Polyfluoro liquid crystal compound, composition and application thereof

Abstract

The invention provides a polyfluorine liquid crystal compound, a composition and application thereof. The polyfluorine liquid crystal compound has a structure as shown in a formula I, has relatively high dielectric anisotropy, good liquid crystal intersolubility and relatively low rotary viscosity, and can be used for improving the performance of a liquid crystal material.

Description

Technical Field

[0001] This invention relates to the field of liquid crystal materials technology, specifically to a polyfluorinated liquid crystal compound and composition, and also to the application of the compound and composition. Background Technology

[0002] Liquid crystal materials are an intermediate phase between solid and liquid. They can flow and have the optical properties of crystallization. They are currently widely used in fields such as information display materials and organic optoelectronic materials.

[0003] Liquid crystal materials themselves play a crucial role in improving the performance of liquid crystal displays (LCDs), especially reducing the rotational viscosity and increasing the dielectric anisotropy (Δε) of liquid crystal materials, which significantly improves LCD performance. Therefore, to improve the performance of liquid crystal materials and adapt them to new requirements, the synthesis of novel liquid crystal compounds and the study of structure-property relationships have become important work in the field of liquid crystals. Summary of the Invention

[0004] To address at least one of the aforementioned technical problems, the present invention provides a polyfluorinated liquid crystal compound possessing excellent properties such as high dielectric anisotropy, good liquid crystal miscibility, and low rotational viscosity, which can be used to improve the performance of liquid crystal materials. Furthermore, the present invention also provides a liquid crystal material composition comprising the polyfluorinated liquid crystal compound, and the applications of the polyfluorinated liquid crystal compound and the liquid crystal material composition.

[0005] In a first aspect, the present invention provides a polyfluorinated liquid crystal compound having a structure as shown in Formula I: Formula I; Where X is selected from O or S; R1 and R2 are each independently selected from any one or more combinations of halogenated or unsubstituted C1-C12 alkyl, halogenated or unsubstituted C1-C12 alkoxy, halogenated or unsubstituted C3-C10 cycloalkyl, halogenated or unsubstituted C2-C12 alkenyl, and halogenated or unsubstituted C2-C12 alkenyloxy. Ring A, ring B, and ring C are each independently selected from any one or more combinations of halogenated or unsubstituted C6-C14 arylene, halogenated or unsubstituted C5-C8 cycloalkyl, halogenated or unsubstituted C5-C8 cycloalkenyl, and halogenated or unsubstituted C3-C8 saturated or unsaturated oxy-containing heterocyclic groups. Z1, Z2, and Z3 are each independently selected from any one or more combinations of single bonds, double bonds, oxygen atoms, C1-C4 alkylene groups, C1-C4 alkoxy groups, -COO-, -OCO-, -O-C1-C4 alkylene-O-, and C2-C4 alkenyl groups; optionally, one or more hydrogen atoms in the C1-C4 alkylene groups, C1-C4 alkoxy groups, and C2-C4 alkenyl groups are substituted with halogen atoms; m, n, and k are each independently selected from 0, 1, or 2.

[0006] In this invention, the halogenated or unsubstituted alkyl group is preferably linear, where "linear" specifically means that all carbon atoms constituting the alkyl group are on the same carbon chain. The halogenated or unsubstituted alkyl group can make the anisotropic arrangement of the above-mentioned liquid crystal compound more ordered, thus enabling it to possess liquid crystal properties. "Liquid crystal properties" refers to the ability of a substance to exhibit the fluidity of a liquid and the anisotropic ordered arrangement of a crystalline substance at a certain temperature.

[0007] In this invention, the halogenated or unsubstituted alkoxy group can be considered as the structure formed by connecting the aforementioned halogenated or unsubstituted alkyl group to an oxygen atom (O). The halogenated or unsubstituted alkoxy group is also preferably linear, and the aforementioned liquid crystal compound containing a linear halogenated or unsubstituted alkoxy group can also exhibit good liquid crystal properties.

[0008] In this invention, the halogenated or unsubstituted alkenyl group can be a straight-chain alkenyl group or a branched alkenyl group, preferably a straight-chain alkenyl group. The above-mentioned liquid crystal compounds containing this halogenated or unsubstituted straight-chain alkenyl group are relatively easy to prepare and can exhibit good liquid crystal properties.

[0009] In this invention, the halogenated or unsubstituted alkenyloxy group can be a straight-chain alkenyloxy group or a branched alkenyloxy group, with a straight-chain alkenyloxy group being preferred. The halogenated or unsubstituted alkenyloxy group can be considered as a structure formed by the connection of a halogenated or unsubstituted alkenyl group to an oxygen atom.

[0010] The substituents of the present invention have a suitable number of carbon atoms, which makes it easier to prepare the liquid crystal compound shown in Formula I and to control its dielectric anisotropy values ​​over a wide range.

[0011] In this invention, "halogenated..." means that any one or more hydrogen atoms in a group are replaced by halogen atoms, that is, the substituent in the group is a halogen atom. For example, haloalkyl specifically refers to an alkyl group replaced by a halogen atom. Similarly, other halogenated groups are treated the same way and will not be elaborated further. The introduction of halogen substituents can increase the dielectric anisotropy of the above-mentioned liquid crystal compounds, making the types of compounds more diverse. "Halogenated" can be partially halogenated or fully halogenated. "Fully halogenated" means that all hydrogen atoms in the above-mentioned group are replaced by halogen atoms. "Partially halogenated" means that some hydrogen atoms in the above-mentioned group are replaced by halogen atoms. The halogen atom can be one or more of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I), with fluorine being the most common.

