CN112812336B - Preparation method of polyimide composite film - Google Patents
Preparation method of polyimide composite film Download PDFInfo
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- CN112812336B CN112812336B CN202011605283.4A CN202011605283A CN112812336B CN 112812336 B CN112812336 B CN 112812336B CN 202011605283 A CN202011605283 A CN 202011605283A CN 112812336 B CN112812336 B CN 112812336B
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 92
- 239000004642 Polyimide Substances 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000835 fiber Substances 0.000 claims abstract description 108
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 84
- 238000007790 scraping Methods 0.000 claims abstract description 45
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000009987 spinning Methods 0.000 claims description 20
- 239000011521 glass Substances 0.000 claims description 18
- 229910001220 stainless steel Inorganic materials 0.000 claims description 17
- 239000010935 stainless steel Substances 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 7
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 6
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- QBAZWXKSCUESGU-UHFFFAOYSA-N yttrium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QBAZWXKSCUESGU-UHFFFAOYSA-N 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229920002939 poly(N,N-dimethylacrylamides) Polymers 0.000 claims description 4
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000003892 spreading Methods 0.000 claims description 3
- 230000007480 spreading Effects 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 238000010009 beating Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 claims description 2
- 230000008595 infiltration Effects 0.000 claims 1
- 238000001764 infiltration Methods 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000013329 compounding Methods 0.000 abstract description 5
- 239000012528 membrane Substances 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 7
- 150000004985 diamines Chemical class 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- 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
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K7/02—Fibres or whiskers
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Abstract
The invention discloses a preparation method of a polyimide composite film, which belongs to the technical field of polyimide films and at least comprises the following steps: 1. preparing oxide fiber paper; 2. preparing a polyimide acid solution; 3. film scraping and compounding; 4. drying; 5. imidization molding. The performance control of the composite membrane is realized by controlling the unit area density, imidization time, film scraping thickness and the like of the fiber paper, and the corona resistance and the structural performance of the composite membrane are controlled. According to the invention, the polyimide and oxide fiber paper are compounded, so that the production process of the polyimide composite film is simplified, the production time is reduced, and the production efficiency is improved. Meanwhile, the structural strength of the polyimide composite film is enhanced by utilizing the high tensile strength of the alumina fiber and the zirconia fiber, and the high-temperature stability and corona resistance of the polyimide film are improved.
Description
Technical Field
The invention belongs to the technical field of polyimide films, and relates to a polyimide composite film, in particular to a preparation method of the polyimide composite film.
Background
The polyimide film is a polymer film containing polyimide rings in molecular chains, and has the characteristics of high strength, radiation resistance, chemical corrosion resistance, high temperature resistance, electric insulation and the like. Therefore, the method is widely applied in the fields of electric, mechanical, aerospace, military industry and the like. The polyimide film is widely used as a motor slot insulating and cable winding material in the field of high-performance electronics due to the characteristic of electric insulation. The market is currently monopolized by several enterprises of dupont, japan department of encyclopedia, brillouin chemistry, mitsubishi gas, korea SKC, and the like.
In the field of high-performance electronic application, the preparation process of the polyimide film mainly utilizes the performances of low heat conductivity, high temperature resistance, chemical stability and the like of inorganic nano particles (silicon oxide, zirconium oxide, aluminum oxide and the like), adopts a sol-gel doping mode to add and disperse in polyimide acid liquid (PAA), and then imidizes to prepare the polyimide composite film hybridized by the nano aluminum oxide particles. The method is limited by the agglomeration of nano particles and the high viscosity of polyimide dispersion liquid, and the prepared film has the defects of poor dispersion uniformity, poor corona resistance and unstable performance of hybridized particles.
Disclosure of Invention
The invention aims to solve the problems of poor dispersion uniformity, low corona resistance and instability of inorganic nano particles in a polyimide film in the prior art, improve the existing polyimide film manufacturing process and improve the physicochemical properties of the polyimide film by compounding with alumina or zirconia fiber paper.
