CN109535422A - Diamine compound, Kapton and flexible display apparatus - Google Patents
Diamine compound, Kapton and flexible display apparatus Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
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- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- 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
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Abstract
The present invention relates to intelligent display technical fields, more particularly to diamine compound, Kapton and flexible display apparatus.The diamine compound has structure shown in formula (I):Wherein, B1~B8In at least one be N atom, remaining be-CH-, n 1,2 or 3.
Description
Technical field
The present invention relates to intelligent display technical fields, aobvious more particularly to diamine compound, Kapton and flexibility
Showing device.
Background technique
In recent years, quick to lightening, fine definition, direction that is flexible, folding and crimp with intelligent display terminal
Development, Flexible Displays have been increasingly becoming a kind of important mainstream display technology of intelligent display terminal, be widely used in smart phone,
In the display fields such as wearable device, large size TV.In flexible display device, flexible parent metal is the pass for realizing Flexible Displays
Key material.The performance of flexible display substrates directly significantly affects the display quality of entire flexible display device.It is all kinds of flexible aobvious
Show in baseplate material, polyimide material a kind of weight since the characteristics such as its good heat resistance and excellent mechanical property have become
The display substrate wanted.
Flexible display device manufacturing process condition requires extremely stringent, it is desirable that flexible parent metal has higher Heat-resistant stable
Property, dimensional stability and excellent mechanical property.For example, being shown in manufacturing process in flexible AMOLED, by elder generation in glass
Substrate surface coating polyimide performed polymer polyamic acid solution, forms polyimide substrate after then passing through hot setting, so
It successively carries out LTPS technique, evaporation process, packaging technology on the substrate afterwards, then uses laser by polyimide flex substrate
Removing forms flexible display element from glass substrate.LTPS manufacturing process requires flexible substrate material can be at least at 450 DEG C
It is lower to keep good heat-resistant stability and dimensional stability, that is, it requires to exist in the polyimides of glass baseplate surface coating film forming
Have excellent heat resistance, extremely low thermal linear expansion coefficient (CTE is suitable with glass substrate) and excellent mechanical property at 450 DEG C
Energy (tensile strength > 200MPa).
Most of polyimide materials in the prior art cannot meet simultaneously high-fire resistance, low thermal coefficient of expansion and compared with
The requirement of high tensile and modulus.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides diamine compound, Kapton and flexible display apparatus.
According to an aspect of the present invention, a kind of diamine compound is provided, there is structure shown in formula (I):
Wherein, B1~B8In at least one be N atom, remaining be-CH-, n 1,2 or 3.
According to embodiment of the present invention, n=1.
According to embodiment of the present invention, any one of diamine compound in following:
Wherein, 1,2 or 3 n.
According to embodiment of the present invention, any one of diamine compound in following:
The present invention also provides the preparation methods of diamine compound as described above, comprising the following steps:
Formula (A) compound and formula (B) compound are coupled, and obtain diamine compound shown in formula (I)；
Wherein, B1~B8In at least one be N atom, remaining be-CH-, n 1,2 or 3.
According to another aspect of the present invention, a kind of polyamic acid is provided, the polyamic acid is by diamine compounds and acid
Compound anhydride reacts to obtain, which includes diamine compound according to the present invention.
According to embodiment of the present invention, anhydride compound be selected from it is one of following or more than one:
According to another aspect of the present invention, a kind of polyimides is provided, the polyimides is by polyamide as described above
Acid dehydration is transformed.
According to another aspect of the present invention, provide a kind of Kapton, including polyamic acid as described above and/
Or polyimides as described above.
According to another aspect of the invention, a kind of flexible display apparatus, including polyimides as described above are additionally provided
Film.
The invention has the following advantages:
Polyamic acid and polyimides of the invention contains the structure of diamine compound according to the present invention, will be of the invention
Polyamides propylhomoserin and polyimides be applied to Kapton, can obtain with high heat resistance stability, low thermal coefficient of expansion
And the Kapton of excellent mechanical performance, the flexible substrate material prepared using the Kapton can satisfy
The condition of Flexible Displays manufacturing process can be used for preparing flexible display apparatus.
Detailed description of the invention
Fig. 1 is the schematic diagram of flexible display apparatus；
Wherein, 1- polyimide flex substrate, 2- luminescent layer, 3- thin-film encapsulation layer.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with implementation of the invention
Example, technical scheme in the embodiment of the invention is clearly and completely described.