[0012] In a preferred embodiment of the present invention, each of the above-mentioned halogenated groups is specifically a corresponding fluorinated group, namely, a halogenated or unsubstituted C1-C12 alkyl group, a halogenated or unsubstituted C1-C12 alkoxy group, a halogenated or unsubstituted C3-C10 cycloalkyl group, a halogenated or unsubstituted C2-C12 alkenyl group, or a halogenated or unsubstituted C2-C12 alkenyl group. Preferably, the halogenated or unsubstituted C1-C12 alkyl group, a halogenated or unsubstituted C1-C12 alkoxy group, a halogenated or unsubstituted C3-C10 cycloalkyl group, a halogenated or unsubstituted C2-C12 alkenyl group, or a halogenated or unsubstituted C2-C12 alkenyl group is preferred, which is beneficial for the liquid crystal compound of Formula I to have a larger dielectric anisotropy value.

[0013] It should be noted that, in this invention, each fluorinated group refers to a group in which at least one (e.g., one, two, three or more) hydrogen atom is replaced by fluorine, including perfluorinated groups and partially fluorinated groups; for example, "fluorinated alkyl" refers to an alkyl group in which all or part of the hydrogen atoms are replaced by fluorine; specifically, for example, "fluorinated n-propyl" includes n-propyl groups in which 1 to 7 hydrogen atoms are replaced by fluorine.

[0014] As one embodiment of the present invention, R1 and R2 are each independently selected from any one or more combinations of halogenated or unsubstituted C1-C5 (e.g., C2, C3, C4, C5, etc.) alkyl, halogenated or unsubstituted C1-C5 (e.g., C2, C3, C4, C5, etc.) alkoxy, halogenated or unsubstituted C3-C8 (e.g., C4, C5, C6, C7, C8, etc.) cycloalkyl, halogenated or unsubstituted C2-C8 (e.g., C3, C4, C5, C6, C7, C8, etc.) alkenyl, and halogenated or unsubstituted C2-C8 (e.g., C3, C4, C5, C6, C7, C8, etc.) alkenyloxy.

[0015] In a preferred embodiment of the present invention, R1 and R2 are each independently selected from any one or more combinations of halogenated or unsubstituted C1-C5 alkyl, halogenated or unsubstituted C1-C5 alkoxy, halogenated or unsubstituted C3-C6 cycloalkyl, halogenated or unsubstituted C2-C4 alkenyl, and halogenated or unsubstituted C2-C4 alkenyloxy.

[0016] As a further preferred embodiment of the present invention, R1 and R2 are each independently selected from any one or more combinations of C1-C5 alkyl, C1-C5 fluoroalkyl, C1-C5 alkoxy, C1-C5 fluoroalkoxy, C3-C6 cycloalkyl, C3-C6 fluorocycloalkyl, C2-C4 alkenyl, and C2-C4 fluoroalkenyl.

[0017] In this invention, C1-C5 alkyl groups can be methyl, ethyl, n-propyl, n-butyl, or n-pentyl; C1-C5 fluoroalkyl groups can be monofluoro or polyfluoro groups of methyl, ethyl, n-propyl, n-butyl, or n-pentyl, such as trifluoromethyl (-CF3), difluoroethyl (-C2F2H3), perfluoroethyl (-C2F5), perfluoron-propyl (-C3F7), perfluoron-butyl (-C4F9), or perfluoron-pentyl (-C5F7). 11 C1-C5 alkoxy groups can be methoxy, ethoxy, propoxy, butoxy, or pentoxy groups; C1-C5 fluoroalkoxy groups can be monofluoro or polyfluoro groups of methoxy, ethoxy, propoxy, butoxy, or pentoxy, such as trifluoromethoxy (-OCF3); C3-C6 cycloalkyl groups can be cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl; C2-C4 alkenyl groups can be vinyl, propenyl, or butenyl groups; C2-C4 fluoroalkenyl groups can be monofluoro or polyfluoro groups of vinyl, propenyl, or butenyl, such as difluorovinyl (CF2=CH-) or perfluorovinyl (CF2=CF-).

[0018] In some embodiments, R1 and R2 are each independently selected from any one or more combinations of methyl, ethyl, n-propyl, n-butyl, n-pentyl, fluoromethyl, fluoroethyl, fluoron-propyl, fluoron-butyl, fluoron-pentyl, methoxy, ethoxy, propoxy, butoxy, pentoxy, fluoromethoxy, fluoroethoxy, fluoropropoxy, fluorobutoxy, fluoropentoxy, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, fluorovinyl, fluoropropenyl, and fluorobutenyl.

[0019] In some embodiments, R1 and R2 are each independently selected from any one or more combinations of C1-C5 alkyl, C1-C5 fluoroalkyl, C1-C5 alkoxy, C1-C5 fluoroalkoxy, C2-C4 alkenyl, and C2-C4 fluoroalkenyl.

[0020] In some embodiments, R1 is selected from any one or more combinations of C1-C5 alkyl, C1-C5 alkoxy, and C2-C4 alkenyl.

[0021] In some embodiments, R2 is selected from any one or more combinations of C1-C5 alkyl and C1-C5 alkoxy groups.

[0022] In some embodiments, R1 and R2 are each independently selected from any one or more combinations of methyl, ethyl, n-propyl, methoxy, ethoxy, propoxy, and vinyl.

