CN112898614A - High-dielectric-constant polyimide three-phase composite material and preparation method thereof - Google Patents
High-dielectric-constant polyimide three-phase composite material and preparation method thereof Download PDFInfo
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- CN112898614A CN112898614A CN202110088631.3A CN202110088631A CN112898614A CN 112898614 A CN112898614 A CN 112898614A CN 202110088631 A CN202110088631 A CN 202110088631A CN 112898614 A CN112898614 A CN 112898614A
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- titanium dioxide
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- polyvinylidene fluoride
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- 239000004642 Polyimide Substances 0.000 title claims abstract description 114
- 229920001721 polyimide Polymers 0.000 title claims abstract description 114
- 239000002131 composite material Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title abstract description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 248
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 108
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 82
- 239000002033 PVDF binder Substances 0.000 claims abstract description 55
- 239000000463 material Substances 0.000 claims abstract description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 99
- 239000002253 acid Substances 0.000 claims description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- 239000000725 suspension Substances 0.000 claims description 34
- 239000011259 mixed solution Substances 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 20
- 239000011521 glass Substances 0.000 claims description 19
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical group C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 18
- 239000005457 ice water Substances 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- 238000009210 therapy by ultrasound Methods 0.000 claims description 17
- 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 claims description 16
- 150000004985 diamines Chemical class 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 5
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical group C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 2
- GWHLJVMSZRKEAQ-UHFFFAOYSA-N 3-(2,3-dicarboxyphenyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O GWHLJVMSZRKEAQ-UHFFFAOYSA-N 0.000 claims description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 claims 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- 239000000945 filler Substances 0.000 abstract description 12
- 239000011159 matrix material Substances 0.000 abstract description 8
- 238000011049 filling Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000004146 energy storage Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 229910003471 inorganic composite material Inorganic materials 0.000 abstract 1
- 239000000853 adhesive Substances 0.000 description 15
- 230000001070 adhesive effect Effects 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 239000011231 conductive filler Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 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
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2427/16—Homopolymers or copolymers of vinylidene fluoride
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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Abstract
The invention belongs to the field of organic/inorganic composite materials, and discloses a polyimide film three-phase composite material with a high dielectric constant and a preparation method thereof. The composite material is formed by three-phase mixing of polyimide serving as a matrix, titanium dioxide serving as a dielectric filler and polyvinylidene fluoride serving as a filling phase. Wherein the mass portion of the polyimide is 100, the mass portion of the titanium dioxide is 10-50, and the mass portion of the polyvinylidene fluoride is 10-50. According to the preparation method provided by the invention, the three-phase compound with higher dielectric constant, extremely low dielectric loss and better mechanical property can be obtained. The presence of polyvinylidene fluoride makes it possible to add a higher content of filler in the matrix. The polyimide three-phase composite film material with the high dielectric constant, prepared by the invention, is used for a high-density energy storage device.
Description
Technical Field
The invention belongs to the field of inorganic/organic composite materials, and designs a high-dielectric-constant polyimide three-phase composite material and a preparation method thereof.
Background
The chemical structure of the polyimide determines that the polyimide has a plurality of distinctive properties and performance characteristics, mainly including excellent heat resistance, mechanical properties, good chemical stability and moisture resistance, and radiation resistance and dielectric properties. With the rapid development of integrated circuits and electronics industries, the demand for materials with high dielectric constant and low dielectric loss is more and more urgent. The method mainly adopted for improving the dielectric constant is to add high-dielectric-constant fillers such as barium titanate, silicon carbide and the like, but for adding a single inorganic filler, the poor dispersibility can cause the generation of extremely many holes in the composite material, and the existence of the holes is not beneficial to the increase of the dielectric constant and can also increase the dielectric loss of the composite material. Another effective method of increasing the dielectric constant is to incorporate conductive filler particles into the matrix material, which results in a higher dielectric constant. But near the percolation theoretical value, extremely high dielectric losses result.
In order to overcome the defects of holes caused by uneven dispersion of introduced single inorganic filler and the extremely high dielectric loss of introduced conductive filler, the invention provides a method for preparing a three-phase composite film material taking polyimide as a matrix.