Based on the above objects, the present invention utilizes inorganic fibers such as zirconia fibers and alumina fibers, which have properties such as low thermal conductivity, high temperature resistance, chemical stability, micro-nano effect, etc. as compared with nanoparticles thereof, and have the advantages of composite reinforcement and easy pretreatment (in the form of a net structure, paper, etc.) which the particles do not have. After the polyimide film is formed into a certain prefabricated member, the polyimide film is compounded with polyimide, so that the defect of uneven dispersion is overcome, the dispersion uniformity of the PAA acid solution in the film forming process is improved, and meanwhile, the matrix film is well reinforced. Specifically, the invention discloses a preparation method of a polyimide composite film, which at least comprises the following steps:
step 1: adding oxide fibers into a high-speed fluffer, performing high-speed fluffing and shorting on the oxide fibers at a rotating speed of 2000r/min-5000r/min, preferably, adjusting the rotating speed of the high-speed fluffer to 2500r/min-3000r/min and 3500r/min-4500r/min to ensure that the length of the oxide fibers reaches 0.5mm-5mm, transferring the fluffed slurry into a vertical mixer for slurry mixing, adding an inorganic adhesive, wherein the inorganic adhesive is water glass or silica sol, and the adding amount is controlled to be 0.1 percent of the total slurry mass-5%, then forming on a sheet machine to obtain wet blank of paper, drying in a drying oven at 100-110 deg.C to obtain the invented product whose unit area density is 40g/m 2 -400g/m 2 Oxide fiber paper with the thickness of 50-500 μm is ready for use;
step 2: the molar ratio is 1: (0.95-1.05) respectively weighing pyromellitic anhydride (PMDA, dianhydride for short) and 4,4 '-diaminodiphenyl ether (ODA, diamine for short), dissolving the diamine in a solvent N, N' -Dimethylacetamide (DMAC), stirring until the diamine is completely dissolved, adding the PDMA into the solution for 5-10 times, and stirring until the monomers completely react to obtain a polyimide acid solution with the viscosity of 400-1000 mPa.s;
step 3: cutting the oxide fiber paper prepared in the step 1 into a rectangle or square, adapting the cutting size to an automatic film scraping machine, then spreading the rectangle or square on a bearing plate which is smooth and difficult to adhere and can be a glass plate or a smooth stainless steel plate of the surface of the automatic film scraping machine, pouring the polyimide acid liquor prepared in the step 2 on the surface of the oxide fiber paper on one side of the bearing plate, adjusting the film scraping thickness parameter of the automatic film scraping machine to be 0-2mm, setting the film scraping speed to be 0-1m/min, setting the film scraping mode to be intermittent film scraping, and scraping the polyimide acid liquor on the surface of the oxide fiber paper by using the automatic film scraping machine to obtain a fiber paper composite prefabricated material with smooth and well-immersed surface;
step 4: placing the fiber paper composite prefabricated material prepared in the step 3 on a glass plate or a stainless steel plate, then placing the glass plate or the stainless steel plate into a drying box, and drying the glass plate or the stainless steel plate for 10-80min at 70-90 ℃ for at most 120min to prepare a dried pre-composite film;
step 5: scraping the pre-composite film prepared in the step 4 from a glass plate or a stainless steel plate, then placing the pre-composite film into a muffle furnace, and imidizing the pre-composite film for 40-90min at 280-350 ℃ to prepare the polyimide composite film.
Preferably, the oxide fibers are alumina fibers or zirconia fibers.
Preferably, the alumina fibers are made of AlCl 3 Reacting 6H2O (AR) with micron-sized aluminum powder to obtain the product with solid content of 8-20% and PH value of 3.0-4.0Contains Al 2 O 3 Silica sol and spinning aid PEO are then added and concentrated to a viscosity of between 500mpa.s and 5000mpa.s, and alumina fibres with a diameter of between 1 and 8 μm are produced by centrifugal spinning.