[0023] In some embodiments, R1 is selected from any one of ethyl, n-propyl, ethoxy, propoxy, and vinyl. In some embodiments, R2 is selected from any one of ethyl, n-propyl, ethoxy, and propoxy.

[0024] In this invention, ring A, ring B, and ring C are each independently selected from any one or more combinations of halogenated or unsubstituted C6-C14 (e.g., C6, C10, C14, etc.) arylene, halogenated or unsubstituted C5-C8 (e.g., C5, C6, C7, C8, etc.) cycloalkyl, halogenated or unsubstituted C5-C8 (e.g., C5, C6, C7, C8, etc.) cycloalkenyl, and halogenated or unsubstituted C3-C8 (e.g., C3, C4, C5, C6, C7, C8, etc.) saturated or unsaturated oxygen-containing heterocyclic groups.

[0025] As one embodiment of the present invention, ring A, ring B, and ring C are each independently selected from any one or more combinations of halogenated or unsubstituted 1,4-phenylene, halogenated or unsubstituted 1,4-cyclohexylene, halogenated or unsubstituted 1,4-cyclohexenylene, halogenated or unsubstituted tetrahydropyranylene, and halogenated or unsubstituted 1,3-dioxane.

[0026] As one embodiment of the present invention, ring A, ring B, and ring C are each independently selected from any one or more combinations of fluorinated or unsubstituted 1,4-phenylene, fluorinated or unsubstituted 1,4-cyclohexylene, fluorinated or unsubstituted 1,4-cyclohexenylene, fluorinated or unsubstituted tetrahydropyranylene, and fluorinated or unsubstituted 1,3-dioxane.

[0027] As one embodiment of the present invention, ring A, ring B, and ring C are each independently selected from any one or more combinations of 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyranylene, 1,3-dioxane, and 1,4-phenylene containing 1-4 fluorine substituents.

[0028] In a preferred embodiment of the present invention, ring A, ring B, and ring C are each independently selected from any of the following groups: , , , , , or .

[0029] As one embodiment of the present invention, Z1, Z2, and Z3 are each independently selected from any one or more combinations of single bonds, double bonds, oxygen atoms, C1-C4 alkylene groups (e.g., C1, C2, C3, C4 alkylene groups), C1-C4 alkoxy groups (e.g., C1, C2, C3, C4 alkoxy groups), -COO-, -OCO-, -O-C1-C4 alkylene groups-O-, and C2-C4 alkenyl groups (e.g., C2, C3, C4 alkenyl groups); optionally, one or more hydrogen atoms in the C1-C4 alkylene groups, C1-C4 alkoxy groups, and C2-C4 alkenyl groups are replaced by fluorine atoms.

[0030] As one embodiment of the present invention, Z1, Z2, and Z3 are each independently selected from any one of single bonds, -CH2-, -CH2CH2-, -OCH2-, -OCH2CH2-, -COO-, -OCO-, -O-CH2-O-, -O-CH2CH2-O-, and -CH=CH-; optionally, one or more hydrogen atoms among -CH2-, -CH2CH2-, -OCH2-, -OCH2CH2-, -O-CH2-O-, -O-CH2CH2-O-, and -CH=CH- are replaced by fluorine atoms.

[0031] As one embodiment of the present invention, Z1, Z2, and Z3 are each independently selected from any one or more combinations of single bonds, double bonds, oxygen atoms, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -CH2CH2-, -COO-, -OCO-, -CHFO-, -OCHF-, -OCHFO-, -CF2-, -CHF-, -CH2-, -CHFCH2-, -CH2CHF-, -CHFCHF-, -CF2CH2-, -CH2CF2-, -CF2CHF-, -CHFCF2-, -CF2CF2-, -CH=CH-, -CF=CH-, -CH=CF-, and -CF=CF-.

[0032] As one embodiment of the present invention, Z1, Z2, and Z3 are each independently selected from single bonds, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -CH2CH2-, -COO-, -OCO-, or -CF2CF2-.

[0033] In a preferred embodiment of the present invention, Z1, Z2, and Z3 are each independently selected from single bonds, -CF2O-, -CH2O-, -CH2CH2-, or -COO-.

[0034] In some implementations, Z1 and Z2 are each independently selected from single bonds, -CF2O-, -CH2O-, -CH2CH2-, or -COO-.

[0035] In some implementations, Z3 is a single bond.

[0036] In one embodiment of the present invention, m, n, and k are each independently selected from 0 or 1.

[0037] In a preferred embodiment of the present invention, m and n are each independently selected from 0 or 1, and k is 0.

[0038] In some implementations, m, n, and k are all 0.

[0039] In some implementations, at least one of m and n is 1, and k is 0.

[0040] In some implementations, either m or n is 1, the other is 0, and k is 1.

[0041] As one embodiment of the present invention, the polyfluorinated liquid crystal compound has any of the following structures:

[0042] , The definitions of each symbol are the same as those defined in the foregoing definition in this invention.

[0043] As one embodiment of the present invention, the polyfluorinated liquid crystal compound has a structure as shown in any of Formulas I-1 to I-120:

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061] The definitions of R1, R2, and X are the same as those in Equation I.

[0062] As a specific embodiment of the present invention, the polyfluorinated liquid crystal compound includes any of the compounds shown in the following structures:

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080] In the compounds LC-1 to LC-142 above, the groups -C3H7, -C3F7, -C4H9, -C4F9, and -C5H are present. 11 -C5F 11 , -OC3H7, -OC3F7, -OC4H9, -OC4F9, -OC5H 11 -OC5F 11 All of them have a linear chain structure.