To achieve an appreciable dielectric constant by incorporating a single inorganic dielectric filler into the polymer matrix, high filler levels must be incorporated. However, the high content of the inorganic filler not only reduces the mechanical properties of the composite material, but also increases the dielectric loss of the composite material, which is very disadvantageous for improving the dielectric properties of the material. According to the method, the inorganic filler titanium dioxide is used as the dielectric filler, the organic matter polyvinylidene fluoride is used as the filling phase, and holes left due to poor titanium dioxide dispersibility are filled, so that the internal structure of the composite material tends to be complete and has no hole defect. The method is not only beneficial to increasing the dielectric constant, but also overcomes the defect that the dielectric and mechanical properties of the composite material are damaged due to the increase of the content of the filler.
Disclosure of Invention
The high-dielectric-constant polyimide three-phase composite film material is characterized in that the composite material is prepared from the following raw materials in parts by mass:
polyimide (I): 100
Titanium dioxide: 10-50
Polyvinylidene fluoride: 10-50
Wherein the polyimide substrate is synthesized from diamine and dianhydride monomers, and the molar ratio of the diamine to the dianhydride monomers is kept at 1: 1. When the mass fraction of the titanium dioxide reaches 50, the brittleness and the dielectric loss of the material are increased sharply, and the dielectric constant is extremely low and is not enough to meet the use requirement. On the other hand, when the mass fraction of the polyvinylidene fluoride reaches 50, better mechanical properties can be maintained due to good compatibility with the matrix polyimide. However, the dielectric constant of the composite material is low, and the dielectric loss is high due to the high spontaneous polarity of the composite material. Neither titanium dioxide nor polyvinylidene fluoride is subjected to further modification and surface treatment before use. In order to meet the requirement of better mechanical property, the molar ratio of the diamine monomer to the dianhydride monomer is strictly kept at 1:1, and the particle size of the titanium dioxide is 100-500nm and the particle size of the polyvinylidene fluoride is 5-15 μm according to the characterization of a field emission electron scanning electron microscope.
In the present invention, the monomer to be used is not particularly limited, and therefore, the dianhydride monomers are selected from the dianhydride monomers 3,3',4,4' -benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3',4,4' -diphenyl ether tetracarboxylic dianhydride, and 2,2',3,3' -biphenyl tetracarboxylic dianhydride; and the diamine monomer is 4,4 '-diaminodiphenyl ether, p-phenylenediamine and m-phenylenediamine, 3',4,4 '-benzophenonetetracarboxylic dianhydride is selected as dianhydride, and 4,4' -diaminodiphenyl ether is selected as diamine. The selected aprotic polar solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide and pyrrolidone, and the aprotic polar solvent is formed by mixing the N, N-dimethylformamide, the N, N-dimethylacetamide and the pyrrolidone according to any proportion.
Preparation method
One of the purposes of the invention is to provide a feasible method for preparing a high-dielectric-constant polyimide three-phase composite film material.
A method for preparing the high dielectric constant polyimide three-phase composite film material of claim 1, comprising the following steps:
(1) dispersing titanium dioxide and polyvinylidene fluoride in an organic solvent, performing ultrasonic treatment for 20-40 minutes at room temperature, and uniformly dispersing until the mixture becomes a suspension to obtain a titanium dioxide @ polyvinylidene fluoride mixed solution;
(2) under the environment of nitrogen and ice water bath, firstly, dissolving a diamine monomer in a suspension liquid in which titanium dioxide and polyvinylidene fluoride are dispersed, stirring until the diamine monomer is completely dissolved, then, adding a dianhydride monomer, maintaining the temperature at 10-15 ℃, and reacting for 4-6 hours until the viscosity in a reaction system is not changed any more, thereby obtaining a polyimide acid/titanium dioxide @ polyvinylidene fluoride mixed solution;
(3) placing the polyimide acid/titanium dioxide @ polyvinylidene fluoride mixed solution on a clean glass plate, completing solution removal at the temperature of 100-plus-150 ℃, and completing imidization at the temperature of 150-plus-330 ℃ to obtain a high-dielectric-constant polyimide three-phase composite film;
in the above reaction (2), the stirring time may be extended to 12 to 18 hours in order to sufficiently uniformly disperse the filler in the matrix material and in consideration of the final properties of the material. In addition, the ultrasonic device used in the present invention is not particularly required, and the purpose of ultrasonic dispersion can be achieved. However, for the ultrasonic equipment with small power, the time needs to be prolonged as much as possible in the ultrasonic process, the ultrasonic time can be adjusted according to the used equipment in consideration of different ultrasonic equipment and power, and the ultrasonic time is set to be 2-8 hours in the invention.
