WO2021196511A1 - Self-adhesive corona-resistant polyimide paint, enameled wire and preparation method therefor - Google Patents

Self-adhesive corona-resistant polyimide paint, enameled wire and preparation method therefor Download PDF

Info

Publication number
WO2021196511A1
WO2021196511A1 PCT/CN2020/111005 CN2020111005W WO2021196511A1 WO 2021196511 A1 WO2021196511 A1 WO 2021196511A1 CN 2020111005 W CN2020111005 W CN 2020111005W WO 2021196511 A1 WO2021196511 A1 WO 2021196511A1
Authority
WO
WIPO (PCT)
Prior art keywords
bis
aminophenoxy
self
adhesive
corona
Prior art date
Application number
PCT/CN2020/111005
Other languages
French (fr)
Chinese (zh)
Inventor
夏宇
虞鑫海
李紫璇
周成
刘艳婷
Original Assignee
苏州巨峰电气绝缘***股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 苏州巨峰电气绝缘***股份有限公司 filed Critical 苏州巨峰电气绝缘***股份有限公司
Publication of WO2021196511A1 publication Critical patent/WO2021196511A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/002—Priming paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/06—Insulating conductors or cables
    • H01B13/065—Insulating conductors with lacquers or enamels
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/06—Insulating conductors or cables
    • H01B13/16—Insulating conductors or cables by passing through or dipping in a liquid bath; by spraying
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/30—Drying; Impregnating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/303—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups H01B3/38 or H01B3/302
    • H01B3/306—Polyimides or polyesterimides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/02—Disposition of insulation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
    • 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
    • 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
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2272—Ferric oxide (Fe2O3)
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

  • the invention belongs to the field of electrical insulating materials and electromagnetic wires, and particularly relates to a self-adhesive corona-resistant polyimide paint, enameled wire and a preparation method thereof
  • Enameled wire occupies a very important position in people's daily life. From small hair dryers to deflection coils of large machines, enameled wires are inseparable. At present, the commonly used enameled wires in the market are coated and wound into coils, and then the turns of the wires are bonded together by immersion and heating. This process has some shortcomings, such as unpredictable penetration inside the coil, and often bubbles and inability to stick; after the dipping varnish penetrates into the coil, the solvent may be evaporated, which may cause more or less physical and chemical effects on the coil. Reaction, and the evaporating solvent will also pollute the environment, and may even cause a fire. Therefore, researchers at home and abroad have been continuously developing new types of enameled wire paint, and self-adhesive wire enameled paint can reduce the process and reduce environmental pollution, and has a good application prospect.
  • Self-adhesive enameled wire is a special type of enameled wire, which is composed of a basic paint film (primer) and an outer self-adhesive paint film.
  • the performance of the outer self-adhesive paint is mainly to improve the bonding strength.
  • a coil made of self-adhesive paint can be heated by baking or energized to make the outer coating bonding layer interact, and the coil is automatically formed after cooling.
  • the self-adhesive enameled wire generally adopts a composite layer structure.
  • the composite layer enameled wire is made of two layers (or three layers) of paint of different materials, compared with a single-coated enameled wire of the same material, the composite wire has the respective properties of two different materials and overcomes the The performance deficiencies caused by the same material.
  • the baseline is the main functional insulation part, which ensures the insulation performance of the self-adhesive enameled wire, and the self-adhesive layer is mainly used to meet the needs of the coil forming process. It has an adhesive effect and protects the baseline. Enhanced role.
  • self-adhesive enameled wire Compared with traditional armature windings, self-adhesive enameled wire also has good winding, formability, embedding and processability. Self-adhesive enameled wire also has a significant feature that greatly simplifies the manufacturing process of coil windings, which is omitted in many occasions. The complicated procedures such as lashing, dipping, cleaning, etc. have been saved in many aspects such as equipment, electric power and labor, which is conducive to the realization of production automation and the improvement of product quality, while also bringing significant social and economic benefits.
  • Polyvinyl butyral self-adhesive enameled wire paint (heat-resistant grade is E grade) is a kind of paint that is widely used in the market. It is generally coated on the outermost layer of insulating paint such as polyvinyl formal and polyurethane to bond The method is heating.
  • insulating paint such as polyvinyl formal and polyurethane to bond The method is heating.
  • Monsanto Company of the United States has developed a self-adhesive paint with better adhesion, that is, adding five thousandths of the mass of amine compounds to butyral.
  • Epoxy resin self-adhesive paint has good dilution, convenient wire coating process, and the heat resistance of epoxy resin enameled wire paint is higher than that of acetal resin.
  • the epoxy system enameled wire mainly includes the following composite systems: modified polyester/epoxy composite self-adhesive enameled wire, polyesterimine/epoxy composite self-adhesive enameled wire, polyesterimide/polyamideimide/epoxy composite self-adhesive enameled wire Viscous enameled wire, polyamideimide/epoxy composite enameled wire, polyimide/epoxy composite enameled wire, the main function of epoxy is to play a bonding role, and the underlying resin paint plays the key insulation performance.
  • polyester resin paint The thermal shock resistance of polyester resin paint is poor, and in a closed oil, the polyester resin quickly ages and decomposes. Therefore, it is necessary to modify the polyester to improve its heat resistance in practical applications.
  • two types of enameled wires BDZ-M and APB from Phelps Dodge in the United States.
  • Polyurethane self-adhesive enameled wire paint has two major characteristics: direct solderability and high frequency.
  • This kind of self-adhesive paint-wound coil can be self-adhesively formed by a baking method, and the paint film does not need to be removed when welding the joint, and can be directly welded, so the process flow is shortened and the production efficiency is improved.
  • the heat resistance grade of polyamide resin self-adhesive paint is as high as 180-200°C.
  • the enameled wire prepared by this kind of resin has the advantages of high abrasion resistance, smooth surface, good adhesion, and low friction coefficient. With the rapid development of high-speed automatic winding machines , The status of this type of enameled wire lacquer has become increasingly prominent.
  • self-adhesive enameled wire paint was first developed by American companies in the last century, different types of self-adhesive enameled wires have been developed around the world, mainly including: direct-welding self-adhesive enameled wires, which can withstand excellent moisture resistance, that is, thermoforming changes A type of enameled wire that is small, low in bonding temperature, and can be directly welded; flame retardant self-adhesive enameled wire, that is, an enameled wire obtained by adding some fire retardant on the original basis of self-adhesive enameled wire; self-lubricating self-adhesive Enameled wire, that is, the self-adhesive material itself has lubricity, which can realize the internal lubrication of the bonding layer; B and F self-adhesive enameled wire, that is, the heat-resistant grade of self-adhesive enameled wire reaches B (130°C) or F (155°C) Wait
  • the global electromagnetic winding wire occupies 41% of the sales in Asia, of which my country accounts for the largest proportion, about 11.7% of the global market. Therefore, as the world's largest market for winding wires, the demand for enameled wire paint consumption in my country is naturally strong. However, the quality and brand of various domestic enameled wire paint products are not yet sufficiently internationally competitive. Especially for high-end enameled wire paint brands, they are even more lackluster and lack competitive advantages. Therefore, the development of high-end enameled wire paint and enameled wire is imminent, and it is inevitable. Row. In particular, high-end variable frequency motors are developing rapidly, with a market share of more than 50%, and they are still growing.
  • the invention provides a self-adhesive corona-resistant polyimide paint, enameled wire and a preparation method thereof.
  • the preparation process of the invention is simple, environmentally friendly, and the obtained product has excellent comprehensive performance, is very suitable for the manufacture of coil windings of high-power motors and large-scale high-power transformers, and has good application prospects.
  • the present invention provides a self-adhesive corona-resistant polyimide paint
  • the self-adhesive corona-resistant polyimide paint is composed of a self-adhesive paint and a corona-resistant polyimide paint;
  • the self-adhesive paint consists of Haiyin epoxy resin with a mass ratio of 1:5 ⁇ 10:3 ⁇ 8:0.5 ⁇ 1:0.1 ⁇ 0.3, N,N,N',N'-tetraglycidyl-2,2- Bis[4-(4-aminophenoxy)phenyl]propane TGBAPP, CE793 epoxy resin, 4,4'-diaminodiphenyl sulfone, m-xylylenediamine;
  • the corona-resistant polyimide paint is composed of a polyamic acid solution with a concentration of 20% (w/w) and an inorganic nanopowder treated with a coupling agent, and a polyamic acid solution with a concentration of 20% (w/w)
  • the mass ratio of the inorganic nanopowder treated with the coupling agent is 100:3-12.
  • the coupling agent is selected from 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyl One or more of triethoxysilanes, more preferably, the coupling agent is selected from 3-aminopropyltrimethoxysilane.
  • the inorganic nano powder is selected from one or more of nano alumina powder, nano silica powder, nano titanium dioxide powder, nano ferric oxide powder, and nano magnesium oxide powder .
  • the second aspect of the present invention also provides a self-adhesive corona-resistant polyimide enameled wire, which is composed of a red copper wire inner core and the self-adhesive corona-resistant polyimide paint outer layer.
  • the third aspect of the present invention also provides a method for preparing the self-adhesive corona-resistant polyimide enameled wire, which includes the following steps:
  • the aromatic dibasic primary amine described in step (2) is selected from the group consisting of p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, trimethyl m-phenylenediamine, o-methyl p-phenylenediamine Phenylenediamine, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-di Amino-5,5'-diethyldiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-Diaminodiphenyl ether, 3,4'-Diaminodiphenyl ether, 3,3'-Diaminodiphenyl ether, 3,3'-Diamin
  • the aromatic dibasic anhydride in step (2) is selected from pyromellitic dianhydride, 3,3',4,4'-tetracarboxylic benzophenone dianhydride, 3,3',4 , 4'-tetracarboxydiphenyl ether dianhydride, 3,3',4,4'-tetracarboxydiphenyl sulfone dianhydride, 3,3',4,4'-tetracarboxydiphenyl dianhydride, 1,4 -Bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 4,4'-bis(3,4-dicarboxyl) Phenoxy) diphenyl sulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) benzophenone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) ) Diphenyl ether
  • the strong polar aprotic organic solvent described in step (2) is selected from N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N -One or more of ethyl-2-pyrrolidone and dimethyl sulfoxide.
  • the highest temperature of the high-temperature drying tunnel described in step (3) is 400°C.
  • the line speed of the power-on routing described in step (3) is controlled at 1 to 5 m/min.
  • drying tunnel described in step (4) has a maximum temperature of 150°C.
  • the linear speed is controlled to be 20-35 m/min.
  • a preparation method of self-adhesive corona-resistant polyimide paint and enameled wire is provided, the main steps include:
  • aromatic dibasic primary amines, strong polar aprotic organic solvents, and aromatic dibasic anhydrides described in step (2) are as defined above.
  • the highest temperature of the high-temperature drying tunnel in step (3) is 400° C.
  • the line speed of the power-on routing is controlled to be 1 to 5 m/min.
  • the maximum temperature of the drying tunnel described in step (4) is 150° C., and the line speed of the power-on routing is controlled to be 20-35 m/min.
  • the "room temperature” in the present invention means “20-30°C”.
  • the "20% (w/w) 20% (w/w) polyamic acid solution” refers to a polyamic acid solution with a concentration of 20% by mass percentage, that is, "w/w” means mass percentage .
  • the preparation method of the self-adhesive corona-resistant polyimide paint and enameled wire provided by the present invention has a simple operation process and is environmentally friendly.
  • the manufacturing of coil windings for high-power motors and large-scale high-power transformers has good application prospects and is easy to produce on a large scale.
  • the high temperature resistant polyimide wire enamel paint provided by the present invention is used as a primer, and after inorganic oxide is added, the corona resistance and other properties can be further improved.
  • a rare hydantoin epoxy resin self-adhesive paint was designed and prepared. The introduction of self-adhesive paint can change the traditional impregnation method of motor coil windings, which can save time, save energy, save labor, and protect the environment.
  • the hydantoin epoxy resin used in the present invention contains nitrogen elements, so it also has a certain flame retardant effect.
  • Hein epoxy resin 800g of N,N,N',N'-tetraglycidyl-2,2-bis[4-(4-aminophenoxy)phenyl]propane TGBAPP, 80g of 4,4'-Diaminodiphenyl sulfone was added to the reactor, stirred, heated to 70°C-80°C, stirred and reacted for 1 hour, 600g of CE793 epoxy resin was added, after stirring, cooled to room temperature, and 20g was added The m-xylylenediamine is mixed evenly at room temperature to obtain the self-adhesive paint, which is recorded as SA-2.
  • Hein epoxy resin 1000g of N,N,N',N'-tetraglycidyl-2,2-bis[4-(4-aminophenoxy)phenyl]propane TGBAPP, 100g of 4,4'-Diaminodiphenyl sulfone was added to the reaction kettle, stirred, heated to 70°C-80°C, stirred and reacted for 0.8 hours, then 800g of CE793 epoxy resin was added, after stirring evenly, cooled to room temperature, and 10g was added The m-xylylenediamine is added and mixed evenly at room temperature to obtain the self-adhesive paint, which is recorded as SA-3.
  • the CAP2000+ viscometer produced by Brookfield Company of the United States was used for the test.
  • the rotor was No. 1 and the temperature range was 25°C.
  • the wound spiral copper wire is immersed in the self-adhesive paint, cured at 180°C for 1 hour, and the bonding force is tested by a microcomputer-controlled electronic universal testing machine. Three samples are tested for each formula, and then the average value is taken.
  • Example 3 For the corona-resistant polyimide paint film of Example 3 (the curing process is: start from room temperature to 100°C, hold for 1 hour, continue to heat up to 200°C, hold for 1 hour, continue to heat up to 300°C for 1 hour, naturally Cooled to room temperature) Perform performance tests, including volume resistivity, dielectric loss, breakdown field strength, and corona resistance. The specific test results are shown in Table 2. The test methods are as follows:
  • the ZC-90G high insulation resistance measuring instrument produced by Shanghai Taiou Electronics Co., Ltd. was used to test the cured paint film copper sheet under the condition of 1kV, and the thickness of the sample was measured.
  • the insulating material Under the action of an external electric field, the insulating material loses its insulating properties due to a short-circuit phenomenon between the electrodes, which is called dielectric breakdown.
  • the voltage when the insulating material is broken down is called the breakdown voltage, and the breakdown field strength is the ratio of the breakdown voltage to the thickness of the dielectric.
  • the CW2672H automatic high voltage breakdown device of Changzhou Micro-Special Motor Factory was used to test the cured paint film copper sheet.
  • Corona resistance time refers to the time that an insulating material takes from corona discharge to when the material is broken down.
  • the corona-resistant life of materials is also related to factors such as frequency, temperature, and electric field strength.
  • the JGM-3F high-frequency pulse voltage tester produced by Shanghai Shenfa Testing Instrument Co., Ltd. was used to test the corona resistance of the prepared paint film. Test conditions: temperature: room temperature; pulse frequency: 20kHz; pulse duty ratio: 50%; pulse voltage peak-to-peak value: 2.5kV.
  • the JR-16A enameled round wire winding tester produced by Yuhang Technology Co., Ltd. is used to wind the enameled wire to observe whether it reaches the preset number of turns.
  • the ZDS-50B automatic voltage tester produced by Yuhang Technology Co., Ltd. is used to test the voltage of the enameled wire. After the pattern is broken down, the voltage is recorded.
  • test conditions test conditions: temperature: 155°C; pulse frequency: 20kHz; pulse duty cycle: 50 %; peak-to-peak pulse voltage: 3.0kV.
  • the enameled wire is tested with the ZDG-25 intelligent one-way paint scraping tester produced by Yuhang Technology Co., Ltd., the enameled wire is placed according to the steps, and then a certain load is set for the scraping force test.
  • the enameled wire is placed in the enameled wire according to the steps with the JLD-10 type jerky breaking tester produced by Xinxiong Instrument Co., Ltd., and the jerky pull test is performed when the barometer reaches 0.7-0.8MPa.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Insulating Materials (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

