CN112225675A - Arylamine compound, liquid crystal aligning agent prepared from arylamine compound, liquid crystal aligning film and liquid crystal display element - Google Patents
Arylamine compound, liquid crystal aligning agent prepared from arylamine compound, liquid crystal aligning film and liquid crystal display element Download PDFInfo
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- CN112225675A CN112225675A CN202011002466.7A CN202011002466A CN112225675A CN 112225675 A CN112225675 A CN 112225675A CN 202011002466 A CN202011002466 A CN 202011002466A CN 112225675 A CN112225675 A CN 112225675A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
- C07C237/28—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton
- C07C237/40—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton having the nitrogen atom of the carboxamide group bound to a carbon atom of a six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
Abstract
The invention discloses an arylamine compound and a liquid crystal orientation agent, a liquid crystal orientation film and a liquid crystal display element prepared from the arylamine compound, and belongs to the technical field of liquid crystal display. The liquid crystal alignment film prepared by the liquid crystal alignment agent has the advantages of high film-forming transmittance and high contrast of the prepared liquid crystal display element.
Description
Technical Field
The invention relates to the technical field of liquid crystal display, in particular to an arylamine compound, a liquid crystal aligning agent prepared from the arylamine compound, a liquid crystal aligning film and a liquid crystal display element.
Background
Liquid crystal display elements are classified into various modes according to the electrode structure and the physical properties of the liquid crystal molecules used. Currently known liquid crystal display devices are classified into various liquid crystal display elements such as Twisted Nematic (TN) type, Super Twisted Nematic (STN) type, Fringe Field Switching (FFS) type Vertical Alignment (VA) type, and In-plane switching (IPS) type. Polyimide is excellent in heat resistance, corrosion resistance, mechanical strength, and affinity with liquid crystal, and thus is a preferred material for liquid crystal alignment films.
The development of the technology of the liquid crystal display element is achieved not only by the improvement of the original structure and the driving method but also by the constituent members used in the element. A liquid crystal alignment film in a liquid crystal display device is one of important materials concerning display quality, and it is apparently important to improve the performance of the liquid crystal alignment film in accordance with the improvement of the quality of the liquid crystal display device. In a liquid crystal display device, if a liquid crystal alignment film having a low transmittance is used, the luminance of the liquid crystal display device is reduced. Meanwhile, the contrast is also an important parameter of the liquid crystal display element, and under a reasonable brightness value, the higher the contrast is, the richer the color gradation which can be realized by the liquid crystal display element is, the stronger the visual sense is, and the clearer and more striking the image is; and the contrast is small, so that the whole picture is shown as dark.
Disclosure of Invention
In order to solve the problems in the prior art, the applicant of the invention provides an arylamine compound, a liquid crystal aligning agent prepared from the arylamine compound, a liquid crystal aligning film and a liquid crystal display element. The liquid crystal alignment film prepared by the liquid crystal alignment agent has the advantages of high film-forming transmittance and high contrast of the prepared liquid crystal display element.
The technical scheme for solving the technical problems is as follows:
an arylamine compound, the structure of which is shown in a general formula (1):
in the general formula (1), R1、R2Each independently represents a H atom or a structure represented by the general formula (2), and R1、R2Not H atoms at the same time; x1、X2Each independently represents a hydrogen atom, a halogen atom, C1-5One of alkyl groups;
in the general formula (2), R3Is represented as C1-5An alkylene group of (a); r4、R5Independently represent H atom, C1-5Alkyl, tert-butoxycarbonyl or tert-butoxycarbonyl substituted alkyl.
In a preferred scheme, the specific structure of the arylamine compound is shown as formula 1-1 to formula 1-5:
the liquid crystal aligning agent is prepared from the arylamine compound, and comprises a polymer A obtained by reacting a tetracarboxylic dianhydride component a with an amine component b; the amine component contains the arylamine compound b-1.
The tetracarboxylic dianhydride component a at least comprises one of 1,2,3, 4-cyclobutane tetracarboxylic dianhydride and 1, 3-dimethyl-1, 2,3, 4-cyclobutane tetracarboxylic dianhydride.
The tetracarboxylic dianhydride component a also comprises one or more of 3,3 ', 4, 4' -diphenyl sulfone tetracarboxylic dianhydride, pyromellitic dianhydride, 1,2,4, 5-cyclohexane tetracarboxylic dianhydride, 3 ', 4, 4' -diphenyl tetracarboxylic dianhydride, 1,2,3, 4-cyclopentane tetracarboxylic dianhydride and 2,3, 5-tricarboxycyclopentyl acetic dianhydride.
The amine component b comprises other arylamine compounds b-2, and the other arylamine compounds b-2 are p-phenylenediamine, m-phenylenediamine, 2-bis (4-aminophenyl) hexafluoropropane, 4- (4-heptylcyclohexyl) phenyl-3, 5-diaminobenzoate, 2 '-dimethyl-4, 4' -diaminobiphenyl, 4 '-diaminodiphenyl ether, 1, 4-bis (4-aminophenoxy) benzene, 4' -diaminobenzophenone, 1, 2-bis (4-aminophenoxy) ethane, 1, 3-bis (4-aminophenoxy) propane, 1, 4-bis (4-aminophenoxy) butane, 1, 5-bis (4-aminophenoxy) pentane, 1, 6-bis (4-aminophenoxy) hexane, N '-bis (4-aminophenyl) piperazine, 1, 5-diaminonaphthalene, 1, 8-diaminonaphthalene, p-aminophenylethylamine, 4' -diaminodiphenylmethane, 4 '-diaminodiphenylethane, 4' -diaminobenzamide, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2, 4-diaminododecyloxybenzene, 2, 4-diaminooctadecyloxybenzene, 1- (4- (4-pentylcyclohexylcyclohexyl) phenoxy) -2, 4-diaminobenzene, 1- (4- (4-heptylcyclohexyl) phenoxy) -2, 4-diaminobenzene and 3, 5-diaminobenzoic acid.