Preferably, siO in the silica sol 2 The mass fraction of the spinning auxiliary PEO is between 10 and 40 percent, and the addition amount of the spinning auxiliary PEO is Al 2 O 3 1-5% of mass fraction.
Preferably, the zirconia fiber is prepared by reacting basic zirconium carbonate with acetic acid in a molar ratio of 1 (1.5-2.0), adding yttrium nitrate hexahydrate as a stabilizer, adding PVA as a spinning aid, concentrating to a viscosity of 500mPa.s-5000mPa.s, and preparing the zirconia fiber with a diameter of 1-8 mu m by a centrifugal spinning method.
Preferably, the adding amount of the yttrium nitrate hexahydrate is 8-12% of the mass fraction of the zirconia, and the adding amount of the PVA is 1-5% of the mass fraction of the zirconia.
Preferably, the automatic film scraping machine has a film scraping size of L310mm and W250mm, the film scraping speed is 0-5m/min, the film scraping mode is intermittent film scraping, and the film scraping thickness is 0-2mm.
Preferably, after the oxide fiber paper is placed on the bearing plate, a layer of DMAC solution is sprayed on the surface of the oxide fiber paper, and the oxide fiber paper is sprayed to the oxide fiber paper.
Preferably, the beating concentration of the oxide fiber is 0.5-2.5%.
Preferably, the thickness of the polyimide acid coating is 0.5-2mm.
The invention has the beneficial effects that: 1. the mode of compounding polyimide and oxide fiber paper simplifies the production process of the polyimide composite film, reduces the production time and improves the production efficiency. 2. The polyimide and the fiber paper are compounded, so that the structural strength of the polyimide composite film can be enhanced by utilizing the high tensile strength of the alumina fiber and the zirconia fiber, and the high-temperature stability of the polyimide film can be improved. 3. The polyimide and the fiber paper are compounded, so that the chemical resistance of the alumina fiber and the zirconia fiber can be utilized, and the chemical stability of the porous membrane is further improved. 4. The bonding performance of polyimide and oxide fiber paper is utilized, so that the lap joint performance among fibers in the fiber paper is improved, the brittleness of ceramic fibers is overcome, and the fiber paper is endowed with good flexibility. 5. The corona resistance of the polyimide composite film is obviously improved, and the defect that the corona resistance of the polyimide film in the prior art is unstable is overcome.
Drawings
The invention will be further described with reference to the drawings and examples.
Fig. 1 is a polyimide composite film prepared by a polyimide composite film preparation method according to an embodiment of the present invention.
Detailed Description
The following detailed description of embodiments of the invention is exemplary and intended to be illustrative of the invention and not to be construed as limiting the invention.
Example 1
A preparation method of a polyimide composite film comprises the following steps:
step 1 (preparation of zirconia fiber):
zirconium hydroxide with the mol ratio of 1:1.8 is reacted with acetic acid, then yttrium nitrate hexahydrate is added as a stabilizer, PVA is added as a spinning auxiliary agent and is concentrated to the viscosity of between 3500mPa.s and 4000mPa.s, wherein the adding amount of the yttrium nitrate hexahydrate is 10 percent of the mass fraction of zirconia, the adding amount of the PVA is 3.5 percent of the mass fraction of zirconia, and the zirconia fiber with the diameter of between 2 mu m and 5 mu m is obtained by sintering at the high temperature of 1000 ℃ to 1300 ℃ after spinning by a centrifugal spinning method.