The polyimide acid/titanium dioxide @ polyvinylidene fluoride three-phase mixed material can be used for a thermal imidization process by being placed in a stainless steel plate, a glass plate, a silicon wafer, a metal aluminum foil, polytetrafluoroethylene or other relatively flat dies which can meet temperature requirements. In the present invention, a glass plate is used.
The invention provides polyimide/titanium dioxide @ polyvinylidene fluorideThe three-phase composite film material of the vinyl fluoride has higher dielectric constant and low dielectric loss, and can be used in energy storage equipment. The dielectric constant of the invention is generally 1MHz, the dielectric constant of the composite material is 6.5-18.12, and the dielectric loss is less than 2.5 multiplied by 10-2。
The invention has the beneficial effects that: according to the invention, titanium dioxide is selected as a dielectric filler, polyvinylidene fluoride is selected as a filling phase, and good compatibility of the polyvinylidene fluoride and matrix polyimide is utilized to fill holes in the composite material and promote the internal structure of the composite material to be complete. The filled holes increase the internal interface area of the material, improve the probability of polarization, and are beneficial to the increase of dielectric constant and the inhibition of dielectric loss. Meanwhile, due to the existence of the polyvinylidene fluoride, the mass fractions of the two fillers can reach higher content values, and the composite material can be kept to have good mechanical properties.
Drawings
FIG. 1: a is adding 40 wt% of titanium dioxide; b is simultaneously adding 40 wt% of polyvinylidene fluoride and 40 wt% of titanium dioxide
Detailed Description
Example 1
(1) Dispersing 0.95g of titanium dioxide and 0.95g of polyvinylidene fluoride in 50ml of N, N-dimethylformamide solution, and performing ultrasonic treatment at room temperature for 1 hour to uniformly disperse the titanium dioxide and the polyvinylidene fluoride to obtain titanium dioxide suspension;
(2) 3.6444g of N, N-dimethylformamide (ODA) was added to the above titanium dioxide suspension under nitrogen and ice water bath conditions, and sufficiently stirred to be completely dissolved, and thereafter 5.8651g of 3,3',4,4' -benzophenonetetracarboxylic dianhydride (BTDA) was added thereto, and the reaction was continued for 6 hours. To obtain evenly dispersed polyimide acid/titanium dioxide @ polyvinylidene fluoride three-phase mixed liquid;
(3) placing the polyimide acid/titanium dioxide @ polyvinylidene fluoride three-phase mixed solution obtained in the step (2) on a clean glass plate, and completing imidization at the temperature of 100-350 ℃ to obtain a polyimide/titanium dioxide composite film;
(4) taking down the polyimide/titanium dioxide @ polyvinylidene fluoride three-phase composite film subjected to imidization, preparing a sample, coating a conductive adhesive on the surface of the sample, placing the sample in a common oven, drying the sample for 30 minutes at 120 ℃, and performing a dielectric test, wherein the dielectric constant of the polyimide/titanium dioxide @ polyvinylidene fluoride three-phase composite film at 1MHz is 7.31, and the dielectric loss is 0.013;
comparative example 1
(1) Dispersing 0.95g of titanium dioxide in 50ml of N, N-dimethylformamide solution, and performing ultrasonic treatment for 1 hour at room temperature to uniformly disperse the titanium dioxide into titanium dioxide suspension;
(2) 3.6444g of N, N-dimethylformamide (ODA) was added to the above titanium dioxide suspension under nitrogen and ice water bath conditions, and sufficiently stirred to be completely dissolved, and thereafter 5.8651g of 3,3',4,4' -benzophenonetetracarboxylic dianhydride (BTDA) was added thereto, and the reaction was continued for 6 hours. To obtain uniformly dispersed polyimide acid/titanium dioxide mixed liquor;
(3) putting the polyimide acid/titanium dioxide mixed solution obtained in the step (2) on a clean glass plate, and completing imidization at the temperature of 100-350 ℃ to obtain a polyimide/titanium dioxide composite film;
(4) taking down the polyimide/titanium dioxide composite film which is imidized to prepare a sample, coating conductive adhesive on the surface of the sample, placing the sample in a common oven to dry for 30 minutes at 120 ℃, and carrying out dielectric test, wherein the dielectric constant of the polyimide/titanium dioxide composite film is 3.98 at 1MHz, and the dielectric loss is 0.004;
