CN106479518A - 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、-CH2CH3With-CH2CH2CH3.The preparation method of this compound includes：Coupling step and step of hydrogenation.The invention discloses diamine compounds and the reaction of anhydrides compound are converted into the preparation method of polyamic acid and the polyamic acid being prepared from according to the method.The invention also discloses the polyimides being transformed by polyamic acid of the present invention dehydration；The invention also discloses including polyamic acid and/or the aligning agent for liquid crystal of polyimides and the liquid crystal cell containing aligning agent for liquid crystal of the present invention 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
Used in liquid crystal display cells, liquid crystal orientation film is that hot setting forms after coating aligning agent for liquid crystal in glass baseplate surface.With becoming more meticulous of TFT LCDs (TFT-LCD) display element, requirement more and more higher to aligning agent for liquid crystal, do not require nothing more than aligning agent for liquid crystal and there is good liquid crystal aligning and electrical property, also require in extreme condition (such as：High temperature) there is high voltage holding ratio, low ion concentration, apply the characteristics such as Accumulating charge during DC voltage is few, accumulated charge rate of release is fast.
At present, under extreme conditions, especially under the high temperature conditions, available liquid crystal alignment agent can not meet high voltage holding ratio, low ion concentration, apply residual charge low requirement during DC voltage, it is therefore desirable to provide a kind of aligning agent for liquid crystal that can meet above-mentioned requirements.
Content of the invention
The invention provides a kind of diamine compound and polyamic acid and preparation method thereof, polyimides, aligning agent for liquid crystal and liquid crystal cell, solve the problems, such as in prior art aligning agent for liquid crystal voltage retention is low at high temperature, high ion density, to apply residual charge during DC voltage high.
According to an aspect of the present invention, there is provided a kind of diamine compound, this compound is shown in formula I：
Wherein, R1、R2、R3And R4It is each independently selected from-H ,-CH3、-CH2CH3With-CH2CH2CH3.
According to a further aspect in the invention, there is provided a kind of preparation method according to the compounds of this invention, the 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 Formula II and compound shown in formula IV1、R2、R3And R4It is each independently selected from-H ,-CH3、-CH2CH3With-CH2CH2CH3.
Alternatively, preparation in accordance with the present invention, described coupling step is specially：
Compound shown in compound shown in Formula II, formula III, sodium tert-butoxide, three (dibenzalacetone) two palladium and 2- (di-t-butyl phosphine) biphenyl are added in toluene and carries out back flow reaction.
Alternatively, preparation in accordance with the present invention, described step of hydrogenation is specially：The hydro-conversion under conditions of palladium carbon is as catalyst of compound shown in formula IV is compound shown in Formulas I.
According to a further aspect in the invention, there is provided a kind of preparation method of polyamic acid, diamine compounds and the reaction of anhydrides compound are converted into polyamic acid, wherein,
Described diamine compounds include compound and at least one following compound according to the Formulas I of the present invention：
Alternatively, preparation in accordance with the present invention, any one in following of described anhydrides compound：
According to a further aspect in the invention, there is provided the polyamic acid that a kind of method produced according to the present invention obtains.
According to a further aspect in the invention, there is provided a kind of polyimides, this polyimides is to be transformed by the polyamic acid dehydration according to the present invention.
According to a further aspect in the invention, there is provided a kind of aligning agent for liquid crystal, this aligning agent for liquid crystal includes the polyamic acid according to the present invention and/or the polyimides according to the present invention.
According to a further aspect in the invention, there is provided a kind of liquid crystal cell, this liquid crystal cell is included according to aligning agent for liquid crystal of the present invention.
Beneficial effects of the present invention are as follows：
The compound of the present invention is the diamine compound containing triazole aromatic heterocycle structure, secondary amine structure and biphenyl structural, this compound is introduced in polyamic acid and polyimides, the polyamides obtaining propylhomoserin and polyimides are used in aligning agent for liquid crystal, even if making aligning agent for liquid crystal still have high voltage holding ratio, low ion concentration under the high temperature conditions, apply residual charge low feature during DC voltage.
