CN117511208B - A polyetherimide-based composite dielectric film material and preparation method thereof - Google Patents
A polyetherimide-based composite dielectric film material and preparation method thereof Download PDFInfo
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- CN117511208B CN117511208B CN202410009676.0A CN202410009676A CN117511208B CN 117511208 B CN117511208 B CN 117511208B CN 202410009676 A CN202410009676 A CN 202410009676A CN 117511208 B CN117511208 B CN 117511208B
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- 239000002131 composite material Substances 0.000 title claims abstract description 81
- 239000004697 Polyetherimide Substances 0.000 title claims abstract description 80
- 229920001601 polyetherimide Polymers 0.000 title claims abstract description 80
- 239000000463 material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 176
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 119
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachloro-phenol Natural products OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 claims abstract description 44
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 claims abstract description 30
- 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 abstract description 27
- 238000004381 surface treatment Methods 0.000 claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 25
- ZHDTXTDHBRADLM-UHFFFAOYSA-N hydron;2,3,4,5-tetrahydropyridin-6-amine;chloride Chemical compound Cl.NC1=NCCCC1 ZHDTXTDHBRADLM-UHFFFAOYSA-N 0.000 claims abstract description 23
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007822 coupling agent Substances 0.000 claims abstract description 11
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004593 Epoxy Substances 0.000 claims abstract description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 40
- 238000001035 drying Methods 0.000 claims description 37
- 239000000758 substrate Substances 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical group CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 12
- 229920005575 poly(amic acid) Polymers 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000007790 scraping Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims 4
- 239000000084 colloidal system Substances 0.000 claims 2
- 238000002525 ultrasonication Methods 0.000 claims 2
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- -1 pentafluorophenol modified barium titanate Chemical class 0.000 abstract description 14
- 238000004146 energy storage Methods 0.000 abstract description 11
- 239000004952 Polyamide Substances 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 8
- 229920002647 polyamide Polymers 0.000 abstract description 8
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- 239000010408 film Substances 0.000 description 54
- 239000011521 glass Substances 0.000 description 28
- 238000004140 cleaning Methods 0.000 description 20
- 238000001132 ultrasonic dispersion Methods 0.000 description 13
- 239000003292 glue Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 10
- 239000002105 nanoparticle Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 238000010345 tape casting Methods 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 1
- 229920004747 ULTEM® 1000 Polymers 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 1
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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Abstract
The invention discloses a polyetherimide-based composite dielectric film material and a preparation method thereof, wherein the raw materials comprise PEI resin and nano barium titanate subjected to surface treatment, and the surface treatment steps of the nano barium titanate are as follows: treating nano barium titanate with hydrogen peroxide solution to obtain hydroxylated barium titanate; reacting the hydroxylated barium titanate with an epoxy silane coupling agent to obtain epoxidized barium titanate; reacting the epoxidized barium titanate with pentafluorophenol to obtain pentafluorophenol-modified barium titanate; reacting pentafluorophenol modified barium titanate with an aminosilane coupling agent to obtain aminated barium titanate; the aminated barium titanate and 4, 4-diaminodiphenyl ether and pyromellitic anhydride are copolymerized. In the invention, after the pentafluorophenol is modified on the surface of nano barium titanate, the nano barium titanate is polymerized with 4, 4-diaminodiphenyl ether and pyromellitic anhydride in situ to obtain the polyamide acid coated barium titanate, so that the dielectric property and the high-temperature energy storage property of the composite dielectric film material can be effectively improved.
Description
Technical Field
The invention relates to the technical field of dielectric materials, in particular to a polyetherimide-based composite dielectric film material and a preparation method thereof.
Background
The thin film capacitor is an important basic electronic component, and has high insulation resistance, high withstand voltage, small dielectric loss, excellent frequency characteristics, self-healing properties and other excellent characteristics compared with ceramic capacitors and aluminum/tantalum capacitors. At present, the most commonly used thin film dielectric in thin film capacitors is BOPP, which has a temperature resistance of about 105 ℃ and a relative dielectric constant of only 2-3, even at high temperaturesThe energy storage density is less than 2J/cm under the field intensity 3 This means that a large volume is required to meet certain energy storage requirements.
