CN105860074A - Polyimide precursor solution, preparation method thereof and method of utilizing polyimide precursor solution to prepare polyimide thin film - Google Patents

Polyimide precursor solution, preparation method thereof and method of utilizing polyimide precursor solution to prepare polyimide thin film Download PDF

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CN105860074A
CN105860074A CN201610473006.XA CN201610473006A CN105860074A CN 105860074 A CN105860074 A CN 105860074A CN 201610473006 A CN201610473006 A CN 201610473006A CN 105860074 A CN105860074 A CN 105860074A
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tertiary amine
polyimide precursor
precursor solution
dianhydride
temperature
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CN105860074B (en
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刘长威
曲春艳
肖万宝
王德志
李洪峰
张杨
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Institute of Petrochemistry of Heilongjiang Academy of Sciences
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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
    • 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
    • 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
    • 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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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Manufacturing & Machinery (AREA)
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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The invention relates to a polyimide precursor solution, a preparation method thereof and a method of utilizing the polyimide precursor solution to prepare a polyimide thin film and aims to solve the problem that high-surface-quality continuous-embrittlement-free polyimide thin films cannot be produced on tape-casting equipment through existing preparation methods and structural composition of polyimide precursor-polyamide acid water solutions. The polyimide precursor solution is prepared from tertiary amine, a waterborne release agent, aromatic dianhydride, aromatic diamine, a polar solvent and water. The preparation method includes: weighing; at nitrogen atmosphere, certain temperature and stirring condition, mixing the water, the polar solvent and aromatic diamine; adding aromatic dianhydride into reaction liquid for reaction; at nitrogen atmosphere, certain temperature and stirring condition, adding tertiary amine and the waterborne release agent for reaction; cooling. The method includes: preparing a self-supporting thin film; curing, and annealing.

Description

A kind of polyimide precursor solution and preparation method thereof and to utilize it to prepare polyamides sub- The method of amine thin film
Technical field
The present invention relates to polyimide precursor solution and preparation method thereof and utilize it to prepare the side of Kapton Method.
Background technology
Polyimides is the aromatic heterocyclic polymer in constitutional repeating unit containing imide ring, and it is up to now in industry The highest macromolecular material of temperature classification of field application, with the combination property of its excellence at thin film, resin, fiber, separation film Etc. being widely used in Aero-Space, the field such as electric.Traditional polyimides is generally by aromatic tetracarboxylic acid anhydride and virtue Fragrant race diamidogen be raw material in aprotic polar solvent, by being initially formed polyamic acid, then imidization dehydration forms polyimides.
Now along with the development of microelectronic, Kapton, especially colorless polyimide, hold promise as soft Property transparent substrates, substitute ito glass, get a lot of applications at flexible wearable equipment and flexible display device.As a rule, Polyimide precursor solution experience blade coating, the process such as casting film-forming and hot imidization, final rolling forms high-quality thin film.And Use polar solvent, such as N,N-dimethylacetamide, DMF, N-Methyl pyrrolidone etc., prepare polyamide After acid, during curtain coating volatilization and hot imidization, it is directed to a large amount of solvent and volatilizees in drying tunnel the waste gas and sedimentation caused After waste liquor contamination.Under normal circumstances, use hot-flow flue can a certain degree of recovery and again purify and utilize solvent, but show Stage technique is difficult to the solvent recovery of 100% and the solvent separating-purifying of 100%.Conventional enterprise can only achieve more than 90% Recovery, but recycling design is difficult to prepare high-quality polymer again；Air and water source also can by the fugitive constituent of remainder Produce impact, have become as the key factor treating the chemical products that Kapton is contamination type from the angle of environmental protection, should Problem has become as the important problem of polyimides masking field face.
Adopt and use water as the solvent of polyamic acid and can greatly solve polyimides, especially Kapton undoubtedly and prepare During puzzlement.In this regard, document is had to report, such as " being prepared polyimides by water-soluble polyamic acid ", insulant 1981 (1): 34-42, polar solvent adds addition ammonia or organic amine after dianhydride/diamidogen forms polyamic acid and is neutralized, Add water dilution and obtain solution.But its solution still introduces the substantial amounts of organic solvent derivant as polymerization.Document (High Performance Polymers, 2003 (15): 269-279.) reports and is first hydrolyzed by dianhydride, then is polymerized with diamidogen Formed polyamic acid separate out in water, by after dry cyclic washing in pressure bottle thermal cyclization obtain polyimide powder.Process The most complicated, higher being simultaneously difficult to of equipment requirements is prepared on a large scale.Obtained by simultaneously, polyamic acid is water insoluble, it is difficult to application In Kapton preparation technology.
The water-soluble polyamic acid solution related in similar document and patent report, is all to polyimide precursor Structural research, by the adjustment to structure, evaluation experimental room blade coating Kapton performance, such as hot property, mechanical performance Deng.The curtain coating coating being all not involved with being produced by polyimide precursor aqueous solution forms self-supported membrane, tension force solidify to form The report of polyimides continuous film.
Meanwhile, the water solublity polyimide precursor-polyamic acid solution related in document and patent all uses one Slaine or amine salt catalysis form polyimide precursor, and aqueous solution carries out being thermally formed the process of self-supporting precursor film In, not yet before imidization, moisture content is evaporated completely (100 DEG C) substantially, uses inorganic metal salt catalysis can cause remaining in thin film；Adopt With a small amount of single kind amine salt, remaining space after catalyst abjection is left, on the one hand in the self-supported membrane surface that can result in Can affect the surface quality ultimately forming Kapton, on the other hand the material property of thin film also can be made by the formation in space Become impact.
Additionally, it is molten generally to select N,N-dimethylacetamide (boiling point 164 DEG C) to form polyimide precursor as solvent Liquid, curtain coating abjection solvent formed self-supported membrane temperature between 150 DEG C to 250 DEG C, the polyimide precursor of high molecular- Polyamic acid has certain film strength, but in imidization conversion process (150 DEG C-250 DEG C), can face molecular weight anxious Reduce sharply little, the danger that film strength declines, use high boiling N,N-dimethylacetamide as solvent, contain solvent by high temperature A certain degree of avoid newly formed self-supported membrane to become fragile, reduce the danger of film breaks during drawing by high temperature, improve 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 Temperature after removing moisture content is 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 stretching imidization, owing to molecular weight reduces (150～250 DEG C), there is greater risk self-supporting Film is difficult to withstand system drawing tension and rupture.
Say from the preparation process angle of above formed body, do not relate to polyimide precursor-polyamic acid water-soluble The different preparation methoies of liquid, different catalysts type, experience the self-supported membrane (polyamide acid film) of polyimides casting films again The film forming difficulty of curing oven and with the surface quality of formed body Kapton, the impact of intensity.
Summary of the invention
The invention solves the problems that preparation method and the structure composition of existing polyimide precursor-polyamic acid aqueous solution are difficult to Realize in casting apparatus production great surface quality and the problem of the Kapton of serialization not embrittlement, and a kind of polyamides is provided Imines precursor solution and preparation method thereof and utilize its method preparing Kapton.
