CN109666170A - The preparation method of uniform high-performance polyimide film - Google Patents

The preparation method of uniform high-performance polyimide film Download PDF

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CN109666170A
CN109666170A CN201710961375.8A CN201710961375A CN109666170A CN 109666170 A CN109666170 A CN 109666170A CN 201710961375 A CN201710961375 A CN 201710961375A CN 109666170 A CN109666170 A CN 109666170A
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film
polyamic acid
solution
preparation
moles
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CN109666170B (en
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刘京妮
崔晶
孙旭阳
陈大为
陈雪
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • 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)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

The present invention provides a kind of preparation method of uniform high-performance polyimide film, mainly solves the problems, such as that Kapton surface is uneven in the prior art and gel particles are more and thin film preparation process is caused to be difficult to control and properties of product decline.By using uniform high-performance polyimide film preparation method, the preparation method of Kapton is made by polyamic acid stoste through film forming, hot-stretch, hot imidization；Wherein, the polyamic acid stoste includes the mixed solution of prepolymer solution 1 and prepolymer solution 2；The reactant reaction of dianhydride of the prepolymer solution 1 by the diamines including X moles with Y moles obtains；The prepolymer solution 2 is by including that the reactant reaction of Z moles of diamines and K moles of dianhydride obtains；X, Y, Z, K meet: 0.5≤Y/X≤0.98, the technical solution of 1.02≤K/Z≤2.0 preferably solve the problems, such as this, can be used in the industrial production of Kapton.

Description

The preparation method of uniform high-performance polyimide film
Technical field
The present invention relates to a kind of surfacings, the preparation method for the uniform high-performance polyimide film haveing excellent performance.
Background technique
The polyimide material engineering plastics best as the heat resistance of industrialized production, while there is excellent heat The features such as stability, mechanical property, lower temperature resistance and insulation performance outstanding, solvent resistance, in aerospace, the micro- electricity of electronics The various fields such as son, mechanical chemical industry have a wide range of applications.Kapton is that the polyimides having the call now produces One of product, excellent corona resistance, radiation resistance, dielectric properties and dimensional stability make high-performance polyimide film material The demand of material is continuously increased.
Due to imide ring a large amount of in polyimides main chain and benzene ring structure, there are stronger intermolecular for molecule interchain Active force shows the characteristic of indissoluble infusibility so that polyimide molecule chain structure is close, becomes polyimides mass production and adds The obstruction of work affects Kapton product in the development of more application fields.In order to avoid deliquescent problem, polyamides The production of imines film mainly uses two-step method, and first synthesizing polyamides acid solution is handled using preliminary drying process and hot imidization The tape casting film-forming process prepare Kapton.
Polyamic acid, which is usually reacted under low temperature in aprotic polar solvent by dianhydride and diamines, to be made.There is patent report Pass through the adjustable average molecular matter of method for adding or adding dianhydride monomer less or a part of dianhydride being fallen using aqueous solvent hydrolysis Amount, however polyamic acid solution is prepared using above-mentioned polymerization and easily there are the drawbacks such as solution uniformity is poor, molecular weight distribution is wide, Seriously affect the uniformity and processing stability for preparing Kapton.
Summary of the invention
To be solved by this invention is to cause polyimides thin since polyamic acid solution is inhomogenous, molecular weight distribution is wider The problem of film surface is uneven, technique is unstable and product quality declines.The present invention provides a kind of uniform high-performance polyamides The Kapton surface of the preparation method of imines film, this method preparation is uniform, has excellent performance, and process is easy to stablize Control, and product is not allowed to be also easy to produce defect, can obtain high-performance polyimide product.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows: a kind of uniform high-performance polyimide The preparation method of film is made by polyamic acid stoste through film forming, hot-stretch, hot imidization；Wherein, the polyamic acid stoste Mixed solution including prepolymer solution 1 and prepolymer solution 2；Wherein, the prepolymer solution 1 is by the diamines including X moles It is obtained with the reactant reaction of Y moles of dianhydride；The prepolymer solution 2 is by including Z moles of diamines and K moles of dianhydride Reactant reaction obtains；Described X, Y, Z, K meet: 0.5≤Y/X≤0.98,1.02≤K/Z≤2.0.
In above-mentioned technical proposal, the preparation method preferably includes following steps:
(1) prepared by stoste:
A) X moles of diamines is dissolved in organic solvent, Y moles of dianhydride, which is added to, to carry out reacting in diamine solution To prepolymer solution 1；
B) Z moles of diamines is dissolved in organic solvent, K moles of dianhydride, which is added to, to carry out reacting in diamine solution To prepolymer solution 2；
C) prepolymer solution 2 is added in prepolymer solution 1, is uniformly mixed, then after filtering, deaeration, obtained Polyamic acid stoste；
(2) casting film-forming: the polyamic acid stoste that step (1) is obtained controls thickness by scraper, on smooth steel band Curtain coating obtains polyamic acid wet film；
(3) preliminary drying is handled: the polyamic acid wet film that step (2) obtains is passed through into constant temperature hot stove under inert gas atmosphere, Self-supporting polyamide acid film is obtained, preliminary drying treatment temperature is 50~150 DEG C；
(4) hot-stretch: the polyamide acid film that step (3) is obtained passes through longitudinal stretching and cross directional stretch, obtains stretching poly- Amide sorrel, draft temperature are 100~300 DEG C；
(5) hot imidization: the drawing polyamide sorrel that step (4) is obtained passes through hot imidization, obtains high-performance polyamides Imines film, hot imidization temperature are 200~500 DEG C.