Polyetherimide (PEI) is a transparent or translucent polymer with a slight amber color, can be used for a long time at 150 ℃, has good heat stability, hydrolysis resistance, good dimensional stability, small molding shrinkage, can keep excellent mechanical properties even at high temperature, has excellent electrical properties in a wide temperature and frequency range, and is one of the most potential high-temperature resistant dielectric film polymers. However, the relative dielectric constant of the simple polyetherimide material is low, and the dielectric constant of the composite material is generally improved by adding a ceramic filler with high dielectric constant into the polyetherimide. The ferroelectric ceramic barium titanate has the characteristics of high dielectric constant, high energy density, excellent stability and the like, and the dielectric constant of the composite material can be effectively improved by adding the ferroelectric ceramic barium titanate into polyetherimide. For example, "a barium titanate/polyetherimide dielectric composite material and a method for preparing the same," disclosed in chinese patent literature, publication No. CN112280297a, the invention prepares a dielectric composite material having high breakdown strength (> 62) and low loss (< 0.14), and the dielectric properties of the dielectric composite material can be conveniently controlled by adjusting the thickness of the laminate.
However, when ceramic particles and a polymer matrix are used for compounding in the prior art, a larger ceramic particle addition amount is generally required to enable the composite material to have a higher dielectric constant and better high-temperature energy storage performance, barium titanate nanoparticles are added more, the nanoparticles are clustered together due to stronger acting force, the effects of improving the dielectric constant and reducing the dielectric loss cannot be achieved, and the toughness and the processability of the composite material are greatly influenced, so that the application of the composite material in a film capacitor is not facilitated.
Disclosure of Invention
The invention aims to overcome the problems of the polyetherimide/barium titanate composite dielectric film material in the prior art, and provides a polyetherimide-based composite dielectric film material and a preparation method thereof.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the polyetherimide-based composite dielectric film material comprises PEI resin and nano barium titanate subjected to surface treatment, wherein the mass ratio of PEI resin to nano barium titanate is 100:5-75, and the surface treatment steps of the nano barium titanate are as follows:
a) Treating nano barium titanate with hydrogen peroxide solution to obtain hydroxylated barium titanate;
b) Reacting the hydroxylated barium titanate with an epoxy silane coupling agent to obtain epoxidized barium titanate;
c) Reacting the epoxidized barium titanate with pentafluorophenol to obtain pentafluorophenol-modified barium titanate;
d) Reacting pentafluorophenol modified barium titanate with an aminosilane coupling agent to obtain aminated barium titanate;
e) Adding the aminated barium titanate and 4, 4-diaminodiphenyl ether into an organic solvent, performing ultrasonic dispersion and stirring, adding pyromellitic anhydride, reacting to obtain polyamic acid coated barium titanate glue solution, centrifuging the glue solution, and filtering to obtain the nano barium titanate after surface treatment.
In order to improve the dispersibility and compatibility of nano barium titanate in PEI resin and improve the performance of an interface between inorganic barium titanate and an organic polymer, the invention modifies pentafluorophenol on the surface of the barium titanate, introduces amino groups on the surface of the barium titanate, and then carries out in-situ polymerization on the barium titanate modified by pentafluorophenol, 4-diaminodiphenyl ether and pyromellitic anhydride to obtain the polyamic acid coated barium titanate. The polyamide acid is coated on the surface of the barium titanate through in-situ polymerization, and the polyamide acid is added into the PEI matrix, so that the dispersibility and compatibility of the barium titanate in the PEI matrix can be effectively improved, interface defects are obviously reduced, and the dielectric loss of the film material is reduced. Meanwhile, after the surface of the barium titanate is modified with the pentafluorophenol, the benzene ring in the pentafluorophenol is negatively charged, the benzene ring in the polyamic acid is positively charged, and the benzene ring in the pentafluorophenol and the benzene ring in the polyamic acid can generate electrostatic force through weak attraction between molecules, so that the interface performance of the inorganic barium titanate particles and the surface organic polyamic acid is optimized, the bonding force at the interface is enhanced, and the dielectric loss of the film material is further reduced; and the benzene ring structure in the pentafluorophenol can effectively prevent the internal carrier of the polymer from being transmitted at high temperature, so that the energy storage density of the composite film material at high temperature can be effectively improved.
