CN110938439B - High-polarity large-optical birefringence liquid crystal composition - Google Patents
High-polarity large-optical birefringence liquid crystal composition Download PDFInfo
- Publication number
- CN110938439B CN110938439B CN201911111704.5A CN201911111704A CN110938439B CN 110938439 B CN110938439 B CN 110938439B CN 201911111704 A CN201911111704 A CN 201911111704A CN 110938439 B CN110938439 B CN 110938439B
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- component
- crystal composition
- composition according
- polarity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C09K19/46—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing esters
-
- 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
- C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
- C09K19/3444—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a six-membered aromatic ring containing one nitrogen atom, e.g. pyridine
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
- C09K19/345—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a six-membered aromatic ring containing two nitrogen atoms
- C09K19/3458—Uncondensed pyrimidines
-
- 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
- C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
- C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
Abstract
The invention discloses a liquid crystal composition with high polarity and large optical birefringence. The liquid crystal molecules with acetylene groups and a polyaromatic ring structure are favorable for improving the birefringence of liquid crystals due to strong conjugation; under the condition of keeping low viscosity, the liquid crystal molecules with the difluoromethoxy group have higher molecular polarity, which is beneficial to enhancing the dielectric anisotropy of the liquid crystal; the existence of pyrimidine, pyridine, isothiocyanic group can enhance the molecular conjugation and the polarity, so that the optical anisotropy and the dielectric anisotropy can be improved simultaneously. The liquid crystal molecules are mixed to achieve balance and optimization of various performances in expectation, and requirements of practical application are met. The liquid crystal composition can be used in a plurality of fields such as liquid crystal displays, liquid crystal light modulators, polymer dispersed liquid crystals, blue phase liquid crystal preparation and the like.
Description
Technical Field
The invention belongs to the field of materials, and relates to a high-polarity large-optical birefringence liquid crystal composition.
Background
Nematic liquid crystal materials having high polarity (Δ ∈) and large optical anisotropy (Δ n) are increasingly used in a variety of fields such as liquid crystal displays, liquid crystal optical modulators, polymer dispersed liquid crystals, and blue phase liquid crystals. In liquid crystal displays and liquid crystal light modulators, the drive voltage of a liquid crystal device is inversely proportional to the dielectric anisotropy (Δ ∈) of the liquid crystal material, and the high polarity of the liquid crystal material contributes to a reduction in the drive voltage of the device. In addition, the liquid crystal material with large optical anisotropy (delta n) is beneficial to obtaining larger phase difference of a liquid crystal device, so that the box thickness of a liquid crystal box is reduced, and the response speed of liquid crystal molecules is improved. In the polymer dispersed liquid crystal, large optical anisotropy contributes to obtaining a sufficiently large scattering effect and improves the contrast of the device. In the blue phase liquid crystal, it is important to improve the kerr coefficient (k) of the blue phase liquid crystal material, and the kerr coefficient of the blue phase liquid crystal and the performance of the liquid crystal material have the following relationship:
both the larger dielectric anisotropy and the higher optical anisotropy contribute to the improvement of the kerr coefficient of blue phase liquid crystal.
Disclosure of Invention
The invention aims to provide a liquid crystal composition with high polarity and large optical birefringence.
The liquid crystal composition provided by the invention comprises the following components a to g in percentage by mass:
20-25% of a compound shown in formula I (namely, an isothiocyanic derivative with an alkynyl pyridine difluoro substituted benzene structure);
the component b is 20-25% of a compound shown in a formula II (namely, an isothiocyanic series derivative with a pyrimidine difluoro substituted benzene structure);
the component c is 10-15% of a compound shown in a formula III (namely, an isocyanuric derivative with a difluorophenol benzoate group structure);
the component d is 5-15% of a compound shown in a formula IV (namely, an isothiocyanic derivative with a pyrimidine phenyl difluoro methoxyl monofluorobenzene structure);
the component e is 5-15% of a compound shown as a formula V (namely a series of derivatives with a pyrimidine difluoro methoxy difluorobenzonitrile structure);
the component f is 5-15% of a compound shown as a formula VI (namely, a series of derivatives with a pyrimidyl trifluoro-substituted biphenyl cyanogen structure);
the component g is 5-15% of a compound (an isothiocyanic derivative with a pyrimidine phenylacetylene monofluoro substituted benzene structure) shown as a formula VII;
in the formulas I to VII, n is an integer of 1-5.
The liquid crystal composition can be a liquid crystal composition a;
in the liquid crystal composition a, the mass percentage of the component a and the component b is 25%;
the mass percentage of the component c is 15 percent;
the mass percentage of the component d, the component e and the component g is 10 percent;
the mass percentage of the component f is 5 percent;
and n is 3.