[0081] In a second aspect, the present invention provides a liquid crystal material composition comprising the polyfluorinated liquid crystal compound described in the first aspect of the present invention.

[0082] As one embodiment of the present invention, the polyfluorinated liquid crystal compound provided by the present invention has a mass percentage content of 1 to 60% in the liquid crystal material composition (e.g., 2%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48%, 50%, 52%, 55%, 58% or any value between them).

[0083] In some embodiments, the polyfluorinated liquid crystal compound provided by the present invention has a mass percentage content of 1 to 40% in the liquid crystal material composition.

[0084] In some embodiments, the polyfluorinated liquid crystal compound provided by the present invention has a mass percentage content of 5-20% in the liquid crystal material composition.

[0085] In some embodiments, the polyfluorinated liquid crystal compound provided by the present invention has a mass percentage content of 5-10% in the liquid crystal material composition.

[0086] According to some embodiments of the present invention, the liquid crystal material composition comprises the polyfluorinated liquid crystal compound described in the first aspect of the present invention and at least one selected from compounds shown in formulas a and b: Formula a, Formula b; Among them, R a and Rb Each is independently selected from C1-C12 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, etc.) alkyl, C1-C12 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, etc.) alkoxy, and C2-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, etc.) alkenyl; Rings a, b, c, d, and e are each independently selected from cyclohexane rings, benzene rings, and fluorobenzene rings.

[0087] In some implementations, R a and R b Each is independently selected from C1-C6 alkyl, C1-C6 alkoxy, and C2-C4 alkenyl groups.

[0088] In this invention, R a and R b The alkyl, alkoxy, and alkenyl groups involved can be either straight-chain or branched-chain structures.

[0089] In some preferred embodiments, R a and R b The alkyl, alkoxy, and alkenyl groups involved are all straight-chain structures.

[0090] In some embodiments, ring a, ring b, ring c, ring d, and ring e are each independently selected from any of the following groups:

[0091] In some embodiments, the compound represented by formula a and / or formula b is present in the liquid crystal material composition at a mass percentage of 40-99% (e.g., 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 99% or any value between them).

[0092] In some embodiments, the liquid crystal material composition comprises the polyfluorinated liquid crystal compound described in the first aspect of the present invention and one or more of the following compounds 1 to 6:

[0093] In some embodiments, the liquid crystal material composition includes the polyfluorinated liquid crystal compound described in the first aspect of the present invention, as well as compounds 1, 2, 3, 4, 5 and 6.

[0094] In some implementations, the compound The mass percentage of the liquid crystal material composition is 35-50% (e.g., 35%, 38%, 40%, 42%, 44%, 45%, 46%, 48%, 50% or any value between them).

[0095] In some implementations, the compound The mass percentage of the liquid crystal material composition is 1-10% (e.g., 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% or any value between them).

[0096] In some implementations, the compound The mass percentage of the liquid crystal material composition is 1-10% (e.g., 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% or any value between them).

[0097] In some implementations, the compound The mass percentage of the liquid crystal material composition is 5-15% (e.g., 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15% or any value between them).

[0098] In some embodiments, the compound The mass percentage of the liquid crystal material composition is 1-15% (e.g., 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 12%, 15% or any value between them).

[0099] In some implementations, the compound The mass percentage of the liquid crystal material composition is 10-25% (e.g., 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25% or any value between them).

[0100] Thirdly, the present invention provides a liquid crystal display device comprising the polyfluorinated liquid crystal compound described in the first aspect of the present invention, or comprising the liquid crystal material composition described in the second aspect of the present invention.

[0101] In this invention, the liquid crystal display device includes, but is not limited to, TN, ADS, VA, PSVA, FFS, or IPS liquid crystal displays.

[0102] Fourthly, the present invention provides the application of the aforementioned polyfluorinated liquid crystal compound or the aforementioned liquid crystal material composition in the field of liquid crystal displays.

[0103] Furthermore, the application of the polyfluorinated liquid crystal compound or the liquid crystal material composition in a liquid crystal display device is preferably as a liquid crystal material in the liquid crystal display device.

[0104] Furthermore, the liquid crystal display device includes, but is not limited to, TN, ADS, VA, PSVA, FFS, and IPS liquid crystal displays.

[0105] Compared with the prior art, the present invention has the following beneficial technical effects: This invention provides a polyfluorinated liquid crystal compound that, compared with existing liquid crystal materials, exhibits higher dielectric anisotropy and lower rotational viscosity, thereby effectively reducing the driving voltage and improving the response speed of the liquid crystal display device. Detailed Implementation

[0106] The technical solution of the present invention will be described in detail below. The following embodiments are used to illustrate the present invention, but are not intended to limit the scope of the present invention. Unless otherwise specified, the raw materials are all available from publicly available commercial sources.

[0107] In this invention, the way the ring structure is represented by "—" indicates that the connection point is located at any position on the ring structure where bonding can occur.

[0108] In this invention, " "" indicates the linking site of a functional group.

[0109] In this invention, "each independently" means that when there are multiple subjects, they can be the same or different from each other.

[0110] In this invention, the expression “Ca-Cb” represents that the number of carbon atoms in the group is any integer between a and b. Unless otherwise specified, the number of carbon atoms does not include the number of carbon atoms in the substituents. For example, alkyl groups of C1-C12 can be alkyl groups of C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11 or C12.