A kind of polyimide precursor solution by tertiary amine, aqueous release agent, aromatic dianhydride, aromatic diamines, polar solvent and Water is made；
Described aromatic diamines is 1:(0.05～1.5 with the mol ratio of tertiary amine)；Described aromatic diamines and the aqueous demoulding The mass ratio of agent is 1:(0.01～1)；Described aromatic diamines is 1:(0.97～1.03 with the mol ratio of aromatic dianhydride)；Described Aromatic dianhydride and the gross mass of aromatic diamines and the mass ratio of water be 1:(2～10)；Described aromatic dianhydride and aromatic diamines The mass ratio of gross mass and polar solvent be 1:(0～10)；
Described aromatic diamines is 4,4 '-diaminodiphenyl ether, 4,4 '-MDA, two (3-aminobenzene oxygen Base) benzophenone, p-phenylenediamine, a kind of or the most several mixture in m-diaminobenzene. and 4,4' diaminodiphenyl sulfone；
Described tertiary amine is the mixture of low boiling tertiary amine or low boiling tertiary amine and high boiling point tertiary amine, described low boiling uncle Amine is 1:(0.01～100 with the molar ratio of high boiling point tertiary amine)；Described low boiling tertiary amine be boiling point below 150 DEG C, and The molecular weight of low boiling tertiary amine is 80g/mol～250g/mol；Described high boiling point tertiary amine is that boiling point is at 150 DEG C～295 DEG C Tertiary amine；
Described polar solvent is DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, ethylene glycol and dimethyl sulfoxide In a kind of or the most several mixture；
When described 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 described polyimide precursor solution Unit is:
Described R1For-O-or
Described R2For
When described aromatic dianhydride is 3,3, during 4 ', 4 '-biphenyl tetracarboxylic dianhydride, described polyimide precursor solution The repetitive of middle polyamic acid is:
Described R3For
When described aromatic dianhydride is pyromellitic acid anhydride, polyamic acid in described polyimide precursor solution Repetitive be:
Described R4For
The preparation method of a kind of polyimide precursor solution is to sequentially include the following steps:
One, tertiary amine, aqueous release agent, aromatic dianhydride, aromatic diamines, polar solvent and water are taken；
Described aromatic diamines is 1:(0.05～1.5 with the mol ratio of tertiary amine)；Described aromatic diamines and the aqueous demoulding The mass ratio of agent is 1:(0.01～1)；Described aromatic diamines is 1:(0.97～1.03 with the mol ratio of aromatic dianhydride)；Described Aromatic dianhydride and the gross mass of aromatic diamines and the mass ratio of water be 1:(2～10)；Described aromatic dianhydride and aromatic diamines The mass ratio of gross mass and polar solvent be 1:(0～10)；
Two, under nitrogen atmosphere, temperature are 2 DEG C～10 DEG C and stirring condition, add in step one in three-necked bottle and weigh Water and polar solvent, be subsequently adding the aromatic diamines weighed in step one, obtain reactant liquor, the fragrance that will weigh in step one Dianhydride is joined in reactant liquor the most in three times by quality, reacts 1h～5h, then reactant liquor is warming up to 20 DEG C～60 DEG C, Nitrogen atmosphere, temperature are under 20 DEG C～60 DEG C and stirring condition, add the tertiary amine weighed in step one and aqueous in reactant liquor Releasing agent, stirring reaction 3h～5h, finally reacting liquid temperature is reduced to 2 DEG C～10 DEG C, stands 1h～10h, obtain polyamides sub- Amine precursor solution；
Aromatic diamines described in step one is 4,4 '-diaminodiphenyl ether, 4,4 '-MDA, two (3-ammonia Phenoxyl) benzophenone, p-phenylenediamine, a kind of or the most several mixed in m-diaminobenzene. and 4,4' diaminodiphenyl sulfone Compound；
Tertiary amine described in step one is the mixture of low boiling tertiary amine or low boiling tertiary amine and high boiling point tertiary amine, described Low boiling tertiary amine is 1:(0.01～100 with the molar ratio of high boiling point tertiary amine)；Described low boiling tertiary amine is that boiling point is at 150 DEG C Hereinafter, and the molecular weight of low boiling tertiary amine is 80g/mol～250g/mol；Described high boiling point tertiary amine be boiling point at 150 DEG C～ The tertiary amine of 295 DEG C；
Polar solvent described in step one is DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, ethylene glycol and two A kind of or the most several mixture in methyl sulfoxide；
When the aromatic dianhydride described in step one 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 described polyimide precursor solution Repetitive be:
Described R1For-O-or
Described R2For
When the aromatic dianhydride described in step one is 3,3, during 4 ', 4 '-biphenyl tetracarboxylic dianhydride, before described polyimides Driving the repetitive of polyamic acid in liquid solution is:
Described R3For
When the aromatic dianhydride described in step one is pyromellitic acid anhydride, in described polyimide precursor solution The repetitive of polyamic acid is:
Described R4For
A kind of method utilizing polyimide precursor solution to prepare Kapton is to sequentially include the following steps:
One, polyimide precursor solution filtered and deaerate, being cast on stainless steel rotary drum along T-shaped slit, so After at temperature is 60 DEG C～180 DEG C, be dried 1min～50min, obtain self-supporting film；
Two, self-supporting film is peeled off from stainless steel rotary drum it is placed in curing oven solidification, be first 150 in temperature DEG C～200 DEG C under conditions of, heat 1min～60min, then under conditions of temperature is 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, make annealing treatment about 1min～20min, obtain Kapton；
And solidification process utilizes holder self-supporting film so that longitudinal length change before and after self-supporting film solidification Percentage rate is 5%～20%, and lateral length change percentage in arid is 10%～80%.
The invention has the beneficial effects as follows: a kind of polyimide precursor solution that the present invention provides and preparation method thereof and profit The method preparing Kapton with it, can solve the preparation side of existing polyimide precursor-polyamic acid aqueous solution Method and structure composition are difficult to produce the asking of Kapton of great surface quality and serialization not embrittlement at casting apparatus Topic.According to the preparation method of polyimide precursor solution, have employed low ratio high bp polar solvent, multiple boiling point tertiary amine again The combination of compound.
On the one hand, high bp polar solvent (such as N,N-dimethylacetamide, DMF etc.) and water are utilized Combination, improve solvent entirety boiling point, it is to avoid the self-supporting polyimide precursor thin film of formation (is less than containing quantity of solvent is very few 20%) and boiling point is low, although self-supported membrane still experiences high temperature imidization (having stretching action or tensionless winkler foundation effect) process (150 DEG C-250 DEG C) in there will be molecular weight and molecular weight and situation that intensity declines, but the lifting containing quantity of solvent and boiling point improve, greatly Degree improves percentage elongation and the pliability of initial imidization (150 DEG C-200 DEG C), it is to avoid lead due to external load at high temperature The danger of the film breaks caused, affects thin film continuous operation.
On the other hand, polyimide precursor solution preparation method have employed multiple boiling point tertiary amine complex, thus at stream When prolonging abjection solvent formation self-supported membrane, still contain multiple boiling point tertiary amine in presoma.By self-supporting in imidization program Film is poured curing oven into and is processed, and especially for the hot imidization processing self-supported membrane of serialization, needs to apply certain Axially outer load provides traction, and after moisture volatilizees substantially (＜ 150 DEG C), conventional single tertiary amines also faces at 150 DEG C The risk of volatilization, it is difficult to (150 DEG C-250 DEG C) low-intensity, low elongation after making up initial imidization as liquid residual lifting. Multiple tertiary amine is used to provide multiple removal temperature and boiling point, it is achieved still to remain with certain liquid residual when more than 150 DEG C.And Mode compound use with high boiling solvent combination, it is possible to further ensure that the thin film under imidization initial temperature condition continues Elongation and the coefficient of expansion, greatly avoid at the initial film destruction of imidization, be especially pulled thin film under power effect Destroy, thus save curing oven and lower the temperature, again wear film, the electric power of intensification and time cost.
It is surprising that the compound use of multiple tertiary amine, not only contribute to promote thin film each stage shaping strength, simultaneously Also improve the surface quality of thin film and reduce defect.Due to lower boiling single tertiary amine and water after volatilizing, polyimides Presoma faces quick imidization and solvent, the dual-pressure of catalyst abjection, the thin film surface planeness that can seriously cause is poor, Surface has the volatilization pore that stays of abjection, imidization to remove the closed pore etc. that a large amount of water stays in short-term, has the surface quality of thin film The biggest impact.By the way of using low boiling and high boiling point tertiary amine, unexpected obtain different imidization under the conditions of hold Continuous volatilization effect, makes to provide not against external force in Kapton forming process the effect of Self-leveling, solves greatly The surface quality problems of thin film.Hot imidization especially for continuous thin film operates, and not only reduces fold and space Appearance, thin film flatness is also strengthened.And polyimide precursor solution prepared by the present invention can be additionally used in formation polyamides Imine fiber.
The present invention is for a kind of polyimide precursor solution and preparation method thereof and utilizes it to prepare Kapton Method.
Accompanying drawing explanation
Fig. 1 is the Kapton photo of embodiment four preparation；
Fig. 2 is the Kapton photo of contrast experiment one preparation.