The liquid crystal composition can also be a liquid crystal composition b;
in the liquid crystal composition b, the mass percentage of the component a and the component b is 20%;
the mass percentage of the component c and the component d is 15 percent;
the mass percentage of the component e to the component g is 10 percent;
and n is 3.
The invention provides a method for preparing the liquid crystal composition, which comprises the following steps: and melting and uniformly mixing the components a to g according to the proportion to obtain the composition.
In the melting step of the method, the temperature is 100-120 ℃; the time is 1-2 hours.
In addition, the application of the liquid crystal composition provided by the invention in liquid crystal display or liquid crystal light modulation, any one of a liquid crystal display, a liquid crystal light modulator, polymer dispersed liquid crystal and blue phase liquid crystal containing the liquid crystal composition, and the application of the liquid crystal composition in preparing any one of a liquid crystal display, a liquid crystal light modulator, polymer dispersed liquid crystal and blue phase liquid crystal also belong to the protection scope of the invention.
The invention has the beneficial effects that: the liquid crystal composition can be used in a plurality of fields such as liquid crystal displays, liquid crystal light modulators, polymer dispersed liquid crystals, blue phase liquid crystal preparation and the like.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
The specific principle design of the invention is as follows: the liquid crystal molecules with acetylene groups and a polyaromatic ring structure are favorable for improving the birefringence of liquid crystals due to strong conjugation; under the condition of keeping low viscosity, the liquid crystal molecules with the difluoromethoxy group have higher molecular polarity, which is beneficial to enhancing the dielectric anisotropy of the liquid crystal; the existence of pyrimidine, pyridine, isothiocyanic group can enhance the molecular conjugation and the polarity, so that the optical anisotropy and the dielectric anisotropy can be improved simultaneously. The liquid crystal molecules are mixed to achieve the balance and optimization of various performances as expected, and the requirements of practical application are met.
The percentage in the invention is weight percentage, the temperature is centigrade, Mp represents the melting point of liquid crystal, Cp represents the clearing point of liquid crystal.
Example 1
The mixed liquid crystal material consists of 25 percent of a component (R)1＝C3H7) 25% of component b (R)1＝C3H7) 15% of component c (R)1＝C3H7) 10% of d component (R)1＝C3H7) 10% of e component (R)1＝C3H7) 5% of f component (R)1＝C3H7) 10% of g component (R)1＝C3H7) Melting at 100-120 ℃ for 1-2 hours and mixing.
Example 2
The mixed liquid crystal material consists of 20 percent of a component (R)1＝C3H7) 20% of component b (R)1＝C3H7) 15% of component c (R)1＝C3H7) 15% of d component (R)1＝C3H7) 10% of e component (R)1＝C3H7) 10% of f component (R)1＝C3H7) 10% of g component (R)1＝C3H7) Melting at 100-120 ℃ for 1-2 hours and mixing.
The liquid crystal physical properties actually tested are shown in table 1:
physical Properties of liquid Crystal compositions obtained in Table 1, examples 1 and 2
As can be seen from Table 1, the mixed liquid crystal obtained from the above components has high polarity and large optical birefringence.
In the above examples, the synthesis method of each raw material used was as follows:
a compound a:
2- (3, 5-difluoro-4-isothiocyanatophenyl) -5- (1-alkynylpentyl) pyridine
Synthesis of 2, 6-difluoro-4- (5- (1-alkynylpentyl) pyridin-2-yl) aniline
18.9 g (0.1mol) of (5- (1-propargyl) pyridin-2-yl) boronic acid and 25.4 g (0.1mol) of 2, 6-difluoro-4-iodoaniline were dissolved in 500 ml of ethanol, and 32 g (0.3mol) of sodium carbonate, 3 g (0.01mol) of tetrabutylammonium bromide, 20 ml of palladium chloride/EDTA catalyst and 300 ml of deionized water were added thereto, and the mixture was refluxed with stirring for 8 hours, cooled and then suction-filtered to obtain 23 g of a gray solid powder product.
Synthesis of 2- (3, 5-difluoro-4-isothiocyanatophenyl) -5- (1-alkynylpentyl) pyridine
27.2 g (0.1mol) of 2, 6-difluoro-4- (5- (1-propargyl) pyridin-2-yl) aniline, 25 g (0.25mol) of calcium carbonate, 1L of chloroform and 500 ml of deionized water are added into a reaction bottle, stirred while the temperature of an ice-water bath is reduced to 0 to 5 ℃, then 18.5 g (0.16mol) of thiophosgene dissolved by 400 ml of dichloromethane is slowly added, the ice-water bath is kept stirred for 4 hours, and then stirred for 24 hours at room temperature, and the reaction is finished. Separating liquid, washing an organic phase once by 300 milliliters of 0.3M hydrochloric acid, washing three times by 350 milliliters of deionized water each time, drying by anhydrous sodium sulfate, spin-drying, passing through a 250 g silica gel column once by petroleum ether, spin-drying again, then dissolving by 2 times weight of tetrahydrofuran, and recrystallizing for two to three times at-30 ℃ until the purity reaches 99 percent to obtain 25 grams of a pure product. 1H NMR (400MHz, CDCl 3): δ 8.72(1H, s), 7.86(2H, d), 7.69(1H, d), 7.55(1H, d), 2.46(2H, t), 1.62(2H, m), 1.05(3H, t); m/z: 314[ M + ].