In above-mentioned technical proposal, the polyamic acid is selected from structure shown in general formula (1):
Wherein, Ar1For the tetravalence aromatic residue containing at least one carbon hexatomic ring, more preferably following structural formula (1) aromatic residue shown in
Ar2The tetravalence aromatic residue of at least one carbon hexatomic ring is preferably comprised, more preferably following structural formula (2) institute The aromatic residue shown:
In structure above (2), R2Preferably select H-, CH3-、Cl-、Br-、F-、CH3Any one group such as O-.
In above-mentioned technical proposal, in the polyamic acid stoste dianhydride monomer and diamine monomer total moles ratio be 0.95~ 1.05:1.
In above-mentioned technical proposal, the stoste preparation in step (1) is preferably carried out under inert gas shield；It is described organic Organic solvent in the prior art well-known to those skilled in the art, preferably N, N- dimethyl formyl can be used in solvent In the highly polar aprotic solvent such as amine, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, dimethyl sulfoxide and sulfolane extremely Few one kind；The step a), b) the middle temperature reacted is -10~40 DEG C, preferably 0~30 DEG C；Gained polyamic acid stoste Solid content is 5~30%, more preferably 10~20%；At least one of the preferred nitrogen of the inert gas, argon gas or helium； The reaction mixing speed is usually at 50~600 revs/min, and preferably 100~400 revs/min；Prepolymer solution in step c) 2 addition speed preferably satisfies following formula:
Further preferably meet following formula:
In above-mentioned technical proposal, water content is preferably less than 800ppmw, more preferably 100ppmw in the organic solvent ~300ppmw.
In above-mentioned technical proposal, the filter process of the polyamic acid stoste uses multistage filtering method, and precision is 0.1~ 10μm。
In above-mentioned technical proposal, the de-aeration is vacuum deaerator, improves deaeration efficiency.
In above-mentioned technical proposal, the casting film-forming process by scraper control, polyamic acid wet-film thickness be 40~ 3000 μm, the final thickness of film product is different because of wet-film thickness variation.
In above-mentioned technical proposal, the preliminary drying treatment process carries out in stream of nitrogen gas protection, and preliminary drying treatment temperature is 50 ~150 DEG C, it is contemplated that production efficiency and energy cost, preferably 60~100 DEG C.
In above-mentioned technical proposal, the hot-stretch temperature of the polyamic acid self-supported membrane is 100~300 DEG C；Hot imidization For stepped heating process, imidization temperature is 200~500 DEG C, preferably 250~400 DEG C.
In above-mentioned technical proposal, the longitudinal stretching multiple is preferably 1.0~2.2 times；The transverse stretch ratio is preferred It is 1.0~2.0 times.
Test equipment used in the present invention and test condition are as follows:
Molecular weight and molecular weight distribution: using 200 high temperature GPC of agilent company PL-GPC, using DMF as mobile phase, prepares PAA is the DMF solution sample of 1mg/ml, and molecular weight and its distribution of PAA are tested under 35 DEG C of constant temperatures.
Apparent viscosity: BROOKFIELD DV- III ULTRA PROGRAMMABLE RHEOMETER in the U.S. is adopted at 25 DEG C It is tested with LV-4 rotor.
Thermal decomposition temperature: U.S. TA company Discovery TGA is used, in a nitrogen atmosphere, with 10 DEG C/min rate liter For temperature to 800 DEG C, taking the temperature of thermal weight loss 5wt% is thermal decomposition temperature.
Glass transition temperature: TA company, U.S. Q 800 carries out DMA test, with 10 DEG C/min rate liter under condition of nitrogen gas For temperature to 600 DEG C, the peak temperature for obtaining sample loss tangent change curve is the glass transition temperature of film.
Thermal expansion coefficient: U.S. TA company Q400 tests the dimensional stability of film sample.With the constant drawing of 0.05N Power, the heating of 10 DEG C/min rate, first time temperature-rise period eliminate thermal history, take in second of temperature-rise period and count between 50-200 DEG C According to according to the dimensional stability of its slope calculating thermal expansion coefficient (CTE) characterization PI film.
Thin film mechanics extension test: the dumbbell shape batten that test width is 5mm is made in film, uses U.S. Instron Company's universal testing machine 3344 carries out extension test with constant stretch rate 100mm/min, until batten is broken, record The tensile strength and elongation at break of sample.