comparative examples 1 to 1
(1) Dispersing 0.95g of polyvinylidene fluoride in 50ml of N, N-dimethylformamide solution, and performing ultrasonic treatment for 1 hour at room temperature to uniformly disperse the polyvinylidene fluoride into titanium dioxide suspension;
(2) 3.6444g of N, N-dimethylformamide (ODA) was added to the above titanium dioxide suspension under nitrogen and ice water bath conditions, and sufficiently stirred to be completely dissolved, and thereafter 5.8651g of 3,3',4,4' -benzophenonetetracarboxylic dianhydride (BTDA) was added thereto, and the reaction was continued for 6 hours. To obtain uniformly dispersed polyimide acid/titanium dioxide mixed liquor;
(3) putting the polyimide acid/polyvinylidene fluoride mixed solution obtained in the step (2) on a clean glass plate, and completing imidization at the temperature of 100-350 ℃ to obtain a polyimide/titanium dioxide composite film;
(4) taking down the polyimide/polyvinylidene fluoride composite film which is imidized, making a sample, coating a conductive adhesive on the surface of the sample, placing the sample in a common oven, drying the sample for 30 minutes at 120 ℃, and carrying out a dielectric test, wherein the dielectric constant of the polyimide/polyvinylidene fluoride composite film is 5.09 at 1MHz, and the dielectric loss is 0.012;
the dielectric constant of the polyimide/titanium dioxide @ polyvinylidene fluoride three-phase composite film is obviously higher than that of the two comparative experiments, and the dielectric loss is kept at a lower level.
Example 2
(1) Dispersing 1.9g of titanium dioxide and 1.9g of polyvinylidene fluoride in 50ml of N, N-dimethylformamide solution, and performing ultrasonic treatment at room temperature for 1 hour to uniformly disperse the titanium dioxide into titanium dioxide suspension;
(2) 3.6444g of N, N-dimethylformamide (ODA) was added to the above titanium dioxide suspension under nitrogen and ice water bath conditions, and sufficiently stirred to be completely dissolved, and thereafter 5.8651g of 3,3',4,4' -benzophenonetetracarboxylic dianhydride (BTDA) was added thereto, and the reaction was continued for 6 hours. To obtain evenly dispersed polyimide acid/titanium dioxide @ polyvinylidene fluoride three-phase mixed liquid;
(3) placing the polyimide acid/titanium dioxide @ polyvinylidene fluoride three-phase mixed solution obtained in the step (2) on a clean glass plate, and completing imidization at the temperature of 100-350 ℃ to obtain a polyimide/titanium dioxide composite film;
(4) taking down the polyimide/titanium dioxide @ polyvinylidene fluoride three-phase composite film subjected to imidization, preparing a sample, coating a conductive adhesive on the surface of the sample, placing the sample in a common oven, drying the sample for 30 minutes at 120 ℃, and performing a dielectric test, wherein the dielectric constant of the polyimide/titanium dioxide @ polyvinylidene fluoride three-phase composite film at 1MHz is 9.71, and the dielectric loss is 0.013;
comparative example 2
(1) Dispersing 1.9g of titanium dioxide in 50ml of N, N-dimethylformamide solution, and performing ultrasonic treatment for 1 hour at room temperature to uniformly disperse the titanium dioxide into titanium dioxide suspension;
(2) 3.6444g of N, N-dimethylformamide (ODA) was added to the above titanium dioxide suspension under nitrogen and ice water bath conditions, and sufficiently stirred to be completely dissolved, and thereafter 5.8651g of 3,3',4,4' -benzophenonetetracarboxylic dianhydride (BTDA) was added thereto, and the reaction was continued for 6 hours. To obtain uniformly dispersed polyimide acid/titanium dioxide mixed liquor;
(3) putting the polyimide acid/titanium dioxide mixed solution obtained in the step (2) on a clean glass plate, and completing imidization at the temperature of 100-350 ℃ to obtain a polyimide/titanium dioxide composite film;
(4) taking down the polyimide/titanium dioxide composite film which is imidized to prepare a sample, coating conductive adhesive on the surface of the sample, placing the sample in a common oven to be dried for 30 minutes at 120 ℃, and carrying out dielectric test, wherein the dielectric constant of the polyimide/titanium dioxide composite film is 4.51 at 1MHz, and the dielectric loss is 0.004;
comparative example 2-1