According to an aspect of the present invention, a kind of diamine compound is provided, there is structure shown in formula (I):
Wherein, B1~B8In at least one be N atom, remaining be-CH-, n 1,2 or 3.
According to embodiment of the present invention, B1~B8In have one, two, three, four, five, six it is former for N
Son, remaining is-CH-.According to embodiment of the present invention, B1~B8In there are two, four, six be N atom, remaining for-
CH-。
In the present invention, polyimide preformed polymer is prepared using the diamine compound containing symmetrical heterocycle/aromatic ring, in polyamides Asia
Symmetrical heterocycle/aromatic ring structure is introduced in amine molecule main chain, by the strong conjugation of intramolecule and hydrogen bond action, enhancing is poly-
Active force between acid imide molecular chain structure rigidity and backbone molecule, improves the degree of orientation of backbone molecule, and strand bulk density increases
Greatly, while guaranteeing high heat resistance stability, polyimide molecule is also made to have lower thermal expansion coefficient, to obtain
It is provided simultaneously with the Kapton of high heat resistance stability, low thermal coefficient of expansion and excellent mechanical performance, has reached the present invention
Effect.
According to embodiment of the present invention, n=1.
According to embodiment of the present invention, any one of diamine compound in following:
Wherein, 1,2 or 3 n.
According to embodiment of the present invention, any one of diamine compound in following:
The present invention also provides the preparation methods of diamine compound as described above, comprising the following steps:
Formula (A) compound and formula (B) compound are coupled, and obtain diamine compound shown in formula (I)；
Wherein, B1~B8In at least one be N atom, remaining be-CH-, n 1,2 or 3.
According to embodiment of the present invention, the process of formula (A) compound and the coupling of formula (B) compound specifically:
By formula (A) compound, formula (B) compound, potassium carbonate, toluene/ethanol/water in the mixed solvent is added and flows back
Reaction.
According to another aspect of the present invention, a kind of polyamic acid is provided, the polyamic acid is by diamine compounds and acid
Compound anhydride reacts to obtain, which includes diamine compound according to the present invention.
According to embodiment of the present invention, which can also include at least one following compound:
According to embodiment of the present invention, which includes at least one of following compound:
Wherein, the diamine compounds of selection can select at least one from above-mentioned diamine compounds, include certainly
But it is not limited to above compound, or the unlisted other diamine compounds that can be reacted, as long as on capable of occurring
The diamine compounds for stating polymerization reaction can be selected, and including within the scope of the present invention.
According to embodiment of the present invention, anhydride compound be selected from it is one of following or more than one:
A preferred embodiment according to the present invention, anhydride compound be selected from it is one of following or more than one:
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
The anhydride compound for stating polymerization reaction can be selected, and including within the scope of the present invention.
One kind in polyamic acid can be indicated using the following general formula according to the present invention:
Wherein, R5Selected from one of following radicals:
R6Are as follows:B1~B8In at least one be N atom, remaining for-
CH-, n 1,2 or 3；
R7It is not present or selected from one of following radicals:
Certain above-mentioned general formula only represents one kind in polyamic acid 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 it is of the invention
In protection scope.
According to another aspect of the present invention, a kind of polyimides is provided, the polyimides is by polyamide as described above
Acid dehydration is transformed.
One kind in polyimides can be indicated using the following general formula according to the present invention:
Wherein, R5Selected from one of following radicals:
R6Are as follows:B1~B8In at least one be N atom, remaining be-CH-,
N is 1,2 or 3；
R7It is not present or selected from one of 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 scope in.
Polyamic acid and polyimides of the invention contains the structure of diamine compound according to the present invention, will be of the invention
Polyamides propylhomoserin and polyimides are applied to Kapton, can obtain with high heat resistance stability, low thermal coefficient of expansion with
And the Kapton of excellent mechanical performance, the flexible substrate material prepared using the Kapton can satisfy soft
Property display manufacturing process condition, can be used for preparing flexible display apparatus, such as show as flexibility LCD and flexibility OLED
Substrate, flexible touch-control substrate and flexible cover plate etc..
According to embodiment of the present invention, polyamic acid is by diamine compounds and anhydride compound in solvent
Reaction obtains in (such as N-Methyl pyrrolidone).Similarly, polyimides is also by diamine compounds and anhydride
Object is closed after the middle reaction of solvent (such as N-Methyl pyrrolidone) obtains polyamic acid, polyamic acid dehydrating condensation obtains.Root
Coating shape is subsequently used for by polyamic acid solution or polyimide solution through membrane filtration according to an embodiment of the invention
At Kapton.