The liquid crystal orientation agent also comprises a solvent component, wherein the solvent component is one or more of N-methyl-2-pyrrolidone, gamma-butyrolactone, N-dimethylformamide, N-dimethylacetamide, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol dimethyl ether and diethylene glycol monomethyl ether ethyl ester.
A liquid crystal alignment film comprises the liquid crystal alignment agent.
A liquid crystal display element comprises the liquid crystal orientation film.
The preparation method of the polymer A obtained by reacting the tetracarboxylic dianhydride component a with the amine component b comprises the following steps: the polyamic acid solution is synthesized by reacting a tetracarboxylic dianhydride component a and an aromatic amine component b in the presence of an organic solvent at-20 to 150 ℃, preferably 0 to 100 ℃, for 30 minutes to 48 hours, preferably 1 to 24 hours. The solvent used for the polymerization reaction may be the same as or different from the solvent in the liquid crystal aligning agent, and the solvent used for the polymerization reaction is not particularly limited as long as it can dissolve the monomer and the polymer. The solvent for the polymerization reaction includes, but is not limited to, N-methyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, and γ -butyrolactone, and may be used in combination of one or more of them. Wherein, in a reaction liquid composed of a reaction mixture obtained by mixing the tetracarboxylic dianhydride component a and the aromatic amine component b and the solvent, the weight ratio of the reaction mixture in the reaction liquid is 1-50%, and more preferably 10-25%.
The polyamic acid solution obtained may be obtained as a polyamic acid solid by evaporating the solvent under reduced pressure, or as a polyamic acid solid powder by pouring the reaction system into a large amount of solvent under sufficient stirring, precipitating several times, washing with the solvent, and then drying at normal temperature or under heating. The solvent used for the precipitation is not particularly limited as long as the solvent used can precipitate the polyamic acid, and examples thereof include one or a mixture of several of methanol, ethanol, water, propanol, isopropanol, butanol, butyl cellosolve, toluene, ethyl acetate, ethylcarboxy and a halogen-containing solvent.
Further, the polyamic acid solid powder obtained by polymerization reaction is dissolved in a solvent to prepare the liquid crystal aligning agent, wherein the weight ratio of the polyamic acid solid accounts for 1-40%, and the liquid crystal aligning agent is more preferably 2-20%.
When the weight ratio of the polyamic acid solid in the liquid crystal aligning agent is less than 2%, the film thickness of the coating film becomes too small to obtain a good liquid crystal alignment film, while when the weight ratio of the polyamic acid solid in the liquid crystal aligning agent exceeds 20%, the film thickness of the coating film becomes too large to obtain a good liquid crystal alignment film, and therefore, the film thickness is more preferably 2% to 20%.
Further, the molar ratio of the tetracarboxylic dianhydride component a to the aromatic amine component b is 100:10 to 200, more preferably 100: 100-120.
Furthermore, in the aromatic amine component b, the molar percentage of the aromatic amine compound b-1 is 0.1-100%, and more preferably 5-70%.
Furthermore, the liquid crystal aligning agent of the present invention may further include a solvent for reducing the surface tension of the solution and increasing the leveling effect of the aligning agent, wherein the solvent includes one or more of methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, tetrahydrofuran, dichloromethane, chlorobenzene, 1, 2-dichloroethane, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclobutanone, methyl acetate, ethyl acetate, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol dimethyl ether, and accounts for 0-70% of the total weight of the solvent components, preferably 10-60% of the total weight of the solvent.
The present invention further provides a method for preparing polyimide, which can adopt but not limited to the following two imidization methods, namely a thermal imidization method or a chemical imidization method.
The thermal imidization method is to directly heat and dehydrate the polyimide solid into a ring, and the heating temperature is preferably 150-300 ℃.
Chemical imidization is to perform imidization at a relatively low temperature, and hydrolysis of a polymer is not likely to occur during imidization, resulting in a decrease in molecular weight.
The chemical imidization method comprises the following steps: the polyamic acid is dehydrated and ring-closed at a lower temperature in the presence of a dehydrating agent and a catalyst to prepare the polyimide.
The solvent for the imidization reaction may be the same as that in the liquid crystal aligning agent.
Wherein the weight ratio of the polyamic acid to the imidization solvent is 1: 2-25; imidization rate of polyamic acid is 10-100%; the temperature of imidization reaction is 0-110 ℃, and more preferably 30-80 ℃; the reaction time is 1 to 100 hours, more preferably 2 to 10 hours; the dehydrating agent can be selected from an acid anhydride compound, such as acetic anhydride, trimellitic anhydride, pyromellitic anhydride, propionic anhydride or trifluoroacetic anhydride; the molar ratio of the raw material tetracarboxylic dianhydride and the dehydrating agent used in the polyamic acid is preferably 1:0.1 to 10, more preferably 1: 1-5; the catalyst can be selected from pyridine, 4-methylpyridine, trimethylamine, triethylamine, tributylamine or trioctylamine; the molar ratio of the dehydrating agent to the catalyst is 1:0.1 to 5, more preferably 1: 2-4.
The liquid crystal aligning agent of the present invention can be formed by recovering the imidized polymer and redissolving the organic solvent, with the catalyst or the like added remaining in the solution after the imidization of the polyamic acid.
The solution of the polyimide obtained as described above is injected into a solvent while sufficiently stirring, whereby a polymer can be precipitated. After several precipitations and drying, the powder of the purified polyamic acid can be obtained.
The precipitation solvent is not particularly limited, and examples thereof include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene.
The invention further provides a preparation method of the liquid crystal aligning agent,
the liquid crystal aligning agent of the present invention contains a polymer A. The liquid crystal aligning agent of the present invention may contain, in addition to the polymer a, other polymers such as: polyamic acids, polyimides, polyamic acid esters, polyesters, polyamides, and the like.