Compound b:
2- (3, 5-difluoro-4-isothiocyanatophenyl) -5-propylpyrimidine
Synthesis of 2, 6-difluoro-4- (5-propylpyrimidin-2-yl) aniline
16.6 g (0.1mol) of (5-propylpyrimidin-2-yl) boric acid and 25.4 g (0.1mol) of 2, 6-difluoro-4-iodoaniline are dissolved in 500 ml of ethanol, and then 32 g (0.3mol) of sodium carbonate, 3 g (0.01mol) of tetrabutylammonium bromide, 20 ml of palladium chloride/EDTA catalyst and 300 ml of deionized water are added, stirred and refluxed for 8 hours, cooled and filtered to obtain 20 g of a gray solid powder product.
Synthesis of 2- (3, 5-difluoro-4-isothiocyanatophenyl) -5-propylpyrimidine
24.9 g (0.1mol) of 2, 6-difluoro-4- (5-propylpyrimidin-2-yl) aniline, 25 g (0.25mol) of calcium carbonate, 1L of chloroform and 500 ml of deionized water are added into a reaction bottle, an ice water bath is cooled to 0-5 ℃ while stirring, then 18.5 g (0.16mol) of thiophosgene dissolved by 400 ml of dichloromethane is slowly added, the ice water bath is kept stirring for 4 hours, then the stirring is carried out for 24 hours at room temperature, and the reaction is finished. Separating the liquid, washing the organic phase once by 300 ml of 0.3M hydrochloric acid, washing three times by 350 ml of deionized water each time, drying by anhydrous sodium sulfate, spin-drying, passing 250 g of silica gel column once by petroleum ether, spin-drying again, then dissolving by 2 times of weight of tetrahydrofuran, and recrystallizing for two to three times at-30 ℃ until the purity reaches 99 percent to obtain 18.1 g of a pure product. 1H NMR (400MHz, CDCl 3): δ 8.83(2H, d), 7.31(2H, d), 2.64(2H, t), 1.66(2H, m), 0.91(3H, t); m/z: 291[ M + ].
Compound c:
3, 5-difluoro-4-isothiocyanatophen-4-propylbenzoate
Synthesis of 3, 5-difluoro-4-isothiocyanatophenol
Adding 14.5 g (0.1mol) of 4-amino-3, 5-difluorophenol, 25 g (0.25mol) of calcium carbonate, 1L of trichloromethane and 500 ml of deionized water into a reaction bottle, cooling to 0-5 ℃ in an ice-water bath while stirring, then slowly adding 18.5 g (0.16mol) of thiophosgene dissolved in 400 ml of dichloromethane, firstly keeping the ice-water bath stirring for 4 hours, and then stirring at room temperature for 24 hours, thus finishing the reaction. Separating, washing the organic phase once with 300 ml of 0.3M hydrochloric acid, washing three times with 350 ml of deionized water each time, drying with anhydrous sodium sulfate, spin-drying, passing through a 250 g silica gel column once with petroleum ether, and spin-drying to obtain 8.1 g of a crude product.
Synthesis of 3, 5-difluoro-4-isothiocyanatophene-4-propyl benzoate
18.7 g (0.1mol) of 3, 5-difluoro-4-isothiocyanatophenol, 16.4 g (0.1mol) of 4-propylbenzoic acid and 30.9 g (0.15mol) of Dicyclohexylcarbodiimide (DCC) were dissolved in 450 ml of chloroform, and 1.2 g (0.01mol) of 4-N, N-Dimethylaminopyridine (DMAP) was added thereto, followed by stirring at room temperature for 8 hours. After the reaction is finished, the reaction solution is filtered, a small amount of trichloromethane is used for leaching a filter cake, filtrate is collected and dried by spinning, petroleum ether is used for passing through a 250 g silica gel column once, and then the filtrate is dried by spinning again, and 5 times of ethanol with weight is used for freezing and crystallizing for 2 to 3 times at the temperature of-20 ℃ to obtain 27.3 g of a final product. 1H NMR (400MHz, CDCl 3): δ 8.18(2H, d), 7.29(2H, d), 6.99(2H, d), 2.62(2H, t), 1.67(2H, m), 0.91(3H, t); m/z: 333[ M + ].