Detailed description of the invention
Detailed description of the invention 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；
Described aromatic diamines is 1:(0.05～1.5 with the mol ratio of tertiary amine)；Described aromatic diamines and the aqueous demoulding The mass ratio of agent is 1:(0.01～1)；Described aromatic diamines is 1:(0.97～1.03 with the mol ratio of aromatic dianhydride)；Described Aromatic dianhydride and the gross mass of aromatic diamines and the mass ratio of water be 1:(2～10)；Described aromatic dianhydride and aromatic diamines The mass ratio of gross mass and polar solvent be 1:(0～10)；
Described aromatic diamines is 4,4 '-diaminodiphenyl ether, 4,4 '-MDA, two (3-aminobenzene oxygen Base) benzophenone, p-phenylenediamine, a kind of or the most several mixture in m-diaminobenzene. and 4,4' diaminodiphenyl sulfone；
Described tertiary amine is the mixture of low boiling tertiary amine or low boiling tertiary amine and high boiling point tertiary amine, described low boiling uncle Amine is 1:(0.01～100 with the molar ratio of high boiling point tertiary amine)；Described low boiling tertiary amine be boiling point below 150 DEG C, and The molecular weight of low boiling tertiary amine is 80g/mol～250g/mol；Described high boiling point tertiary amine is that boiling point is at 150 DEG C～295 DEG C Tertiary amine；
Described polar solvent is DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, ethylene glycol and dimethyl sulfoxide In a kind of or the most several mixture；
When described 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 described polyimide precursor solution Unit is:
Described R1For-O-or
Described R2For
When described aromatic dianhydride is 3,3, during 4 ', 4 '-biphenyl tetracarboxylic dianhydride, described polyimide precursor solution The repetitive of middle polyamic acid is:
Described R3For
When described aromatic dianhydride is pyromellitic acid anhydride, polyamic acid in described polyimide precursor solution Repetitive be:
Described R4For
Present embodiment provides the benefit that: a kind of polyimide precursor solution of present embodiment offer and preparation thereof Method and utilize its method preparing Kapton, can solve existing polyimide precursor-polyamic acid aqueous solution Preparation method and structure composition be difficult to produce great surface quality and the polyimides of serialization not embrittlement at casting apparatus The problem of thin film.According to the preparation method of polyimide precursor solution, have employed low ratio high bp polar solvent, multiple boiling The combination of some tertiary amine complex.
On the one hand, high bp polar solvent (such as N,N-dimethylacetamide, DMF etc.) and water are utilized Combination, improve solvent entirety boiling point, it is to avoid the self-supporting polyimide precursor thin film of formation (is less than containing quantity of solvent is very few 20%) and boiling point is low, although self-supported membrane still experiences high temperature imidization (having stretching action or tensionless winkler foundation effect) process (150 DEG C-250 DEG C) in there will be molecular weight and molecular weight and situation that intensity declines, but the lifting containing quantity of solvent and boiling point improve, greatly Degree improves percentage elongation and the pliability of initial imidization (150 DEG C-200 DEG C), it is to avoid lead due to external load at high temperature The danger of the film breaks caused, affects thin film continuous operation.
On the other hand, polyimide precursor solution preparation method have employed multiple boiling point tertiary amine complex, thus at stream When prolonging abjection solvent formation self-supported membrane, still contain multiple boiling point tertiary amine in presoma.By self-supporting in imidization program Film is poured curing oven into and is processed, and especially for the hot imidization processing self-supported membrane of serialization, needs to apply certain Axially outer load provides traction, and after moisture volatilizees substantially (＜ 150 DEG C), conventional single tertiary amines also faces at 150 DEG C The risk of volatilization, it is difficult to (150 DEG C-250 DEG C) low-intensity, low elongation after making up initial imidization as liquid residual lifting. Multiple tertiary amine is used to provide multiple removal temperature and boiling point, it is achieved still to remain with certain liquid residual when more than 150 DEG C.And Mode compound use with high boiling solvent combination, it is possible to further ensure that the thin film under imidization initial temperature condition continues Elongation and the coefficient of expansion, greatly avoid at the initial film destruction of imidization, be especially pulled thin film under power effect Destroy, thus save curing oven and lower the temperature, again wear film, the electric power of intensification and time cost.
It is surprising that the compound use of multiple tertiary amine, not only contribute to promote thin film each stage shaping strength, simultaneously Also improve the surface quality of thin film and reduce defect.Due to lower boiling single tertiary amine and water after volatilizing, polyimides Presoma faces quick imidization and solvent, the dual-pressure of catalyst abjection, the thin film surface planeness that can seriously cause is poor, Surface has the volatilization pore that stays of abjection, imidization to remove the closed pore etc. that a large amount of water stays in short-term, has the surface quality of thin film The biggest impact.By the way of using low boiling and high boiling point tertiary amine, unexpected obtain different imidization under the conditions of hold Continuous volatilization effect, makes to provide not against external force in Kapton forming process the effect of Self-leveling, solves greatly The surface quality problems of thin film.Hot imidization especially for continuous thin film operates, and not only reduces fold and space Appearance, thin film flatness is also strengthened.And polyimide precursor solution prepared by detailed description of the invention can be additionally used in shape Become polyimide fiber.
Detailed description of the invention two: present embodiment is unlike detailed description of the invention one: described low boiling tertiary amine is A kind of or the most several mixing in triethylamine, Dodecyl Dimethyl Amine, diethanol monoisopropanolamine and picoline Compound.Other is identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment is unlike one of detailed description of the invention one or two: described high boiling Point tertiary amine is a kind of or the most several mixture in tri-n-butylamine, triisopropanolamine and dimethylamino formyl chloride.Other with Detailed description of the invention one or two is identical.
Detailed description of the invention four: present embodiment is unlike one of detailed description of the invention one to three: described aqueous Releasing agent is can be miscible with water less than under conditions of 100 DEG C in temperature, and the releasing agent that do not separates out or mould release.Other is with concrete Embodiment one to three is identical.
Detailed description of the invention five: present embodiment is unlike one of detailed description of the invention one to four: described aqueous Releasing agent is RPLUS S02-004, Sepaluck RA715W, Sepaluck RA733W, NS-100 or Sepaluck RA780W.Other is identical with detailed description of the invention one to four.
RPLUS S02-004 is that the vigorous company of Crewe of Germany produces；Sepaluck RA715W、Sepaluck RA733W、NS- 100 and Sepaluck RA780W are that mountain one chemical company of Japan produces.
Detailed description of the invention six: present embodiment is unlike one of detailed description of the invention one to five: described fragrance The gross mass of dianhydride and aromatic diamines and the mass ratio of polar solvent are 1:(0～1.5)；Described low boiling tertiary amine and high boiling point The molar ratio of tertiary amine is 1:(0.5～100).Other is identical with detailed description of the invention one to five.
The gross mass of this detailed description of the invention aromatic dianhydride and aromatic diamines and the mass-energy density of polar solvent provide low molten Agent burden and holding better effects.
Detailed description of the invention seven: the preparation method of a kind of polyimide precursor solution described in present embodiment be by with Lower step is carried out:
One, tertiary amine, aqueous release agent, aromatic dianhydride, aromatic diamines, polar solvent and water are taken；
Described aromatic diamines is 1:(0.05～1.5 with the mol ratio of tertiary amine)；Described aromatic diamines and the aqueous demoulding The mass ratio of agent is 1:(0.01～1)；Described aromatic diamines is 1:(0.97～1.03 with the mol ratio of aromatic dianhydride)；Described Aromatic dianhydride and the gross mass of aromatic diamines and the mass ratio of water be 1:(2～10)；Described aromatic dianhydride and aromatic diamines The mass ratio of gross mass and polar solvent be 1:(0～10)；
Two, under nitrogen atmosphere, temperature are 2 DEG C～10 DEG C and stirring condition, add in step one in three-necked bottle and weigh Water and polar solvent, be subsequently adding the aromatic diamines weighed in step one, obtain reactant liquor, the fragrance that will weigh in step one Dianhydride is joined in reactant liquor the most in three times by quality, reacts 1h～5h, then reactant liquor is warming up to 20 DEG C～60 DEG C, Nitrogen atmosphere, temperature are under 20 DEG C～60 DEG C and stirring condition, add the tertiary amine weighed in step one and aqueous in reactant liquor Releasing agent, stirring reaction 3h～5h, finally reacting liquid temperature is reduced to 2 DEG C～10 DEG C, stands 1h～10h, obtain polyamides sub- Amine precursor solution；
Aromatic diamines described in step one is 4,4 '-diaminodiphenyl ether, 4,4 '-MDA, two (3-ammonia Phenoxyl) benzophenone, p-phenylenediamine, a kind of or the most several mixed in m-diaminobenzene. and 4,4' diaminodiphenyl sulfone Compound；
Tertiary amine described in step one is the mixture of low boiling tertiary amine or low boiling tertiary amine and high boiling point tertiary amine, described Low boiling tertiary amine is 1:(0.01～100 with the molar ratio of high boiling point tertiary amine)；Described low boiling tertiary amine is that boiling point is at 150 DEG C Hereinafter, and the molecular weight of low boiling tertiary amine is 80g/mol～250g/mol；Described high boiling point tertiary amine be boiling point at 150 DEG C～ The tertiary amine of 295 DEG C；
Polar solvent described in step one is DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, ethylene glycol and two A kind of or the most several mixture in methyl sulfoxide；
When the aromatic dianhydride described in step one 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 described polyimide precursor solution Repetitive be:
Described R1For-O-or
Described R2For
When the aromatic dianhydride described in step one is 3,3, during 4 ', 4 '-biphenyl tetracarboxylic dianhydride, before described polyimides Driving the repetitive of polyamic acid in liquid solution is:
Described R3For
When the aromatic dianhydride described in step one is pyromellitic acid anhydride, in described polyimide precursor solution The repetitive of polyamic acid is:
Described R4For
Detailed description of the invention eight: present embodiment is unlike detailed description of the invention seven: the low boiling described in step one Point tertiary amine is the one in triethylamine, Dodecyl Dimethyl Amine, diethanol monoisopropanolamine and picoline or wherein Several mixture.Other is identical with detailed description of the invention seven.
