CN115322478A - Ultrathin high-temperature-resistant polypropylene capacitor film and manufacturing method thereof - Google Patents
Ultrathin high-temperature-resistant polypropylene capacitor film and manufacturing method thereof Download PDFInfo
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- CN115322478A CN115322478A CN202210906208.4A CN202210906208A CN115322478A CN 115322478 A CN115322478 A CN 115322478A CN 202210906208 A CN202210906208 A CN 202210906208A CN 115322478 A CN115322478 A CN 115322478A
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- -1 polypropylene Polymers 0.000 title claims abstract description 171
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 159
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 159
- 239000003990 capacitor Substances 0.000 title claims abstract description 65
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 50
- 229920005989 resin Polymers 0.000 claims abstract description 50
- 239000002994 raw material Substances 0.000 claims abstract description 33
- 229920001577 copolymer Polymers 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000002667 nucleating agent Substances 0.000 claims abstract description 17
- 238000000227 grinding Methods 0.000 claims abstract description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 238000002844 melting Methods 0.000 claims abstract description 4
- 230000008018 melting Effects 0.000 claims abstract description 4
- 238000000465 moulding Methods 0.000 claims abstract description 4
- 238000007493 shaping process Methods 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 20
- 239000012528 membrane Substances 0.000 claims description 17
- 239000011941 photocatalyst Substances 0.000 claims description 16
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 15
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000000155 melt Substances 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000012530 fluid Substances 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 8
- 230000009471 action Effects 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 229920005631 polypropylene heterophasic copolymer Polymers 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 230000015556 catabolic process Effects 0.000 claims description 5
- 238000009998 heat setting Methods 0.000 claims description 5
- 230000001678 irradiating effect Effects 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 239000004711 α-olefin Substances 0.000 claims description 3
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 claims description 2
- 239000002612 dispersion medium Substances 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- QWQNFXDYOCUEER-UHFFFAOYSA-N 2,3-ditert-butyl-4-methylphenol Chemical group CC1=CC=C(O)C(C(C)(C)C)=C1C(C)(C)C QWQNFXDYOCUEER-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 11
- 229920000642 polymer Polymers 0.000 abstract description 8
- 238000004381 surface treatment Methods 0.000 abstract description 6
- 239000000654 additive Substances 0.000 abstract description 3
- 238000007598 dipping method Methods 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 104
- 239000000243 solution Substances 0.000 description 17
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- FQNKQTQMOUYNIQ-UHFFFAOYSA-J [Mo+4].[Cl-].C1=CC=CC1.[Cl-].[Cl-].[Cl-] Chemical compound [Mo+4].[Cl-].C1=CC=CC1.[Cl-].[Cl-].[Cl-] FQNKQTQMOUYNIQ-UHFFFAOYSA-J 0.000 description 7
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 7
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical group CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 238000003851 corona treatment Methods 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 239000004115 Sodium Silicate Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 5
- 229910052911 sodium silicate Inorganic materials 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000001282 organosilanes Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 239000011104 metalized film Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JYLUAHPKLGKVNL-UHFFFAOYSA-J C1(C=CC=C1)[Mo](Cl)(Cl)(Cl)Cl Chemical compound C1(C=CC=C1)[Mo](Cl)(Cl)(Cl)Cl JYLUAHPKLGKVNL-UHFFFAOYSA-J 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- NHYFIJRXGOQNFS-UHFFFAOYSA-N dimethoxy-bis(2-methylpropyl)silane Chemical compound CC(C)C[Si](OC)(CC(C)C)OC NHYFIJRXGOQNFS-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000048 melt cooling Methods 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 230000004001 molecular interaction Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/14—Organic dielectrics
- H01G4/18—Organic dielectrics of synthetic material, e.g. derivatives of cellulose
-
- 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
-
- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—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
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
-
- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—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
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/14—Copolymers of propene
-
- 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
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
- C08K2003/2213—Oxides; Hydroxides of metals of rare earth metal of cerium
-
- 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
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Power Engineering (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Abstract
The invention discloses an ultrathin high-temperature-resistant polypropylene capacitor film which is prepared from the following raw materials in percentage by mass: 14 to 30 percent of polypropylene resin B, 4 to 10 percent of polypropylene multiphase copolymer, 2 to 4 percent of maleic anhydride, 1 to 2 percent of nano inorganic powder, 0.3 to 0.5 percent of anti-heat and anti-deterioration agent, 0.02 to 0.06 percent of beta nucleating agent and the balance of polypropylene resin A; the invention also discloses a preparation method of the polypropylene capacitor film, which is prepared by grinding, mixing, melting and extruding different polypropylene raw materials and other additives, molding, biaxial stretching and photochemical surface treatment. According to the invention, through optimizing raw materials, modified polymers and compound additives, the temperature resistance and mechanical properties of the film are improved, and through controlling the process and parameters thereof, the coarsening degree of two surfaces of the film can be effectively controlled in the film production process, and the dipping property and the electric resistance property of the film are improved.
Description
Technical Field
The invention belongs to the technical field of polymer films, and particularly relates to an ultrathin high-temperature-resistant polypropylene capacitor film and a preparation method thereof.
