CN106479518B - Diamine compound and polyamic acid and preparation method thereof, polyimides, aligning agent for liquid crystal and liquid crystal cell - Google Patents
Diamine compound and polyamic acid and preparation method thereof, polyimides, aligning agent for liquid crystal and liquid crystal cell Download PDFInfo
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Abstract
The invention discloses a kind of diamine compound and polyamic acid and preparation method, polyimides, aligning agent for liquid crystal and liquid crystal cell.Compound disclosed by the invention is shown in formula I：Wherein, R1、R2、R3And R4It is each independently selected from H, CH3、‑CH2CH3And CH2CH2CH3.The preparation method of the compound includes：Coupling step and step of hydrogenation.The invention discloses diamine compounds and anhydride compound to react the polyamic acid for being converted into the preparation method of polyamic acid and being prepared according to this method.The invention also discloses be dehydrated the polyimides being transformed by polyamic acid of the present invention；Liquid crystal cell the invention also discloses the aligning agent for liquid crystal of polyamic acid and/or polyimides including the present invention and containing aligning agent for liquid crystal of the present invention.
Description
Technical field
The present invention relates to field of liquid crystal display more particularly to a kind of diamine compound and polyamic acid and preparation method thereof,
Polyimides, aligning agent for liquid crystal and liquid crystal cell.
Background technology
The liquid crystal orientation film used in liquid crystal display element is by high after glass baseplate surface coats aligning agent for liquid crystal
Temperature cures.With the fining of thin film field effect transistor liquid crystal display (TFT-LCD) display element, to aligning agent for liquid crystal
Requirement it is higher and higher, do not require nothing more than aligning agent for liquid crystal have good liquid crystal aligning and electrical property, also require in extreme item
Part is (such as：High temperature) Accumulating charge is few, accumulated charge release when having high voltage holding ratio, low ion concentration, applying DC voltage
The characteristics such as speed is fast.
Currently, under extreme conditions, especially under the high temperature conditions, available liquid crystal alignment agent cannot meet high voltage holding
Residual charge low requirement when rate, low ion concentration, application DC voltage, can meet above-mentioned requirements it is therefore desirable to provide a kind of
Aligning agent for liquid crystal.
Invention content
The present invention provides a kind of diamine compound and polyamic acid and preparation method thereof, polyimides, aligning agent for liquid crystal
And liquid crystal cell, solving aligning agent for liquid crystal in the prior art, voltage retention is low at high temperature, high ion density, applies direct current
Residual charge high problem when pressure.
According to an aspect of the present invention, a kind of diamine compound is provided, the compound is shown in formula I：
Wherein, R1、R2、R3And R4It is each independently selected from-H ,-CH3、-CH2CH3With-CH2CH2CH3。
According to another aspect of the present invention, a kind of preparation method according to the compounds of this invention is provided, this method includes：
Coupling step：Compound shown in Formula II is reacted with compound shown in formula III, is converted into compound shown in formula IV；
Step of hydrogenation：- NO in compound shown in formula IV2It is reduced to-NH2Afterwards, it is converted into compound shown in Formulas I；
Wherein, the R in compound shown in Formula II and formula IV1、R2、R3And R4It is each independently selected from-H ,-CH3、-CH2CH3
With-CH2CH2CH3。
Optionally, preparation in accordance with the present invention, the coupling step are specially：
By compound, sodium tert-butoxide, tris(dibenzylideneacetone) dipalladium and 2- (two shown in compound, formula III shown in Formula II
Tertiary butyl phosphine) biphenyl be added toluene in carry out back flow reaction.
Optionally, preparation in accordance with the present invention, the step of hydrogenation are specially：Compound shown in formula IV is made in palladium carbon
It is compound shown in Formulas I for hydro-conversion under conditions of catalyst.
According to another aspect of the present invention, a kind of preparation method of polyamic acid, diamine compounds and acid anhydrides are provided
The reaction of class compound is converted into polyamic acid, wherein
The diamine compounds include compound shown in Formulas I according to the present invention and at least one following compounds：
Optionally, preparation in accordance with the present invention, any one of the anhydride compound in following：
According to another aspect of the present invention, a kind of polyamic acid that method produced according to the present invention obtains is provided.
