CN109369613B - Diamine compound for preparing liquid crystal aligning agent and application thereof - Google Patents
Diamine compound for preparing liquid crystal aligning agent and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/76—Dibenzothiophenes
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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
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3491—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur as hetero atom
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—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
Abstract
The invention relates to a diamine compound for preparing a liquid crystal orientation agent and application thereof, belonging to the technical field of liquid crystal display, wherein the diamine compound contains a dibenzosulfolane conjugated group, has better electron transmission capability, and the prepared liquid crystal display element has the antistatic characteristic, and meanwhile, the dibenzosulfolane is of a rigid structure, and the prepared liquid crystal display element has the characteristics of high stability and excellent orientation.
Description
Technical Field
The invention relates to a diamine compound for preparing a liquid crystal aligning agent and application thereof, belonging to the technical field of liquid crystal display.
Background
Liquid crystal display elements are classified into various modes according to the electrode structure and the physical properties of liquid crystal molecules used, and currently known liquid crystal display devices are classified into: TN mode (twisted nematic mode), STN mode (super twisted nematic mode), VA mode (vertical alignment mode), IPS mode (in-plane switching mode), FFS mode (fringe field switching mode), or OCB mode (optically compensated bend mode).
At present, resin materials such as polyamic acid, polyimide, polyamide and polyester are mainly used as liquid crystal alignment film materials used in various liquid crystal display elements, wherein polyamic acid or polyimide is the preferred material for liquid crystal alignment films due to its excellent high temperature resistance, mechanical strength, corrosion resistance and affinity with liquid crystal.
With the continuous expansion of the application range of L CD, electrostatic interference can occur in many times, if antistatic treatment is not carried out in advance, the part on electrostatic induction can be displayed for a long time, and the required content can not be displayed normally, and meanwhile, static electricity generated in the most popular friction orientation alignment process in the industry at present in the production process can easily break through an orientation layer, so that a liquid crystal box is short-circuited or poor in orientation, and the requirements on the antistatic performance of a liquid crystal orientation film are more and more strict along with the higher requirements on the display picture quality and the yield of a production line.
In order to eliminate the electrostatic interference, the following three methods are adopted: the method adopts an antistatic polarizer, adopts an antistatic TOP material or adds an antistatic agent into the liquid crystal, but the methods have certain limitations, such as limited ground color, poor stability, increased cost and the like. Therefore, how to improve the antistatic property of the liquid crystal alignment film is a problem to be solved urgently.
Disclosure of Invention
In order to solve the technical defects, the invention provides a diamine compound for preparing a liquid crystal aligning agent and application thereof, and the prepared liquid crystal aligning film and a liquid crystal display element have strong antistatic performance, high stability and excellent aligning property.
The technical scheme of the invention is as follows: a diamine compound for preparing a liquid crystal aligning agent has a structural general formula,
in the general formula (1), X1And X2Are each a single bond, -O-),
One of (1);
in the general formula (1), R1, R2, R3 and R4 are respectively hydrogen atom, halogen and C1-20Alkyl group, substituted derivative, and C2-20Alkenyl group and substituent-containing derivative, C2-20The alkyne of (2) and one or more of an alkyne containing a substituent, an alkyl compound containing 1-10 alicyclic rings and a derivative containing a substituent, an aryl compound containing 1-10 aromatic rings and a derivative containing a substituent, a compound containing 1-10 heterocyclic rings and a derivative containing a substituent.
The technical scheme of the invention also comprises: the structure of the compound comprises that,
compared with the prior art, the diamine compound contains dibenzosulfolane conjugated groups, has better electron transport capability, and the liquid crystal display element prepared by the orientation agent has antistatic property; meanwhile, the dibenzosulfolane is a rigid structure, and the prepared liquid crystal display element has the characteristics of high stability and excellent orientation.
In addition, the invention also provides a liquid crystal aligning agent prepared from the diamine compound, which comprises a polymer obtained by the reaction of a tetracarboxylic dianhydride component a and a diamine component b, wherein the diamine component b comprises a diamine compound b-1, the structural general formula of the diamine compound b-1 is,
compared with the prior art, the liquid crystal orientation agent is prepared by polymerizing a diamine monomer containing a dibenzosulfolane conjugated group and a tetracarboxylic dianhydride monomer, and the diamine monomer contains the dibenzosulfolane conjugated group, so that the liquid crystal orientation agent has better electron transmission capability, and a liquid crystal display element prepared from the orientation agent has antistatic property; meanwhile, the dibenzosulfolane is a rigid structure, and the prepared liquid crystal display element has the characteristics of high stability and excellent orientation. Therefore, the liquid crystal orientation film and the liquid crystal display element made of the liquid crystal orientation agent have strong antistatic performance, high stability and excellent orientation.
