CN116218008A - Polypropylene metallized film and metallized film capacitor - Google Patents
Polypropylene metallized film and metallized film capacitor Download PDFInfo
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- CN116218008A CN116218008A CN202211594207.7A CN202211594207A CN116218008A CN 116218008 A CN116218008 A CN 116218008A CN 202211594207 A CN202211594207 A CN 202211594207A CN 116218008 A CN116218008 A CN 116218008A
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- -1 Polypropylene Polymers 0.000 title claims abstract description 118
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 118
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 118
- 239000011104 metalized film Substances 0.000 title claims abstract description 47
- 239000003990 capacitor Substances 0.000 title claims abstract description 28
- 239000010408 film Substances 0.000 claims abstract description 105
- NPFYZDNDJHZQKY-UHFFFAOYSA-N 4-Hydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 NPFYZDNDJHZQKY-UHFFFAOYSA-N 0.000 claims abstract description 30
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 27
- 239000011737 fluorine Substances 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 19
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 229920001973 fluoroelastomer Polymers 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 10
- 238000007738 vacuum evaporation Methods 0.000 claims description 7
- 229920006378 biaxially oriented polypropylene Polymers 0.000 claims description 6
- 239000011127 biaxially oriented polypropylene Substances 0.000 claims description 6
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims description 5
- 238000004544 sputter deposition Methods 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000012024 dehydrating agents Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 10
- 238000004146 energy storage Methods 0.000 abstract description 8
- 239000000243 solution Substances 0.000 description 25
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 18
- 229910052782 aluminium Inorganic materials 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 235000006408 oxalic acid Nutrition 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000001771 vacuum deposition Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/33—Thin- or thick-film capacitors
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
- C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/20—Metallic material, boron or silicon on organic substrates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Power Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
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Abstract
The invention provides a polypropylene metallized film and a metallized film capacitor, wherein the polypropylene metallized film comprises a modified polypropylene film and a metal layer positioned on the surface of the modified polypropylene film; the modified polypropylene film is prepared by the following steps: immersing a polypropylene film in a potassium permanganate solution for oxidation reaction, immersing the polypropylene film in a 4-hydroxybenzophenone solution for heating reaction, and immersing the polypropylene film in a fluorine-containing functional monomer solution for photoinitiated free radical polymerization reaction so as to grow fluorine-containing polymer chains on the surface of the polypropylene film, thereby obtaining the modified polypropylene film; here, the fluorine-containing functional monomer is obtained by reacting a carboxyl-terminated fluororubber with hydroxyethyl acrylate. According to the polypropylene metallized film and the metallized film capacitor provided by the invention, the modified polypropylene film is used as the base film, so that the breakdown strength and the energy storage density of the obtained metallized film are obviously improved.
Description
Technical Field
The invention relates to the technical field of capacitors, in particular to a polypropylene metallized film and a metallized film capacitor.
Background
In recent years, with the rapid development of modern power electronic technology, capacitors are widely applied in the field of power electronics, and the development of capacitor energy storage technology also puts higher demands on the energy storage performance of the capacitors. Aluminum electrolytic capacitors have been widely used with excellent properties such as small volume, large capacity, high energy storage density, etc., but with the development of technology, various disadvantages such as large loss, short life, poor high voltage resistance, etc. of aluminum electrolytic capacitors are more remarkable, and their application is correspondingly limited. The metallized film capacitor has the advantages of high breakdown strength, low dielectric loss, good bit property, low inductance, good self-healing property and the like, so that the metallized film capacitor is more widely applied than other types of capacitors.
In order to manufacture metallized film capacitors with small volume and high capacitance, the modern industry generally uses ion sputtering technology or vacuum evaporation technology to add an extremely thin metal film on a dielectric film. The dielectric film materials used for metallized film capacitors are of a wide variety and include a wide variety of high molecular weight polymers such as polypropylene, polycarbonate, etc., and among them polypropylene is the most widely used. However, films using polypropylene as a main material, which are widely used at present, have difficulty in increasing specific capacity and energy storage density of film capacitors due to low dielectric constants, and are an obstacle to miniaturization, integration and high functionality of electronic/electrical equipment. Therefore, the improvement of the breakdown strength and the energy storage density of the polypropylene film is imperative and significant.
Disclosure of Invention
Based on the technical problems in the background technology, the invention provides a polypropylene metallized film and a metallized film capacitor, and the breakdown strength and the energy storage density of the obtained metallized film are obviously improved by taking a modified polypropylene film as a base film.