(1) Dispersing 1.9g of polyvinylidene fluoride in 50ml of N, N-dimethylformamide solution, and performing ultrasonic treatment at room temperature for 1 hour to uniformly disperse the polyvinylidene fluoride into titanium dioxide suspension;
(2) 3.6444g of N, N-dimethylformamide (ODA) was added to the above titanium dioxide suspension under nitrogen and ice water bath conditions, and sufficiently stirred to be completely dissolved, and thereafter 5.8651g of 3,3',4,4' -benzophenonetetracarboxylic dianhydride (BTDA) was added thereto, and the reaction was continued for 6 hours. To obtain uniformly dispersed polyimide acid/titanium dioxide mixed liquor;
(3) putting the polyimide acid/polyvinylidene fluoride mixed solution obtained in the step (2) on a clean glass plate, and completing imidization at the temperature of 100-350 ℃ to obtain a polyimide/titanium dioxide composite film;
(4) taking down the polyimide/polyvinylidene fluoride composite film which is imidized, making a sample, coating a conductive adhesive on the surface of the sample, placing the sample in a common oven, drying the sample for 30 minutes at 120 ℃, and carrying out a dielectric test, wherein the dielectric constant of the polyimide/polyvinylidene fluoride composite film is 5.09 at 1MHz, and the dielectric loss is 0.012;
example 3
(1) Dispersing 2.85g of titanium dioxide and 2.85g of polyvinylidene fluoride in 50ml of N, N-dimethylformamide solution, and performing ultrasonic treatment at room temperature for 1 hour to uniformly disperse the titanium dioxide into titanium dioxide suspension;
(2) 3.6444g of N, N-dimethylformamide (ODA) was added to the above titanium dioxide suspension under nitrogen and ice water bath conditions, and sufficiently stirred to be completely dissolved, and thereafter 5.8651g of 3,3',4,4' -benzophenonetetracarboxylic dianhydride (BTDA) was added thereto, and the reaction was continued for 6 hours. To obtain evenly dispersed polyimide acid/titanium dioxide @ polyvinylidene fluoride three-phase mixed liquid;
(3) placing the polyimide acid/titanium dioxide @ polyvinylidene fluoride three-phase mixed solution obtained in the step (2) on a clean glass plate, and completing imidization at the temperature of 100-350 ℃ to obtain a polyimide/titanium dioxide composite film;
(4) taking down the polyimide/titanium dioxide @ polyvinylidene fluoride three-phase composite film subjected to imidization, making a sample, coating a conductive adhesive on the surface of the sample, placing the sample in a common oven, drying the sample for 30 minutes at 120 ℃, and carrying out a dielectric test, wherein the dielectric constant of the polyimide/titanium dioxide @ polyvinylidene fluoride three-phase composite film at 1MHz is 13.1, and the dielectric loss is 0.021;
comparative example 3
(1) Dispersing 2.85g of titanium dioxide in 50ml of N, N-dimethylformamide solution, and performing ultrasonic treatment for 1 hour at room temperature to uniformly disperse the titanium dioxide into titanium dioxide suspension;
(2) 3.6444g of N, N-dimethylformamide (ODA) was added to the above titanium dioxide suspension under nitrogen and ice water bath conditions, and sufficiently stirred to be completely dissolved, and thereafter 5.8651g of 3,3',4,4' -benzophenonetetracarboxylic dianhydride (BTDA) was added thereto, and the reaction was continued for 6 hours. To obtain uniformly dispersed polyimide acid/titanium dioxide mixed liquor;
(3) putting the polyimide acid/titanium dioxide mixed solution obtained in the step (2) on a clean glass plate, and completing imidization at the temperature of 100-350 ℃ to obtain a polyimide/titanium dioxide composite film;
(4) taking down the polyimide/titanium dioxide composite film which is imidized to prepare a sample, coating conductive adhesive on the surface of the sample, placing the sample in a common oven to be dried for 30 minutes at 120 ℃, and carrying out dielectric test, wherein the dielectric constant of the polyimide/titanium dioxide composite film is 5.23 at 1MHz, and the dielectric loss is 0.005;
comparative example 3-1
(1) Dispersing 2.85g of polyvinylidene fluoride in 50ml of N, N-dimethylformamide solution, and performing ultrasonic treatment for 1 hour at room temperature to uniformly disperse the polyvinylidene fluoride into titanium dioxide suspension;