Disclosed are a self-adhesive corona-resistant polyimide paint, an enameled wire and a preparation method therefor. The self-adhesive corona-resistant polyimide paint is composed of a self-adhesive paint and a corona-resistant polyimide paint. The enameled wire is composed of a red copper wire inner core and a self-adhesive corona-resistant polyimide paint outer layer. The preparation method for the self-adhesive corona-resistant polyimide paint and the enameled wire is simple in process and environmentally friendly, and the obtained product is suitable for manufacturing coil windings of high-power electric motors and large-scale high-power transformers.

Description

一种自粘性耐电晕聚酰亚胺漆、漆包线及其制备方法Self-adhesive corona-resistant polyimide paint, enameled wire and preparation method thereof
本申请要求了申请日为2020年03月31日，申请号为202010245572.1的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application whose application date is March 31, 2020 and the application number is 202010245572.1, the entire content of which is incorporated into this application by reference.
技术领域Technical field
本发明属于电气绝缘材料与电磁线领域，特别是涉及一种自粘性耐电晕聚酰亚胺漆、漆包线及其制备方法The invention belongs to the field of electrical insulating materials and electromagnetic wires, and particularly relates to a self-adhesive corona-resistant polyimide paint, enameled wire and a preparation method thereof
技术背景technical background
漆包线在人们的日常生活中占据着非常重要的地位，从小的电吹风到大型机器的偏转线圈，都离不开漆包线。而当前市场上常用的漆包线都是通过涂线后绕成线圈再通过浸渍加热使各匝导线粘结在一起。这种工艺有一些不足之处，比如线圈内部渗透无法预测，经常会出现气泡和不能粘住的情况；浸渍漆渗入线圈后，经过蒸发溶剂，可能会或多或少的对线圈产生一些物理化学反应，而且蒸发的溶剂也会污染环境，甚至有引发火灾的可能。因此，国内外的研究员一直不断开发新型的漆包线漆，而自粘性漆包线漆可以减少工艺，减少环境污染，具有很好的应用前景。Enameled wire occupies a very important position in people's daily life. From small hair dryers to deflection coils of large machines, enameled wires are inseparable. At present, the commonly used enameled wires in the market are coated and wound into coils, and then the turns of the wires are bonded together by immersion and heating. This process has some shortcomings, such as unpredictable penetration inside the coil, and often bubbles and inability to stick; after the dipping varnish penetrates into the coil, the solvent may be evaporated, which may cause more or less physical and chemical effects on the coil. Reaction, and the evaporating solvent will also pollute the environment, and may even cause a fire. Therefore, researchers at home and abroad have been continuously developing new types of enameled wire paint, and self-adhesive wire enameled paint can reduce the process and reduce environmental pollution, and has a good application prospect.
自粘性漆包线是一类特种漆包线，是由基本漆膜(底漆)和外层自粘性漆膜所构成的，外层自粘漆性能的主要是提高粘结强度。使用自粘漆绕制的线圈，可以通过烘培加热或通电加热，使外涂粘结层相互作用，冷却后线圈自动成型的一种漆包线。Self-adhesive enameled wire is a special type of enameled wire, which is composed of a basic paint film (primer) and an outer self-adhesive paint film. The performance of the outer self-adhesive paint is mainly to improve the bonding strength. A coil made of self-adhesive paint can be heated by baking or energized to make the outer coating bonding layer interact, and the coil is automatically formed after cooling.
自粘性漆包线一般采用复合层结构，目前国外对复合层漆包线相当重视，品种多、性能好。由于复合层漆包线是由两层(或三层)不同材料的漆涂制而成，因此与同一材料的单一涂层漆包线相比，复合线兼具了两种不同材料的各自性能，克服了由同一材料带来的性能上的不足。复合层自粘性漆包线结构中，基线是主要的功能绝缘部分，它保证了自粘性漆包线的绝缘性能，自粘层则主要是为了满足线圈成型工艺的需要，起粘合作用并对基线有保护和增强的作用。The self-adhesive enameled wire generally adopts a composite layer structure. At present, foreign countries attach great importance to the composite layer enameled wire, which has many varieties and good performance. Since the composite enameled wire is made of two layers (or three layers) of paint of different materials, compared with a single-coated enameled wire of the same material, the composite wire has the respective properties of two different materials and overcomes the The performance deficiencies caused by the same material. In the self-adhesive enameled wire structure of the composite layer, the baseline is the main functional insulation part, which ensures the insulation performance of the self-adhesive enameled wire, and the self-adhesive layer is mainly used to meet the needs of the coil forming process. It has an adhesive effect and protects the baseline. Enhanced role.
和传统电枢绕组相比，自粘性漆包线同样具有良好的绕制性、成型性、嵌入性、加工性，自粘性漆包线还有个显著特点是大大简化线圈绕组的制造工艺，在 许多场合中省略了绑扎、浸渍、清理等繁杂的工序，设备、电能及劳动力等许多方面获得节约，有利于实现生产自动化、提高产品质量，同时也带来了显著的社会和经济效益。Compared with traditional armature windings, self-adhesive enameled wire also has good winding, formability, embedding and processability. Self-adhesive enameled wire also has a significant feature that greatly simplifies the manufacturing process of coil windings, which is omitted in many occasions. The complicated procedures such as lashing, dipping, cleaning, etc. have been saved in many aspects such as equipment, electric power and labor, which is conducive to the realization of production automation and the improvement of product quality, while also bringing significant social and economic benefits.
自粘性漆包线漆从开发成功以来，根据社会发展进步以及市场的需求多次改进，目前从使用的角度来看，主要有以下5个类型。Since the successful development of self-adhesive enameled wire paint, it has been improved many times in accordance with social development and market demand. At present, from the perspective of use, there are mainly the following five types.
1缩醛类自粘性漆包线漆1 Acetal type self-adhesive enameled wire paint
聚乙烯醇缩丁醛自粘性漆包线漆(耐热等级为E级)是市场上应用较多的一种漆，一般涂覆于聚乙烯醇缩甲醛、聚氨酯等绝缘漆的最外层，粘合方式为加热。其中美国Monsanto公司开发了一种粘合性能更好的自粘性漆，即在缩丁醛中加入千分之五质量的胺类化合物。Polyvinyl butyral self-adhesive enameled wire paint (heat-resistant grade is E grade) is a kind of paint that is widely used in the market. It is generally coated on the outermost layer of insulating paint such as polyvinyl formal and polyurethane to bond The method is heating. Among them, Monsanto Company of the United States has developed a self-adhesive paint with better adhesion, that is, adding five thousandths of the mass of amine compounds to butyral.
2环氧树脂自粘性漆包线漆2 Epoxy resin self-adhesive enameled wire paint
环氧树脂自粘性漆稀释性较好，涂线工艺方便，且环氧树脂漆包线漆耐热性能高于缩醛树脂。环氧体系的漆包线主要有下列复合体系：改性聚酯/环氧复合自粘性漆包线、聚酯亚胺/环氧复合自粘性漆包线、聚酯亚胺/聚酰胺酰亚胺/环氧复合自粘性漆包线、聚酰胺酰亚胺/环氧复合漆包线、聚酰亚胺/环氧复合漆包线，其中环氧的主要功能是起粘合作用，底层树脂漆起关键的绝缘性能。Epoxy resin self-adhesive paint has good dilution, convenient wire coating process, and the heat resistance of epoxy resin enameled wire paint is higher than that of acetal resin. The epoxy system enameled wire mainly includes the following composite systems: modified polyester/epoxy composite self-adhesive enameled wire, polyesterimine/epoxy composite self-adhesive enameled wire, polyesterimide/polyamideimide/epoxy composite self-adhesive enameled wire Viscous enameled wire, polyamideimide/epoxy composite enameled wire, polyimide/epoxy composite enameled wire, the main function of epoxy is to play a bonding role, and the underlying resin paint plays the key insulation performance.
相关的参考文献如下：The relevant references are as follows:
魏文康，虞鑫海，李远波[中国胶粘剂，2019，28(05)：18-20+30.]研制了综合性能优异的高性能环氧树脂胶粘剂。Wei Wenkang, Yu Xinhai, Li Yuanbo [China Adhesives, 2019, 28(05): 18-20+30.] developed a high-performance epoxy resin adhesive with excellent comprehensive performance.
魏文康，虞鑫海[中国胶粘剂，2019，28(02)：12-15.]对环氧基体树脂的制备与性能表征进行了***的研究。方界凤，蔡澄霖，叶辛，林诗韵，虞鑫海[粘接，2019，40(05)：92-95.]采用端羧基丁腈橡胶增韧改性环氧树脂进行了研究。Wei Wenkang, Yu Xinhai [China Adhesives, 2019, 28(02): 12-15.] conducted a systematic study on the preparation and performance characterization of epoxy matrix resins. Fang Jiefeng, Cai Chenglin, Ye Xin, Lin Shiyun, Yu Xinhai [Adhesive, 2019, 40(05): 92-95.] A study was carried out using carboxyl-terminated nitrile rubber to toughen modified epoxy resin.
吴冯，虞鑫海，周兴平[粘接，2016，37(05)：53-56.]研究制备了新型耐高温双组分环氧胶粘剂体系。Wu Feng, Yu Xinhai, Zhou Xingping [Adhesive, 2016, 37(05):53-56.] studied and prepared a new high temperature resistant two-component epoxy adhesive system.
罗忠文，虞鑫海，陈戚，陈吉伟，刘万章，唐兴发[粘接，2015，36(12)：56-59.]采用双马来酰亚胺树脂对环氧树脂进行了改性研究，获得了双马来酰亚胺改性环氧胶粘剂。Luo Zhongwen, Yu Xinhai, Chen Qi, Chen Jiwei, Liu Wanzhang, Tang Xingfa [Adhesive, 2015, 36(12):56-59.] The epoxy resin was modified with bismaleimide resin, and the double Maleimide modified epoxy adhesive.
童超梅，虞鑫海，陈吉伟，刘万章，唐新发[绝缘材料，2016，49(02)：18-21+27.]对无溶剂耐高温环氧基体树脂的制备及性能进行了研究。Tong Chaomei, Yu Xinhai, Chen Jiwei, Liu Wanzhang, Tang Xinfa [Insulating Materials, 2016, 49(02): 18-21+27.] The preparation and properties of solvent-free high temperature epoxy matrix resin were studied.
郭翔，虞鑫海，刘万章[粘接，2014，35(09)：56-60.]对耐高温环氧胶粘剂及其固化 动力学进行了研究。Guo Xiang, Yu Xinhai, Liu Wanzhang [Adhesive, 2014, 35(09): 56-60.] studied high temperature epoxy adhesives and their curing kinetics.