A compound d:
2- (4- (difluoro (3-fluoro-4-isothiocyanatophenyloxy) methyl) phenyl) -5-propylpyrimidine
Synthesis of 5-propyl-2- (4- (trifluoromethyl) phenyl) pyrimidine
22.4 g (0.1mol) of 1-bromo-4- (trifluoromethyl) benzene, 16.6 g (0.1mol) of (5-propylpyrimidin-2-yl) boronic acid, 3.5 g (3mmol) of tetrakis (triphenylphosphine) palladium, 32 g (0.3mol) of sodium carbonate, 150 ml of toluene, 100 ml of ethanol and 100 ml of deionized water were stirred under reflux for 12 hours, the reaction was cooled to completion, 100 ml of toluene was added thereto, liquid was separated, the aqueous phase was extracted 3 times with toluene, 50 ml each time, the organic phases were combined, washed once with 100 ml of 0.3M hydrochloric acid and twice with 100 ml of saturated brine. Drying with anhydrous sodium sulfate, spin-drying, passing through 300 g silica gel column with petroleum ether, and spin-drying to obtain 14.1 g crude product.
Synthesis of 2- (4- (bromodifluoromethyl) phenyl) -5-propylpyrimidine
26.6 g (0.1mol) of 5-propyl-2- (4- (trifluoromethyl) phenyl) pyrimidine is dissolved in 100 ml of toluene, 2.5 g (0.01mol) of boron tribromide is slowly added while stirring under the protection of nitrogen, stirring and refluxing are carried out for 2 hours after the room temperature reaction is carried out for 1 hour, 500 ml of ice water is added after cooling, liquid separation is carried out, the water phase is extracted by dichloromethane for 3 times, 100 ml of water is added each time, the organic phase is combined and washed twice by 100 ml of water, and then dried by anhydrous sodium sulfate, dried by spinning, and distilled by reducing the pressure of an oil pump, so that 11.5 g of oily product is obtained.
Synthesis of 3-fluoro-4-isothiocyanatophenol
Adding 12.7 g (0.1mol) of 3-fluoro-4-aminophenol, 25 g (0.25mol) of calcium carbonate, 1L of trichloromethane and 500 ml of deionized water into a reaction bottle, cooling to 0-5 ℃ in an ice-water bath while stirring, slowly adding 18.5 g (0.16mol) of thiophosgene dissolved by 400 ml of dichloromethane, firstly keeping the ice-water bath stirring for 4 hours, and then stirring at room temperature for 24 hours to finish the reaction. Separating, washing the organic phase once with 300 ml of 0.3M hydrochloric acid, washing three times with 350 ml of deionized water each time, drying with anhydrous sodium sulfate, spin-drying, passing through a 250 g silica gel column once with petroleum ether, and spin-drying to obtain 10.48 g of crude product.
Synthesis of 2- (4- (difluoro (3-fluoro-4-isothiocyanatophenyloxy) methyl) phenyl) -5-propylpyrimidine
32.6 g (0.1mol) of 2- (4- (bromodifluoromethyl) phenyl) -5-propylpyrimidine and 16.9 g (0.1mol) of 3-fluoro-4-isothiocyanatophenol were dissolved in 350 g of acetone, and 27.6 g (0.2mol) of potassium carbonate was added thereto, followed by stirring under reflux for 16 hours, cooling, filtration and rotary drying to give a crude product. After passing through a 300 g silica gel column once with petroleum ether, it was crystallized two to three times with 3 times the weight of tetrahydrofuran to obtain 19.9 g of a product. 1H NMR (400MHz, CDCl 3): δ 8.83(2H, d), 8.56(2H, d), 7.42(2H, d), 7.22-7.16(2H, m), 6.75(1H, d), 2.67(2H, t), 1.67(2H, m), 0.91(3H, t); m/z: 415[ M + ].
Compound e:
4- (difluoro (4- (5-propylpyrimidin-2-yl) phenyl) methoxy) -2, 6-difluorobenzonitrile
Step reference compound d was synthesized prior to 2- (4- (bromodifluoromethyl) phenyl) -5-propylpyrimidine.
Synthesis of 4- (difluoro (4- (5-propylpyrimidin-2-yl) phenyl) methoxy) -2, 6-difluorobenzonitrile
32.6 g (0.1mol) of 2- (4- (bromodifluoromethyl) phenyl) -5-propylpyrimidine and 15.5 g (0.1mol) of 2, 6-difluoro-4-hydroxybenzonitrile were dissolved in 350 g of acetone, 27.6 g (0.2mol) of potassium carbonate was added, and the mixture was refluxed for 16 hours with stirring, cooled, filtered and dried to give a crude product. After passing through a 300 g silica gel column once with petroleum ether, it was crystallized two to three times with 3 times the weight of tetrahydrofuran to obtain 25.7 g of a product. 1H NMR (400MHz, CDCl 3): δ 8.83(2H, d), 8.58(2H, d), 7.42(2H, d), 7.10(2H, d), 2.64(2H, t), 1.67(2H, m), 0.91(3H, t); m/z: 401[ M + ].