Using technical solution of the present invention, obtained Kapton is few using micro- sem observation surfacing, defect, surveys It is good to try film gauge uniformity, 250~500MPa of tensile strength, elongation at break is 5~50%, and 5% temperature of thermal decomposition reaches 600 DEG C or so, glass transition temperature is 300~450 DEG C, and thermal expansion coefficient is 5~50ppm/K, can be at relatively high temperatures Long-time service is not decomposed and is remained dimensionally-stable, and is met in multiple fields to high-performance polyimide film application requirement, is obtained Preferable technical effect.
Specific embodiment
[embodiment 1]
1, prepared by stoste: 0.973kg (9mol) PDA being dissolved in 19kg DMAc, stirs, is completely dissolved at 25 DEG C Afterwards, be added 2.383kg (8.1mol) BPDA, sufficiently reaction after obtain prepolymer solution 1 (dianhydride, diamines molar ratio 0.9, admittedly contain Amount 15%, rear same).0.108kg (1mol) PDA, 3.363kg DMAc, 0.4854kg (1.65mol) are used with same method Prepolymer solution 2 (molar ratio 1.65, solid content 15%) is made in BPDA.Prepolymer solution 2 is added to the speed of 2.0kg/h It in prepolymer solution 1, is sufficiently stirred at 25 DEG C, obtains final polyamic acid solution (molar ratio 0.975, solid content 15%).It surveys The apparent viscosity for obtaining final solution is 23Pas.After solution to be passed through to 2 μm of glass filter membrane, by strainer in ultraviolet fluorescent lamp Irradiate lower foreign.Polyamic acid solution vacuum deaerator after 5 μm and the filtering of 0.5 μm of filtering material, obtain polyamic acid at Film stoste.
2. casting film-forming: it is 500 μm that polyamic acid stoste, which passed through scraper control wet-film thickness, is cast on smooth steel band Film forming.
3. preliminary drying is handled: polyamic acid wet film, by 100 DEG C of hot stoves, removes most of solvent under nitrogen flow atmosphere, Obtain self-supporting polyamide acid film.
4. hot-stretch: self-supporting polyamide acid film, by 1.8 times of longitudinal stretchings and 1.8 times of cross directional stretch, is obtained at 160 DEG C To drawing polyamide sorrel.
5. hot imidization: drawing polyamide sorrel passes through stepped heating hot imidization, obtains high-performance polyimide film, Sequence passes through 200 DEG C of the first warm area, the second 300 DEG C of warm area, the 400 DEG C of imidizations of third warm area.Splitting winding.
Using the smooth zero defect of PI film surface obtained by micro- sem observation, testing film the thickness uniformity is excellent, and film is drawn Stretching intensity is 442MPa, and elongation at break 15% thermally decomposes 605 DEG C of 5% temperature, and glass transition temperature is 441 DEG C, and heat is swollen Swollen coefficient is 2.2ppm/K.
[embodiment 2]
1, prepared by stoste: 1.0814kg (10mol) p-phenylenediamine (PDA) is dissolved in 14.9kg N, N- dimethyl formyl It in amine (DMF), is stirred at 40 DEG C, after being completely dissolved, 2.648kg (9mol) bibenzene tetracarboxylic dianhydride (BPDA) is added, sufficiently Prepolymer solution 1 (molar ratio 0.9, solid content 20%) is obtained after reaction.0.2704kg (2.5mol) is used with same method Prepolymer solution 2 (molar ratio 1.5, solid content 10%) is made in PDA, 10.9kg DMF, 1.1034kg (3.75mol) BPDA.It will Prepolymer solution 2 is added in prepolymer solution 1 with the speed of 2.5kg/h, is sufficiently stirred at 40 DEG C, and final polyamic acid is obtained Solution (molar ratio 1.02, solid content 17.9%).The apparent viscosity for measuring final solution is 91Pas.Solution is passed through 2 μm After glass filter membrane, by strainer under ultraviolet fluorescent light irradiation foreign.Polyamic acid solution passes through 8 μm and 1 μm of filtering material Vacuum deaerator after filtering obtains polyamic acid film forming stoste.
Remaining step is according to embodiment 1.
Using the smooth zero defect of PI film surface obtained by micro- sem observation, testing film the thickness uniformity is excellent, and film is drawn Stretching intensity is 419MPa, and elongation at break 17%, for 5% temperature of thermal decomposition close to 601 DEG C, glass transition temperature is 428 DEG C, Thermal expansion coefficient is 3.4ppm/K.
[embodiment 3]
1, prepared by stoste: 2.0024kg (10mol) ODA being dissolved in 27.2kg DMAc, is stirred at 25 DEG C, completely After dissolution, 2.7949kg (9.5mol) BPDA is added, sufficiently obtains prepolymer solution 1 (molar ratio 0.95, solid content after reaction 15%).It is made with same method using 0.4445kg (2.22mol) ODA, 8.1kg DMAc, 0.9797kg (3.33mol) BPDA Prepolymer solution 2 (molar ratio 1.50, solid content 15%).Prepolymer solution is added with the speed of 9.5kg/h in prepolymer solution 2 It in 1, is sufficiently stirred at 25 DEG C, obtains final polyamic acid solution (molar ratio 1.05, solid content 15%).Measure final solution Apparent viscosity is 122Pas.After solution to be passed through to 2 μm of glass filter membrane, strainer is no different under ultraviolet fluorescent light irradiation Object.Polyamic acid solution vacuum deaerator after 10 μm and 1 μm of filtering material filtering, obtains polyamic acid film forming stoste.