虞鑫海，陈戚，陈吉伟，刘万章，唐新发[绝缘材料，2016，49(01)：25-28+33.]对耐高温环氧基体树脂的制备及其固化动力学进行了研究。Yu Xinhai, Chen Qi, Chen Jiwei, Liu Wanzhang, Tang Xinfa [Insulation Materials, 2016, 49(01): 25-28+33.] The preparation and curing kinetics of high temperature epoxy matrix resins were studied.
虞鑫海，孙兆琪[绝缘材料，2017，50(10)：6-9.]研制得到了新型耐高温聚酰亚胺改性环氧粘合剂体系。Yu Xinhai, Sun Zhaoqi [Insulating Materials, 2017, 50(10): 6-9.] A new type of high temperature resistant polyimide modified epoxy adhesive system was developed.
虞鑫海，郭翔，陈吉伟，刘万章，胡彬[粘接，2014，35(01)：33-35+39.]研制得到了新型耐高温无溶剂环氧胶粘剂。Yu Xinhai, Guo Xiang, Chen Jiwei, Liu Wanzhang, Hu Bin [Adhesive, 2014, 35(01): 33-35+39.] developed a new type of high temperature resistant solvent-free epoxy adhesive.
3聚酯自粘性漆包线漆3Polyester self-adhesive enameled wire paint
聚酯树脂漆的抗热冲击性能较差，而且在密闭的油中，聚酯树脂很快老化、分解，所以需要在实际的应用中一般是对聚酯进行改性来提高其耐热性，如美国Phelps Dodge公司的BDZ-M及APB两种型号的漆包线。The thermal shock resistance of polyester resin paint is poor, and in a closed oil, the polyester resin quickly ages and decomposes. Therefore, it is necessary to modify the polyester to improve its heat resistance in practical applications. For example, two types of enameled wires, BDZ-M and APB from Phelps Dodge in the United States.
4聚氨酯自粘性漆包线漆4Polyurethane self-adhesive enameled wire paint
聚氨酯自粘性漆包线漆拥有两大特点：直焊性、高频性。此种自粘漆绕制的线圈可以采用陪烘的方法自行粘合成型，而且在焊接头时不需要除去漆膜，可以直接焊接，所以工艺流程缩短，生产效率得到提高。Polyurethane self-adhesive enameled wire paint has two major characteristics: direct solderability and high frequency. This kind of self-adhesive paint-wound coil can be self-adhesively formed by a baking method, and the paint film does not need to be removed when welding the joint, and can be directly welded, so the process flow is shortened and the production efficiency is improved.
5聚酰胺树脂自粘性漆包线漆5 Polyamide resin self-adhesive enameled wire paint
聚酰胺类树脂自粘漆耐热等级高达180-200℃，此类树脂制备的漆包线具有耐磨性高、表面光洁、附着力好、摩擦系数小等优点，随着高速自动绕线机高速发展，该类漆包线漆地位也日益显著。The heat resistance grade of polyamide resin self-adhesive paint is as high as 180-200℃. The enameled wire prepared by this kind of resin has the advantages of high abrasion resistance, smooth surface, good adhesion, and low friction coefficient. With the rapid development of high-speed automatic winding machines , The status of this type of enameled wire lacquer has become increasingly prominent.
自从自粘性漆包线漆在上世纪被美国公司首先研制成功以后，世界范围内相继开发了不同类型的自粘性漆包线，主要包括：直焊型自粘漆包线，即可以承受耐潮性优异、即热成型变化小、粘合温度低、可以直接焊接的一种漆包线；阻燃型自粘漆包线，即在自粘漆包线原来的基础上，添加一些防火阻燃剂而得到的一种漆包线；自润滑型自粘性漆包线，即自粘材料本身带有润滑性，可以实现粘结层内部润滑；B、F级自粘漆包线，即自粘性漆包线的耐热等级达到B级(130℃)或者F级(155℃)等。Since self-adhesive enameled wire paint was first developed by American companies in the last century, different types of self-adhesive enameled wires have been developed around the world, mainly including: direct-welding self-adhesive enameled wires, which can withstand excellent moisture resistance, that is, thermoforming changes A type of enameled wire that is small, low in bonding temperature, and can be directly welded; flame retardant self-adhesive enameled wire, that is, an enameled wire obtained by adding some fire retardant on the original basis of self-adhesive enameled wire; self-lubricating self-adhesive Enameled wire, that is, the self-adhesive material itself has lubricity, which can realize the internal lubrication of the bonding layer; B and F self-adhesive enameled wire, that is, the heat-resistant grade of self-adhesive enameled wire reaches B (130℃) or F (155℃) Wait.
全球电磁绕组线在亚洲占有41％的销量，其中我国所占比重最大，约有全球市场的11.7％，所以作为全球绕组线最大的市场，我国的漆包线漆用量需求自然旺盛。但是国内的各种漆包线漆产品的质量和品牌还没有足够的国际竞争力，尤其在高端漆包线漆品牌上面，更是乏善可陈，缺乏竞争优势，所以对高端漆包线 漆以及漆包线的开发迫在眉睫，势在必行。尤其高端变频电机发展迅猛，市场占有率已经达到50％以上，而且还在不断发展壮大，所以为了满足市场的需求，发展耐电晕的聚酰亚胺漆包线就成了当务之急，而纳米漆包线具有耐电晕和抗变频电机脉冲能力，可满足变频电机对漆包线的高技术要求。除此之外，高端漆包线还能够满足国民经济基础建设的需要，带动相关产业链的发展，推动行业和产品的更新迭代，提高国内产品在国际市场上的竞争力；有利于调整电线电缆产业结构向高水平迈进；有利于提高电线电缆行业的整体技术开发能力；有利于带动电机、变压器行业的产品升级换代。The global electromagnetic winding wire occupies 41% of the sales in Asia, of which my country accounts for the largest proportion, about 11.7% of the global market. Therefore, as the world's largest market for winding wires, the demand for enameled wire paint consumption in my country is naturally strong. However, the quality and brand of various domestic enameled wire paint products are not yet sufficiently internationally competitive. Especially for high-end enameled wire paint brands, they are even more lackluster and lack competitive advantages. Therefore, the development of high-end enameled wire paint and enameled wire is imminent, and it is inevitable. Row. In particular, high-end variable frequency motors are developing rapidly, with a market share of more than 50%, and they are still growing. Therefore, in order to meet the needs of the market, the development of corona-resistant polyimide enameled wire has become a top priority, and nano enameled wire is resistant to Corona and anti-frequency motor pulse ability can meet the high technical requirements of variable frequency motor for enameled wire. In addition, high-end enameled wire can also meet the needs of the national economic infrastructure, drive the development of related industrial chains, promote the renewal and iteration of industries and products, and improve the competitiveness of domestic products in the international market; it is conducive to adjusting the wire and cable industry structure To move to a high level; help to improve the overall technological development capabilities of the wire and cable industry; help drive product upgrades in the motor and transformer industries.
发明内容Summary of the invention
本发明提供了一种自粘性耐电晕聚酰亚胺漆、漆包线及其制备方法。本发明制备工艺简单、环境友好、所得产品综合性能优异，非常适合于大功率电机、大型高功率变压器的线圈绕组制造，具有良好的应用前景。The invention provides a self-adhesive corona-resistant polyimide paint, enameled wire and a preparation method thereof. The preparation process of the invention is simple, environmentally friendly, and the obtained product has excellent comprehensive performance, is very suitable for the manufacture of coil windings of high-power motors and large-scale high-power transformers, and has good application prospects.
第一方面，本发明提供了一种自粘性耐电晕聚酰亚胺漆，所述自粘性耐电晕聚酰亚胺漆由自粘漆、耐电晕聚酰亚胺漆组成；其中，In the first aspect, the present invention provides a self-adhesive corona-resistant polyimide paint, the self-adhesive corona-resistant polyimide paint is composed of a self-adhesive paint and a corona-resistant polyimide paint; wherein,
自粘漆由质量比为1∶5～10∶3～8∶0.5～1∶0.1～0.3的海茵环氧树脂、N，N，N’，N’-四缩水甘油基-2，2-双[4-(4-氨基苯氧基)苯基]丙烷TGBAPP、CE793环氧树脂、4，4’-二氨基二苯砜、间苯二甲胺组成；The self-adhesive paint consists of Haiyin epoxy resin with a mass ratio of 1:5～10:3～8:0.5～1:0.1～0.3, N,N,N',N'-tetraglycidyl-2,2- Bis[4-(4-aminophenoxy)phenyl]propane TGBAPP, CE793 epoxy resin, 4,4'-diaminodiphenyl sulfone, m-xylylenediamine;
耐电晕聚酰亚胺漆由浓度为20％(w/w)的聚酰胺酸溶液和偶联剂处理的无机纳米粉体组成，其中浓度为20％(w/w)的聚酰胺酸溶液和偶联剂处理的无机纳米粉体的质量比为100∶3～12。The corona-resistant polyimide paint is composed of a polyamic acid solution with a concentration of 20% (w/w) and an inorganic nanopowder treated with a coupling agent, and a polyamic acid solution with a concentration of 20% (w/w) The mass ratio of the inorganic nanopowder treated with the coupling agent is 100:3-12.
进一步的，所述的偶联剂选自3-氨丙基三甲氧基硅烷、3-氨丙基三乙氧基硅烷、环氧丙氧基丙基三甲氧基硅烷、环氧丙氧基丙基三乙氧基硅烷中的一种或几种，更优选的，所述偶联剂选自3-氨丙基三甲氧基硅烷。Further, the coupling agent is selected from 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyl One or more of triethoxysilanes, more preferably, the coupling agent is selected from 3-aminopropyltrimethoxysilane.
进一步的，所述的无机纳米粉体选自纳米氧化铝粉体、纳米二氧化硅粉体、纳米二氧化钛粉体、纳米三氧化二铁粉体、纳米氧化镁粉体中的一种或几种。Further, the inorganic nano powder is selected from one or more of nano alumina powder, nano silica powder, nano titanium dioxide powder, nano ferric oxide powder, and nano magnesium oxide powder .
进一步的，所述的海茵环氧树脂的结构式为：Further, the structural formula of the Hein epoxy resin is:
Figure PCTCN2020111005-appb-000001
Figure PCTCN2020111005-appb-000001
本发明第二方面，还提供了一种自粘性耐电晕聚酰亚胺漆包线，所述漆包线由紫铜线内芯和所述的自粘性耐电晕聚酰亚胺漆外层组成。The second aspect of the present invention also provides a self-adhesive corona-resistant polyimide enameled wire, which is composed of a red copper wire inner core and the self-adhesive corona-resistant polyimide paint outer layer.
本发明第三方面，还提供了一种所述自粘性耐电晕聚酰亚胺漆包线的制备方法，包括以下步骤：The third aspect of the present invention also provides a method for preparing the self-adhesive corona-resistant polyimide enameled wire, which includes the following steps:
(1)将海茵环氧树脂、N，N，N’，N’-四缩水甘油基-2，2-双[4-(4-氨基苯氧基)苯基]丙烷TGBAPP和4，4’-二氨基二苯砜加入反应釜中，搅拌，加热升温至70℃～80℃，搅拌反应0.5～1小时后，加入CE793环氧树脂，搅拌均匀后，冷却至室温，然后加入间苯二甲胺，室温下搅拌均匀，得到自粘漆；(1) Combine Haiin epoxy resin, N,N,N',N'-tetraglycidyl-2,2-bis[4-(4-aminophenoxy)phenyl]propane TGBAPP and 4,4 '-Diaminodiphenyl sulfone was added to the reaction kettle, stirred, heated to 70°C to 80°C, stirred for 0.5 to 1 hour, then added CE793 epoxy resin, stirred evenly, cooled to room temperature, and then added isophthalic acid Methylamine, stir evenly at room temperature to obtain self-adhesive paint;