Furthermore, the liquid crystal aligning agent can also comprise a molecular weight regulator, and the molecular weight regulator is added in the synthesis process of the polymer to regulate the molecular weight of the polymer, so that the feasibility of a subsequent coating process is ensured. The molecular weight regulator comprises one or more of n-heptylamine, phenyl isocyanate, aniline, n-butylamine, n-pentylamine, n-hexylamine, naphthyl isocyanate, maleic anhydride, phthalic anhydride, o-cyclohexanedicarboxylic anhydride and succinic anhydride, and the molar ratio of the molecular weight regulator to the tetracarboxylic dianhydride component a is 0.001-15: 100. preferably, the molar ratio of the molecular weight regulator to the tetracarboxylic dianhydride component a is from 0.4 to 6: 100.
further, the liquid crystal aligning agent of the present invention may further include an additive for increasing the stability of the liquid crystal alignment film or improving the adhesion between the liquid crystal alignment film and the substrate, and the liquid crystal aligning agent may be prepared by mixing the polymer and the additive in a solvent at 10 to 100 ℃ under stirring, more preferably 25 to 75 ℃.
The additive comprises an epoxy additive and/or a silane compound additive with functional groups, wherein the addition amount of the epoxy additive is 0.01-15% of the total weight of polyamic acid or polyimide in the liquid crystal phase taking agent, preferably, the addition amount of the epoxy additive is 0.5-10% of the total weight of the polymer, the addition amount of the silane compound additive with functional groups is 0.01-10% of the total weight of the polymer, and preferably, the addition amount of the silane compound additive with functional groups is 0.5-5% of the total weight of the polymer;
the epoxy additive is one or more of polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, glycerol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, N, N, N ', N ' -tetracyclooxypropyl-4, 4 ' -diaminodiphenylmethane or 3- (N, N-diglycidyl) aminopropyltrimethoxysilane;
the silane compound additive with functional groups is one or more of 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane or N-bis (ethylene oxide) -3-aminopropyltriethoxysilane.
The invention also provides an application of the liquid crystal orientation agent in a liquid crystal orientation film, and the liquid crystal orientation film is prepared by using the liquid crystal orientation agent.
The liquid crystal orientation film contains the liquid crystal orientation agent, the aromatic amine monomer used for preparing the liquid crystal orientation agent contains the aromatic amine compound b-1 with a specific structure, the prepared liquid crystal orientation agent is light in color, and meanwhile, the polar group in the b-1 monomer can improve the van der Waals force of the liquid crystal orientation agent on the surface of liquid crystal molecules, so that the anchoring capability of the liquid crystal orientation agent on the liquid crystal molecules is improved, and a liquid crystal display element has the characteristic of high contrast. Therefore, the liquid crystal alignment film prepared by the liquid crystal alignment agent has the advantages of high film-forming transmittance and high contrast of the prepared liquid crystal display element. In the examples, the transmittance of the liquid crystal alignment film prepared using the alignment agent was evaluated: more than 95% of the samples are judged to be optimal; and (3) evaluating the contrast ratio: when the contrast ratio of the liquid crystal display element prepared by the aligning agent is 1800 or more, the contrast ratio is evaluated to be excellent.
The liquid crystal alignment film is obtained by applying a liquid crystal alignment agent to a substrate and curing the liquid crystal alignment agent. The alignment method of the liquid crystal alignment film is not particularly limited, and a photo-alignment method or a rubbing alignment method may be used, but not limited thereto. Wherein, the photo-alignment refers to exposing the surface of the film by polarized light to form a photo-aligned liquid crystal alignment film; the rubbing orientation is that a cloth made of nylon, rayon, cotton or other fibers is wound on a roller and rubbed in a certain direction to form a rubbing oriented orientation film.
The invention also provides an application of the liquid crystal aligning agent in a liquid crystal display element, and the liquid crystal display element is prepared by using the liquid crystal aligning agent.
The preparation method of the liquid crystal display element comprises the following steps: two substrates are prepared, each of which is coated with a layer of liquid crystal alignment film prepared from the liquid crystal alignment agent of the invention, and a liquid crystal box is prepared by filling liquid crystal between the two substrates.
The liquid crystal display element produced by using the liquid crystal aligning agent of the present invention is suitable for various types of liquid crystal display elements, and may be a Twisted Nematic (TN) type or Super Twisted Nematic (STN) type, a Vertical Alignment (VA) type, an In-plane switching (IPS) type, a Fringe Field Switching (FFS) type, or the like. Among the above liquid crystal display elements, IPS and FFS type liquid crystal display elements are preferable.
The beneficial technical effects of the invention are as follows:
the liquid crystal alignment film of the liquid crystal aligning agent of the present invention has a high transmittance, and the mechanism of the occurrence of the advantageous effect is not clear, and it is considered that the liquid crystal alignment film obtained by the aligning agent has a high transmittance because the absorption of light in the visible light region by the specific arylamine compound b-1 monomer used is small.
The liquid crystal alignment film of the liquid crystal aligning agent of the present invention has a characteristic of high contrast, and the mechanism of the occurrence of the advantageous effect is not clear, and it is considered that the polar group in the monomer of the specific arylamine compound b-1 used can improve the van der waals force to the surface liquid crystal molecules, thereby improving the anchoring ability to the liquid crystal molecules, and the liquid crystal display element exhibits a characteristic of high contrast.
The method is simple, has wide market prospect and is suitable for large-scale application and popularization.
Drawings
FIG. 1 is a UV-Vis spectrum of the liquid crystal alignment film obtained in example 1.
FIG. 2 is a UV-Vis spectrum of the liquid crystal alignment film obtained in comparative example 1.
Detailed Description
In the following specific examples, the liquid crystal aligning agent will be described only with respect to IPS and FFS type liquid crystal display devices, but the present invention is not limited thereto.