Remaining step is according to embodiment 1.
Using the smooth zero defect of PI film surface obtained by micro- sem observation, testing film the thickness uniformity is excellent, and film is drawn Stretching intensity is 328MPa, and elongation at break 29%, for 5% temperature of thermal decomposition close to 561 DEG C, glass transition temperature is 379 DEG C, Thermal expansion coefficient is 34.3ppm/K.
[embodiment 4]
1, prepared by stoste: 1.0814kg (10mol) p-phenylenediamine (PDA) is dissolved in 8.7kg N,N-dimethylformamide (DMF) it in, is stirred at -10 DEG C, after being completely dissolved, 2.648kg (9mol) bibenzene tetracarboxylic dianhydride (BPDA) is added, it is sufficiently anti- Should after obtain prepolymer solution 1 (molar ratio 0.9, solid content 30%).0.0636kg (0.588mol) is used with same method Prepolymer solution 2 (molar ratio 1.8, solid content 30%) is made in PDA, 0.874kg DMF, 0.311kg (1.058mol) BPDA.It will Prepolymer solution 2 is added in prepolymer solution 1 with the speed of 2.4kg/h, is sufficiently stirred at -10 DEG C, and final polyamide is obtained Acid solution (molar ratio 0.95, solid content 30%).The apparent viscosity for measuring final solution is 39Pas.Solution is passed through 2 μm After glass filter membrane, by strainer, foreign is generated under ultraviolet fluorescent light irradiation.Polyamic acid solution passes through 6 μm and 0.1 μm of mistake Vacuum deaerator after filter filtration of material obtains polyamic acid film forming stoste.
Remaining step is according to embodiment 1.
Using the smooth zero defect of PI film surface obtained by micro- sem observation, testing film the thickness uniformity is excellent, and film is drawn Stretching intensity is 410MPa, and elongation at break 12%, for 5% temperature of thermal decomposition close to 585 DEG C, glass transition temperature is 394 DEG C, Thermal expansion coefficient is 7.9ppm/K.
[embodiment 5]
1, prepared by stoste: 2.0024kg (10mol) ODA being dissolved in 27.8kg N-Methyl pyrrolidone (NMP), 0 It is stirred at DEG C, after being completely dissolved, 1.0906kg (5mol) PMDA is added, sufficiently obtains 1 (molar ratio of prepolymer solution after reaction 0.5, solid content 10%).1.0012kg (5mol) ODA, 28.6416kg NMP, 2.1812kg (10mol) are used with same method Prepolymer solution 2 (molar ratio 2.0, solid content 10%) is made in PMDA.By 31.82kg prepolymer solution 2 with the speed of 5.3kg/h It is added in prepolymer solution 1, is sufficiently stirred at 0 DEG C, obtain final polyamic acid solution (molar ratio 1.0, solid content 10%). The apparent viscosity for measuring final solution is 138Pas.After solution to be passed through to 2 μm of glass filter membrane, by strainer in ultraviolet fluorescent Foreign generates under light irradiation.Polyamic acid solution vacuum deaerator after 7 μm and 0.4 μm of filtering material filtering, obtains polyamides Amino acid film forming stoste.
Remaining step is according to embodiment 1.
Using the smooth zero defect of PI film surface obtained by micro- sem observation, testing film the thickness uniformity is excellent, and film is drawn Stretching intensity is 341MPa, and elongation at break 26%, for 5% temperature of thermal decomposition close to 573 DEG C, glass transition temperature is 408 DEG C, Thermal expansion coefficient is 42.8ppm/K.
[embodiment 6]
1, prepared by stoste: 1.8022kg (9mol) ODA is dissolved in 32.9kg NMP, is stirred at 10 DEG C, it is completely molten Xie Hou is added 1.854kg (8.5mol) PMDA, sufficiently obtains prepolymer solution 1 (molar ratio 0.944, solid content after reaction 10%).It is made with same method using 0.1081kg (1mol) PDA, 5.4750kg DMAc, 0.5002kg (1.7mol) BPDA Prepolymer solution 2 (molar ratio 1.7, solid content 10%).6.0833kg prepolymer solution 2 is added to the speed of 3kg/h pre- It in oligomer solution 1, is sufficiently stirred at 10 DEG C, obtains final polyamic acid solution (molar ratio 1.02, solid content 10%).It measures most The apparent viscosity of whole solution is 26Pas.After solution to be passed through to 2 μm of glass filter membrane, by strainer in ultraviolet fluorescent light irradiation Lower foreign generates.Polyamic acid solution vacuum deaerator after 9 μm and the filtering of 0.7 μm of filtering material, obtain polyamic acid at Film stoste.