When the surface treatment is carried out on the barium titanate, firstly, hydroxyl groups are introduced into the surface of the nano barium titanate through the step A), and then epoxy groups are introduced into the surface of the barium titanate through the reaction of an epoxy silane coupling agent and the hydroxyl groups on the surface of the barium titanate through the step B); then, through the step C), the pentafluorophenol is modified on the surface of the nano barium titanate through the ring-opening reaction of phenolic hydroxyl groups and epoxy groups in the pentafluorophenol; then introducing amino on the surface of the barium titanate by utilizing the reaction of an aminosilane coupling agent and hydroxyl on the surface of the barium titanate in the step D); finally, through the step E), the aminated barium titanate and 4, 4-diaminodiphenyl ether and pyromellitic anhydride are polymerized in situ, and finally the polyamic acid coated barium titanate is obtained.
Preferably, the epoxy silane coupling agent in the step B) is 3-glycidol ether oxypropyl trimethoxy silane, and the mass ratio of the hydroxylated barium titanate to the epoxy silane coupling agent is 1:0.3-0.5; the mass ratio of pentafluorophenol to the epoxidized barium titanate in the step C) is 0.5-1:1; the aminosilane coupling agent in the step D) is 3-aminopropyl trimethoxy silane, and the mass ratio of the pentafluorophenol modified barium titanate to the aminosilane coupling agent is 1:1-2; the molar ratio of the 4, 4-diaminodiphenyl ether to the pyromellitic anhydride added in the step E) is 1.3-1.5:1, and the ratio of the mass of the aminated barium titanate to the total mass of the 4, 4-diaminodiphenyl ether and the pyromellitic anhydride is 1:4-6.
Preferably, the treatment method in step a) is as follows: adding nano barium titanate with the particle size of 30-500nm into hydrogen peroxide solution, carrying out ultrasonic dispersion uniformly, reacting for 2-4 hours at the temperature of 95-105 ℃, separating, cleaning and drying the product, and thus obtaining the hydroxylated barium titanate.
Preferably, the reaction conditions in step B) are: and (3) ultrasonically dispersing the hydroxylated barium titanate into water and ethanol, adding an epoxy silane coupling agent, stirring at 20-80 ℃ for reaction for 8-24 hours, separating, cleaning and drying the product to obtain the epoxidized barium titanate.
Preferably, the reaction conditions in step C) are: and adding pentafluorophenol into a sodium hydroxide solution with the mass concentration of 50-60%, stirring and dissolving, adding epoxidized barium titanate under the protection of inert gas, stirring and reacting for 1-3 hours at the temperature of 60-70 ℃, and separating, cleaning and drying the product to obtain the pentafluorophenol modified barium titanate.
Preferably, the reaction conditions in step D) are: dispersing the pentafluorophenol modified barium titanate into water and ethanol by ultrasonic, adding an aminosilane coupling agent, stirring at 20-80 ℃ for reaction for 8-24 hours, and separating, cleaning and drying the product to obtain the aminated barium titanate.
Preferably, the reaction time in step E) is 18 to 30 hours.
The invention also provides a preparation method of the polyetherimide-based composite dielectric film material, which comprises the following steps:
(1) Adding PEI resin into an organic solvent, and dissolving to obtain a polyetherimide solution;
(2) Adding the nano barium titanate subjected to surface treatment into a polyetherimide solution, performing ultrasonic dispersion, and uniformly stirring to obtain a composite solution;
(3) The composite solution is coated on a substrate in a scraping way to form a composite film, and imidization treatment is carried out after drying;
(4) And (3) placing the imidized substrate in deionized water to strip the composite film, and vacuum drying the composite film to obtain the polyetherimide-based composite dielectric film material.
Preferably, the mass concentration of the polyetherimide solution in the step (1) is 10-50%.
Preferably, the ultrasonic power in the step (2) is 1000-1800W, and the ultrasonic time is 30-60min.