According to another aspect of the present invention, a kind of polyimides is provided, which is by according to the present invention poly-
Amic acid dehydration is transformed.
According to another aspect of the present invention, a kind of aligning agent for liquid crystal is provided, which includes according to the present invention
Polyamic acid and/or polyimides according to the present invention.
According to another aspect of the present invention, a kind of liquid crystal cell is provided, which includes liquid according to the present invention
Brilliant alignment agent.
Beneficial effects of the present invention are as follows：
The compound of the present invention is two amine compounds containing triazole aromatic heterocycle structure, secondary amine structure and biphenyl structural
The compound is introduced into polyamic acid and polyimides by object, and obtained polyamides propylhomoserin and polyimides are used for liquid crystal aligning
In agent, though make aligning agent for liquid crystal under the high temperature conditions still have high voltage holding ratio, low ion concentration, apply DC voltage when
The low feature of residual charge.
Specific implementation mode
Specific implementation mode is only the description of the invention, without constituting the limitation to the content of present invention, below in conjunction with
Invention is further explained and description for specific embodiment.
According to an aspect of the present invention, a kind of diamine compounds are provided, the compound is shown in formula I：
Wherein, R1、R2、R3And R4It is each independently selected from-H ,-CH3、-CH2CH3With-CH2CH2CH3。
Compound according to the present invention, shown in formula I, triazole structure and secondary amine structure can make the compound in high temperature
Under the conditions of have high voltage holding ratio and low charge residue, biphenyl structural make the compound have good liquid crystal aligning.Cause
Compound shown in Formulas I is introduced into polyamides propylhomoserin or polyimides by this, then takes polyamic acid and polyimides for liquid crystal
Into agent, can make aligning agent for liquid crystal have good liquid crystal aligning performance, under the high temperature conditions still have high voltage holding ratio,
Residual charge is low when low ion concentration, application DC voltage.
According to another aspect of the present invention, a kind of preparation method according to the compounds of this invention is provided, this method includes：
Coupling step：Compound shown in Formula II is contacted with compound shown in formula III, is converted into compound shown in formula IV；
Step of hydrogenation：- NO in compound shown in formula IV2It is reduced to-NH2Afterwards, it is converted into compound shown in Formulas I；
Wherein, the R in compound shown in Formula II and formula IV1、R2、R3And R4It is each independently selected from-H ,-CH3、-CH2CH3
With-CH2CH2CH3。
A kind of embodiment of method produced according to the present invention, coupling step are specially：
By compound, sodium tert-butoxide, tris(dibenzylideneacetone) dipalladium and 2- (two shown in compound, formula III shown in Formula II
Tertiary butyl phosphine) biphenyl be added toluene in carry out back flow reaction.
A kind of embodiment of method produced according to the present invention, step of hydrogenation are specially：Compound is in palladium carbon shown in formula IV
It is compound shown in Formulas I as hydro-conversion under conditions of catalyst.
According to the preparation method of the compounds of this invention, compound according to the present invention can be prepared, is set forth below specific
The synthesis of compound illustrates the preparation method of the present invention.
The particular compound of synthesis is as shown in Formulas I -1：
Specific synthetic route reaction equation is as follows：
Specifically synthetic method is：
Coupling step is carried out first：By 10.71g (50mmol, 1eq) 3,5- bis- bromo- 1,2,4- triazoles, 27.22g
(120mmol, 2.4eq) 4- amino -4 '-nitrobiphenyl, 14.4g (150mmol, 3eq) sodium tert-butoxide are dissolved in 350mL toluene
In, be then added in the solution 1.8g (2mmol, 0.04eq) tris(dibenzylideneacetone) dipalladiums and 1.19g (4mmol,
0.08eq) 2- (di-t-butyl phosphine) biphenyl, above-mentioned mixed solution flow back 12h under a nitrogen atmosphere, and reaction, which finishes, to be cooled to room temperature
It is filtered, filtered solid is dissolved in the in the mixed solvent of 300mL acetone and dichloromethane, with the hydrochloric acid of 200mL 5%
Aqueous solution washs organic layer, is concentrated after organic layer is dried with anhydrous magnesium sulfate, and obtained crude product is crossed silicagel column
Purifying obtains 18.6g intermediates, and yield 75% identifies obtained intermediate with nuclear-magnetism, and nuclear magnetic spectrogram parses such as
Under：
1H-NMR (400MHz, DMSO-d6), δ (ppm)：9.78 (1H, s), 8.29 (4H, d), 7.95 (4H, d), 7.55
(4H, d), 7.37 (4H, d).