(2)将芳香族二元伯胺、强极性非质子有机溶剂加入反应釜中，室温下搅拌溶解后，加入芳香族二元酐，室温下搅拌反应1～4小时，加入偶联剂处理的无机纳米粉体，搅拌研磨均匀，即得耐电晕聚酰亚胺漆；其中，芳香族二元伯胺与芳香族二元酐的摩尔比为1.05～1.15∶1.00。(2) Add aromatic dibasic primary amine and strong polar aprotic organic solvent into the reaction kettle, stir to dissolve at room temperature, add aromatic dibasic anhydride, stir at room temperature for 1-4 hours, add coupling agent for treatment The inorganic nanopowders are stirred and ground uniformly to obtain corona resistant polyimide paint; wherein, the molar ratio of aromatic dibasic primary amine to aromatic dibasic anhydride is 1.05-1.15:1.00.
(3)将耐电晕聚酰亚胺漆放入漆包线机的漆槽中，紫铜线穿过漆槽12道～18道、经过高温烘道，开机走线，高温固化，收卷，得到耐电晕聚酰亚胺漆包线；(3) Put the corona-resistant polyimide paint into the paint tank of the enamelled wire machine, and the red copper wire passes through the paint tank for 12 to 18 times, passes through the high-temperature drying tunnel, starts the line, high-temperature curing, and winding to obtain the resistance Corona polyimide enameled wire;
(4)将自粘漆放入漆包线机的漆槽中，耐电晕聚酰亚胺漆包线穿过漆槽、经过烘道，开机走线，加热半固化，收卷，得到自粘性耐电晕聚酰亚胺漆包线。(4) Put the self-adhesive paint into the paint tank of the enameled wire machine, pass the corona-resistant polyimide enameled wire through the paint tank, pass through the drying tunnel, turn on the wire, heat it for semi-curing, and rewind to obtain the self-adhesive corona resistant Polyimide enameled wire.
上述方法中，优选的，步骤(2)中所述的芳香族二元伯胺选自对苯二胺、间苯二胺、邻苯二胺、三甲基间苯二胺、邻甲基对苯二胺、4，4’-二氨基二苯甲烷、3，3’-二甲基-4，4’-二氨基二苯甲烷、3，3’-二甲基-4，4’-二氨基-5，5’-二乙基二苯甲烷、3，3’，5，5’-四甲基-4，4’-二氨基二苯甲烷、3，3’-二氨基二苯甲烷、4，4’-二氨基二苯醚、3，4’-二氨基二苯醚、3，3’-二氨基二苯醚、4，4’-二氨基二苯甲酮、4，4’-二氨基二苯砜、3，3’-二氨基二苯砜、4，4’-二氨基二苯硫醚、4，4’-二氨基联苯、2，2’-二甲基-4，4’-二氨基联苯、2，2’-二(三氟甲基)-4，4’-二氨基联苯、1，4-双(4-氨基苯氧基)苯、1，4-双(3-氨基苯氧基)苯、1，3-双(4-氨基苯氧基)苯、1，3-双(3-氨基苯氧基)苯、1，4-双(2-三氟甲基-4-氨基苯氧基)苯、1，3-双(2-三氟甲基-4-氨基苯氧基)苯、4，4’-双(4-氨基苯氧基)联苯、4，4’-双(2-三氟甲基-4-氨基苯氧基)联苯、4，4’-双(3-氨基苯氧基)联苯、4，4’-双(4-氨基苯氧基)-3，3’，5，5’-四甲基联苯、4，4’-双(2-三氟甲基-4-氨基苯氧基)-3，3’，5，5’-四甲基联苯、4，4’-双(3-氨基苯氧基)-3，3’，5，5’-四甲基联苯、4，4’-双(4-氨基苯氧基)二苯醚、4，4’-双(2-三氟甲基-4-氨基苯氧基)二苯醚、4，4’-双(3-氨基苯氧基)二苯醚、4，4’-双(4-氨基苯氧基) 二苯硫醚、4，4’-双(2-三氟甲基-4-氨基苯氧基)二苯硫醚、4，4’-双(3-氨基苯氧基)二苯硫醚、4，4’-双(4-氨基苯氧基)二苯砜、4，4’-双(2-三氟甲基-4-氨基苯氧基)二苯砜、4，4’-双(3-氨基苯氧基)二苯砜、4，4’-双(4-氨基苯氧基)二苯甲酮、4，4’-双(2-三氟甲基-4-氨基苯氧基)二苯甲酮、4，4’-双(3-氨基苯氧基)二苯甲酮、4，4’-双(4-氨基苯氧基)二苯甲烷、4，4’-双(2-三氟甲基-4-氨基苯氧基)二苯甲烷、4，4’-双(3-氨基苯氧基)二苯甲烷、2，2-双[4-(4-氨基苯氧基)苯基]丙烷、2，2-双[4-(2-三氟甲基-4-氨基苯氧基)苯基]丙烷、2，2-双[4-(3-氨基苯氧基)苯基]丙烷、2，2-双[4-(4-氨基苯氧基)苯基]六氟丙烷、2，2-双[4-(2-三氟甲基-4-氨基苯氧基)苯基]六氟丙烷、2，2-双[4-(3-氨基苯氧基)苯基]六氟丙烷、2-(4-氨基苯基)-5-氨基苯并咪唑、4，4’-二氨基-4”-羟基三苯甲烷、2，2-双(3-羟基-4-氨基苯基)丙烷、2，2-双(3-羟基-4-氨基苯基)六氟丙烷、3，5-二氨基苯甲酸、3，5-双(4-氨基苯氧基)苯甲酸中的一种或几种。In the above method, preferably, the aromatic dibasic primary amine described in step (2) is selected from the group consisting of p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, trimethyl m-phenylenediamine, o-methyl p-phenylenediamine Phenylenediamine, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-di Amino-5,5'-diethyldiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-Diaminodiphenyl ether, 3,4'-Diaminodiphenyl ether, 3,3'-Diaminodiphenyl ether, 4,4'-Diaminobenzophenone, 4,4'- Diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl, 2,2'-dimethyl-4, 4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 1,4-bis(4-aminophenoxy)benzene, 1,4- Bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(2-tri Fluoromethyl-4-aminophenoxy)benzene, 1,3-bis(2-trifluoromethyl-4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy) Benzene, 4,4'-bis(2-trifluoromethyl-4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis( 4-aminophenoxy)-3,3',5,5'-tetramethylbiphenyl, 4,4'-bis(2-trifluoromethyl-4-aminophenoxy)-3,3' , 5,5'-tetramethylbiphenyl, 4,4'-bis(3-aminophenoxy)-3,3',5,5'-tetramethylbiphenyl, 4,4'-bis( 4-aminophenoxy)diphenyl ether, 4,4'-bis(2-trifluoromethyl-4-aminophenoxy)diphenyl ether, 4,4'-bis(3-aminophenoxy) Diphenyl ether, 4,4'-bis(4-aminophenoxy) diphenyl sulfide, 4,4'-bis(2-trifluoromethyl-4-aminophenoxy) diphenyl sulfide, 4 , 4'-bis(3-aminophenoxy)diphenyl sulfide, 4,4'-bis(4-aminophenoxy)diphenyl sulfone, 4,4'-bis(2-trifluoromethyl- 4-Aminophenoxy)diphenylsulfone, 4,4'-bis(3-aminophenoxy)diphenylsulfone, 4,4'-bis(4-aminophenoxy)benzophenone, 4, 4'-bis(2-trifluoromethyl-4-aminophenoxy)benzophenone, 4,4'-bis(3-aminophenoxy)benzophenone, 4,4'-bis( 4-aminophenoxy)diphenylmethane, 4,4'-bis(2-trifluoromethyl-4-aminophenoxy)diphenylmethane, 4,4'-bis(3-aminophenoxy) Diphenylmethane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(2-trifluoromethyl-4-aminophenoxy)phenyl ]Propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminobenzene) Oxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-trifluoromethyl-4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(3 -Aminophenoxy)phenyl]hexafluoropropane, 2-(4-aminophenyl)-5-aminobenzimidazole, 4,4'-diamino-4"-hydroxytriphenylmethane, 2,2- Bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 3,5-diaminobenzoic acid, 3,5-bis(4 -One or more of aminophenoxy)benzoic acid.
进一步的，步骤(2)中所述的芳香族二元酐选自均苯四甲酸二酐、3，3’，4，4’-四羧基二苯甲酮二酐、3，3’，4，4’-四羧基二苯醚二酐、3，3’，4，4’-四羧基二苯砜二酐、3，3’，4，4’-四羧基联苯二酐、1，4-双(3，4-二羧基苯氧基)苯二酐、1，3-双(3，4-二羧基苯氧基)苯二酐、4，4’-双(3，4-二羧基苯氧基)二苯砜二酐、4，4’-双(3，4-二羧基苯氧基)二苯甲酮二酐、4，4’-双(3，4-二羧基苯氧基)二苯醚二酐、4，4’-双(3，4-二羧基苯氧基)联苯二酐、2，2-双[4-(3，4-二羧基苯氧基)苯基]丙烷二酐、2，2-双[4-(3，4-二羧基苯氧基)苯基]六氟丙烷二酐、2，2-双(3，4-二羧基苯基)六氟丙烷二酐中的一种或几种。Further, the aromatic dibasic anhydride in step (2) is selected from pyromellitic dianhydride, 3,3',4,4'-tetracarboxylic benzophenone dianhydride, 3,3',4 , 4'-tetracarboxydiphenyl ether dianhydride, 3,3',4,4'-tetracarboxydiphenyl sulfone dianhydride, 3,3',4,4'-tetracarboxydiphenyl dianhydride, 1,4 -Bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 4,4'-bis(3,4-dicarboxyl) Phenoxy) diphenyl sulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) benzophenone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) ) Diphenyl ether dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl ]Propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoro One or more of propane dianhydride.
进一步的，步骤(2)中所述的强极性非质子有机溶剂选自N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、二甲基亚砜中的一种或几种。Further, the strong polar aprotic organic solvent described in step (2) is selected from N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N -One or more of ethyl-2-pyrrolidone and dimethyl sulfoxide.
进一步的，步骤(3)中所述的高温烘道，其最高温度为400℃。Furthermore, the highest temperature of the high-temperature drying tunnel described in step (3) is 400°C.
进一步的优选，步骤(3)中所述的开机走线，其线速度控制在1～5m/min。Further preferably, the line speed of the power-on routing described in step (3) is controlled at 1 to 5 m/min.
进一步的，步骤(4)中所述的烘道，其最高温度为150℃。Further, the drying tunnel described in step (4) has a maximum temperature of 150°C.
进一步的优选，步骤(4)中所述的开机走线，其线速度控制为20～35m/min。Further preferably, in the power-on routing described in step (4), the linear speed is controlled to be 20-35 m/min.
在本发明的另一个更具体的实施方式中提供了一种自粘性耐电晕聚酰亚胺漆、漆包线的制备方法，主要步骤包括：In another more specific embodiment of the present invention, a preparation method of self-adhesive corona-resistant polyimide paint and enameled wire is provided, the main steps include:
(1)将海茵环氧树脂、N，N，N’，N’-四缩水甘油基-2，2-双[4-(4-氨基苯氧基)苯基] 丙烷TGBAPP、4，4’-二氨基二苯砜加入反应釜中，搅拌，加热升温至70℃～80℃，搅拌反应0.5～1小时后，加入CE793环氧树脂，搅拌均匀后，冷却至室温，加入间苯二甲胺，室温下加拌均匀，即得自粘漆；(1) Combine Hein epoxy resin, N,N,N',N'-tetraglycidyl-2,2-bis[4-(4-aminophenoxy)phenyl]propane TGBAPP, 4,4 '-Diaminodiphenyl sulfone was added to the reaction kettle, stirred, heated to 70°C ~ 80°C, stirred for 0.5 to 1 hour, then added CE793 epoxy resin, stirred evenly, cooled to room temperature, and added metaxylylene Amine, mix evenly at room temperature to obtain self-adhesive paint;
(2)将芳香族二元伯胺、强极性非质子有机溶剂加入反应釜中，室温下搅拌溶解后，加入芳香族二元酐，室温下搅拌反应1～4小时，加入偶联剂处理的无机纳米粉体，搅拌研磨均匀，即得耐电晕聚酰亚胺漆；其中，芳香族二元伯胺与芳香族二元酐的摩尔比为1.05～1.15∶1.00。(2) Add aromatic dibasic primary amine and strong polar aprotic organic solvent into the reaction kettle, stir to dissolve at room temperature, add aromatic dibasic anhydride, stir at room temperature for 1-4 hours, add coupling agent for treatment The inorganic nanopowders are stirred and ground uniformly to obtain corona resistant polyimide paint; wherein, the molar ratio of aromatic dibasic primary amine to aromatic dibasic anhydride is 1.05-1.15:1.00.
(3)将耐电晕聚酰亚胺漆放入漆包线机的漆槽中，紫铜线穿过漆槽12道～18道、经过高温烘道，开机走线，高温固化，收卷，得到耐电晕聚酰亚胺漆包线；(3) Put the corona-resistant polyimide paint into the paint tank of the enamelled wire machine, and the red copper wire passes through the paint tank for 12 to 18 times, passes through the high-temperature drying tunnel, starts the line, high-temperature curing, and winding to obtain the resistance Corona polyimide enameled wire;