Preferably, the doctor-blading thickness of the composite solution in the step (3) is 30-80 mu m; the drying temperature is 30-80 ℃ and the drying time is 2-6 hours; the imidization treatment is carried out at a temperature of 100-300 ℃ for 4-8 hours.
Preferably, the vacuum drying temperature in the step (4) is 50-100 ℃ and the vacuum drying time is 1-4 hours.
Therefore, the invention has the following beneficial effects:
(1) Amino is introduced to the surface of nano barium titanate, and then in-situ polymerization is carried out on the nano barium titanate, 4-diaminodiphenyl ether and pyromellitic anhydride to obtain polyamide acid coated barium titanate, and the polyamide acid coated barium titanate is added into a PEI matrix, so that the dispersibility and compatibility of the barium titanate in the PEI matrix can be effectively improved, the interface defect is obviously reduced, and the dielectric loss of the composite film material is reduced;
(2) The pentafluorophenol is modified on the surface of the nano barium titanate, so that the interface performance of the inorganic barium titanate and the polyamide acid with the organic surface can be improved, the dielectric loss of the composite film material can be further reduced, and the high-temperature energy storage performance of the composite film material can be improved.
Detailed Description
The invention is further described below in connection with the following detailed description.
In the present invention, all the equipment and raw materials are commercially available or commonly used in the industry, and the methods in the following examples are conventional in the art unless otherwise specified.
In each embodiment of the invention, nano barium titanate is purchased from microphone company and has the particle size of 30-500nm; the PEI resin used was Sabic Ultem 1000.
Example 1:
a preparation method of a polyetherimide-based composite dielectric film material comprises the following steps:
(1) Surface treatment is carried out on nano barium titanate:
a) Adding nano barium titanate into hydrogen peroxide solution with the concentration of 30wt%, wherein the mass volume ratio of barium titanate nano particles to the hydrogen peroxide solution is 1g:50mL, carrying out reflux reaction for 3h at 100 ℃ after ultrasonic dispersion is uniform, and separating, cleaning and drying the product to obtain hydroxylated barium titanate;
b) Ultrasonically dispersing hydroxylated barium titanate into water and ethanol with the volume ratio of 1:9, adding 3-glycidoxypropyl trimethoxysilane, stirring and reacting for 12 hours at 60 ℃ with the mass ratio of the hydroxylated barium titanate to the 3-glycidoxypropyl trimethoxysilane of 1:0.4, separating, cleaning and drying the product to obtain epoxidized barium titanate;
c) Adding pentafluorophenol into a sodium hydroxide solution with the mass concentration of 55%, stirring and dissolving, and then adding epoxidized barium titanate under the protection of nitrogen, wherein the mass ratio of the pentafluorophenol to the epoxidized barium titanate is 0.8:1; stirring and reacting for 2 hours at 65 ℃, and separating, cleaning and drying the product to obtain the pentafluorophenol modified barium titanate;
d) Adding pentafluorophenol modified barium titanate into a mixed solvent of water and ethanol in a volume ratio of 1:9, adding 3-aminopropyl trimethoxysilane, mixing the pentafluorophenol modified barium titanate and the 3-aminopropyl trimethoxysilane uniformly by ultrasonic waves in a mass ratio of 1:1.5, stirring at 80 ℃ for reaction for 18 hours, and separating, cleaning and drying a product to obtain aminated barium titanate;
e) Adding the aminated barium titanate and 4, 4-diaminodiphenyl ether into N, N-dimethylacetamide, performing ultrasonic dispersion and stirring, and then adding pyromellitic anhydride in batches, wherein the molar ratio of the added 4, 4-diaminodiphenyl ether to pyromellitic anhydride is 1.4:1, and the ratio of the mass of the aminated barium titanate to the total mass of the 4, 4-diaminodiphenyl ether and pyromellitic anhydride is 1:5; after 24 hours of reaction, obtaining polyamic acid coated barium titanate glue solution, centrifuging the glue solution, and filtering to obtain nano barium titanate after surface treatment;
(2) Adding PEI resin into N, N-dimethylacetamide, heating to 60 ℃, and stirring until the PEI resin is completely dissolved to obtain a polyetherimide solution with the mass concentration of 20%;
(3) Adding the nano barium titanate subjected to surface treatment into a polyetherimide solution, stirring for 30min, and performing ultrasonic treatment at 1400 power for 30min to obtain a uniform composite solution, wherein the mass ratio of the nano barium titanate subjected to surface treatment to PEI resin is 10:100;
(4) Uniformly dripping the composite solution on a glass substrate by using a dropper, adjusting the height of a scraper to 50 mu m, and doctor-blading to obtain a uniform composite film; placing the glass substrate scraped with the composite film in a vacuum oven at 50 ℃ for vacuum drying for 2 hours, heating to 80 ℃ for vacuum drying for 2 hours, and transferring to a high-temperature blast oven for imidization treatment, wherein the treatment process is 120 ℃/1h+160 ℃/1h+200 ℃/1h+240 ℃/1h+300 ℃/1h;
(5) And taking out the glass substrate from the blast oven, placing the glass substrate in deionized water, peeling the composite film after 10min, placing the glass substrate in a vacuum oven, and vacuumizing and drying the glass substrate for 2h at 60 ℃ to obtain the polyetherimide-based composite dielectric film material.