A compound f:
2 ', 3, 5-trifluoro-4 ' - (5-propylpyrimidin-2-yl) - [1,1 ' -biphenyl ] -4-carbonitrile
Synthesis of 4 ' -bromo-2 ', 3, 5-trifluoro- [1,1 ' -biphenyl ] -4-carbonitrile
30.0 g (0.1mol) of 2-fluoro-4-bromo-iodobenzene, 18.3 g (0.1mol) of 3, 5-difluoro-4-cyanophenylboronic acid, 3.5 g (3mmol) of tetrakis (triphenylphosphine) palladium, 32 g (0.3mol) of sodium carbonate, 150 ml of toluene, 100 ml of ethanol and 100 ml of deionized water were stirred under reflux for 12 hours, the reaction was cooled to completion, 100 ml of toluene was added thereto, liquid was separated, the aqueous phase was extracted 3 times with toluene, 50 ml each time, the organic phases were combined, washed once with 100 ml of 0.3M hydrochloric acid and twice with 100 ml of saturated brine, and 100 ml each time. Drying with anhydrous sodium sulfate, spin-drying, passing through 300 g silica gel column with petroleum ether, and spin-drying to obtain 16.2 g crude product.
Synthesis of 2 ', 3, 5-trifluoro-4 ' - (5-propylpyrimidin-2-yl) - [1,1 ' -biphenyl ] -4-carbonitrile
31.2 g (0.1mol) of 4 ' -bromo-2 ', 3, 5-trifluoro- [1,1 ' -biphenyl ] -4-carbonitrile, 16.6 g (0.1mol) of (5-propylpyrimidin-2-yl) boronic acid, 3.5 g (3mmol) of tetrakis (triphenylphosphine) palladium, 32 g (0.3mol) of sodium carbonate, 150 ml of toluene, 100 ml of ethanol and 100 ml of deionized water were refluxed with stirring for 12 hours, the reaction was completed, 100 ml of toluene was added, the liquid was separated, the aqueous phase was extracted 3 times with 50 ml of toluene, the organic phases were combined, washed once with 100 ml of 0.3M hydrochloric acid and twice with 100 ml of saturated brine. Dried over anhydrous sodium sulfate, spin-dried, and passed through a 300 g silica gel column with petroleum ether once, and then crystallized two to three times with 3 times the weight of tetrahydrofuran to give 14.8 g of a product. 1H NMR (400MHz, CDCl 3): δ 8.83(2H, d), 7.81(1H, m), 7.63-7.57(2H, m), 7.45(2H, d), 2.64(2H, t), 1.67(2H, m), 0.91(3H, t); m/z: 353[ M + ].
Compound g:
2- (4- ((3-fluoro-4-isothiocyanatophenyl) ethynyl) phenyl) -5-propylpyrimidine
Synthesis of (4-bromophenyl) ethynyl) trimethylsilane
28.3 g (0.1mol) of 4-bromo-iodobenzene, 9.8 g (0.1mol) of trimethylsilylacetylene, 2.3 g (3.3 mmol) of bis (triphenylphosphine) palladium dichloride, 2.6 g (0.01mol) of triphenylphosphine, 1.9 g (0.01mol) of cuprous iodide, 150 ml of triethylamine and 60 ml of toluene are mixed and added into a reaction bottle, stirred and heated in an oil bath at 90 ℃ for 12 hours, then cooled and dried, petroleum ether passes through a 300 g silica gel column once and dried to obtain a crude product of 25.8 g.
Synthesis of 5-propyl-2- (4- ((trimethylsilyl) ethynyl) phenyl) pyrimidine
25.2 g (0.1mol) of ((4-bromophenyl) ethynyl) trimethylsilane, to which 16.6 g (0.1mol) of (5-propylpyrimidin-2-yl) boronic acid, 3.5 mg (3mmol) of tetrakis (triphenylphosphine) palladium, 32 g (0.3mol) of sodium carbonate, 150 ml of toluene, 100 ml of ethanol and 100 ml of deionized water were added, and the mixture was stirred under reflux for 12 hours, cooled after completion of the reaction, charged with 100 ml of toluene, separated into liquids, and the aqueous phase was extracted with toluene 3 times and 50 ml each time, followed by combining the organic phases, washing with 100 ml of 0.3M hydrochloric acid once, and washing with saturated brine twice and 100 ml each time. Drying with anhydrous sodium sulfate, spin-drying, passing through 300 g silica gel column with petroleum ether, and spin-drying to obtain 14.1 g crude product.