Step 2 (preparation of zirconia fiber paper):
adding the zirconia fiber prepared in the step 1 into a high-speed fluffer, performing high-speed fluffing and shorting on the zirconia fiber at the rotating speed of 2500r/min-3000r/min to ensure that the length of the zirconia fiber reaches 1.0mm-3.5mm, transferring the fluffed slurry into a vertical mixer for slurry mixing, and adding an inorganic adhesive and an inorganic adhesiveThe additive amount is controlled to be 3.0 percent of the total slurry mass, and then the wet blank of the paper is obtained by molding on a sheet making machine, and the wet blank is dried for 60 minutes in a drying box at the temperature of 100-110 ℃ to obtain the paper with the density of 40g/m per unit area 2 -60g/m 2 Zirconia fiber paper with the thickness of 50-120 mu m is ready for use;
step 3 (preparation of polyimide acid solution):
the molar ratio is 1:1.01 respectively weighing pyromellitic anhydride (PMDA, dianhydride for short) and 4,4 '-diaminodiphenyl ether (ODA, diamine for short), dissolving the diamine in a solvent N, N' -Dimethylacetamide (DMAC), stirring until the diamine is completely dissolved, adding PDMA into the solution for 8 times, and stirring until the monomers are completely reacted to obtain a polyimide acid solution with the viscosity of 600-750 mPa.s;
step 4 (composite):
taking the thickness of 75 mu m and the density per unit area of 43.11g/m obtained in the step 2 2 Cutting zirconia fiber paper into a rectangle with the thickness of 200mm and 150mm, then spreading the rectangle on a bearing plate with the smooth surface and difficult adhesion of an automatic film scraping machine, wherein the bearing plate is a glass plate with the thickness of 6mm, spraying DMAC solution on the surface of the zirconia fiber paper until the zirconia fiber paper is soaked, then introducing polyimide acid liquor with the viscosity of 680 mPa.s prepared in the step 2 into the surface of the zirconia fiber paper on one side of the bearing plate, adjusting the film scraping parameter of the automatic film scraping machine to be 1mm, setting the film scraping speed to be 0.5m/min, setting the film scraping mode to be intermittent film scraping, and utilizing the automatic film scraping machine to scrape the polyimide acid liquor on the surface of the zirconia fiber paper to obtain a fiber paper composite prefabricated material with the smooth surface and good soaking;
step 5 (dry):
placing the fiber paper composite prefabricated material prepared in the step 4 on a glass plate or a stainless steel plate, then placing the glass plate or the stainless steel plate into a drying box, and drying the glass plate or the stainless steel plate for 60 minutes at 80 ℃ to prepare a dried pre-composite film;
step 6 (imidization molding):
the pre-composite film prepared in step 5 was scraped off from a glass plate or a stainless steel plate, and then put into a muffle furnace, imidized at 330 ℃ for 60min, to prepare a polyimide composite film, as shown in fig. 1.
Step 7 (detection):
measuring and weighing the polyimide film obtained in the step 6 to obtain a polyimide film with a thickness of 75 mu m and a density of 43.12g/m per unit area 2 Samples were prepared with reference to standard NB/T21020-2011, tested for corona resistance at 20KHZ,3000V (+ -1500), pulse rise time of 100ns, pulse duty cycle of 50%, corona breakdown resistance time of 34min, sample preparation with reference to standard GB/T13542.2-2009, tensile strength of 127MPa, elongation at break of 0.2%.
Example 2
The thickness of the polyimide film obtained in step 7 by measuring and weighing the film in the same manner as in example 1 was found to be 0.5mm in the thickness of the film and 43.11g/m in the unit area density 2 Samples were prepared with reference to standard NB/T21020-2011, tested for corona resistance at 20KHZ,3000V (+ -1500), pulse rise time of 100ns, pulse duty cycle of 50%, corona breakdown resistance time of 15min, sample preparation with reference to standard GB/T13542.2-2009, tensile strength of 121MPa, elongation at break of 0.2%.
Example 3
The thickness of the polyimide film obtained in step 7 by measuring and weighing the film in the same manner as in example 1 was 1.5mm in thickness of the dope film in step 4, and the thickness of the dope film was 75. Mu.m, and the density per unit area was 43.15g/m 2 Samples were prepared with reference to standard NB/T21020-2011, tested for corona resistance at 20KHZ,3000V (+ -1500), pulse rise time of 100ns, pulse duty cycle of 50%, and tested for 45min corona breakdown resistance, samples were prepared with reference to standard GB/T13542.2-2009, tested for 155MPa tensile strength, and elongation at break of 0.4%.