Background
The polypropylene film has small specific gravity and stable chemical performance, and the biaxially oriented polypropylene film (BOPP) can keep smaller dielectric thickness and better electric strength at the working voltage of the capacitor, so that the biaxially oriented polypropylene film becomes the main dielectric material of the film capacitor. With the rapid development of the electronic information industry and the power industry, the thin film capacitor is developing towards the direction of large capacity, miniaturization and high safety and reliability, and higher requirements are put forward on indexes of the thin film capacitor, such as volume, temperature resistance and reliability. The existing polypropylene film has large thickness, poor temperature resistance and relatively high thermal shrinkage, and a capacitor formed by winding the film has rapid internal temperature rise along with the lengthening of the working time, so that the stability of the capacitor is rapidly reduced, even the capacitor fails, and serious potential safety hazards are brought to a power grid.
In order to reduce the thickness of a polypropylene film, a patent with the application number of CN201310389997.X discloses a high-performance ultrathin polypropylene capacitor film and a preparation method thereof, wherein a high-purity electrical-grade polypropylene raw material is adopted, and is sequentially subjected to melt extrusion, sheet casting, bidirectional synchronous stretching at a stretching ratio of 40-50 times, cooling setting, edge cutting and corona treatment to obtain a finished polypropylene capacitor film with the thickness of 2-4 microns. In order to further improve the temperature resistance of the polypropylene metallized film, the patent with the application number of CN201610520576.X discloses an ultrathin high-temperature-resistant polypropylene capacitor metallized film, which comprises a base film, an aluminum coating and a zinc coating, wherein the aluminum coating and the zinc coating are sequentially plated on the base film, and a polyurethane layer high-temperature-resistant layer is arranged on the zinc coating; the polypropylene basal membrane is prepared by adopting electrical isotactic regular polypropylene resin as a raw material and sequentially carrying out melting plasticization, die head extrusion, sheet casting, biaxial stretching, cooling and shaping, fixed-width edge cutting, thickness inspection and corona treatment. The two methods obtain the ultrathin polypropylene capacitor film with better heat shrinkage rate by matching the high-purity polypropylene raw material with stretching process parameters, heat setting temperature and the like.
Because the surface structure and the performance of the polypropylene film directly influence the subsequent processing, the two methods adopt corona to carry out surface treatment on the BOPP film so as to improve the surface polarity and the surface roughness of the BOPP film. The corona treatment is to discharge between an electrode and a corona treatment roller to ionize air to form ozone and nitrogen oxide, break the bond molecules of the ozone and the nitrogen oxide to generate free radicals and generate reactions such as oxidation crosslinking, and simultaneously, high-energy electrons and ions are injected into the film to generate micro-concave dense holes on the surface of the film, so that the surface of the film is roughened, and the surface polarity of the film is improved. In the corona treatment process, the requirements on parallelism between other traction rollers and uniformity of compression roller pressure on the corona treatment roller are strict, otherwise, the film is wrinkled and inclined on the corona roller; in addition, in actual production, air or dust is easily clamped between the film and the corona roller, and the inevitable clamping between the electrode and the corona roller of the ultrathin polypropylene film which is not subjected to antistatic treatment can cause surface defects and influence the using effect of the film.
In addition, the polypropylene film generally has poor temperature resistance, and the prior document "preparation of high temperature resistant polypropylene for film and its properties" mentions: the addition of the alpha nucleating agent enables the temperature resistance of the polypropylene to be improved better. For a capacitor flat film with a smooth surface, the crystallinity of polypropylene can be improved by adding the nucleating agent, so that the density is improved, and the temperature resistance of the polypropylene is improved. However, after a quantitative nucleating agent is added, the mechanical property and the processing property of the material are changed, and for the coarsened film prepared by biaxial stretching, due to the limitation of the surface structure and the mechanical property, the ultrathin property and the electric resistance property of the polypropylene film are difficult to achieve simultaneously. Therefore, how to improve the temperature resistance and the electric resistance of the ultra-thin polypropylene film with a roughened surface is an urgent problem to be solved.
Disclosure of Invention
Aiming at the technical problems, the invention provides the ultrathin high-temperature-resistant polypropylene capacitor film, which is characterized in that the temperature resistance and the mechanical property are improved simultaneously by optimizing raw materials, modified polymers and compound additives; the invention also discloses a preparation method of the ultrathin high-temperature-resistant polypropylene capacitor film, and the coarsening degree of the two surfaces of the film can be effectively controlled in the production process of the film through the cooperation of biaxial stretching and photochemical surface treatment, so that the dipping performance and the electric resistance performance of the film are improved.
In order to achieve the above object of the invention, there is provided one of the following:
an ultrathin high-temperature-resistant polypropylene capacitor film is prepared from the following raw materials in percentage by mass: 14 to 30 percent of polypropylene resin B, 4 to 10 percent of polypropylene multiphase copolymer, 2 to 4 percent of maleic anhydride, 1 to 2 percent of nano inorganic powder, 0.3 to 0.5 percent of heat and inferior resistant agent, 0.02 to 0.06 percent of beta nucleating agent and the balance of polypropylene resin A;
wherein the weight average molecular weight Mw of the polypropylene resin A is 25-35 ten thousand, and the melt flow rate is 4.0-8.0 g/10min; the weight average molecular weight Mw of the polypropylene resin B is 35-38 ten thousand, and the melt flow rate is 1.0-4.0 g/10min; the polypropylene multiphase copolymer is obtained by taking propylene, ethylene and alpha-olefin as monomer raw materials and carrying out polymerization reaction in the presence of a main catalyst and a cocatalyst, wherein the weight average molecular weight Mw of the polypropylene multiphase copolymer is 35-45 ten thousand, and the melt flow rate is 1.0-2.5 g/10min.
