yield and 85-86 ℃ of melting point; ir (kbr) v: 2976, 2933, 2861, 1907, 1652, 1613, 1513, 1468, 1462, 912, 830. (when the above-mentioned 4-alkylbromobenzene added is 4-butylbenzene, 1b is obtained)
(E) -1-bromo-4- (1, 2-difluoro-2- (4-pentylphenyl) vinyl) benzene (1 c); 5.6g of white powdery solid, 42.3 percent of yield and 81-83 ℃ of melting point; ir (kbr) v: 2959, 2929, 2855, 1913, 1655, 1611, 1513, 1478, 1452, 918, 827. (when the above-mentioned 4-alkylbromobenzene added is 4-pentylbromobenzene, 1c is obtained)
(3) Synthesis of acetylene aniline or fluorine-containing acetylene aniline
To a three-necked flask were added 4-bromoaniline or fluorine-containing 4-bromoaniline (0.1mol), methylbutynol (0.15mol, 12.6g), Pd (PPh)3)2Cl2(1mol％，0.70g)、PPh3(3 mol%, 0.78g) and CuI (2 mol%, 0.35g), then adding 300mL triethylamine, vacuumizing, replacing with nitrogen for three times, heating to reflux under the protection of nitrogen, reacting for 16h, and tracking the reaction progress by TLC. After the reaction, suction filtration was performed, the solvent was removed from the filtrate by distillation under reduced pressure, 100mL of methylene chloride was added, the mixture was washed with saturated NH4Cl solution 3 times, the organic layer was separated, the organic layer was washed with saturated brine 3 times, dried over anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure to give a crude alkynol product.
Adding KOH powder (0.2mol, 11.2g) and 200mL of isopropanol into a three-neck flask, stirring to dissolve, cooling to room temperature, adding the alkynol into the three-neck flask, vacuumizing, replacing with nitrogen for three times, heating to reflux for 8h under the protection of nitrogen, and tracking the reaction progress by TLC. After completion of the reaction, the reaction mixture was cooled to room temperature, filtered, the solvent was removed from the filtrate by distillation under the reduced pressure, 100mL of dichloromethane was added, the filtrate was washed with water to neutrality, the organic layer was separated, dried over anhydrous sodium sulfate, the solvent was removed by distillation under the reduced pressure, and the mixture was subjected to silica gel column chromatography (eluent, petroleum ether: ethyl acetate 5: 1).
4-ethynylaniline: 8.3g of light brown liquid, the yield is 71.0 percent; (when 4-bromoaniline was added as described above, the product was obtained as 4-ethynylaniline)
4-ethynyl-2-fluoroaniline: 7.6g of light brown liquid, and the yield is 56.1%; (when the fluorine-containing 4-bromoaniline added above is 4-bromo-2-fluoroaniline, the product obtained is 4-ethynyl-2-fluoroaniline)
4-ethynyl-2, 6-difluoroaniline: 9.6g of light yellow solid, yield 64.3%; (when the fluorine-containing 4-bromoaniline added above is 4-bromo-2, 6-difluoroaniline, the product obtained is 4-ethynyl-2, 6-difluoroaniline).
(4) Synthesis of difluorovinyltriphenylacetylene-based liquid Crystal Compounds (2a to 2 c):
adding one of 1a to 1c (0.01mol) and the product (0.01mol, namely acetylene aniline or fluorine-containing acetylene aniline) obtained in the step (3) and Pd (PPh) into a three-neck flask with a nitrogen protection device3)2Cl2(1mol％，0.07g)、PPh3(3 mol%, 0.07g) and CuI (2 mol%, 0.04g), then 100mL triethylamine is added, vacuum pumping is carried out, nitrogen is replaced for three times, temperature is raised to reflux under the protection of nitrogen, and reaction is carried out for 12 h. The dot plate tracks the progress of the reaction. After the reaction, the reaction mixture was filtered, the filtrate was distilled under reduced pressure to remove the solvent, 50mL of methylene chloride was added, and saturated NH was used4And washing the Cl solution for 3 times, separating liquid, washing an organic layer for 3 times by using saturated saline solution, drying the organic layer by using anhydrous sodium sulfate, and recrystallizing the organic layer by using anhydrous ethanol to obtain the product.