Synthesis example of Compound (I)
Synthesis example of arylamine Compound
Compound Synthesis example 1
The compound represented by the structural formula (1-1) can be synthesized according to the following synthetic scheme 1:
(1) synthesis of Compound 1-1-a
A1L three-necked round-bottomed flask was charged with 2, 4-diaminoiodobenzene (23.40g, 100 mmol), Et3N (50.60g, 500 mmol) and 200g of toluene, heating the system to 60 ℃, then slowly adding a mixed solution of 3-nitro-4-methylbenzoyl chloride (41.91g, 210 mmol) and 200g of toluene dropwise into the system, completing dropwise addition within 0.5 hour, then heating the system to 80 ℃, stirring for 8 to 10 hours, and tracking by TLC until no 2, 4-diaminoiodobenzene remains as a raw material. Cooling the reaction system to room temperature, washing with 500mL of 3 deionized water for three times, removing the upper organic phase to obtain a light yellow solid, and adding500mL of a methanol/water mixture was slurried, and the suspension was filtered and dried to give compound 1-1-a in 75% yield.
(2) Synthesis of Compound 1-1-b
A1L three-necked round-bottomed flask was charged with 1-1-a (56.03g, 100 mmol) and Pd (PPh)3)4(2.31g, 2 mmol), CuI (0.38g, 2 mmol), Et3N (50.60g, 500 mmol) and 200mL of DMF solvent are stirred at 20-40 ℃ for 30min, then a mixed solution of propargylamine (9.14g, 110 mmol) and 100mL of DMF solvent is added dropwise into the system, the dropwise addition is finished within 1-2 h, and the reaction is carried out at 20-40 ℃ for 4-10 h under the condition of heat preservation.
After the reaction, 500mL of 1, 2-dichloroethane and 500mL of hydrochloric acid solution with the concentration of 1mol/L are added into the system, the organic phase is washed with 500mL of 3 deionized water for three times, the organic phase is dried to obtain a light yellow solid, and the compound 1-1-b is obtained with the yield of 63%.
(3) Synthesis of Compound 1-1
The obtained compound 1-1-b (25.78g, 50 mmol), 5% palladium on carbon (2.86g, water, solid content: 45%) and 600g of tetrahydrofuran were charged into a 1L autoclave, the autoclave was sealed, and after replacement with hydrogen gas for 3 to 5 times, the pressure of hydrogen gas was increased to 0.5 to 1.0MPa, and the reaction was carried out at 45 to 55 ℃ with stirring. After the reaction is finished, filtering the catalyst by using a filter membrane with the aperture of 0.2 mu m, removing the solvent from the filtrate, adding 60g of ethanol into the obtained solid, stirring for 30min, and obtaining a white solid compound 1-1 with the yield of 92% through suction filtration and drying.
The compound 1-1 has high resolution mass spectrum, ESI source, positive ion mode and molecular formula C27H33N5O2Theoretical value 459.26, test value 459.48. Elemental analysis (C)27H33N5O2) Theoretical value C: 70.59, H: 7.24, N: 15.24, O: 6.96, found C: 70.61, H: 7.23, N: 15.25, O: 6.94. elemental analysis tester brand: united states alliance, model number: CE-440.
Compound Synthesis example 2
The compound represented by structural formula (1-2) can be synthesized according to the following synthetic scheme 2:
(1) synthesis of Compound 1-2-a
A1L three-necked round-bottomed flask was charged with 1, 4-diamino-2, 5-diiodobenzene (35.99g, 100 mmol), Et3N (50.60g, 500 mmol) and 200g of toluene, the system was warmed to 60 ℃ and then a mixed solution of 2-nitro-5-fluorobenzoyl chloride (42.75g, 210 mmol) and 200g of toluene was slowly added dropwise to the system over about 0.5 hour, and then the system was warmed to 80 ℃ and stirred for 8 to 10 hours, followed by TLC until no 1, 4-diamino-2, 5-diiodobenzene remained as a raw material. Then cooling the reaction system to room temperature, washing with 500mL of 3 deionized water for three times, removing the upper organic phase to obtain a light yellow solid, adding 500mL of a methanol/water mixed solution for pulping, filtering and drying the suspension to obtain the compound 1-2-a with 76% yield.
(2) Synthesis of Compound 1-2-b
1-2-a (64.91g, 100 mmol) and Pd (PPh) were placed in a 1L three-necked round-bottomed flask3)4(2.31g, 2 mmol), CuI (0.38g, 2 mmol), Et3N (50.60g, 500 mmol) and 200mL of DMF solvent are stirred for 30min at 20-40 ℃, then a mixed solution of propargylamine (7.60g, 110 mmol) and 100mL of DMF solvent is added dropwise into the system, the dropwise addition is finished within 1-2 hours, and the temperature is raised to 20-40 ℃ for reaction for 4-10 hours under the condition of heat preservation.
After the reaction, 500mL of 1, 2-dichloroethane and 500mL of hydrochloric acid solution with the concentration of 1mol/L are added into the system, the organic phase is washed with 500mL of 3 deionized water for three times, the organic phase is dried to obtain a light yellow solid, and the compound 1-1-b is obtained with the yield of 65%.
(3) Synthesis of Compound 1-2-c
1-2-b (57.65g, 100 mmol), ethyl iodide (32.75g, 210 mmol), potassium tert-butoxide (23.56g, 210 mmol), palladium acetate (0.224g, 1 mmol), XPhos (0.953g, 2 mmol) and 300g toluene were put into a 1L three-necked round-bottomed flask, the mixture was heated to 110 ℃ and refluxed with stirring for 3 hours, followed by TLC until no starting material 1-2-b remained, the reaction mixture was transferred to a separatory funnel and washed with water to neutrality, the solvent toluene was removed, the filtrate was concentrated to 100g, 220g of ethanol was added to precipitate a yellow solid, the cake was filtered and dried to obtain 49.98g of yellow crystals, and the reaction yield was 79%.
(4) Synthesis of Compound 1-2
The obtained compound 1-2-c (31.63g, 50 mmol), 5% palladium on carbon (3.51g, water content, solid content: 45%) and 600g of tetrahydrofuran were charged into a 1L autoclave, the autoclave was sealed, and after replacing 3 to 5 times with hydrogen, the pressure of hydrogen was increased to 0.5 to 1.0MPa, and the reaction was carried out at 45 to 55 ℃ with stirring. After the reaction is finished, filtering the catalyst by using a filter membrane with the aperture of 0.2 mu m, removing the solvent from the filtrate, adding 60g of ethanol into the obtained solid, stirring for 30min, and obtaining a white solid compound 1-2 with the yield of 90% through suction filtration and drying.