The invention adopts low molecular weight linear polypropylene resin (polypropylene resin A), high molecular weight linear polypropylene resin (polypropylene resin B) and high molecular weight long chain branched polypropylene resin (polypropylene multiphase copolymer) as polypropylene raw materials, which all present a three-phase mixed state when forming sheet fluid, and the component configuration of the film formed after biaxial stretching is complicated, and the electric strength at high temperature is obviously improved compared with the single use of one linear polypropylene resin. And the polypropylene resin A, the polypropylene resin B and the polypropylene multiphase copolymer have specific flow characteristics in a molten state, and the uniform film thickness in the film preparation process can be ensured by mixing raw materials with different melt flow rates, so that melt fracture and tensile fracture are not easy to generate. The polypropylene multiphase copolymer polymerized by propylene, ethylene and alpha-olefin has a certain branch structure, plays a role in connection and buffering among molecular chains, has a large number of flexible long-chain functional groups on the surface, can form a spatial three-dimensional network structure more easily through molecular interaction in a system, and improves the toughness of the polypropylene and the compatibility of the polypropylene with other particles. The nano particles have the characteristics of large specific surface, few surface defects and the like, the crystallization performance of a high polymer can be influenced by utilizing the nano effect by adding the nano inorganic powder, and a proper amount of nano particles can also influence the mechanical property of the composite material, so that the strength and the toughness are improved, and the processability of raw materials is improved. The affinity and the dispersibility of the nano inorganic powder can be greatly improved through maleic anhydride grafting, and the polypropylene capacitor film is beneficial to improving the tensile strength and the impact strength.
Preferably, the beta nucleating agent comprises an amide compound and/or a rare earth compound organic matter; by using the nucleating agent, the surface roughness of the thin film can be adjusted. The deterioration preventing agent is di-tert-butyl-p-cresol, which is used for inhibiting the heat deterioration in an extruder, and the addition amount of the deterioration preventing agent is basically used up during the sheet fluid forming process, and the deterioration preventing agent hardly remains in the polypropylene capacitor film. The nano inorganic powder is nano titanium dioxide or nano cerium dioxide, compared with a polypropylene raw material, the nano particles belong to inorganic rigid particles, and in the stretching process, the nano particles which do not elastically deform are in a dispersed state on the surface of the film, so that the nano inorganic powder has a certain ultraviolet shielding effect and can prevent the inside of the polypropylene capacitor film from aging due to illumination.
Preferably, the mass percentage of propylene in the monomer raw material of the polypropylene multiphase copolymer is more than 90%, and the main catalyst takes silicon dioxide as a carrier and loads a coordination compound formed by connecting transition metal and cyclopentadiene; the cocatalyst is alkoxy silane. According to the invention, alkoxy silane is used as an external electron donor, and the assistant main catalyst plays a catalytic role.
Further, the transition metal is molybdenum, the molar ratio of silicon dioxide, molybdenum and cyclopentadiene in the main catalyst is 1-10 and is 1-2, and the amount of each mole of molybdenum corresponding to the catalytic monomer raw material is 600-800 kg; the molar ratio of the cocatalyst to the transition metal is 4-10.
The molecular weight distribution index Mw/Mn of the polypropylene resin A is 9.0-12.0, the molecular weight distribution index Mw/Mn of the polypropylene resin B is 7.5-8.5, the isotacticity of the polypropylene resin A and the polypropylene resin B is not less than 95%, and the ash content is less than 20ppm; the polypropylene heterophasic copolymer has a molecular weight distribution index Mw/Mn of 2.0 to 3.0 and an ash content of 200 to 400ppm. Selecting polypropylene with wide molecular weight distribution to ensure fluidity, and selecting polypropylene with narrow molecular weight distribution to ensure impact resistance; by selecting the polypropylene resin with higher isotacticity and low ash content, the sheet fluid can achieve good curing speed during molding, and the crystallinity is moderately improved, so that the stretchability is improved, the power resistance is improved, and the dielectric property of the polypropylene capacitor film is ensured.
The thickness of the polypropylene capacitor film is 1.5-4.0 μm; the roughness Ra of one side surface of the polypropylene capacitor film is 0.30-0.35 μm, and the roughness Ra of the other side surface of the polypropylene capacitor film is 0.20-0.30 μm; the direct-current voltage breakdown resistance strength of the polypropylene capacitor film at 100 ℃ is more than 580V/mum. Therefore, the polypropylene capacitor film has small thickness and different roughness on two sides, can ensure the dipping requirement of the film when used for capacitors, and has higher electric strength.