Then step of hydrogenation is carried out：The midbody compound 18g of above-mentioned synthesis is dissolved in 150mL absolute ethyl alcohols and dimethyl
Formamide (DMF) mixed solvent (volume ratio 1:1) in, 2.5g palladium carbons (Pd/C) is added, mixed solution is added under a hydrogen atmosphere
Pressure reaction 8h.After reaction, Filtration of catalyst rotates filtrate, is carried out being recrystallized to give 11.2g formulas with absolute ethyl alcohol
Diamine compound shown in I-1, yield 71% have carried out nuclear-magnetism characterization, to nuclear-magnetism to -1 compound represented of Formulas I of synthesis
Spectrum elucidation is as follows：
1H-NMR (400MHz, DMSO-d6), δ (ppm)：9.76 (1H, s), 7.54 (4H, d), 7.38 (8H, t), 6.48
(4H, d), 4.02 (4H, s).
According to another aspect of the present invention, a kind of preparation method of polyamic acid, diamine compounds and acid anhydrides are provided
The reaction of class compound is converted into polyamic acid, wherein
Diamine compounds include compound shown in Formulas I according to the present invention and at least one following compounds：
Wherein, must include in the diamine compounds of selection according to compound shown in formula I, in addition can be from
At least one, certainly including but not limited to above-mentioned shown compound, or can occur is selected in above-mentioned diamine compounds
Unlisted other diamine compounds of reaction, can select as long as the diamine compounds of above-mentioned polymerisation can occur
With, and include within the scope of the present invention.
A kind of embodiment of method produced according to the present invention, any one of anhydride compound in following：
Wherein, the anhydride compound of selection can select at least one from above-mentioned anhydride compound, include certainly
But it is not limited to above compound, or the unlisted other anhydride compounds that can be reacted, as long as on capable of occurring
Stating the anhydride compound of polymerisation can select, and include within the scope of the present invention.
According to another aspect of the present invention, a kind of polyamic acid that method produced according to the present invention obtains is provided.
The following general formula may be used according to one kind in polyamic acid of the present invention to indicate：
Wherein, R5One kind in following radicals：
R6For：
R7It is a kind of in following radicals：
Certain above-mentioned general formula only represents one kind in polyamides propylhomoserin of the present invention, can not cover method produced according to the present invention
Obtained all polyamic acids, as long as therefore the obtained polyamic acid of method produced according to the present invention be all contained in the present invention's
In protection domain.
According to another aspect of the present invention, a kind of polyimides is provided, which is by according to the present invention poly-
Amic acid dehydration is transformed.
The following general formula may be used according to one kind in polyimides of the present invention to indicate：
Wherein, R5One kind in following radicals：
R6For：
R7It is a kind of in following radicals：
Certainly, above-mentioned general formula only represents one kind in polyimides of the present invention, can not cover side produced according to the present invention
All polyimides that method obtains, as long as therefore the obtained polyimides of method produced according to the present invention be all contained in the present invention
Protection domain in.
Structure of the polyamic acid and polyimides of the present invention containing with good grounds the compounds of this invention, by the polyamides of the present invention
Propylhomoserin and polyimides are applied to aligning agent for liquid crystal, aligning agent for liquid crystal can be made to have good liquid crystal aligning performance, and in high temperature
Under the conditions of still there is high voltage holding ratio, low ion concentration, Accumulating charge is few, accumulated charge release speed when applying DC voltage
Spend fast feature.