(2) 3.6444g of N, N-dimethylformamide (ODA) was added to the above titanium dioxide suspension under nitrogen and ice water bath conditions, and sufficiently stirred to be completely dissolved, and thereafter 5.8651g of 3,3',4,4' -benzophenonetetracarboxylic dianhydride (BTDA) was added thereto, and the reaction was continued for 6 hours. To obtain uniformly dispersed polyimide acid/titanium dioxide mixed liquor;
(3) putting the polyimide acid/polyvinylidene fluoride mixed solution obtained in the step (2) on a clean glass plate, and completing imidization at the temperature of 100-350 ℃ to obtain a polyimide/titanium dioxide composite film;
(4) taking down the polyimide/polyvinylidene fluoride composite film which is imidized, making a sample, coating a conductive adhesive on the surface of the sample, placing the sample in a common oven, drying the sample for 30 minutes at 120 ℃, and carrying out a dielectric test, wherein the dielectric constant of the polyimide/polyvinylidene fluoride composite film is 8.13 at 1MHz, and the dielectric loss is 0.020;
example 4
(1) Dispersing 3.8g of titanium dioxide and 3.8g of polyvinylidene fluoride in 50ml of N, N-dimethylformamide solution, and performing ultrasonic treatment at room temperature for 1 hour to uniformly disperse the titanium dioxide and the polyvinylidene fluoride to obtain titanium dioxide suspension;
(2) 3.6444g of N, N-dimethylformamide (ODA) was added to the above titanium dioxide suspension under nitrogen and ice water bath conditions, and sufficiently stirred to be completely dissolved, and thereafter 5.8651g of 3,3',4,4' -benzophenonetetracarboxylic dianhydride (BTDA) was added thereto, and the reaction was continued for 6 hours. To obtain evenly dispersed polyimide acid/titanium dioxide @ polyvinylidene fluoride three-phase mixed liquid;
(3) placing the polyimide acid/titanium dioxide @ polyvinylidene fluoride three-phase mixed solution obtained in the step (2) on a clean glass plate, and completing imidization at the temperature of 100-350 ℃ to obtain a polyimide/titanium dioxide composite film;
(4) and taking down the polyimide/titanium dioxide @ polyvinylidene fluoride three-phase composite film subjected to imidization to prepare a sample, coating a conductive adhesive on the surface of the sample, drying the sample in a common oven at 120 ℃ for 30 minutes, and performing dielectric test, wherein the dielectric constant of the polyimide/titanium dioxide @ polyvinylidene fluoride three-phase composite film at 1MHz is 18.14, and the dielectric loss is 0.025. The microstructure of the interface is shown in FIG. 1 (b);
comparative example 1
(1) Dispersing 3.8 of titanium dioxide in 50ml of N, N-dimethylformamide solution, and performing ultrasonic treatment for 1 hour at room temperature to uniformly disperse the titanium dioxide into titanium dioxide suspension;
(2) 3.6444g of N, N-dimethylformamide (ODA) was added to the above titanium dioxide suspension under nitrogen and ice water bath conditions, and sufficiently stirred to be completely dissolved, and thereafter 5.8651g of 3,3',4,4' -benzophenonetetracarboxylic dianhydride (BTDA) was added thereto, and the reaction was continued for 6 hours. To obtain uniformly dispersed polyimide acid/titanium dioxide mixed liquor;
(3) putting the polyimide acid/titanium dioxide mixed solution obtained in the step (2) on a clean glass plate, and completing imidization at the temperature of 100-350 ℃ to obtain a polyimide/titanium dioxide composite film;
(4) taking down the polyimide/titanium dioxide composite film which is imidized, preparing a sample, coating conductive adhesive on the surface of the sample, drying the sample in a common oven at 120 ℃ for 30 minutes, and carrying out a dielectric test, wherein the dielectric constant of the polyimide/titanium dioxide composite film at 1MHz is 6.48, the dielectric loss is 0.006, and the interface microstructure of the polyimide/titanium dioxide composite film is shown in a figure 1 (a);
comparative example 4-1
(1) Dispersing 3.8g of polyvinylidene fluoride in 50ml of N, N-dimethylformamide solution, and performing ultrasonic treatment for 1 hour at room temperature to uniformly disperse the polyvinylidene fluoride into titanium dioxide suspension;
(2) 3.6444g of N, N-dimethylformamide (ODA) was added to the above titanium dioxide suspension under nitrogen and ice water bath conditions, and sufficiently stirred to be completely dissolved, and thereafter 5.8651g of 3,3',4,4' -benzophenonetetracarboxylic dianhydride (BTDA) was added thereto, and the reaction was continued for 6 hours. To obtain uniformly dispersed polyimide acid/titanium dioxide mixed liquor;