The preparation method of the ultrathin high-temperature-resistant polypropylene capacitor film comprises the following steps:
step one, carrying out cryogenic treatment on polypropylene resin A, polypropylene resin B and polypropylene multiphase copolymer, grinding and mixing with other raw materials at low temperature for 5-10 min, and extruding after melting and plasticizing to obtain sheet fluid;
step two, carrying out cast sheet molding on the flaky fluid obtained in the step one through a chill roll and a high-pressure air knife to obtain a membrane;
thirdly, longitudinally stretching and transversely stretching the membrane obtained in the second step by adopting a longitudinal stretcher and a transverse stretcher in sequence to obtain a membrane substrate;
and step four, immersing the film substrate obtained in the step three into a solution containing a photocatalyst under the action of ultrasound, irradiating for 1.5-3 min by adopting ultraviolet light or irradiating for 5-8 min by adopting a fluorescent lamp, taking out, washing, preserving heat and drying to obtain the film substrate.
On the basis of the original production line, the low-temperature grinding treatment is additionally arranged on the raw materials, so that the material has larger surface energy and lattice distortion energy, the diffusion of atoms, the migration elimination of pores and the like can be promoted at lower temperature, the crystallization refinement of polypropylene is promoted, and the processing performance is improved; and adding ultrasonic synergistic photochemical surface treatment (namely step four), wherein in a liquid medium environment, the photocatalyst catalytically decomposes water to generate gas under the action of illumination, and a heterogeneous system consisting of the liquid medium, the photocatalyst and the gas enables generated free radicals to be attached to the surface of the film under the action of the ultrasonic, so that the bonding molecules of the film are broken, the surface activity of the film is increased, coarsening is further performed, and meanwhile, the insulativity of the film is also improved. In the whole preparation process, the environmental humidity range is controlled in the steps one to three, and the raw materials and the membrane are prevented from contacting with the aqueous solution.
Preferably, in the third step, during the longitudinal stretching, the temperature in the membrane body is raised to 120-130 ℃ by preheating, then one surface or two surfaces of the membrane is controlled to be raised to 150-160 ℃, the longitudinal stretching is carried out, the longitudinal stretching magnification is 4-6 times, the shaping after the longitudinal stretching adopts the steps of firstly controlling tension heat shaping and then freely shrinking heat shaping, the additional stretching degree is 1.01-1.05 during the control of the tension heat shaping, and the shaping temperature is 150-160 ℃; when in transverse stretching, the stretching temperature is controlled to be 160-180 ℃, the transverse stretching multiplying power is 7-10 times, the shaping after the transverse stretching adopts fixed-length heat shaping and then free shrinkage heat shaping, and the shaping temperature is 170-180 ℃. When the film is stretched bidirectionally, a preheating method with different temperatures on the surface and inside is adopted, so that the electric strength of the film under the high-temperature condition can be improved, the mechanical strength and the rigidity of the film can be ensured, and the service life of the film is prolonged. Meanwhile, the recrystallization process of the film material is changed by controlling the tension in the stretching process, so that the heat shrinkage rate of the film is reduced, and the high-temperature resistance is improved.
In the first step, the grinding temperature is not higher than 0 ℃, and the extrusion temperature is 200-230 ℃; in the second step, the temperature of the chilling roller is 95-100 ℃, and the gas temperature of the high-pressure air knife is 95-100 ℃. According to the invention, the crystallization rate and the crystallization form are controlled by the melt cooling temperature, the effect of coarsening uniformity of the film is achieved after crystal conversion, the roughness in a certain range is formed after subsequent stretching process treatment, and the good processing adaptability of the film is maintained without losing pressure resistance.
Preferably, in the fourth step, the solution containing the photocatalyst takes water as a dispersion medium, the pH is 4 to 6, and the photocatalyst is titanium dioxide, bismuth molybdate or graphite-like carbon nitride; the drying temperature is not more than 60 ℃, the rolled paper is dried and placed in the dark for 1 to 2 days at the room temperature.
Under the irradiation of an ultraviolet lamp or a fluorescent lamp, the acidic aqueous solution is catalyzed and decomposed by the photocatalyst to generate free radicals, so that the surface of the film is subjected to transient oxidation, polar groups can be introduced, the surface free energy is improved, and the wettability of the surface of the film is improved; and moreover, a dense insulating barrier is formed on the surface of the polymer matrix through photocatalytic surface oxidation treatment, so that leakage current and space charge transmission are hindered, the migration of charges to an electrode is limited, the conductivity of the film is reduced, the breakdown strength is improved, and the insulativity of the film is ensured.
According to the invention, the polypropylene resin with high isotacticity and the polypropylene multiphase copolymer are selected and compounded through low-temperature grinding, so that the processing performance and the temperature resistance of the polypropylene capacitor film are improved, a large amount of beta crystals are promoted to be formed through the beta nucleating agent, the impact strength and the heat distortion temperature of the polypropylene are improved, the tensile toughness and the ductility of the polypropylene are better at high temperature, and the thickness of the tensile film is reduced; the crystallinity is moderately increased through temperature control in the preparation process, the mechanical strength and the rigidity of the film are further ensured, and the film has good rigidity and toughness balance; the surface of the film is enabled to form concave-convex by stretching, and then the impregnation performance and the electric strength at high temperature of the film are improved by regulating and controlling the film interface through ultrasonic cooperating with photocatalytic oxidation in a water-based system.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the following examples, the characteristics of the polypropylene feedstock were tested as follows: testing the melt flow rate of the polypropylene by using a melt flow rate tester according to GB/T3682-2000, and simultaneously meeting the requirements of ISO1133-97 and ASTM1238 standards; measuring the molecular weight distribution Mw/Mn by using a PL-GPC 220 gel permeation chromatograph; the isotacticity was measured by infrared method. The beta nucleating agent and the nano titanium dioxide are common commercial products; wherein the beta nucleating agent is purchased from Guangdong Weilinnan New materials science and technology Co., ltd, and the model is WBG-II; the nano titanium dioxide adopts P25, and the particle size is 20-30 nm.