Further, the polymer of the present invention contains at least one polymer selected from the group consisting of polyamic acid and polyimide.
The preparation method of the polyamic acid can adopt a conventional method and comprises the following steps: the mixture comprising the tetracarboxylic dianhydride component a and the diamine component b is first dissolved in a solvent and subjected to polymerization reaction at a temperature of 0 to 100 ℃ for 1 to 24 hours to obtain a polyamic acid solution, and then the solvent may be distilled off under reduced pressure to obtain a polyamic acid solid, or the reaction system may be poured into a large amount of a poor solvent and the precipitate dried to obtain a polyamic acid solid.
The technical scheme of the invention also comprises: the solvent component is one or more of N-methyl-2-pyrrolidone, gamma-butyrolactone, N-dimethylacetamide, N-dimethylformamide, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol methyl ethyl ether, ethylene glycol dimethyl ether and diethylene glycol monomethyl ether ethyl ester. Wherein, in the liquid crystal orientation liquid composed of the polymer and the solvent component, the weight ratio of the polymer is 1-30%, and the preferred weight ratio is 3-10%.
The technical scheme of the invention also comprises: the tetracarboxylic dianhydride component a is one or more of 1,2,3, 4-cyclobutane tetracarboxylic dianhydride, 1,2,3, 4-cyclopentane tetracarboxylic dianhydride, 2,3, 5-tricarboxycyclopentyl acetic dianhydride, pyromellitic dianhydride, 1,2,4, 5-cyclohexane tetracarboxylic dianhydride, 3 ', 4, 4' -biphenyl tetracarboxylic dianhydride and 3,3 ', 4, 4' -biphenyl sulfone tetracarboxylic dianhydride.
The technical scheme of the invention also comprises: the diamine component b comprises a diamine compound b-2, wherein the diamine compound b-2 is p-phenylenediamine, m-phenylenediamine, 1, 5-diaminonaphthalene, 1, 8-diaminonaphthalene, p-aminophenylethylamine, 4 '-diaminodiphenylmethane, 4' -diaminodiphenylethane, 4 '-diaminodiphenylether, 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, n '-bis (4-aminophenyl) piperazine, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2, 4-diaminododecyloxybenzene, 2, 4-diaminooctadecyloxybenzene, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2-bis (4-aminophenyl) hexafluoropropane, 4- (4-heptylcyclohexyl) phenyl-3, 5-diaminobenzoate, 2' -dimethyl-4, 4 '-diaminobiphenyl, 4' -diaminobenzamide, 1- (4- (4-pentylcyclohexylcyclohexyl) phenoxy) -2, 4-diaminobenzene, 1- (4- (4-heptylcyclohexyl) phenoxy) -2, 4-diaminobenzene and 3, 5-diaminobenzoic acid.
Further, the molar ratio of the tetracarboxylic dianhydride component a to the diamine component b is 100: 20-200, more preferably 100: 100-120.
Further, in the diamine component b, the percentage molar ratio of the diamine compound b-1 is 0.1 to 100 mol%, and more preferably 20 to 70 mol%.
Further, 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 reactants. Solvents for the polymerization reaction include, but are not limited to, N-methyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, γ -butyrolactone. Wherein, in the reaction liquid formed by the mixture and the solvent, the weight ratio of the mixture to the reaction liquid is 1-50%, and more preferably 10-20%.
The technical scheme of the invention also comprises: the solvent component comprises an adverse solvent which does not cause polymer precipitation, the adverse solvent comprises one or more of methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclobutanone, methyl acetate, ethyl acetate, butyl acetate, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol methyl ethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, chlorobenzene and 1, 2-dichloroethane, and the adverse solvent accounts for 0-50% of the total weight of the solvent component, preferably 0-30% of the total weight of the solvent.