According to another aspect of the present invention, provide a kind of Kapton, including polyamic acid as described above and/
Or polyimides as described above.
It coats in glass baseplate surface as at least one of the polyamic acid of polyimide prepolymer or polyimides,
Then hot setting is removed Kapton from glass substrate, obtain the flexible polyimide substrate of self-supporting.
According to another aspect of the invention, a kind of flexible display apparatus, including polyimides as described above are additionally provided
Film.Flexible display apparatus for example can be flexible display panels.
The structure of flexible display apparatus can be as shown in Figure 1, wherein contains polyimides in polyimide flex substrate
Film.
Embodiment
The abbreviation for the compound used in embodiment and comparative example is as follows:
Tetracarboxylic dianhydride:
A-1:3,3 ', 4,4 '-biphenyltetracarboxylic dianhydride
A-2: pyromellitic acid dianhydride
Diamine compound:
B-1: p-phenylenediamine
B-2:4,4 '-diaminodiphenyl ether
Bis- (4- the aminophenyl) -1,10- ferrosins of C-1:3,8-
Bis- (4- the aminophenyl) -1,7- ferrosins of C-2:3,8-
Bis- (4- the aminophenyl) -1,4,5,8- pyrazine quinoxalines of C-3:2,7-
Bis- (p-aminodiphenyl the base) -1,10- ferrosins of C-4:3,8-
Bis- (to amino the terphenyl) -1,10- ferrosins of C-5:3,8-
Organic solvent:
NMP:N- methyl pyrrolidone
The synthesis of diamine compound
The synthesis of C-1
The preparation of compound a -1
Sequentially added into single-necked flask 18g (0.1mol) 1,10- ferrosin, 44.5g (0.33mol) disulphur dichloride,
26.10g (0.33mol) pyridine, 47.4g (0.3mol) bromine and 500mL1- chlorobutane.Open mechanical stirring, system N2It sets
It is opened after changing 3 times and is heated to flowing back, system temperature carries out back flow reaction for 24 hours at a reflux temperature.Have in reaction process a large amount of solid
Body generates, and cooled to room temperature, filtering reacting liquid, solid are washed with a large amount of NaOH solutions after reaction, filtrate trichlorine
It is concentrated after methane extraction, loading crosses silicagel column together after merging with filter cake, and column chromatographs liquid concentration, is recrystallized to give in toluene
White solid fine work a-1 19.6g, yield 58%.1H-NMR (500Mz, CDCl3), δ (ppm): 9.2 (2H, s), 8.8 (2H, s),
7.9 (2H, s).
The preparation of diamine compound C-1
16.56g potassium carbonate, 16.9g (0.05mol) a-1,0.08g Pd-132,100mL are sequentially added into four-hole boiling flask
Ultrapure water and 100mL toluene.Open mechanical stirring, system N2Heating is opened after displacement 3 times, system temperature is warming up to 85-
It flows back at 90 DEG C.It weighs 13.7g (0.1mol) 4- amino phenyl boric acid to be dissolved in 65mL dehydrated alcohol, is slowly dropped to reaction
In system, control system temperature is in 85-90 DEG C of progress back flow reaction.After being added dropwise to complete, system continues back flow reaction 3h, then cold
But cool down, stop stirring.200mL toluene is added into system, continues to pour into separatory funnel and stand after stirring 10min at room temperature
Liquid separation, water phase are poured into flask, continue extraction once after 200mL toluene is added, water phase is discarded after standing, merges organic phase.With
Organic phase is concentrated afterwards, obtains solid crude product.Crude product is after silicagel column rapidly purifies, using toluene/ethanol mixed solvent
Recrystallization, obtains solid fine work 15.92g, yield 88%.Mass spectrometric data MS (m/e) 362, nuclear magnetic data1H-NMR (500Mz,
CDCl3), δ (ppm): 8.3 (2H, s), 7.9 (2H, s), 7.7 (2H, s), 7.4 (4H, d), 6.5 (4H, d), 5.0 (4H, s).
Referring to the synthetic method of diamine compound C-1, two amine compounds can be synthesized respectively using raw material as shown in table 1
Object C-2 and C-3.