The polypropylene heterophasic copolymer is prepared by the following method: feeding a main catalyst and a cocatalyst into a pre-contact tank to be fully contacted, feeding the main catalyst and the cocatalyst into a prepolymerization reactor, carrying out prepolymerization with propylene for 3-8 min at 10-20 ℃, feeding the main catalyst and the cocatalyst into two serially connected loop reactors to carry out polymerization reaction at 60-80 ℃, wherein the injection amount of ethylene in a first loop reactor is 0.5 percent of the propylene amount, the injection amount of 1-butene is 3.0 percent of the propylene amount, the injection amount of ethylene in a second loop reactor is 0.5 percent of the propylene amount, and the injection amount of 1-butene is 2.0 percent of the propylene amount, flashing and separating propylene, ethylene and 1-butene from a polymer discharged from the second loop reactor, removing the activity of the catalyst in the reactors, and drying the polymer to obtain the powdery multiphase polypropylene copolymer.
The main catalyst is prepared by the following method: dissolving sodium silicate in an ethanol aqueous solution, adding organosilane, dropwise adding dilute hydrochloric acid to adjust the pH value to 8-11, heating to 40-60 ℃, stirring to react for 1-2 h, adjusting the pH value to 7-8, adding cyclopentadiene molybdenum tetrachloride, heating to 60-80 ℃, stirring for 2-3 h, filtering, washing with water, and drying at 100-110 ℃ to obtain the supported metal-organic framework material which takes silicon dioxide as a carrier and couples cyclopentadiene molybdenum tetrachloride through organosilane. Wherein the mol ratio of the sodium silicate to the organosilane to the cyclopentadiene molybdenum tetrachloride is 1-10.
Example 1
An ultrathin high-temperature-resistant polypropylene capacitor film is prepared from the following raw materials in percentage by mass: 20% of polypropylene resin B, 5% of polypropylene multiphase copolymer, 3% of maleic anhydride, 1.5% of nano titanium dioxide, 0.5% of di-tert-butyl-p-cresol, 0.05% of beta nucleating agent and the balance of polypropylene resin A.
The polypropylene resin A and the polypropylene resin B are both propylene homopolymers (only by adopting propylene homopolymerization in the prior art in the field), the weight average molecular weight Mw of the polypropylene resin A is about 30 ten thousand, the molecular weight distribution index Mw/Mn is 10.5, the melt flow rate is 6.8g/10min, the isotacticity is 98 percent, and the ash content is less than 15ppm; the polypropylene resin B had a weight average molecular weight Mw of about 36 ten thousand, a molecular weight distribution index Mw/Mn of 7.8, a melt flow rate of 3.0g/10min, an isotacticity of 95%, and an ash content of less than 20ppm.
The polypropylene multiphase copolymer is obtained by polymerization reaction of propylene, ethylene and 1-butene serving as monomer raw materials in the presence of a main catalyst (silicon dioxide loaded cyclopentadiene molybdenum tetrachloride) and a cocatalyst (diisobutyldimethoxysilane), and comprises the following specific steps:
(1) Preparing a main catalyst: dissolving sodium silicate in an ethanol water solution to form a sodium silicate solution with the mass fraction of 5%, adding gamma-aminoethyl aminopropyl trimethoxy silane, dropwise adding dilute hydrochloric acid to adjust the pH value to 9-10, heating to 50 ℃, stirring for reaction for 1.5h, adjusting the pH value to 7-8, adding cyclopentadiene molybdenum tetrachloride, heating to 70 ℃, stirring for 2h, filtering, washing with water, and drying at 105 ℃ to obtain the catalyst; wherein the molar ratio of the sodium silicate to the gamma-aminoethyl aminopropyltrimethoxysilane to the cyclopentadienyl molybdenum tetrachloride is 5;
(2) Polymerization reaction: feeding a main catalyst and a cocatalyst into a pre-contact tank for sufficient contact, feeding the main catalyst and the cocatalyst into a prepolymerization reactor, prepolymerizing the main catalyst and propylene at 15 ℃ for 6min, feeding the main catalyst and the cocatalyst into two serially connected loop reactors at 70 ℃ for polymerization, wherein the injection amount of ethylene in the first loop reactor is 0.5 percent of the amount of propylene, the injection amount of 1-butene is 3.0 percent of the amount of propylene, the injection amount of ethylene in the second loop reactor is 0.5 percent of the amount of propylene, and the injection amount of 1-butene is 2.0 percent of the amount of propylene, flashing and separating the propylene, the ethylene and the 1-butene from the polymer discharged from the second loop reactor, removing the activity of the catalyst in the reactors, and drying the polymer to obtain a powdery polypropylene multiphase copolymer; wherein, the amount of catalytic propylene per mol of cyclopentadiene molybdenum tetrachloride is 650kg, and the molar ratio of the cocatalyst to the cyclopentadiene molybdenum tetrachloride is 6.