The preparation method of the polyimide can adopt, but is not limited to, the following two imidization methods, namely a thermal imidization method or a chemical imidization method.
The thermal imidization method refers to that polyimide solid (which has a relationship with the diamine monomer containing the dibenzosulfolane conjugated group in the main invention point of the scheme) is directly heated for dehydration and cyclization, and the heating temperature is preferably 150-300 ℃.
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: 2-30; imidization rate of polyamic acid is 10-100%; the temperature of imidization reaction is 0-100 ℃, and more preferably 30-70 ℃; the reaction time is 1 to 100 hours, more preferably 2 to 8 hours; the dehydrating agent can be selected from an acid anhydride compound, such as acetic 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: 2-5; the catalyst can be selected from pyridine, 4-methylpyridine, trimethylamine or triethylamine; the molar ratio of the dehydrating agent to the catalyst is 1:0.1 to 5, more preferably 1: 2-3.
The technical scheme of the invention also comprises: the polymer is synthesized by adding a molecular weight regulator, wherein the molecular weight regulator comprises one or more of maleic anhydride, phthalic anhydride, o-cyclohexane dicarboxylic anhydride, succinic anhydride, aniline, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, phenyl isocyanate and naphthyl isocyanate, and the molar ratio of the molecular weight regulator to the tetracarboxylic dianhydride component a is 0.01-10: 100. preferably, the molar ratio of the molecular weight regulator to the tetracarboxylic dianhydride component a is from 0.5 to 5: and 100, regulating the molecular weight of the polymer by adding a molecular weight regulator in the synthesis process of the polymer, and ensuring the feasibility of a subsequent coating process.
The technical scheme of the invention also comprises: the additive comprises an epoxy additive and/or a silane compound additive with functional groups, wherein the addition amount of the epoxy additive is 0.1-20% of the total weight of the polymer, preferably the addition amount of the epoxy additive is 3-10% of the total weight of the polymer, the addition amount of the silane compound additive with functional groups is 0.1-10% of the total weight of the polymer, and preferably the addition amount of the silane compound additive with functional groups is 0.5-3% of the total weight of the polymer;
the epoxy additive is one or more of ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerol diglycidyl ether, N, N, N ', N ' -tetracyclooxypropyl-m-xylene diamine, 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-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane or N-bis (oxyethylene) -3-aminopropyltriethoxysilane. The additive functions to increase the stability of the liquid crystal alignment film or to improve the adhesion between the liquid crystal alignment film and the substrate, and the liquid crystal alignment agent can be prepared by mixing the polymer and the additive in a solvent at 10 to 100 ℃ under stirring, more preferably 25 to 60 ℃.
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, a diamine monomer used by the orientation agent contains a dibenzosulfolane conjugated group, so that the liquid crystal orientation film has good electron transport capability, and a liquid crystal display element prepared from the orientation agent has antistatic property; meanwhile, the dibenzosulfolane is of a rigid structure, and the prepared liquid crystal display element has the characteristics of high stability and excellent orientation. Therefore, the liquid crystal orientation film and the liquid crystal display element made of the liquid crystal orientation agent have strong antistatic performance, high stability and excellent orientation. In the examples, the antistatic properties of liquid crystal display elements prepared using the aligning agent were evaluated: ts is less than or equal to 3s, and the antistatic property is evaluated to be excellent; no abnormal phenomenon was observed in both the aging test and the flash test, and the results were evaluated as excellent stability and excellent alignment properties.
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. 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 liquid crystal display element contains the liquid crystal orientation film, the diamine monomer used by the liquid crystal orientation agent contains dibenzosulfolane conjugated groups, so that the liquid crystal orientation film has better electron transport capability, and the liquid crystal display element prepared by the orientation agent has antistatic property; meanwhile, the dibenzosulfolane is of a rigid structure, and the prepared liquid crystal display element has the characteristics of high stability and excellent orientation. Therefore, the liquid crystal orientation film and the liquid crystal display element made of the liquid crystal orientation agent have strong antistatic performance, high stability and excellent orientation.
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 TN mode (twisted nematic mode), an STN mode (super twisted nematic mode), a VA mode (vertical alignment mode), an IPS mode (in-plane switching mode), an FFS mode (fringe field switching mode), or an OCB mode (optically compensated bend mode). Among the above liquid crystal display elements, an IPS mode liquid crystal display element is preferable.