Example 4
Otherwise as in example 1, step 4: taking the film with the thickness of 105 mu m and the density of 54.21g/m in unit area obtained in the step 2 2 The zirconia fiber paper is cut into a rectangle with the diameter of 200mm being 150mm, and then is flatly paved on a bearing plate with the smooth surface and difficult adhesion of an automatic film scraping machine, and the bearing plate is used for bearingSpraying DMAC solution on the surface of zirconia fiber paper until the zirconia fiber paper is soaked, then introducing polyimide acid solution with the viscosity of 680 mPa.s prepared in the step 2 into the surface of the zirconia fiber paper on one side of the carrier plate, adjusting the film scraping thickness parameter of an automatic film scraping machine to be 1mm, setting the film scraping speed to be 0.2m/min, setting the film scraping mode to be intermittent film scraping, and scraping the polyimide acid solution on the surface of the zirconia fiber paper by using the automatic film scraping machine to obtain a fiber paper composite prefabricated material with a smooth surface and good soaking;
step 5: placing the fiber paper composite prefabricated material prepared in the step 4 on a glass plate or a stainless steel plate, then placing the glass plate or the stainless steel plate into a drying box, and drying the glass plate or the stainless steel plate for 60 minutes at 80 ℃ to prepare a dried pre-composite film;
step 6: scraping the pre-composite film prepared in the step 5 from a glass plate or a stainless steel plate, then placing the pre-composite film into a muffle furnace, and imidizing the pre-composite film for 60 minutes at 330 ℃ to prepare the polyimide composite film.
Step 7: measuring and weighing the polyimide film obtained in the step 6 to obtain a polyimide film with a thickness of 105 mu m and a density of 54.25g/m per unit area 2 Samples were prepared with reference to standard NB/T21020-2011, tested for corona resistance at 20KHZ,3000V (+ -1500), pulse rise time of 100ns, pulse duty cycle of 50%, and tested for 57min corona breakdown resistance, 146MPa tensile strength and 0.6% elongation at break with reference to standard GB/T13542.2-2009.
Example 5
Otherwise, the imidization time in step 6 was 90min, and the polyimide film was measured and weighed in step 7 to obtain a polyimide film having a thickness of 75 μm and a density of 43.13g/m per unit area 2 Samples were prepared with reference to standard NB/T21020-2011, tested for corona resistance at 20KHZ,3000V (+ -1500), pulse rise time of 100ns, pulse duty cycle of 50%, and tested for 41min corona breakdown resistance, samples were prepared with reference to standard GB/T13542.2-2009, tested for 143MPa tensile strength, and 0.1% elongation at break.
Example 6
Otherwise, the imidization time in step 6 was 20min, and the polyimide film was measured and weighed in step 7 to obtain a polyimide film having a thickness of 75 μm and a density of 43.13g/m per unit area 2 Samples were prepared with reference to standard NB/T21020-2011, tested for corona resistance at 20KHZ,3000V (+ -1500), pulse rise time of 100ns, pulse duty cycle of 50%, corona breakdown resistance time of 21min, tensile strength of 127MPa, and elongation at break of 0.6% with reference to standard GB/T13542.2-2009.
Example 7
Step 1 (preparation of alumina fibers):
AlCl 3 ·6H 2 o (AR) reacts with micron-sized aluminum powder to prepare the aluminum-containing powder with the solid content of 10-15 percent and the PH value of 3.2-3.5 2 O 3 Then adding silica sol and spinning aid PEO and concentrating to viscosity of 3500mPa.s, wherein SiO in the silica sol 2 The mass fraction of the spinning auxiliary PEO is 25%, and the addition amount of the spinning auxiliary PEO is Al 2 O 3 3.5% of mass fraction. Spinning by centrifugal spinning, and sintering at 1000-1300 deg.C to obtain alumina fiber with diameter of 3-6 μm.