According to another aspect of the present invention, a kind of aligning agent for liquid crystal is provided, which includes according to the present invention
Polyamic acid and/or polyimides according to the present invention.
According to another aspect of the present invention, a kind of liquid crystal cell is provided, which includes that liquid crystal according to the present invention takes
To agent.
Aligning agent for liquid crystal and liquid crystal cell according to the present invention contain liquid crystal polyamides propylhomoserin according to the present invention and polyamides is sub-
Amine, therefore aligning agent for liquid crystal according to the present invention and liquid crystal cell all have good liquid crystal aligning performance, and under the high temperature conditions
Still with high voltage holding ratio, low ion concentration, apply DC voltage when Accumulating charge is few, accumulated charge rate of release is fast
Feature.
It can thus be seen that compound according to the present invention, polyamic acid, polyimides and preparation method thereof, liquid crystal take
To agent and liquid crystal cell, optional factor is more, and claim according to the present invention can be combined into a variety of different embodiments, therefore real
It is only the description of the invention to apply example, rather than limiting the invention.Below in conjunction with embodiment, present invention is described.
Following embodiment is specially the embodiment about polyamides propylhomoserin, polyimides, aligning agent for liquid crystal and liquid crystal cell.
In the present invention, abridge representative compound title it is as follows：
Formula IV -1：1,2,3,4- cyclobutane tetracarboxylic dianhydrides；
Formula IV -2：Bicyclic [3,3,0] octane -2,4,6,8- tetracarboxylic dianhydrides；
Formula IV -3：Equal benzene tertacarbonic acid's dianhydride；
Formula V -1：P-phenylenediamine；
Formula V -2：4,4 '-diaminodiphenylmethane；
Formula V -3：3,5- diaminostilbenes, 2,4- triazoles；
Formula V -4：Bis- (4- amino-benzene oxygens) pentanes of 1,5-；
Compound shown in Formulas I is the compound of the present invention；
NMP：N-Methyl pyrrolidone；
BC：Butyl cellosolve；
GBL：Gamma-butyrolacton.
Wherein, Examples 1 to 4 is the embodiment about polyamic acid preparation method.
Embodiment 1
- 1 (p-phenylenediamine) 8.64g (80mmol, 0.8eq) of diamine compound Formula V, formula are added in 500ml three-necked flasks
Compound 8.67g shown in I-1 (20mmol, 0.2eq) and 210mL NMP (N-Methyl pyrrolidone) solvent, at room temperature magnetic force stir
Dissolving is mixed, with the air in nitrogen displacement flask, Formula VI-1 (1,2,3,4- rings are then slowly added into mixed solution
Butane tetracarboxylic acid dianhydride) 19.6g (100mmol, 1eq), it is stirred at room temperature and obtains the polyamide that mass concentration is 15% for 24 hours
Acid solution is labeled as PAA-1.
Embodiment 2
- 1 (p-phenylenediamine) 8.64g (80mmol, 0.8eq) of diamine compound Formula V is added in 500ml three-necked flasks, changes
Close -3 (3,5- diaminostilbenes, 2,4- triazoles) 1.0g (10mmol, 0.1eq), compound 4.33g shown in Formulas I -1 of object Formula V
(10mmol, 0.1eq) and 190mL NMP (N-Methyl pyrrolidone) solvent, magnetic agitation dissolving, is used in combination nitrogen to replace at room temperature
Air in flask.Formula VI-1 (1,2,3,4- cyclobutane tetracarboxylic dianhydride) 19.6g is slowly added into mixed solution
(100mmol, 1.0eq) is stirred at room temperature and obtains the polyamic acid solution that mass concentration is 15% for 24 hours, be labeled as PAA-2.
Embodiment 3
- 1 (p-phenylenediamine) 8.64g (80mmol, 0.8eq) of diamine compound Formula V is added in the three-necked flask of 500ml,
Formula V-4 (1,5- bis- (4- amino-benzene oxygens) pentanes) 2.86g (10mmol, 0.1eq), compound 4.33g shown in Formulas I -1
(10mmol, 0.1eq) and 230mL NMP (N-Methyl pyrrolidone) solvent, magnetic agitation dissolving, is used in combination nitrogen to replace at room temperature
Air in flask is slowly added to Formula VI-2 (bicyclic [3,3,0] octane -2,4,6,8- tetrabasic carboxylic acids into mixed solution
Dianhydride) 25.0g (100mmol, 1eq), it is stirred at room temperature and obtains the polyamic acid solution that mass concentration is 15% for 24 hours, label
For PAA-3.