(4)将自粘漆放入漆包线机的漆槽中，耐电晕聚酰亚胺漆包线穿过漆槽、经过烘道，开机走线，加热半固化，收卷，得到自粘性耐电晕聚酰亚胺漆包线。(4) Put the self-adhesive paint into the paint tank of the enameled wire machine, pass the corona-resistant polyimide enameled wire through the paint tank, pass through the drying tunnel, turn on the wire, heat it for semi-curing, and rewind to obtain the self-adhesive corona resistant Polyimide enameled wire.
其中步骤(2)中所述的芳香族二元伯胺、强极性非质子有机溶剂，香族二元酐定义如前述。The aromatic dibasic primary amines, strong polar aprotic organic solvents, and aromatic dibasic anhydrides described in step (2) are as defined above.
其中，步骤(3)中的高温烘道，其最高温度为400℃，所述开机走线，其线速度控制为1～5m/min。Wherein, the highest temperature of the high-temperature drying tunnel in step (3) is 400° C., and the line speed of the power-on routing is controlled to be 1 to 5 m/min.
步骤(4)中所述的烘道，其最高温度为150℃，所述的开机走线，其线速度控制为20～35m/min。The maximum temperature of the drying tunnel described in step (4) is 150° C., and the line speed of the power-on routing is controlled to be 20-35 m/min.
术语解释：Term explanation:
本发明所述的“室温”是指“20～30℃”。The "room temperature" in the present invention means "20-30°C".
所述的“20％(w/w)的20％(w/w)的聚酰胺酸溶液”是指质量百分比浓度为20％的聚酰胺酸溶液，即其中的“w/w”表示质量百分比。The "20% (w/w) 20% (w/w) polyamic acid solution" refers to a polyamic acid solution with a concentration of 20% by mass percentage, that is, "w/w" means mass percentage .
本发明提供的自粘性耐电晕聚酰亚胺漆、漆包线的制备方法操作工艺简单，对环境友好，自粘漆漆体系为无溶剂体系；其次，本发明所得产品综合性能优异，非常适合于大功率电机、大型高功率变压器的线圈绕组制造，具有良好的应用前景，易于规模化生产。The preparation method of the self-adhesive corona-resistant polyimide paint and enameled wire provided by the present invention has a simple operation process and is environmentally friendly. The manufacturing of coil windings for high-power motors and large-scale high-power transformers has good application prospects and is easy to produce on a large scale.
本发明提供的耐高温的聚酰亚胺漆包线漆作为底漆，在加入无机氧化物后，可以进一步提高耐电晕等性能。同时设计并制备了一种少见的海因环氧树脂自粘漆，自粘漆的引入可以改变传统的电机线圈绕组的浸渍方法，可以达到省时、节约能源、节约劳动力、保护环境等优势，此外本发明所使用的海因环氧树脂中含有氮元素，所以还具备一定的阻燃效果。The high temperature resistant polyimide wire enamel paint provided by the present invention is used as a primer, and after inorganic oxide is added, the corona resistance and other properties can be further improved. At the same time, a rare hydantoin epoxy resin self-adhesive paint was designed and prepared. The introduction of self-adhesive paint can change the traditional impregnation method of motor coil windings, which can save time, save energy, save labor, and protect the environment. In addition, the hydantoin epoxy resin used in the present invention contains nitrogen elements, so it also has a certain flame retardant effect.
具体实施方式Detailed ways
以下实施例对本发明作进一步的详细说明，包括但并不限于本发明的权利要求范围。The following examples further illustrate the present invention in detail, including but not limited to the scope of the claims of the present invention.
实施例1Example 1
将100g的海茵环氧树脂、500g的N，N，N’，N’-四缩水甘油基-2，2-双[4-(4-氨基苯氧基)苯基]丙烷TGBAPP、50g的4，4’-二氨基二苯砜加入反应釜中，搅拌，加热升温至70℃-80℃，搅拌反应0.5小时后，加入300g的CE793环氧树脂，搅拌均匀后，冷却至室温，加入30g的间苯二甲胺，室温下加拌均匀，即得自粘漆，记作SA-1。Combine 100g of Hein epoxy resin, 500g of N,N,N',N'-tetraglycidyl-2,2-bis[4-(4-aminophenoxy)phenyl]propane TGBAPP, 50g of 4,4'-Diaminodiphenylsulfone was added to the reaction kettle, stirred, heated to 70℃-80℃, stirred and reacted for 0.5 hours, then added 300g of CE793 epoxy resin, after stirring evenly, cooled to room temperature, added 30g The m-xylylenediamine is added and mixed evenly at room temperature to obtain the self-adhesive paint, which is recorded as SA-1.
将100g的海茵环氧树脂、800g的N，N，N’，N’-四缩水甘油基-2，2-双[4-(4-氨基苯氧基)苯基]丙烷TGBAPP、80g的4，4’-二氨基二苯砜加入反应釜中，搅拌，加热升温至70℃-80℃，搅拌反应1小时后，加入600g的CE793环氧树脂，搅拌均匀后，冷却至室温，加入20g的间苯二甲胺，室温下加拌均匀，即得自粘漆，记作SA-2。Put 100g of Hein epoxy resin, 800g of N,N,N',N'-tetraglycidyl-2,2-bis[4-(4-aminophenoxy)phenyl]propane TGBAPP, 80g of 4,4'-Diaminodiphenyl sulfone was added to the reactor, stirred, heated to 70°C-80°C, stirred and reacted for 1 hour, 600g of CE793 epoxy resin was added, after stirring, cooled to room temperature, and 20g was added The m-xylylenediamine is mixed evenly at room temperature to obtain the self-adhesive paint, which is recorded as SA-2.
将100g的海茵环氧树脂、1000g的N，N，N’，N’-四缩水甘油基-2，2-双[4-(4-氨基苯氧基)苯基]丙烷TGBAPP、100g的4，4’-二氨基二苯砜加入反应釜中，搅拌，加热升温至70℃-80℃，搅拌反应0.8小时后，加入800g的CE793环氧树脂，搅拌均匀后，冷却至室温，加入10g的间苯二甲胺，室温下加拌均匀，即得自粘漆，记作SA-3。100g of Hein epoxy resin, 1000g of N,N,N',N'-tetraglycidyl-2,2-bis[4-(4-aminophenoxy)phenyl]propane TGBAPP, 100g of 4,4'-Diaminodiphenyl sulfone was added to the reaction kettle, stirred, heated to 70°C-80°C, stirred and reacted for 0.8 hours, then 800g of CE793 epoxy resin was added, after stirring evenly, cooled to room temperature, and 10g was added The m-xylylenediamine is added and mixed evenly at room temperature to obtain the self-adhesive paint, which is recorded as SA-3.
实施例2Example 2
对实施例1的自粘漆进行性能测试，包括黏度、黏结力、固化物体积电阻率、固化物介电损耗、固化物击穿场强，具体测试结果如表1所示，测试方法如下：The performance test of the self-adhesive paint of Example 1, including viscosity, bonding force, volume resistivity of cured product, dielectric loss of cured product, and cured product breakdown field strength, the specific test results are shown in Table 1, and the test methods are as follows:
1、黏度测试1. Viscosity test
采用美国博勒飞公司生产的CAP2000+型的黏度计进行测试，选择转子为1号，温度范围25℃。The CAP2000+ viscometer produced by Brookfield Company of the United States was used for the test. The rotor was No. 1 and the temperature range was 25°C.
2、黏结力测试2. Bonding force test
将绕好的螺旋铜线浸入自粘漆中，180℃条件下固化1h，采用微机控制电子万能试验机进行黏结力测试，其中每个配方进行三个试样的测试，然后取平均值。The wound spiral copper wire is immersed in the self-adhesive paint, cured at 180°C for 1 hour, and the bonding force is tested by a microcomputer-controlled electronic universal testing machine. Three samples are tested for each formula, and then the average value is taken.
3、体积电阻率测试3. Volume resistivity test
将自粘漆均匀涂于直径为110mm的圆形模具中，180℃条件下固化1h后自然冷却取下。用上海第六电表厂有限公司生产的ZC36型绝缘电阻测试仪对电阻进行测试，测试电压为1kV。Spread the self-adhesive paint uniformly on a circular mold with a diameter of 110mm, cure it at 180°C for 1 hour, and then take it off by natural cooling. The resistance was tested with the ZC36 insulation resistance tester produced by Shanghai No.6 Electric Meter Factory Co., Ltd., and the test voltage was 1kV.
4、介电损耗测试4. Dielectric loss test
将已测试体积电阻率的样品放在夹具上，用武汉华瑞测控科技有限公司的S6000-H+型介质损耗测试仪进行介电测试，测试电压为1kV。Place the sample with the tested volume resistivity on the fixture, and use the S6000-H+ dielectric loss tester of Wuhan Huarui Measurement and Control Technology Co., Ltd. to conduct dielectric test, and the test voltage is 1kV.
5、击穿场强测试5. Breakdown field strength test
将样品用HT-50c型击穿电压测试仪测试其击穿场强，测量击穿位置的样品厚度，并计算出试样的击穿场强。Test the breakdown field strength of the sample with the HT-50c breakdown voltage tester, measure the thickness of the sample at the breakdown position, and calculate the breakdown field strength of the sample.
测试结果如表1所示。The test results are shown in Table 1.
表1 自粘漆的性能数据Table 1 Performance data of self-adhesive paint
Figure PCTCN2020111005-appb-000002
Figure PCTCN2020111005-appb-000002
实施例3Example 3
将19.8g(0.1mol)的4，4’-二氨基二苯甲烷、26.0g(0.13mol)的3，4’-二氨基二苯醚和36.6g(0.1mol)的2，2-双(3-羟基-4-氨基苯基)六氟丙烷的芳香族二元伯胺、400.0g的N，N-二甲基甲酰胺和232.8g的N-甲基-2-吡咯烷酮的强极性非质子有机溶剂加入反应釜中，室温下搅拌溶解后，加入43.6g(0.2mol)的均苯四甲酸二酐和32.2g(0.1mol)的3，3’，4，4’-四羧基二苯甲酮二酐的芳香族二元酐，室温下搅拌反应1小时，加入69.1g的3-氨丙基三甲氧基硅烷偶联剂处理的二氧化硅无机纳米粉体和10.0g的3-氨丙基三甲氧基硅烷偶联剂处理的二氧化钛无机纳米粉体，搅拌研磨均匀，即得870.1g耐电晕聚酰亚胺漆，记作CR-1。19.8g (0.1mol) of 4,4'-diaminodiphenylmethane, 26.0g (0.13mol) of 3,4'-diaminodiphenyl ether and 36.6g (0.1mol) of 2,2-bis( 3-hydroxy-4-aminophenyl) hexafluoropropane aromatic dibasic primary amine, 400.0g of N,N-dimethylformamide and 232.8g of N-methyl-2-pyrrolidone are strongly polar The protic organic solvent is added to the reaction kettle, after stirring and dissolving at room temperature, 43.6g (0.2mol) of pyromellitic dianhydride and 32.2g (0.1mol) of 3,3',4,4'-tetracarboxydiphenyl are added The aromatic dibasic anhydride of ketone dianhydride, stirred and reacted at room temperature for 1 hour, added 69.1g of 3-aminopropyltrimethoxysilane coupling agent treated silica inorganic nanopowder and 10.0g of 3-ammonia The titanium dioxide inorganic nano-powder treated with propyltrimethoxysilane coupling agent is stirred and ground uniformly to obtain 870.1g of corona-resistant polyimide paint, denoted as CR-1.