Remaining step is according to embodiment 1.
Using the smooth zero defect of PI film surface obtained by micro- sem observation, testing film the thickness uniformity is excellent, and film is drawn Stretching intensity is 394MPa, and elongation at break 21%, for 5% temperature of thermal decomposition close to 589 DEG C, glass transition temperature is 410 DEG C, Thermal expansion coefficient is 20.4ppm/K.
[embodiment 7]
1, prepared by stoste: 2.0024kg (10mol) ODA being dissolved in 44.1kg DMSO, is stirred at 30 DEG C, completely After dissolution, 2.9001kg (9mol) 3,3 ', 4,4 '-benzophenone tetracid dianhydride (BTDA) is added, sufficiently obtains performed polymer after reaction Solution 1 (molar ratio 0.9, solid content 10%).With same method using 0.553kg (2.76mol) ODA, 17.0kg DMSO, Prepolymer solution 2 (molar ratio 1.5, solid content 10%) is made in 1.3339kg (4.14mol) BTDA.By prepolymer solution 2 with The speed of 10kg/h is added in prepolymer solution 1, is sufficiently stirred at 30 DEG C, and final polyamic acid solution (molar ratio is obtained 1.05, solid content 10%).The apparent viscosity for measuring final solution is 96Pas.It, will after solution to be passed through to 2 μm of glass filter membrane Strainer foreign under ultraviolet fluorescent light irradiation.Polyamic acid solution depressurizes de- after 8 μm and 0.3 μm of filtering material filtering Bubble obtains polyamic acid film forming stoste.
Remaining step is according to embodiment 1.
Using the smooth zero defect of PI film surface obtained by micro- sem observation, testing film the thickness uniformity is excellent, and film is drawn Stretching intensity is 337MPa, and elongation at break 20%, for 5% temperature of thermal decomposition close to 579 DEG C, glass transition temperature is 403 DEG C, Thermal expansion coefficient is 23.0ppm/K.
[embodiment 8]
1, prepared by stoste: 1.802kg (9mol) ODA is dissolved in 25.6kg DMAc, is stirred at 20 DEG C, it is completely molten Xie Hou, be added 2.730kg (8.8mol) 4,4 '-biphenyl ether dianhydride (ODPA), sufficiently reaction after obtain solution A (molar ratio 0.98, Solid content 15%).0.108kg (1mol) PDA, 2.546kg DMAc, 0.341kg (1.1mol) ODPA system are used with same method It obtains prepolymer solution 2 (molar ratio 1.1, solid content 15%).It is molten that prepolymer solution 2 with the speed of 3kg/h is added to performed polymer It in liquid 1, is sufficiently stirred at 20 DEG C, obtains final polyamic acid solution (molar ratio 0.99, solid content 15%).Measure final solution Apparent viscosity be 1.1Pas.After solution to be passed through to 2 μm of glass filter membrane, strainer is no different under ultraviolet fluorescent light irradiation Object.Polyamic acid solution vacuum deaerator after 6 μm and 0.2 μm of filtering material filtering, obtains polyamic acid film forming stoste.
Remaining step is according to embodiment 1.
Using the smooth zero defect of PI film surface obtained by micro- sem observation, testing film the thickness uniformity is excellent, and film is drawn Stretching intensity is 276MPa, and elongation at break 41%, for 5% temperature of thermal decomposition close to 544 DEG C, glass transition temperature is 347 DEG C, Thermal expansion coefficient is 46.6ppm/K.
[embodiment 9]
1, prepared by stoste: 1.8022kg (9mol) ODA is dissolved in 67.810kg DMAc, is stirred at -10 DEG C, it is complete After fully dissolved, 1.7668kg (8.1mol) PMDA is added, sufficiently obtains prepolymer solution 1 (molar ratio 0.9, solid content after reaction 5%).It is made pre- using 0.2002kg (1mol) ODA, 10.85kg DMAc, 0.3708kg (1.7mol) PMDA with same method Oligomer solution 2 (molar ratio 1.7, solid content 5%).Prepolymer solution 2 is added to prepolymer solution 1 with the speed of 3.8kg/h In, it is sufficiently stirred at -10 DEG C, obtains final polyamic acid solution (molar ratio 0.98, solid content 5%).Measure final solution Apparent viscosity is 0.8Pas.After solution to be passed through to 2 μm of glass filter membrane, strainer is no different under ultraviolet fluorescent light irradiation Object.Polyamic acid solution vacuum deaerator after 4 μm and 0.1 μm of filtering material filtering, obtains polyamic acid film forming stoste.
Remaining step is according to embodiment 1.
Using the smooth zero defect of PI film surface obtained by micro- sem observation, testing film the thickness uniformity is excellent, and film is drawn Stretching intensity is 323MPa, and elongation at break 19%, for 5% temperature of thermal decomposition close to 566 DEG C, glass transition temperature is 381 DEG C, Thermal expansion coefficient is 41.4ppm/K.