Example 2:
a preparation method of a polyetherimide-based composite dielectric film material comprises the following steps:
(1) Surface treatment is carried out on nano barium titanate:
a) Adding nano barium titanate into hydrogen peroxide solution with the concentration of 30wt%, wherein the mass volume ratio of the barium titanate nano particles to the hydrogen peroxide solution is 1g to 50mL, carrying out reflux reaction for 4 hours at 95 ℃ after ultrasonic dispersion is uniform, and separating, cleaning and drying the product to obtain hydroxylated barium titanate;
b) Ultrasonically dispersing hydroxylated barium titanate into water and ethanol with the volume ratio of 2:8, adding 3-glycidoxypropyl trimethoxysilane, stirring and reacting for 24 hours at 25 ℃ with the mass ratio of the hydroxylated barium titanate to the 3-glycidoxypropyl trimethoxysilane being 1:0.3, separating, cleaning and drying the product to obtain epoxidized barium titanate;
c) Adding pentafluorophenol into a sodium hydroxide solution with the mass concentration of 50%, stirring and dissolving, and then adding epoxidized barium titanate under the protection of nitrogen, wherein the mass ratio of the pentafluorophenol to the epoxidized barium titanate is 0.5:1; stirring at 60 ℃ for reaction for 3 hours, and separating, cleaning and drying the product to obtain the pentafluorophenol modified barium titanate;
d) Adding pentafluorophenol modified barium titanate into a mixed solvent of water and ethanol in a volume ratio of 2:8, adding 3-aminopropyl trimethoxysilane, mixing the pentafluorophenol modified barium titanate and the 3-aminopropyl trimethoxysilane uniformly by ultrasonic at a mass ratio of 1:1, stirring at 25 ℃ for reaction for 24 hours, and separating, cleaning and drying the product to obtain aminated barium titanate;
e) Adding the aminated barium titanate and 4, 4-diaminodiphenyl ether into N, N-dimethylacetamide, performing ultrasonic dispersion and stirring, and then adding pyromellitic anhydride in batches, wherein the molar ratio of the added 4, 4-diaminodiphenyl ether to pyromellitic anhydride is 1.3:1, and the ratio of the mass of the aminated barium titanate to the total mass of the 4, 4-diaminodiphenyl ether and pyromellitic anhydride is 1:4; after 24 hours of reaction, obtaining polyamic acid coated barium titanate glue solution, centrifuging the glue solution, and filtering to obtain nano barium titanate after surface treatment;
(2) Adding PEI resin into N, N-dimethylacetamide, heating to 60 ℃, and stirring until the PEI resin is completely dissolved to obtain a polyetherimide solution with the mass concentration of 20%;
(3) Adding the nano barium titanate subjected to surface treatment into a polyetherimide solution, stirring for 30min, and performing ultrasonic treatment at 1400 power for 30min to obtain a uniform composite solution, wherein the mass ratio of the nano barium titanate subjected to surface treatment to PEI resin is 20:100;
(4) Uniformly dripping the composite solution on a glass substrate by using a dropper, adjusting the height of a scraper to 50 mu m, and doctor-blading to obtain a uniform composite film; placing the glass substrate scraped with the composite film in a vacuum oven at 50 ℃ for vacuum drying for 2 hours, heating to 80 ℃ for vacuum drying for 2 hours, and transferring to a high-temperature blast oven for imidization treatment, wherein the treatment process is 120 ℃/1h+160 ℃/1h+200 ℃/1h+240 ℃/1h+300 ℃/1h;
(5) And taking out the glass substrate from the blast oven, placing the glass substrate in deionized water, peeling the composite film after 10min, placing the glass substrate in a vacuum oven, and vacuumizing and drying the glass substrate for 2h at 60 ℃ to obtain the polyetherimide-based composite dielectric film material.