The invention has the beneficial effects that:
1. compared with the prior art, the liquid crystal aligning agent has better electron transport capability because the used diamine monomer contains dibenzosulfolane conjugated groups, and the liquid crystal display element prepared from the aligning agent has antistatic property. Particularly, for a liquid crystal alignment film which is aligned by rubbing, static electricity generated by rubbing can be eliminated in time; meanwhile, the static electricity generated by the liquid crystal display element after long-time use can be eliminated in time, so that the liquid crystal display element has the advantages of wide process window, high product yield and long service life.
2. Compared with the prior art, the liquid crystal aligning agent has the characteristics of high stability and excellent alignment property because the diamine monomer contains the dibenzosulfolane conjugated group which is a stable rigid structure.
3. The method is simple, has wide market prospect and is suitable for large-scale application and popularization.
Detailed Description
The present invention is further illustrated by the following examples.
In the following specific examples, the liquid crystal aligning agent is described in an IPS type liquid crystal display device, but the present invention is not limited thereto.
Synthesis example of Compound (I)
Synthesis example of diamine Compound b-1
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 b-1-1a
2, 8-dihydroxy dibenzosulfolane (24.8g, 100 mmol), p-nitrochlorobenzene (33.1g, 210 mmol), anhydrous potassium carbonate (8.28g, 60 mmol) and 300g toluene were put into a 1000m L three-neck round-bottom flask, the bath temperature was raised to 110 ℃, the mixture was stirred and refluxed for 3 hours, followed by T L C until no 2, 8-dihydroxy dibenzosulfolane remained, the system was cooled to room temperature, the stirring was stopped, the reaction solution was transferred to a separatory funnel and washed with water to neutrality, the solvent toluene was removed to obtain a yellow solid, 240g of anhydrous ethanol and 120g of THF were added, the mixture was stirred for 30 minutes and filtered, and the filter cake was dried to obtain 41.69g of yellow crystal, the product was measured as HP L C-MS, m/z ═ 490.05, it was confirmed to be the target product b-1-1a, the reaction yield was 85% based on 2, 8-dihydroxy dibenzosulfolane.
(2) Synthesis of Compound b-1-1
The obtained compound b-1-1a (24.52g, 50 mmol), 5% palladium carbon (2.8g, water content, solid content 44%) and 400g tetrahydrofuran are put into a 1L autoclave, the autoclave is sealed, after 3-5 times of replacement with hydrogen, the hydrogen is pressurized to 0.5-1.0MPa, and the reaction is carried out at 45-55 ℃ under stirring, after the reaction is finished, a filter membrane with the aperture of 0.2um is used for filtering the catalyst, the solvent is removed from the filtrate, 100g ethanol is added into the obtained solid and stirred for 30 minutes, and after suction filtration and drying, the yellow solid compound b-1-1 is obtained with the yield of 90%, and the total yield of the two steps of the product is 76.5%.
The compound b-1-1 has high resolution mass spectrum, ESI source, positive ion mode, molecular formula of C23H24N4O2, theoretical value of 430.48 and test value of 430.10. Elemental analysis (C24H18N2O4S), theoretical value C: 66.96, H: 4.21, N: 6.51, O: 14.87, S: 7.45, found C: 66.97, H: 4.20, N: 6.51, O: 14.87, S: 7.45.
synthesis example 2
The compounds represented by structural formulas (1-2) to (1-4) can be synthesized according to scheme 1 using each dibenzosulfolane compound and each parent nitrobenzene compound, the specific yields, high resolution mass spectrometry results and elemental analysis results of each product are shown in table 1, synthesis examples 2 to 4 in table 1, the high resolution mass spectrometry is HP L C-MC, and the molecular ion peaks of the corresponding compounds are characterized by [ M +1 ]:
TABLE 1 yield, Mass Spectrometry, elemental analysis data for each of the compounds of Synthesis examples 2-4
Synthesis example 5
The compounds represented by structural formulae (1-5) can be synthesized according to the following scheme 2:
(1) synthesis of Compound b-1-5a
3, 7-dicarboxydiphenylsulfone (30.43g, 100 mmol), 3-fluoro-4-nitrophenol (32.99g, 210 mmol), DCC (43.30g, 210 mmol) and 500g toluene were put into a 1000m L three-neck round-bottom flask, the bath temperature was raised to 110 ℃ and the mixture was stirred and refluxed for 3 hours, followed by T L C until no 3, 7-dicarboxydiphenylsulfone remained, the system was cooled to room temperature and suction-filtered, the filtrate was concentrated to 140g, 200g of ethanol was added to precipitate a yellow solid, the filtrate was suction-filtered and dried to obtain 44.81g of yellow crystals, HP L C-MS and m/z 582.02 were measured as the target products b-1-5a, and the reaction yield was 82% based on 3, 7-dicarboxydiphenylsulfone.