Specific embodiment
Specific embodiment is only the description of the invention, and does not constitute the restriction to present invention, below in conjunction with specific embodiment, the present invention is further described and describes.
According to an aspect of the present invention, there is provided a kind of diamine compounds, this compound is shown in formula I：
Wherein, R1、R2、R3And R4It is each independently selected from-H ,-CH3、-CH2CH3With-CH2CH2CH3.
According to the compound of the present invention, shown in formula I, triazole structure and secondary amine structure can make this compound have high voltage holding ratio and low charge residue under the high temperature conditions, and biphenyl structural makes this compound have good liquid crystal aligning.Therefore compound shown in Formulas I is introduced in polyamides propylhomoserin or polyimides, then polyamic acid and polyimides are used in aligning agent for liquid crystal, aligning agent for liquid crystal can be made to have good liquid crystal aligning performance, when still having high voltage holding ratio, low ion concentration, applying DC voltage under the high temperature conditions, residual charge is low.
According to a further aspect in the invention, there is provided a kind of preparation method according to the compounds of this invention, the 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 Formula II and compound shown in formula IV1、R2、R3And R4It is each independently selected from-H ,-CH3、-CH2CH3With-CH2CH2CH3.
A kind of embodiment of method produced according to the present invention, coupling step is specially：
Compound shown in compound shown in Formula II, formula III, sodium tert-butoxide, three (dibenzalacetone) two palladium and 2- (di-t-butyl phosphine) biphenyl are added in toluene and carries out back flow reaction.
A kind of embodiment of method produced according to the present invention, step of hydrogenation is specially：The hydro-conversion under conditions of palladium carbon is as catalyst of compound shown in formula IV is compound shown in Formulas I.
According to the preparation method of the compounds of this invention, the compound according to the present invention can be prepared, the synthesis that particular compound is set forth below illustrates to the preparation method of the present invention.
The particular compound of synthesis is as shown in Formulas I -1：
Concrete synthetic route reaction equation is as follows：
Specifically synthetic method is：
Carry out coupling step first：By 10.71g (50mmol，1eq)3,5- bis- bromo- 1,2,4- triazole，27.22g(120mmol，2.4eq) 4- amino -4 '-nitrobiphenyl，14.4g(150mmol，3eq) sodium tert-butoxide is dissolved in 350mL toluene，Then add 1.8g (2mmol in the solution，0.04eq) three (dibenzalacetone) two palladium and 1.19g (4mmol，0.08eq) 2- (di-t-butyl phosphine) biphenyl，Above-mentioned mixed solution flows back 12h under a nitrogen atmosphere，Reaction finishes and is cooled to room temperature and is filtered，Solid after filtering is dissolved in the mixed solvent that 300mL acetone is with dichloromethane，With the aqueous hydrochloric acid solution of 200mL 5%, organic layer is washed，Concentrate after organic layer is dried with anhydrous magnesium sulfate，The crude product obtaining is crossed silica column purification and obtains 18.6g intermediate，Yield is 75%，The intermediate obtaining is identified with nuclear-magnetism，Nuclear magnetic spectrogram parsing is as follows：
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 carry out step of hydrogenation：The midbody compound 18g of above-mentioned synthesis is dissolved in 150mL dehydrated alcohol and dimethylformamide (DMF) mixed solvent, and (volume ratio is 1:1), in, add 2.5g palladium carbon (Pd/C), by mixed solution compressive reaction 8h under a hydrogen atmosphere.After reaction terminates, Filtration of catalyst, filtrate revolving carries out being recrystallized to give the diamine compound shown in 11.2g Formulas I -1 with dehydrated alcohol, yield is 71%, has carried out nuclear-magnetism sign to the compound shown in the Formulas I -1 synthesizing, nuclear magnetic spectrogram is parsed 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 a further aspect in the invention, there is provided a kind of preparation method of polyamic acid, diamine compounds and the reaction of anhydrides compound are converted into polyamic acid, wherein,
Diamine compounds include compound and at least one following compound according to the Formulas I of the present invention：
Wherein, compound according to formula I must be included in the diamine compounds selected; in addition can be from least one from above-mentioned diamine compounds; certainly include but is not limited to above-mentioned shown compound; can also be the unlisted other diamine compounds that can react; as long as the diamine compounds that above-mentioned polyreaction can occur all can be selected, and include within the scope of the present invention.