Detailed description of the invention nine: present embodiment is unlike one of detailed description of the invention seven or eight: institute in step one The high boiling point tertiary amine stated is a kind of or the most several mixing in tri-n-butylamine, triisopropanolamine and dimethylamino formyl chloride Thing.Other is identical with detailed description of the invention seven or eight.
Detailed description of the invention ten: present embodiment is unlike one of detailed description of the invention seven to nine: institute in step one The aqueous release agent stated is for can be miscible with water less than under conditions of 100 DEG C in temperature, and the releasing agent that do not separates out or mould release.Its It is identical with detailed description of the invention seven to nine.
Detailed description of the invention 11: present embodiment is unlike one of detailed description of the invention seven to ten: in step one Described aqueous release agent is RPLUS S02-004, Sepaluck RA715W, Sepaluck RA733W, NS-100 or Sepaluck RA780W.Other is identical with detailed description of the invention seven to ten.
RPLUS S02-004 is that the vigorous company of Crewe of Germany produces；Sepaluck RA715W、Sepaluck RA733W、NS- 100 and Sepaluck RA780W are that mountain one chemical company of Japan produces.
Detailed description of the invention 12: present embodiment is unlike one of detailed description of the invention seven to ten one: step one Described in aromatic dianhydride and the gross mass of aromatic diamines and the mass ratio of polar solvent be 1:(0～1.5)；Described in step The molar ratio of low boiling tertiary amine and high boiling point tertiary amine be 1:(0.5～100).Other and detailed description of the invention seven to ten one phase With.
The gross mass of this detailed description of the invention aromatic dianhydride and aromatic diamines and the mass-energy density of polar solvent provide low molten Agent burden and holding better effects.
Detailed description of the invention 13: it is thin that the utilization one polyimide precursor solution of present embodiment prepares polyimides The method of film, is carried out the most according to the following steps:
One, polyimide precursor solution filtered and deaerate, being cast on stainless steel rotary drum along T-shaped slit, so After at temperature is 60 DEG C～180 DEG C, be dried 1min～50min, obtain self-supporting film；
Two, self-supporting film is peeled off from stainless steel rotary drum it is placed in curing oven solidification, be first 150 in temperature DEG C～200 DEG C under conditions of, heat 1min～60min, then under conditions of temperature is 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, make annealing treatment about 1min～20min, obtain Kapton；
And solidification process utilizes holder self-supporting film so that longitudinal length change before and after self-supporting film solidification Percentage rate is 5%～20%, and lateral length change percentage in arid is 10%～80%.
The Kapton of present embodiment can be by making to obtain as the polyamic acid imidizate of presoma.This Outward, the raw material of workman, reaction condition etc. can be used in it manufactures.Furthermore, it is possible to need add inorganic or have according to function The filler of machine thing.
Then by self-supported membrane from substrate surface peel off carry out curing process, can pass through aqueous impregnation solution, to additionally The methods such as tension force realize.
Kapton is the Kapton obtained according to polyimide precursor solution.Thin as polyimides Film can be as liquid crystal orientation film, fuel cell porous polyimide film, separation film, pcb board monolayer, bilayer, multilamellar, R- F, HDI film substrate, electric wire dielectric film, high-temperature resistant membrane etc..
Present embodiment provides the benefit that: a kind of polyimide precursor solution of present embodiment offer and preparation thereof Method and utilize its method preparing Kapton, can solve existing polyimide precursor-polyamic acid aqueous solution Preparation method and structure composition be difficult to produce great surface quality and the polyimides of serialization not embrittlement at casting apparatus The problem of thin film.According to the preparation method of polyimide precursor solution, have employed low ratio high bp polar solvent, multiple boiling The combination of some tertiary amine complex.
On the one hand, high bp polar solvent (such as N,N-dimethylacetamide, DMF etc.) and water are utilized Combination, improve solvent entirety boiling point, it is to avoid the self-supporting polyimide precursor thin film of formation (is less than containing quantity of solvent is very few 20%) and boiling point is low, although self-supported membrane still experiences high temperature imidization (having stretching action or tensionless winkler foundation effect) process (150 DEG C-250 DEG C) in there will be molecular weight and molecular weight and situation that intensity declines, but the lifting containing quantity of solvent and boiling point improve, greatly Degree improves percentage elongation and the pliability of initial imidization (150 DEG C-200 DEG C), it is to avoid lead due to external load at high temperature The danger of the film breaks caused, affects thin film continuous operation.
On the other hand, polyimide precursor solution preparation method have employed multiple boiling point tertiary amine complex, thus at stream When prolonging abjection solvent formation self-supported membrane, still contain multiple boiling point tertiary amine in presoma.By self-supporting in imidization program Film is poured curing oven into and is processed, and especially for the hot imidization processing self-supported membrane of serialization, needs to apply certain Axially outer load provides traction, and after moisture volatilizees substantially (＜ 150 DEG C), conventional single tertiary amines also faces at 150 DEG C The risk of volatilization, it is difficult to (150 DEG C-250 DEG C) low-intensity, low elongation after making up initial imidization as liquid residual lifting. Multiple tertiary amine is used to provide multiple removal temperature and boiling point, it is achieved still to remain with certain liquid residual when more than 150 DEG C.And Mode compound use with high boiling solvent combination, it is possible to further ensure that the thin film under imidization initial temperature condition continues Elongation and the coefficient of expansion, greatly avoid at the initial film destruction of imidization, be especially pulled thin film under power effect Destroy, thus save curing oven and lower the temperature, again wear film, the electric power of intensification and time cost.
It is surprising that the compound use of multiple tertiary amine, not only contribute to promote thin film each stage shaping strength, simultaneously Also improve the surface quality of thin film and reduce defect.Due to lower boiling single tertiary amine and water after volatilizing, polyimides Presoma faces quick imidization and solvent, the dual-pressure of catalyst abjection, the thin film surface planeness that can seriously cause is poor, Surface has the volatilization pore that stays of abjection, imidization to remove the closed pore etc. that a large amount of water stays in short-term, has the surface quality of thin film The biggest impact.By the way of using low boiling and high boiling point tertiary amine, unexpected obtain different imidization under the conditions of hold Continuous volatilization effect, makes to provide not against external force in Kapton forming process the effect of Self-leveling, solves greatly The surface quality problems of thin film.Hot imidization especially for continuous thin film operates, and not only reduces fold and space Appearance, thin film flatness is also strengthened.And polyimide precursor solution prepared by detailed description of the invention can be additionally used in shape Become polyimide fiber.
Detailed description of the invention 14: present embodiment is unlike detailed description of the invention 13: then exist in step one Temperature is at 80 DEG C～160 DEG C, is dried 10min～30min.Other is identical with detailed description of the invention 13.