(2) Synthesis of Compound (b-1-5)
The obtained compound b-1-5a (21.86g, 40 mmol), 5% palladium carbon (2.48g, water content, solid content 44%) and 400g tetrahydrofuran are put into a 1L autoclave, the autoclave is sealed, after 3-5 times of replacement with hydrogen, the hydrogen is pressurized to 0.5-1.0MPa, and the reaction is carried out at 45-55 ℃ under stirring, after the reaction is finished, the catalyst is filtered out by a filter membrane with the pore diameter of 0.2um, the solvent is removed from the filtrate, 200g ethanol is added into the obtained solid and stirred for 30 minutes, and after suction filtration and drying, the yellow solid compound b-1-5 is obtained with the yield of 90%, and the total yield of the two steps is 73.8%.
The compound b-1-5 has high resolution mass spectrum, ESI source, positive ion mode, molecular formula of C26H16F2N2O6S, theoretical value of 522.07 and test value of 523.42. Elemental analysis (C26H16F2N2O6S), theoretical value C: 59.77, H: 3.09, F: 7.27, N: 5.36, O: 18.37, S: 6.14 found C: 59.78, H: 3.09, F: 7.28, N: 5.36, O: 18.37, S: 6.15.
synthesis example 6
The compounds represented by structural formulae (1-6) can be synthesized according to the following scheme 3:
(1) synthesis of Compound b-1-6a
P-nitrobenzoic acid (83.56g, 500 mmol), thionyl chloride (297.43g, 2.5 mol), toluene (300 g) and DMF (N, N-dimethylformamide) 2ml are put into a 1000m L three-neck round-bottom flask, the reaction solution is stirred and heated to reflux for 3 hours, T L C tracks that after the reaction of the product is completed, the system is dried to obtain p-nitrobenzoyl chloride with 100% yield, and 200g toluene is added into the acyl chloride for standby.
Putting 2, 8-diaminodibenzosulfolane (49.26g, 200 mmol), toluene 600ml and triethylamine (50.59g, 500 mmol) into a 2000ml three-neck round-bottom flask, heating the system to 60 ℃, then slowly dropwise adding the mixed solution of the p-nitrobenzoyl chloride and 200g of toluene into the system for about 0.5 hour until dropwise adding is completed, then heating the system to 80 ℃ for reaction for 3 hours, tracking the reaction end point by T L C, then cooling the reaction system to room temperature, washing with 500ml of distilled water of 3 x three times, removing the upper organic phase to obtain a light yellow solid, adding 500ml of methanol/water mixed solution for pulping, filtering and drying the suspension to obtain the compound b-1-6a with 71% yield.
(2) Synthesis of Compound b-1-6
The obtained compound b-1-6(27.22g, 50 mmol), 5% palladium carbon (3.1g, water content, solid content 44%) and 600g tetrahydrofuran were charged into a 1L autoclave, the autoclave was sealed, after 3-5 times replacement with hydrogen, hydrogen was pressurized to 0.5-1.0MPa, and reacted at 45-55 ℃ under stirring, after the reaction was completed, the catalyst was filtered off with a filter membrane having a pore size of 0.2um, the filtrate was desolventized, the obtained solid was added with 60g of ethanol and stirred for 30 minutes, and after suction filtration and drying, a yellow solid compound b-1-6 was obtained in 90% yield.