A kind of embodiment of method produced according to the present invention, any one in following of anhydrides compound：
Wherein, from anhydrides compound can be from least one from above-mentioned anhydrides compound; certainly include but is not limited to above-claimed cpd; can also be the unlisted other anhydrides compounds that can react; as long as the anhydrides compound that above-mentioned polyreaction can occur all can be selected, and include within the scope of the present invention.
According to a further aspect in the invention, there is provided the polyamic acid that a kind of method produced according to the present invention obtains.
Can be represented using following formulas according to the class in polyamic acid of the present invention：
Wherein, R5Selected from one of following radicals：
R6For：
R7A kind of in following radicals：
Certainly above-mentioned formula only represents the class in polyamides propylhomoserin of the present invention, can not cover all polyamic acids that method produced according to the present invention obtains, as long as the polyamic acid that method therefore produced according to the present invention obtains is all contained in protection scope of the present invention.
According to a further aspect in the invention, there is provided a kind of polyimides, this polyimides is to be transformed by the polyamic acid dehydration according to the present invention.
Can be represented using following formulas according to the class in polyimides of the present invention：
Wherein, R5Selected from one of following radicals：
R6For：
R7A kind of in following radicals：
Certainly, above-mentioned formula only represents the class in polyimides of the present invention, can not cover all polyimides that method produced according to the present invention obtains, as long as the polyimides that method therefore produced according to the present invention obtains are all contained in protection scope of the present invention.
The polyamic acid of the present invention and polyimides structure all containing with good grounds the compounds of this invention, the polyamides propylhomoserin of the present invention 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 still there is high voltage holding ratio, low ion concentration under the high temperature conditions, apply that during DC voltage Accumulating charge is few, accumulated charge rate of release is fast.
According to a further aspect in the invention, there is provided a kind of aligning agent for liquid crystal, this aligning agent for liquid crystal includes the polyamic acid according to the present invention and/or the polyimides according to the present invention.
According to a further aspect in the invention, there is provided a kind of liquid crystal cell, this liquid crystal cell includes the aligning agent for liquid crystal according to the present invention.
Liquid crystal polyamides propylhomoserin all containing the with good grounds present invention of aligning agent for liquid crystal according to the present invention and liquid crystal cell and polyimides, aligning agent for liquid crystal therefore according to the present invention and liquid crystal cell are respectively provided with good liquid crystal aligning performance, and still have the characteristics that high voltage holding ratio, low ion concentration under the high temperature conditions, apply that during DC voltage Accumulating charge is few, accumulated charge rate of release is fast.
It can be seen that, according to the compound of the present invention, polyamic acid, polyimides and preparation method thereof, aligning agent for liquid crystal and liquid crystal cell, optional many factors, various different embodiments be can be combined out according to the claim of the present invention, therefore embodiment is only the description of the invention, rather than limitation of the present invention.Below in conjunction with embodiment, present invention is described.Following examples are specially the embodiment with regard to polyamides propylhomoserin, polyimides, aligning agent for liquid crystal and liquid crystal cell.
In the present invention, the title of the compound that abbreviation represents is as follows：
Formula IV -1：1,2,3,4- Tetramethylene. tetracarboxylic dianhydride；
Formula IV -2：Bicyclic [3,3,0] octane -2,4,6,8- tetracarboxylic dianhydride；
Formula IV -3：All benzene tertacarbonic acid's dianhydrides；
Formula V -1：P-phenylenediamine；
Formula V -2：4,4 '-MDA；
Formula V -3：3,5- diaminostilbene, 2,4- triazole；
Formula V -4：Double (4- amino-benzene oxygen) pentane 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, embodiment 1～4 is the embodiment with regard to polyamic acid preparation method.