1 diamine compound of table, starting material and property
Compound C-2 nuclear magnetic data1H-NMR (500Mz, CDCl3), δ (ppm): 8.6 (1H, s), 8.2 (2H, d), 8.0
(4H, m), 7.4 (2H, d), 7.2 (1H, d), 6.5 (4H, d), 5.0 (4H, s).
Compound C-3 nuclear magnetic data1H-NMR (500Mz, CDCl3), δ (ppm): 8.8 (2H, s), 8.2 (4H, d), 7.6
(2H, s), 6.8 (4H, d), 5.0 (4H, s).
Referring to the synthetic method of diamine compound C-1, compound C-4 is by 4 '-amino -4- biphenylboronic acids and compound a -
1 occurs coupling reaction preparation.Raw material 4 '-amino -4- biphenylboronic acid is coupled by Isosorbide-5-Nitrae-biphenylboronic acids and 4- amino bromobenzene
Reaction preparation.The nuclear magnetic data of 4 '-amino -4- biphenylboronic acids1H-NMR (500Mz, DMSO-d6), δ (ppm): 7.9 (2H, d),
7.7 (2H, d), 7.4 (2H, d), 6.5 (2H, d), 5.2 (2H, s), 4.0 (2H, s).The nuclear magnetic data of compound C-41H-NMR
(500Mz, DMSO-d6), δ (ppm): 8.3 (2H, s), 8.2 (2H, s), 7.9 (2H, s), 7.4 (4H, d), 7.2 (8H, s), 6.6
(4H, d), 5.0 (4H, s).
Referring to the synthetic method of diamine compound C-1, compound C-5 is by amino terphenyl boric acid and compound a -1
Coupling reaction preparation occurs.Raw material to amino terphenyl boric acid is occurred occasionally by Isosorbide-5-Nitrae-biphenylboronic acids and 4- amino -4 '-bromo biphenyl
Connection reaction preparation.To the nuclear magnetic data of amino terphenyl boric acid1H-NMR (500Mz, DMSO-d6), δ (ppm): 7.9 (2H, d),
7.7 (2H, d), 7.4 (2H, d), 7.2 (4H, s), 6.5 (2H, d), 5.2 (2H, s), 4.2 (2H, s).The nuclear-magnetism number of compound C-5
According to1H-NMR (500Mz, DMSO-d6), δ (ppm): 8.25 (2H, s), 8.21 (2H, s), 8.0 (2H, s), 7.5 (4H, d), 7.2
(14H, s), 6.6 (4H, d), 5.0 (4H, s).
Using the synthetic method similar with C-1 to C-5, other compounds according to the present invention are prepared.
The preparation of Kapton
Polyimide prepolymer polyamic acid solution or soluble polyimide solution are used in deaerated under vacuum 30min
Sol evenning machine is spun on glass baseplate surface, and preliminary drying 30min is then distinguished on 80 DEG C and 120 DEG C of hot plates, obtains initial thickness
The wet film that degree is 16-18 μm.Glass substrate containing wet film is put into high temperature roaster and carries out heat cure, using following procedure liter
Warm mode heats up, i.e., is started to warm up at room temperature with 4min/ DEG C of speed, keeps 30min, 180 when being warming up to 120 DEG C respectively
DEG C when keep 30mn, 240 DEG C when keep 30min, 350 DEG C when keep 30min, 450 DEG C when keep 30min, obtaining thickness is about
The glass substrate of 10 μm of Kapton.Substrate is placed in and carries out boiling 30min in 90 DEG C of water-baths, polyimides is thin
Film is removed from glass substrate, obtains the flexible polyimide substrate of self-supporting.
Kapton performance evaluation
The test of viscosity
Using the rotary viscosity of Brookfield viscometer (LVDVC) viscosimeter test polymer solution, by polyamides
Imines performed polymer polyamic acid solution is placed in test measuring cup, is selected suitable rotor model and revolving speed, is polymerize at 25 DEG C of test
The viscosity of object.
The evaluation of heat resistance
Using the thermal decomposition temperature of METER TGA-1 test Kapton, film is cut into small pieces, 10mg is weighed and sets
In dry pot, the speed at 30 DEG C with 4min/ DEG C is in N2It is warming up to 800 DEG C under atmosphere, records within the scope of 50 DEG C -800 DEG C
Thermogravimetric curve calculates the thermal decomposition temperature T of material 1%d(1%).