Present embodiment provides the benefit that:
Employing following example checking beneficial effects of the present invention:
Embodiment one:
A kind of polyimide precursor solution by tertiary amine, aqueous release agent, aromatic dianhydride, aromatic diamines, polar solvent and Water is made；
Described aromatic diamines is 1:0.05 with the mol ratio of tertiary amine；Described aromatic diamines and the quality of aqueous release agent Ratio is 1:0.01；Described aromatic diamines is 1:1 with the mol ratio of aromatic dianhydride；Described aromatic dianhydride and aromatic diamines total Quality is 1:8 with the mass ratio of water；The mass ratio of described aromatic dianhydride and the gross mass of aromatic diamines and polar solvent is 1: 1；
Described aromatic diamines is p-phenylenediamine；
Described tertiary amine is diethanol monoisopropanolamine；
Described polar solvent is DMAC N,N' dimethyl acetamide；Described aqueous release agent is that mountain one chemical company of Japan is raw The NS-100 produced；
Described aromatic dianhydride is 3,3,4 ', 4 '-biphenyl tetracarboxylic dianhydride, poly-in described polyimide precursor solution The repetitive of amic acid is:
The preparation method of above-mentioned a kind of polyimide precursor solution is to sequentially include the following steps:
One, 8.16g diethanol 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 acetamide and 3218.88g Water；
Two, under nitrogen atmosphere, temperature are 5 DEG C and stirring condition, in three-necked bottle, 3218.88g water and 402.36g are added N,N-dimethylacetamide, is subsequently adding 108.14g p-phenylenediamine (1mol), obtains reactant liquor, by 294.22g 3, and 3,4 ', 4 '-biphenyl tetracarboxylic dianhydride (1mol) is joined in reactant liquor the most in three times by quality, reacts 5h, is then heated up by reactant liquor To 20 DEG C, under nitrogen atmosphere, temperature are 20 DEG C and stirring condition, in reactant liquor, add 8.16g diethanol monoisopropanolamine (0.05mol) with 1.08g NS-100, stirring reaction 5h, finally reacting liquid temperature is reduced to 5 DEG C, stands 10h, obtain polyamides Imines precursor solution；
The method utilizing above-mentioned a kind of polyimide precursor solution to prepare Kapton is to sequentially include the following steps:
One, polyimide precursor solution filtered and deaerate, being cast on stainless steel rotary drum along T-shaped slit, so After at temperature is 120 DEG C, be dried 10min, obtain self-supporting film；
Two, self-supporting film is peeled off from stainless steel rotary drum it is placed in curing oven solidification, be first 150 in temperature Under conditions of DEG C, heat 3min, then under conditions of temperature is 250 DEG C, heat 3min, then in the condition that temperature is 400 DEG C Under, heat 70s, finally under conditions of temperature is 300 DEG C, make annealing treatment about 1min, obtain Kapton；
And solidification process utilizes holder self-supporting film so that longitudinal length change before and after self-supporting film solidification Percentage rate is 10%, and lateral length change percentage in arid is 50%.
The thickness of Kapton prepared by 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；
Described aromatic diamines is 1:0.05 with the mol ratio of tertiary amine；Described aromatic diamines and the quality of aqueous release agent Ratio is 1:0.01；Described aromatic diamines is 1:1 with the mol ratio of aromatic dianhydride；Described aromatic dianhydride and aromatic diamines total Quality is 1:8 with the mass ratio of water；The mass ratio of described aromatic dianhydride and the gross mass of aromatic diamines and polar solvent is 1: 1；
Described aromatic diamines is 4,4 '-diaminodiphenyl ether；
Described tertiary amine is diethanol monoisopropanolamine；
Described polar solvent is DMAC N,N' dimethyl acetamide；
Described aqueous release agent is the NS-100 that mountain one chemical company of Japan produces；
When described aromatic dianhydride is pyromellitic acid anhydride, polyamic acid in described polyimide precursor solution Repetitive is:
The preparation method of above-mentioned a kind of polyimide precursor solution is to sequentially include the following steps:
One, the equal benzene tetramethyl of NS-100,218.12g of the diethanol monoisopropanolamine (0.05mol) of 8.16g, 2.00g is taken Acid dianhydride (1mol), the 4,4 '-diaminodiphenyl ether (1mol) of 200.24g, the DMAC N,N' dimethyl acetamide of 418.36g and 3346.88g water；
Two, under nitrogen atmosphere, temperature are 5 DEG C and stirring condition, in three-necked bottle, the water of the 3346.88g weighed is added With the N,N-dimethylacetamide of 418.36g, it is subsequently adding the 4 of 200.24g, 4 '-diaminodiphenyl ether (1mol), is reacted Liquid, is joined in reactant liquor by quality the most in three times by the pyromellitic acid anhydride (1mol) of 218.12g, reacts 2h, then Reactant liquor is warming up to 20 DEG C, under nitrogen atmosphere, temperature are 20 DEG C and stirring condition, in reactant liquor, adds the two of 8.16g Ethanol monoisopropanolamine (0.05mol) and the NS-100 of 2.00g, stirring reaction 5h, finally reacting liquid temperature is reduced to 5 DEG C, Stand 10h, obtain polyimide precursor solution；
The method utilizing above-mentioned a kind of polyimide precursor solution to prepare Kapton is to sequentially include the following steps:
One, polyimide precursor solution filtered and deaerate, being cast on stainless steel rotary drum along T-shaped slit, so After at temperature is 120 DEG C, be dried 10min, obtain self-supporting film；
Two, self-supporting film is peeled off from stainless steel rotary drum it is placed in curing oven solidification, be first 150 in temperature Under conditions of DEG C, heat 3min, then under conditions of temperature is 250 DEG C, heat 3min, then in the condition that temperature is 400 DEG C Under, heat 70s, finally under conditions of temperature is 300 DEG C, make annealing treatment about 1min, obtain Kapton；
And solidification process utilizes holder self-supporting film so that longitudinal length change before and after self-supporting film solidification Percentage rate is 10%, and lateral length change percentage in arid is 50%.
The thickness of Kapton prepared by the present embodiment is 25 microns.
Embodiment three:
A kind of polyimide precursor solution is made up of tertiary amine, aqueous release agent, aromatic dianhydride, aromatic diamines and water；
Described aromatic diamines is 1:0.05 with the mol ratio of tertiary amine；Described aromatic diamines and the quality of aqueous release agent Ratio is 1:0.01；Described aromatic diamines is 1:1 with the mol ratio of aromatic dianhydride；Described aromatic dianhydride and aromatic diamines total Quality is 1:9 with the mass ratio of water；
Described aromatic diamines is p-phenylenediamine；
Described tertiary amine is the mixture of low boiling tertiary amine and high boiling point tertiary amine, described low boiling tertiary amine and high boiling point uncle The molar ratio of amine is 1:1；
Described low boiling tertiary amine is diethanol monoisopropanolamine；
Described high boiling point tertiary amine is dimethylamino formyl chloride；
Described aqueous release agent is the NS-100 that mountain one chemical company of Japan produces；
Described aromatic dianhydride is 3,3,4 ', 4 '-biphenyl tetracarboxylic dianhydride, poly-in described polyimide precursor solution The repetitive of amic acid is:
The preparation method of above-mentioned a kind of polyimide precursor solution is to sequentially include the following steps:
One, the diethanol monoisopropanolamine (0.025mol) of 4.08g, the dimethylamino formyl chloride of 2.69g are taken (0.025mol), 3,3,4 ', the 4 '-biphenyl tetracarboxylic dianhydride (1mol) of NS-100,294.22g of 1.08g, 108.14g right Phenylenediamine (1mol) and the water of 3621.24g；
Two, under nitrogen atmosphere, temperature are 5 DEG C and stirring condition, in three-necked bottle, add the water of 3621.24g, then add Enter the p-phenylenediamine (1mol) of 108.14g, obtain reactant liquor, by the 3 of 294.22g, 3,4 ', 4 '-biphenyl tetracarboxylic dianhydride (1mol) join the most in three times in reactant liquor by quality, react 5h, then reactant liquor is warming up to 20 DEG C, at nitrogen gas Atmosphere, temperature are under 20 DEG C and stirring condition, add in reactant liquor 4.08g diethanol monoisopropanolamine (0.025mol), The dimethylamino formyl chloride (0.025mol) of 2.69g and the NS-100 of 1.08g, stirring reaction 5h, finally drops reacting liquid temperature As little as 5 DEG C, stand 10h, obtain polyimide precursor solution；
The method utilizing above-mentioned a kind of polyimide precursor solution to prepare Kapton is to sequentially include the following steps:
One, polyimide precursor solution filtered and deaerate, being cast on stainless steel rotary drum along T-shaped slit, so After at temperature is 120 DEG C, be dried 10min, obtain self-supporting film；
Two, self-supporting film is peeled off from stainless steel rotary drum it is placed in curing oven solidification, be first 150 in temperature Under conditions of DEG C, heat 3min, then under conditions of temperature is 250 DEG C, heat 3min, then in the condition that temperature is 400 DEG C Under, heat 70s, finally under conditions of temperature is 300 DEG C, make annealing treatment about 1min, obtain Kapton；
And solidification process utilizes holder self-supporting film so that longitudinal length change before and after self-supporting film solidification Percentage rate is 10%, and lateral length change percentage in arid is 50%.