Example 3:
a preparation method of a polyetherimide-based composite dielectric film material comprises the following steps:
(1) Surface treatment is carried out on nano barium titanate:
a) Adding nano barium titanate into hydrogen peroxide solution with the concentration of 30wt%, wherein the mass volume ratio of barium titanate nano particles to the hydrogen peroxide solution is 1g:50mL, carrying out reflux reaction for 2h at 105 ℃ after ultrasonic dispersion is uniform, and separating, cleaning and drying the product to obtain hydroxylated barium titanate;
b) Ultrasonically dispersing hydroxylated barium titanate into water and ethanol with the volume ratio of 3:7, adding 3-glycidoxypropyl trimethoxysilane, stirring and reacting for 8 hours at 80 ℃ with the mass ratio of the hydroxylated barium titanate to the 3-glycidoxypropyl trimethoxysilane of 1:0.5, separating, cleaning and drying the product to obtain epoxidized barium titanate;
c) Adding pentafluorophenol into a sodium hydroxide solution with the mass concentration of 60%, stirring and dissolving, and then adding epoxidized barium titanate under the protection of nitrogen, wherein the mass ratio of the pentafluorophenol to the epoxidized barium titanate is 1:1; stirring at 70 ℃ for reaction for 2 hours, and separating, cleaning and drying the product to obtain the pentafluorophenol modified barium titanate;
d) Adding pentafluorophenol modified barium titanate into a mixed solvent of water and ethanol with the volume ratio of 3:7, adding 3-aminopropyl trimethoxysilane, mixing the pentafluorophenol modified barium titanate and the 3-aminopropyl trimethoxysilane uniformly by ultrasonic at the temperature of 80 ℃ for stirring and reacting for 8 hours, and separating, cleaning and drying the product to obtain aminated barium titanate;
e) Adding the aminated barium titanate and 4, 4-diaminodiphenyl ether into N, N-dimethylacetamide, performing ultrasonic dispersion and stirring, and then adding pyromellitic anhydride in batches, wherein the molar ratio of the added 4, 4-diaminodiphenyl ether to pyromellitic anhydride is 1.5:1, and the ratio of the mass of the aminated barium titanate to the total mass of the 4, 4-diaminodiphenyl ether and pyromellitic anhydride is 1:6; after 24 hours of reaction, obtaining polyamic acid coated barium titanate glue solution, centrifuging the glue solution, and filtering to obtain nano barium titanate after surface treatment;
(2) Adding PEI resin into N, N-dimethylacetamide, heating to 60 ℃, and stirring until the PEI resin is completely dissolved to obtain a polyetherimide solution with the mass concentration of 20%;
(3) Adding the nano barium titanate subjected to surface treatment into a polyetherimide solution, stirring for 30min, and performing ultrasonic treatment at 1400 power for 30min to obtain a uniform composite solution, wherein the mass ratio of the nano barium titanate subjected to surface treatment to PEI resin is 30:100;
(4) Uniformly dripping the composite solution on a glass substrate by using a dropper, adjusting the height of a scraper to 50 mu m, and doctor-blading to obtain a uniform composite film; placing the glass substrate scraped with the composite film in a vacuum oven at 50 ℃ for vacuum drying for 2 hours, heating to 80 ℃ for vacuum drying for 2 hours, and transferring to a high-temperature blast oven for imidization treatment, wherein the treatment process is 120 ℃/1h+160 ℃/1h+200 ℃/1h+240 ℃/1h+300 ℃/1h;
(5) And taking out the glass substrate from the blast oven, placing the glass substrate in deionized water, peeling the composite film after 10min, placing the glass substrate in a vacuum oven, and vacuumizing and drying the glass substrate for 2h at 60 ℃ to obtain the polyetherimide-based composite dielectric film material.