Hot expansibility evaluation
Using the hot expansibility of TMA-Q400 type dynamic thermomechanical analysis apparatus test Kapton, by polyimides
It is 4cm that film, which is cut into length, and width is the bulk sample of 5mm, and using film stretch mode, static chucking power is set as 0.02N,
In N2It with 10min/ DEG C of rate heating and cooling under atmosphere, is heated up for the first time to eliminate the internal stress of film, is recorded second
Kapton length data within the scope of 50 DEG C -400 DEG C in temperature-rise period, according to formula CTE=△ L/ (L* △ T), wherein L
For the initial length for the preceding Kapton that heats up, △ L is the changing value of heating front and back Kapton length, and △ T is temperature
Changing value is spent, the thermal expansion coefficient of Kapton is calculated.
Evaluating Mechanical Properties
Using the mechanical property of XLW type Intelligent electronic tensil testing machine test Kapton, by Kapton
Being cut into length is 10cm, and width is the bulk sample of 5mm, is drawn according to the method for ASTM-D882 with the speed of 50mm/min
Test is stretched, is measured in parallel 5 times, is averaged the tensile strength as Kapton.
Embodiment 1
Be separately added into four-hole boiling flask diamine compound B-1 3.24g (30mmol), C-1 7.24g (20mmol) and
141g nmp solvent, mechanical stirring dissolves at room temperature, and with the air in nitrogen displacement flask.By above-mentioned reaction solution as ice water
It in bath, after system temperature is down to 4 DEG C, is added portionwise in Xiang Shangshu mixed solution A-2 14.7g (50mmol), control reaction temperature
Degree is no more than 15 DEG C.Entirely reacted after charging stir at room temperature obtain for 24 hours mass concentration be 15% polyamic acid it is molten
Liquid (PAA-1).Testing viscosity of the polyamic acid solution at 25 DEG C is 4800mPas.The PAA-1 solution of preparation is passed through
0.45 micron membrane filter forms a film according to aforementioned film build method, obtains the polyimide flex substrate of self-supporting.And according to above-mentioned
Material property evaluation method tests its heat resistance, hot expansibility and mechanical property.
Embodiment 2
Be separately added into four-hole boiling flask diamine compound B-1 3.24g (30mmol), C-2 7.24g (20mmol) and
141g nmp solvent, mechanical stirring dissolves at room temperature, and with the air in nitrogen displacement flask.By above-mentioned reaction solution as ice water
It in bath, after system temperature is down to 4 DEG C, is added portionwise in Xiang Shangshu mixed solution A-2 14.7g (50mmol), control reaction temperature
Degree is no more than 15 DEG C.Entirely reacted after charging stir at room temperature obtain for 24 hours mass concentration be 15% polyamic acid it is molten
Liquid (PAA-2).Testing viscosity of the polyamic acid solution at 25 DEG C is 4800mPas.The PAA-2 solution of preparation is passed through
0.45 micron membrane filter forms a film according to aforementioned film build method, obtains the polyimide flex substrate of self-supporting.And according to above-mentioned
Material property evaluation method tests its heat resistance, hot expansibility and mechanical property.
Embodiment 3
Be separately added into four-hole boiling flask diamine compound B-1 3.24g (30mmol), C-3 7.28g (20mmol) and
138g nmp solvent, mechanical stirring dissolves at room temperature, and with the air in nitrogen displacement flask.By above-mentioned reaction solution as ice water
In bath, after system temperature is down to 4 DEG C, A-1 2.18g (10mmol) A-2 11.75g is added portionwise in Xiang Shangshu mixed solution
(40mmol), control reaction temperature are no more than 15 DEG C.It entirely reacts and is stirred at room temperature for 24 hours after charging, it is dense to obtain quality
The polyamic acid solution (PAA-3) that degree is 15%.Testing viscosity of the polyamic acid solution at 25 DEG C is 5080mPas.It will
The PAA-3 solution of preparation forms a film according to aforementioned film build method by 0.45 micron membrane filter, obtains the polyimides of self-supporting
Flexible base board.And its heat resistance, hot expansibility and mechanical property are tested according to above-mentioned material method of evaluating performance.