(E) -4- ((4- (1, 2-difluoro-2- (4-propylphenyl) ethenyl) phenyl) ethynyl) -2, 6-di-fluoroaniline (2 a)1): white solid 0.65g, yield 39%; IR (Vmax/cm)-1) (KB) v 3458, 3364, 2940, 2931, 2852, 1645, 1558, 1431, 1420, 978, 944, 839, 828. (obtained when 1a and 4-ethynyl-2, 6-difluoroaniline were added as described above)
(E) -4- ((4- (1, 2-difluoro-2- (4-butylphenyl) ethenyl) phenyl) ethynyl) -2, 6-di-fluoroaniline (2 a)2): 1.31g of white solid, yield 62%; IR (Vmax/cm)-1) (KBr) v 3449, 3371, 2939, 2919, 2839, 1638, 1559, 1439, 1431, 958, 944, 839, 831. (obtained when 1b and 4-ethynyl-2, 6-difluoroaniline were added as described above)
(E) -4- ((4- (1, 2-difluoro-2- (4-pentylphenyl) ethenyl) phenyl) ethynyl) -2, 6-di-fluoroaniline (2 a)3): 1.29g of white solid, yield 59%; IR (Vmax/cm)-1) (KBr) v 3451, 3369, 2945, 2931, 2843, 1649, 1569, 1432, 1428, 949, 938, 847, 831. (obtained when 1c and 4-ethynyl-2, 6-difluoroaniline were added as described above)
(E) -4- ((4- (1, 2-difluoro-2- (4-butylphenyl) ethenyl) phenyl) ethynyl) -2-fluoroaniline (2 b)1): 0.71g of white solid, yield 44%; IR (Vmax/cm)-1) (KB) v 3449, 3368, 2943, 2929, 2839, 1642, 1549, 1438, 1418, 969, 941, 845, 828. (obtained when 1b and 4-ethynyl-2-fluoroaniline were added as described above)
(E) -4- ((4- (1, 2-difluoro-2- (4-pentylphenyl) ethenyl) phenyl) ethynyl) -2-fluoroaniline (2 b)2): 0.71g of white solid, yield 44%; IR (Vmax/cm)-1) (KB) v 3449, 3368, 2943, 2929, 2839, 1642, 1549, 1438, 1418, 969, 941, 845, 828. (obtained when 1c and 4-ethynyl-2-fluoroaniline were added as described above)
(E) -4- ((4- (1, 2-difluoro-2- (4-pentylphenyl) ethenyl) phenyl) ethynyl) aniline (2 c): white solid 0.73g, yield 41%; IR (Vmax/cm)-1) (KB) v 3451, 3371, 2939, 2933, 2841, 1638, 1539, 1437, 1421, 971, 938, 839, 828. (obtained when 1c and 4-ethynylaniline were added as described above)
(5) Synthesis of the target Compound series (formulae Ia to Ic)
Adding one of the compounds prepared in the step (4) (0.01mol), CaCO into a three-necked flask with a constant pressure dropping funnel and a thermometer3(0.02mol, 2.0g), adding 30mL of water and 100mL of dichloromethane, stirring to dissolve, cooling in an ice-water bath to 0 ℃, and adding CSCl2(0.02mol, 2.3g) and 20mL of dichloromethane are added into a constant pressure dropping funnel, slowly dropped into a three-necked bottle, the temperature is controlled to be 0-5 ℃, dropping is completed within 20-25 min, heat preservation is carried out for 1.5h, the temperature is naturally raised to room temperature, stirring is carried out for 30min, heating is carried out until reflux is carried out for 1h, and the reaction process is tracked by TLC. Then 30mL of absolute ethanol was added, refluxed for 30min, and excess CSCl was removed2. Cooling to room temperature, vacuum filtering, separating, extracting water layer with 15mL dichloromethane for three times, mixing organic layers, drying with anhydrous sodium sulfate, removing solvent, subjecting to silica gel column chromatography (petroleum ether as eluent) to obtain crude product, and purifying with silica gel column chromatographyRecrystallization from a mixed solution of petroleum ether and methanol (petroleum ether: methanol ═ 1:3) gave the pure product.
(E) -4- ((4- (1, 2-difluoro-2- (4-propylphenyl) ethenyl) phenyl) ethynyl) -2, 6-difluoro-1-isothiocyanatobenzene (formula Ia)1): 0.89g of white solid, yield 70%; IR (Vmax/cm)-1)(KBr)v:2953，2925，2846，2011，1952，1553，1521，1458，1422，1267，1146，1104，1022，852，830；1HNMR(400MHZ，CDCl3)δ:7.66(d，2H)，7.63(d，2H)，7.51(d，2H)，7.28(d，2H)，7.15(d，2H)，2.58(t，2H)，1.61(m，2H)，0.93(t，3H)；13CNMR(100HZ，CDCl3)δ:13.8，23.1，34.9，88.5，93.5，105.2，116.5，121.7，126.2，132.4，136.7，141.3，158.5；19FNMR(376.29MHz，CDCl3)δ:-117.18(d，2F，Ar-F)，-148.55(d，1F，-CH＝CH-F)，-154.07(d，1F，F-CH＝CH-).Ms(70ev)m/z(％):451.43([M+H]+，100).
