CN106496612A - A kind of preparation method of the Kapton of structure-controllable - Google Patents
A kind of preparation method of the Kapton of structure-controllable Download PDFInfo
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- CN106496612A CN106496612A CN201610919424.7A CN201610919424A CN106496612A CN 106496612 A CN106496612 A CN 106496612A CN 201610919424 A CN201610919424 A CN 201610919424A CN 106496612 A CN106496612 A CN 106496612A
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- dianhydride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract
The invention discloses a kind of preparation method of the Kapton of structure-controllable, comprises the steps：S1. room temperature, add solvent, diamidogen and dianhydride under inert gas shielding, obtain polyamic acid glue A；S2. room temperature, add solvent, diamidogen and dianhydride under inert gas shielding, obtain polyamic acid glue liquid B；Then polyamic acid glue liquid B reaction in polyamic acid glue A and S2 in S1 is obtained block polyamide acid glue, after the glue is processed, obtains final product Kapton；In S1, diamidogen is x with the reaction mol ratio of dianhydride：（x+1）；In S2, diamidogen with the reaction mol ratio of dianhydride is（y+1）：y.X, y are the integers being not zero.The method that the present invention is provided structurally ordered to polyimide material can carry out good control, therefore, it is possible to the thermostability and mechanical strength of material is kept in multiple preparation process, possesses preferable application prospect in photoelectric fields such as flexible solar battery base plate, liquid crystal display alignment films, the optical waveguide materials of communication connection.
Description
Technical field
The invention belongs to technical field of polymer materials, more particularly, to a kind of Kapton of structure-controllable
Preparation method.
Background technology
Heat resistance that polyimides (Polyimide, PI) are projected due to which, mechanical performance, dielectric properties etc. are comprehensive
Can and be widely used in the fields such as Aero-Space, microelectronics industry.With new and high technology and the fast development of industry, polyimides
Become the requisite class material of development high technology industry, and be also dual-use rising material.Polyamides is sub-
In application of the amine in terms of photoelectric material（The light for for example connecting in flexible solar battery base plate, liquid crystal display alignment films, communication
The aspects such as waveguide material）, very high requirement is proposed to its thermal coefficient of expansion and thermostability.
The conventional method of existing synthesis of polyimides is to be formed to gather by dianhydride and diamidogen in non-proton intensive polar solvent
Amic acid（PAA）, polyimides are formed under high temperature.Wherein, non-proton intensive polar solvent can be, dimethyl sulfoxide, N, N-
One or more of dimethylformamide, DMAC N,N' dimethyl acetamide or N-Methyl pyrrolidone, pyridine, acetonitrile etc..But adopt at present
The polyimides being synthesized with the existing method（PI）In structure be substantially random, molecular weight also it cannot be guaranteed that, lead
The polyimides for causing each batch to be synthesized are widely different in performance, and product quality fluctuation is larger.
Content of the invention
It is an object of the invention to according to deficiency of the prior art, there is provided a kind of Kapton of structure-controllable
Preparation method.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of the Kapton of structure-controllable, comprises the steps：
S1. room temperature, add solvent, diamidogen and dianhydride under inert gas shielding, obtain polyamic acid glue A；
S2. room temperature, add solvent, diamidogen and dianhydride under inert gas shielding, obtain polyamic acid glue liquid B；
S3. polyamic acid glue liquid B in polyamic acid glue A and S2 in S1 is mixed under inert gas atmosphere, reaction obtains embedding
Gained block polyamide acid glue is filtered, after deaeration, is coated on substrate, solidifies, peel off after cooling by section polyamic acid glue,
Obtain final product the Kapton；
In S1, diamidogen is x with the reaction mol ratio of dianhydride：（x+1）；
In S2, diamidogen with the reaction mol ratio of dianhydride is（y+1）：y.
X, y are the integers being not zero.
Wherein, in S1 and S2, course of reaction is as follows：
Wherein R1、 R3For the residue of diamidogen, R2、R4Residue for dianhydride.
Preferably, in S3, cured is：Solidify 0.5h at 50 DEG C, then at 80 DEG C, solidify 1h, then at 120 DEG C
Lower solidification 1h, then solidifies 1h at 180 DEG C, and then solidifies 1h at 230 DEG C, and then solidify 1h at 280 DEG C, followed by
Solidify 1h at 330 DEG C.
Preferably, the diamidogen includes diphenyldiamine, and p-phenylenediamine, in m-diaminobenzene., diaminodiphenyl-methane
One or more, the dianhydride includes pyromellitic acid anhydride, diphenyl ether tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, benzophenone
One or more in tetracarboxylic dianhydride or 4,4`- hexafluoroisopropyli,enes-phthalic anhydride.
Preferably, in the polyamic acid glue A or polyamic acid glue liquid B, the quality summation of diamidogen and dianhydride accounts for solvent matter
The 5% ~ 25% of amount.
Preferably, the temperature that reacts in S3 is -10 DEG C ~ 15 DEG C, and the time of reaction is 10 ~ 24h.
Preferably, in S1, diamidogen is identical or different with diamidogen in S2, and in S1, dianhydride is identical or different with dianhydride in S2.
As, in random copolymerization acid imide (r-PI), the different diamidogen of length is random on molecular backbone with dianhydride segment
Distribution, and for block copolymerization acid imide (b-PI), both segments are then long according to certain sequence on molecular backbone
Degree is formed by connecting, and therefore the alignment degree of b-PI molecules chain alignment is higher than r-PI.In consideration of it, the present invention by control diamidogen and
The synthesis ratio of dianhydride, which is prepared into the prepolymer of carboxy blocking and amido end-blocking respectively, then by above-mentioned carboxy blocking and amine
The prepolymer of base end-blocking is fitted together to, thus the prepolymer of above two segment can be again according to certain in chimeric copolymerization
Repetitives sequence is polymerized, and realizes the control of polymerization process middle-molecular-weihydroxyethyl, so as to ensure stablizing for performance.
Compared with prior art, the present invention has advantages below and beneficial effect：
The present invention controls polyimide structures using specific preparation method, and raw material is easy to get, easy to operate, can overcome existing
The unstable defect of polyimide molecule amount that synthesizes in preparation method, it is ensured that its performance is stablized, polyamides prepared by the present invention
Imines thin film has excellent thermal coefficient of expansion and has high tack to various types of materials.Itself and aluminium plate, Copper Foil, glass, pottery
Adhesive force Deng substrate surface is very excellent, and steaming and decocting in 100 DEG C of water does not fall off for 500 hours completely；Polyamides prepared by the present invention is sub-
Amine thin film maintains high-fire resistance and mechanical strength, and its tensile strength is 53.11 MPa-82.9 MPa；Prepared by the present invention
Kapton have very superior thermal coefficient of expansion, its value in 7.95-23.46 um/m DEG C, with copper wire, copper cash etc.
Thermal coefficient of expansion matches.In light such as flexible solar battery base plate, liquid crystal display alignment films, the optical waveguide materials of communication connection
Electrical domain has good application prospect.
Description of the drawings
Fig. 1 is Kapton PI-A, PI-B and PI-C's that embodiment 1, embodiment 2 and embodiment 3 are prepared
Infrared Characterization figure.
Specific embodiment
Further illustrate the present invention below in conjunction with specific embodiments and the drawings, but embodiment the present invention is not done any
The restriction of form.Unless stated otherwise, the reagent for adopting of the invention, method and apparatus are for the art conventional reagent, method
And equipment.
Unless stated otherwise, agents useful for same of the present invention and material are commercial.
Diamidogen in embodiments of the present invention（Diphenyldiamine, p-phenylenediamine, m-diaminobenzene., diaminodiphenyl-methane）、
Dianhydride（Pyromellitic acid anhydride, diphenyl ether tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, 4,4 '-six
Fluorine isopropylidene-phthalic anhydride）There is provided by Shanghai Aladdin biochemical technology limited company, its purity is 99%.Polarity
Solution is（Dimethyl sulfoxide, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or N-Methyl pyrrolidone）Try for Guangzhou
Agent factory provides.
Embodiment 1
The synthesis of polyimides PI-A series：
In a there-necked flask, under room temperature, nitrogen atmosphere, add N-Methyl pyrrolidone, mechanical agitation to add to benzene two
Amine, after which is completely dissolved, by metering than being added thereto pyromellitic dianhydride, metering is than being diamidogen:Dianhydride=10:11 (mole
Than).After reaction 24h, polyamic acid glue A is obtained.In the polyamic acid glue A, the quality summation of diamidogen and dianhydride accounts for solution
The 5% ~ 25% of quality.
B, addition N-Methyl pyrrolidone, mechanical agitation, addition under room temperature, nitrogen atmosphere in another there-necked flask
Diphenyldiamine, after which is completely dissolved in solvent, by metering than adding biphenyl tetracarboxylic dianhydride, metering is than being diamidogen:Dianhydride=
11:10 (mol ratios).After reaction 24h, polyamic acid glue liquid B is obtained.The matter of diamidogen and dianhydride in the polyamic acid glue liquid B
Amount summation accounts for the 5% ~ 25% of solution quality.
C, polyamic acid glue A and polyamic acid glue liquid B are merged in a nitrogen atmosphere, the temperature control of reaction is -10
DEG C ~ 15 DEG C, continue reaction 24h, obtain block polyamide acid glue.Gained block polyamide acid glue is filtered and deaeration
Process, filter out insoluble matter that may be present and impurity, remove the bubble in block polyamide acid glue.
D, by the block polyamide for obtaining acid glue at room temperature uniform application on clean flat board, the flat board can be
Glass plate, and be put in nitrogen oven and solidified, solidification process is：Solidify 0.5h at 50 DEG C, then solidify at 80 DEG C
1h, then solidifies 1h at 120 DEG C, then solidifies 1h at 180 DEG C, and then solidifies 1h at 230 DEG C, and then at 280 DEG C
Lower solidification 1h, solidifies 1h followed by 330 DEG C, obtains the polyimides of film like.Treat that the polyimides of film like are naturally cold
But to room temperature, the polyimides of film like are stripped down from glass plate using warm water, it is the yellowish of 15 um to obtain thickness
The polyimides PI-A-1 of the film like of color.
Repeat synthesis once according to above-mentioned method, obtain the polyimides PI-A-2 of flaxen film like.
Repeat synthesis once according to above-mentioned method, obtain the polyimides PI-A-3 of flaxen film like.
Embodiment 2
The synthesis of polyimides PI-B series：
A, in a there-necked flask under room temperature, nitrogen atmosphere add N-Methyl pyrrolidone, mechanical agitation, add to benzene two
Amine, after which is completely dissolved, by metering than being added thereto biphenyl tetracarboxylic dianhydride, metering is than being diamidogen:Dianhydride=10:11 (rub
You compare).After reaction 24h, polyamic acid glue A is obtained.In the polyamic acid glue A, the quality summation of diamidogen and dianhydride accounts for molten
The 5% ~ 25% of agent quality.
B, addition N-Methyl pyrrolidone, mechanical agitation, addition under room temperature, nitrogen atmosphere in another there-necked flask
Diphenyldiamine, after which is completely dissolved in solvent, by metering than adding pyromellitic dianhydride, metering is than being diamidogen:Dianhydride=11:
10 (mol ratios).After reaction 24h, polyamic acid glue liquid B is obtained.In the polyamic acid glue liquid B, the quality of diamidogen and dianhydride is total
With account for the 5% ~ 25% of solvent quality.
C, polyamic acid glue A and polyamic acid glue liquid B are merged in a nitrogen atmosphere, the temperature control of reaction is -10
DEG C ~ 15 DEG C, continue reaction 24h, obtain block polyamide acid glue.Gained block polyamide acid glue is filtered and deaeration
Process, filter out insoluble matter that may be present and impurity, remove the bubble in block polyamide acid glue.
D, by the block polyamide for obtaining acid glue at room temperature uniform application on clean flat board, the flat board can be
Glass plate, and be put in nitrogen oven and solidified, solidification process is：Solidify 0.5h at 50 DEG C, then solidify at 80 DEG C
1h, then solidifies 1h at 120 DEG C, then solidifies 1h at 180 DEG C, and then solidifies 1h at 230 DEG C, and then at 280 DEG C
Lower solidification 1h, solidifies 1h followed by 330 DEG C, obtain the polyimides of film like.Treat that the polyimides of film like are naturally cold
But to room temperature, the polyimides of film like are stripped down from glass plate using warm water, it is the yellowish of 15 um to obtain thickness
The polyimides PI-B-1 of the film like of color.
Repeat synthesis once according to above-mentioned method, obtain the polyimides PI-B-2 of flaxen film like.
Repeat synthesis once according to above-mentioned method, obtain the polyimides PI-B-3 of flaxen film like.
Embodiment 3
The synthesis of polyimides PI-C series：
A, in a there-necked flask under room temperature, nitrogen atmosphere add N-Methyl pyrrolidone, mechanical agitation, add to benzene two
Amine, after which is completely dissolved, by metering than being added thereto pyromellitic dianhydride, metering is than being diamidogen:Dianhydride=10:11 (mole
Than).After reaction 24h, polyamic acid glue A is obtained.In the polyamic acid glue A, the quality summation of diamidogen and dianhydride accounts for solvent
The 5% ~ 25% of quality.
B, addition N-Methyl pyrrolidone, mechanical agitation, addition under room temperature, nitrogen atmosphere in another there-necked flask
Diphenyldiamine, after which is completely dissolved in solvent, by metering than adding pyromellitic dianhydride, metering is than being diamidogen:Dianhydride=11:
10 (mol ratios).After reaction 24h, polyamic acid glue liquid B is obtained.In the polyamic acid glue liquid B, the quality of diamidogen and dianhydride is total
With account for the 5% ~ 25% of solvent quality.
C, polyamic acid glue A and polyamic acid glue liquid B are merged in a nitrogen atmosphere, the temperature control of reaction is -10
DEG C ~ 15 DEG C, continue reaction 24h, obtain block polyamide acid glue.Gained block polyamide acid glue is filtered and deaeration
Process, filter out insoluble matter that may be present and impurity, remove the bubble in block polyamide acid glue.
D, by the block polyamide for obtaining acid glue at room temperature uniform application on clean flat board, the flat board can be
Glass plate, and be put in nitrogen oven and solidified, solidification process is：Solidify 0.5h at 50 DEG C, then solidify at 80 DEG C
1h, then solidifies 1h at 120 DEG C, then solidifies 1h at 180 DEG C, and then solidifies 1h at 230 DEG C, and then at 280 DEG C
Lower solidification 1h, solidifies 1h followed by 330 DEG C, obtain the polyimides of film like.Treat that the polyimides of film like are naturally cold
But to room temperature, the polyimides of film like are stripped down from glass plate using warm water, it is the yellowish of 15 um to obtain thickness
The polyimides PI-C-1 of the film like of color.
Repeat synthesis once according to above-mentioned method, obtain the polyimides PI-C-2 of flaxen film like.
Repeat synthesis once according to above-mentioned method, obtain the polyimides PI-C-3 of flaxen film like.
Embodiment 4
The Kapton PI-A-1 that prepared by infrared spectrometer testing example 1, embodiment 2 and embodiment 3,
PI-B-1 and PI-C-1, as a result as shown in Figure 1.It will be seen from figure 1 that in 1786cm-1And 1732cm-1Occur in that polyimides
Characteristic absorption peak, and very sharp, and in 1650cm-1And 1560cm-1Characteristic absorption peak of the place without polyamic acid, shows to gather
Acid imide imidization is substantially completely.
1st, Infrared Characterization
2nd, thermal coefficient of expansion is characterized
Kapton PI-A-1, PI-A-2, PI- embodiment 1, embodiment 2 and embodiment 3 prepared by TMA
B-1, PI-B-2, PI-C-1 and PI-C-2 are characterized, and the result for obtaining is as shown in table 1 below.
The thermal coefficient of expansion and glass transition temperature of table 1 PI-A, PI-B, PI-C
| Sample name | CTE（um/m℃） | Glass transition temperature（℃） |
| PI-A-1 | 11.62 | 348 |
| PI-A-2 | 7.95 | 343 |
| PI-A-3 | 10.68 | 345 |
| PI-B-1 | 19.35 | 335 |
| PI-B-2 | 21.74 | 338 |
| PI-B-3 | 23.46 | 332 |
| PI-C-1 | 12.75 | 367 |
| PI-C-2 | 11.47 | 368 |
| PI-C-3 | 14.64 | 365 |
As shown in Table 1, each sample has done 3 batches, and sample has been carried out reperformance test, can by glass transition temperature
Know, its repeating effect is very good.And the thermal coefficient of expansion of sample（CTE）With copper closely, and sample glass transition
Temperature is very high, maintains excellent thermal property.
3rd, tack test：
Serial batch products prepared by the embodiment of the present invention 1 ~ 3 are carried out tack test, method of testing is directly to be attached to
Material on base material carries out decocting in water, it is found that above-mentioned material steaming and decocting in 100 DEG C of water does not fall off for 500 hours completely, show which is attached
Put forth effort.Above-mentioned base material can equally be aluminium plate, Copper Foil or pottery etc..
4th, Mechanics Performance Testing
Film sample in embodiment 1-3 tests its mechanical property by ASTMD882 method universal electrical puller systems, obtains
Result as shown in table 2 below
The mechanical property of table 2 PI-A-1, PI-B-1, PI-C-1
| Sample name | Elastic modelling quantity (MPa) | Elongation at break (%) | Tensile strength (MPa) |
| PI-A-1 | 3428.42 | 5.232 | 82.09 |
| PI-B-1 | 2323.42 | 4.066 | 53.11 |
| PI-C-1 | 2503.30 | 4.572 | 54.94 |
As shown in Table 2, with the increase of phenyl ring and imide ring containing rigidity in polyimide molecule chain, tensile strength and disconnected
Percentage elongation decline is split, but the elastic modelling quantity of PI-A-1, PI-B-1, PI-C-1 is all close in 3GPa, mechanical property has certain journey
The reduction of degree；But its tensile strength is all in more than 50Mpa, elastic modelling quantity all in more than 2.3GPa, elongation at break all 4 with
On, maintain good mechanical property.
Kapton prepared by the present invention maintains high-fire resistance and mechanical strength, and its tensile strength is
53.11 MPa-82.9 MPa；Kapton prepared by the present invention has very superior thermal coefficient of expansion, and its value is in 7.95-
23.46 um/m DEG C, match with the thermal coefficient of expansion of copper wire, copper cash etc..
Comparative example 1：
According to the method for existing synthesis of polyimides, we have been the contrast experiment, synthesize r-PI
A：In a there-necked flask, under room temperature, nitrogen atmosphere, add N-Methyl pyrrolidone, mechanical agitation to add to benzene two
Amine and diphenyldiamine（The amount of addition is with the amount sum added in S1 and S2 in embodiment 1）, after which is completely dissolved, by equal benzene
It is added thereto after tetracarboxylic acid anhydride and biphenyl tetracarboxylic dianhydride mix homogeneously（The amount of addition is with addition in S1 and S2 in embodiment 1
Amount sum）, the quality summation of diacid and dianhydride accounts for the 5% ~ 25% of solvent quality, the temperature control of reaction at -10 DEG C ~ 15 DEG C, instead
After answering 24h, polyamic acid glue is obtained.