[embodiment 10]
1, prepared by stoste: according to the stoste preparation process of embodiment 1.
2, casting film-forming: according to the casting film-forming process of embodiment 1.
3, preliminary drying is handled: polyamic acid wet film, by 100 DEG C of hot stoves, obtains self-supporting polyamides under nitrogen flow atmosphere Amino acid film.
4, hot-stretch: self-supporting polyamide acid film is at 200 DEG C, by 2.0 times of longitudinal stretchings and 1.5 times of cross directional stretch.
5, hot imidization: drawing polyamide sorrel carries out hot imidization by 3 stages, sequentially passes through the first warm area 280 DEG C, the second 330 DEG C of warm area, 380 DEG C of third warm area.Splitting winding.
Using the smooth zero defect of PI film surface obtained by micro- sem observation, testing film the thickness uniformity is excellent, and film is drawn Stretching intensity is 438MPa, and elongation at break 13% thermally decomposes 606 DEG C of 5% temperature, and glass transition temperature is 432 DEG C, and heat is swollen Swollen coefficient is 5.7ppm/K.
[embodiment 11]
1, prepared by stoste: according to the stoste preparation process of embodiment 1.
2, casting film-forming: polyamic acid stoste is 3000 μm by scraper control wet-film thickness, is cast on smooth steel band Film forming.
3, preliminary drying is handled: polyamic acid wet film, by 150 DEG C of hot stoves, obtains self-supporting polyamides under nitrogen flow atmosphere Amino acid film.
Remaining step is according to embodiment 1.
Using the smooth zero defect of PI film surface obtained by micro- sem observation, testing film the thickness uniformity is excellent, and film is drawn Stretching intensity is 429MPa, and elongation at break 12% thermally decomposes 582 DEG C of 5% temperature, and glass transition temperature is 409 DEG C, and heat is swollen Swollen coefficient is 11.8ppm/K.
[embodiment 12]
1, prepared by stoste: according to the stoste preparation process of embodiment 1.
2, casting film-forming, preliminary drying processing: according to 1 process of embodiment.
3, hot-stretch: self-supporting polyamide acid film is at 300 DEG C, by 1.5 times of longitudinal stretchings and 1.2 times of cross directional stretch.
Remaining step is according to embodiment 1.
Using the smooth zero defect of PI film surface obtained by micro- sem observation, testing film the thickness uniformity is excellent, and film is drawn Stretching intensity is 404MPa, and elongation at break 16% thermally decomposes 592 DEG C of 5% temperature, and glass transition temperature is 417 DEG C, and heat is swollen Swollen coefficient is 6.6ppm/K.
[embodiment 13]
1, prepared by stoste: according to the stoste preparation process of embodiment 1.
2, casting film-forming, preliminary drying processing, hot-stretch: according to 1 process of embodiment.
3, hot imidization: drawing polyamide sorrel carries out hot imidization by 3 stages, sequentially passes through the first warm area 250 DEG C, the second 350 DEG C of warm area, 500 DEG C of third warm area.Splitting winding.
Using the smooth zero defect of PI film surface obtained by micro- sem observation, testing film the thickness uniformity is excellent, and film is drawn Stretching intensity is 462MPa, and elongation at break 8% thermally decomposes 615 DEG C of 5% temperature, and glass transition temperature is 457 DEG C, and heat is swollen Swollen coefficient is 3.6ppm/K.
[embodiment 14]
1, prepared by stoste: according to the stoste preparation process of embodiment 1.
2, casting film-forming: polyamic acid stoste is 40 μm by scraper control wet-film thickness, is cast on smooth steel band Film.
3, preliminary drying is handled: polyamic acid wet film, by 50 DEG C of hot stoves, removes most of solvent under nitrogen flow atmosphere, Obtain self-supporting polyamide acid film.
4, hot-stretch: self-supporting polyamide acid film is at 100 DEG C, by 1.7 times of longitudinal stretchings and 1.1 times of cross directional stretch.
Remaining step is according to embodiment 1.
Using the smooth zero defect of PI film surface obtained by micro- sem observation, testing film the thickness uniformity is excellent, and film is drawn Stretching intensity is 402MPa, and elongation at break 17% thermally decomposes 593 DEG C of 5% temperature, and glass transition temperature is 411 DEG C, and heat is swollen Swollen coefficient is 8.5ppm/K.
[embodiment 15]
1, prepared by stoste: according to the stoste preparation process of embodiment 1.
2, casting film-forming: polyamic acid stoste is 1000 μm by scraper control wet-film thickness, is cast on smooth steel band Film forming.
3, preliminary drying is handled: polyamic acid wet film, by 100 DEG C of hot stoves, removes most of solvent under nitrogen flow atmosphere, Obtain self-supporting polyamide acid film.
4, hot-stretch: self-supporting polyamide acid film, by 2.2 times of longitudinal stretchings and 1.2 times of cross directional stretch, is obtained at 200 DEG C To drawing polyamide sorrel.