The polypropylene heterophasic copolymer has a weight average molecular weight Mw of about 41 million, a molecular weight distribution index Mw/Mn of 2.5, a melt flow rate of 2.0g/10min, and an ash content of the polypropylene heterophasic copolymer of 290 to 300ppm.
The preparation method of the ultrathin high-temperature-resistant polypropylene capacitor film comprises the following steps:
step one, polypropylene resin A, polypropylene resin B and polypropylene multiphase copolymer are subjected to liquid nitrogen cryogenic treatment, then mixed with other raw materials, ground and mixed for 6min by a low-temperature grinding machine (the working temperature is lower than 0 ℃), melted and plasticized at 220 ℃, and then extruded to obtain flaky fluid;
adjusting the gas temperature of the chilling roll and the high-pressure air knife to be 100 ℃, and carrying out cast sheet forming on the obtained sheet fluid through the chilling roll and the high-pressure air knife to obtain a membrane;
thirdly, sequentially carrying out longitudinal stretching and transverse stretching on the membrane obtained in the second step by adopting a longitudinal stretcher and a transverse stretcher to obtain a membrane substrate with the thickness of 2.0 mu m; wherein, during the longitudinal stretching, the temperature in the membrane body is raised to 125 ℃ by preheating, then one surface of the membrane is controlled to be rapidly raised to 150 ℃ for longitudinal stretching, the longitudinal stretching multiplying power is 5 times,
the shaping after longitudinal stretching adopts the steps of firstly controlling tension heat shaping and then freely shrinking heat shaping, wherein the additional stretching degree is controlled to be 1.02 during the tension heat shaping, and the shaping temperature is 160 ℃; when in transverse stretching, the stretching temperature is controlled to be 170 ℃, the transverse stretching multiplying power is 8.7 times, the fixed-length heat setting and then the free shrinkage heat setting are adopted for the setting after the transverse stretching, and the setting temperature is 175 ℃;
step four, dripping dilute sulphuric acid into water to adjust the pH value to 5, and then under the ultrasonic action, concentrating the nano titanium dioxide according to the concentration of 1.0g/LThe photocatalyst is dispersed in the solution to obtain a solution containing the photocatalyst; immersing the film substrate (cooled to room temperature) obtained in the step three in a solution containing the photocatalyst, applying an ultraviolet lamp above the solution containing the photocatalyst for irradiation treatment for 2min, taking out, washing with deionized water, drying at 55 ℃, rolling, and placing in a dark place for 1 day at room temperature (25 +/-3 ℃), with the humidity less than 60% and the purification level of 10 ten thousand, thus obtaining the film substrate; wherein, the titanium dioxide can be recycled, and the pH value of the solution is maintained to be 4.5-5 in the photocatalysis process; the frequency of the ultrasonic is 40kHz, and the light intensity irradiated by the ultraviolet lamp is 10W/m 2 。
Example 2
An ultrathin high-temperature-resistant polypropylene capacitor film is characterized in that according to the technical scheme of the embodiment 1:
step four, dropwise adding dilute sulfuric acid into water to adjust the pH value to 4, then dispersing the nano titanium dioxide into the water according to the concentration of 1.0g/L under the ultrasonic action, and adding hydrogen peroxide as an auxiliary agent (H) 2 O 2 With a concentration of 0.8 mmol/L) to obtain a solution containing the photocatalyst; immersing the film substrate (cooled to room temperature) obtained in the step three in a solution containing the photocatalyst, irradiating for 6min by adopting a fluorescent lamp, taking out, washing by using deionized water, drying at 55 ℃, rolling, and placing for 1 day in a dark place in an environment with room temperature (25 +/-3 ℃), humidity less than 60% and purification level of 10 ten thousand grade to obtain the film substrate; wherein, the titanium dioxide can be recycled, and the pH value of the solution is maintained to be 4-4.5 in the photocatalysis process; the frequency of the ultrasonic wave is 40kHz, and the light intensity irradiated by the fluorescent lamp is 70W/m 2 。
Example 3
The technical scheme of the embodiment 2 is that the ultrathin high-temperature-resistant polypropylene capacitor film is prepared from the following raw materials in percentage by mass: 14 percent of polypropylene resin B, 10 percent of polypropylene multiphase copolymer, 2 percent of maleic anhydride, 1 percent of nano titanium dioxide, 0.5 percent of di-tert-butyl-p-cresol, 0.05 percent of beta nucleating agent and the balance of polypropylene resin A.
Example 4
The technical scheme of the embodiment 2 is that the ultrathin high-temperature-resistant polypropylene capacitor film is prepared from the following raw materials in percentage by mass: 30% of polypropylene resin B, 4% of polypropylene multiphase copolymer, 4% of maleic anhydride, 2% of nano cerium dioxide, 0.5% of di-tert-butyl-p-cresol, 0.05% of beta nucleating agent and the balance of polypropylene resin A.