Example 4:
in the step (3) of example 4, the mass ratio of the nano barium titanate after the surface treatment to the polyetherimide resin was 40:100, and the rest was the same as in example 1.
Example 5:
in the step (3) of example 5, the mass ratio of the nano barium titanate after the surface treatment to the polyetherimide resin was 50:100, and the rest was the same as in example 1.
Comparative example 1 (no nano barium titanate added):
a preparation method of a polyetherimide film material comprises the following steps:
(1) Adding PEI resin into N, N-dimethylacetamide solvent, heating to 60 ℃, and stirring until the PEI resin is completely dissolved to obtain polyetherimide solution with the mass concentration of 20%;
(2) Uniformly dripping the polyetherimide solution on a glass substrate by using a dropper, adjusting the height of a scraper to 50 mu m, and doctor-blading to obtain a uniform polyetherimide film; the glass substrate scraped with the polyetherimide film is firstly placed in a vacuum oven at 40 ℃ for vacuum drying for 4 hours, then transferred to a blast oven at 180 ℃ for drying for 4 hours, and the organic solvent is removed;
(3) And taking out the glass substrate from the blast oven, placing the glass substrate in deionized water, peeling the polyetherimide film after 10min, placing the polyetherimide film in a vacuum oven, and vacuumizing and drying the polyetherimide film material for 4h at 50 ℃ to obtain the polyetherimide film material.
Comparative example 2 (nano barium titanate directly mixed with PEI resin):
a preparation method of a polyetherimide/barium titanate film material comprises the following steps:
(1) Adding PEI resin into N, N-dimethylacetamide solvent, heating to 60 ℃, and stirring until the PEI resin is completely dissolved to obtain polyetherimide solution with the mass concentration of 20%;
(2) Adding nano barium titanate into the polyetherimide solution, stirring for 30min, and performing ultrasonic treatment at 1400 power for 30min to obtain a uniform composite solution, wherein the mass ratio of the nano barium titanate to the polyetherimide is 10:100;
(3) Uniformly dripping the composite solution on a glass substrate by using a dropper, adjusting the height of a scraper to 50 mu m, and doctor-blading to obtain a uniform composite film; the glass substrate scraped with the composite film is firstly placed in a vacuum oven at 40 ℃ for vacuum drying for 4 hours, then transferred to a blast oven at 180 ℃ for drying for 4 hours, and the organic solvent is removed;
(4) And taking out the glass substrate from the blast oven, placing the glass substrate in deionized water, peeling the composite film after 10min, placing the glass substrate in a vacuum oven, and vacuumizing and drying the glass substrate for 4h at 50 ℃ to obtain the polyetherimide/barium titanate composite dielectric film material.
Comparative example 3 (no modification of pentafluorophenol on the surface of nano-barium titanate):
comparative example 3 is different from example 1 in that the nano barium titanate surface treatment method in step (1) is:
a) Adding nano barium titanate into hydrogen peroxide solution with the concentration of 30wt%, wherein the mass volume ratio of barium titanate nano particles to the hydrogen peroxide solution is 1g:50mL, carrying out reflux reaction for 3h at 100 ℃ after ultrasonic dispersion is uniform, and separating, cleaning and drying the product to obtain hydroxylated barium titanate;
b) Adding hydroxylated barium titanate into a mixed solvent of water and ethanol in a volume ratio of 1:9, adding 3-aminopropyl trimethoxysilane, uniformly mixing the hydroxylated barium titanate and the 3-aminopropyl trimethoxysilane by ultrasonic waves, stirring at 80 ℃ for reaction for 18 hours, and separating, cleaning and drying a product to obtain aminated barium titanate;
c) Adding the aminated barium titanate and 4, 4-diaminodiphenyl ether into N, N-dimethylacetamide, performing ultrasonic dispersion and stirring, and then adding pyromellitic anhydride in batches, wherein the molar ratio of the added 4, 4-diaminodiphenyl ether to pyromellitic anhydride is 1.4:1, and the ratio of the mass of the aminated barium titanate to the total mass of the 4, 4-diaminodiphenyl ether and pyromellitic anhydride is 1:5; after 24 hours of reaction, obtaining polyamic acid coated barium titanate glue solution, centrifuging the glue solution, and filtering to obtain nano barium titanate after surface treatment;
the remainder was the same as in example 1.