5, hot imidization: drawing polyamide sorrel passes through stepped heating hot imidization, obtains high-performance polyimide film, Sequence pass through 200 DEG C of the first warm area, the second 300 DEG C of warm area, 350 DEG C of third warm area, the imidization of 400 DEG C of four-temperature region.Cutting is received Volume.
Using the smooth zero defect of PI film surface obtained by micro- sem observation, testing film the thickness uniformity is excellent, and film is stretched Intensity is 454MPa, and elongation at break 10% thermally decomposes 615 DEG C of 5% temperature, and glass transition temperature is 447 DEG C, thermal expansion Coefficient is 2.7ppm/K.
[comparative example 1]
1, prepared by stoste: 1.001kg (5mol) diphenyldiamine (ODA) is dissolved in 11.8kg N, N- dimethylacetamide It in amine (DMAc), is stirred at 25 DEG C, after being completely dissolved, 1.084kg (4.97mol) pyromellitic acid dianhydride (PMDA) powder is added End sufficiently obtains polyamic acid solution after reaction, above-mentioned experiment in triplicate, and the apparent viscosity for measuring final solution is respectively 281Pas, 304Pas and 295Pas, stability is not so good as embodiment 1 between batch.Solution is passed through to 2 μm of glass filter membrane Afterwards, strainer there are into a large amount of white foreign matters under ultraviolet fluorescent light irradiation.
Remaining step prepares PI film according to embodiment 1.
Using PI film surface obtained by micro- sem observation, there are a large amount of defects.Testing film the thickness uniformity is poor, film Tensile strength be 186MPa, elongation at break 19%, thermally decompose 579 DEG C of 5% temperature, glass transition temperature be 388 DEG C, Thermal expansion coefficient is 42.2ppm/K.
[comparative example 2]
1, prepared by stoste: 1.001kg (5mol) diphenyldiamine (ODA) is dissolved in 11.8kg N, N- dimethylacetamide In amine (DMAc), is stirred in the case where 25 DEG C of N2 are protected, after being completely dissolved, be added at one time 1.084kg (4.97mol) pyromellitic acid two Acid anhydride (PMDA) continues after charging in 25 DEG C of sufficiently reactions.After tested, which is in 25 DEG C, apparent viscosity Strainer is had a large amount of white foreign matters after solution to be passed through to 2 μm of glass filter membrane by 181Pas under ultraviolet fluorescent light irradiation.
Remaining step prepares PI film according to embodiment 1.
Using PI film surface obtained by micro- sem observation, there are a large amount of defects.Testing film the thickness uniformity is poor, performance Lower, the tensile strength of film is 230MPa, and elongation at break 9% thermally decomposes 583 DEG C of 5% temperature, glass transition temperature It is 376 DEG C, thermal expansion coefficient 37.3ppm/K.
[comparative example 3]
1, prepared by stoste: the 4,4 '-diphenyldiamines of 2.0024kg (10mol) are dissolved in 23.7kgN, N- dimethyl second In amide, N at room temperature2Protection stirring to monomer is completely dissolved, and 2.1812kg (10mol) pyromellitic acid dianhydride powder is added, 0 It is stirred under the conditions of DEG C temperature, being uniformly mixing to obtain solid content is 7.0% thick pale yellow solution.
2, casting film-forming: polyamic acid stoste is 2000 μm by scraper control wet-film thickness, is cast on smooth steel band Film forming.
3, preliminary drying is handled: polyamic acid wet film, by 150 DEG C of hot stoves, removes most of solvent under nitrogen flow atmosphere, Obtain self-supporting polyamide acid film.
4, hot-stretch: self-supporting polyamide acid film, by 1.5 times of longitudinal stretchings and 1.5 times of cross directional stretch, is obtained at 150 DEG C To drawing polyamide sorrel.
5, hot imidization: drawing polyamide sorrel passes through stepped heating hot imidization, obtains high-performance polyimide film, Sequence passes through 300 DEG C of the first warm area, the second 350 DEG C of warm area, the 400 DEG C of imidizations of third warm area.Splitting winding.
Using PI film surface obtained by micro- sem observation, there are a large amount of defects.Testing film the thickness uniformity is poor, performance Lower, gained film tensile strength is 249MPa, and elongation at break 13% thermally decomposes 572 DEG C of 5% temperature, glass transition Temperature is 369 DEG C, thermal expansion coefficient 38ppm/K.