Synthesis of 2- (4-ethynylphenyl) -5-propylpyrimidine
29.4 g (0.1mol) of 5-propyl-2- (4- ((trimethylsilyl) ethynyl) phenyl) pyrimidine is dissolved in 500 ml of methanol, stirred in a water bath at 35 ℃, simultaneously added with 6.7 g (0.12 mol) of potassium hydroxide in batches, continuously reacted for 1 hour after the addition, then immediately added with a large amount of deionized water, extracted with petroleum ether for 8 times, 300 ml each time, then combined with organic phases, washed once with 300 ml of deionized water, dried by anhydrous sodium sulfate, dried by spinning, filtered once with 300 g of silica gel column by using petroleum ether, dried by spinning again, dissolved with 2 times of the weight of petroleum ether, crystallized at-30 ℃ to obtain 14.6 g of slightly yellow crystals.
Synthesis of 3-fluoro-4- ((4- (5-propylpyrimidin-2-yl) phenyl) ethynyl) aniline
22.2 g (0.1mol) of 2- (4-ethynylphenyl) -5-propylpyrimidine, 23.7 g (0.1mol) of 2-fluoro-4-iodoaniline, 2.3 g (3.3 mmol) of palladium dichloride (triphenylphosphine), 2.6 g (0.01mol) of triphenylphosphine, 1.9 g (0.01mol) of cuprous iodide, 150 ml of triethylamine and 60 ml of toluene were mixed and added into a reaction flask, and the mixture was stirred while being heated in an oil bath at 90 ℃ for 12 hours, then cooled and dried, and the crude product was dissolved in 600 ml of tetrahydrofuran, 30 g of activated carbon was then added and refluxed for 1 hour, filtered while hot, the filtrate was dried, and then crystallized with 3 times the weight of tetrahydrofuran at 0 ℃ to give 17.5 g of dark crystals.
Synthesis of 2- (4- ((3-fluoro-4-isothiocyanatophenyl) ethynyl) phenyl) -5-propylpyrimidine
Adding 33.1 g (0.1mol) of 3-fluoro-4- ((4- (5-propylpyrimidin-2-yl) phenyl) ethynyl) aniline, 25 g (0.25mol) of calcium carbonate, 1L of trichloromethane and 500 ml of deionized water into a reaction bottle, stirring while cooling to 0-5 ℃ in an ice water bath, then slowly adding 18.5 g (0.16mol) of thiophosgene dissolved in 400 ml of dichloromethane, firstly keeping the ice water bath stirring for 4 hours, and then stirring at room temperature for 24 hours to finish the reaction. Separating liquid, washing an organic phase once by 300 milliliters of 0.3M hydrochloric acid, washing three times by 350 milliliters of deionized water each time, drying by anhydrous sodium sulfate, spin-drying, passing a 250 g silica gel column once by petroleum ether, spin-drying again, then dissolving by 2 times weight of tetrahydrofuran, and recrystallizing for two to three times at-30 ℃ until the purity reaches 99 percent to obtain 17.9 grams of a product. 1H NMR (400MHz, CDCl 3): δ 8.83(2H, d), 7.75-7.67(4H, m), 7.31-7.25(3H, m), 2.63(2H, t), 1.66(2H, m), 0.91(3H, t); m/z: 373[ M + ].
While the invention has been described with reference to preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention is defined by the claims.
Claims (15)
1. A liquid crystal composition comprises the following components a to g in percentage by mass:
the component a is 20-25% of a compound shown in the formula I;
the component b is 20-25% of a compound shown as a formula II;
the component c is 10-15% of a compound shown in a formula III;
the component d is 5-15% of a compound shown as a formula IV;
the component e is 5-15% of a compound shown as a formula V;
the component f is 5-15% of a compound shown as a formula VI;
the component g is 5-15% of a compound shown as a formula VII;
in the formulas I to VII, n is an integer of 1-5.
2. The liquid crystal composition according to claim 1, wherein: the liquid crystal composition is a liquid crystal composition a;
in the liquid crystal composition a, the mass percentage of the component a and the component b is 25%;
the mass percentage of the component c is 15 percent;
the mass percentage of the component d, the component e and the component g is 10 percent;
the mass percentage of the component f is 5 percent;
and n is 3.
3. The liquid crystal composition according to claim 1, wherein: the liquid crystal composition is a liquid crystal composition b;
in the liquid crystal composition b, the mass percentage of the component a and the component b is 20%;
the mass percentage of the component c and the component d is 15 percent;
the mass percentage of the component e to the component g is 10 percent;
and n is 3.
4. A method of preparing a liquid crystal composition according to any one of claims 1 to 3, comprising: melting and uniformly mixing the component a to the component g in the liquid crystal composition of any one of claims 1 to 3 according to a ratio.