The thickness of Kapton prepared by the present embodiment is 25 microns.
Embodiment four:
A kind of polyimide precursor solution by tertiary amine, aqueous release agent, aromatic dianhydride, aromatic diamines, polar solvent and Water is made；
Described aromatic diamines is 1:0.05 with the mol ratio of tertiary amine；Described aromatic diamines and the quality of aqueous release agent Ratio is 1:0.01；Described aromatic diamines is 1:1 with the mol ratio of aromatic dianhydride；Described aromatic dianhydride and aromatic diamines total Quality is 1:8 with the mass ratio of water；The mass ratio of described aromatic dianhydride and the gross mass of aromatic diamines and polar solvent is 1: 1；
Described aromatic diamines is p-phenylenediamine；
Described tertiary amine is the mixture of low boiling tertiary amine and high boiling point tertiary amine, described low boiling tertiary amine and high boiling point uncle The molar ratio of amine is 1:1；
Described low boiling tertiary amine is diethanol monoisopropanolamine；
Described high boiling point tertiary amine is dimethylamino formyl chloride；
Described polar solvent is DMAC N,N' dimethyl acetamide；
Described aqueous release agent is the NS-100 that mountain one chemical company of Japan produces；
Described aromatic dianhydride is 3,3,4 ', 4 '-biphenyl tetracarboxylic dianhydride, poly-in described polyimide precursor solution The repetitive of amic acid is:
The preparation method of above-mentioned a kind of polyimide precursor solution is to sequentially include the following steps:
One, the diethanol monoisopropanolamine (0.025mol) of 4.08g, the dimethylamino formyl chloride of 2.69g are taken (0.025mol), 3,3,4 ', the 4 '-biphenyl tetracarboxylic dianhydride (1mol) of NS-100,294.22g of 1.08g, 108.14g right Phenylenediamine (1mol), the DMAC N,N' dimethyl acetamide of 402.36g and the water of 3218.88g；
Two, under nitrogen atmosphere, temperature are 5 DEG C and stirring condition, add in three-necked bottle 3218.88g water and The N,N-dimethylacetamide of 402.36g, is subsequently adding the p-phenylenediamine (1mol) of 108.14g, obtains reactant liquor, will The 3 of 294.22g, 3,4 ', 4 '-biphenyl tetracarboxylic dianhydride (1mol) is joined in reactant liquor the most in three times by quality, reacts 5h, Then reactant liquor is warming up to 20 DEG C, under nitrogen atmosphere, temperature are 20 DEG C and stirring condition, in reactant liquor, adds 4.08g Diethanol monoisopropanolamine (0.025mol), the dimethylamino formyl chloride (0.025mol) of 2.69g and the NS-100 of 1.08g, Stirring reaction 5h, is finally reduced to reacting liquid temperature 5 DEG C, stands 10h, obtain polyimide precursor solution；
The method utilizing above-mentioned a kind of polyimide precursor solution to prepare Kapton is to sequentially include the following steps:
One, polyimide precursor solution filtered and deaerate, being cast on stainless steel rotary drum along T-shaped slit, so After at temperature is 120 DEG C, be dried 10min, obtain self-supporting film；
Two, self-supporting film is peeled off from stainless steel rotary drum it is placed in curing oven solidification, be first 150 in temperature Under conditions of DEG C, heat 3min, then under conditions of temperature is 250 DEG C, heat 3min, then in the condition that temperature is 400 DEG C Under, heat 70s, finally under conditions of temperature is 300 DEG C, make annealing treatment about 1min, obtain Kapton；
And solidification process utilizes holder self-supporting film so that longitudinal length change before and after self-supporting film solidification Percentage rate is 10%, and lateral length change percentage in arid is 50%.
The thickness of Kapton prepared by 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；
Described aromatic diamines is 1:0.05 with the mol ratio of tertiary amine；Described aromatic diamines and the quality of aqueous release agent Ratio is 1:0.01；Described aromatic diamines is 1:1 with the mol ratio of aromatic dianhydride；Described aromatic dianhydride and aromatic diamines total Quality is 1:8 with the mass ratio of water；The mass ratio of described aromatic dianhydride and the gross mass of aromatic diamines and polar solvent is 1: 1；
Described aromatic diamines is p-phenylenediamine；
Described tertiary amine is the mixture of low boiling tertiary amine and high boiling point tertiary amine, described low boiling tertiary amine and high boiling point uncle The molar ratio of amine is 1:1；
Described low boiling tertiary amine is diethanol monoisopropanolamine；
Described high boiling point tertiary amine is dimethylamino formyl chloride；
Described polar solvent is DMAC N,N' dimethyl acetamide；
Described aqueous release agent is the NS-100 that mountain one chemical company of Japan produces；
Described aromatic dianhydride is 3,3,4 ', 4 '-biphenyl tetracarboxylic dianhydride, poly-in described polyimide precursor solution The repetitive of amic acid is:
The preparation method of above-mentioned a kind of polyimide precursor solution is to sequentially include the following steps:
One, the diethanol monoisopropanolamine (0.025mol) of 4.08g, the dimethylamino formyl chloride of 2.69g are taken (0.025mol) and 3,3,4 ', the 4 '-biphenyl tetracarboxylic dianhydride (1mol) of NS-100,294.22g of 1.08g, 108.14g right Phenylenediamine (1mol), the DMAC N,N' dimethyl acetamide of 402.36g and the water of 3218.88g；
Two, under nitrogen atmosphere, temperature are 5 DEG C and stirring condition, add in three-necked bottle 3218.88g water and The N,N-dimethylacetamide of 402.36g, is subsequently adding the p-phenylenediamine (1mol) of 108.14g, obtains reactant liquor, will The 3 of 294.22g, 3,4 ', 4 '-biphenyl tetracarboxylic dianhydride (1mol) is joined in reactant liquor the most in three times by quality, reacts 5h, Then reactant liquor is warming up to 20 DEG C, under nitrogen atmosphere, temperature are 20 DEG C and stirring condition, in reactant liquor, adds 4.08g Diethanol monoisopropanolamine (0.025mol), the dimethylamino formyl chloride (0.025mol) of 2.69g and the NS-100 of 1.08g, Stirring reaction 5h, is finally reduced to reacting liquid temperature 5 DEG C, stands 10h, obtain polyimide precursor solution；
The method utilizing above-mentioned a kind of polyimide precursor solution to prepare Kapton is to sequentially include the following steps:
One, polyimide precursor solution filtered and deaerate, being cast on stainless steel rotary drum along T-shaped slit, so After at temperature is 120 DEG C, be dried 10min, obtain self-supporting film；
Two, self-supporting film is peeled off from stainless steel rotary drum it is placed in curing oven solidification, be first 150 in temperature Under conditions of DEG C, heat 3min, then under conditions of temperature is 250 DEG C, heat 3min, then in the condition that temperature is 400 DEG C Under, heat 70s, finally under conditions of temperature is 300 DEG C, make annealing treatment about 1min, obtain Kapton；
And solidification process utilizes holder self-supporting film so that longitudinal length change before and after self-supporting film solidification Percentage rate is 5%, and lateral length change percentage in arid is 20%.
The thickness of Kapton prepared by the present embodiment is 25 microns.