Embodiment 4
- 1 (p-phenylenediamine) 6.48g (60mmol, 0.6eq) of diamine compound Formula V is added in 500ml three-necked flasks, changes
Close -3 (3,5- diaminostilbenes, 2,4- triazoles) 1.98g (20mmol, 0.2eq), compound 8.67g shown in Formulas I -1 of object Formula V
(20mmol, 0.2eq) and 214mL NMP (N-Methyl pyrrolidone) solvent, at room temperature magnetic agitation dissolving, is replaced with nitrogen and is burnt
Air in bottle.Formula VI-1 (1,2,3,4- cyclobutane tetracarboxylic dianhydride) 15.68g is slowly added into mixed solution
(80mmol, 0.8eq), Formula VI-2 (bicyclic [3,3,0] octane -2,4,6,8- tetracarboxylic dianhydrides) 5.0g (20mmol,
0.2eq), it is stirred at room temperature and obtains the polyamic acid solution that mass concentration is 15% for 24 hours, be labeled as PAA-4.
Embodiment 5~6 is about the embodiment for preparing polyimides.
Embodiment 5
- 1 (p-phenylenediamine) 7.56g (70mmol, 0.7eq) of diamine compound Formula V is added in the three-necked flask of 500ml,
Formula V-3 (3,5- diaminostilbenes, 2,4- triazoles) 1.0g (10mmol, 0.1eq), compound 8.67g shown in Formulas I -1
(20mmol, 0.2eq) and 210mL NMP (N-Methyl pyrrolidone) solvent, at room temperature magnetic agitation dissolving, is replaced with nitrogen and is burnt
Air in bottle.Formula VI-1 (1,2,3,4- cyclobutane tetracarboxylic dianhydride) is slowly added into above-mentioned mixed solution
19.6g (100mmol, 1eq), after being stirred at room temperature for 24 hours, NMP (N-Methyl pyrrolidone) solvent of additional 215mL is prepared
The polyamic acid solution for being 8% at mass concentration.
The polyamic acid solution that the above-mentioned mass concentrations of 100g are 8% is weighed, 5.4g acetic anhydride and 4.18g pyridines is added, in
3h is reacted at 80 DEG C, solution is poured into excessive methanol and is precipitated, is dried under reduced pressure, obtains after washing 3 times to sediment with methanol
Polyimide powder is labeled as SPI-1.
Embodiment 6
- 1 (p-phenylenediamine) 8.64g (80mmol, 0.8eq) of diamine compound Formula V is added in 500ml three-necked flasks, changes
Close -4 (1,5- bis- (4- amino-benzene oxygens) pentanes) 2.86g (10mmol, 0.1eq), compound 4.33g shown in Formulas I -1 of object Formula V
(10mmol, 0.1eq) and 200mL NMP (N-Methyl pyrrolidone) solvent, magnetic agitation dissolving, is used in combination nitrogen to replace at room temperature
Air in flask.Formula VI-1 (1,2,3,4- cyclobutane tetracarboxylic dianhydride) 15.68g is slowly added into mixed solution
(80mmol, 0.8eq) and Formula VI-3 (equal benzene tertacarbonic acid's dianhydride) 4.36g (20mmol, 0.2eq), is stirred at room temperature
After for 24 hours, NMP (N-Methyl pyrrolidone) solvent of additional 210mL is configured to the polyamic acid solution that mass concentration is 8%.
The polyamic acid solution that the above-mentioned mass concentrations of 100g are 8% is weighed, 4.6g acetic anhydride and 3.56g pyridines is added, in
3h is reacted at 80 DEG C, solution is poured into excessive methanol and is precipitated, precipitation is dried under reduced pressure after washing 3 times with methanol, is gathered
Acid imide powder is labeled as SPI-2.