5. The method of claim 4, wherein: in the melting step, the temperature is 100-120 ℃; the time is 1-2 hours.
6. Use of a liquid crystal composition according to any of claims 1 to 3 for the modulation of liquid crystal light.
7. Use of the liquid crystal composition according to any one of claims 1 to 3 in liquid crystal displays.
8. A liquid crystal light modulator comprising the liquid crystal composition according to any one of claims 1 to 3.
9. A liquid crystal display comprising the liquid crystal composition according to any one of claims 1 to 3.
10. A polymer dispersed liquid crystal comprising the liquid crystal composition according to any one of claims 1 to 3.
11. A blue phase liquid crystal comprising the liquid crystal composition according to any one of claims 1 to 3.
12. Use of a liquid crystal composition according to any of claims 1 to 3 for the preparation of a liquid crystal light modulator.
13. Use of a liquid crystal composition according to any of claims 1 to 3 for the preparation of a liquid crystal display.
14. Use of a liquid crystal composition according to any of claims 1 to 3 for the preparation of polymer dispersed liquid crystals.
15. Use of a liquid crystal composition according to any of claims 1 to 3 for the preparation of blue phase liquid crystals.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911111704.5A CN110938439B (en) | 2019-11-14 | 2019-11-14 | High-polarity large-optical birefringence liquid crystal composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911111704.5A CN110938439B (en) | 2019-11-14 | 2019-11-14 | High-polarity large-optical birefringence liquid crystal composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110938439A CN110938439A (en) | 2020-03-31 |
| CN110938439B true CN110938439B (en) | 2021-03-19 |
Family
ID=69906599
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911111704.5A Active CN110938439B (en) | 2019-11-14 | 2019-11-14 | High-polarity large-optical birefringence liquid crystal composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110938439B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112029514B (en) * | 2020-09-03 | 2021-11-30 | 清华大学 | Polymer-stabilized blue-phase liquid crystal composition and preparation method thereof |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5888421A (en) * | 1991-03-13 | 1999-03-30 | The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Anisotropic organic compounds |
| CN1232442A (en) * | 1996-08-20 | 1999-10-20 | 智索公司 | Liquid-crystal alkenyltolan deriv., liquid-crystal composition, and liquid-crystal display element |
| US5986096A (en) * | 1995-03-28 | 1999-11-16 | The Secretary Of State For Defence In Her Britannic Majesty's A Government Of The U.K. Of Gt. Britain & N. Ireland Of Defence Evaluation & Research Agency | Pyrimidine compounds |
| EP1054001A1 (en) * | 1999-05-19 | 2000-11-22 | MERCK PATENT GmbH | Isothiocyanate tolanes and liquid crystal mixtures containing them |
| CN101323596A (en) * | 2008-08-07 | 2008-12-17 | 石家庄永生华清液晶有限公司 | 2-site ethynyl contained pyrimidine ring liquid crystal compounds and method for preparing the same |
| CN101544892A (en) * | 2009-05-07 | 2009-09-30 | 石家庄永生华清液晶有限公司 | Method for synthesizing diaryl acetylene monomer liquid crystal |
| CN101580716A (en) * | 2008-05-15 | 2009-11-18 | 石家庄永生华清液晶有限公司 | Terminal isothiocyano liquid-crystal compound containing pyrimidine ring and preparation method thereof |
| CN102433133A (en) * | 2011-09-14 | 2012-05-02 | 深圳超多维光电子有限公司 | Nematic liquid crystal composition |
| CN102604649A (en) * | 2012-02-27 | 2012-07-25 | 中国科学院长春光学精密机械与物理研究所 | Fast response liquid crystal material for liquid crystal wave-front corrector and preparation method thereof |
| CN102816572A (en) * | 2012-08-28 | 2012-12-12 | 石家庄诚志永华显示材料有限公司 | Large-dielectric-anisotropy high-optical-anisotropy liquid crystal composition and preparation method and application thereof |
| CN102876333A (en) * | 2012-10-08 | 2013-01-16 | 南京大学 | Mixed liquid crystal material having high double-refractivity within terahertz frequency band |
| CN103880735A (en) * | 2014-03-27 | 2014-06-25 | 清华大学 | Smectic-phase liquid crystal compound as well as preparation method and application thereof |
| CN104130196A (en) * | 2014-07-21 | 2014-11-05 | 北京大学 | Pyrimidine liquid crystal compound with high birefringence and preparation method thereof |
| CN106190174A (en) * | 2014-08-25 | 2016-12-07 | 深圳超多维光电子有限公司 | Liquid-crystal composition and liquid crystal lens |
-
2019
- 2019-11-14 CN CN201911111704.5A patent/CN110938439B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5888421A (en) * | 1991-03-13 | 1999-03-30 | The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Anisotropic organic compounds |