Contrast experiment one:
A kind of polyimide precursor solution is made up of tertiary amine, aromatic dianhydride, aromatic diamines and water；
Described aromatic diamines is 1:0.05 with the mol ratio of tertiary amine；Described aromatic diamines and the mol ratio of aromatic dianhydride For 1:1；The mass ratio of described aromatic dianhydride and the gross mass of aromatic diamines and water is 1:9；
Described aromatic diamines is p-phenylenediamine；
Described tertiary amine is triethylamine；
Described aromatic dianhydride is 3,3,4 ', 4 '-biphenyl tetracarboxylic dianhydride, poly-in described polyimide precursor solution The repetitive of amic acid is:
The preparation method of above-mentioned a kind of polyimide precursor solution is to sequentially include the following steps:
One, take the triethylamine (0.05mol) of 5.06g, the 3,3,4 ' of 294.22g, 4 '-biphenyl tetracarboxylic dianhydride (1mol), the p-phenylenediamine (1mol) of 108.14g and the water of 3621.24g；
Two, under nitrogen atmosphere, temperature are 5 DEG C and stirring condition, in three-necked bottle, add the water of 3621.24g, then add Enter the p-phenylenediamine (1mol) of 108.14g, obtain reactant liquor, by the 3 of 294.22g, 3,4 ', 4 '-biphenyl tetracarboxylic dianhydride (1mol) join the most in three times in reactant liquor by quality, react 5h, then reactant liquor is warming up to 20 DEG C, at nitrogen gas Atmosphere, temperature are under 20 DEG C and stirring condition, add the triethylamine (0.05mol) of 5.06g in reactant liquor, stirring reaction 5h, Finally reacting liquid temperature is reduced to 5 DEG C, stands 10h, obtain polyimide precursor solution；
The method utilizing above-mentioned a kind of polyimide precursor solution to prepare Kapton is to sequentially include the following steps:
One, polyimide precursor solution filtered and deaerate, being cast on stainless steel rotary drum along T-shaped slit, so After at temperature is 120 DEG C, be dried 10min, obtain self-supporting film；
Two, self-supporting film is peeled off from stainless steel rotary drum it is placed in curing oven, in the condition that temperature is 150 DEG C Lower solidification, utilizes holder self-supporting film in solidification process, the lower self-supported membrane of traction heating ruptures, during fracture longitudinally Percentage elongation, 5%, obtains polyimides thin.
Contrast experiment one cannot obtain continuous print Kapton.
Contrast experiment two:
A kind of polyimide precursor solution is made up of tertiary amine, aqueous release agent, aromatic dianhydride, aromatic diamines and water；
Described aromatic diamines is 1:0.05 with the mol ratio of tertiary amine；Described aromatic diamines and the quality of aqueous release agent Ratio is 1:0.01；Described aromatic diamines is 1:1 with the mol ratio of aromatic dianhydride；Described aromatic dianhydride and aromatic diamines total Quality is 1:9 with the mass ratio of water；
Described aromatic diamines is p-phenylenediamine；
Described tertiary amine is diethanol monoisopropanolamine；
Described aqueous release agent is the NS-100 that mountain one chemical company of Japan produces；
Described aromatic dianhydride is 3,3,4 ', 4 '-biphenyl tetracarboxylic dianhydride, seals in described polyimide precursor solution The repetitive of the polyamic acid of end is:
The preparation method of above-mentioned a kind of polyimide precursor solution is to sequentially include the following steps:
One, 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；
Two, under nitrogen atmosphere, temperature are 5 DEG C and stirring condition, in three-necked bottle, add the water of 3621.24g, then add Enter the p-phenylenediamine (1mol) of 108.14g, obtain reactant liquor, by the 3 of 294.22g, 3,4 ', 4 '-biphenyl tetracarboxylic dianhydride (1mol) join the most in three times in reactant liquor by quality, react 5h, then reactant liquor is warming up to 20 DEG C, at nitrogen gas Atmosphere, temperature are under 20 DEG C and stirring condition, add in reactant liquor 8.16g diethanol monoisopropanolamine (0.05mol) and The NS-100 of 1.08g, stirring reaction 5h, be finally reduced to reacting liquid temperature 5 DEG C, stand 10h, obtain polyimide precursor Solution；
The method utilizing above-mentioned a kind of polyimide precursor solution to prepare Kapton is to sequentially include the following steps:
One, polyimide precursor solution filtered and deaerate, being cast on stainless steel rotary drum along T-shaped slit, so After at temperature is 120 DEG C, be dried 10min, obtain self-supporting film；
Two, self-supporting film is peeled off from stainless steel rotary drum be placed in curing oven solidification, in solidification process utilize Holder self-supporting film, solidifies 3min under conditions of temperature is 150 DEG C, then leads under conditions of temperature is 250 DEG C Drawing self-supported membrane in heating process to rupture, during fracture, longitudinal tensile strain rate is 8%, obtains polyimides thin.
Contrast experiment two cannot obtain continuous print Kapton.
The table thin to the Kapton of embodiment one and five preparation and the polyimides of contrast experiment one and two preparation Face quality, is evaluated by crizzle, surface smoothness, blibbing mode.
1., crizzle:
Evaluating the micro-crack on Kapton surface, evaluation criterion is as follows:
A: do not find that film surface exists micro-crack；
B: can confirm that on the surface (less than the 5% of film surface area) of thin film and there is crizzle；
C: thin film surface (more than film surface area 5%, less than 10%) on can confirm that and there is crizzle；
D: can confirm that on the surface (more than the 10% of film surface area) of thin film and there is crizzle.
2., surface smoothness:
Evaluating the surface smoothness of Kapton, evaluation criterion is as follows:
A: using micrometer caliper to test the thickness of thin film, (each region accounts for unit fabric width table to take zones of different The ratio of area is no less than 15%) 5 number of test points evidences, obtain the maximum of data, minima deducts meansigma methods, and averagely The ratio of value is all within ± 5%；
B: using micrometer caliper to test the thickness of thin film, (each region accounts for unit fabric width table to take zones of different The ratio of area is no less than 15%) 5 number of test points evidences, obtain the maximum of data, minima deducts meansigma methods, and averagely The ratio of value is all within ± 10%；
C: using micrometer caliper to test the thickness of thin film, (each region accounts for unit fabric width table to take zones of different The ratio of area is no less than 15%) 5 number of test points evidences, obtain the maximum of data, minima deducts meansigma methods, and averagely The ratio of value is all within ± 15%；
D: using micrometer caliper to test the thickness of thin film, (each region accounts for unit fabric width table to take zones of different The ratio of area is no less than 15%) 5 number of test points evidences, obtain the maximum of data, minima deducts meansigma methods, and averagely The ratio of value is all beyond ± 15%.
3., blibbing:
Evaluating the blibbing that Kapton surface exists, evaluation criterion is as follows:
A: Kapton surface does not exist blibbing；
Blibbing more than one that B: Kapton surface (10cm X 10cm) exists but be less than 5；
The blibbing that C: Kapton surface (10cm X 10cm) exists is more than 5 but is less than 50；
The blibbing that D: Kapton surface (10cm X 10cm) exists is more than 50.
The Kapton of embodiment one and five preparation and the Kapton of contrast experiment one and two preparation are surveyed Try 5% thermal weight loss temperature: test uses thermal gravimetric analyzer (TGA).Heating rate: 10 DEG C/min；Measurement atmosphere: air.
The Kapton of embodiment one and five preparation and the Kapton of contrast experiment one and two preparation are surveyed Try 800% carbon yield: test uses thermal gravimetric analyzer (TGA).Heating rate: 10 DEG C/min；Measurement atmosphere: nitrogen.
The Kapton of embodiment one and five preparation and the Kapton of contrast experiment one and two preparation are surveyed Examination glass transition temperature: test uses dynamic thermomechanical analysis apparatus (DMA).Heating rate: 5 DEG C/min；Measurement atmosphere: empty Gas.
The Kapton of embodiment one and five preparation and the Kapton of contrast experiment one and two preparation are entered Row mechanical test, uses ASTM D882 standard to test.
Table 1 is Kapton surface quality and film property, and table 2 is for preparing Kapton performance continuously.By table 1 Understanding, contrast experiment cannot complete serialization Kapton and prepare, and in curing oven operates, irreversible self-supporting occurs Film ruptures, and longitudinal tensile strain rate is not reaching to standard, not yet carries out transverse extension operation simultaneously.Additionally, contrast experiment is in surface matter Amount aspect all far below embodiment, is all worse than embodiment including surface smoothness, crizzle and blibbing aspect.Its In, embodiment four and embodiment five, it is combined high boiling solvent owing to have employed multiple amines catalyst so that the thin film of formation, Compared to embodiment one to three, there is the most excellent surface smoothness.
As shown in Table 2, contrast experiment prepares owing to cannot complete continuous thin film.So can not 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 owing to not using suitable elongation to be orientated, and the hot property of polyimide material is caused certain impact.Comparative example Five and embodiment four, it is due to elongation orientation two-way in not having suitable face, hot property and the mechanical performance to thin film equally The impact all caused, especially mechanical property.
Fig. 1 is the Kapton photo of embodiment four preparation；Fig. 2 is the Kapton of contrast experiment one preparation Photo.Knowable to figure, the Kapton surface quality that contrast test obtains is bad, simultaneously because thin film midway brittle failure, nothing Method carries out cross directional stretch, causes film surface fold occur, and fracture lines occurs in end.