(E) -4- ((4- (1, 2-difluoro-2- (4-butylphenyl) ethenyl) phenyl) ethynyl) -2, 6-difluoro-1-isothiocyanatobenzene (formula Ia)2): white solid 1.05g, yield 73%; IR (Vmax/cm)-1)(KBr)v:2953，2925，2846，2011，1952，1553，1521，1458，1422，1267，1146，1104，1022，852，830；1HNMR(400MHZ，CDCl3)δ:7.68(d，2H)，7.61(d，2H)，7.48(d，2H)，7.19(d，2H)，7.01(d，2H)，2.61(t，2H)，1.59(m，2H)，1.31(m，2H)，0.91(t，3H)；13CNMR(100HZ，CDCl3)δ:14.2，22.3，33.4，53.4，89.7，93.3，105.4，116.2，121.9，126.2，132.2，136.9，141.8，158.7；19FNMR(376.29MHz，CDCl3)δ:-117.21(d，2F，Ar-F)，-148.54(d，1F，-CH＝CH-F)，-154.04(d，1F，F-CH＝CH-).Ms(70ev)m/z(％):465.51([M+H]+，100).
(E) -4- ((4- (1, 2-difluoro-2- (4-pentylphenyl) ethenyl) phenyl) ethynyl) -2, 6-difluoro-1-isothiocyanatobenzene (formula Ia)3)): 0.97g of white solid, yield 69%; IR (Vmax/cm)-1)(KBr)v:2967，2934，2831，2018，1948，1545，1526，1448，1419，1256，1139，1109，1034，861，830；1HNMR(400MHZ，CDCl3)δ:7.72(d，2H),7.65(d，2H)，7.53(d，2H),7.25(d，2H)，7.10(d，2H)，2.65(t,2H)，1.65(m，2H)，1.34(m，4H)，0.90(t，3H)；13CNMR(100HZ，CDCl3)δ:14.1，22.6，30.9，31.5，35.8，77.3，87.9，92.8，115.1，122.3，125.4，128.6，131.8，144.7，145.7，156.4，158.9；19FNMR(376.29MHz，CDCl3)δ:-117.19(d，2F，Ar-F)，-148.56(d，1F，-CH＝CH-F)，-154.06(d，1F，F-CH＝CH-).Ms(70ev)m/z(％):479.13([M+H]+，100).
(E) -5- ((4- (1, 2-difluoro-2- (4-butylphenyl) ethenyl) phenyl) ethynyl) -1-fluoro-2-isothiocyanatobenzene (formula Ib)1): 0.46g of white solid, yield 70%; IR (Vmax/cm)-1)(KBr)v:2951，2931，2838，2010，1947，1531，1508，1442，1419，1243，1131，1030，1005，842，828；1HNMR(400MHZ，CDCl3)δ:7.59(d，2H)，7.46(m，4H)，7.36(t，3H)，7.01(d，2H)，2.65(t，2H)，1.59(m，2H)，1.34(m，2H)，0.91(t，3H)；13CNMR(100HZ，CDCl3)δ:14.2，23.5，35.5，37.5，88.6，92.5，118.5，120.7，123.5，126.7，129.5，133.4，138.3，142.5，159.4；19FNMR(376.29MHz，CDCl3)δ:-119.32(d，1F，Ar-F)，-148.82(d，1F，-CH＝CH-F)，-153.97(d，1F，F-CH＝CH-).Ms(70ev)m/z(％):447.51([M+H]+，100).
(E) -5- ((4- (1, 2-difluoro-2- (4-pentylphenyl) ethenyl) phenyl) ethynyl) -1-fluoro-2-isothiocyanatobenzene (formula Ib)2): 0.53g of white solid, yield 66%; IR (Vmax/cm)-1)(KBr)v:2958，2938，2839，2015，1941，1538，1505，1443，1416，1238，1125，1029，1004，842，828；1HNMR(400MHZ，CDCl3)δ:7.62(d，2H)，7.48(m，4H)，7.39(t，3H)，7.08(d，2H)，2.62(t，2H)，1.57(m，2H)，1.34(m，2H)，1.29(m，2H)，0.93(t，3H)；13CNMR(100HZ，CDCl3)δ:14.9，24.5，36.5，36.5，89.6，93.5，119.5，122.6，125.5，128.5，132.2，135.1，141.3，145.5，162.4；19FNMR(376.29MHz，CDCl3)δ:-119.31(d，1F，Ar-F)，-148.81(d，1F，-CH＝CH-F)，-153.99(d，1F，F-CH＝CH-).Ms(70ev)m/z(％):461.54([M+H]+，100).