The invention provides a polypropylene metallized film, which comprises a modified polypropylene film and a metal layer positioned on the surface of the modified polypropylene film;
the modified polypropylene film is prepared by the following steps: immersing a polypropylene film in a potassium permanganate solution for oxidation reaction, immersing the polypropylene film in a 4-hydroxybenzophenone solution for heating reaction, and immersing the polypropylene film in a fluorine-containing functional monomer solution for photoinitiated free radical polymerization reaction so as to grow fluorine-containing polymer chains on the surface of the polypropylene film, thereby obtaining the modified polypropylene film; here, the fluorine-containing functional monomer is obtained by reacting a carboxyl-terminated fluororubber with hydroxyethyl acrylate.
Preferably, the polypropylene film is a biaxially oriented polypropylene film having a thickness of 1 to 15 μm.
Preferably, the potassium permanganate solution is sulfuric acid solution of potassium permanganate, and the concentration of the potassium permanganate solution is 0.2-0.4mol/L;
preferably, the temperature of the oxidation reaction is 60-80 ℃ and the time is 3-6h.
Preferably, the 4-hydroxybenzophenone solution is butanone solution of 4-hydroxybenzophenone, and the concentration of the butanone solution is 5-15wt%;
preferably, the temperature of the heating reaction is 50-70 ℃ and the time is 8-10h.
Preferably, the fluorine-containing functional monomer is obtained by reacting carboxyl-terminated fluororubber and hydroxyethyl acrylate under the catalysis of an acid binding agent DMAP and a dehydrating agent DCC;
preferably, the carboxyl-terminated fluororubber is a vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer containing carboxyl-terminated, and the mass ratio of the carboxyl-terminated fluororubber to the hydroxyethyl acrylate is 4-6:1.
Preferably, the wavelength of light for the photoinitiated free radical polymerization reaction is 220-365nm.
Preferably, the metal layer is at least one of an aluminum metal layer or a zinc metal layer.
Preferably, the polypropylene metallized film is obtained by forming a metal layer on the surface of the modified polypropylene film by adopting a vacuum evaporation or sputtering coating process.
The invention also provides a metallized film capacitor which comprises the polypropylene metallized film.
In the invention, the polypropylene film is immersed in the potassium permanganate solution for oxidation reaction, and the strong oxidizing property of the potassium permanganate solution is utilized to carry out surface modification on the polypropylene film, so that polar groups such as carboxyl (-COOH) and the like are generated on the surface of the polypropylene film; then immersing the polypropylene film into 4-hydroxybenzophenone solution for heating reaction, and reacting the 4-hydroxybenzophenone with carboxyl (-COOH) groups generated on the surface of the polypropylene film to bond the benzophenone photopolymerization initiator to the surface of the polypropylene film; and then immersing the film in a fluorine-containing functional monomer solution, and using the benzophenone photopolymerization initiator as a starting point to perform free radical polymerization on the fluorine-containing functional monomer, thereby preparing the polypropylene film with the surface provided with the fluorine-containing polymer chains, namely the modified polypropylene film.
In the modified polypropylene film, the outermost surface of the polypropylene film comprises the polymer layer containing the fluorine polymer chains, which can bring ideal effects to the metallized film taking the modified polypropylene film as a base film, thereby effectively improving the breakdown strength and the energy storage density of the obtained metallized film.
Detailed Description
The technical scheme of the present invention will be described in detail by means of specific examples, which should be explicitly set forth for illustration, but should not be construed as limiting the scope of the present invention.
Example 1
A polypropylene metallized film comprises a modified polypropylene film and a metal layer positioned on the surface of the modified polypropylene film; the preparation method comprises the following steps:
immersing a biaxially oriented polypropylene film (with the thickness of 6 mu m) in a sulfuric acid aqueous solution of potassium permanganate (the concentration of potassium permanganate is 0.3mol/L and the concentration of sulfuric acid is 0.3 mol/L), reacting for 5 hours in a water bath at the temperature of 70 ℃, taking out the polypropylene film, cleaning the polypropylene film by using oxalic acid solution (the concentration of oxalic acid is 0.1 mol/L), cleaning the polypropylene film by using deionized water until the surface is cleaned, and then drying the polypropylene film in an oven at the temperature of 80 ℃ to obtain the polypropylene film after oxidation reaction;
immersing the polypropylene film after the oxidation reaction in butanone solution of 4-hydroxybenzophenone (the content of the 4-hydroxybenzophenone is 9 wt%) for reaction for 9 hours in water bath at 60 ℃, taking out the polypropylene film, drying, immersing in fluorine-containing functional monomer solution (the content of the fluorine-containing functional monomer is 26 wt%) and processing for 25 minutes under ultraviolet irradiation with the wavelength of 365nm so as to grow fluorine-containing polymer chains on the surface of the polypropylene film, thus obtaining a modified polypropylene film;
the fluorine-containing functional monomer solution is prepared by adding a vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer containing terminal carboxyl groups and hydroxyethyl acrylate into butanone according to a mass ratio of 5:1, adding DMAP accounting for 5wt% of the hydroxyethyl acrylate and DCC accounting for 10wt% of the hydroxyethyl acrylate as catalysts, and stirring and reacting for 30 hours at room temperature;
and (3) fixing the modified polypropylene film in a vacuum coating machine, and forming an Al metal layer (thickness of 0.2 mu m) on the surface of the modified polypropylene film by adopting a vacuum evaporation process, wherein the heating current of an aluminum evaporator evaporation boat is 80A, the aluminum feeding speed is 600mm/min, and the diameter of an fed aluminum wire is 2mm, so that the polypropylene metallized film is obtained.