Embodiment 1
Diamine compound Formula V -1 (p-phenylenediamine) 8.64g (80mmol is added in 500ml there-necked flask, 0.8eq), (the 20mmol of compound 8.67g shown in Formulas I -1,0.2eq) with 210mL NMP (N-Methyl pyrrolidone) solvent, magnetic agitation dissolving under room temperature, with the air in nitrogen displacement flask, then it is slowly added to Formula VI-1 (1 in mixed solution, 2,3,4- Tetramethylene. tetracarboxylic dianhydrides) 19.6g (100mmol, 1eq), 24h is stirred at room temperature, obtains the polyamic acid solution that mass concentration is 15%, be labeled as PAA-1.
Embodiment 2
Diamine compound Formula V -1 (p-phenylenediamine) 8.64g (80mmol is added in 500ml there-necked flask, 0.8eq), Formula V-3 (3,5- diaminostilbenes, 2,4- triazole) 1.0g (10mmol, 0.1eq), compound 4.33g shown in Formulas I -1 (10mmol, 0.1eq) and 190mL NMP (N-Methyl pyrrolidone) solvent, magnetic agitation dissolving under room temperature, and with the air in nitrogen displacement flask.It is slowly added to Formula VI-1 (1,2,3,4- Tetramethylene. tetracarboxylic dianhydride) 19.6g (100mmol, 1.0eq) in mixed solution, 24h is stirred at room temperature, obtains the polyamic acid solution that mass concentration is 15%, be labeled as PAA-2.
Embodiment 3
Diamine compound Formula V -1 (p-phenylenediamine) 8.64g (80mmol is added in the there-necked flask of 500ml， 0.8eq)，Formula V-4 (1,Double (4- amino-benzene oxygen) pentane of 5-) 2.86g (10mmol，0.1eq)，(the 10mmol of compound 4.33g shown in Formulas I -1，0.1eq) with 230mL NMP (N-Methyl pyrrolidone) solvent，Magnetic agitation dissolving under room temperature，And with the air in nitrogen displacement flask，It is slowly added to Formula VI-2 (bicyclic [3 in mixed solution,3,0] octane -2,4,6,8- tetracarboxylic dianhydride) 25.0g (100mmol，1eq)，24h is stirred at room temperature，Obtain the polyamic acid solution that mass concentration is 15%，It is labeled as PAA-3.
Embodiment 4
Diamine compound Formula V -1 (p-phenylenediamine) 6.48g (60mmol is added in 500ml there-necked flask, 0.6eq), Formula V-3 (3,5- diaminostilbenes, 2,4- triazole) 1.98g (20mmol, 0.2eq), compound 8.67g shown in Formulas I -1 (20mmol, 0.2eq) and 214mL NMP (N-Methyl pyrrolidone) solvent, magnetic agitation dissolving under room temperature, with the air in nitrogen displacement flask.It is slowly added to Formula VI-1 (1,2,3 in mixed solution, 4- Tetramethylene. tetracarboxylic dianhydride) 15.68g (80mmol, 0.8eq), Formula VI-2 (bicyclic [3,3,0] octane -2,4,6,8- tetracarboxylic dianhydride) 5.0g (20mmol, 0.2eq), 24h is stirred at room temperature, obtain the polyamic acid solution that mass concentration is 15%, be labeled as PAA-4.
Embodiment 5～6 is the embodiment with regard to preparing polyimides.
Embodiment 5
Diamine compound Formula V -1 (p-phenylenediamine) 7.56g (70mmol is added in the there-necked flask of 500ml, 0.7eq), Formula V-3 (3,5- diaminostilbenes, 2,4- triazole) 1.0g (10mmol, 0.1eq), compound 8.67g shown in Formulas I -1 (20mmol, 0.2eq) and 210mL NMP (N-Methyl pyrrolidone) solvent, magnetic agitation dissolving under room temperature, with the air in nitrogen displacement flask.It is slowly added to Formula VI-1 (1 in above-mentioned mixed solution, 2,3,4- Tetramethylene. tetracarboxylic dianhydride) 19.6g (100mmol, 1eq), after 24h is stirred at room temperature, NMP (N-Methyl pyrrolidone) solvent of additional 215mL, it is configured to the polyamic acid solution that mass concentration is 8%.