[0111] Unless otherwise specified, the reagents used in the following embodiments and comparative examples of this invention are all conventional biochemical reagents; the raw materials, instruments and equipment used in the following embodiments and comparative examples can all be obtained by purchasing from the market or by existing methods; unless otherwise specified, the reagent dosages are all reagent dosages used in conventional experimental operations; unless otherwise specified, the experimental methods are all conventional methods.

[0112] Synthesis Example 1: Synthesis of Compound LC-5

[0113] (1-1) Synthesis of intermediate S1-1: Under nitrogen protection, starting material M1-1 (0.1 mol), starting material M1-2 (0.11 mol), potassium carbonate (0.2 mol), tetra(triphenylphosphine)palladium (0.001 mol), tetrabutylammonium bromide (TBAB) (0.015 mol), toluene (150 mL), isopropanol (150 mL), and water (150 mL) were added to a dry three-necked reaction flask. The mixture was heated to reflux with stirring for 5 h. After the reaction was completed, the reaction solution was cooled to room temperature and extracted three times with toluene (50 mL). The organic phases were combined, washed with water until neutral, dried over anhydrous magnesium sulfate, filtered, and the solvent was evaporated. The solution was purified by silica gel column chromatography to obtain intermediate S1-1 (yield 80%).

[0114] (1-2) Synthesis of intermediate S1-2: Under nitrogen protection, intermediate S1-1 (0.1 mol) was dissolved in DMF (290 mL), followed by the addition of zinc powder (0.3 mol) and zinc chloride (0.05 mol). The mixture was stirred and heated to approximately 80 °C for 8 h. After the reaction was complete, the reaction solution was cooled to room temperature and quenched in 1N-hydrochloric acid aqueous solution (200 mL). The solution was extracted three times with toluene (60 mL), and the organic phases were combined, washed with water until neutral, dried over anhydrous magnesium sulfate, filtered, and the solvent was evaporated. The solution was then purified by silica gel column chromatography to obtain intermediate S1-2 (63% yield).

[0115] (1-3) Synthesis of intermediate S1-3: Add 0.4 mol of 2-iodobenzoic acid IBX to 300 mL of DMSO and stir at room temperature for 30 min. Add intermediate S1-2 (0.1 mol) and continue stirring for 3 h. Filter the reaction solution, add 200 mL of water to the filtrate, and extract three times with 90 mL of ethyl acetate. Combine the organic phases, wash with saturated sodium bicarbonate solution, water, and saturated brine, dry with anhydrous magnesium sulfate, filter, evaporate the solvent, recrystallize from toluene, filter and dry to obtain intermediate S1-3 (yield 47%).

[0116] (1-4) Synthesis of intermediate S1-4: Under nitrogen protection, intermediate S1-3 (0.1 mol) and dichloromethane (400 mL) were added to a dry three-necked reaction flask. The mixture was stirred and cooled to below -78 °C. Diethylaminosulfur trifluoride (DAST) (0.6 mol) was slowly added dropwise. After the addition was complete, the reaction solution was brought back to room temperature and quenched in water (200 mL). The mixture was separated, and the organic phase was washed with saturated sodium bicarbonate solution, water, and saturated brine. The solution was dried over anhydrous magnesium sulfate, filtered, and the solvent was evaporated. The solution was purified by silica gel column chromatography to obtain intermediate S1-4 (77% yield).

[0117] (1-5) Synthesis of intermediate S1-5: Under nitrogen protection, intermediate S1-4 (0.1 mol) was dissolved in DMF (200 mL), followed by the addition of NaHS (0.1 mol). The mixture was stirred and heated to 70 °C for 14 h. After the reaction was complete, the mixture was cooled to room temperature and quenched in water (200 mL). The mixture was extracted three times with ethyl acetate (100 mL), and the organic phase was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, and concentrated to obtain intermediate S1-5 (71% yield).

[0118] (1-6) Synthesis of intermediate S1-6: Under nitrogen protection, intermediate S1-5 (0.1 mol), THF (100 mL), and sodium ethoxide (0.11 mol) were added to a dry three-necked reaction flask and stirred for 15 min. Then, bromoacetaldehyde diethanolamide (0.1 mol) was added, and the mixture was refluxed with stirring for 2 h. After the reaction was completed, the mixture was cooled to room temperature, and saturated sodium hydroxide solution (20 mL) was added. The mixture was extracted three times with ethyl acetate (50 mL), dried over anhydrous magnesium sulfate, concentrated, and purified by silica gel column chromatography to obtain intermediate S1-6 (75% yield).

[0119] (1-7) Synthesis of intermediate S1-7: Under nitrogen protection, intermediate S1-6 (0.1 mol), polyphosphate PPA (0.2 mol), and toluene (500 mL) were added to a dry three-necked reaction flask. The mixture was heated to 110 °C and refluxed for 8 h with stirring. After the reaction was completed, the mixture was cooled to room temperature and quenched in 200 mL of 1N-hydrochloric acid aqueous solution. The mixture was extracted three times with toluene (60 mL), and the organic phases were combined, washed with water until neutral, dried over anhydrous magnesium sulfate, filtered, and the solvent was evaporated. The mixture was then purified by silica gel column chromatography to obtain intermediate S1-7 (yield 63%).