The polypropylene capacitor films prepared in examples 1 to 4 had smooth and wrinkle-free surfaces, no visible cracks, bubbles, inclusions and other defects, and had neat and wrinkle-free end surfaces after being dipped in a vacuum tank. The detection proves that the longitudinal tensile strength is more than 150MPa, the transverse tensile strength is more than 260MPa, and the elongation at break is more than or equal to 40 percent, which all meet the requirements of the national standard on the physical and chemical properties of the biaxially oriented polypropylene film for the capacitor.
Comparative example 1
A polypropylene capacitor film, according to the technical solution of example 1, with the difference that: the preparation method does not include the step four.
Comparative example 2
A polypropylene capacitor film is prepared according to the technical scheme of the embodiment 1, and the differences are that: the preparation method does not adopt low-temperature grinding in the step one.
Comparative example 3
The polypropylene capacitor film is prepared according to the technical scheme of the embodiment 1, and is characterized by being prepared from the following raw materials in percentage by mass: 25% of polypropylene resin B, 3% of maleic anhydride, 1.5% of nano titanium dioxide, 0.5% of di-tert-butyl-p-cresol, 0.05% of beta nucleating agent and the balance of polypropylene resin A.
Comparative example 4
The polypropylene capacitor film is prepared according to the technical scheme of the embodiment 1, and is characterized by being prepared from the following raw materials in percentage by mass: 25% of polypropylene multiphase copolymer, 3% of maleic anhydride, 1.5% of nano titanium dioxide, 0.5% of di-tert-butyl-p-cresol, 0.05% of beta nucleating agent and the balance of polypropylene resin A.
Comparative example 5
A polypropylene capacitor film, according to the technical solution of example 2, with the difference that: in step four, the light treatment is carried out for 60min.
Comparative example 6
A polypropylene capacitor film, according to the technical solution of example 2, with the difference that: and step four, the solution containing the photocatalyst is not subjected to ultrasonic treatment.
The polypropylene capacitor films prepared in the examples and comparative examples were tested, the thermal shrinkage was measured after heating at 120 ℃ for 15min, and the roughness (both sides are respectively designated as A and B) and the DC test were performed according to GB/T13542.2-2009, the results are shown in Table 1.
TABLE 1 Performance test results for Polypropylene capacitor films
As can be seen from Table 1, the comparison between example 1 and comparative example 1 shows that the biaxially oriented polypropylene capacitor film has slightly improved roughness and obviously improved breakdown strength after being subjected to photochemical surface treatment; as can be seen from the comparison between the example 1 and the comparative example 2, the electric strength of the polypropylene raw material is obviously improved after the low-temperature grinding treatment, which indicates that the low-temperature grinding is beneficial to the crystallization refinement and the uniform tissue; as can be seen from the comparison between example 1 and comparative examples 3 and 4, when one linear polypropylene raw material is used alone in a mixing ratio of more than two polypropylene raw materials, the electrical strength of the prepared film at high temperature is obviously improved, but too much polypropylene multiphase copolymer can reduce the temperature resistance of the film, thereby having negative effects on the thermal shrinkage rate and the high-temperature electrical strength; compared with the comparative example 5, the photochemical surface treatment time is not easy to be overlong, although the insulation performance of the surface of the polypropylene capacitor film can be increased by photocatalytic oxidation, the polypropylene capacitor film becomes brittle and thick due to overlong photocatalytic time, and the breakdown resistance is reduced on the contrary; as can be seen from the comparison between example 2 and comparative example 6, the ultrasound promotes the photocatalytic oxidation reaction on the surface of the film and increases the coarsening degree of the film. In a word, the polypropylene capacitor film prepared by controlling the raw materials and the process has the advantages of small thickness, low thermal shrinkage, high temperature resistance, good roughness and good electric strength.
The above examples are merely illustrative of several embodiments of the present invention, and the description thereof is more specific and detailed, but not to be construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The ultrathin high-temperature-resistant polypropylene capacitor film is characterized by being prepared from the following raw materials in percentage by mass: 14 to 30 percent of polypropylene resin B, 4 to 10 percent of polypropylene multiphase copolymer, 2 to 4 percent of maleic anhydride, 1 to 2 percent of nano inorganic powder, 0.3 to 0.5 percent of heat and inferior resistant agent, 0.02 to 0.06 percent of beta nucleating agent and the balance of polypropylene resin A;
wherein the weight average molecular weight Mw of the polypropylene resin A is 25-35 ten thousand, and the melt flow rate is 4.0-8.0 g/10min; the weight average molecular weight Mw of the polypropylene resin B is 35-38 ten thousand, and the melt flow rate is 1.0-4.0 g/10min; the polypropylene multiphase copolymer is obtained by polymerization reaction of propylene, ethylene and alpha-olefin serving as monomer raw materials in the presence of a main catalyst and a cocatalyst, the weight average molecular weight Mw of the polypropylene multiphase copolymer is 35-45 ten thousand, and the melt flow rate is 1.0-2.5 g/10min.