Following comparative examples for about polyamides propylhomoserin preparation method
Comparative example 1
- 1 (p-phenylenediamine) 8.64g (80mmol, 0.8eq) of diamine compound Formula V is added in the three-necked flask of 500ml,
Formula V-2 (4,4 '-diaminodiphenylmethane) 3.97g (20mmol, 0.2eq) and 210mL NMP (N- crassitudes
Ketone) solvent, at room temperature magnetic agitation dissolve, be used in combination nitrogen displacement flask in air.It is slowly added into above-mentioned mixed solution
Formula VI-1 (1,2,3,4- cyclobutane tetracarboxylic dianhydride) 19.6g (100mmol, 1eq), is stirred at room temperature for 24 hours, obtains
The polyamic acid solution that mass concentration is 15% is labeled as PAA-5.
Comparative example 1 compared with Example 1, the compound of the present invention Formulas I -1 is not added, add 0.2eq Formula V -2 (4,
4 '-diaminodiphenylmethane), other conditions are identical.
Comparative example 2
- 1 (p-phenylenediamine) 7.56g (70mmol, 0.7eq) of diamine compound Formula V is added in the three-necked flask of 500ml,
Formula V-4 (1,5- bis- (4- amino-benzene oxygens) pentanes) 8.60g (30mmol, 0.3eq) and 215mL NMP (N- methyl pyrroles
Pyrrolidone) solvent, at room temperature magnetic agitation dissolve, be used in combination nitrogen displacement flask in air.Slowly into above-mentioned mixed solution
Formula VI-3 (equal benzene tertacarbonic acid's dianhydride) 21.8g (100mmol, 1eq) is added, entire reaction is stirred for 24 hours, obtained at room temperature
The polyamic acid solution for being 15% to mass concentration is labeled as PAA-6.
The compound of the present invention I-1 is not added compared with embodiment 1-4 for comparative example 2.
Embodiment 7-12 is about the embodiment for preparing aligning agent for liquid crystal
Embodiment 7
Polyamic acid solution (PAA-1) 50g obtained in embodiment 1 is weighed, 41g NMP (N-Methyl pyrrolidone) are added
With 34g BC (butyl cellosolve), magnetic agitation, is configured to the aligning agent for liquid crystal 1 that mass concentration is 6% at room temperature.
Embodiment 8-10
Other than changing the polyamic acid solution in embodiment 7 into PAA-2, PAA-3, PAA-4 respectively, other conditions and reality
Apply it is identical in example 7, be configured to respectively mass concentration be 6% aligning agent for liquid crystal 2, aligning agent for liquid crystal 3, aligning agent for liquid crystal 4.
Embodiment 11
The polyimide solids SPI-13g obtained in embodiment 5 is weighed in 100mL flasks, sequentially adds 20g GBL
(gamma-butyrolacton), 17g NMP (N-Methyl pyrrolidone) and 10g BC (butyl cellosolve), mixture abundant magnetic at 50 DEG C
Power stirring and dissolving is configured to the aligning agent for liquid crystal 5 that mass concentration is 6%.
Embodiment 12
Polyimide solids (SPI-2) 4.5g obtained in embodiment 6 is weighed in 100mL flasks, sequentially adds 35g
GBL (gamma-butyrolacton), 20.5g NMP (N-Methyl pyrrolidone) and 15g BC (butyl cellosolve), mixture fill at 50 DEG C
Divide magnetic agitation dissolving, is configured to the aligning agent for liquid crystal 6 that mass concentration is 6%.
Comparative example 3
Polyamic acid solution (PAA-5) 50g obtained in comparative example 1 is weighed, 41g NMP (N-Methyl pyrrolidone) are added
With 34g BC (butyl cellosolve), magnetic agitation, is configured to the aligning agent for liquid crystal 7 that mass concentration is 6% at room temperature.