| US5986096A (en) * | 1995-03-28 | 1999-11-16 | The Secretary Of State For Defence In Her Britannic Majesty's A Government Of The U.K. Of Gt. Britain & N. Ireland Of Defence Evaluation & Research Agency | Pyrimidine compounds |
| CN1232442A (en) * | 1996-08-20 | 1999-10-20 | 智索公司 | Liquid-crystal alkenyltolan deriv., liquid-crystal composition, and liquid-crystal display element |
| EP1054001A1 (en) * | 1999-05-19 | 2000-11-22 | MERCK PATENT GmbH | Isothiocyanate tolanes and liquid crystal mixtures containing them |
| CN101580716A (en) * | 2008-05-15 | 2009-11-18 | 石家庄永生华清液晶有限公司 | Terminal isothiocyano liquid-crystal compound containing pyrimidine ring and preparation method thereof |
| CN101323596A (en) * | 2008-08-07 | 2008-12-17 | 石家庄永生华清液晶有限公司 | 2-site ethynyl contained pyrimidine ring liquid crystal compounds and method for preparing the same |
| CN101544892A (en) * | 2009-05-07 | 2009-09-30 | 石家庄永生华清液晶有限公司 | Method for synthesizing diaryl acetylene monomer liquid crystal |
| CN102433133A (en) * | 2011-09-14 | 2012-05-02 | 深圳超多维光电子有限公司 | Nematic liquid crystal composition |
| CN102604649A (en) * | 2012-02-27 | 2012-07-25 | 中国科学院长春光学精密机械与物理研究所 | Fast response liquid crystal material for liquid crystal wave-front corrector and preparation method thereof |
| CN102816572A (en) * | 2012-08-28 | 2012-12-12 | 石家庄诚志永华显示材料有限公司 | Large-dielectric-anisotropy high-optical-anisotropy liquid crystal composition and preparation method and application thereof |
| CN102876333A (en) * | 2012-10-08 | 2013-01-16 | 南京大学 | Mixed liquid crystal material having high double-refractivity within terahertz frequency band |
| CN103880735A (en) * | 2014-03-27 | 2014-06-25 | 清华大学 | Smectic-phase liquid crystal compound as well as preparation method and application thereof |
| CN104130196A (en) * | 2014-07-21 | 2014-11-05 | 北京大学 | Pyrimidine liquid crystal compound with high birefringence and preparation method thereof |
| CN106190174A (en) * | 2014-08-25 | 2016-12-07 | 深圳超多维光电子有限公司 | Liquid-crystal composition and liquid crystal lens |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110938439A (en) | 2020-03-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR20150108325A (en) | 4,6-difluorodibenzofuran derivatives | |
| CN108531196B (en) | Liquid crystal compound containing dibenzofuran ring and preparation method and application thereof | |
| JP4876420B2 (en) | Difluorobenzene derivative | |
| JPS6144845A (en) | Optically active compounds and liquid crystal composition containing them | |
| JP5604809B2 (en) | Fluorobenzene derivative and liquid crystal composition containing the compound | |
| JPH0334987A (en) | Derivative of benzoate silide,its manufacture inter- mediate product and its manufacture, liyuid crystal display device containing new compound | |
| JP4691893B2 (en) | Liquid crystal composition, display element and compound containing trifluoronaphthalene derivative. | |
| CN100509724C (en) | Multifluoro substituted diphenyl acetylene derivative, composition containing multifluoro substituted diphenyl acetylene derivatire, preparation method and use thereof | |
| CN110938439B (en) | High-polarity large-optical birefringence liquid crystal composition | |
| TWI385240B (en) | Liquid crystal compounds and liquid crystal compositions comprising the same | |
| CN112480048B (en) | Compound, liquid crystal medium, liquid crystal display element and liquid crystal display | |
| JPH05286872A (en) | Cis-1,4-substituted 2-butene derivative | |
| CN103788039B (en) | Liquid-crystal compounds containing oxinane difluoromethylenedioconnecting linking group and preparation method and application | |
| JP3692430B2 (en) | 4- (2-Cyclohexylpropyl) benzene derivative | |
| JP4521738B2 (en) | Benzothiazole compound, process for producing the same, liquid crystal composition, and liquid crystal element | |
| JP3981844B2 (en) | New alkenyltolane derivatives | |
| CN112457865B (en) | Liquid crystal compound and composition and application thereof | |
| CN113528148A (en) | Liquid crystal medium for high-frequency technology and assembly thereof | |
| CN112500867B (en) | Liquid crystal compound, liquid crystal composition composed of same and application | |
| JP3841178B2 (en) | Alkenylbenzene derivative and method for producing the same | |
| CN112029514B (en) | Polymer-stabilized blue-phase liquid crystal composition and preparation method thereof | |
| CN114262614B (en) | Positive liquid crystal composition and application | |
| KR100662192B1 (en) | Liquid crystal composition comprising novel indane compounds and liquid crystal display device using the same | |
| Yu et al. | Chiral dimesogenic compounds having cholesterol and 4-(trans-4-n-hexylcyclohexyl) benzoic acid moieties | |
| CN111607411A (en) | Difluoromethoxyl liquid crystal compound containing benzoxazole heterocycle, and synthesis method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |