CN105860074B - A kind of polyimide precursor solution and preparation method thereof and prepare the method for Kapton using it - Google Patents
A kind of polyimide precursor solution and preparation method thereof and prepare the method for Kapton using it Download PDFInfo
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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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- 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
- 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
A kind of polyimide precursor solution and preparation method thereof and the method for Kapton is prepared using it, the method for Kapton is prepared the present invention relates to polyimide precursor solution and preparation method thereof and using it.Preparation method and structure composition the invention solves existing polyimide precursor polyamic acid aqueous solution are difficult to realize casting apparatus produces the Kapton of great surface quality and serialization not embrittlement the problem of.A kind of polyimide precursor solution is made of tertiary amine, aqueous release agent, aromatic dianhydride, aromatic diamines, polar solvent and water；Preparation method：It weighs；Under nitrogen atmosphere, certain temperature and stirring condition, water, polar solvent and aromatic diamines are mixed, the aromatic dianhydride weighed is added in reaction solution and is reacted, under nitrogen atmosphere, certain temperature and stirring condition, the tertiary amine weighed and aqueous release agent reaction are added in, is finally cooled down.Prepare Kapton：Self-supporting film is prepared, then cures, anneal.
Description
Technical field
The side of Kapton is prepared the present invention relates to polyimide precursor solution and preparation method thereof and using it
Method.
Background technology
Polyimides is the aromatic heterocyclic polymer containing imide ring in constitutional repeating unit, it is so far in industry
The highest high molecular material of temperature classification of field application, with its excellent comprehensive performance in film, resin, fiber, seperation film
Etc. being widely used in the fields such as aerospace, electric.Traditional polyimides is usually by aromatic tetracarboxylic acid anhydride and virtue
Fragrant race's diamines is raw material in aprotic polar solvent, and by being initially formed polyamic acid, then imidization is dehydrated to form polyimides.
Now with the development of field of microelectronics, Kapton, especially colorless polyimide are held promise as soft
Property transparent substrates, substitute ito glass, got a lot of applications in flexible wearable equipment and flexible display device.Usually,
Polyimide precursor solution experience blade coating, the processes such as casting film-forming and hot imidization, final winding form high-quality thin film.And
Using polar solvent, such as n,N-dimethylacetamide, n,N-Dimethylformamide, N-Methyl pyrrolidone etc., polyamide is prepared
After acid, during curtain coating volatilization and hot imidization, exhaust gas and sedimentation caused by a large amount of solvents volatilize in drying tunnel are directed to
Waste liquor contamination afterwards.Under normal conditions, it a degree of can be recycled using hot-flow flue and purification utilizes solvent again, but it is existing
Stage technique is difficult to realize 100% solvent recovery and 100% solvent separating-purifying.Conventional enterprise can only achieve more than 90%
Recycling, but recycling design is difficult to prepare the polymer of high quality again；The fugitive constituent of remainder also can to air and water source
Have an impact, from environmental protection angle have become treat Kapton be contamination type chemical products an important factor for, should
Problem has become the important problem of polyimides film field face.
Polyimides, especially Kapton undoubtedly can be greatly solved using water as the solvent of polyamic acid to prepare
Puzzlement in the process.In this regard, it has been reported that such as《Polyimides is prepared by water-soluble polyamic acid》, insulating materials
1981(1):34-42, added in polar solvent dianhydride/diamines formed after polyamic acid add in ammonia or organic amine carry out in and,
Water is added to dilute to obtain solution.But derivant of the substantial amounts of organic solvent as polymerization is still introduced in its solution.Document
(High Performance Polymers,2003(15):It 269-279.) reports and first hydrolyzes dianhydride, then polymerize with diamines
It forms polyamic acid to be precipitated in water, thermal cyclization obtains polyimide powder in pressure bottle after dry is washed repeatedly.Process
It is extremely complicated, it is higher to equipment requirement while be difficult to be prepared on a large scale.Polyamic acid is not soluble in water obtained by simultaneously, it is difficult to apply
In Kapton preparation process.
The water-soluble polyamic acid solution arrived involved in similar document and patent report is to polyimide precursor
Structural research, pass through the adjustment to structure, evaluation experimental room blade coating Kapton performance, such as hot property, mechanical performance
Deng.Be not involved with the curtain coating produced by polyimide precursor aqueous solution coat form self-supported membrane, tension is formed by curing
The report of polyimides continuous film.
Meanwhile the water-soluble polyimide precursor-polyamic acid solution arrived involved in document and patent is using one kind
Metal salt or amine salt are catalyzed to form polyimide precursor, and aqueous solution be thermally formed the process of self-supporting precursor film
In, moisture content is evaporated completely (100 DEG C) substantially not yet before imidization, can cause residual into film using inorganic metal salt catalysis；It adopts
With a small amount of single kind amine salt, remaining gap after catalyst abjection is left on the self-supported membrane surface that can be resulted in, on the one hand
The surface quality of Kapton can be influenced to ultimately form, the formation in another aspect gap can also make the material property of film
Into influence.
In addition, usually select n,N-dimethylacetamide (164 DEG C of boiling point) molten as solvent formation polyimide precursor
Liquid, curtain coating prolapse solvent form the temperature of self-supported membrane between 150 DEG C to 250 DEG C, and the polyimide precursor of high molecular weight-
Polyamic acid has certain film strength, but in imidization conversion process (150 DEG C -250 DEG C), can face molecular weight urgency
The danger small, film strength declines is reduced sharply, using high boiling n,N-dimethylacetamide as solvent, solvent is contained by high temperature
It is a degree of that newly formed self-supported membrane is avoided to become fragile, the danger of the film breaks during drawing by high temperature is reduced, is improved
The continuous production efficiency of formed body.And the boiling point of water is 100 DEG C in polyimide precursor aqueous solution, during cast coat
The temperature after moisture content is removed between 60 DEG C to 120 DEG C, less than the temperature of imidization, so forming solvent-free self-supporting polyamides
After amino acid film, during experience stretches imidization, since molecular weight reduces (150~250 DEG C), there is greater risk self-supporting
Film is difficult to withstand system drawing tension and be broken.
It is said from the preparation process angle of more than formed body, it is water-soluble not to be related to polyimide precursor-polyamic acid
Different preparation methods, the different catalysts type of liquid undergo the self-supported membrane (polyamide acid film) of polyimides casting films again
The film forming difficulty of curing oven and the influence with the surface quality, intensity of formed body Kapton.
The content of the invention
Preparation method and structure composition the invention solves existing polyimide precursor-polyamic acid aqueous solution are difficult to
The problem of realizing the Kapton in casting apparatus production great surface quality and serialization not embrittlement, and a kind of polyamides is provided
Imines precursor solution and preparation method thereof and prepare the method for Kapton using it.
A kind of polyimide precursor solution by tertiary amine, aqueous release agent, aromatic dianhydride, aromatic diamines, polar solvent and
Water is made；
The aromatic diamines and the molar ratio of tertiary amine are 1:(0.05~1.5)；The aromatic diamines and the aqueous demoulding
The mass ratio of agent is 1:(0.01~1)；The aromatic diamines and the molar ratio of aromatic dianhydride are 1:(0.97~1.03)；It is described
Aromatic dianhydride and aromatic diamines gross mass and water mass ratio be 1:(2~10)；The aromatic dianhydride and aromatic diamines
Gross mass and polar solvent mass ratio be 1:(0~10)；
The aromatic diamines are 4,4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenylmethane, two (3- aminobenzene oxygen
Base) one kind in benzophenone, p-phenylenediamine, m-phenylene diamine (MPD) and 4,4' diaminodiphenyl sulfone or wherein several mixtures；
The tertiary amine is the mixture of low boiling point tertiary amine or low boiling point tertiary amine and higher boiling tertiary amine, the low boiling point uncle
The molar ratio of amine and higher boiling tertiary amine is 1:(0.01~100)；The low boiling point tertiary amine for boiling point below 150 DEG C, and
The molecular weight of low boiling point tertiary amine is 80g/mol~250g/mol；The higher boiling tertiary amine is boiling point at 150 DEG C~295 DEG C
Tertiary amine；
The polar solvent is DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, ethylene glycol and dimethyl sulfoxide (DMSO)
In one kind or wherein several mixtures；
When the aromatic dianhydride is 3,3,4 ', 4 '-diphenyl ether tetracarboxylic dianhydride, 3,3,4 ', 4 '-two sulfuryl tetrabasic carboxylic acids two
Acid anhydride or 3,3, during 4 ', 4 '-benzophenone tetracarboxylic dianhydride, the repetition list of polyamic acid in the polyimide precursor solution
Member is：
The R1For-O- or
The R2For
When the aromatic dianhydride is 3,3, during 4 ', 4 '-biphenyl tetracarboxylic dianhydride, the polyimide precursor solution
The repetitive unit of middle polyamic acid is：
The R3For
When the aromatic dianhydride is pyromellitic acid anhydride, polyamic acid in the polyimide precursor solution
Repetitive unit be：
The R4For
A kind of preparation method of polyimide precursor solution is to carry out according to the following steps：
First, tertiary amine, aqueous release agent, aromatic dianhydride, aromatic diamines, polar solvent and water are taken；
The aromatic diamines and the molar ratio of tertiary amine are 1:(0.05~1.5)；The aromatic diamines and the aqueous demoulding
The mass ratio of agent is 1:(0.01~1)；The aromatic diamines and the molar ratio of aromatic dianhydride are 1:(0.97~1.03)；It is described
Aromatic dianhydride and aromatic diamines gross mass and water mass ratio be 1:(2~10)；The aromatic dianhydride and aromatic diamines
Gross mass and polar solvent mass ratio be 1:(0~10)；
2nd, in the case where nitrogen atmosphere, temperature are 2 DEG C~10 DEG C and stirring condition, add in step 1 and weigh into three-necked bottle
Water and polar solvent, then add in the aromatic diamines that weigh in step 1, obtain reaction solution, the fragrance that will be weighed in step 1
Dianhydride is added in reaction solution in three times by quality is average, reacts 1h~5h, reaction solution then is warming up to 20 DEG C~60 DEG C,
Nitrogen atmosphere, temperature is under 20 DEG C~60 DEG C and stirring condition, add in the tertiary amine that is weighed in step 1 and aqueous into reaction solution
Releasing agent is stirred to react 3h~5h, and reacting liquid temperature finally is reduced to 2 DEG C~10 DEG C, stands 1h~10h, obtains polyamides Asia
Amine precursor solution；
Aromatic diamines described in step 1 are 4,4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenylmethane, two (3- ammonia
Phenoxyl) one kind in benzophenone, p-phenylenediamine, m-phenylene diamine (MPD) and 4,4' diaminodiphenyl sulfone or wherein several mixed
Close object；
Tertiary amine described in step 1 is the mixture of low boiling point tertiary amine or low boiling point tertiary amine and higher boiling tertiary amine, described
The molar ratio of low boiling point tertiary amine and higher boiling tertiary amine is 1:(0.01~100)；The low boiling point tertiary amine is boiling point at 150 DEG C
Hereinafter, and the molecular weight of low boiling point tertiary amine is 80g/mol~250g/mol；The higher boiling tertiary amine for boiling point 150 DEG C~
295 DEG C of tertiary amine；
Polar solvent described in step 1 is DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, ethylene glycol and two
One kind or wherein several mixtures in methyl sulfoxide；
Aromatic dianhydride described in step 1 is 3,3,4 ', 4 '-diphenyl ether tetracarboxylic dianhydride, 3,3,4 ', 4 '-two sulfuryls
Tetracarboxylic dianhydride or 3,3, during 4 ', 4 '-benzophenone tetracarboxylic dianhydride, polyamic acid in the polyimide precursor solution
Repetitive unit be：
The R1For-O- or
The R2For
Aromatic dianhydride described in the step 1 is 3,3, during 4 ', 4 '-biphenyl tetracarboxylic dianhydride, before the polyimides
The repetitive unit of polyamic acid is in drive liquid solution：
The R3For
When aromatic dianhydride described in the step 1 is pyromellitic acid anhydride, in the polyimide precursor solution
The repetitive unit of polyamic acid is：
The R4For
A kind of method that Kapton is prepared using polyimide precursor solution is to carry out according to the following steps：
First, polyimide precursor solution is filtered and deaerated, be cast to along T-shaped slit on stainless steel rotary drum, so
Afterwards in the case where temperature is 60 DEG C~180 DEG C, dry 1min~50min obtains self-supporting film；
2nd, self-supporting film from stainless steel rotary drum is removed and is placed in curing in curing oven, be 150 first in temperature
DEG C~200 DEG C under conditions of, heat 1min~60min, then in temperature under conditions of 200 DEG C~250 DEG C, heating 1min~
60min then under conditions of temperature is 250 DEG C~450 DEG C, heats 1min~60min, is finally 290 DEG C~310 in temperature
Under conditions of DEG C, about 1min~20min is made annealing treatment, obtains Kapton；
And self-supporting film is clamped using fixture so that longitudinal length changes before and after self-supporting film cures in solidification process
Percentage is 5%~20%, and lateral length percentage change is 10%~80%.
The beneficial effects of the invention are as follows：A kind of polyimide precursor solution provided by the invention and preparation method thereof and profit
The method of Kapton is prepared with it, the preparation side of existing polyimide precursor-polyamic acid aqueous solution can be solved
Method and structure composition are difficult to realize produce asking for the Kapton of great surface quality and serialization not embrittlement in casting apparatus
Topic.According to the preparation method of polyimide precursor solution, low ratio high bp polar solvent is employed, a variety of boiling point tertiary amines are answered
Close the combination of object.
On the one hand, high bp polar solvent (such as n,N-dimethylacetamide, n,N-Dimethylformamide) and water are utilized
Combination, improve solvent entirety boiling point, the self-supporting polyimide precursor film avoided the formation of (is less than containing quantity of solvent is very few
20%) and low boiling point, although self-supported membrane still undergoes high temperature imidization (having stretching action or tensionless winkler foundation effect) process (150
DEG C -250 DEG C) in be present with the situation that molecular weight and molecular weight and intensity decline, but the promotion containing quantity of solvent and boiling point improve, greatly
Degree improves the elongation and flexibility of initial imidization (150 DEG C -200 DEG C), avoids in high temperature since external load is led
The danger of the film breaks of cause influences film continuous operation.
On the other hand, polyimide precursor solution preparation method employs a variety of boiling point tertiary amine compounds, so as to flow
When prolonging prolapse solvent formation self-supported membrane, still containing there are many boiling point tertiary amines in presoma.By self-supporting in imidization program
Film pours into curing oven and is handled, especially for serialization processing self-supported membrane hot imidization, it is necessary to apply certain
Axially outer load provides traction, after moisture volatilizees substantially (150 DEG C of ＜), commonly uses single tertiary amines and also faces at 150 DEG C
The risk of volatilization, it is difficult to be promoted as liquid residual and make up (150 DEG C -250 DEG C) low-intensity, low elongation after initial imidization.
A variety of removal temperatures and boiling point are provided using a variety of tertiary amines, certain liquid residual is still remained with when reality is now greater than 150 DEG C.And
It is used in combination with the mode of high boiling solvent combination, can further ensure that the film under imidization initial temperature condition continues
Elongation and the coefficient of expansion, greatly avoid in the initial film destruction of imidization, are especially pulled the lower film of power effect
It destroys, so as to save curing oven cooling, wear film, the electric power and time cost that heat up again.
It is surprising that the compound use of a variety of tertiary amines, not only contributes to promote each stage shaping strength of film, simultaneously
It also improves the surface quality of film and reduces defect.Due to low-boiling single tertiary amine and water after volatilizing, polyimides
Presoma faces quick imidization and solvent, the dual-pressure of catalyst abjection, can it is serious caused by thin film surface planeness it is poor,
Surface has the stomata that leaves of volatilization abjection, imidization to remove closed pore that a large amount of water leave etc. in short-term, has to the surface quality of film
Very big influence.By the way of low boiling point and higher boiling tertiary amine, unexpected obtain is held under the conditions of different imidizations
Continuous volatilization effect makes the effect for providing Self-leveling in Kapton forming process not against external force, greatly solves
The surface quality problems of film.It is operated especially for the hot imidization of continuous thin film, not only reduces fold and gap
Appearance, film flatness also enhanced.And polyimide precursor solution prepared by the present invention can also be used to form polyamides
Imine fiber.
The present invention for a kind of polyimide precursor solution and preparation method thereof and prepares Kapton using it
Method.
Description of the drawings
Fig. 1 is Kapton photo prepared by example IV；
Fig. 2 is Kapton photo prepared by contrast experiment one.
Specific embodiment
Specific embodiment one：A kind of polyimide precursor solution of present embodiment is by tertiary amine, aqueous release agent, virtue
Fragrant dianhydride, aromatic diamines, polar solvent and water are made；
The aromatic diamines and the molar ratio of tertiary amine are 1:(0.05~1.5)；The aromatic diamines and the aqueous demoulding
The mass ratio of agent is 1:(0.01~1)；The aromatic diamines and the molar ratio of aromatic dianhydride are 1:(0.97~1.03)；It is described
Aromatic dianhydride and aromatic diamines gross mass and water mass ratio be 1:(2~10)；The aromatic dianhydride and aromatic diamines
Gross mass and polar solvent mass ratio be 1:(0~10)；
The aromatic diamines are 4,4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenylmethane, two (3- aminobenzene oxygen
Base) one kind in benzophenone, p-phenylenediamine, m-phenylene diamine (MPD) and 4,4' diaminodiphenyl sulfone or wherein several mixtures；
The tertiary amine is the mixture of low boiling point tertiary amine or low boiling point tertiary amine and higher boiling tertiary amine, the low boiling point uncle
The molar ratio of amine and higher boiling tertiary amine is 1:(0.01~100)；The low boiling point tertiary amine for boiling point below 150 DEG C, and
The molecular weight of low boiling point tertiary amine is 80g/mol~250g/mol；The higher boiling tertiary amine is boiling point at 150 DEG C~295 DEG C
Tertiary amine；
The polar solvent is DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, ethylene glycol and dimethyl sulfoxide (DMSO)
In one kind or wherein several mixtures；
When the aromatic dianhydride is 3,3,4 ', 4 '-diphenyl ether tetracarboxylic dianhydride, 3,3,4 ', 4 '-two sulfuryl tetrabasic carboxylic acids two
Acid anhydride or 3,3, during 4 ', 4 '-benzophenone tetracarboxylic dianhydride, the repetition list of polyamic acid in the polyimide precursor solution
Member is：
The R1For-O- or
The R2For
When the aromatic dianhydride is 3,3, during 4 ', 4 '-biphenyl tetracarboxylic dianhydride, the polyimide precursor solution
The repetitive unit of middle polyamic acid is：
The R3For
When the aromatic dianhydride is pyromellitic acid anhydride, polyamic acid in the polyimide precursor solution
Repetitive unit be：
The R4For
The advantageous effect of present embodiment is：A kind of polyimide precursor solution and its preparation that present embodiment provides
Method and the method for Kapton is prepared using it, existing polyimide precursor-polyamic acid aqueous solution can be solved
Preparation method and structure composition be difficult to realize produce the polyimides of great surface quality and serialization not embrittlement in casting apparatus
The problem of film.According to the preparation method of polyimide precursor solution, low ratio high bp polar solvent, a variety of boilings are employed
The combination of point tertiary amine compound.
On the one hand, high bp polar solvent (such as n,N-dimethylacetamide, n,N-Dimethylformamide) and water are utilized
Combination, improve solvent entirety boiling point, the self-supporting polyimide precursor film avoided the formation of (is less than containing quantity of solvent is very few
20%) and low boiling point, although self-supported membrane still undergoes high temperature imidization (having stretching action or tensionless winkler foundation effect) process (150
DEG C -250 DEG C) in be present with the situation that molecular weight and molecular weight and intensity decline, but the promotion containing quantity of solvent and boiling point improve, greatly
Degree improves the elongation and flexibility of initial imidization (150 DEG C -200 DEG C), avoids in high temperature since external load is led
The danger of the film breaks of cause influences film continuous operation.
On the other hand, polyimide precursor solution preparation method employs a variety of boiling point tertiary amine compounds, so as to flow
When prolonging prolapse solvent formation self-supported membrane, still containing there are many boiling point tertiary amines in presoma.By self-supporting in imidization program
Film pours into curing oven and is handled, especially for serialization processing self-supported membrane hot imidization, it is necessary to apply certain
Axially outer load provides traction, after moisture volatilizees substantially (150 DEG C of ＜), commonly uses single tertiary amines and also faces at 150 DEG C
The risk of volatilization, it is difficult to be promoted as liquid residual and make up (150 DEG C -250 DEG C) low-intensity, low elongation after initial imidization.
A variety of removal temperatures and boiling point are provided using a variety of tertiary amines, certain liquid residual is still remained with when reality is now greater than 150 DEG C.And
It is used in combination with the mode of high boiling solvent combination, can further ensure that the film under imidization initial temperature condition continues
Elongation and the coefficient of expansion, greatly avoid in the initial film destruction of imidization, are especially pulled the lower film of power effect
It destroys, so as to save curing oven cooling, wear film, the electric power and time cost that heat up again.
It is surprising that the compound use of a variety of tertiary amines, not only contributes to promote each stage shaping strength of film, simultaneously
It also improves the surface quality of film and reduces defect.Due to low-boiling single tertiary amine and water after volatilizing, polyimides
Presoma faces quick imidization and solvent, the dual-pressure of catalyst abjection, can it is serious caused by thin film surface planeness it is poor,
Surface has the stomata that leaves of volatilization abjection, imidization to remove closed pore that a large amount of water leave etc. in short-term, has to the surface quality of film
Very big influence.By the way of low boiling point and higher boiling tertiary amine, unexpected obtain is held under the conditions of different imidizations
Continuous volatilization effect makes the effect for providing Self-leveling in Kapton forming process not against external force, greatly solves
The surface quality problems of film.It is operated especially for the hot imidization of continuous thin film, not only reduces fold and gap
Appearance, film flatness also enhanced.And polyimide precursor solution prepared by specific embodiment can be additionally used in shape
Into polyimide fiber.
Specific embodiment two：The present embodiment is different from the first embodiment in that：The low boiling point tertiary amine is
Triethylamine, Dodecyl Dimethyl Amine, diethanol monoisopropanolamine and one kind in picoline are wherein several mixed
Close object.It is other same as the specific embodiment one.
Specific embodiment three：Unlike one of present embodiment and specific embodiment one or two：The height boiling
Point tertiary amine is tri-n-butylamine, triisopropanolamine and one kind in dimethylamino formyl chloride or wherein several mixtures.It is other with
Specific embodiment one or two is identical.
Specific embodiment four：Unlike one of present embodiment and specific embodiment one to three：Described is aqueous
Releasing agent is can releasing agent or mould release miscible with water, and not being precipitated under conditions of temperature is less than 100 DEG C.It is other with it is specific
Embodiment one to three is identical.
Specific embodiment five：Unlike one of present embodiment and specific embodiment one to four：Described is aqueous
Releasing agent is RPLUS S02-004, Sepaluck RA715W, Sepaluck RA733W, NS-100 or Sepaluck
RA780W.It is other identical with specific embodiment one to four.
RPLUS S02-004 are the vigorous company's production of German Crewe；Sepaluck RA715W、Sepaluck RA733W、NS-
100 and Sepaluck RA780W are Japanese one chemical company of mountain production.
Specific embodiment six：Unlike one of present embodiment and specific embodiment one to five：The fragrance
The mass ratio of the gross mass and polar solvent of dianhydride and aromatic diamines is 1:(0~1.5)；The low boiling point tertiary amine and higher boiling
The molar ratio of tertiary amine is 1:(0.5~100).It is other identical with specific embodiment one to five.
The mass-energy density of the gross mass and polar solvent of present embodiment aromatic dianhydride and aromatic diamines provides low molten
Agent bears and keeps better effects.
Specific embodiment seven：A kind of preparation method of polyimide precursor solution described in present embodiment be by with
Lower step carries out：
First, tertiary amine, aqueous release agent, aromatic dianhydride, aromatic diamines, polar solvent and water are taken；
The aromatic diamines and the molar ratio of tertiary amine are 1:(0.05~1.5)；The aromatic diamines and the aqueous demoulding
The mass ratio of agent is 1:(0.01~1)；The aromatic diamines and the molar ratio of aromatic dianhydride are 1:(0.97~1.03)；It is described
Aromatic dianhydride and aromatic diamines gross mass and water mass ratio be 1:(2~10)；The aromatic dianhydride and aromatic diamines
Gross mass and polar solvent mass ratio be 1:(0~10)；
2nd, in the case where nitrogen atmosphere, temperature are 2 DEG C~10 DEG C and stirring condition, add in step 1 and weigh into three-necked bottle
Water and polar solvent, then add in the aromatic diamines that weigh in step 1, obtain reaction solution, the fragrance that will be weighed in step 1
Dianhydride is added in reaction solution in three times by quality is average, reacts 1h~5h, reaction solution then is warming up to 20 DEG C~60 DEG C,
Nitrogen atmosphere, temperature is under 20 DEG C~60 DEG C and stirring condition, add in the tertiary amine that is weighed in step 1 and aqueous into reaction solution
Releasing agent is stirred to react 3h~5h, and reacting liquid temperature finally is reduced to 2 DEG C~10 DEG C, stands 1h~10h, obtains polyamides Asia
Amine precursor solution；
Aromatic diamines described in step 1 are 4,4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenylmethane, two (3- ammonia
Phenoxyl) one kind in benzophenone, p-phenylenediamine, m-phenylene diamine (MPD) and 4,4' diaminodiphenyl sulfone or wherein several mixed
Close object；
Tertiary amine described in step 1 is the mixture of low boiling point tertiary amine or low boiling point tertiary amine and higher boiling tertiary amine, described
The molar ratio of low boiling point tertiary amine and higher boiling tertiary amine is 1:(0.01~100)；The low boiling point tertiary amine is boiling point at 150 DEG C
Hereinafter, and the molecular weight of low boiling point tertiary amine is 80g/mol~250g/mol；The higher boiling tertiary amine for boiling point 150 DEG C~
295 DEG C of tertiary amine；
Polar solvent described in step 1 is DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, ethylene glycol and two
One kind or wherein several mixtures in methyl sulfoxide；
Aromatic dianhydride described in step 1 is 3,3,4 ', 4 '-diphenyl ether tetracarboxylic dianhydride, 3,3,4 ', 4 '-two sulfuryls
Tetracarboxylic dianhydride or 3,3, during 4 ', 4 '-benzophenone tetracarboxylic dianhydride, polyamic acid in the polyimide precursor solution
Repetitive unit be：
The R1For-O- or
The R2For
Aromatic dianhydride described in the step 1 is 3,3, during 4 ', 4 '-biphenyl tetracarboxylic dianhydride, before the polyimides
The repetitive unit of polyamic acid is in drive liquid solution：
The R3For
When aromatic dianhydride described in the step 1 is pyromellitic acid anhydride, in the polyimide precursor solution
The repetitive unit of polyamic acid is：
The R4For
Specific embodiment eight：Present embodiment is unlike specific embodiment seven：Low boiling described in step 1
Point tertiary amine is triethylamine, Dodecyl Dimethyl Amine, diethanol monoisopropanolamine and one kind in picoline or wherein
Several mixtures.It is other identical with specific embodiment seven.
Specific embodiment nine：Unlike one of present embodiment and specific embodiment seven or eight：Institute in step 1
The higher boiling tertiary amine stated is tri-n-butylamine, triisopropanolamine and one kind in dimethylamino formyl chloride or wherein several mixing
Object.It is other identical with specific embodiment seven or eight.
Specific embodiment ten：Unlike one of present embodiment and specific embodiment seven to nine：Institute in step 1
The aqueous release agent stated is can releasing agent or mould release miscible with water, and not being precipitated under conditions of temperature is less than 100 DEG C.Its
It is identical with specific embodiment seven to nine.
Specific embodiment 11：Unlike one of present embodiment and specific embodiment seven to ten：In step 1
The aqueous release agent for RPLUS S02-004, Sepaluck RA715W, Sepaluck RA733W, NS-100 or
Sepaluck RA780W.It is other identical with specific embodiment seven to ten.
RPLUS S02-004 are the vigorous company's production of German Crewe；Sepaluck RA715W、Sepaluck RA733W、NS-
100 and Sepaluck RA780W are Japanese one chemical company of mountain production.
Specific embodiment 12：Present embodiment is unlike specific embodiment seven to one of 11：Step 1
Described in aromatic dianhydride and aromatic diamines gross mass and polar solvent mass ratio be 1:(0~1.5)；Described in step 1
The molar ratio of low boiling point tertiary amine and higher boiling tertiary amine be 1:(0.5~100).It is other with seven to 11 phase of specific embodiment
Together.
The mass-energy density of the gross mass and polar solvent of present embodiment aromatic dianhydride and aromatic diamines provides low molten
Agent bears and keeps better effects.
Specific embodiment 13：It is thin that a kind of polyimide precursor solution of utilization of present embodiment prepares polyimides
The method of film specifically carries out according to the following steps：
First, polyimide precursor solution is filtered and deaerated, be cast to along T-shaped slit on stainless steel rotary drum, so
Afterwards in the case where temperature is 60 DEG C~180 DEG C, dry 1min~50min obtains self-supporting film；
2nd, self-supporting film from stainless steel rotary drum is removed and is placed in curing in curing oven, be 150 first in temperature
DEG C~200 DEG C under conditions of, heat 1min~60min, then in temperature under conditions of 200 DEG C~250 DEG C, heating 1min~
60min then under conditions of temperature is 250 DEG C~450 DEG C, heats 1min~60min, is finally 290 DEG C~310 in temperature
Under conditions of DEG C, about 1min~20min is made annealing treatment, obtains Kapton；
And self-supporting film is clamped using fixture so that longitudinal length changes before and after self-supporting film cures in solidification process
Percentage is 5%~20%, and lateral length percentage change is 10%~80%.
The Kapton of present embodiment can be by obtaining the polyamic acid imidizate for being used as presoma.This
Outside, raw material, reaction condition of worker etc. can be used in its manufacture.Furthermore, it is possible to it needs to add inorganic or have according to function
The filler of machine object.
Then self-supported membrane from substrate surface is removed and carries out curing process, can by aqueous impregnation solution, give it is additional
The methods of tension, is realized.
Kapton is the Kapton obtained according to polyimide precursor solution.It is thin as polyimides
Film can be used as liquid crystal orientation film, fuel cell porous polyimide film, seperation film, pcb board individual layer, bilayer, multilayer, R-
F, HDI film substrates, electric wire insulating film, high-temperature resistant membrane etc..
The advantageous effect of present embodiment is：A kind of polyimide precursor solution and its preparation that present embodiment provides
Method and the method for Kapton is prepared using it, existing polyimide precursor-polyamic acid aqueous solution can be solved
Preparation method and structure composition be difficult to realize produce the polyimides of great surface quality and serialization not embrittlement in casting apparatus
The problem of film.According to the preparation method of polyimide precursor solution, low ratio high bp polar solvent, a variety of boilings are employed
The combination of point tertiary amine compound.
On the one hand, high bp polar solvent (such as n,N-dimethylacetamide, n,N-Dimethylformamide) and water are utilized
Combination, improve solvent entirety boiling point, the self-supporting polyimide precursor film avoided the formation of (is less than containing quantity of solvent is very few
20%) and low boiling point, although self-supported membrane still undergoes high temperature imidization (having stretching action or tensionless winkler foundation effect) process (150
DEG C -250 DEG C) in be present with the situation that molecular weight and molecular weight and intensity decline, but the promotion containing quantity of solvent and boiling point improve, greatly
Degree improves the elongation and flexibility of initial imidization (150 DEG C -200 DEG C), avoids in high temperature since external load is led
The danger of the film breaks of cause influences film continuous operation.
On the other hand, polyimide precursor solution preparation method employs a variety of boiling point tertiary amine compounds, so as to flow
When prolonging prolapse solvent formation self-supported membrane, still containing there are many boiling point tertiary amines in presoma.By self-supporting in imidization program
Film pours into curing oven and is handled, especially for serialization processing self-supported membrane hot imidization, it is necessary to apply certain
Axially outer load provides traction, after moisture volatilizees substantially (150 DEG C of ＜), commonly uses single tertiary amines and also faces at 150 DEG C
The risk of volatilization, it is difficult to be promoted as liquid residual and make up (150 DEG C -250 DEG C) low-intensity, low elongation after initial imidization.
A variety of removal temperatures and boiling point are provided using a variety of tertiary amines, certain liquid residual is still remained with when reality is now greater than 150 DEG C.And
It is used in combination with the mode of high boiling solvent combination, can further ensure that the film under imidization initial temperature condition continues
Elongation and the coefficient of expansion, greatly avoid in the initial film destruction of imidization, are especially pulled the lower film of power effect
It destroys, so as to save curing oven cooling, wear film, the electric power and time cost that heat up again.
It is surprising that the compound use of a variety of tertiary amines, not only contributes to promote each stage shaping strength of film, simultaneously
It also improves the surface quality of film and reduces defect.Due to low-boiling single tertiary amine and water after volatilizing, polyimides
Presoma faces quick imidization and solvent, the dual-pressure of catalyst abjection, can it is serious caused by thin film surface planeness it is poor,
Surface has the stomata that leaves of volatilization abjection, imidization to remove closed pore that a large amount of water leave etc. in short-term, has to the surface quality of film
Very big influence.By the way of low boiling point and higher boiling tertiary amine, unexpected obtain is held under the conditions of different imidizations
Continuous volatilization effect makes the effect for providing Self-leveling in Kapton forming process not against external force, greatly solves
The surface quality problems of film.It is operated especially for the hot imidization of continuous thin film, not only reduces fold and gap
Appearance, film flatness also enhanced.And polyimide precursor solution prepared by specific embodiment can be additionally used in shape
Into polyimide fiber.
Specific embodiment 14：Present embodiment is unlike specific embodiment 13：Then exist in step 1
Temperature is dry 10min~30min at 80 DEG C~160 DEG C.It is other identical with specific embodiment 13.
The advantageous effect of present embodiment is：
Beneficial effects of the present invention are verified using following embodiment：
Embodiment one：
A kind of polyimide precursor solution by tertiary amine, aqueous release agent, aromatic dianhydride, aromatic diamines, polar solvent and
Water is made；
The aromatic diamines and the molar ratio of tertiary amine are 1:0.05；The aromatic diamines and the quality of aqueous release agent
Than for 1:0.01；The aromatic diamines and the molar ratio of aromatic dianhydride are 1:1；The aromatic dianhydride and aromatic diamines it is total
The mass ratio of quality and water is 1:8；The mass ratio of the aromatic dianhydride and the gross mass of aromatic diamines and polar solvent is 1:
1；
The aromatic diamines are p-phenylenediamine；
The tertiary amine is diethanol monoisopropanolamine；
The polar solvent is DMAC N,N' dimethyl acetamide；The aqueous release agent is Japanese one chemical company of mountain life
The NS-100 of production；
The aromatic dianhydride is 3,3,4 ', 4 '-biphenyl tetracarboxylic dianhydride, is gathered in the polyimide precursor solution
The repetitive unit of amic acid is：
A kind of preparation method of above-mentioned polyimide precursor solution is to carry out according to the following steps：
First, 8.16g diethanols monoisopropanolamine (0.05mol), 1.08g NS-100,294.22g 3,3,4 ', 4 '-connection are taken
Benzene tertacarbonic acid's dianhydride (1mol), 108.14g p-phenylenediamine (1mol), 402.36g DMAC N,N' dimethyl acetamides and 3218.88g
Water；
2nd, in the case where nitrogen atmosphere, temperature are 5 DEG C and stirring condition, 3218.88g water and 402.36g are added in into three-necked bottle
Then n,N-dimethylacetamide adds in 108.14g p-phenylenediamine (1mol), obtains reaction solution, by 294.22g 3,3,4 ',
4 '-biphenyl tetracarboxylic dianhydride (1mol) is added in reaction solution in three times by quality is average, reacts 5h, then reaction solution heats up
To 20 DEG C, in the case where nitrogen atmosphere, temperature are 20 DEG C and stirring condition, 8.16g diethanol monoisopropanolamines are added in into reaction solution
(0.05mol) and 1.08g NS-100, are stirred to react 5h, and reacting liquid temperature finally is reduced to 5 DEG C, stand 10h, obtain polyamides
Imines precursor solution；
It is to carry out according to the following steps using the method that a kind of above-mentioned polyimide precursor solution prepares Kapton：
First, polyimide precursor solution is filtered and deaerated, be cast to along T-shaped slit on stainless steel rotary drum, so
Afterwards in the case where temperature is 120 DEG C, dry 10min obtains self-supporting film；
2nd, self-supporting film from stainless steel rotary drum is removed and is placed in curing in curing oven, be 150 first in temperature
Under conditions of DEG C, 3min is heated, then under conditions of temperature is 250 DEG C, heats 3min, then in the condition that temperature is 400 DEG C
Under, 70s is heated, finally under conditions of temperature is 300 DEG C, about 1min is made annealing treatment, obtains Kapton；
And self-supporting film is clamped using fixture so that longitudinal length changes before and after self-supporting film cures in solidification process
Percentage is 10%, and lateral length percentage change is 50%.
The thickness of Kapton manufactured in the present embodiment is 25 microns.
Embodiment two：
A kind of polyimide precursor solution by tertiary amine, aqueous release agent, aromatic dianhydride, aromatic diamines, polar solvent and
Water is made；
The aromatic diamines and the molar ratio of tertiary amine are 1:0.05；The aromatic diamines and the quality of aqueous release agent
Than for 1:0.01；The aromatic diamines and the molar ratio of aromatic dianhydride are 1:1；The aromatic dianhydride and aromatic diamines it is total
The mass ratio of quality and water is 1:8；The mass ratio of the aromatic dianhydride and the gross mass of aromatic diamines and polar solvent is 1:
1；
The aromatic diamines are 4,4 '-diaminodiphenyl ether；
The tertiary amine is diethanol monoisopropanolamine；
The polar solvent is DMAC N,N' dimethyl acetamide；
The aqueous release agent is the NS-100 of Japanese one chemical company of mountain production；
When the aromatic dianhydride is pyromellitic acid anhydride, polyamic acid in the polyimide precursor solution
Repetitive unit is：
A kind of preparation method of above-mentioned polyimide precursor solution is to carry out according to the following steps：
First, take the diethanol monoisopropanolamine (0.05mol) of 8.16g, 2.00g NS-100,218.12g equal benzene tetramethyl
Acid dianhydride (1mol), 4,4 '-diaminodiphenyl ether (1mol) of 200.24g, 418.36g DMAC N,N' dimethyl acetamide and
3346.88g water；
2nd, in the case where nitrogen atmosphere, temperature are 5 DEG C and stirring condition, the water of the 3346.88g weighed is added in into three-necked bottle
With the n,N-dimethylacetamide of 418.36g, the 4 of 200.24g is then added in, 4 '-diaminodiphenyl ether (1mol) is reacted
The pyromellitic acid anhydride (1mol) of 218.12g by quality is average is added in reaction solution, reacts 2h, then by liquid in three times
Reaction solution is warming up to 20 DEG C, in the case where nitrogen atmosphere, temperature are 20 DEG C and stirring condition, the two of 8.16g is added in into reaction solution
The NS-100 of ethyl alcohol monoisopropanolamine (0.05mol) and 2.00g, is stirred to react 5h, and reacting liquid temperature finally is reduced to 5 DEG C,
10h is stood, obtains polyimide precursor solution；
It is to carry out according to the following steps using the method that a kind of above-mentioned polyimide precursor solution prepares Kapton：
First, polyimide precursor solution is filtered and deaerated, be cast to along T-shaped slit on stainless steel rotary drum, so
Afterwards in the case where temperature is 120 DEG C, dry 10min obtains self-supporting film；
2nd, self-supporting film from stainless steel rotary drum is removed and is placed in curing in curing oven, be 150 first in temperature
Under conditions of DEG C, 3min is heated, then under conditions of temperature is 250 DEG C, heats 3min, then in the condition that temperature is 400 DEG C
Under, 70s is heated, finally under conditions of temperature is 300 DEG C, about 1min is made annealing treatment, obtains Kapton；
And self-supporting film is clamped using fixture so that longitudinal length changes before and after self-supporting film cures in solidification process
Percentage is 10%, and lateral length percentage change is 50%.
The thickness of Kapton manufactured in the present embodiment is 25 microns.
Embodiment three：
A kind of polyimide precursor solution is made of tertiary amine, aqueous release agent, aromatic dianhydride, aromatic diamines and water；
The aromatic diamines and the molar ratio of tertiary amine are 1:0.05；The aromatic diamines and the quality of aqueous release agent
Than for 1:0.01；The aromatic diamines and the molar ratio of aromatic dianhydride are 1:1；The aromatic dianhydride and aromatic diamines it is total
The mass ratio of quality and water is 1:9；
The aromatic diamines are p-phenylenediamine；
The tertiary amine is the mixture of low boiling point tertiary amine and higher boiling tertiary amine, the low boiling point tertiary amine and higher boiling uncle
The molar ratio of amine is 1:1；
The low boiling point tertiary amine is diethanol monoisopropanolamine；
The higher boiling tertiary amine is dimethylamino formyl chloride；
The aqueous release agent is the NS-100 of Japanese one chemical company of mountain production；
The aromatic dianhydride is 3,3,4 ', 4 '-biphenyl tetracarboxylic dianhydride, is gathered in the polyimide precursor solution
The repetitive unit of amic acid is：
A kind of preparation method of above-mentioned polyimide precursor solution is to carry out according to the following steps：
First, diethanol monoisopropanolamine (0.025mol), the dimethylamino formyl chloride of 2.69g of 4.08g is taken
3,3,4 ', 4 '-biphenyl tetracarboxylic dianhydride (1mol), pair of 108.14g of NS-100,294.22g of (0.025mol), 1.08g
The water of phenylenediamine (1mol) and 3621.24g；
2nd, in the case where nitrogen atmosphere, temperature are 5 DEG C and stirring condition, the water of 3621.24g, Ran Houjia are added in into three-necked bottle
Enter the p-phenylenediamine (1mol) of 108.14g, obtain reaction solution, by the 3 of 294.22g, 3,4 ', 4 '-biphenyl tetracarboxylic dianhydride
(1mol) is added in reaction solution in three times by quality is average, is reacted 5h, reaction solution then is warming up to 20 DEG C, in nitrogen gas
Atmosphere, temperature under 20 DEG C and stirring condition, added in into reaction solution the diethanol monoisopropanolamine (0.025mol) of 4.08g,
The dimethylamino formyl chloride (0.025mol) of 2.69g and the NS-100 of 1.08g, are stirred to react 5h, finally drop reacting liquid temperature
Down to 5 DEG C, 10h is stood, obtains polyimide precursor solution；
It is to carry out according to the following steps using the method that a kind of above-mentioned polyimide precursor solution prepares Kapton：
First, polyimide precursor solution is filtered and deaerated, be cast to along T-shaped slit on stainless steel rotary drum, so
Afterwards in the case where temperature is 120 DEG C, dry 10min obtains self-supporting film；
2nd, self-supporting film from stainless steel rotary drum is removed and is placed in curing in curing oven, be 150 first in temperature
Under conditions of DEG C, 3min is heated, then under conditions of temperature is 250 DEG C, heats 3min, then in the condition that temperature is 400 DEG C
Under, 70s is heated, finally under conditions of temperature is 300 DEG C, about 1min is made annealing treatment, obtains Kapton；
And self-supporting film is clamped using fixture so that longitudinal length changes before and after self-supporting film cures in solidification process
Percentage is 10%, and lateral length percentage change is 50%.
The thickness of Kapton manufactured in the present embodiment is 25 microns.
Example IV：
A kind of polyimide precursor solution by tertiary amine, aqueous release agent, aromatic dianhydride, aromatic diamines, polar solvent and
Water is made；
The aromatic diamines and the molar ratio of tertiary amine are 1:0.05；The aromatic diamines and the quality of aqueous release agent
Than for 1:0.01；The aromatic diamines and the molar ratio of aromatic dianhydride are 1:1；The aromatic dianhydride and aromatic diamines it is total
The mass ratio of quality and water is 1:8；The mass ratio of the aromatic dianhydride and the gross mass of aromatic diamines and polar solvent is 1:
1；
The aromatic diamines are p-phenylenediamine；
The tertiary amine is the mixture of low boiling point tertiary amine and higher boiling tertiary amine, the low boiling point tertiary amine and higher boiling uncle
The molar ratio of amine is 1:1；
The low boiling point tertiary amine is diethanol monoisopropanolamine；
The higher boiling tertiary amine is dimethylamino formyl chloride；
The polar solvent is DMAC N,N' dimethyl acetamide；
The aqueous release agent is the NS-100 of Japanese one chemical company of mountain production；
The aromatic dianhydride is 3,3,4 ', 4 '-biphenyl tetracarboxylic dianhydride, is gathered in the polyimide precursor solution
The repetitive unit of amic acid is：
A kind of preparation method of above-mentioned polyimide precursor solution is to carry out according to the following steps：
First, diethanol monoisopropanolamine (0.025mol), the dimethylamino formyl chloride of 2.69g of 4.08g is taken
3,3,4 ', 4 '-biphenyl tetracarboxylic dianhydride (1mol), pair of 108.14g of NS-100,294.22g of (0.025mol), 1.08g
Phenylenediamine (1mol), the DMAC N,N' dimethyl acetamide of 402.36g and the water of 3218.88g；
2nd, in the case where nitrogen atmosphere, temperature is 5 DEG C and stirring conditions, added in into three-necked bottle 3218.88g water and
Then the n,N-dimethylacetamide of 402.36g adds in the p-phenylenediamine (1mol) of 108.14g, obtains reaction solution, will
The 3 of 294.22g, 3,4 ', 4 '-biphenyl tetracarboxylic dianhydride (1mol) is added in reaction solution in three times by quality is average, reacts 5h,
Then reaction solution is warming up to 20 DEG C, in the case where nitrogen atmosphere, temperature are 20 DEG C and stirring condition, 4.08g is added in into reaction solution
Diethanol monoisopropanolamine (0.025mol), the dimethylamino formyl chloride (0.025mol) of 2.69g and the NS-100 of 1.08g,
5h is stirred to react, reacting liquid temperature is finally reduced to 5 DEG C, 10h is stood, obtains polyimide precursor solution；
It is to carry out according to the following steps using the method that a kind of above-mentioned polyimide precursor solution prepares Kapton：
First, polyimide precursor solution is filtered and deaerated, be cast to along T-shaped slit on stainless steel rotary drum, so
Afterwards in the case where temperature is 120 DEG C, dry 10min obtains self-supporting film；
2nd, self-supporting film from stainless steel rotary drum is removed and is placed in curing in curing oven, be 150 first in temperature
Under conditions of DEG C, 3min is heated, then under conditions of temperature is 250 DEG C, heats 3min, then in the condition that temperature is 400 DEG C
Under, 70s is heated, finally under conditions of temperature is 300 DEG C, about 1min is made annealing treatment, obtains Kapton；
And self-supporting film is clamped using fixture so that longitudinal length changes before and after self-supporting film cures in solidification process
Percentage is 10%, and lateral length percentage change is 50%.
The thickness of Kapton manufactured in the present embodiment is 25 microns.
Embodiment five：
A kind of polyimide precursor solution by tertiary amine, aqueous release agent, aromatic dianhydride, aromatic diamines, polar solvent and
Water is made；
The aromatic diamines and the molar ratio of tertiary amine are 1:0.05；The aromatic diamines and the quality of aqueous release agent
Than for 1:0.01；The aromatic diamines and the molar ratio of aromatic dianhydride are 1:1；The aromatic dianhydride and aromatic diamines it is total
The mass ratio of quality and water is 1:8；The mass ratio of the aromatic dianhydride and the gross mass of aromatic diamines and polar solvent is 1:
1；
The aromatic diamines are p-phenylenediamine；
The tertiary amine is the mixture of low boiling point tertiary amine and higher boiling tertiary amine, the low boiling point tertiary amine and higher boiling uncle
The molar ratio of amine is 1:1；
The low boiling point tertiary amine is diethanol monoisopropanolamine；
The higher boiling tertiary amine is dimethylamino formyl chloride；
The polar solvent is DMAC N,N' dimethyl acetamide；
The aqueous release agent is the NS-100 of Japanese one chemical company of mountain production；
The aromatic dianhydride is 3,3,4 ', 4 '-biphenyl tetracarboxylic dianhydride, is gathered in the polyimide precursor solution
The repetitive unit of amic acid is：
A kind of preparation method of above-mentioned polyimide precursor solution is to carry out according to the following steps：
First, diethanol monoisopropanolamine (0.025mol), the dimethylamino formyl chloride of 2.69g of 4.08g is taken
3,3,4 ', 4 '-biphenyl tetracarboxylic dianhydride (1mol), pair of 108.14g of NS-100,294.22g of (0.025mol) and 1.08g
Phenylenediamine (1mol), the DMAC N,N' dimethyl acetamide of 402.36g and the water of 3218.88g；
2nd, in the case where nitrogen atmosphere, temperature is 5 DEG C and stirring conditions, added in into three-necked bottle 3218.88g water and
Then the n,N-dimethylacetamide of 402.36g adds in the p-phenylenediamine (1mol) of 108.14g, obtains reaction solution, will
The 3 of 294.22g, 3,4 ', 4 '-biphenyl tetracarboxylic dianhydride (1mol) is added in reaction solution in three times by quality is average, reacts 5h,
Then reaction solution is warming up to 20 DEG C, in the case where nitrogen atmosphere, temperature are 20 DEG C and stirring condition, 4.08g is added in into reaction solution
Diethanol monoisopropanolamine (0.025mol), the dimethylamino formyl chloride (0.025mol) of 2.69g and the NS-100 of 1.08g,
5h is stirred to react, reacting liquid temperature is finally reduced to 5 DEG C, 10h is stood, obtains polyimide precursor solution；
It is to carry out according to the following steps using the method that a kind of above-mentioned polyimide precursor solution prepares Kapton：
First, polyimide precursor solution is filtered and deaerated, be cast to along T-shaped slit on stainless steel rotary drum, so
Afterwards in the case where temperature is 120 DEG C, dry 10min obtains self-supporting film；
2nd, self-supporting film from stainless steel rotary drum is removed and is placed in curing in curing oven, be 150 first in temperature
Under conditions of DEG C, 3min is heated, then under conditions of temperature is 250 DEG C, heats 3min, then in the condition that temperature is 400 DEG C
Under, 70s is heated, finally under conditions of temperature is 300 DEG C, about 1min is made annealing treatment, obtains Kapton；
And self-supporting film is clamped using fixture so that longitudinal length changes before and after self-supporting film cures in solidification process
Percentage is 5%, and lateral length percentage change is 20%.
The thickness of Kapton manufactured in the present embodiment is 25 microns.
Contrast experiment one：
A kind of polyimide precursor solution is made of tertiary amine, aromatic dianhydride, aromatic diamines and water；
The aromatic diamines and the molar ratio of tertiary amine are 1:0.05；The aromatic diamines and the molar ratio of aromatic dianhydride
For 1:1；The mass ratio of the aromatic dianhydride and the gross mass of aromatic diamines and water is 1:9；
The aromatic diamines are p-phenylenediamine；
The tertiary amine is triethylamine；
The aromatic dianhydride is 3,3,4 ', 4 '-biphenyl tetracarboxylic dianhydride, is gathered in the polyimide precursor solution
The repetitive unit of amic acid is：
A kind of preparation method of above-mentioned polyimide precursor solution is to carry out according to the following steps：
First, take 5.06g triethylamine (0.05mol), the 3,3,4 ' of 294.22g, 4 '-biphenyl tetracarboxylic dianhydride
The p-phenylenediamine (1mol) of (1mol), 108.14g and the water of 3621.24g；
2nd, in the case where nitrogen atmosphere, temperature are 5 DEG C and stirring condition, the water of 3621.24g, Ran Houjia are added in into three-necked bottle
Enter the p-phenylenediamine (1mol) of 108.14g, obtain reaction solution, by the 3 of 294.22g, 3,4 ', 4 '-biphenyl tetracarboxylic dianhydride
(1mol) is added in reaction solution in three times by quality is average, is reacted 5h, reaction solution then is warming up to 20 DEG C, in nitrogen gas
Atmosphere, temperature are to add in the triethylamine (0.05mol) of 5.06g under 20 DEG C and stirring condition into reaction solution, are stirred to react 5h,
Reacting liquid temperature is finally reduced to 5 DEG C, 10h is stood, obtains polyimide precursor solution；
It is to carry out according to the following steps using the method that a kind of above-mentioned polyimide precursor solution prepares Kapton：
First, polyimide precursor solution is filtered and deaerated, be cast to along T-shaped slit on stainless steel rotary drum, so
Afterwards in the case where temperature is 120 DEG C, dry 10min obtains self-supporting film；
2nd, self-supporting film from stainless steel rotary drum is removed and be placed in curing oven, in the condition that temperature is 150 DEG C
Lower curing clamps self-supporting film in solidification process using fixture, and the lower self-supported membrane of traction heating is broken, and when fracture is longitudinal
It is thin to obtain polyimides 5% for elongation.
Contrast experiment one can not obtain continuous Kapton.
Contrast experiment two：
A kind of polyimide precursor solution is made of tertiary amine, aqueous release agent, aromatic dianhydride, aromatic diamines and water；
The aromatic diamines and the molar ratio of tertiary amine are 1:0.05；The aromatic diamines and the quality of aqueous release agent
Than for 1:0.01；The aromatic diamines and the molar ratio of aromatic dianhydride are 1:1；The aromatic dianhydride and aromatic diamines it is total
The mass ratio of quality and water is 1:9；
The aromatic diamines are p-phenylenediamine；
The tertiary amine is diethanol monoisopropanolamine；
The aqueous release agent is the NS-100 of Japanese one chemical company of mountain production；
The aromatic dianhydride is 3,3,4 ', 4 '-biphenyl tetracarboxylic dianhydride, is sealed in the polyimide precursor solution
The repetitive unit of the polyamic acid at end is：
A kind of preparation method of above-mentioned polyimide precursor solution is to carry out according to the following steps：
First, take the diethanol monoisopropanolamine (0.05mol) of 8.16g, 1.08g NS-100,294.22g 3,3,4 ',
4 '-biphenyl tetracarboxylic dianhydride (1mol), the p-phenylenediamine (1mol) of 108.14g and the water of 3621.24g；
2nd, in the case where nitrogen atmosphere, temperature are 5 DEG C and stirring condition, the water of 3621.24g, Ran Houjia are added in into three-necked bottle
Enter the p-phenylenediamine (1mol) of 108.14g, obtain reaction solution, by the 3 of 294.22g, 3,4 ', 4 '-biphenyl tetracarboxylic dianhydride
(1mol) is added in reaction solution in three times by quality is average, is reacted 5h, reaction solution then is warming up to 20 DEG C, in nitrogen gas
Atmosphere, temperature under 20 DEG C and stirring condition, added in into reaction solution the diethanol monoisopropanolamine (0.05mol) of 8.16g and
The NS-100 of 1.08g is stirred to react 5h, and reacting liquid temperature finally is reduced to 5 DEG C, stands 10h, obtains polyimide precursor
Solution；
It is to carry out according to the following steps using the method that a kind of above-mentioned polyimide precursor solution prepares Kapton：
First, polyimide precursor solution is filtered and deaerated, be cast to along T-shaped slit on stainless steel rotary drum, so
Afterwards in the case where temperature is 120 DEG C, dry 10min obtains self-supporting film；
2nd, self-supporting film from stainless steel rotary drum is removed and is placed in curing in curing oven, utilized in solidification process
Fixture clamps self-supporting film, cures 3min under conditions of temperature is 150 DEG C, is then led under conditions of temperature is 250 DEG C
Draw self-supported membrane in heating process to be broken, it is thin to obtain polyimides 8% for longitudinal tensile strain rate during fracture.
Contrast experiment two can not obtain continuous Kapton.
The thin table of polyimides prepared by the Kapton and contrast experiment one and two prepared to embodiment one and five
Face quality is evaluated by crizzle, surface smoothness, blibbing mode.
1., crizzle：
The micro-crack on Kapton surface is evaluated, evaluation criterion is as follows：
A:Do not find that there are micro-cracks for film surface；
B:It can confirm that there are crizzles on the surface of film (be less than film surface product 5%)；
C:It can confirm that there are crizzles on the surface of film (being more than the 5% of film surface product, less than 10%)；
D:It can confirm that there are crizzles on the surface of film (be more than film surface product 10%).
2., surface smoothness：
The surface smoothness of Kapton is evaluated, evaluation criterion is as follows：
A:The thickness of film is tested using micrometer caliper, taking different zones, (each region accounts for unit breadth table
The ratio of area is no less than 5 number of test points evidences 15%), obtains the maximum of data, minimum value subtracts average value, and average
The ratio of value is within ± 5%；
B:The thickness of film is tested using micrometer caliper, taking different zones, (each region accounts for unit breadth table
The ratio of area is no less than 5 number of test points evidences 15%), obtains the maximum of data, minimum value subtracts average value, and average
The ratio of value is within ± 10%；
C:The thickness of film is tested using micrometer caliper, taking different zones, (each region accounts for unit breadth table
The ratio of area is no less than 5 number of test points evidences 15%), obtains the maximum of data, minimum value subtracts average value, and average
The ratio of value is within ± 15%；
D:The thickness of film is tested using micrometer caliper, taking different zones, (each region accounts for unit breadth table
The ratio of area is no less than 5 number of test points evidences 15%), obtains the maximum of data, minimum value subtracts average value, and average
The ratio of value is beyond ± 15%.
3., blibbing：
Blibbing existing for Kapton surface is evaluated, evaluation criterion is as follows：
A:Blibbing is not present in Kapton surface；
B:Blibbing more than one existing for Kapton surface (10cm X 10cm) but it is less than 5；
C:Blibbing existing for Kapton surface (10cm X 10cm) is more than 5 but is less than 50；
D:Blibbing existing for Kapton surface (10cm X 10cm) is more than 50.
Kapton prepared by the Kapton and contrast experiment one and two prepared to embodiment one and five is surveyed
Try 5% thermal weight loss temperature：Test is using thermal gravimetric analyzer (TGA).Heating rate：10℃/min；Measurement atmosphere：Air.
Kapton prepared by the Kapton and contrast experiment one and two prepared to embodiment one and five is surveyed
Try 800% carbon yield：Test is using thermal gravimetric analyzer (TGA).Heating rate：10℃/min；Measurement atmosphere：Nitrogen.
Kapton prepared by the Kapton and contrast experiment one and two prepared to embodiment one and five is surveyed
Try glass transition temperature：Test is using dynamic thermomechanical analysis apparatus (DMA).Heating rate：5℃/min；Measurement atmosphere：It is empty
Gas.
To embodiment one and five prepare Kapton and contrast experiment one and two prepare Kapton into
Row mechanical test is tested using ASTM D882 standards.
Table 1 is Kapton surface quality and film forming, and table 2 is continuously to prepare Kapton performance.By table 1
It understands, contrast experiment can not complete the preparation of serialization Kapton, and irreversible self-supporting occurs in curing oven operation
Film is broken, and longitudinal tensile strain rate is not reaching to standard, while not yet carries out transverse extension operation.In addition, contrast experiment is in surface matter
In terms of amount embodiment is worse than including surface smoothness, crizzle and blibbing aspect far below embodiment.Its
In, example IV and embodiment five, as a result of the compound high boiling solvent of a variety of amines catalysts so that the film of formation,
Compared to embodiment one to three, there is more excellent surface smoothness.
As shown in Table 2, contrast experiment is prepared due to that can not complete continuous thin film.So it is unable to the mechanical property of testing film
Energy (ND) has only carried out thermal performance test to sample segment.From test, the hot property data of contrast test are below implementing
Example is due to not being orientated using suitable elongation, the hot property of polyimide material is had some impact on.Comparative example
Five and example IV, equally it is due to elongation orientation two-way in unsuitable face, to the hot property and mechanical performance of film
Influence, especially mechanical property caused by all.
Fig. 1 is Kapton photo prepared by example IV；Fig. 2 is Kapton prepared by contrast experiment one
Photo.It was found from figure, the Kapton surface quality that contrast test obtains is bad, simultaneously because the brittle failure of film midway, nothing
Method carries out cross directional stretch, and film surface is caused fold occur, and fracture lines occurs in end.
1 Kapton surface quality of table and film forming
The Kapton performance that table 2 is continuously prepared
Claims (4)
1. the method for Kapton is prepared using a kind of polyimide precursor solution, it is characterised in that utilize a kind of polyamides
The method that imines precursor solution prepares Kapton is to carry out according to the following steps：
First, polyimide precursor solution is filtered and deaerated, be cast to along T-shaped slit on stainless steel rotary drum, Ran Hou
Temperature is at 60 DEG C~180 DEG C, and dry 1min~50min obtains self-supporting film；
2nd, self-supporting film from stainless steel rotary drum is removed and is placed in curing in curing oven, first temperature for 150 DEG C~
Under conditions of 200 DEG C, 1min~60min is heated, then under conditions of temperature is 200 DEG C~250 DEG C, heats 1min~60min,
Then under conditions of temperature is 250 DEG C~450 DEG C, 1min~60min is heated, finally in the item that temperature is 290 DEG C~310 DEG C
Under part, 1min~20min is made annealing treatment, obtains Kapton；
And self-supporting film is clamped using fixture so that longitudinal length variation percentage before and after self-supporting film cures in solidification process
Rate is 5%~20%, and lateral length percentage change is 10%~80%；
Polyimide precursor solution described in step 1 is by tertiary amine, aqueous release agent, aromatic dianhydride, aromatic diamines, polarity
Solvent and water are made；
The aromatic diamines and the molar ratio of tertiary amine are 1:(0.05~1.5)；The aromatic diamines and aqueous release agent
Mass ratio is 1:(0.01~1)；The aromatic diamines and the molar ratio of aromatic dianhydride are 1:(0.97~1.03)；The virtue
The mass ratio of the gross mass and water of fragrant dianhydride and aromatic diamines is 1:(2~10)；The aromatic dianhydride and aromatic diamines it is total
The mass ratio of quality and polar solvent is 1:(0~10)；
The aromatic diamines are 4,4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenylmethane, two (3- amino-benzene oxygens) two
One kind or wherein several mixtures in Benzophenone, p-phenylenediamine, m-phenylene diamine (MPD) and 4,4' diaminodiphenyl sulfone；
The tertiary amine is the mixture of low boiling point tertiary amine and higher boiling tertiary amine, the low boiling point tertiary amine and higher boiling tertiary amine
Molar ratio is 1:1；
The low boiling point tertiary amine is triethylamine, Dodecyl Dimethyl Amine, diethanol monoisopropanolamine and picoline
In one kind or wherein several mixtures；
The higher boiling tertiary amine is tri-n-butylamine, triisopropanolamine and one kind or wherein several in dimethylamino formyl chloride
Mixture；
The polar solvent be DMAC N,N' dimethyl acetamide, N,N-dimethylformamide and dimethyl sulfoxide (DMSO) in one kind or its
In several mixture；
When the aromatic dianhydride be 3,3,4 ', 4 '-diphenyl ether tetracarboxylic dianhydride or 3,3,4 ', 4 '-benzophenone tetrabasic carboxylic acid two
During acid anhydride, the repetitive unit of polyamic acid is in the polyimide precursor solution：
The R1For-O- or
The R2For
When the aromatic dianhydride is 3,3, during 4 ', 4 '-biphenyl tetracarboxylic dianhydride, gather in the polyimide precursor solution
The repetitive unit of amic acid is：
The R3For
When the aromatic dianhydride is pyromellitic acid anhydride, the weight of polyamic acid in the polyimide precursor solution
Unit is again：
The R4For
2. a kind of method according to claim 1 that Kapton is prepared using polyimide precursor solution,
It is the energy releasing agent miscible with water, and not being precipitated under conditions of temperature is less than 100 DEG C to be characterized in that the aqueous release agent
Or mould release.
3. a kind of method according to claim 1 that Kapton is prepared using polyimide precursor solution,
It is characterized in that the polyimide precursor solution described in step 1 is prepared according to the following steps：
First, tertiary amine, aqueous release agent, aromatic dianhydride, aromatic diamines, polar solvent and water are taken；
The aromatic diamines and the molar ratio of tertiary amine are 1:(0.05~1.5)；The aromatic diamines and aqueous release agent
Mass ratio is 1:(0.01~1)；The aromatic diamines and the molar ratio of aromatic dianhydride are 1:(0.97~1.03)；The virtue
The mass ratio of the gross mass and water of fragrant dianhydride and aromatic diamines is 1:(2~10)；The aromatic dianhydride and aromatic diamines it is total
The mass ratio of quality and polar solvent is 1:(0~10)；
2nd, the water in nitrogen atmosphere, temperature under 2 DEG C~10 DEG C and stirring condition, to be weighed into three-necked bottle in addition step 1
And polar solvent, the aromatic diamines weighed in step 1 are then added in, obtain reaction solution, the aromatic dianhydride that will be weighed in step 1
It is added in three times in reaction solution by quality is average, reacts 1h~5h, reaction solution is then warming up to 20 DEG C~60 DEG C, in nitrogen
Atmosphere, temperature are the tertiary amine weighed under 20 DEG C~60 DEG C and stirring condition into reaction solution in addition step 1 and the aqueous demoulding
Agent is stirred to react 3h~5h, and reacting liquid temperature finally is reduced to 2 DEG C~10 DEG C, 1h~10h is stood, before obtaining polyimides
Drive liquid solution.
4. a kind of method according to claim 1 that Kapton is prepared using polyimide precursor solution,
It is characterized in that in step 1 and then in the case where temperature is 80 DEG C~160 DEG C, dry 10min~30min.
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| CN109880126B (en) * | 2019-02-22 | 2021-10-08 | 黑龙江省科学院石油化学研究院 | Polyimide precursor gel capable of preparing polyimide with high strength and heat resistance and light complex structure and application |
| CN109880129B (en) * | 2019-02-22 | 2021-10-08 | 黑龙江省科学院石油化学研究院 | Polyimide precursor gel capable of preparing insulating, heat-conducting and heat-resistant polyimide light complex structure and application |
| CN109897199B (en) * | 2019-02-22 | 2021-10-08 | 黑龙江省科学院石油化学研究院 | Polyimide precursor gel capable of preparing wave-absorbing and heat-resistant polyimide light complex structure and application |
| CN114044901B (en) * | 2021-12-14 | 2022-12-20 | 北京科技大学 | Polyimide material and preparation method and application thereof |
| CN116162271A (en) * | 2023-03-02 | 2023-05-26 | 中国工程物理研究院激光聚变研究中心 | In-situ composite fly-sheet material and preparation method thereof |
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| CN101081906A (en) * | 2001-02-27 | 2007-12-05 | 钟渊化学工业株式会社 | Polyimide film and process for producing the same |
| CN104710788A (en) * | 2013-12-16 | 2015-06-17 | 富士施乐株式会社 | Polyimide precursor composition, method of producing polyimide precursor composition, method of producing polyimide molded article, polyimide molded article, liquid crystal alignment film, passivation film, wire coating material, and adhesive film |
| CN105461926A (en) * | 2016-01-29 | 2016-04-06 | 黑龙江省科学院石油化学研究院 | Environment-friendly stable polyamide acid solution and preparation method thereof |
| CN105694091A (en) * | 2016-04-18 | 2016-06-22 | 成都正威新材料研发有限公司 | Low-density polyimide aerogel and preparation method thereof |
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| CN101081906A (en) * | 2001-02-27 | 2007-12-05 | 钟渊化学工业株式会社 | Polyimide film and process for producing the same |
| CN104710788A (en) * | 2013-12-16 | 2015-06-17 | 富士施乐株式会社 | Polyimide precursor composition, method of producing polyimide precursor composition, method of producing polyimide molded article, polyimide molded article, liquid crystal alignment film, passivation film, wire coating material, and adhesive film |
| CN105461926A (en) * | 2016-01-29 | 2016-04-06 | 黑龙江省科学院石油化学研究院 | Environment-friendly stable polyamide acid solution and preparation method thereof |
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