[0120] (1-8) Synthesis of compound LC-5: Under nitrogen protection, intermediate S1-7 (0.1 mol) was dissolved in THF (200 mL), cooled to below -78 °C, and a 2.5 M, 45 mL solution of n-butyllithium in n-hexane was slowly added dropwise. After the addition was complete, the mixture was stirred for 1 h. Iodopropane (0.12 mol) was then slowly added dropwise. After the addition was complete, the reaction mixture was brought back to room temperature and quenched in 2N-hydrochloric acid aqueous solution (200 mL). The mixture was stirred at room temperature for 1 h, extracted three times with ethyl acetate (90 mL), and the organic phases were combined, washed with water until neutral, dried over anhydrous magnesium sulfate, filtered, and the solvent was evaporated. Crystallization was carried out in toluene and filtered to give compound LC-5 (67% yield). MS (m / z) of compound LC-5: 412.02; 1 HNMR (CDCl3, 400MHz): δ8.08-7.01(m,5H), 4.17-4.10(m,2H), 2.78-0.96(m,10H).

[0121] Synthesis Example 2: Synthesis of Compound LC-13

[0122] (2-1) Synthesis of intermediate S2-1: Under nitrogen protection, intermediate S1-7 (0.1 mol, preparation method as described in Synthesis Example 1) was dissolved in THF (200 mL), stirred and cooled to below -78 °C. A solution of n-butyllithium in n-hexane (2.5 M, 45 mL) was slowly added dropwise. After the addition was complete, the reaction was stirred for 1 h. A solution of elemental iodine (0.11 mol) in THF (40 mL) was slowly added dropwise. After the addition was complete, the reaction solution was brought back to room temperature and quenched in 2N-hydrochloric acid aqueous solution (200 mL). The mixture was stirred at room temperature for 1 h. After stirring was stopped, the mixture was extracted three times with ethyl acetate (90 mL). The organic phases were combined, washed with water until neutral, dried over anhydrous magnesium sulfate, filtered, the solvent was evaporated, crystallized from toluene, and filtered to obtain intermediate S2-1 (yield 83%).

[0123] (2-2) Synthesis of compound LC-13: Under nitrogen protection, intermediate S2-1 (0.1 mol), starting material M2-1 (0.11 mol), potassium carbonate (0.2 mol), tetra(triphenylphosphine)palladium (0.001 mol), tetrabutylammonium bromide (TBAB) (0.015 mol), toluene (150 mL), isopropanol (150 mL), and water (150 mL) were added to a dry three-necked reaction flask. The mixture was heated to reflux with stirring for 5 h. After the reaction was completed, the mixture was cooled to room temperature and extracted three times with toluene (50 mL). The organic phases were combined, washed with water until neutral, dried over anhydrous magnesium sulfate, filtered, and the solvent was evaporated. The mixture was then purified by silica gel column chromatography to give compound LC-13 (yield 84%). MS (m / z) of compound LC-13: 488.35; 1 HNMR (CDCl3, 400MHz): δ8.09-7.00 (m, 9H), 4.18-4.10 (m, 2H), 2.64-0.92 (m, 10H).

[0124] Synthesis Example 3: Synthesis of Compound LC-31

[0125] Under nitrogen protection, intermediate S1-7 (0.1 mol, preparation method as described in Synthesis Example 1) was dissolved in THF (200 mL), stirred, and cooled to below -78 °C. A 2.5 M, 45 mL solution of n-butyllithium in n-hexane was slowly added dropwise. After the addition was complete, the reaction was stirred for 1 h. Then, a 50 mL solution of THF containing 0.12 mol of starting material M3-1 was slowly added dropwise. After the addition was complete, the reaction solution was brought back to room temperature and quenched in 200 mL of 2N-hydrochloric acid aqueous solution. The mixture was extracted three times with toluene (90 mL), and the organic phases were combined and transferred to a dry three-necked reaction flask. 0.001 mol of p-toluenesulfonic acid was added, and the mixture was heated under reflux for 3 h with stirring. After the reaction was completed, the mixture was cooled to room temperature, the aqueous phase was separated, washed with saturated sodium bicarbonate solution, water, and saturated brine, dried over anhydrous magnesium sulfate, filtered, the solvent was evaporated, crystallized from anhydrous ethanol, and filtered to obtain compound LC-31 (yield 80%). MS (m / z) of compound LC-31: 464.42; 1 HNMR (CDCl3, 400MHz): δ 8.09-7.01 (m, 5H), 5.97-5.91 (m, 1H), 4.18-4.10 (m, 2H), 2.79-0.89 (m, 13H).

[0126] Synthesis Example 4: Synthesis of Compound LC-86

[0127]

[0128] (4-1) Synthesis of intermediate S4-7: Referring to the synthesis method in steps (1-1) to (1-7) of the above-mentioned synthesis example 1, only the raw material M1-1 is replaced with the raw material M4-1 to obtain intermediate S4-7.

[0129] (4-2) Synthesis of intermediate S4-8: Referring to the synthesis method in step (2-1) of the above-mentioned synthesis example 2, intermediate S4-8 can be obtained by simply replacing intermediate S1-7 with intermediate S4-7.

[0130] (4-3) Synthesis of compound LC-86: Under nitrogen protection, intermediate S4-8 (0.1 mol), starting material M4-2 (0.1 mol), CuI (0.02 mol), potassium carbonate (0.2 mol), and DMF (400 mL) were added to a dry three-necked reaction flask. The mixture was stirred and heated to 100 °C for 14 h. After the reaction was complete, the mixture was cooled to room temperature, washed with water, extracted with dichloromethane, and the organic phase was collected. The phase was washed with saturated sodium chloride solution, dried over anhydrous sodium sulfate, and purified by column chromatography to give compound LC-86 (72% yield). MS (m / z) of compound LC-86: 504.36; 1 HNMR (CDCl3, 400MHz): δ8.10-6.75(m,9H),5.24-5.20(m,2H),3.78(s,3H),2.68-0.93(m,7H).