Example 2
A polypropylene metallized film comprises a modified polypropylene film and a metal layer positioned on the surface of the modified polypropylene film; the preparation method comprises the following steps:
immersing a biaxially oriented polypropylene film (with the thickness of 6 mu m) in a sulfuric acid aqueous solution of potassium permanganate (the concentration of potassium permanganate is 0.2mol/L and the concentration of sulfuric acid is 0.2 mol/L), reacting for 6 hours in a water bath at 60 ℃, taking out the polypropylene film, cleaning the polypropylene film by using an oxalic acid solution (the concentration of oxalic acid is 0.1 mol/L), cleaning the polypropylene film by using deionized water until the surface is cleaned, and then drying the polypropylene film in an oven at 80 ℃ to obtain the polypropylene film after oxidation reaction;
immersing the polypropylene film after the oxidation reaction in butanone solution of 4-hydroxybenzophenone (the content of 4-hydroxybenzophenone is 5 wt%) for reaction for 8 hours in water bath at 70 ℃, taking out the polypropylene film, drying, immersing in fluorine-containing functional monomer solution (the content of fluorine-containing functional monomer is 20 wt%) and processing for 25 minutes under ultraviolet irradiation with 365nm wavelength to grow fluorine-containing polymer chains on the surface of the polypropylene film, thus obtaining a modified polypropylene film;
the fluorine-containing functional monomer solution is prepared by adding a vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer containing terminal carboxyl groups and hydroxyethyl acrylate into butanone according to a mass ratio of 6:1, adding DMAP accounting for 5wt% of the hydroxyethyl acrylate and DCC accounting for 10wt% of the hydroxyethyl acrylate as catalysts, and stirring and reacting for 30 hours at room temperature;
and (3) fixing the modified polypropylene film in a vacuum coating machine, and forming an Al metal layer (thickness of 0.2 mu m) on the surface of the modified polypropylene film by adopting a vacuum evaporation process, wherein the heating current of an aluminum evaporator evaporation boat is 80A, the aluminum feeding speed is 600mm/min, and the diameter of an fed aluminum wire is 2mm, so that the polypropylene metallized film is obtained.
Example 3
A polypropylene metallized film comprises a modified polypropylene film and a metal layer positioned on the surface of the modified polypropylene film; the preparation method comprises the following steps:
immersing a biaxially oriented polypropylene film (with the thickness of 6 mu m) in a sulfuric acid aqueous solution of potassium permanganate (the concentration of potassium permanganate is 0.4mol/L and the concentration of sulfuric acid is 0.4 mol/L), reacting for 3 hours in a water bath at 80 ℃, taking out the polypropylene film, cleaning the polypropylene film by using oxalic acid solution (the concentration of oxalic acid is 0.1 mol/L), cleaning the polypropylene film by using deionized water until the surface is cleaned, and then drying the polypropylene film in an oven at 80 ℃ to obtain the polypropylene film after oxidation reaction;
immersing the polypropylene film after the oxidation reaction in butanone solution of 4-hydroxybenzophenone (the content of the 4-hydroxybenzophenone is 15 wt%) for reaction for 10 hours in water bath at 50 ℃, taking out the polypropylene film, drying, immersing in fluorine-containing functional monomer solution (the content of the fluorine-containing functional monomer is 30 wt%) and processing for 25 minutes under ultraviolet irradiation with the wavelength of 365nm so as to grow fluorine-containing polymer chains on the surface of the polypropylene film, thus obtaining a modified polypropylene film;
the fluorine-containing functional monomer solution is prepared by adding a vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer containing terminal carboxyl groups and hydroxyethyl acrylate into butanone according to a mass ratio of 4:1, adding DMAP accounting for 5wt% of the hydroxyethyl acrylate and DCC accounting for 10wt% of the hydroxyethyl acrylate as catalysts, and stirring and reacting for 30 hours at room temperature;
and (3) fixing the modified polypropylene film in a vacuum coating machine, and forming an Al metal layer (thickness of 0.2 mu m) on the surface of the modified polypropylene film by adopting a vacuum evaporation process, wherein the heating current of an aluminum evaporator evaporation boat is 80A, the aluminum feeding speed is 600mm/min, and the diameter of an fed aluminum wire is 2mm, so that the polypropylene metallized film is obtained.