B：Above-mentioned gained polyamic acid glue is carried out filtering and deaeration is processed, filter out insoluble matter that may be present and miscellaneous
Matter, removes the bubble in polyamic acid glue.By the polyamic acid glue for obtaining at room temperature uniform application in clean flat board
On, the flat board can be glass plate, and be put in nitrogen oven and solidified, and solidification process is：Solidify 0.5h at 50 DEG C, so
Solidify 1h afterwards at 80 DEG C, at 120 DEG C, then solidify 1h, at 180 DEG C, then solidify 1h, and then solidify 1h at 230 DEG C,
Then solidify 1h at 280 DEG C again, solidify 1h followed by 330 DEG C, obtain the polyimides of film like.Treat film like
After polyimides naturally cool to room temperature, the polyimides of film like are stripped down from glass plate using warm water, obtain thickness
Spend the polyimides r-PI-1. of the flaxen film like for 15 um
Repeat synthesis once according to above-mentioned method, obtain the polyimides r-PI-2 of flaxen film like.
Repeat synthesis once according to above-mentioned method, obtain the polyimides r-PI-3 of flaxen film like.
Kapton r-PI-1 comparative example prepared by TMA, r-PI-2 and r-PI-3 are characterized, are obtained
The result for arriving is as shown in table 3 below.
The thermal coefficient of expansion and glass transition temperature of table 3 r-PI-1, r-PI-2, r-PI-3
| Sample name | CTE（um/m℃） | Glass transition temperature（℃） |
| r-PI-1 | 18.94 | 305 |
| r-PI-2 | 7.95 | 343 |
| r-PI-3 | 26.73 | 326 |
From table 3 it is observed that its glass transition temperature and thermal coefficient of expansion data fluctuations are larger, embody what its synthesis was obtained
The stability of polyimides is a greater impact.
In sum, the Kapton of the copolyreaction synthesis for being provided by the present invention has excellent comprehensive
Energy.Copolymerization is carried out by controlling the sample-adding amount reacted, while polyimide structures are realized and performance is controllable, synthesis is stablized
It is greatly improved in terms of property and thermal coefficient of expansion scalable, and its mechanical property and thermal property does not produce significant shadow
Ring.The quasi-polyimide is before the photoelectric fields such as liquid crystal display, solar energy-electric energy, optics device protecting film are widely used
Scape.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all spirit in the present invention and
Within principle, any modification, equivalent substitution and improvements that is made etc. should be included within the scope of the present invention.
Claims (8)
1. a kind of preparation method of the Kapton of structure-controllable, it is characterised in that comprise the steps：
S1. room temperature, add solvent, diamidogen and dianhydride under inert gas shielding, obtain polyamic acid glue A；
S2. room temperature, add solvent, diamidogen and dianhydride under inert gas shielding, obtain polyamic acid glue liquid B；
S3. polyamic acid glue liquid B in polyamic acid glue A and S2 in S1 is mixed under inert gas atmosphere, reaction obtains embedding
Gained block polyamide acid glue is filtered, after deaeration, is coated on substrate, solidifies, peel off after cooling by section polyamic acid glue,
Obtain final product the Kapton；
In S1, diamidogen is x with the reaction mol ratio of dianhydride：（x+1）；
In S2, diamidogen with the reaction mol ratio of dianhydride is（y+1）：y.
X, y are the integers being not zero.
2. method according to claim 1, it is characterised in that the diamidogen is aromatic diamine, the dianhydride is fragrance
Race's dianhydride.
3. method according to claim 2, it is characterised in that the aromatic diamine includes diphenyldiamine, to benzene two
Amine, one or more in m-diaminobenzene., diaminodiphenyl-methane, the aromatic dianhydride include pyromellitic acid anhydride,
Diphenyl ether tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride or 4,4`- hexafluoroisopropyli,ene-O-phthalic
One or more in anhydride.
4. method according to claim 1, it is characterised in that two in the polyamic acid glue A or polyamic acid glue liquid B
The quality summation of amine and dianhydride accounts for the 5% ~ 25% of solution quality.
5. method according to claim 1, it is characterised in that cured is in S3：Solidify 0.5h at 50 DEG C, then
Solidify 1h at 80 DEG C, at 120 DEG C, then solidify 1h, at 180 DEG C, then solidify 1h, and then solidify 1h at 230 DEG C, and
Then solidify 1h at 280 DEG C, followed by solidification 1h at 330 DEG C.