Comparative example 4
Polyamic acid solution (PAA-6) 75g obtained in comparative example 2 is weighed, 62g NMP (N-Methyl pyrrolidone) are added
With 50g BC (butyl cellosolve), magnetic agitation, is configured to the aligning agent for liquid crystal 8 that mass concentration is 6% at room temperature.
By embodiment 1-6, after liquid crystal cell is made in aligning agent for liquid crystal prepared by comparative example 1-2, orientation characteristic, electricity are carried out respectively
Press the measurement of conservation rate, residual charge, ion concentration.
The preparation of liquid crystal cell
By aligning agent for liquid crystal be spun on cleaning after ito glass substrate surface, the preliminary drying 55s on 85 DEG C of hot plate, then
Cure 30min in 230 DEG C of drying boxes, the film that thickness is about 100nm is formed on ito glass substrate surface.It is taken using friction
To device with fixed friction condition (substrate speed of service 30mm/sec, roller intrusion 0.4mm and friction velocity 1000rpm)
It rubs to the film, obtains the ito glass substrate with liquid crystal aligning ability.Take 2 pieces of above-mentioned bases with aligning agent for liquid crystal
After placing 6 μm of spacer on one piece of glass substrate wherein, fabric width frame is applied according to preset program in substrate surface for plate
Glue then fits on another piece of substrate in such a way that alignment layer surface is antiparallel relative to frictional direction and sky liquid crystal cell is made.
Liquid crystal (MAT-09-1284, Merck KGaA corporation) is injected into the liquid crystal cell, and lateral electric field type is made in injection hole sealing
(FFS or IPS) type liquid crystal cell.
The measurement of liquid crystal aligning
The liquid crystal cell of above-mentioned making is observed using petrographic microscope, it will be almost without the liquid crystal cell for finding that light penetrates
It is considered as liquid crystal aligning " excellent ", find minute quantity light transmission is considered as " good ", there is being considered as " bad " for a large amount of light transmissions.
The measurement of voltage retention
Using the voltage retention of liquid crystal evaluation of physical property system measurement liquid crystal cell, 4V is applied to liquid crystal cell at 25 DEG C and 60 DEG C
Voltage measures the voltage retention after 16.67ms.
The measurement of residual charge
Using the residual charge of liquid crystal evaluation of physical property system measurement liquid crystal cell, 10V voltages are applied to liquid crystal cell at 60 DEG C
Discharge 1min after 30min, measures the residual voltage value (mV) after 30min.
The evaluation of ion concentration
Using the ion concentration of liquid crystal evaluation of physical property system measurement liquid crystal cell, 10V, 0.01Hz are applied to liquid crystal cell at 60 DEG C
Triangular wave, ion concentration is calculated by triangle approximation method.
After liquid crystal cell is made in the embodiment 7-14 aligning agent for liquid crystal prepared, respectively carry out orientation characteristic, voltage retention,
The evaluation of ion concentration and residual charge, evaluation result are as shown in table 1
Table 1
As shown in Table 1, it is carried with comparative example 3~4 by using 7-12 of the embodiment of the present invention aligning agent for liquid crystal 1~6 provided
The aligning agent for liquid crystal 7~8 of confession all has good liquid crystal aligning performance；The aligning agent for liquid crystal 1 that the embodiment of the present invention 7~12 provides
~6 have high voltage holding ratio compared with the aligning agent for liquid crystal 7~8 that comparative example 3~4 provides at higher temperature (60 DEG C),
It is all higher than 98%, or even 99.1% can be reached, and is then less than 98% in the aligning agent for liquid crystal 7~8 that comparative example 3~4 provides, even
Only 95.6%；The liquid crystal the most significantly provided with comparative example 3~4 for the aligning agent for liquid crystal 1~6 that embodiment 7-12 is provided takes
It is compared to agent 7~8, its residual charge has obtained great reduction, even as low as 60 under the determination condition of 60 DEG C of high temperature, and compares
It is even high to 550 compared with the residual charge of example 3~4；Ion concentration in additional embodiment 7~12 also obtains compared with comparative example
It greatly reduces, it might even be possible to down to 10, and 240 are then up in comparative example.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art
God and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent technologies
Within, then the present invention is also intended to include these modifications and variations.