[0131] Synthesis Example 5: Synthesis of Compound LC-116

[0132] Under nitrogen protection, intermediate S4-8 (0.1 mol, prepared according to synthesis example 4), starting material M5-1 (0.11 mol), potassium carbonate (0.2 mol), tetra(triphenylphosphine)palladium (0.001 mol), tetrabutylammonium bromide (TBAB) (0.015 mol), toluene (150 mL), isopropanol (150 mL), and water (150 mL) were added to a dry three-necked reaction flask. The mixture was heated to reflux with stirring for 5 h. After the reaction was completed, the reaction solution was cooled to room temperature and extracted three times with toluene (50 mL). The organic phases were combined, washed with water until neutral, dried over anhydrous magnesium sulfate, filtered, and the solvent was evaporated. The solution was purified by silica gel column chromatography to give compound LC-116 (yield 82%). MS (m / z) of compound LC-116: 570.04; 1 HNMR (CDCl3, 400MHz): δ8.11-7.12(m,9H), 3.84-3.45(m,3H), 2.69-0.93(m,19H).

[0133] This invention provides exemplary methods for synthesizing the above-mentioned compounds. Other compounds for which no specific synthesis method is provided can also be prepared using similar methods, requiring only the replacement of raw materials. These methods will not be elaborated here. Alternatively, those skilled in the art can prepare these compounds using other methods in the prior art.

[0134] It should be noted that the following performance parameters of the liquid crystal compound are obtained by linear fitting according to conventional testing methods in the art. The specific meanings of each performance parameter are as follows: Δε represents dielectric anisotropy (25℃, 1000Hz); γ1 represents rotational viscosity (mPa·s, 25℃); Δn represents optical anisotropy (25℃); and Cp is the clearing point (℃).

[0135] Test Example 1 The performance parameters of the liquid crystal compounds obtained in Synthesis Examples 1-5 and liquid crystal compound D-1 were compared, and the results are shown in Table 1. Compound D-1 was prepared using a method similar to that in Synthesis Examples 1-5. .

[0136] Table 1 Performance test results of liquid crystal compounds

[0137] As can be clearly seen from the test results in Table 1, compared with compound D-1, the liquid crystal compound provided by the present invention has suitable rotational viscosity, higher dielectric anisotropy and optical anisotropy.

[0138] Composition Example 1 The liquid crystal compound LC-5 prepared in Example 1 of this invention was combined with other liquid crystal monomers to form a composition. The composition and proportions of the composition are shown in Table 2 below, where the proportions of the components are by weight percentage.

[0139] Table 2

[0140] Comparative Example 1 The only difference from the composition example 1 is that the liquid crystal compound LC-5 is replaced with the liquid crystal compound D-1 described above.

[0141] Test Example 2 The performance parameters of the compositions in Example 1 and Comparative Example 1 were tested, and the results are shown in Table 3 below: Table 3

[0142] As can be seen from Table 3, when the liquid crystal compound LC-5 of the present invention is specifically applied to a conventional liquid crystal composition, the dielectric anisotropy Δε of the liquid crystal composition can be improved, while maintaining a relatively low rotational viscosity γ1 and an appropriate refractive index anisotropy Δn. The resulting liquid crystal composition has significant fast response characteristics and low voltage driving characteristics.

[0143] Although the present invention has been described in detail above with general descriptions and specific embodiments, modifications or improvements can be made to it, which will be obvious to those skilled in the art. Therefore, all such modifications or improvements made without departing from the spirit of the present invention fall within the scope of protection claimed by the present invention.

Claims

1. A polyfluorinated liquid crystal compound having the structure shown in Formula I: Equation I; in, X is selected from O or S; R1 and R2 are each independently selected from any one or more combinations of halogenated or unsubstituted C1-C12 alkyl, halogenated or unsubstituted C1-C12 alkoxy, halogenated or unsubstituted C3-C10 cycloalkyl, halogenated or unsubstituted C2-C12 alkenyl, and halogenated or unsubstituted C2-C12 alkenyloxy. Ring A, ring B, and ring C are each independently selected from any one or more combinations of halogenated or unsubstituted C6-C14 arylene, halogenated or unsubstituted C5-C8 cycloalkyl, halogenated or unsubstituted C5-C8 cycloalkenyl, and halogenated or unsubstituted C3-C8 saturated or unsaturated oxy-containing heterocyclic groups. Z1, Z2, and Z3 are each independently selected from any one or more combinations of single bonds, double bonds, oxygen atoms, C1-C4 alkylene groups, C1-C4 alkoxy groups, -COO-, -OCO-, -O-C1-C4 alkylene-O-, and C2-C4 alkenyl groups; optionally, one or more hydrogen atoms in the C1-C4 alkylene groups, C1-C4 alkoxy groups, and C2-C4 alkenyl groups are substituted with halogen atoms; m, n, and k are each independently selected from 0, 1, or 2.