将23.0g(0.115mol)的4，4’-二氨基二苯醚、20.0g(0.1mol)的3，4’-二氨基二苯醚和36.6g(0.1mol)的2，2-双(3-羟基-4-氨基苯基)六氟丙烷的芳香族二元伯胺、616.8g的N，N-二甲基乙酰胺强极性非质子有机溶剂加入反应釜中，室温下搅拌溶解后，加入43.6g(0.2mol)的均苯四甲酸二酐和31.0g(0.1mol)的3，3’，4，4’-四羧 基二苯醚二酐的芳香族二元酐，室温下搅拌反应4小时，加入13.2克3-氨丙基三乙氧基硅烷偶联剂处理的二氧化硅无机纳米粉体和10.0g的3-氨丙基三乙氧基硅烷偶联剂处理的氧化铝无机纳米粉体，搅拌研磨均匀，即得794.2g耐电晕聚酰亚胺漆，记作CR-2。Combine 23.0g (0.115mol) of 4,4'-diaminodiphenyl ether, 20.0g (0.1mol) of 3,4'-diaminodiphenyl ether and 36.6g (0.1mol) of 2,2-bis( 3-Hydroxy-4-aminophenyl) hexafluoropropane aromatic dibasic primary amine, 616.8g of N,N-dimethylacetamide strong polar aprotic organic solvent are added to the reactor, after stirring at room temperature to dissolve , Add 43.6g (0.2mol) of pyromellitic dianhydride and 31.0g (0.1mol) of 3,3',4,4'-tetracarboxydiphenyl ether dianhydride, and stir at room temperature After reacting for 4 hours, 13.2 g of inorganic nano-silica powder treated with 3-aminopropyl triethoxy silane coupling agent and 10.0 g of alumina treated with 3-aminopropyl triethoxy silane coupling agent were added. Inorganic nano powder, stir and grind evenly to obtain 794.2g of corona-resistant polyimide paint, denoted as CR-2.
将29.2g(0.1mol)的1，3-双(4-氨基苯氧基)苯和49.0g(0.245mol)的3，4’-二氨基二苯醚的芳香族二元伯胺、689.6g的N-甲基-2-吡咯烷酮强极性非质子有机溶剂加入反应釜中，室温下搅拌溶解后，加入62.0g(0.2mol)的3，3’，4，4’-四羧基二苯醚二酐和32.2g(0.1mol)的3，3’，4，4’-四羧基二苯甲酮二酐的芳香族二元酐，室温下搅拌反应3小时，加入53.1g的3-氨丙基三甲氧基硅烷偶联剂处理的二氧化硅无机纳米粉体和50.2g的3-氨丙基三甲氧基硅烷偶联剂处理的三氧化二铁无机纳米粉体，搅拌研磨均匀，即得965.3g耐电晕聚酰亚胺漆，记作CR-3。Combine 29.2g (0.1mol) of 1,3-bis(4-aminophenoxy)benzene and 49.0g (0.245mol) of 3,4'-diaminodiphenyl ether aromatic dibasic primary amine, 689.6g The N-methyl-2-pyrrolidone strong polar aprotic organic solvent was added to the reaction kettle, after stirring and dissolving at room temperature, 62.0g (0.2mol) of 3,3',4,4'-tetracarboxydiphenyl ether was added The aromatic dianhydride of dianhydride and 32.2g (0.1mol) of 3,3',4,4'-tetracarboxylic benzophenone dianhydride, stir and react at room temperature for 3 hours, add 53.1g of 3-aminopropyl Inorganic nano-silica powder treated with trimethoxysilane coupling agent and 50.2g of inorganic nano-iron oxide powder treated with 3-aminopropyltrimethoxysilane coupling agent, stir and grind uniformly, and then get 965.3g corona resistant polyimide paint, denoted as CR-3.
实施例4Example 4
对实施例3的耐电晕聚酰亚胺漆膜(固化工艺为：室温开始升温至100℃，保持1小时，继续升温至200℃，保持1小时，继续升温至300℃保持1小时，自然冷却至室温)进行性能测试，包括体积电阻率、介电损耗、击穿场强、耐电晕性能，具体测试结果如表2所示，测试方法如下：For the corona-resistant polyimide paint film of Example 3 (the curing process is: start from room temperature to 100°C, hold for 1 hour, continue to heat up to 200°C, hold for 1 hour, continue to heat up to 300°C for 1 hour, naturally Cooled to room temperature) Perform performance tests, including volume resistivity, dielectric loss, breakdown field strength, and corona resistance. The specific test results are shown in Table 2. The test methods are as follows:
1、体积电阻率测试1. Volume resistivity test
采用上海太欧电子有限公司生产的ZC-90G高绝缘电阻测量仪对固化后的漆膜铜片在1kV的条件下进行测试，并测量样品厚度。The ZC-90G high insulation resistance measuring instrument produced by Shanghai Taiou Electronics Co., Ltd. was used to test the cured paint film copper sheet under the condition of 1kV, and the thickness of the sample was measured.
2、介电损耗测试2. Dielectric loss test
将样品剪取长宽均为2cm的形状，然后采用常州市同惠电子有限公司生产的TH2828S型自动元件分析仪进行测试。Cut the sample into a shape of 2 cm in length and width, and then use the TH2828S automatic component analyzer produced by Changzhou Tonghui Electronics Co., Ltd. for testing.
3、击穿场强测试3. Test of breakdown field strength
在外加电场作用之下，绝缘材料失去绝缘性能，是由于电极间出现短路的现象，称之为电介质的击穿。绝缘材料被击穿时的电压叫做击穿电压，击穿场强为击穿电压和介质厚度之比。Under the action of an external electric field, the insulating material loses its insulating properties due to a short-circuit phenomenon between the electrodes, which is called dielectric breakdown. The voltage when the insulating material is broken down is called the breakdown voltage, and the breakdown field strength is the ratio of the breakdown voltage to the thickness of the dielectric.
采用常州微特电机总厂的CW2672H型自动高压击穿装置对固化后的漆膜铜片进行测试。The CW2672H automatic high voltage breakdown device of Changzhou Micro-Special Motor Factory was used to test the cured paint film copper sheet.
4、耐电晕测试4. Corona resistance test
耐电晕时间是指绝缘材料从电晕放电到材料被击穿时所发生的时间。材料的 耐电晕寿命除了自身原因之外，还与频率、温度、电场强度等因素有关。Corona resistance time refers to the time that an insulating material takes from corona discharge to when the material is broken down. In addition to its own reasons, the corona-resistant life of materials is also related to factors such as frequency, temperature, and electric field strength.
实验中采用上海申发检测仪器有限公司产的JGM-3F高频脉冲电压测试仪，对所制备漆膜的耐电晕性能进行测试。测试条件：温度：室温；脉冲频率：20kHz；脉冲占空率：50％；脉冲电压峰峰值：2.5kV。In the experiment, the JGM-3F high-frequency pulse voltage tester produced by Shanghai Shenfa Testing Instrument Co., Ltd. was used to test the corona resistance of the prepared paint film. Test conditions: temperature: room temperature; pulse frequency: 20kHz; pulse duty ratio: 50%; pulse voltage peak-to-peak value: 2.5kV.
测试结果如表2所示。The test results are shown in Table 2.
表2 耐电晕聚酰亚胺漆膜的性能数据Table 2 Performance data of corona resistant polyimide paint film
Figure PCTCN2020111005-appb-000003
Figure PCTCN2020111005-appb-000003
实施例5Example 5
分别将实施例3的耐电晕聚酰亚胺漆CR-1、CR-2、CR-3，放入漆包线机的漆槽中，紫铜线穿过漆槽12道～18道、经过高温烘道，开机走线，线速度分别为1m/min、3m/min、5m/min，高温固化，最高温度为400℃，收卷，分别得到耐电晕聚酰亚胺漆包线ECR-1、ECR-2、ECR-3。Put the corona-resistant polyimide paint CR-1, CR-2, and CR-3 of Example 3 into the paint tank of the enameled wire machine. The red copper wire passes through the paint tank in 12 to 18 passes, and is baked at high temperature. After turning on the wire, the line speeds are 1m/min, 3m/min, 5m/min, high temperature curing, the highest temperature is 400℃, and winding, and the corona-resistant polyimide enameled wire ECR-1 and ECR- are obtained. 2. ECR-3.
分别将实施例1的自粘漆SA-1、SA-2、SA-3，放入漆包线机的漆槽中，分别依次将耐电晕聚酰亚胺漆包线ECR-1、ECR-2、ECR-3穿过漆槽、经过烘道，开机走线，线速度分别为20m/min、30m/min、35m/min，加热半固化，最高温度为150℃，收卷，分别得到自粘性耐电晕聚酰亚胺漆包线SECR-1、SECR-2、SECR-3。Put the self-adhesive varnishes SA-1, SA-2, and SA-3 of Example 1 into the paint tank of the enameled wire machine, and respectively put the corona-resistant polyimide enameled wires ECR-1, ECR-2, and ECR in sequence. -3 Pass through the paint tank, pass through the drying tunnel, start the wire, the line speeds are 20m/min, 30m/min, 35m/min, heat semi-cured, the highest temperature is 150℃, rewind, and obtain self-adhesive electricity resistance. Halo polyimide enameled wire SECR-1, SECR-2, SECR-3.
采用以下方法进行性能测试，具体测试数据如表3所示：The following methods are used for performance testing, and the specific test data is shown in Table 3:
1、漆膜厚度测试1. Paint film thickness test
采用德清盛泰芯电子科技有限公司生产的千分尺对漆包线进行直径测试。A micrometer produced by Deqing Shengtaixin Electronic Technology Co., Ltd. was used to test the diameter of the enameled wire.
2、伸长率测试2. Elongation test
采用鑫雄仪器有限公司生产的SC-5B型伸长率拉力试验仪对漆包线进行伸长率测试，直至式样拉断。Use the SC-5B elongation tensile tester produced by Xinxiong Instrument Co., Ltd. to test the elongation of the enameled wire until the pattern breaks.
3、圆棒卷绕测试3. Round rod winding test
采用宇航科技有限公司生产的JR-16A型漆包圆线卷绕试验仪对漆包线进行卷绕测试，观察是否达到预置圈数。The JR-16A enameled round wire winding tester produced by Yuhang Technology Co., Ltd. is used to wind the enameled wire to observe whether it reaches the preset number of turns.
4、击穿电压测试4. Breakdown voltage test
采用宇航科技有限公司生产的ZDS-50B型自动电压试验仪对漆包线进行电压测试，式样击穿后记录下电压。The ZDS-50B automatic voltage tester produced by Yuhang Technology Co., Ltd. is used to test the voltage of the enameled wire. After the pattern is broken down, the voltage is recorded.
5、耐电晕测试5. Corona resistance test
采用上海申发检测仪器有限公司生产的JGM-3F型高频脉冲绝缘测试仪对漆包线进行耐电晕测试，测试条件：测试条件：温度：155℃；脉冲频率：20kHz；脉冲占空率：50％；脉冲电压峰峰值：3.0kV。Use the JGM-3F high-frequency pulse insulation tester produced by Shanghai Shenfa Testing Instrument Co., Ltd. to test the corona resistance of the enameled wire. Test conditions: test conditions: temperature: 155℃; pulse frequency: 20kHz; pulse duty cycle: 50 %; peak-to-peak pulse voltage: 3.0kV.
6、耐刮测试6. Scratch resistance test
采用宇航科技有限公司生产的ZDG-25型智能单向刮漆试验仪对漆包线进行测试，按照步骤放置好漆包线，然后设置一定的负荷进行刮破力测试。The enameled wire is tested with the ZDG-25 intelligent one-way paint scraping tester produced by Yuhang Technology Co., Ltd., the enameled wire is placed according to the steps, and then a certain load is set for the scraping force test.
7、急拉断测试7, jerky pull test
采用鑫雄仪器有限公司生产的JLD-10型急拉断试验仪对漆包线进行按照步骤放置好漆包线，待到气压表到达0.7-0.8MPa时进行急拉测试。The enameled wire is placed in the enameled wire according to the steps with the JLD-10 type jerky breaking tester produced by Xinxiong Instrument Co., Ltd., and the jerky pull test is performed when the barometer reaches 0.7-0.8MPa.
表3 漆包线的性能测试数据Table 3 Performance test data of enameled wire
Figure PCTCN2020111005-appb-000004
Figure PCTCN2020111005-appb-000004