Step 2 (preparation of alumina fiber paper):
adding the alumina fiber prepared in the step 1 into a high-speed fluffer, fluffing and shorting the alumina fiber at 4500r/min to enable the length of the alumina fiber to reach between 0.5 and 2.5mm, transferring the fluffed slurry into a vertical mixer to mix the slurry, adding inorganic adhesive water glass with the addition of which the total mass is 4.5 percent of the mass of the slurry, forming on a sheet machine to obtain wet blanks of paper, cutting the edge positions of the wet blanks to ensure that the thickness of the wet blanks is uniform, drying the wet blanks in a drying box at 100-110 ℃ for 50min, and obtaining the paper with the unit area density of 40g/m after drying 2 -95g/m 2 Alumina fiber paper with thickness of 150-200 μm is ready for use.
Step 3 is the same as in example 1. Step 4, the thickness is 75 mu m, the unitArea density is 48.02g/m 2 The same as in example 1, step 7, the polyimide film was measured and weighed to obtain a polyimide film having a thickness of 75 μm and a density of 48.05g/m per unit area 2 Samples were prepared with reference to standard NB/T21020-2011, tested for corona resistance at 20KHZ,3000V (+ -1500), pulse rise time of 100ns, pulse duty cycle of 50%, and tested for 49min corona breakdown resistance, samples were prepared with reference to standard GB/T13542.2-2009, tested for 153MPa tensile strength, and elongation at break of 0.1%.
Example 8
Preparation of zirconia fibers step 1 of example 1, preparation of alumina fibers step 1 of example 7, preparation of fiber paper (zirconia fiber mass: alumina fiber mass=1:1) by mixing zirconia fibers and alumina fibers step 2, and other examples 1, selection of a fiber paper thickness of 75 μm and a unit area density of 47.11g/m 2 。
In step 7, the polyimide film was measured and weighed to obtain a polyimide film having a thickness of 75 μm and a density per unit area of 47.13g/m 2 Samples were prepared with reference to standard NB/T21020-2011 and tested for corona resistance at 20KHZ,3000V (+ -1500), pulse rise time of 100ns, pulse duty cycle of 50%, corona breakdown resistance of 69min, tensile strength of 159MPa, and elongation at break of 0.1%.
Comparative example
Polyimide acid solution was prepared in the same manner as in example 1 in step 3, except that a pure polyimide film was prepared by using a doctor blade machine, and the polyimide film was measured and weighed to obtain a polyimide film having a thickness of 33. Mu.m, a density of 38.95g/m, and a specific area 2 Samples were prepared with reference to standard NB/T21020-2011, tested for corona resistance at 20KHZ,3000V (+ -1500), pulse rise time of 100ns, pulse duty cycle of 50%, corona breakdown resistance time of 3min, sample preparation with reference to standard GB/T13542.2-2009, tensile strength of 113MPa, elongation at break of 23%.