The compound 1-2 has high resolution mass spectrum, ESI source, positive ion mode and molecular formula C32H42F2N6O2Theoretical value 580.33, test value 580.58. Elemental analysis (C)32H42F2N6O2) Theoretical value C: 66.18, H: 7.29, F: 6.54, N: 14.47, O: 5.51, found C: 66.16, H: 7.30, F: 6.55, N: 14.46, O: 5.52. elemental analysis tester brand: united states alliance, model number: CE-440.
Compound Synthesis example 3
The compounds represented by structural formulae (1-3) can be synthesized according to the following scheme 3:
(1) synthesis of Compound 1-3-a
A1L three-necked round-bottomed flask was charged with 2, 4-diaminoiodobenzene (23.40g, 100 mmol), Et3N (50.60g, 500 mmol) and 200g of toluene, heating the system to 60 ℃, then slowly dropwise adding a mixed solution of p-nitrobenzoyl chloride (38.97g, 210 mmol) and 200g of toluene into the system for about 0.5 hour until dropwise adding is finished, then heating the system to 80 ℃, and stirringStirring for 8-10 h, and tracking by TLC until no 2, 4-diaminoiodobenzene remains. Then cooling the reaction system to room temperature, washing with 500mL of 3 deionized water for three times, removing the upper organic phase to obtain a light yellow solid, adding 500mL of a methanol/water mixed solution for pulping, filtering and drying the suspension to obtain the compound 1-3-a with 73% yield.
(2) Synthesis of Compound 1-3-b
1-3-a (53.23g, 100 mmol) and Pd (PPh) were put in a 1L three-necked round-bottomed flask3)4(2.31g, 2 mmol), CuI (0.38g, 2 mmol), Et3N (50.60g, 500 mmol) and 200mL of DMF solvent are stirred at 20-40 ℃ for 30min, then a mixed solution of propargylamine (6.06g, 110 mmol) and 100mL of DMF solvent is added dropwise into the system, the dropwise addition is finished within 1-2 h, and the reaction is carried out at 20-40 ℃ for 4-10 h under the condition of heat preservation.
After the reaction, 500mL of 1, 2-dichloroethane and 500mL of hydrochloric acid solution with the concentration of 1mol/L are added into the system, the organic phase is washed with 500mL of 3 deionized water for three times, and the organic phase is dried to obtain a light yellow solid with the yield of 68%.
(3) Synthesis of Compound 1-3-c
1-3-b (45.94g, 100 mmol) and 300g of dichloroethane were charged into a 1L three-necked round-bottomed flask, the temperature was lowered to 0 to 10 ℃ and a solution of di-tert-butyl dicarbonate (21.83g, 100 mmol) in 200g of dichloroethane was added dropwise over 0.5 to 1 hour. After the addition, the mixture was stirred at room temperature for 24 hours. After the reaction was completed, the reaction solution was washed with 500mL of deionized water to remove methylene chloride, whereby 49.8g of a pale yellow solid was obtained in a yield of 89%.
(4) Synthesis of Compounds 1-3
The obtained compound 1-3-c (27.98g, 50 mmol), 5% palladium on carbon (3.11g, water, solid content: 45%) and 600g of tetrahydrofuran were charged into a 1L autoclave, the autoclave was sealed, and after replacing 3 to 5 times with hydrogen, the pressure of hydrogen was increased to 0.5 to 1.0MPa, and the reaction was carried out at 45 to 55 ℃ with stirring. After the reaction is finished, filtering the catalyst by using a filter membrane with the aperture of 0.2 mu m, removing the solvent from the filtrate, adding 60g of ethanol into the obtained solid, stirring for 30min, and obtaining a white solid compound 1-3 with the yield of 92% through suction filtration and drying.
The compound 1-3 has high resolution mass spectrum, ESI source, positive ion mode and molecular formula C28H33N5O4Theoretical value 503.25, test value 503.58. Elemental analysis (C)28H33N5O4) Theoretical value C: 66.78, H: 6.61, N: 13.91, O: 12.71, found C: 66.80, H: 6.60, N: 13.92, O: 12.68. elemental analysis tester brand: united states alliance, model number: CE-440.
Compound Synthesis example 4
The compounds represented by structural formulae (1-4) can be synthesized according to the following scheme 4:
(1) synthesis of Compound 1-4-a
A1L three-necked round-bottomed flask was charged with 2, 5-diaminoiodobenzene (23.40g, 100 mmol), Et3N (50.60g, 500 mmol) and 200g of toluene, the system was heated to 60 ℃ and then a mixed solution of 4-nitro-3-chlorobenzoyl chloride (46.20g, 210 mmol) and 200g of toluene was slowly added dropwise to the system over about 0.5 hour, and then the system was heated to 80 ℃ and stirred for 8 to 10 hours, followed by TLC until no 2, 5-diaminoiodobenzene remained as a starting material. Then cooling the reaction system to room temperature, washing with 500mL of 3 deionized water for three times, removing the upper organic phase to obtain a light yellow solid, adding 500mL of a methanol/water mixed solution for pulping, filtering and drying the suspension to obtain the compound 1-4-a with 78% yield.
(2) Synthesis of Compound 1-4-b
1-4-a (60.11g, 100 mmol) and Pd (PPh) were placed in a 1L three-necked round-bottomed flask3)4(2.31g, 2 mmol), CuI (0.38g, 2 mmol), Et3N (50.60g, 500 mmol) and 200mL of DMF solvent are stirred at 20-40 ℃ for 30min, then a mixed solution of propargylamine (6.06g, 110 mmol) and 100mL of DMF solvent is added dropwise into the system, the dropwise addition is finished within 1-2 h, and the reaction is carried out at 20-40 ℃ for 4-10 h under the condition of heat preservation.