Weigh the polyamic acid solution that the above-mentioned mass concentration of 100g is 8%, add 5.4g acetic anhydride and 4.18g pyridine, react 3h at 80 DEG C, solution is poured into precipitation in excessive methanol, with methanol, drying under reduced pressure after 3 times is washed to precipitate, obtain polyimide powder, be labeled as SPI-1.
Embodiment 6
Diamine compound Formula V -1 (p-phenylenediamine) 8.64g (80mmol is added in 500ml there-necked flask, 0.8eq), Formula V-4 (1, double (4- amino-benzene oxygen) pentane of 5-) 2.86g (10mmol, 0.1eq), compound 4.33g shown in Formulas I -1 (10mmol, 0.1eq) and 200mL NMP (N-Methyl pyrrolidone) solvent, magnetic agitation dissolving under room temperature, and with the air in nitrogen displacement flask.It is slowly added to Formula VI-1 (1 in mixed solution, 2,3,4- Tetramethylene. tetracarboxylic dianhydride) 15.68g (80mmol, 0.8eq) with Formula VI-3 (equal benzene tertacarbonic acid's dianhydride) 4.36g (20mmol, 0.2eq), after 24h is stirred at room temperature, NMP (N-Methyl pyrrolidone) solvent of additional 210mL, is configured to the polyamic acid solution that mass concentration is 8%.
Weigh the polyamic acid solution that the above-mentioned mass concentration of 100g is 8%, add 4.6g acetic anhydride and 3.56g pyridine, react 3h at 80 DEG C, solution is poured into precipitation in excessive methanol, precipitation methanol wash 3 times after drying under reduced pressure, obtain polyimide powder, be labeled as SPI-2.
Following is comparative example with regard to polyamide processed with acid Preparation Method
Comparative example 1
Diamine compound Formula V -1 (p-phenylenediamine) 8.64g (80mmol is added in the there-necked flask of 500ml, 0.8eq), Formula V-2 (4,4 '-MDA) 3.97g (20mmol, 0.2eq) with 210mL NMP (N-Methyl pyrrolidone) solvent, magnetic agitation dissolving under room temperature, and with the air in nitrogen displacement flask.It is slowly added to Formula VI-1 (1,2,3,4- Tetramethylene. tetracarboxylic dianhydride) 19.6g (100mmol, 1eq) in above-mentioned mixed solution, 24h is stirred at room temperature, obtains the polyamic acid solution that mass concentration is 15%, be labeled as PAA-5.
Comparative example 1 compared with Example 1, does not add the Formula I-1 of the present invention, adds the Formula V -2 (4,4 '-MDA) of 0.2eq, other conditions are identical.
Comparative example 2
Diamine compound Formula V -1 (p-phenylenediamine) 7.56g (70mmol is added in the there-necked flask of 500ml, 0.7eq), Formula V-4 (1, double (4- amino-benzene oxygen) pentane of 5-) 8.60g (30mmol, 0.3eq) with 215mL NMP (N-Methyl pyrrolidone) solvent, magnetic agitation dissolving under room temperature, and with the air in nitrogen displacement flask.It is slowly added to Formula VI-3 (equal benzene tertacarbonic acid's dianhydride) 21.8g (100mmol, 1eq) in above-mentioned mixed solution, whole reaction stirs 24h at room temperature, obtains the polyamic acid solution that mass concentration is 15%, is labeled as PAA-6.
Comparative example 2, compared with embodiment 1-4, does not add the compound I-1 of the present invention.
Embodiment 7-12 is the embodiment with regard to preparing aligning agent for liquid crystal
Embodiment 7
Weigh polyamic acid solution (PAA-1) 50g obtaining in embodiment 1, add 41g NMP (N-Methyl pyrrolidone) and 34g BC (butyl cellosolve), magnetic agitation under room temperature, is configured to the aligning agent for liquid crystal 1 that mass concentration is 6%.