2. The polyfluorinated liquid crystal compound according to claim 1, characterized in that, R1 and R2 are each independently selected from any one or more combinations of halogenated or unsubstituted C1-C5 alkyl, halogenated or unsubstituted C1-C5 alkoxy, halogenated or unsubstituted C3-C8 cycloalkyl, halogenated or unsubstituted C2-C8 alkenyl, and halogenated or unsubstituted C2-C8 alkenyloxy. Preferably, R1 and R2 are each independently selected from any one or more combinations of C1-C5 alkyl, C1-C5 fluoroalkyl, C1-C5 alkoxy, C1-C5 fluoroalkoxy, C3-C6 cycloalkyl, C3-C6 fluorocycloalkyl, C2-C4 alkenyl, and C2-C4 fluoroalkenyl. Preferably, R1 and R2 are each independently selected from any one or more combinations of methyl, ethyl, n-propyl, n-butyl, n-pentyl, fluoromethyl, fluoroethyl, fluoron-propyl, fluoron-butyl, fluoron-pentyl, methoxy, ethoxy, propoxy, butoxy, pentoxy, fluoromethoxy, fluoroethoxy, fluoropropoxy, fluorobutoxy, fluoropentoxy, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, propenyl, butenyl, fluorovinyl, fluoropropenyl, and fluorobutenyl. Preferably, R1 and R2 are each independently selected from any one or more combinations of methyl, ethyl, n-propyl, methoxy, ethoxy, propoxy, and vinyl.

3. The polyfluorinated liquid crystal compound according to claim 1 or 2, characterized in that, Ring A, ring B, and ring C are each independently selected from any one or more combinations of halogenated or unsubstituted 1,4-phenylene, halogenated or unsubstituted 1,4-cyclohexylene, halogenated or unsubstituted 1,4-cyclohexenylene, halogenated or unsubstituted tetrahydropyranylene, and halogenated or unsubstituted 1,3-dioxane. Preferably, ring A, ring B, and ring C are each independently selected from any one or more combinations of fluorinated or unsubstituted 1,4-phenylene, fluorinated or unsubstituted 1,4-cyclohexylene, fluorinated or unsubstituted 1,4-cyclohexenylene, fluorinated or unsubstituted tetrahydropyranylene, and fluorinated or unsubstituted 1,3-dioxane. Preferably, ring A, ring B, and ring C are each independently selected from any one or more combinations of 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyranylene, 1,3-dioxane, and 1,4-phenylene containing 1-4 fluorine substituents; Preferably, ring A, ring B, and ring C are each independently selected from any of the following groups: , , , , , or .

4. The polyfluorinated liquid crystal compound according to any one of claims 1-3, characterized in that, Z1, Z2, and Z3 are each independently selected from any one or more combinations of single bonds, double bonds, oxygen atoms, C1-C4 alkylene groups, C1-C4 alkoxy groups, -COO-, -OCO-, -O-C1-C4 alkylene-O-, and C2-C4 alkenyl groups; optionally, one or more hydrogen atoms in the C1-C4 alkylene groups, C1-C4 alkoxy groups, and C2-C4 alkenyl groups are replaced by fluorine atoms; Preferably, Z1, Z2, and Z3 are each independently selected from any one or more combinations of single bonds, double bonds, oxygen atoms, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -CH2CH2-, -COO-, -OCO-, -CHFO-, -OCHF-, -OCHFO-, -CF2-, -CHF-, -CH2-, -CHFCH2-, -CH2CHF-, -CHFCHF-, -CF2CH2-, -CH2CF2-, -CF2CHF-, -CHFCF2-, -CF2CF2-, -CH=CH-, -CF=CH-, -CH=CF-, and -CF=CF-. Preferably, Z1, Z2, and Z3 are each independently selected from single bonds, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -CH2CH2-, -COO-, -OCO-, or -CF2CF2-; Preferably, Z1, Z2, and Z3 are each independently selected from single bonds, -CF2O-, -CH2O-, -CH2CH2-, or -COO-; Preferably, Z1 and Z2 are each independently selected from single bonds, -CF2O-, -CH2O-, -CH2CH2- or -COO-, and Z3 is a single bond.

5. The polyfluorinated liquid crystal compound according to any one of claims 1-4, characterized in that, The polyfluorinated liquid crystal compound has any of the following structures: ， ， ， ， The definitions of each symbol are the same as those in Equation I.

6. The polyfluorinated liquid crystal compound according to any one of claims 1-5, characterized in that, The polyfluorinated liquid crystal compound has a structure as shown in any of Formulas I-1 to I-120: 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , In the above equations, the definitions of R1, R2, and X are the same as those in Equation I.

7. The liquid crystal compound according to any one of claims 1-6, characterized in that, The polyfluorinated liquid crystal compound includes any of the compounds shown in the following structures: 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 。 8. A liquid crystal material composition comprising the polyfluorinated liquid crystal compound according to any one of claims 1-7; Preferably, the polyfluorinated liquid crystal compound has a mass percentage content of 1-60% in the liquid crystal material composition, more preferably 1-40%, more preferably 5-20%, and even more preferably 5-10%.

9. A liquid crystal display device comprising a polyfluorinated liquid crystal compound according to any one of claims 1-7, or comprising a liquid crystal material composition according to claim 8; Preferably, the liquid crystal display device includes TN, ADS, VA, PSVA, FFS, and IPS liquid crystal displays.

10. The application of the polyfluorinated liquid crystal compound as described in any one of claims 1-7 or the liquid crystal material composition as described in claim 8 in the field of liquid crystal displays; Preferably, the application includes the use of the polyfluorinated liquid crystal compound or the liquid crystal material composition in a liquid crystal display device; Preferably, the polyfluorinated liquid crystal compound or the liquid crystal material composition is used as the liquid crystal material in the liquid crystal display device; Preferably, the liquid crystal display device includes TN, ADS, VA, PSVA, FFS, and IPS liquid crystal displays.

Images