Table 1 Kapton surface quality and film property
The Kapton performance that table 2 is prepared continuously

Claims (10)

1. a polyimide precursor solution, it is characterised in that a kind of polyimide precursor solution is by tertiary amine, the aqueous demoulding Agent, aromatic dianhydride, aromatic diamines, polar solvent and water are made；
Described aromatic diamines is 1:(0.05～1.5 with the mol ratio of tertiary amine)；Described aromatic diamines and aqueous release agent Mass ratio is 1:(0.01～1)；Described aromatic diamines is 1:(0.97～1.03 with the mol ratio of aromatic dianhydride)；Described virtue Fragrant dianhydride and the gross mass of aromatic diamines are 1:(2～10 with the mass ratio of water)；Described aromatic dianhydride and aromatic diamines total Quality is 1:(0～10 with the mass ratio of polar solvent)；
Described aromatic diamines is 4,4 '-diaminodiphenyl ether, 4,4 '-MDA, two (3-amino-benzene oxygens) two A kind of or the most several mixture in benzophenone, p-phenylenediamine, m-diaminobenzene. and 4,4' diaminodiphenyl sulfone；
Described tertiary amine is the mixture of low boiling tertiary amine or low boiling tertiary amine and high boiling point tertiary amine, described low boiling tertiary amine with The molar ratio of high boiling point tertiary amine is 1:(0.01～100)；Described low boiling tertiary amine be boiling point below 150 DEG C, and low boiling The molecular weight of some tertiary amine is 80g/mol～250g/mol；Described high boiling point tertiary amine is that boiling point is at 150 DEG C～the tertiary amine of 295 DEG C；
Described polar solvent is in DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, ethylene glycol and dimethyl sulfoxide Or the most several a kind of mixture；
When described aromatic dianhydride be 3,3,4 ', 4 '-diphenyl ether tetracarboxylic dianhydride, 3,3,4 ', 4 '-two sulfuryl tetracarboxylic dianhydrides or 3,3, during 4 ', 4 '-benzophenone tetracarboxylic dianhydride, the repetitive of polyamic acid in described polyimide precursor solution For:
Described R1For-O-or
Described R2For
When described aromatic dianhydride is 3,3, during 4 ', 4 '-biphenyl tetracarboxylic dianhydride, poly-in described polyimide precursor solution The repetitive of amic acid is:
Described R3For
When described aromatic dianhydride is pyromellitic acid anhydride, the weight of polyamic acid in described polyimide precursor solution Multiple unit is:
Described R4For
A kind of polyimide precursor solution the most according to claim 1, it is characterised in that described low boiling tertiary amine is A kind of or the most several mixing in triethylamine, Dodecyl Dimethyl Amine, diethanol monoisopropanolamine and picoline Compound.
A kind of polyimide precursor solution the most according to claim 1, it is characterised in that described high boiling point tertiary amine is A kind of or the most several mixture in tri-n-butylamine, triisopropanolamine and dimethylamino formyl chloride.
A kind of polyimide precursor solution the most according to claim 1, it is characterised in that described aqueous release agent is Can be miscible with water less than under conditions of 100 DEG C in temperature, and the releasing agent that do not separates out or mould release.
The preparation method of a kind of polyimide precursor solution the most as claimed in claim 1, it is characterised in that a kind of polyamides is sub- The preparation method of amine precursor solution is to sequentially include the following steps:
One, tertiary amine, aqueous release agent, aromatic dianhydride, aromatic diamines, polar solvent and water are taken；
Described aromatic diamines is 1:(0.05～1.5 with the mol ratio of tertiary amine)；Described aromatic diamines and aqueous release agent Mass ratio is 1:(0.01～1)；Described aromatic diamines is 1:(0.97～1.03 with the mol ratio of aromatic dianhydride)；Described virtue Fragrant dianhydride and the gross mass of aromatic diamines are 1:(2～10 with the mass ratio of water)；Described aromatic dianhydride and aromatic diamines total Quality is 1:(0～10 with the mass ratio of polar solvent)；
Two, under nitrogen atmosphere, temperature are 2 DEG C～10 DEG C and stirring condition, in three-necked bottle, the water weighed in step one is added And polar solvent, it is subsequently adding the aromatic diamines weighed in step one, obtains reactant liquor, the aromatic dianhydride that will weigh in step one Join the most in three times in reactant liquor by quality, react 1h～5h, then reactant liquor is warming up to 20 DEG C～60 DEG C, at nitrogen Atmosphere, temperature are under 20 DEG C～60 DEG C and stirring condition, add the tertiary amine weighed in step one and the aqueous demoulding in reactant liquor Agent, stirring reaction 3h～5h, finally reacting liquid temperature is reduced to 2 DEG C～10 DEG C, stands 1h～10h, before obtaining polyimides Drive liquid solution；
Aromatic diamines described in step one is 4,4 '-diaminodiphenyl ether, 4,4 '-MDA, two (3-aminobenzenes Epoxide) benzophenone, p-phenylenediamine, a kind of or the most several mixture in m-diaminobenzene. and 4,4' diaminodiphenyl sulfone；
Tertiary amine described in step one is the mixture of low boiling tertiary amine or low boiling tertiary amine and high boiling point tertiary amine, described low boiling Point tertiary amine is 1:(0.01～100 with the molar ratio of high boiling point tertiary amine)；Described low boiling tertiary amine be boiling point 150 DEG C with Under, and the molecular weight of low boiling tertiary amine is 80g/mol～250g/mol；Described high boiling point tertiary amine is that boiling point is at 150 DEG C～295 DEG C tertiary amine；
Polar solvent described in step one is DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, ethylene glycol and dimethyl A kind of or the most several mixture in sulfoxide；
When the aromatic dianhydride described in step one is 3,3,4 ', 4 '-diphenyl ether tetracarboxylic dianhydride, 3,3,4 ', 4 '-two sulfuryl tetracarboxylic acids Acid dianhydride or 3,3, during 4 ', 4 '-benzophenone tetracarboxylic dianhydride, the weight of polyamic acid in described polyimide precursor solution Multiple unit is:
Described R1For-O-or
Described R2For
When the aromatic dianhydride described in step one is 3,3, during 4 ', 4 '-biphenyl tetracarboxylic dianhydride, described polyimide precursor In solution, the repetitive of polyamic acid is:
Described R3For
When the aromatic dianhydride described in step one is pyromellitic acid anhydride, polyamides in described polyimide precursor solution The repetitive of amino acid is:
Described R4For
The preparation method of a kind of polyimide precursor solution the most according to claim 5, it is characterised in that in step one Described low boiling tertiary amine is in triethylamine, Dodecyl Dimethyl Amine, diethanol monoisopropanolamine and picoline Or the most several a kind of mixture.
The preparation method of a kind of polyimide precursor solution the most according to claim 5, it is characterised in that in step one Described high boiling point tertiary amine is a kind of or the most several mixing in tri-n-butylamine, triisopropanolamine and dimethylamino formyl chloride Thing.
The preparation method of a kind of polyimide precursor solution the most according to claim 5, it is characterised in that in step one Described aqueous release agent is can be miscible with water less than under conditions of 100 DEG C in temperature, and the releasing agent that do not separates out or mould release.
9. utilize the method that a kind of polyimide precursor solution described in claim 1 prepares Kapton, its feature It is that a kind of method utilizing polyimide precursor solution to prepare Kapton is to sequentially include the following steps:
One, polyimide precursor solution filtered and deaerate, being cast on stainless steel rotary drum along T-shaped slit, then exist Temperature is at 60 DEG C～180 DEG C, is dried 1min～50min, obtains self-supporting film；
Two, self-supporting film is peeled off from stainless steel rotary drum be placed in curing oven solidification, first temperature be 150 DEG C～ Under conditions of 200 DEG C, heat 1min～60min, then under conditions of temperature is 200 DEG C～250 DEG C, heat 1min～60min, Then, under conditions of temperature is 250 DEG C～450 DEG C, heat 1min～60min, be finally 290 DEG C～the bar of 310 DEG C in temperature Under part, make annealing treatment about 1min～20min, obtain Kapton；
And solidification process utilizes holder self-supporting film so that longitudinal length change percentage before and after self-supporting film solidification Rate is 5%～20%, and lateral length change percentage in arid is 10%～80%.
A kind of method utilizing polyimide precursor solution to prepare Kapton the most according to claim 9, its It is characterised by step one then at temperature is 80 DEG C～160 DEG C, is dried 10min～30min.
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