After the reaction, 500mL of 1, 2-dichloroethane and 500mL of hydrochloric acid solution with the concentration of 1mol/L are added into the system, the organic phase is washed with 500mL of deionized water by 3 times, and the organic phase is dried to obtain a light yellow solid with the yield of 61%.
(3) Synthesis of Compound 1-4-c
1-4-b (52.83g, 100 mmol) and 300g DMF were charged in a 1L three-necked round-bottomed flask, and a solution of t-butyl bromoacetate (19.51g, 100 mmol) in 200g dichloroethane was added dropwise over 0.5 to 1 hour at a temperature of 0 to 10 ℃. Stirring at room temperature for 20-24h after the dropwise addition. After the reaction was completed, 1L of ethyl acetate was added, and washed with 500mL of deionized water to remove ethyl acetate, thereby obtaining 42.41g of a pale yellow solid with a yield of 66%.
(4) Synthesis of Compound 1-4-d
1-4-c (64.25g, 100 mmol) and 300g of dichloroethane were charged into a 1L three-necked round-bottomed flask, and a solution of di-tert-butyl dicarbonate (21.83g, 100 mmol) in 200g of dichloroethane was added dropwise at a temperature of 0 to 10 ℃ for 0.5 to 1 hour. After the dropwise addition, the mixture was stirred at room temperature for 24 hours. After the reaction was completed, the reaction solution was washed with 500mL of deionized water to remove methylene chloride, whereby 63.12g of a pale yellow solid was obtained in a yield of 85%.
(5) Synthesis of Compounds 1-4
The obtained compound 1-4-d (37.13g, 50 mmol), 5% palladium on carbon (4.13g, water, solid content: 45%) and 600g of tetrahydrofuran were charged into a 1L autoclave, the autoclave was sealed, and after replacement with hydrogen gas for 3 to 5 times, the pressure of hydrogen gas was increased to 0.5 to 1.0MPa, and the reaction was carried out at 45 to 55 ℃ with stirring. After the reaction is finished, filtering the catalyst by using a filter membrane with the aperture of 0.2 mu m, removing the solvent from the filtrate, adding 60g of ethanol into the obtained solid, stirring for 30min, and obtaining a white solid compound 1-4 with the yield of 90% through suction filtration and drying.
The compound 1-4 has high resolution mass spectrum, ESI source, positive ion mode and molecular formula C34H41Cl2N5O6Theoretical value 685.24, test value 685.47. Elemental analysis (C)34H41Cl2N5O6) Theoretical value C: 59.48, H: 6.02, Cl: 10.33, N: 10.20,o: 13.98, found C: 59.47, H: 6.03, Cl: 10.35, N: 10.21, O: 13.99. elemental analysis tester brand: united states alliance, model number: CE-440.
Compound Synthesis example 5
The compounds represented by structural formulae (1-5) can be synthesized according to the following scheme 5:
(1) synthesis of Compound 1-5-a
A1L three-necked round-bottomed flask was charged with 1, 2-diamino-3, 5-diiodobenzene (35.99g, 100 mmol), Et3N (50.60g, 500 mmol) and 200g of toluene, the system was heated to 60 ℃, then a mixed solution of 4-nitro-3-isopropylbenzoyl chloride (47.80g, 210 mmol) and 200g of toluene was slowly added dropwise to the system over about 0.5 hour, then the system was heated to 80 ℃ and stirred for 8 to 10 hours, followed by TLC until no 1, 2-diamino-3, 5-diiodobenzene remained as a raw material. Then cooling the reaction system to room temperature, washing with 500mL of 3 deionized water for three times, removing the upper organic phase to obtain a light yellow solid, adding 500mL of a methanol/water mixed solution for pulping, filtering and drying the suspension to obtain the compound 1-5-a with 77% yield.
(2) Synthesis of Compound 1-5-b
A1L three-necked round-bottomed flask was charged with 1-5-a (74.23g, 100 mmol) and Pd (PPh)3)4(2.31g, 2 mmol), CuI (0.38g, 2 mmol), Et3N (50.60g, 500 mmol) and 200mL of DMF solvent are stirred at 20-40 ℃ for 30min, then a mixed solution of propargylamine (6.06g, 110 mmol) and 100mL of DMF solvent is added dropwise into the system, the dropwise addition is finished within 1-2 h, and the reaction is carried out at 20-40 ℃ for 4-10 h under the condition of heat preservation.
After the reaction is finished, 500mL of 1, 2-dichloroethane and 500mL of hydrochloric acid solution with the concentration of 1mol/L are added into the system, the organic phase is washed with 500mL of 3 deionized water for three times, and the organic phase is dried to obtain a light yellow solid.
(3) Synthesis of Compound 1-5-c
1-5-b (59.66g, 100 mmol) and 300g of dichloroethane were charged into a 1L three-necked round-bottomed flask, the temperature was lowered to 0-10 ℃ and a solution of di-tert-butyl dicarbonate (45.83g, 210 mmol) in 200g of dichloroethane was added dropwise over 0.5-1 hour. After the addition, the mixture was stirred at room temperature for 24 hours. After the reaction was completed, the reaction solution was washed with 500mL of deionized water to remove methylene chloride, whereby 68.53g of a pale yellow solid was obtained in a yield of 86%.
(5) Synthesis of Compounds 1-5
The obtained compound 1-5-c (39.84g, 50 mmol), 5% palladium on carbon (4.43g, water, solid content: 45%) and 600g of tetrahydrofuran were charged into a 1L autoclave, the autoclave was sealed, and after replacing 3 to 5 times with hydrogen, hydrogen was pressurized to 0.5 to 1.0MPa, and reacted at 45 to 55 ℃ with stirring. After the reaction is finished, filtering the catalyst by using a filter membrane with the aperture of 0.2 mu m, removing the solvent from the filtrate, adding 80g of ethanol into the obtained solid, stirring for 30min, and obtaining white solid compounds 1-5 with the yield of 88% through suction filtration and drying.