Comparative example 1
A polypropylene metallized film, comprising a polypropylene film and a metal layer positioned on the surface of the polypropylene film; the preparation method comprises the following steps:
and (3) placing the biaxially oriented polypropylene film (with the thickness of 6 mu m) in a vacuum coating machine for fixation, and forming an Al metal layer (with the thickness of 0.2 mu m) on the surface of the modified polypropylene film by adopting a vacuum evaporation process, wherein the heating current of an aluminum evaporator evaporation boat is 80A, the aluminum feeding speed is 600mm/min, and the diameter of an fed aluminum wire is 2mm, so that the polypropylene metallized film is obtained.
The polypropylene metallized film in the embodiment 1 and the polypropylene metallized film in the comparative embodiment 1 are cut into films with preset widths and then wound into a capacitor core, and the upper and lower staggered edges ensure that the metallized film is contacted with one side face only; forming capacitor electrodes by spraying metal on two sides, and improving the performance of the capacitor core through heat treatment and energization; and then welding, assembling, packaging and detecting to finally obtain the needed metallized film capacitor.
The capacitor was subjected to a withstand voltage test with a voltage amplifier, the maximum current was limited to 20mA, the breakdown was determined as a breakdown by boosting the voltage at a rate of 100V/s until the leakage current of the capacitor exceeded 20mA, and the breakdown strength of the capacitor was calculated in combination with the film thickness.
Table 1 examples and comparative examples correspond to breakdown strength and storage density improvement rate of metallized film capacitors
As can be seen from table 1 above, the example significantly improved the breakdown strength and the storage density of the metallized film after the polypropylene film was modified as compared to the comparative example.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (9)
1. The polypropylene metallized film is characterized by comprising a modified polypropylene film and a metal layer positioned on the surface of the modified polypropylene film;
the modified polypropylene film is prepared by the following steps: immersing a polypropylene film in a potassium permanganate solution for oxidation reaction, immersing the polypropylene film in a 4-hydroxybenzophenone solution for heating reaction, and immersing the polypropylene film in a fluorine-containing functional monomer solution for photoinitiated free radical polymerization reaction so as to grow fluorine-containing polymer chains on the surface of the polypropylene film, thereby obtaining the modified polypropylene film; here, the fluorine-containing functional monomer is obtained by reacting a carboxyl-terminated fluororubber with hydroxyethyl acrylate.
2. The polypropylene metallized film according to claim 1, wherein the polypropylene film is biaxially oriented polypropylene film having a thickness of 1 to 15 μm.
3. The polypropylene metallized film according to any one of claims 1-2, wherein the potassium permanganate solution is a sulfuric acid solution of potassium permanganate at a concentration of 0.2-0.4mol/L;
preferably, the temperature of the oxidation reaction is 60-80 ℃ and the time is 3-6h.
4. A polypropylene metallized film according to any one of claims 1 to 3, wherein the 4-hydroxybenzophenone solution is a butanone solution of 4-hydroxybenzophenone in a concentration of 5 to 15% by weight;
preferably, the temperature of the heating reaction is 50-70 ℃ and the time is 8-10h.
5. The metallized polypropylene film according to any one of claims 1 to 4, wherein the fluorine-containing functional monomer is obtained by reacting carboxyl-terminated fluororubber with hydroxyethyl acrylate under the catalysis of an acid-binding agent DMAP and a dehydrating agent DCC;
preferably, the carboxyl-terminated fluororubber is a vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer containing carboxyl-terminated, and the mass ratio of the carboxyl-terminated fluororubber to the hydroxyethyl acrylate is 4-6:1.
6. The polypropylene metallized film of any one of claims 1-5, wherein the photoinitiated free radical polymerization has a wavelength of light ranging from 220 nm to 365nm.
7. The polypropylene metallized film of any one of claims 1-6, wherein the metal layer is at least one of an aluminum metal layer or a zinc metal layer.
8. The metallized polypropylene film according to any one of claims 1 to 7, wherein the metallized polypropylene film is obtained by forming a metal layer on the surface of the modified polypropylene film by vacuum evaporation or sputtering.
9. Metallized film capacitor, characterized in that it comprises a polypropylene metallized film according to any one of claims 1 to 8.
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Cited By (1)
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