The theoretical value of [ M +1] ═ 485.2 and the test value of 485.5 in the high-resolution mass spectrum of the compound b-1-6. Elemental analysis (C26H20N4O4S), theoretical value C: 64.45, H: 4.16, N: 11.56, O: 13.21, S: 6.62, found C: 64.55, H: 4.18, N: 11.56, O: 13.21, S: 6.62.
synthesis example 7
Compounds represented by structural formulas (1-7) can be synthesized from 3, 7-diamino-2-methyldibenzosulfolane and p-nitrobenzoyl chloride according to scheme 3. the specific yields, high resolution mass spectrometry results and elemental analysis results for each product are shown in Table 2, FIG. 2 for Synthesis example 7, high resolution mass spectrometry is HP L C-MC, and the molecular ion peaks of the corresponding compounds are characterized by [ M +1 ]:
table 2 yield, mass spectrum, elemental analysis data of each compound in synthesis example 7
Synthesis example of (di) Polymer A
Synthesis example A-1
A diamine compound represented by the structural formula (1-1) (21.52g, 50 mmol) (hereinafter referred to as b-1-1), p-phenylenediamine (2.16g, 20 mmol) (hereinafter referred to as b-2-1), 4, 4' -diaminodiphenylmethane (5.85g, 30 mmol) (hereinafter referred to as b-2-2) and 139.2g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) were put into a 500m L three-necked round-bottomed flask under a nitrogen atmosphere, and the resulting suspension was stirred until a yellow solution was obtained, then 19.6g (100 mmol) of 1,2,3, 4-cyclobutanetetracarboxylic dianhydride (hereinafter referred to as a-1) and 139.2g of NMP were added to the system, and the reaction was allowed to proceed with heat generation and stirred at room temperature for 4 hours to obtain a polyamic acid polymer A-1-1 having a solid content of 15% dissolved in NMP.
Synthesis examples A-1-2 to A-1-19 and comparative Synthesis examples A-2-1 to A-2-8
Synthesis examples A-1-2 to A-1-19 and comparative Synthesis examples A-2-1 to A-2-8 were prepared by the same method as in Synthesis example A-1-1, except that: the types and amounts of the monomers used were varied, and the specific results are shown in tables 3 and 4 below, which are not repeated herein.
In tables 3 and 4:
a-1: 1,2,3, 4-cyclobutanetetracarboxylic dianhydride;
a-2: pyromellitic dianhydride;
a-3: 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride;
b-1-1: a compound represented by the formula (I-1),
b-1-4: a compound represented by the formula (I-4),
b-1-5: a compound represented by the formula (I-5),
b-1-7: a compound represented by the formula (I-7),
b-2-1: p-phenylenediamine;
b-2-2: 4, 4' -diaminodiphenylmethane;
b-2-3: p-aminophenylethylamine;
b-2-4: 3, 5-diaminobenzoic acid;
b-2-5: 2, 4-diaminododecyloxybenzene.
TABLE 3 Synthesis examples the types and amounts of monomers used for the respective polymers
Table 4 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 polymer (A-1-1), 150 parts by weight of NMP (hereinafter referred to as B-1) and 150 parts by weight of ethylene glycol monobutyl ether (hereinafter referred to as B-2) were put into a three-necked round-bottomed flask under the protection of nitrogen, 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.
b. Liquid crystal alignment film and liquid crystal display element
The liquid crystal aligning agent of example 1 was coated on a first glass substrate having an ITO electrode by means of spin coating to form a precoat layer. Pre-curing (hot plate, 80 ℃, 10 minutes), main curing (circulating oven, 220 ℃, 50 minutes), exposing (254nm polarized light, 5 mW/cm)2、1000mj/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.
An ultraviolet curing adhesive was coated on the periphery of one of the first glass substrate and the second glass substrate, and a spacer of 3.5 μm was sprinkled on the other substrate. Then, the two glass substrates were bonded in a manner antiparallel to the orientation direction (5kg, 30min), and then irradiated with an ultraviolet lamp to cure the ultraviolet-curable adhesive. Then, the liquid crystal is injected, the injection port of the liquid crystal is sealed by using ultraviolet curing glue, the ultraviolet curing glue is cured by using ultraviolet light, and then polarizing plates are respectively attached to the outer sides of the two glass substrates, so that the IPS mode liquid crystal display element of embodiment 1 can be obtained.
The liquid crystal display element of example 1 was evaluated, and the results are shown in table 5.
Example 2 to example 19
Examples 2 to 19 of the liquid crystal aligning agent, the liquid crystal alignment film, and the liquid crystal display element can be prepared by the same procedure as example 1 except that: the kind and amount of the polymer (A) and the solvent (B) used are changed, and the orientation process is also changed. The liquid crystal display elements of examples 2 to 19 were evaluated and the results are shown in table 5.