Claims (10)
1. a kind of diamine compound, which is characterized in that the compound is shown in formula I：
Wherein, R1、R2、R3And R4It is each independently selected from-H ,-CH3、-CH2CH3With-CH2CH2CH3。
2. a kind of preparation method of diamine compound as described in claim 1, which is characterized in that this method includes：
Coupling step：Compound shown in Formula II is reacted with compound shown in formula III, is converted into compound shown in formula IV；
Step of hydrogenation：- NO in compound shown in formula IV2It is reduced to-NH2Afterwards, it is converted into compound shown in Formulas I；
Wherein, the R in compound shown in Formula II and formula IV1、R2、R3And R4It is each independently selected from-H ,-CH3、-CH2CH3With-
CH2CH2CH3。
3. preparation method as claimed in claim 2, which is characterized in that the coupling step is specially：
By compound, sodium tert-butoxide, tris(dibenzylideneacetone) dipalladium shown in compound, formula III shown in Formula II and 2- (two tertiary fourths
Base phosphine) biphenyl be added toluene in carry out back flow reaction.
4. preparation method as claimed in claim 2, which is characterized in that the step of hydrogenation is specially：Compound shown in formula IV
Hydro-conversion is compound shown in Formulas I under conditions of palladium carbon is as catalyst.
5. a kind of preparation method of polyamic acid, which is characterized in that diamine compounds and the reaction of anhydride compound are converted into
Polyamic acid, wherein
The diamine compounds include compound shown in Formulas I and at least one following compounds in claim 1：
6. preparation method as claimed in claim 5, which is characterized in that the anhydride compound is any one in following
Kind：
7. a kind of polyamic acid that the preparation method as described in claim 5 or 6 obtains.
8. a kind of polyimides, which is characterized in that the polyimides be by described in claim 7 polyamic acid dehydration conversion and
At.
9. a kind of aligning agent for liquid crystal, which is characterized in that the aligning agent for liquid crystal include polyamic acid as claimed in claim 7 and/
Or polyimides according to any one of claims 8.
10. a kind of liquid crystal cell, which is characterized in that the liquid crystal cell includes the aligning agent for liquid crystal described in claim 9.
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| KR102020030B1 (en) * | 2017-08-24 | 2019-09-10 | 주식회사 엘지화학 | Polymer for liquid crystal aligning agent, amd liquid crystal aligning agent composition comprising the same, and liquid crystal aligning film, liquid crystal display device using the same |
| CN109535073A (en) * | 2018-11-26 | 2019-03-29 | 阜阳欣奕华材料科技有限公司 | Diamine compound and preparation method, polyamic acid and preparation method, polyimides, alignment agent and alignment films, display device |
| CN110041276B (en) * | 2019-04-24 | 2022-09-27 | 吉林大学 | Polyamine monomer of polyimide containing triazole structure, polymer thereof, preparation method and application |
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| CN101715459A (en) * | 2007-03-29 | 2010-05-26 | 阿克伦聚合物系统公司 | Optical compensation films with birefringence enhancing substituents for liquid crystal display |
| CN102604653A (en) * | 2011-01-19 | 2012-07-25 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display device, and compound and polymer used for producing the same |
| CN103911163A (en) * | 2012-12-28 | 2014-07-09 | Jsr株式会社 | Liquid crystal orientating agent, liquid crystal orientating film and liquid crystal display device |
| CN104046369A (en) * | 2013-03-14 | 2014-09-17 | 捷恩智株式会社 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
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| CN101715459A (en) * | 2007-03-29 | 2010-05-26 | 阿克伦聚合物系统公司 | Optical compensation films with birefringence enhancing substituents for liquid crystal display |
| CN102604653A (en) * | 2011-01-19 | 2012-07-25 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display device, and compound and polymer used for producing the same |
| CN103911163A (en) * | 2012-12-28 | 2014-07-09 | Jsr株式会社 | Liquid crystal orientating agent, liquid crystal orientating film and liquid crystal display device |
| CN104046369A (en) * | 2013-03-14 | 2014-09-17 | 捷恩智株式会社 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
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