Embodiment 8-10
Except the polyamic acid solution in embodiment 7 is changed in addition to PAA-2, PAA-3, PAA-4 respectively, other conditions with identical in embodiment 7, be configured to aligning agent for liquid crystal 2, aligning agent for liquid crystal 3, aligning agent for liquid crystal 4 that mass concentration is 6% respectively.
Embodiment 11
Weigh the polyimide solids SPI-13g obtaining in embodiment 5 in 100mL flask, sequentially add 20g GBL (gamma-butyrolacton), 17g NMP (N-Methyl pyrrolidone) and 10g BC (butyl cellosolve), mixture abundant magnetic agitation dissolving at 50 DEG C, is configured to the aligning agent for liquid crystal 5 that mass concentration is 6%.
Embodiment 12
Weigh polyimide solids (SPI-2) 4.5g obtaining in embodiment 6 in 100mL flask, sequentially add 35g GBL (gamma-butyrolacton), 20.5g NMP (N-Methyl pyrrolidone) and 15g BC (butyl cellosolve), mixture abundant magnetic agitation dissolving at 50 DEG C, is configured to the aligning agent for liquid crystal 6 that mass concentration is 6%.
Comparative example 3
Weigh polyamic acid solution (PAA-5) 50g obtaining in comparative example 1, add 41g NMP (N-Methyl pyrrolidone) and 34g BC (butyl cellosolve), magnetic agitation under room temperature, is configured to the aligning agent for liquid crystal 7 that mass concentration is 6%.
Comparative example 4
Weigh polyamic acid solution (PAA-6) 75g obtaining in comparative example 2, add 62g NMP (N-Methyl pyrrolidone) and 50g BC (butyl cellosolve), magnetic agitation under room temperature, is configured to the aligning agent for liquid crystal 8 that mass concentration is 6%.
By embodiment 1-6, after the aligning agent for liquid crystal of comparative example 1-2 preparation makes liquid crystal cell, carry out the mensure of orientation characteristic, voltage retention, residual charge, ion concentration respectively.
The preparation of liquid crystal cell
Aligning agent for liquid crystal is spun on the ito glass substrate surface after cleaning, preliminary drying 55s on 85 DEG C of hot plate, with solidifying 30min in 230 DEG C of drying baker, form, on ito glass substrate surface, the thin film that thickness is about 100nm.Adopt friction orientation device with fixing friction condition (substrate speed of service 30mm/sec, running roller intrusion 0.4mm and friction velocity 1000rpm), this thin film to be rubbed, obtain the ito glass substrate with liquid crystal aligning ability.Take 2 pieces of above-mentioned substrates with aligning agent for liquid crystal, after 6 μm of sept is placed wherein on one piece of glass substrate, it is coated with sealed plastic box according to program set in advance in substrate surface, subsequently fitted to respect to the antiparallel mode of frictional direction with alignment layer surface and make sky liquid crystal cell on another piece of substrate.Injection liquid crystal (MAT-09-1284, Merck KGaA company system) into this liquid crystal cell, lateral electric field type (FFS or IPS) type liquid crystal cell is made in hand-hole sealing.
The mensure of liquid crystal aligning
The liquid crystal cell of above-mentioned making is observed using polarizing microscope, is not almost found that the liquid crystal cell of light transmission is considered as liquid crystal aligning " excellent ", find very small amount light transmission is considered as " good ", and have a large amount of light transmissions is considered as " bad ".
The mensure of voltage retention
Using the voltage retention of liquid crystal evaluation of physical property system measurement liquid crystal cell, at 25 DEG C and 60 DEG C, 4V voltage is applied to liquid crystal cell, measure the voltage retention after 16.67ms.
The mensure of residual charge
Using the residual charge of liquid crystal evaluation of physical property system measurement liquid crystal cell, apply to discharge after 10V voltage 30min at 60 DEG C 1min to liquid crystal cell, 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, at 60 DEG C, 10V, the triangular wave of 0.01Hz are applied to liquid crystal cell, ion concentration is calculated by triangle method of approximation.