Comparative example 1 to comparative example 8
Comparative examples 1 to 8 of liquid crystal aligning agents, liquid crystal alignment films, and liquid crystal display devices were prepared by the same procedure as in example 1 except that the kinds and amounts of the polymer (a) and the solvent (B) used were changed and the alignment process was also changed, and the liquid crystal display devices of comparative examples 1 to 8 were evaluated and the results are shown in table 5.
Evaluation method
(1) Characterization of antistatic Properties
Two identical liquid crystal display elements 1,2 are prepared simultaneously and placed in an environment at 25 c and one atmosphere. The common electrode of the two liquid crystal display elements 1 and 2 is set to a potential of 0V (ground potential). Two liquid crystal display elements are simultaneously placed over the backlight.
The pixel electrode of the liquid crystal display element 1 was discharged twice by an electrostatic discharge generator (manufactured by Shanghai Prolimei electronics Co., Ltd., model No. ESD61002, set discharge potential: 20KV), and then the time from the start of lighting of the display element 1 until the difference in luminance between the display element 1 and the display element 2 could not be confirmed visually was measured and expressed as Ts, and the shorter this time, the better the antistatic property of the liquid crystal display element.
The antistatic performance evaluation results were as follows:
ts is less than or equal to 3 seconds, and the antistatic property is excellent;
○, Ts is less than or equal to 10 seconds and is less than or equal to 3 seconds, and the antistatic property is good;
△, Ts is more than or equal to 10 seconds and less than or equal to 60 seconds, and the antistatic performance is general;
ts is more than or equal to 60 seconds, and the antistatic property is poor;
x X: static electricity breaks down the alignment film to short the liquid crystal element.
(2) Characterization of stability
The stability of the liquid crystal display element is characterized by the aging test result of the liquid crystal display element, and the specific experimental process is as follows: two identical liquid crystal display elements 1,2 are prepared simultaneously and placed in an environment at a temperature of 85 ℃ and a relative humidity of 85%. The same saturated ac voltage was applied to the two liquid crystal display elements 1 and 2 to drive them, and the display state was tested 200 hours after the driving.
The stability evaluation results were as follows:
both the display elements 1 and 2 normally display, have no black spots, pockmarks, uneven orientation and the like, and have excellent stability;
x is that the display element 1 or 2 is abnormally displayed, and has black spots, pocks or uneven orientation, and the stability is poor.
(3) Characterization of liquid Crystal orientation
In the IPS mode liquid crystal display device manufactured as described above, the presence or absence of an abnormal region of a bright-dark change when a voltage of 5V is applied and released was observed with a microscope at a magnification of 50 times. The case where no abnormal region was observed was regarded as "good" in liquid crystal alignment, and the case where an abnormal region was observed was regarded as "poor" in liquid crystal alignment.
In table 5:
b-1: n-methyl-2-pyrrolidone;
b-2: ethylene glycol monobutyl ether.
Table 5 evaluation results of the liquid crystal display elements of the examples
Therefore, compared with the prior art, the liquid crystal aligning agent has better electron transport capability because the diamine monomer contains the dibenzosulfolane conjugated group, and the liquid crystal display element prepared from the aligning agent has antistatic property. Particularly, for a liquid crystal alignment film which is aligned by rubbing, static electricity generated by rubbing can be eliminated in time; meanwhile, the static electricity generated by the liquid crystal display element after long-time use can be eliminated in time, so that the liquid crystal display element has the advantages of wide process window, high product yield and long service life. Meanwhile, because the diamine monomer contains dibenzosulfolane conjugated groups which are rigid structures, the prepared liquid crystal display element has the characteristics of high stability and excellent orientation. The implementation method is simple, has wide market prospect and is suitable for large-scale application and popularization.
The above description is only exemplary of the present invention and should not be taken as limiting the invention in any way, and any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A diamine compound for preparing a liquid crystal aligning agent, characterized in that: the general structural formula of the compound is shown as,
in the general formula (1), X1And X2Are each a single bond, -O-),
One of (1);
in the general formula (1), R1, R2, R3 and R4 are respectively hydrogen atom, halogen and C1-20One or more of alkyl groups.