2. The ultra-thin high temperature resistant polypropylene capacitor film as claimed in claim 1, wherein: the beta nucleating agent comprises an amide compound and/or a rare earth compound organic matter; the anti-heat and anti-deterioration agent is ditert-butyl-p-cresol; the nano inorganic powder is powdered nano titanium dioxide or nano cerium dioxide.
3. The ultra-thin high temperature resistant polypropylene capacitor film as claimed in claim 1, wherein: the mass percentage of propylene in the monomer raw material of the polypropylene multiphase copolymer is more than 90 percent, and the main catalyst takes silicon dioxide as a carrier and loads a coordination compound formed by connecting transition metal and cyclopentadiene; the cocatalyst is alkoxy silane.
4. The ultra-thin high temperature resistant polypropylene capacitor film as claimed in claim 3, wherein: the transition metal is molybdenum, the molar ratio of silicon dioxide, molybdenum and cyclopentadiene in the main catalyst is 1-10; the molar ratio of the cocatalyst to the transition metal is 4-10.
5. The ultra-thin high temperature resistant polypropylene capacitor film as claimed in claim 1, wherein: the molecular weight distribution index Mw/Mn of the polypropylene resin A is 9.0-12.0, the molecular weight distribution index Mw/Mn of the polypropylene resin B is 7.5-8.5, the isotacticity of the polypropylene resin A and the polypropylene resin B is not less than 95%, and the ash content is less than 20ppm; the molecular weight distribution index Mw/Mn of the polypropylene heterophasic copolymer is 2.0-3.0, and the ash content of the polypropylene heterophasic copolymer is 200-400 ppm.
6. The ultra-thin high temperature resistant polypropylene capacitor film as claimed in claim 1, wherein: the thickness of the polypropylene capacitor film is 1.5-4.0 μm; the roughness Ra of one side surface of the polypropylene capacitor film is 0.30-0.35 mu m, and the roughness Ra of the other side surface of the polypropylene capacitor film is 0.20-0.30 mu m; the polypropylene capacitor film has a breakdown strength against direct voltage of more than 580V/mum at 100 ℃.
7. The method for manufacturing the ultra-thin high temperature resistant polypropylene capacitor film as claimed in any one of claims 1 to 6, comprising the steps of:
step one, carrying out cryogenic treatment on polypropylene resin A, polypropylene resin B and polypropylene multiphase copolymer, grinding and mixing the polypropylene resin A, the polypropylene resin B and the polypropylene multiphase copolymer with other raw materials at low temperature for 5-10 min, and extruding after melting and plasticizing to obtain sheet fluid;
step two, carrying out cast sheet molding on the flaky fluid obtained in the step one through a chilling roller and a high-pressure air knife to obtain a membrane;
thirdly, sequentially carrying out longitudinal stretching and transverse stretching on the membrane obtained in the second step by adopting a longitudinal stretcher and a transverse stretcher to obtain a membrane substrate;
and step four, immersing the film substrate obtained in the step three in a solution containing a photocatalyst under the action of ultrasound, irradiating for 1.5-3 min by adopting ultraviolet light or irradiating for 5-8 min by adopting a fluorescent lamp, taking out, washing, preserving heat and drying to obtain the film substrate.
8. The method for manufacturing the ultra-thin high temperature resistant polypropylene capacitor film as claimed in claim 7, wherein: in the third step, during the longitudinal stretching, preheating to raise the temperature in the membrane to 120-130 ℃, then controlling the temperature of one surface or two surfaces of the membrane to 150-160 ℃, and carrying out longitudinal stretching, wherein the longitudinal stretching multiplying power is 4-6 times, the shaping after the longitudinal stretching adopts the steps of firstly controlling tension heat shaping and then freely shrinking heat shaping, the additional stretching degree during the tension heat shaping is controlled to be 1.01-1.05, and the shaping temperature is 150-160 ℃; when in transverse stretching, the stretching temperature is controlled to be 160-180 ℃, the transverse stretching multiplying power is 7-10 times, the fixed length heat setting and then the free shrinkage heat setting are adopted for the shaping after the transverse stretching, and the shaping temperature is 170-180 ℃.
9. The method for manufacturing the ultra-thin high temperature polypropylene capacitor film as claimed in claim 8, wherein: in the first step, the temperature of the low-temperature grinding is not higher than 0 ℃, and the extrusion temperature is 200-230 ℃; in the second step, the temperature of the chilling roller is 95-100 ℃, and the gas temperature of the high-pressure air knife is 95-100 ℃.
10. The method for manufacturing the ultra-thin high temperature resistant polypropylene capacitor film as claimed in claim 7, wherein: in the fourth step, the solution containing the photocatalyst takes water as a dispersion medium, the pH value is 4-6, and the photocatalyst is titanium dioxide, bismuth molybdate or graphite-like phase carbon nitride; the drying temperature is not more than 60 ℃, and the mixture is rolled after drying and placed in the dark for 1 to 2 days at room temperature.
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| CN202210906208.4A Active CN115322478B (en) | 2022-07-29 | 2022-07-29 | Ultrathin high-temperature-resistant polypropylene capacitor film and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117484817A (en) * | 2023-12-06 | 2024-02-02 | 江苏新义薄膜有限公司 | Preparation method and device of ultrathin antistatic polypropylene film |
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| CN115322478B (en) | 2023-04-25 |
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