(E) -4- ((4- (1, 2-difluoro-2- (4-pentylphenyl) ethenyl) phenyl) ethynyl) -isothiocyanatobenzene (formula Ic): 0.41g of white solid, yield 45%; IR (Vmax/cm)-1)(KBr)v:2971，2923，2821，2029，1942，1529，1518，1440，1420，1243，1134，1113，1041，863，829；1HNMR(400MHZ，CDCl3)δ:7.52(m，4H),7.41(m，4H)，7.28(d，2H),7.16(d，2H)，7.13(d，2H)，2.67(t,2H)，1.63(m，2H)，1.32(m，4H)，0.94(t，3H)；13CNMR(100HZ，CDCl3)δ:14.8，23.6，33.7，32.7，38.8，75.1，85.4，95.7，117.3，124.3，126.8，129.6，132.9，147.7，149.7，158.4，163.8；19FNMR(376.29MHz，CDCl3)δ:-149.04(d，1F，-CH＝CH-F)，-153.88(d，1F，F-CH＝CH-).Ms(70ev)m/z(％):443.55([M+H]+,100).
TABLE 2 liquid Crystal Performance of liquid Crystal Compounds of series Ia (nPVFPTUS)
TABLE 3 liquid Crystal Performance of the object Compound of the formula Ib (nPVFPTGS)
TABLE 4 liquid Crystal Performance of target Compounds of series formula Ic (nPVFPTPS)
Wherein, in tables 2 to 3, Cr represents a transition temperature from a solid state to a liquid crystal state; n represents a liquid crystal nematic phase transition temperature; iso is the clearing point temperature (. degree. C.) of the phase state of the liquid crystal composition.
Example 2
The liquid crystal composition of example 2 was formulated with the compounds and their weight percentages listed in the following table. The specific method comprises the following steps: and (2) putting the metered compounds into a boron glass beaker, heating and melting the compounds on a magnetic stirring instrument, putting the beaker into a magnetic rotor after most of the mixture is melted, uniformly stirring the liquid crystal mixture, heating the beaker to a clearing point, and cooling the beaker to room temperature to obtain the liquid crystal composition M1.
The liquid crystal mixture is placed between two substrates of a liquid crystal display for performance test, and the test data are shown in the following table.
TABLE 5 compositional and dielectric Properties of liquid Crystal composition M1
Example 3
The liquid crystal composition of example 3 was prepared according to the compounds listed in the following table and their weight percentages, in a specific manner as in example 2, to obtain said liquid crystal composition M2.
The liquid crystal mixture is placed between two substrates of a liquid crystal display for performance test, and the test data are shown in the following table.
TABLE 6 compositional and dielectric Properties of liquid Crystal composition M2
Example 4
The liquid crystal composition of example 4 was prepared according to the compounds listed in the following table and their weight percentages, in a specific manner as in example 2, to give the liquid crystal mixture M3.
The liquid crystal mixture is placed between two substrates of a liquid crystal display for performance test, and the test data are shown in the following table.
TABLE 7 composition and dielectric Properties of liquid Crystal composition M3
Example 5
The liquid crystal composition of example 5 was prepared according to the compounds listed in the following table and their weight percentages, in a specific manner as shown in example 2, to obtain the liquid crystal mixture M4.
The liquid crystal mixture is placed between two substrates of a liquid crystal display for performance test, and the test data are shown in the following table.
TABLE 8 composition and dielectric Properties of liquid Crystal composition M4
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (4)
1. A liquid crystal composition, comprising: a first, second, third, fourth and fifth component composition;
the liquid crystal display panel comprises a first group of liquid crystal compounds, a second group of liquid crystal compounds, a third group of liquid crystal compounds, a fourth group of liquid crystal compounds and a fifth group of liquid crystal compounds, wherein the first group of liquid crystal compounds are liquid crystal compounds shown in a formula Ia and liquid crystal compounds shown in a formula Ib, the second group of liquid crystal compounds are at least one of liquid crystal compounds shown in a formula IIa and liquid crystal compounds shown in a formula IIb, the third group of liquid crystal compounds are liquid crystal compounds shown in a formula IIIa and liquid crystal compounds shown in a formula IIIb, the fourth group of liquid crystal compounds are liquid crystal compounds shown in a formula IVa, and the fifth group;
wherein in the formulas, n is an integer of 1-8, m is an integer of 1-8, and q is 0 or 1;
the liquid crystal composition comprises the following components in percentage by weight based on the total weight of the liquid crystal composition: 5-15 wt% of first component composition, 25-55 wt% of second component composition, 5-15 wt% of third component composition, 5-30 wt% of fourth component composition and 5-25 wt% of fifth component composition.
2. The liquid crystal composition of claim 1, wherein each component compound in the liquid crystal composition is a compound purified by an electric field adsorption method.
3. The liquid crystal composition according to claim 1, wherein the liquid crystal composition has a birefringence value of 0.38 to 0.45; the phase modulation amount in the microwave band of 4-40GHz is 0.20-0.40, and the maximum microwave insertion loss is less than or equal to 0.015.
4. Use of a liquid crystal composition according to any one of claims 1 to 3 as a liquid crystal material for a microwave phase shifter element.
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