Claims (9)

  1. 一种自粘性耐电晕聚酰亚胺漆，其特征在于，所述自粘性耐电晕聚酰亚胺漆由自粘漆、耐电晕聚酰亚胺漆组成；其中，A self-adhesive corona-resistant polyimide paint, characterized in that the self-adhesive corona-resistant polyimide paint is composed of self-adhesive paint and corona-resistant polyimide paint; wherein,
    自粘漆由质量比为1∶5～10∶3～8∶0.5～1∶0.1～0.3的海茵环氧树脂、N，N，N’，N’-四缩水甘油基-2，2-双[4-(4-氨基苯氧基)苯基]丙烷TGBAPP、CE793环氧树脂、4，4’-二氨基二苯砜、间苯二甲胺组成；The self-adhesive paint consists of Haiyin epoxy resin with a mass ratio of 1:5～10:3～8:0.5～1:0.1～0.3, N,N,N',N'-tetraglycidyl-2,2- Bis[4-(4-aminophenoxy)phenyl]propane TGBAPP, CE793 epoxy resin, 4,4'-diaminodiphenyl sulfone, m-xylylenediamine;
    耐电晕聚酰亚胺漆由浓度为20％(w/w)的聚酰胺酸溶液和偶联剂处理的无机纳米粉体组成，其中浓度为20％(w/w)的聚酰胺酸溶液和偶联剂处理的无机纳米粉体的质量比为100∶3～12。2.根据权利要求1所述的自粘性耐电晕聚酰亚胺漆，其特征在于，所述的偶联剂选自3-氨丙基三甲氧基硅烷、3-氨丙基三乙氧基硅烷、环氧丙氧基丙基三甲氧基硅烷、环氧丙氧基丙基三乙氧基硅烷中的一种或几种。The corona-resistant polyimide paint is composed of a polyamic acid solution with a concentration of 20% (w/w) and an inorganic nanopowder treated with a coupling agent, and a polyamic acid solution with a concentration of 20% (w/w) The mass ratio of the inorganic nanopowder treated with the coupling agent is 100:3-12. 2. The self-adhesive corona-resistant polyimide paint according to claim 1, characterized in that the coupling agent One selected from 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane Kind or several kinds.
  2. 根据权利要求1所述的一种自粘性耐电晕聚酰亚胺漆，其特征在于，所述的无机纳米粉体选自纳米氧化铝粉体、纳米二氧化硅粉体、纳米二氧化钛粉体、纳米三氧化二铁粉体、纳米氧化镁粉体中的一种或几种。The self-adhesive corona-resistant polyimide paint according to claim 1, wherein the inorganic nano powder is selected from the group consisting of nano alumina powder, nano silica powder, and nano titanium dioxide powder. , One or more of nanometer ferric oxide powder and nanometer magnesium oxide powder.
  3. 根据权利要求1所述的一种自粘性耐电晕聚酰亚胺漆，其特征在于，所述的海茵环氧树脂的结构式为：The self-adhesive corona-resistant polyimide paint according to claim 1, wherein the structural formula of the Hyin epoxy resin is:
    Figure PCTCN2020111005-appb-100001
    Figure PCTCN2020111005-appb-100001
  4. 一种自粘性耐电晕聚酰亚胺漆包线，其特征在于，所述漆包线由紫铜线内芯和权利要求1～4任一项所述的自粘性耐电晕聚酰亚胺漆外层组成。A self-adhesive corona-resistant polyimide enameled wire, characterized in that, the enameled wire is composed of a red copper wire inner core and the self-adhesive corona-resistant polyimide varnish outer layer of any one of claims 1 to 4 .
  5. 一种权利要求5所述的自粘性耐电晕聚酰亚胺漆包线的制备方法，包括以下步骤：A method for preparing the self-adhesive corona-resistant polyimide enameled wire according to claim 5, comprising the following steps:
    (1)将海茵环氧树脂、N，N，N’，N’-四缩水甘油基-2，2-双[4-(4-氨基苯氧基)苯基]丙烷TGBAPP、4，4’-二氨基二苯砜加入反应釜中，搅拌，加热升温至70℃～80℃，搅拌反应0.5～1小时后，加入CE793环氧树脂，搅拌均匀后，冷却至室温，加入间苯二甲胺，室温下搅拌均匀，得到自粘漆；(1) Combine Hein epoxy resin, N,N,N',N'-tetraglycidyl-2,2-bis[4-(4-aminophenoxy)phenyl]propane TGBAPP, 4,4 '-Diaminodiphenyl sulfone was added to the reaction kettle, stirred, heated to 70°C ~ 80°C, stirred for 0.5 to 1 hour, then added CE793 epoxy resin, stirred evenly, cooled to room temperature, and added metaxylylene Amine, stir evenly at room temperature to obtain self-adhesive paint;
    (2)将芳香族二元伯胺、强极性非质子有机溶剂加入反应釜中，室温下搅拌溶解后，加入芳香族二元酐，室温下搅拌反应1～4小时，加入偶联剂处理的无机纳米粉体，搅拌研磨均匀，即得耐电晕聚酰亚胺漆；其中，芳香族二元伯胺与芳 香族二元酐的摩尔比为1.05～1.15∶1.00。(2) Add aromatic dibasic primary amine and strong polar aprotic organic solvent into the reaction kettle, stir to dissolve at room temperature, add aromatic dibasic anhydride, stir at room temperature for 1-4 hours, add coupling agent for treatment The inorganic nanopowders are stirred and ground uniformly to obtain corona resistant polyimide paint; wherein, the molar ratio of aromatic dibasic primary amine to aromatic dibasic anhydride is 1.05-1.15:1.00.
    (3)将步骤(2)制备的耐电晕聚酰亚胺漆放入漆包线机的漆槽中，紫铜线穿过漆槽12道～18道、经过高温烘道，开机走线，高温固化，收卷，得到耐电晕聚酰亚胺漆包线；(3) Put the corona-resistant polyimide paint prepared in step (2) into the paint tank of the enamelled wire machine, and the copper wire passes through 12 to 18 paint tanks, passes through the high-temperature drying tunnel, turns on the wire, and cures at high temperature. , Rewinding to obtain corona-resistant polyimide enameled wire;
    (4)将步骤(1)制备的自粘漆放入漆包线机的漆槽中，耐电晕聚酰亚胺漆包线穿过漆槽、经过烘道，开机走线，加热半固化，收卷，得到自粘性耐电晕聚酰亚胺漆包线。(4) Put the self-adhesive paint prepared in step (1) into the paint tank of the enameled wire machine, pass the corona-resistant polyimide enameled wire through the paint tank, pass through the drying tunnel, turn on the wire, heat it for semi-curing, and rewind. A self-adhesive corona-resistant polyimide enameled wire was obtained.
  6. 根据权利要求6所述的自粘性耐电晕聚酰亚胺漆包线的制备方法，其特征在于，步骤(2)中所述的芳香族二元伯胺选自对苯二胺、间苯二胺、邻苯二胺、三甲基间苯二胺、邻甲基对苯二胺、4，4’-二氨基二苯甲烷、3，3’-二甲基-4，4’-二氨基二苯甲烷、3，3’-二甲基-4，4’-二氨基-5，5’-二乙基二苯甲烷、3，3’，5，5’-四甲基-4，4’-二氨基二苯甲烷、3，3’-二氨基二苯甲烷、4，4’-二氨基二苯醚、3，4’-二氨基二苯醚、3，3’-二氨基二苯醚、4，4’-二氨基二苯甲酮、4，4’-二氨基二苯砜、3，3’-二氨基二苯砜、4，4’-二氨基二苯硫醚、4，4’-二氨基联苯、2，2’-二甲基-4，4’-二氨基联苯、2，2’-二(三氟甲基)-4，4’-二氨基联苯、1，4-双(4-氨基苯氧基)苯、1，4-双(3-氨基苯氧基)苯、1，3-双(4-氨基苯氧基)苯、1，3-双(3-氨基苯氧基)苯、1，4-双(2-三氟甲基-4-氨基苯氧基)苯、1，3-双(2-三氟甲基-4-氨基苯氧基)苯、4，4’-双(4-氨基苯氧基)联苯、4，4’-双(2-三氟甲基-4-氨基苯氧基)联苯、4，4’-双(3-氨基苯氧基)联苯、4，4’-双(4-氨基苯氧基)-3，3’，5，5’-四甲基联苯、4，4’-双(2-三氟甲基-4-氨基苯氧基)-3，3’，5，5’-四甲基联苯、4，4’-双(3-氨基苯氧基)-3，3’，5，5’-四甲基联苯、4，4’-双(4-氨基苯氧基)二苯醚、4，4’-双(2-三氟甲基-4-氨基苯氧基)二苯醚、4，4’-双(3-氨基苯氧基)二苯醚、4，4’-双(4-氨基苯氧基)二苯硫醚、4，4’-双(2-三氟甲基-4-氨基苯氧基)二苯硫醚、4，4’-双(3-氨基苯氧基)二苯硫醚、4，4’-双(4-氨基苯氧基)二苯砜、4，4’-双(2-三氟甲基-4-氨基苯氧基)二苯砜、4，4’-双(3-氨基苯氧基)二苯砜、4，4’-双(4-氨基苯氧基)二苯甲酮、4，4’-双(2-三氟甲基-4-氨基苯氧基)二苯甲酮、4，4’-双(3-氨基苯氧基)二苯甲酮、4，4’-双(4-氨基苯氧基)二苯甲烷、4，4’-双(2-三氟甲基-4-氨基苯氧基)二苯甲烷、4，4’-双(3-氨基苯氧基)二苯甲烷、2，2-双[4-(4-氨基苯氧基)苯基]丙烷、2，2-双[4-(2-三氟甲基-4-氨基苯氧基)苯基]丙烷、2，2-双[4-(3-氨基苯氧基)苯基]丙烷、2，2-双[4-(4-氨基苯氧基)苯基]六氟丙烷、2，2-双[4-(2-三氟甲基-4-氨基苯氧基)苯基]六氟丙烷、2，2-双[4-(3- 氨基苯氧基)苯基]六氟丙烷、2-(4-氨基苯基)-5-氨基苯并咪唑、4，4’-二氨基-4”-羟基三苯甲烷、2，2-双(3-羟基-4-氨基苯基)丙烷、2，2-双(3-羟基-4-氨基苯基)六氟丙烷、3，5-二氨基苯甲酸、3，5-双(4-氨基苯氧基)苯甲酸中的一种或几种。The method for preparing self-adhesive corona-resistant polyimide enameled wire according to claim 6, wherein the aromatic dibasic primary amine in step (2) is selected from the group consisting of p-phenylenediamine and m-phenylenediamine , O-phenylenediamine, trimethyl-m-phenylenediamine, o-methyl-p-phenylenediamine, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiamine Phenylmethane, 3,3'-dimethyl-4,4'-diamino-5,5'-diethyldiphenylmethane, 3,3',5,5'-tetramethyl-4,4' -Diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether , 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 4,4 '-Diaminobiphenyl, 2,2'-Dimethyl-4,4'-Diaminobiphenyl, 2,2'-Bis(trifluoromethyl)-4,4'-Diaminobiphenyl, 1 , 4-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis( 3-aminophenoxy)benzene, 1,4-bis(2-trifluoromethyl-4-aminophenoxy)benzene, 1,3-bis(2-trifluoromethyl-4-aminophenoxy) ) Benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(2-trifluoromethyl-4-aminophenoxy)biphenyl, 4,4'-bis (3-Aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)-3,3',5,5'-tetramethylbiphenyl, 4,4'-bis(2 -Trifluoromethyl-4-aminophenoxy)-3,3',5,5'-tetramethylbiphenyl, 4,4'-bis(3-aminophenoxy)-3,3', 5,5'-tetramethylbiphenyl, 4,4'-bis(4-aminophenoxy)diphenyl ether, 4,4'-bis(2-trifluoromethyl-4-aminophenoxy) Diphenyl ether, 4,4'-bis(3-aminophenoxy)diphenyl ether, 4,4'-bis(4-aminophenoxy)diphenyl sulfide, 4,4'-bis(2- Trifluoromethyl-4-aminophenoxy)diphenyl sulfide, 4,4'-bis(3-aminophenoxy)diphenyl sulfide, 4,4'-bis(4-aminophenoxy) Diphenylsulfone, 4,4'-bis(2-trifluoromethyl-4-aminophenoxy)diphenylsulfone, 4,4'-bis(3-aminophenoxy)diphenylsulfone, 4,4 '-Bis(4-aminophenoxy)benzophenone, 4,4'-bis(2-trifluoromethyl-4-aminophenoxy)benzophenone, 4,4'-bis(3 -Aminophenoxy)benzophenone, 4,4'-bis(4-aminophenoxy)diphenylmethane, 4,4'-bis(2-trifluoromethyl-4-aminophenoxy) Diphenylmethane, 4,4'-bis(3-aminophenoxy)diphenylmethane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4 -(2-Trifluoromethyl-4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-amino Phenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-trifluoromethyl-4- Aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2-(4-aminophenyl)-5-aminobenzo Imidazole, 4,4'-diamino-4"-hydroxytriphenylmethane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminobenzene) One or more of hexafluoropropane, 3,5-diaminobenzoic acid, and 3,5-bis(4-aminophenoxy)benzoic acid.
  7. 根据权利要求6所述的自粘性耐电晕聚酰亚胺漆包线的制备方法，其特征在于，步骤(2)中所述的芳香族二元酐选自均苯四甲酸二酐、3，3’，4，4’-四羧基二苯甲酮二酐、3，3’，4，4’-四羧基二苯醚二酐、3，3’，4，4’-四羧基二苯砜二酐、3，3’，4，4’-四羧基联苯二酐、1，4-双(3，4-二羧基苯氧基)苯二酐、1，3-双(3，4-二羧基苯氧基)苯二酐、4，4’-双(3，4-二羧基苯氧基)二苯砜二酐、4，4’-双(3，4-二羧基苯氧基)二苯甲酮二酐、4，4’-双(3，4-二羧基苯氧基)二苯醚二酐、4，4’-双(3，4-二羧基苯氧基)联苯二酐、2，2-双[4-(3，4-二羧基苯氧基)苯基]丙烷二酐、2，2-双[4-(3，4-二羧基苯氧基)苯基]六氟丙烷二酐、2，2-双(3，4-二羧基苯基)六氟丙烷二酐中的一种或几种。The method for preparing self-adhesive corona-resistant polyimide enameled wire according to claim 6, wherein the aromatic dianhydride in step (2) is selected from pyromellitic dianhydride, 3, 3 ',4,4'-Tetracarboxybenzophenone dianhydride, 3,3',4,4'-tetracarboxydiphenyl ether dianhydride, 3,3',4,4'-tetracarboxydiphenyl sulfone two Anhydride, 3,3',4,4'-tetracarboxybiphthalic anhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,3-bis(3,4-di Carboxyphenoxy)phthalic anhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)di Benzophenone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl ether dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride , 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]hexa One or more of fluoropropane dianhydride and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride.
  8. 根据权利要求6所述的自粘性耐电晕聚酰亚胺漆包线的制备方法，其特征在于，步骤(2)中所述的强极性非质子有机溶剂选自N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、二甲基亚砜中的一种或几种。The method for preparing self-adhesive corona-resistant polyimide enameled wire according to claim 6, wherein the strong polar aprotic organic solvent in step (2) is selected from N, N-dimethylformaldehyde One or more of amide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and dimethyl sulfoxide.
  9. 根据权利要求6所述自粘性耐电晕聚酰亚胺漆包线的制备方法，其特征在于，步骤(3)中所述的高温烘道，其最高温度为400℃；The method for preparing self-adhesive corona-resistant polyimide enameled wire according to claim 6, wherein the high temperature drying tunnel in step (3) has a maximum temperature of 400°C;
    进一步优选的，根据权利要求6所述的自粘性耐电晕聚酰亚胺漆包线的制备方法，其特征在于，步骤(3)中所述的开机走线，其线速度控制在1～5m/min；Further preferably, the preparation method of self-adhesive corona-resistant polyimide enameled wire according to claim 6, characterized in that, the start-up wiring in step (3) is controlled at a linear speed of 1-5m/ min;
    进一步优选的，根据权利要求6所述的自粘性耐电晕聚酰亚胺漆包线的制备方法，其特征在于，步骤(4)中所述的烘道，其最高温度为150℃；Further preferably, the method for preparing self-adhesive corona-resistant polyimide enameled wire according to claim 6, characterized in that the drying tunnel in step (4) has a maximum temperature of 150°C;
    进一步优选的，根据权利要求6所述的自粘性耐电晕聚酰亚胺漆的制备方法，其特征在于，所述步骤(4)中的开机走线，其线速度控制为20～35m/min。Further preferably, the preparation method of the self-adhesive corona-resistant polyimide paint according to claim 6, characterized in that, in the step (4), the line speed is controlled to be 20～35m/ min.
PCT/CN2020/111005 2020-03-31 2020-08-25 Self-adhesive corona-resistant polyimide paint, enameled wire and preparation method therefor WO2021196511A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202010245572.1A CN111410891A (en) 2020-03-31 2020-03-31 Self-adhesive corona-resistant polyimide paint, enameled wire and preparation method thereof
CN202010245572.1 2020-03-31