(3) putting the polyimide acid/polyvinylidene fluoride mixed solution obtained in the step (2) on a clean glass plate, and completing imidization at the temperature of 100-350 ℃ to obtain a polyimide/titanium dioxide composite film;
(4) taking down the polyimide/polyvinylidene fluoride composite film which is imidized, preparing a sample, coating a conductive adhesive on the surface of the sample, placing the sample in a common oven, drying the sample for 30 minutes at 120 ℃, and carrying out a dielectric test, wherein the dielectric constant of the polyimide/polyvinylidene fluoride composite film is 8.68 at 1MHz, and the dielectric loss is 0.020;
example 5
(1) Dispersing 4.75g of titanium dioxide and 4.75g of polyvinylidene fluoride in 50ml of N, N-dimethylformamide solution, and performing ultrasonic treatment at room temperature for 1 hour to uniformly disperse the titanium dioxide into titanium dioxide suspension;
(2) 3.6444g of N, N-dimethylformamide (ODA) was added to the above titanium dioxide suspension under nitrogen and ice water bath conditions, and sufficiently stirred to be completely dissolved, and thereafter 5.8651g of 3,3',4,4' -benzophenonetetracarboxylic dianhydride (BTDA) was added thereto, and the reaction was continued for 6 hours. To obtain evenly dispersed polyimide acid/titanium dioxide @ polyvinylidene fluoride three-phase mixed liquid;
(3) placing the polyimide acid/titanium dioxide @ polyvinylidene fluoride three-phase mixed solution obtained in the step (2) on a clean glass plate, and completing imidization at the temperature of 100-350 ℃ to obtain a polyimide/titanium dioxide composite film;
(4) taking down the polyimide/titanium dioxide @ polyvinylidene fluoride three-phase composite film subjected to imidization, making a sample, coating a conductive adhesive on the surface of the sample, placing the sample in a common oven, drying the sample for 30 minutes at 120 ℃, and performing a dielectric test, wherein the dielectric constant of the polyimide/titanium dioxide @ polyvinylidene fluoride three-phase composite film at 1MHz is 11.38, and the dielectric loss is 0.008;
comparative example 5
(1) Dispersing 4.75g of titanium dioxide in 50ml of N, N-dimethylformamide solution, and performing ultrasonic treatment for 1 hour at room temperature to uniformly disperse the titanium dioxide into titanium dioxide suspension;
(2) 3.6444g of N, N-dimethylformamide (ODA) was added to the above titanium dioxide suspension under nitrogen and ice water bath conditions, and sufficiently stirred to be completely dissolved, and thereafter 5.8651g of 3,3',4,4' -benzophenonetetracarboxylic dianhydride (BTDA) was added thereto, and the reaction was continued for 6 hours. To obtain uniformly dispersed polyimide acid/titanium dioxide mixed liquor;
(3) putting the polyimide acid/titanium dioxide mixed solution obtained in the step (2) on a clean glass plate, and completing imidization at the temperature of 100-350 ℃ to obtain a polyimide/titanium dioxide composite film;
(4) taking down the polyimide/titanium dioxide composite film which is imidized to prepare a sample, coating conductive adhesive on the surface of the sample, placing the sample in a common oven to be dried for 30 minutes at 120 ℃, and carrying out a dielectric test, wherein the dielectric constant of the polyimide/titanium dioxide composite film is 5.10 at 1MHz, and the dielectric loss is 0.009;
comparative example 5-1
(1) Dispersing 4.75g of polyvinylidene fluoride in 50ml of N, N-dimethylformamide solution, and performing ultrasonic treatment for 1 hour at room temperature to uniformly disperse the polyvinylidene fluoride into titanium dioxide suspension;
(2) 3.6444g of N, N-dimethylformamide (ODA) was added to the above titanium dioxide suspension under nitrogen and ice water bath conditions, and sufficiently stirred to be completely dissolved, and thereafter 5.8651g of 3,3',4,4' -benzophenonetetracarboxylic dianhydride (BTDA) was added thereto, and the reaction was continued for 6 hours. To obtain uniformly dispersed polyimide acid/titanium dioxide mixed liquor;
(3) putting the polyimide acid/polyvinylidene fluoride mixed solution obtained in the step (2) on a clean glass plate, and completing imidization at the temperature of 100-350 ℃ to obtain a polyimide/titanium dioxide composite film;