2. The diamine compound for producing a liquid crystal aligning agent according to claim 1, wherein: the structure of the compound is as follows,
the formula (1-7).
3. A liquid crystal aligning agent prepared from the diamine compound of claim 1 or 2, characterized in that: comprises a polymer obtained by reaction of a tetracarboxylic dianhydride component a and a diamine component b, wherein the diamine component b is a diamine compound b-1, the structural general formula of the diamine compound b-1 is,
general formula (1)
In the general formula (1), X1And X2Are each a single bond, -O-),
One of (1);
in the general formula (1), R1, R2, R3 and R4 are respectively hydrogen atom, halogen and C1-20One or more of alkyl groups.
4. The liquid crystal aligning agent according to claim 3, wherein: the tetracarboxylic dianhydride component a is one or more of 1,2,3, 4-cyclobutane tetracarboxylic dianhydride, 1,2,3, 4-cyclopentane tetracarboxylic dianhydride, 2,3, 5-tricarboxycyclopentyl acetic dianhydride, pyromellitic dianhydride, 1,2,4, 5-cyclohexane tetracarboxylic dianhydride, 3 ', 4, 4' -biphenyl tetracarboxylic dianhydride and 3,3 ', 4, 4' -biphenyl sulfone tetracarboxylic dianhydride.
5. The liquid crystal aligning agent according to claim 3 or 4, wherein: the diamine component b is a diamine compound b-2, the diamine compound b-2 is p-phenylenediamine, m-phenylenediamine, 1, 5-diaminonaphthalene, 1, 8-diaminonaphthalene, p-aminophenylethylamine, 4 '-diaminodiphenylmethane, 4' -diaminodiphenylethane, 4 '-diaminodiphenylether, 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, n '-bis (4-aminophenyl) piperazine, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2, 4-diaminododecyloxybenzene, 2, 4-diaminooctadecyloxybenzene, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2-bis (4-aminophenyl) hexafluoropropane, 4- (4-heptylcyclohexyl) phenyl-3, 5-diaminobenzoate, 2' -dimethyl-4, 4 '-diaminobiphenyl, 4' -diaminobenzamide, 1- (4- (4-pentylcyclohexylcyclohexyl) phenoxy) -2, 4-diaminobenzene, 1- (4- (4-heptylcyclohexyl) phenoxy) -2, 4-diaminobenzene and 3, 5-diaminobenzoic acid.
6. The liquid crystal aligning agent according to claim 3, wherein: the solvent component is one or more of N-methyl-2-pyrrolidone, gamma-butyrolactone, N-dimethylacetamide, N-dimethylformamide, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol methyl ethyl ether, ethylene glycol dimethyl ether and diethylene glycol monomethyl ether ethyl ester.
7. The liquid crystal aligning agent according to claim 6, wherein: the solvent component comprises an adverse solvent which can not cause polymer precipitation, the adverse solvent is one or more of methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclobutanone, methyl acetate, ethyl acetate, butyl acetate, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol methyl ethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, chlorobenzene and 1, 2-dichloroethane, and the adverse solvent accounts for 0-50% of the total weight of the solvent component.
8. The liquid crystal aligning agent according to claim 3, wherein: the polymer is synthesized by adding a molecular weight regulator, wherein the molecular weight regulator is one or more of maleic anhydride, phthalic anhydride, o-cyclohexane dicarboxylic anhydride, succinic anhydride, aniline, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, phenyl isocyanate and naphthyl isocyanate, and the molar ratio of the molecular weight regulator to the tetracarboxylic dianhydride component a is 0.01-10: 100.
9. the liquid crystal aligning agent according to claim 3, wherein: the additive is epoxy additive and/or silane compound additive with functional groups, the addition amount of the epoxy additive is 0.1-20% of the total weight of the polymer, and the addition amount of the silane compound additive with functional groups is 0.1-10% of the total weight of the polymer;
the epoxy additive is one or more of ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerol diglycidyl ether, N, N, N ', N ' -tetracyclooxypropyl-m-xylene diamine, 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-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane or N-bis (oxyethylene) -3-aminopropyltriethoxysilane.
10. Use of the liquid crystal aligning agent according to any one of claims 3 to 9 in a liquid crystal alignment film and/or a liquid crystal display element.
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