The thickness, density per unit area and doctor blade thickness, imidization time, polyimide composite film thickness, density per unit area, corona breakdown resistance time, tensile strength, elongation at break of the oxide fiber papers of examples 1 to 8 and comparative examples were prepared as follows:
table 1 polyimide composite film data sheet
As can be seen from comparative examples 1-3, with the increase of the thickness of the scratch film, the bonding capability of polyimide and zirconia fiber paper is improved, the corona breakdown resistance time of the prepared polyimide composite film is prolonged, meanwhile, the tensile strength of the polyimide composite film is enhanced, the elongation at break is increased, and the comprehensive performance is improved; in comparative examples 1 and 4, the thickness of the fiber paper is increased, the corona breakdown resistance time of the prepared polyimide composite film is prolonged, meanwhile, the tensile strength of the polyimide composite film is enhanced, the elongation at break is increased, the comprehensive performance is improved, but the bending flexibility of the polyimide composite film is lower as the thickness of the fiber paper is larger. As can be seen from comparative examples 1, 5 and 6, as the imidization time is prolonged, the binding ability of polyimide to zirconia fiber paper is improved, and the corona breakdown resistance time of the prepared polyimide composite film is prolonged, and at the same time, the tensile strength of the polyimide composite film is enhanced, the elongation at break is reduced, and the comprehensive performance is improved. As can be seen from comparative examples 1, 7 and 8, the polyimide composite film prepared from the alumina fiber has various properties generally superior to those of the polyimide composite film prepared from the zirconia fiber, and the various properties of the polyimide composite film can be further improved by compounding the alumina and the zirconia. As can be seen from comparative examples 1 and 1, the compounding of the oxide fiber paper with polyimide greatly improves corona resistance of the polyimide film, and at the same time, tensile strength is also significantly improved. According to examples 1 to 8, in order to increase corona resistance of the polyimide composite film, it is possible to start from several aspects such as increasing the thickness of the oxide fiber paper, increasing the doctor blade thickness, and extending the imidization time, but it is considered that if a polyimide composite film having better flexibility is to be obtained, it is necessary to reduce the thickness of the zirconia fiber paper.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the foregoing examples, and that the foregoing description and description are merely illustrative of the principles of this invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (1)
1. The preparation method of the polyimide composite film is characterized by comprising the following steps of:
step 1: adding oxide fibers into a high-speed fluffer, fluffing and shorting the oxide fibers at a rotating speed of 2000-5000 r/min to ensure that the length of the oxide fibers is between 0.5 and 5mm, transferring the fluffed slurry into a vertical mixer to mix, adding an inorganic adhesive, forming on a sheet machine to obtain wet blanks of paper, and drying in a drying oven at 100-110 ℃ to obtain the paper with unit area density of 40g/m 2 -400g/m 2 Oxide fiber paper with the thickness of 50-500 μm is ready for use;
the oxide fiber is alumina fiber or zirconia fiber, and the alumina fiber is AlCl fiber 3 ·6H 2 O reacts with micron-sized aluminum powder to prepare the aluminum-containing powder with the solid content of 8-20 percent and the PH value of 3.0-4.0 2 O 3 Adding silica sol and spinning auxiliary PEO and concentrating to viscosity of 500mPa.s-5000mPa.s, and obtaining alumina fiber with diameter of 1 μm-8 μm by centrifugal spinning;
the silica solSiO of (B) 2 The mass fraction of the spinning auxiliary PEO is between 10 and 40 percent, and the addition amount of the spinning auxiliary PEO is Al 2 O 3 1% -5% of mass fraction;
the zirconia fiber is prepared by reacting basic zirconium carbonate with acetic acid in a molar ratio of 1 (1.5-2.0), adding yttrium nitrate hexahydrate as a stabilizer, adding PVA as a spinning auxiliary agent, concentrating to a viscosity of 500mPa.s-5000mPa.s, and preparing the zirconia fiber with a diameter of 1-8 mu m by a centrifugal spinning method;
the adding amount of the yttrium nitrate hexahydrate is 8-12% of the mass fraction of the zirconia, and the adding amount of the PVA is 1-5% of the mass fraction of the zirconia;