(4) taking down the polyimide/polyvinylidene fluoride composite film which is imidized, making a sample, coating a conductive adhesive on the surface of the sample, placing the sample in a common oven, drying the sample for 30 minutes at 120 ℃, and carrying out a dielectric test, wherein the dielectric constant of the polyimide/polyvinylidene fluoride composite film is 7.88 at 1MHz, and the dielectric loss is 0.025;
table one: comparing the value of the dielectric constant with the value of the increase in the dielectric constant
It is apparent from the table that the dielectric constant of the composite increases very slowly with PVDF alone, and reaches ε at a PVDF mass fraction of 40 wt%PI/PVDFDielectric constant increase of Δ ∈ 8.68, compared to pure (e ═ 3.5) polyimide15.18. In contrast, TiO alone was added2And less contribution to the increase of the dielectric constant of the composite film, and TiO is added2The highest dielectric constant of the composite film is epsilonPI/TiO26.48, the dielectric constant increase value is Delta epsilon22.98. The addition of the two fillers alone to the polyimide had no significant effect on the increase in dielectric constant. For comparison with the dielectric constant of a three-phase composite film, Δ ε is selected1And Δ ε2Adding, i.e. Δ ε1+Δε28.16. After mixing PVDF and TiO2When added together to the polyimide, it can be seen that εPI/PVDF@TiO218.14. Compared to pure polyimide, Δ ∈ 14.64, which is a value much greater than the value of the dielectric constant of filler alone added to polyimide.
Claims (8)
1. A high dielectric constant polyimide three-phase composite film material is characterized in that:
(1) dispersing titanium dioxide and polyvinylidene fluoride in an organic solvent, performing ultrasonic treatment for 20-40 minutes at room temperature, and uniformly dispersing until the mixture becomes a suspension to obtain a titanium dioxide @ polyvinylidene fluoride mixed solution;
(2) under the environment of nitrogen and ice water bath, firstly, dissolving a diamine monomer in a suspension liquid in which titanium dioxide and polyvinylidene fluoride are dispersed, stirring until the diamine monomer is completely dissolved, then, adding a dianhydride monomer, maintaining the temperature at 10-15 ℃, and reacting for 4-6 hours until the viscosity in a reaction system is not changed any more, thereby obtaining a polyimide acid/titanium dioxide @ polyvinylidene fluoride mixed solution;
(3) placing the polyimide acid/titanium dioxide @ polyvinylidene fluoride mixed solution on a clean glass plate, completing solution removal at the temperature of 100-plus-150 ℃, and completing imidization at the temperature of 150-plus-330 ℃ to obtain a high-dielectric-constant polyimide three-phase composite film;
wherein the polyimide substrate is synthesized from diamine and dianhydride monomers, and the molar ratio of the diamine to the dianhydride monomers is kept at 1: 1.
2. The high dielectric constant polyimide three-phase composite film material as claimed in claim 1, wherein: the particle size of the nano-scale titanium dioxide is 100-500 nm.
3. The high dielectric constant polyimide three-phase composite film material as claimed in claim 1, wherein: the particle size of the micron-sized polyvinylidene fluoride is 5-15 μm.
4. The high dielectric constant polyimide three-phase composite film material as claimed in claim 1, wherein: the dianhydride monomer is 3,3',4,4' -benzophenonetetracarboxylic dianhydride.
5. The high dielectric constant polyimide three-phase composite film material as claimed in claim 1, wherein: the diamine monomer is 4,4' -diaminodiphenyl ether.
6. A method for preparing the high dielectric constant polyimide three-phase composite film material as claimed in claim 1, wherein: the micron-sized polyvinylidene fluoride promotes the dispersion of the nano-sized titanium dioxide in the polyimide to obtain the three-phase composite film with better dielectric property and mechanical property.
7. The method of claim 1, wherein: the organic solvent is N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone or tetrahydrofuran.
8. The method of claim 1, wherein: the dianhydride monomer is 3,3',4,4' -benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3',4,4' -diphenyl ether tetracarboxylic dianhydride and 2,2',3,3' -biphenyl tetracarboxylic dianhydride; the diamine monomer is 4,4' -diaminodiphenyl ether, p-phenylenediamine and m-phenylenediamine.
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