Publications (1)

Publication Number Publication Date
WO2021196511A1 true WO2021196511A1 (en) 2021-10-07

Family

ID=71489412

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/111005 WO2021196511A1 (en) 2020-03-31 2020-08-25 Self-adhesive corona-resistant polyimide paint, enameled wire and preparation method therefor

Country Status (2)

Country Link
CN (1) CN111410891A (en)
WO (1) WO2021196511A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114093556A (en) * 2021-10-11 2022-02-25 铜陵精达新技术开发有限公司 Corona-resistant electromagnetic wire for new energy automobile driving motor and preparation method thereof
CN117551387A (en) * 2024-01-12 2024-02-13 沈阳宏远电磁线股份有限公司 Polyimide high-temperature-resistant paint for new energy electromagnetic wire and preparation method thereof

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111410891A (en) * 2020-03-31 2020-07-14 苏州巨峰电气绝缘***股份有限公司 Self-adhesive corona-resistant polyimide paint, enameled wire and preparation method thereof
CN116082682B (en) * 2023-03-03 2024-04-05 四川大学 Polyimide/fluorinated nano Al 2 O 3 Composite film and preparation method thereof

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101928444A (en) * 2010-08-20 2010-12-29 广东生益科技股份有限公司 Halogen-free thermosetting resin composition, prepreg and metal clad foil laminated plate manufactured by using same
CN103514990A (en) * 2012-06-28 2014-01-15 上海敏桦特种漆包线制品有限公司 220-level high-temperature-resistance alcohol-melting self-adhesion enameled wire and producing method thereof
CN103773302A (en) * 2014-02-14 2014-05-07 东华大学 Single-component halogen-free flame-retardant epoxy adhesive and preparation method thereof
CN104449252A (en) * 2014-12-29 2015-03-25 无锡统力电工有限公司 Heat-resistant self-adhesive paint and preparation method thereof
CN105111927A (en) * 2015-09-02 2015-12-02 东华大学 High temperature resistant BAHPFP (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane) wire enamel and preparation method thereof
CN105229752A (en) * 2013-03-18 2016-01-06 施韦林&哈塞电线有限公司 Enamelled wire
CN105219233A (en) * 2015-11-02 2016-01-06 苏州巨峰电气绝缘***股份有限公司 A kind of corona-resistant wire enamel and preparation method thereof
CN106336795A (en) * 2016-08-30 2017-01-18 上海电缆研究所 Aromatic polyimide enameled wire paint and preparation method thereof
CN111410891A (en) * 2020-03-31 2020-07-14 苏州巨峰电气绝缘***股份有限公司 Self-adhesive corona-resistant polyimide paint, enameled wire and preparation method thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102838840A (en) * 2012-09-07 2012-12-26 黄山金瑞泰投资发展有限公司 Epoxy resin composition solution and preparation method thereof
CN103172859B (en) * 2013-04-16 2015-08-19 株洲时代电气绝缘有限责任公司 Polyamic acid dispersion liquid and preparation method thereof and Kapton
CN204651033U (en) * 2015-05-05 2015-09-16 浙江乔兴建设集团湖州智能科技有限公司 A kind of Novel enameled wire

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101928444A (en) * 2010-08-20 2010-12-29 广东生益科技股份有限公司 Halogen-free thermosetting resin composition, prepreg and metal clad foil laminated plate manufactured by using same
CN103514990A (en) * 2012-06-28 2014-01-15 上海敏桦特种漆包线制品有限公司 220-level high-temperature-resistance alcohol-melting self-adhesion enameled wire and producing method thereof
CN105229752A (en) * 2013-03-18 2016-01-06 施韦林&哈塞电线有限公司 Enamelled wire
CN103773302A (en) * 2014-02-14 2014-05-07 东华大学 Single-component halogen-free flame-retardant epoxy adhesive and preparation method thereof
CN104449252A (en) * 2014-12-29 2015-03-25 无锡统力电工有限公司 Heat-resistant self-adhesive paint and preparation method thereof
CN105111927A (en) * 2015-09-02 2015-12-02 东华大学 High temperature resistant BAHPFP (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane) wire enamel and preparation method thereof
CN105219233A (en) * 2015-11-02 2016-01-06 苏州巨峰电气绝缘***股份有限公司 A kind of corona-resistant wire enamel and preparation method thereof
CN106336795A (en) * 2016-08-30 2017-01-18 上海电缆研究所 Aromatic polyimide enameled wire paint and preparation method thereof
CN111410891A (en) * 2020-03-31 2020-07-14 苏州巨峰电气绝缘***股份有限公司 Self-adhesive corona-resistant polyimide paint, enameled wire and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114093556A (en) * 2021-10-11 2022-02-25 铜陵精达新技术开发有限公司 Corona-resistant electromagnetic wire for new energy automobile driving motor and preparation method thereof
CN117551387A (en) * 2024-01-12 2024-02-13 沈阳宏远电磁线股份有限公司 Polyimide high-temperature-resistant paint for new energy electromagnetic wire and preparation method thereof
CN117551387B (en) * 2024-01-12 2024-03-12 沈阳宏远电磁线股份有限公司 Polyimide high-temperature-resistant paint for new energy electromagnetic wire and preparation method thereof

Also Published As

Publication number Publication date
CN111410891A (en) 2020-07-14

Similar Documents

Publication Publication Date Title
WO2021196511A1 (en) Self-adhesive corona-resistant polyimide paint, enameled wire and preparation method therefor
EP1717820B1 (en) Polyamide-imide resin insulating coating material, insulated wire and method of making the same
JP4473916B2 (en) Polyamideimide resin insulating paint and insulated wire using the same
US8193451B2 (en) Polyamide-imide resin insulating varnish and insulated wire using the same
CN102676046B (en) Self-lubricating polyimide wire enamel and preparation method thereof
JP5609732B2 (en) Insulating paint and insulated wire using the same
CN109135554A (en) polyimide varnish and its preparation method and application
JP7140432B2 (en) Conductor coating polyimide varnish containing aromatic carboxylic acid and method for producing the same
CN105567076A (en) High-temperature-resistant enamelled wire paint composition based on fluorinated polyaryletherketone copolymerization modified polyimide and preparation method of high-temperature-resistant enamelled wire paint composition
JP2012224697A (en) Polyimide resin varnish, and electric insulated wire, electric appliance coil and motor using the same
CN106832277A (en) A kind of white Kapton with high-elongation and preparation method thereof
WO2021196512A1 (en) Self-bonding paint, corona-resistant polyimide paint and preparation method therefor
WO2020203192A1 (en) Insulated wire, coil, and electrical and electronic equipment
JP2013051030A (en) Insulated wire and armature coil using the same, motor
WO2020203193A1 (en) Insulated electrical wire, coil, and electrical/electronic appliance
CN102676047B (en) Self-lubricating wire enamel and preparing method thereof
JP2014152285A (en) Insulating paint and insulated wire using the same
JP2010037506A (en) Method for producing aqueous polyimide resin dispersion
JP2013155281A (en) Insulating coating, insulated wire using the insulating coating, and coil using the insulated wire
CN111234693A (en) High-temperature-resistant insulating polyimide wire enamel and preparation method thereof
JP5837397B2 (en) Insulated wire and electric coil and motor using the same
JP2011154819A (en) Insulated wire
JP2016183228A (en) Application liquid composition, coating layer formation method, and coil having coating layer formed by coating layer formation method
JP2023108491A (en) insulated wire
JP5081258B2 (en) Polyamideimide resin insulating paint and insulated wire using the same

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20929246

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20929246

Country of ref document: EP

Kind code of ref document: A1