The aligning agent for liquid crystal of embodiment 7-14 preparation is made after liquid crystal cell, carries out the evaluation of orientation characteristic, voltage retention, ion concentration and residual charge respectively, evaluation result is as shown in table 1
Table 1
As shown in Table 1, it is respectively provided with good liquid crystal aligning performance by using the aligning agent for liquid crystal 7～8 that the aligning agent for liquid crystal 1～6 that embodiment of the present invention 7-12 provides is provided with comparative example 3～4；The aligning agent for liquid crystal 1～6 that the embodiment of the present invention 7～12 provides has 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%, even 99.1% can be reached, and in the aligning agent for liquid crystal 7～8 that comparative example 3～4 provides, be then less than 98%, or even only 95.6%；Compared with the aligning agent for liquid crystal 7～8 that the aligning agent for liquid crystal 1～6 the most significantly providing for embodiment 7-12 is provided with comparative example 3～4, under the condition determination of 60 DEG C of high temperature, its residual charge has obtained great reduction, even as low as 60, and the residual charge of comparative example 3～4 even high to 550；Ion concentration in additional embodiment 7～12 has also obtained greatly reducing it might even be possible to as little as 10 compared with comparative example, and then up to 240 in comparative example.
Obviously, those skilled in the art the present invention can be carried out various change and modification without departing from the spirit and scope of the present invention.So, if these modifications of the present invention and modification belong within the scope of the claims in the present invention and its equivalent technologies, then the present invention is also intended to comprise these changes and modification.
Claims (10)
1. a kind of diamine compound it is characterised in that this compound 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 claimed in claim 1 is it is characterised in that the method
Including：
Coupling step：Compound shown in Formula II is reacted with compound shown in formula III, is converted into formula IV shownization
Compound；
Step of hydrogenation：- NO in compound shown in formula IV2It is reduced to-NH2Afterwards, it is converted into shown in Formulas I
Compound；
Wherein, the R in Formula II and compound shown in formula IV1、R2、R3And R4Be each independently selected from-H,
-CH3、-CH2CH3With-CH2CH2CH3.
3. preparation method as claimed in claim 2 is it is characterised in that described coupling step is specially：
By compound shown in compound shown in Formula II, formula III, sodium tert-butoxide, three (dibenzalacetones)
Carry out back flow reaction in two palladiums and 2- (di-t-butyl phosphine) biphenyl addition toluene.
4. preparation method as claimed in claim 2 is it is characterised in that described step of hydrogenation is specially：
The hydro-conversion under conditions of palladium carbon is as catalyst of compound shown in formula IV is compound shown in Formulas I.
5. a kind of preparation method of polyamic acid is it is characterised in that diamine compounds and anhydrides chemical combination
Thing reaction is converted into polyamic acid, wherein,
Described diamine compounds include compound shown in Formulas I and at least one following chemical combination in claim 1
Thing：
6. preparation method as claimed in claim 5 is it is characterised in that described anhydrides compound is selected from
Any one in following：
7. the polyamic acid that a kind of preparation method as described in claim 5 or 6 obtains.
8. a kind of polyimides are it is characterised in that this polyimides is by the polyamides described in claim 7
Amino acid dehydration is transformed.
9. a kind of aligning agent for liquid crystal is it is characterised in that this aligning agent for liquid crystal includes as claimed in claim 7
Polyamic acid and/or claim 8 described in polyimides.
10. a kind of liquid crystal cell is it is characterised in that this liquid crystal cell includes the liquid crystal aligning described in claim 9
Agent.
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| 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 |
| CN110041276A (en) * | 2019-04-24 | 2019-07-23 | 吉林大学 | The polynary amine monomers and its polymer and preparation method and application of polyimides containing triazole structure |
| US11287700B2 (en) | 2017-05-22 | 2022-03-29 | Lg Chem, Ltd. | Polymer for liquid crystal alignment agent, liquid crystal alignment agent comprising the same, and liquid crystal alignment film and liquid crystal display device using the same |
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