Claims (10)

1. a kind of preparation method of Kapton is made by polyamic acid stoste through film forming, hot-stretch, hot imidization；Its It is characterized in that the polyamic acid stoste includes the mixed solution of prepolymer solution 1 and prepolymer solution 2；Wherein, the pre-polymerization Liquid solution 1 is obtained by the reactant reaction of diamines and Y moles of dianhydride including X moles；The prepolymer solution 2 is by including Z Mole diamines and the reactant reaction of K moles of dianhydride obtain；Described X, Y, Z, K meet: 0.5≤Y/X≤0.98,1.02≤ K/Z≤2.0。
2. the preparation method of Kapton according to claim 1, which is characterized in that the preparation method is specific The following steps are included:
(1) prepared by polyamic acid stoste:
A) X moles of diamines is dissolved in organic solvent, Y moles of dianhydride be added in diamine solution reacted to obtain it is pre- Oligomer solution 1；
B) Z moles of diamines is dissolved in organic solvent, K moles of dianhydride be added in diamine solution reacted to obtain it is pre- Oligomer solution 2；
C) prepolymer solution 2 is added in prepolymer solution 1, is uniformly mixed, then after filtering, deaeration, obtain polyamides Amino acid stoste；
(2) casting film-forming: the polyamic acid stoste that step (1) is obtained controls thickness by scraper, is cast on smooth steel band Obtain polyamic acid wet film；
(3) preliminary drying is handled: the polyamic acid wet film that step (2) obtains being passed through constant temperature hot stove under inert gas atmosphere, is obtained Self-supporting polyamide acid film, preliminary drying treatment temperature are 50~150 DEG C；
(4) hot-stretch: the polyamide acid film that step (3) is obtained passes through longitudinal stretching, cross directional stretch, obtains drawing polyamide acid Film, draft temperature are 100~300 DEG C；
(5) hot imidization: the drawing polyamide sorrel that step (4) is obtained passes through hot imidization, obtains high-performance polyimide Film, hot imidization temperature are 200~500 DEG C.
3. the preparation method of Kapton according to claim 1, which is characterized in that the polyamic acid is selected from Structure shown in general formula (1):
Wherein, Ar1For the tetravalence aromatic residue containing at least one carbon hexatomic ring, Ar2To contain at least one carbon hexatomic ring O divalent aromatic residue.
4. the preparation method of Kapton according to claim 1, which is characterized in that the polyamic acid stoste Middle dianhydride monomer and diamine monomer total moles ratio are 0.95~1.05:1.
5. the preparation method of Kapton according to claim 1, it is characterised in that performed polymer is molten in step c) The addition speed of liquid 2 meets following formula:
6. the preparation method of Kapton according to claim 1, which is characterized in that the organic solvent choosing From at least one of N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone and dimethyl sulfoxide.
7. the preparation method of Kapton according to claim 1, which is characterized in that anti-in the step (1) The temperature answered is -10~40 DEG C；The solid content of the polyamic acid stoste is 5~30%.
8. the preparation method of Kapton according to claim 1, it is characterised in that the polyamic acid is former Liquid filter process uses multistage filtering method, and precision is 0.1~10 μm.
9. the preparation method of Kapton according to claim 1, it is characterised in that the casting film-forming process Controlling polyamic acid wet-film thickness by scraper is 40~3000 μm.
10. the preparation method of Kapton according to claim 1, it is characterised in that the polyamic acid solution De-aeration is vacuum deaerator.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111087632A (en) * 2018-10-23 2020-05-01 中国石油化工股份有限公司 Preparation method of block type colorless transparent polyimide film, film and transparent substrate
CN114369361A (en) * 2021-12-31 2022-04-19 广州惠利电子材料有限公司 Insulating PI membrane material
CN115260492A (en) * 2022-06-14 2022-11-01 安徽国风新材料股份有限公司 Preparation method of polyimide film with low thermal expansion coefficient

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JPH0895054A (en) * 1994-09-22 1996-04-12 Sharp Corp Liquid crystal display element and manufacture thereof
KR20100138787A (en) * 2009-06-25 2010-12-31 짓쏘 가부시끼가이샤 Liquid crystal aligning agents, liquid crystal aligning layers and liquid crystal display devices
CN104327291A (en) * 2014-09-23 2015-02-04 青岛文创科技有限公司 Polyimide composite film preparation method

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JPH0895054A (en) * 1994-09-22 1996-04-12 Sharp Corp Liquid crystal display element and manufacture thereof
KR20100138787A (en) * 2009-06-25 2010-12-31 짓쏘 가부시끼가이샤 Liquid crystal aligning agents, liquid crystal aligning layers and liquid crystal display devices
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Publication number Priority date Publication date Assignee Title
CN111087632A (en) * 2018-10-23 2020-05-01 中国石油化工股份有限公司 Preparation method of block type colorless transparent polyimide film, film and transparent substrate
CN111087632B (en) * 2018-10-23 2022-11-04 中国石油化工股份有限公司 Preparation method of block type colorless transparent polyimide film, film and transparent substrate
CN114369361A (en) * 2021-12-31 2022-04-19 广州惠利电子材料有限公司 Insulating PI membrane material
CN115260492A (en) * 2022-06-14 2022-11-01 安徽国风新材料股份有限公司 Preparation method of polyimide film with low thermal expansion coefficient
CN115260492B (en) * 2022-06-14 2024-04-26 安徽国风新材料股份有限公司 Preparation method of polyimide film with low thermal expansion coefficient

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