Embodiment 4
Be separately added into four-hole boiling flask diamine compound B-1 3.24g (30mmol), C-4 10.28g (20mmol) and
160g nmp solvent, mechanical stirring dissolves at room temperature, and with the air in nitrogen displacement flask.By above-mentioned reaction solution as ice water
It in bath, after system temperature is down to 4 DEG C, is added portionwise in Xiang Shangshu mixed solution A-2 14.7g (50mmol), control reaction temperature
Degree is no more than 15 DEG C.Entirely reacted after charging stir at room temperature obtain for 24 hours mass concentration be 15% polyamic acid it is molten
Liquid (PAA-4).Testing viscosity of the polyamic acid solution at 25 DEG C is 5500mPas.The PAA-4 solution of preparation is passed through
0.45 micron membrane filter forms a film according to aforementioned film build method, obtains the polyimide flex substrate of self-supporting.And according to above-mentioned
Material property evaluation method tests its heat resistance, hot expansibility and mechanical property.
Embodiment 5
Be separately added into four-hole boiling flask diamine compound B-1 3.24g (30mmol), C-5 13.32g (20mmol) and
178g nmp solvent, mechanical stirring dissolves at room temperature, and with the air in nitrogen displacement flask.By above-mentioned reaction solution as ice water
It in bath, after system temperature is down to 4 DEG C, is added portionwise in Xiang Shangshu mixed solution A-2 14.7g (50mmol), control reaction temperature
Degree is no more than 15 DEG C.Entirely reacted after charging stir at room temperature obtain for 24 hours mass concentration be 15% polyamic acid it is molten
Liquid (PAA-5).Testing viscosity of the polyamic acid solution at 25 DEG C is 6700mPas.The PAA-5 solution of preparation is passed through
0.45 micron membrane filter forms a film according to aforementioned film build method, obtains the polyimide flex substrate of self-supporting.And according to above-mentioned
Material property evaluation method tests its heat resistance, hot expansibility and mechanical property.
Comparative example 1
Diamine compound B-1 10.8g (100mmol) and 227g nmp solvent are separately added into four-hole boiling flask, at room temperature
Mechanical stirring dissolution, and with the air in nitrogen displacement flask.By above-mentioned reaction solution as in ice-water bath, it is down to system temperature
It after 4 DEG C, is added portionwise in Xiang Shangshu mixed solution A-2 29.4g (100mmol), control reaction temperature is no more than 15 DEG C.Charging
After entirely react and stir 6h at room temperature, obtain the polyamic acid solution (PAA-6) that mass concentration is 15%.It is poly- to test this
Viscosity of the amide acid solution at 25 DEG C is 6500mPas.By the PAA-6 solution of preparation by 0.45 micron membrane filter, according to preceding
It states film build method to form a film, obtains the polyimide flex substrate of self-supporting.And it is surveyed according to above-mentioned material method of evaluating performance
Try its heat resistance, hot expansibility and mechanical property.
Comparative example 2
Be separately added into four-hole boiling flask diamine compound B-1 8.64g (80mmol), B-2 4.0g (20mmol) and
237g nmp solvent, mechanical stirring dissolves at room temperature, and with the air in nitrogen displacement flask.By above-mentioned reaction solution as ice water
It in bath, after system temperature is down to 4 DEG C, is added portionwise in Xiang Shangshu mixed solution A-2 29.4g (100mmol), control reaction
Temperature is no more than 15 DEG C.It is entirely reacted after charging and stirs 6h at room temperature, obtain the polyamic acid that mass concentration is 15%
Solution (PAA-7).Testing viscosity of the polyamic acid solution at 25 DEG C is 6250mPas.The PAA-7 solution of preparation is led to
0.45 micron membrane filter is crossed, is formed a film according to aforementioned film build method, the polyimide flex substrate of self-supporting is obtained.And according to upper
It states material property evaluation method and tests its heat resistance, hot expansibility and mechanical property.
Comparative example 3
Diamine compound B-1 10.8g (100mmol) and 217g nmp solvent are separately added into four-hole boiling flask, at room temperature
Mechanical stirring dissolution, and with the air in nitrogen displacement flask.By above-mentioned reaction solution as in ice-water bath, it is down to system temperature
After 4 DEG C, A-1 4.36g (20mmol) and A-2 23.5g (80mmol), control reaction temperature are added portionwise in Xiang Shangshu mixed solution
Degree is no more than 15 DEG C.It is entirely reacted after charging and stirs 6h at room temperature, it is molten to obtain the polyamic acid that mass concentration is 15%
Liquid (PAA-8).Testing viscosity of the polyamic acid solution at 25 DEG C is 6100mPas.The PAA-8 solution of preparation is passed through
0.45 micron membrane filter forms a film according to aforementioned film build method, obtains the polyimide flex substrate of self-supporting.And according to above-mentioned
Material property evaluation method tests its heat resistance, hot expansibility and mechanical property.