Comparative example 4 (pentafluorophenol direct mixture):
comparative example 4 is different from example 1 in that the nano barium titanate surface treatment method in step (1) is:
a) Adding nano barium titanate into hydrogen peroxide solution with the concentration of 30wt%, wherein the mass volume ratio of barium titanate nano particles to the hydrogen peroxide solution is 1g:50mL, carrying out reflux reaction for 3h at 100 ℃ after ultrasonic dispersion is uniform, and separating, cleaning and drying the product to obtain hydroxylated barium titanate;
b) Adding hydroxylated barium titanate into a mixed solvent of water and ethanol in a volume ratio of 1:9, adding 3-aminopropyl trimethoxysilane, uniformly mixing the hydroxylated barium titanate and the 3-aminopropyl trimethoxysilane by ultrasonic waves, stirring at 80 ℃ for reaction for 18 hours, and separating, cleaning and drying a product to obtain aminated barium titanate;
c) Adding the aminated barium titanate, the pentafluorophenol and the 4, 4-diaminodiphenyl ether into N, N-dimethylacetamide, performing ultrasonic dispersion and stirring, and then adding pyromellitic anhydride in batches, wherein the mass ratio of the added pentafluorophenol to the aminated barium titanate is 0.8:1, the mole ratio of the added pentafluorophenol to the aminated barium titanate is 1.4:1, and the mass ratio of the aminated barium titanate to the total mass of the 4, 4-diaminodiphenyl ether and the pyromellitic anhydride is 1:5; after 24 hours of reaction, obtaining polyamic acid coated barium titanate glue solution, centrifuging the glue solution, and filtering to obtain nano barium titanate after surface treatment;
the remainder was the same as in example 1.
The dielectric constants and dielectric losses of the thin film materials prepared in the above examples and comparative examples were tested, and polarization curves and storage densities were tested at a frequency of 10Hz, and the results of the related performance tests are shown in table 1.
Table 1: film Material Performance test results
As can be seen from Table 1, by adopting the method of the invention in examples 1-5, the dielectric constant and the energy storage density of the composite dielectric film material are significantly improved compared with those of the pure polyetherimide film in comparative example 1, and the composite dielectric film material has lower dielectric loss.
In comparative example 2, barium titanate is directly compounded with PEI resin, and the dielectric loss of the composite material is remarkably increased compared with that in the example; for this reason, in the embodiment of the invention, the aminated barium titanate, 4-diaminodiphenyl ether and pyromellitic anhydride are polymerized in situ, so that the barium titanate nano particles are directly connected to a polyamide acid molecular chain, the molecular-level dispersion is realized, meanwhile, the barium titanate nano particles are well dispersed in the finally prepared composite film due to the excellent compatibility of polyamide acid and a polyetherimide matrix, the dielectric loss of the composite film material is reduced, the leakage current of the composite film material is reduced, the breakdown field strength of the composite film material at a high temperature is improved, and the energy storage density of the composite film material at a high temperature is remarkably improved.
In comparative example 3, the dielectric loss and the energy storage density of the composite material are reduced compared with those in example 1 without modifying the surface of nano barium titanate with pentafluorophenol; in comparative example 4, pentafluorophenol was not chemically bonded to the barium titanate surface, but was directly blended with aminated barium titanate, 4-diaminodiphenyl ether, and pyromellitic anhydride during polymerization, and the energy storage density of the composite material was also lowered as compared with that in example 1. The fluorine-free phenol is modified on the surface of the barium titanate, so that the interface performance between the inorganic particles and the polymer coating layer can be improved, and the dielectric energy storage performance of the composite material can be further improved.
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