6. method according to claim 1, it is characterised in that the temperature that reacts in S3 is -10 DEG C ~ 15 DEG C, reaction when
Between be 10 ~ 24h.
7. method according to claim 1, it is characterised in that S1 is identical with solvent in S2, including dimethyl sulfoxide, N, N-
One or more in dimethylformamide, DMAC N,N' dimethyl acetamide or N-Methyl pyrrolidone.
8. method according to claim 1, it is characterised in that diamidogen is identical or different with diamidogen in S2 in S1, two in S1
Acid anhydride is identical or different with dianhydride in S2.
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| CN201610919424.7A CN106496612A (en) | 2016-10-21 | 2016-10-21 | A kind of preparation method of the Kapton of structure-controllable |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111087616A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Method for preparing block type polyamic acid solution |
| CN111423613A (en) * | 2020-04-29 | 2020-07-17 | 中山大学 | Method for preparing specific conductive metal pattern on surface of polyimide film |
| CN112354381A (en) * | 2020-10-13 | 2021-02-12 | 中山大学 | 'full polyimide' mixed matrix gas separation membrane and preparation method and application thereof |
| WO2021027099A1 (en) * | 2019-08-15 | 2021-02-18 | 武汉华星光电半导体显示技术有限公司 | Polyimide, preparation method therefor and flexible oled panel |
| CN112521603A (en) * | 2019-09-19 | 2021-03-19 | 臻鼎科技股份有限公司 | Polyamide acid block copolymer and preparation method thereof, polyimide copper-clad plate and circuit board |
| CN112980014A (en) * | 2019-12-14 | 2021-06-18 | 上海市合成树脂研究所有限公司 | Blended polyimide film, preparation method thereof and application thereof in flexible display substrate |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105111476A (en) * | 2015-09-16 | 2015-12-02 | 安徽鑫柏格电子股份有限公司 | Preparation method for polyimide film |
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Patent Citations (1)
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| CN105111476A (en) * | 2015-09-16 | 2015-12-02 | 安徽鑫柏格电子股份有限公司 | Preparation method for polyimide film |
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| CN111087616A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Method for preparing block type polyamic acid solution |
| CN111087616B (en) * | 2018-10-23 | 2022-10-11 | 中国石油化工股份有限公司 | Method for preparing block type polyamic acid solution |
| WO2021027099A1 (en) * | 2019-08-15 | 2021-02-18 | 武汉华星光电半导体显示技术有限公司 | Polyimide, preparation method therefor and flexible oled panel |
| CN112521603A (en) * | 2019-09-19 | 2021-03-19 | 臻鼎科技股份有限公司 | Polyamide acid block copolymer and preparation method thereof, polyimide copper-clad plate and circuit board |
| CN112521603B (en) * | 2019-09-19 | 2023-06-02 | 臻鼎科技股份有限公司 | Polyamic acid block copolymer, preparation method thereof, polyimide copper-clad plate and circuit board |
| CN112980014A (en) * | 2019-12-14 | 2021-06-18 | 上海市合成树脂研究所有限公司 | Blended polyimide film, preparation method thereof and application thereof in flexible display substrate |
| CN112980014B (en) * | 2019-12-14 | 2023-08-08 | 上海市合成树脂研究所有限公司 | Blended polyimide film, preparation method thereof and application thereof in flexible display substrate |
| CN111423613A (en) * | 2020-04-29 | 2020-07-17 | 中山大学 | Method for preparing specific conductive metal pattern on surface of polyimide film |
| CN112354381A (en) * | 2020-10-13 | 2021-02-12 | 中山大学 | 'full polyimide' mixed matrix gas separation membrane and preparation method and application thereof |
| CN115216007A (en) * | 2022-08-12 | 2022-10-21 | 航天特种材料及工艺技术研究所 | Preparation method of polyamide acid solution and polyimide film |
| CN115216007B (en) * | 2022-08-12 | 2024-01-16 | 航天特种材料及工艺技术研究所 | Preparation method of polyamic acid solution and polyimide film |
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