the beating concentration of the oxide fiber is 0.5-2.5%
Step 2: the molar ratio is 1: (0.95-1.05) respectively weighing pyromellitic anhydride (PMDA) and 4,4 '-diaminodiphenyl ether (ODA), dissolving the ODA in a solvent N, N' -Dimethylacetamide (DMAC), stirring until the ODA is completely dissolved, adding the PDMA into the solution for 5-10 times, and stirring until the monomers completely react to obtain a polyimide acid solution with the viscosity of 400 mPa.s-1000 mPa.s;
step 3: cutting the oxide fiber paper prepared in the step 1 into a rectangle or square, then spreading the rectangle or square on a bearing plate with a smooth surface and difficult adhesion of an automatic film scraping machine, then flowing the polyimide acid liquor prepared in the step 2 on the surface of the oxide fiber paper on one side of the bearing plate, adjusting the film scraping thickness parameter of the automatic film scraping machine to be less than or equal to 2mm, setting the film scraping speed to be less than or equal to 1m/min, and scraping the polyimide acid liquor on the surface of the oxide fiber paper by using the automatic film scraping machine to obtain a fiber paper composite prefabricated material with a smooth surface and good infiltration;
after the oxide fiber paper is placed on the bearing plate, a layer of PDMA solution is sprayed on the surface of the oxide fiber paper, and the oxide fiber paper is sprayed until the oxide fiber paper is completely soaked;
the film scraping size of the automatic film scraping machine is L310mmxW250mm, and the film scraping mode is intermittent film scraping;
step 4: placing the fiber paper composite prefabricated material prepared in the step 3 on a glass plate or a stainless steel plate, then placing the glass plate or the stainless steel plate into a drying box, and drying the glass plate or the stainless steel plate for 10-80min at the temperature of 70-90 ℃ to prepare a dried pre-composite film;
step 5: scraping the pre-composite film prepared in the step 4 from a glass plate or a stainless steel plate, then placing the pre-composite film into a muffle furnace, and imidizing the pre-composite film for 40-80 min at 280-350 ℃ to prepare the polyimide composite film.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001323092A (en) * | 2000-05-17 | 2001-11-20 | Teijin Ltd | Composite porous film, method for manufacturing the same, and prepreg and heat-resistant insulating base material using the same |
| CN101381225A (en) * | 2008-10-10 | 2009-03-11 | 厦门大学 | Continuous aluminium oxide base ceramic fibre preparation method |
| CN108752929A (en) * | 2018-05-04 | 2018-11-06 | 常州储能材料与器件研究院 | A kind of basalt fiber composite material and preparation method thereof |
| CN109370216A (en) * | 2018-08-22 | 2019-02-22 | 中国人民解放军国防科技大学 | Three-dimensional fiber fabric reinforced polyimide resin-based composite material and preparation method thereof |
| CN109680552A (en) * | 2017-10-18 | 2019-04-26 | 江苏先诺新材料科技有限公司 | Polyimide/Nano fibre composite paper and preparation method thereof |
| CN110592723A (en) * | 2019-08-16 | 2019-12-20 | 山东德艾普节能材料有限公司 | Micro-nano zirconia fiber and preparation method thereof |
-
2020
- 2020-12-30 CN CN202011605283.4A patent/CN112812336B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001323092A (en) * | 2000-05-17 | 2001-11-20 | Teijin Ltd | Composite porous film, method for manufacturing the same, and prepreg and heat-resistant insulating base material using the same |
| CN101381225A (en) * | 2008-10-10 | 2009-03-11 | 厦门大学 | Continuous aluminium oxide base ceramic fibre preparation method |
| CN109680552A (en) * | 2017-10-18 | 2019-04-26 | 江苏先诺新材料科技有限公司 | Polyimide/Nano fibre composite paper and preparation method thereof |
| CN108752929A (en) * | 2018-05-04 | 2018-11-06 | 常州储能材料与器件研究院 | A kind of basalt fiber composite material and preparation method thereof |
| CN109370216A (en) * | 2018-08-22 | 2019-02-22 | 中国人民解放军国防科技大学 | Three-dimensional fiber fabric reinforced polyimide resin-based composite material and preparation method thereof |
| CN110592723A (en) * | 2019-08-16 | 2019-12-20 | 山东德艾普节能材料有限公司 | Micro-nano zirconia fiber and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张运展等.1.《加工纸与特种纸》.中国轻工业出版社,2001,第280-288页. * |
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Denomination of invention: A method for preparing polyimide composite films Effective date of registration: 20231228 Granted publication date: 20230505 Pledgee: Weihai commercial bank Limited by Share Ltd. Dongying branch Pledgor: Shandong Dongheng national fiber new material Co.,Ltd. Registration number: Y2023980074970 |