The compound 1-5 has high resolution mass spectrum, ESI source, positive ion mode and molecular formula C42H60N6O6Theoretical value 744.46, test value 744.96. Elemental analysis (C)42H60N6O6) Theoretical value C: 67.72, H: 8.12, N: 11.28, O: 12.89, found C: 67.70, H: 8.13, N: 11.29, O: 12.88. elemental analysis tester brand: united states alliance, model number: CE-440.
Synthesis example of (II) Polymer
Polymer Synthesis example 1
A500 mL three-necked round-bottomed flask was charged with 22.98g, 50 mmol of an arylamine compound represented by the formula (1-1) (hereinafter referred to as 1-1), 2.16g, 20 mmol of p-phenylenediamine (hereinafter referred to as 2-1), 6.37g, 30 mmol of 4, 4' -diaminodiphenylethane (hereinafter referred to as 2-2) and 144.84g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) under a nitrogen atmosphere, and the resulting suspension was stirred until a yellow solution was obtained. Then, 19.61g (100 mmol) of 1,2,3, 4-cyclobutanetetracarboxylic dianhydride (hereinafter referred to as a-1) and 144.84g of NMP were added to the system. The reaction was allowed to exotherm and stirred at room temperature for 4 hours to give a polyamic acid polymer having a concentration of 15% dissolved in NMP.
Polymer synthesis examples 1 to 20 and polymer synthesis comparative examples 1 to 10 were prepared by a similar method to that of polymer synthesis example 1, with 15% each, and NMP as a solvent, except that: the types and amounts of the monomers used were varied, and the specific results are shown in tables 1 and 2 below, which are not repeated herein.
In tables 1 and 2:
a-1: 1,2,3, 4-cyclobutanetetracarboxylic dianhydride
a-2: 1, 3-dimethyl-1, 2,3, 4-cyclobutanetetracarboxylic dianhydride
a-3: 2,3, 5-tricarboxylic cyclopentyl acetic dianhydride
1-1: a compound represented by the formula (1-1)
1-2: a compound represented by the formula (1-2)
1-3: a compound represented by the formula (1-3)
1-4: compounds represented by the formula (1-4)
1-5: compounds represented by the formula (1-5)
2-1: p-phenylenediamine
2-2: 4, 4' -diaminodiphenylethane
2-3: 4, 4' -diaminodiphenyl ether
2-4: 2,2 '-dimethyl-4, 4' -diaminobiphenyl
2-5: 1, 3-bis (4-aminophenoxy) propane
2-6: a compound represented by the formula (2-6)
TABLE 1 Synthesis examples the types and amounts of monomers used for the respective polymers
Table 2 compares the types and amounts of monomers used in the respective polymers of the synthesis examples
(III) liquid Crystal alignment agent, liquid Crystal alignment film, and examples and comparative examples of liquid Crystal display element
Example 1
a. Liquid crystal aligning agent
100 parts by weight of the polymer (polymer synthesis example 1), 86 parts by weight of NMP and 114 parts by weight of ethylene glycol monobutyl ether were put into a three-necked round-bottomed flask under nitrogen protection, the system was stirred at room temperature for 60 minutes, and then the solution was filtered through a 0.2 μm filter to obtain a liquid crystal aligning agent of example 1, the concentration of which was 5%, and the solvent was NMP: BC 60: 40.
b. Liquid crystal alignment film and liquid crystal display element
In the embodiments of the present invention, the present invention is explained only with the IPS and FFS type liquid crystal display elements, but the present invention is not limited thereto.
The liquid crystal aligning agent of example 1 was coated on one piece of a first glass substrate having IPS (in-plane switching) or FFS (fringe field switching) ITO electrodes by means of spin coating to form a precoat layer. Pre-curing (hot plate, 85 ℃, 10 minutes), main curing (circulating oven, 225 ℃, 50 minutes), exposing (254nm polarized light, 5 mW/cm)2、500mj/cm2) A first glass substrate having an ITO electrode on which the liquid crystal alignment film of example 1 was formed was obtained.
The liquid crystal aligning agent of example 1 was coated on a second glass substrate having no ITO electrode by spin coating to form a precoat layer. The second glass substrate on which the liquid crystal alignment film of example 1 was formed was also obtained after the above-described precuring, main curing, and exposure to light.
A sealant was applied to the periphery of the first glass substrate with a liquid crystal inlet, and a spacer of 3.5 μm was applied to the other substrate. Then, the two glass substrates were bonded in an antiparallel manner to the alignment direction (5kg, 30min), the sealant was cured, the liquid crystal was injected, the liquid crystal injection port was sealed with an ultraviolet curing adhesive, the ultraviolet curing adhesive was cured with ultraviolet light, and the polarizing plates were attached to the outer sides of the two glass substrates, respectively, to obtain the IPS or FFS type liquid crystal display device of example 1.
The transmittance of the transparent glass substrate on which the liquid crystal alignment film was not formed was set to 100%, and the substrate on which the liquid crystal alignment film was formed was subjected to UV-Vis spectroscopy, and the measurement result is shown in fig. 1, where the ultraviolet-visible spectrophotometer model is Cary100 (manufactured by agilent corporation). The average of the transmittances of 390nm to 550nm was calculated from the test results as the transmittance of the liquid crystal alignment film, and the result was 95.8%.
The liquid crystal display element of example 1 was evaluated, and the results are shown in table 3.
Examples 2 to 20
Examples 2 to 20 of a liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal display element can be prepared by the same procedure as example 1 except that: the polymers used were replaced with the corresponding polymers of examples 2 to 20, the liquid crystal aligning agents were prepared in concentrations of 5% and the solvent ratios were NMP: BC 60:40, and the liquid crystal display elements of examples 2 to 20 were evaluated and the results are shown in Table 3.