The flexible polyimide substrate performance that embodiment 1-3, comparative example 1-3 are formed is as shown in table 2 below.
The flexible polyimide substrate results of property of 2 embodiment of table and comparative example
As shown in Table 2, in comparative example 1-3, thermal linear expansion coefficient is higher, in 15ppm/K-1More than.With comparative example 1-3
It compares, flexible base board made of the Kapton provided using 1-3 of the embodiment of the present invention has lower linear thermal expansion
Coefficient (CTE < 10ppm/K-1), heat-resistant stability (Td1%) > 550 DEG C, tensile strength > 200MPa can satisfy Flexible Displays use
Substrate process process requirements.Therefore, it can be provided simultaneously with using polyimide flex substrate prepared by the present invention excellent heat-resisting
Property and extremely low thermal expansion coefficient and good mechanical property, may be used as flexible LCD and flexibility OLED show in substrate
Material, flexible touch-control substrate and flexible cover plate material etc..
The above, above embodiments are only described in detail to the technical solution to the application, but the above implementation
The method that the explanation of example is merely used to help understand the embodiment of the present invention, should not be construed as the limitation to the embodiment of the present invention.This
Any changes or substitutions that can be easily thought of by those skilled in the art, should all cover the embodiment of the present invention protection scope it
It is interior.
Claims (10)
1. a kind of diamine compound, which is characterized in that have structure shown in formula (I):
Wherein, B1~B8In at least one be N atom, remaining be-CH-, n 1,2 or 3.
2. diamine compound according to claim 1, which is characterized in that n=1.
3. diamine compound according to claim 1, which is characterized in that the diamine compound is any in following
It is a kind of:
Wherein, 1,2 or 3 n.
4. diamine compound according to claim 1, which is characterized in that the diamine compound is any in following
It is a kind of:
5. the preparation method of the described in any item diamine compounds of Claims 1 to 4, which comprises the following steps:
Formula (A) compound and formula (B) compound are coupled, and obtain diamine compound shown in formula (I)；
Wherein, B1~B8In at least one be N atom, remaining be-CH-, n 1,2 or 3.
6. a kind of polyamic acid, which is characterized in that react to obtain with anhydride compound by diamine compounds, the Diamines
Compound includes the described in any item diamine compounds of Claims 1 to 4.
7. polyamic acid according to claim 6, which is characterized in that the anhydride compound is selected from one of following
Or more than one:
8. a kind of polyimides, which is characterized in that the dehydration of polyimides polyamic acid as described in claim 6 or 7 turns
Change.
9. a kind of Kapton, which is characterized in that including as described in any one of claim 6 and 7 polyamic acid,
And/or polyimides as claimed in claim 8.
10. a kind of flexible display apparatus, which is characterized in that including Kapton as claimed in claim 9.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070243410A1 (en) * | 2004-08-07 | 2007-10-18 | Poopathy Kathirgamanathan | Electroluminescent Materials and Devices |
-
2018
- 2018-11-05 CN CN201811306411.8A patent/CN109535422B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070243410A1 (en) * | 2004-08-07 | 2007-10-18 | Poopathy Kathirgamanathan | Electroluminescent Materials and Devices |
Non-Patent Citations (4)
| Title |
|---|
| JACK PRESTON等: "Intermediates for the preparation of thermally stable polymers. IV. Symmetrical quinoxalines and benzoylbenzimidazoles", 《JOURNAL OF HETEROCYCLIC CHEMISTRY》 * |
| LI XP等: "Novel polyimide containing 1,10-phenanthroline and its europium(III) complex: synthesis, characterization,and luminescence properties", 《J MATER SCI》 * |
| PUBCHEM: "CID-70658132", 《PUBCHEM》 * |
| SILVIA ROSCALES等: "Synthesis of Di(hetero)arylamines from Nitrosoarenes and Boronic Acids: A General, Mild, and Transition-Metal-Free Coupling", 《ORG. LETT.》 * |
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|---|---|---|---|---|
| WO2024067649A1 (en) * | 2022-09-30 | 2024-04-04 | 比亚迪股份有限公司 | Diamine compound, polyimide acid, polyimide, and preparation method therefor and use thereof |
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