Comparative examples 1 to 12
Comparative examples 1 to 12 of a liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal display element were prepared by the same procedure as in example 1 except that the polymers used were replaced with the corresponding polymers in comparative examples 1 to 12, the concentrations of the corresponding liquid crystal aligning agents were all 5%, and the solvent ratios were all NMP: BC 60: 40. The UV-Vis spectra were determined as in example 1, except that the polymers used were varied. The UV-Vis spectrum of comparative example 1 is shown in FIG. 2, and the result is 85.9%. The evaluation results of the liquid crystal display elements of comparative examples 1 to 12 are shown in Table 3.
TABLE 3
Evaluation method
(1) Characterization of the transmittance
The transmittance of the transparent glass substrate on which the liquid crystal alignment film was not formed was set to 100%, and the substrate on which the liquid crystal alignment film was formed was subjected to a transmittance test at a full wavelength (200-. The average of the transmittances at 390nm to 550nm was calculated from the test results, and the transmittance was judged to be poor when 80 to 90%, good when 90 to 95%, and excellent when 95% or more.
(2) Characterization of contrast
The contrast of the liquid crystal display element (liquid crystal cell to which no polarizing plate was attached) thus produced was measured after driving at a saturated ac voltage for 30 hours. The instrument was a luminance meter (device model: 3298F, manufacturer: YOKOGAWA), and the liquid crystal display element was tested under a polarizing microscope equipped with a crossed Nicol (cross nicol) and the minimum luminance tested was taken as the blackness. And applying any rectangular wave voltage to the liquid crystal element, and testing the maximum brightness as the whiteness. Contrast is defined as the ratio of whiteness to blackness.
The liquid crystal display element contrast evaluation results are as follows:
a liquid crystal display element having a V-shaped cross-section with a contrast ratio of 1800 or more and an excellent contrast ratio
1200. ltoreq. contrast ratio < 1800, and liquid crystal display element contrast ratio is general
X is contrast ratio less than 1200, and contrast ratio of liquid crystal display element is poor
Therefore, compared with the prior art, the liquid crystal orientation agent provided by the invention contains the arylamine compound b-1 with a specific structure in the arylamine monomer, so that the liquid crystal orientation film prepared by the liquid crystal orientation agent has the advantages of high film-forming transmittance and high contrast of the prepared liquid crystal display element, and the liquid crystal orientation agent is simple in implementation method, wide in market prospect and suitable for large-scale application and popularization.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. An arylamine compound is characterized in that the structure of the arylamine compound is shown as a general formula (1):
in the general formula (1), R1、R2Each independently represents a H atom or a structure represented by the general formula (2), and R1、R2Not H atoms at the same time; x1、X2Each independently represents a hydrogen atom, a halogen atom, C1-5One of alkyl groups;
in the general formula (2), R3Is represented as C1-5An alkylene group of (a); r4、R5Independently represent H atom, C1-5Alkyl, tert-butoxycarbonyl or tert-butoxycarbonyl substituted alkyl.
2. The arylamine compound according to claim 1, wherein the specific structure of the arylamine compound is represented by formula 1-1 to formula 1-5:
3. a liquid crystal orientation agent prepared from the arylamine compound in the claim 1, which is characterized in that the liquid crystal orientation agent comprises a polymer A obtained by the reaction of a tetracarboxylic dianhydride component a and an amine component b; the amine component b contains the aromatic amine compound b-1 described in claim 1.
4. The liquid crystal aligning agent according to claim 3, wherein the tetracarboxylic dianhydride component a comprises at least one of 1,2,3, 4-cyclobutanetetracarboxylic dianhydride and 1, 3-dimethyl-1, 2,3, 4-cyclobutanetetracarboxylic dianhydride.
5. The liquid crystal aligning agent according to claim 4, wherein the tetracarboxylic dianhydride component a further comprises one or more of 3,3 ', 4, 4' -biphenylsulfone tetracarboxylic dianhydride, pyromellitic dianhydride, 1,2,4, 5-cyclohexanetetracarboxylic dianhydride, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride, 1,2,3, 4-cyclopentanetetracarboxylic dianhydride, 2,3, 5-tricarboxycyclopentylacetic acid dianhydride.
6. The liquid crystal aligning agent of claim 3, wherein the amine component b comprises another aromatic amine compound b-2, and the other aromatic amine compound b-2 is p-phenylenediamine, m-phenylenediamine, 2-bis (4-aminophenyl) hexafluoropropane, 4- (4-heptylcyclohexyl) phenyl-3, 5-diaminobenzoate, 2 '-dimethyl-4, 4' -diaminobiphenyl, 4 '-diaminodiphenyl ether, 1, 4-bis (4-aminophenoxy) benzene, 4' -diaminobenzophenone, 1, 2-bis (4-aminophenoxy) ethane, 1, 3-bis (4-aminophenoxy) propane, 1, 4-bis (4-aminophenoxy) butane, or a mixture thereof, 1, 5-bis (4-aminophenoxy) pentane, 1, 6-bis (4-aminophenoxy) hexane, N '-bis (4-aminophenyl) piperazine, 1, 5-diaminonaphthalene, 1, 8-diaminonaphthalene, p-aminophenylethylamine, 4' -diaminodiphenylmethane, 4 '-diaminodiphenylethane, 4' -diaminobenzamide, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2, 4-diaminododecyloxybenzene, 2, 4-diaminooctadecyloxybenzene, 1- (4- (4-pentylcyclohexylcyclohexyl) phenoxy) -2, 4-diaminobenzene, 1- (4- (4-heptylcyclohexyl) phenoxy) -2, 4-diaminobenzene, 3, 5-diaminobenzoic acid.
7. The liquid crystal aligning agent according to claim 3, further comprising a solvent component, wherein the solvent component is one or more of N-methyl-2-pyrrolidone, γ -butyrolactone, N-dimethylformamide, N-dimethylacetamide, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol dimethyl ether, and diethylene glycol monomethyl ether ethyl ester.
8. A liquid crystal alignment film comprising the liquid crystal aligning agent according to any one of claims 3 to 7.
9. A liquid crystal display element comprising the liquid crystal alignment film according to claim 8.
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