CN115141539B - High-frequency-resistant low-temperature soldering tin H-grade insulating varnish and enameled wire - Google Patents

High-frequency-resistant low-temperature soldering tin H-grade insulating varnish and enameled wire Download PDF

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CN115141539B
CN115141539B CN202210563808.5A CN202210563808A CN115141539B CN 115141539 B CN115141539 B CN 115141539B CN 202210563808 A CN202210563808 A CN 202210563808A CN 115141539 B CN115141539 B CN 115141539B
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parts
mixing
polyurethane resin
stirring
polyimide
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CN115141539A (en
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袁锦标
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DONGGUAN YULONG ELECTRIC MATERIALS CO LTD
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DONGGUAN YULONG ELECTRIC MATERIALS CO LTD
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    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
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    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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    • 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
    • H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
    • H01B3/04—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances mica
    • 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
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    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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    • 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
    • H01B3/42—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 polyesters; polyethers; polyacetals
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    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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    • 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
    • H01B7/18—Protection against damage caused by wear, mechanical force or pressure; Sheaths; Armouring
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    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
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    • H01B7/28—Protection against damage caused by moisture, corrosion, chemical attack or weather
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    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/28—Protection against damage caused by moisture, corrosion, chemical attack or weather
    • H01B7/2806—Protection against damage caused by corrosion
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    • H01B7/282—Preventing penetration of fluid, e.g. water or humidity, into conductor or cable
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Abstract

The invention discloses a high-frequency-resistant low-temperature soldering tin H-grade insulating varnish and an enameled wire, which comprise the following components in parts by weight: 67-78 parts of water-based closed polyurethane resin emulsion, 12-20 parts of copper cobaltate @ polyimide microspheres, 8-14 parts of inorganic filler, 0.8-1.2 parts of dispersant, 0.3-0.6 part of defoaming agent, 0.4-0.8 part of neutralizer, 0.5-1 part of flatting agent and 4.2-5.6 parts of curing agent. The insulating paint prepared by the invention belongs to water-based environment-friendly paint, and the main raw materials comprise water-based closed polyurethane resin emulsion, copper cobaltate @ polyimide microspheres, inorganic filler and some auxiliaries. The insulating paint prepared by the invention not only keeps the direct welding property of the polyurethane paint film, but also improves the high temperature resistance and the mechanical strength, so that the insulating paint can keep the insulation grade above the H grade, and simultaneously has better wear resistance and weather resistance.

Description

High-frequency-resistant low-temperature soldering tin H-grade insulating varnish and enameled wire
Technical Field
The invention relates to the field of enameled wires, in particular to high-frequency and low-temperature soldering tin H-grade insulating paint and an enameled wire.
Background
The motor electrical appliance and the electronic product are indispensable components of electric power, communication equipment and household electrical appliances, the insulating material is one of indispensable important materials of the motor electrical appliance and the electronic product, and meanwhile, the enameled wire insulating varnish is one of necessary conditions for ensuring normal work of the electrical equipment and plays an important role in the field of electrical insulation.
Because the insulation grade of the insulating paint is the heat-resistant grade of the insulating material, most of the insulating paints select benzene solvents with good solubility and volatilization rate in order to enable the insulation grade to reach the H grade (180 ℃), although the insulation grade of the paint film is improved to a certain extent, the benzene solvents have high baking temperature and long baking time, not only a large amount of energy is consumed, but also the benzene solvents are easy to damage the health of human bodies and cause environmental pollution after volatilizing in the construction environment because of high toxicity, flammability and explosiveness; in addition, according to the market demand of the current insulating paint application, secondary soldering tin is needed after the high-frequency electronic transformer contains the immersion insulating paint, most of the direct-welding paint used in the current market is polyurethane paint and polyimide paint, the polyurethane paint has better direct-welding performance, but the soldering tin can cause the softening breakdown temperature of the polyurethane paint to be reduced and the dielectric loss to be increased, and meanwhile, the polyurethane paint has the defects of insufficient high temperature resistance, low mechanical strength, poor acid and alkali resistance and the like, so that the polyurethane insulating paint needs to be modified, and the high-frequency electronic transformer has more performance.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide high-frequency and low-temperature soldering tin H-grade insulating paint and an enameled wire.
The purpose of the invention is realized by adopting the following technical scheme:
in a first aspect, the invention provides a high-frequency-resistant low-temperature soldering tin H-grade insulating paint which comprises the following components in parts by weight:
67-78 parts of water-based closed polyurethane resin emulsion, 12-20 parts of copper cobaltate @ polyimide microspheres, 8-14 parts of inorganic filler, 0.8-1.2 parts of dispersant, 0.3-0.6 part of defoaming agent, 0.4-0.8 part of neutralizer, 0.5-1 part of flatting agent and 4.2-5.6 parts of curing agent.
Preferably, the water-based blocked polyurethane resin emulsion is obtained by uniformly mixing blocked polyurethane resin, a surfactant and deionized water; wherein the mass ratio of the blocked polyurethane resin to the surfactant to the deionized water is 1.2-0.4.
Preferably, the surfactant is gamma-aminopropyltriethoxysilane or gamma-methacryloxypropyltrimethoxysilane.
Preferably, the preparation method of the blocked polyurethane resin comprises the following steps:
step a, weighing polyethylene glycol adipate and toluene diisocyanate, mixing the weighed polyethylene glycol adipate and the toluene diisocyanate into a container, adding a catalyst dibutyltin dilaurate, introducing nitrogen as a protective gas, heating to 75-85 ℃, and stirring for reaction for 3-5 hours to obtain a prepolymer product;
and b, mixing the prepolymer product and a solvent butanone into a reaction container, adding a sealant dimethylglyoxime and a chain extender ethylenediamine while stirring, heating to 75-85 ℃ after stirring for 0.2-0.5h at room temperature, and stirring for 2-4h to obtain the closed polyurethane resin.
Preferably, in the step a, the mass ratio of the polyethylene glycol adipate to the toluene diisocyanate is 2.1-2.8, and the adding amount of the dibutyltin dilaurate is 0.1-0.3% of the mass of the polyethylene glycol adipate.
Preferably, in the step b, the mass ratio of the prepolymer product, the dimethylglyoxime and the butanone is 1.15-0.24, and the adding amount of the ethylenediamine is 2-4% of the mass of the polyethylene glycol adipate.
Preferably, the inorganic filler comprises mica powder and light calcium carbonate; wherein the mass ratio of the mica powder to the light calcium carbonate is 2.2-2.8.
Preferably, the particle size of the copper cobaltate @ polyimide microspheres is 10-20 microns
Preferably, the dispersant is one of BYK-110, BYK-108 and BYK-192.
Preferably, the defoaming agent is TEGO-902W or TEGO-901W.
Preferably, the neutralizing agent is one of dimethylethanolamine, triethylamine and ethylenediamine.
Preferably, the leveling agent is BYK307 or BYK310.
Preferably, the curing agent is an aqueous amine curing agent of the type Vast EPIKURE 8536-MY-60 or Vast EPIKURE 8545-W-52.
Preferably, the preparation method of the copper cobaltate @ polyimide microsphere comprises the following steps:
s1, preparing polyimide porous microspheres:
(1) weighing 4,4' -diaminodiphenyl ether, mixing in N, N-dimethylformamide, adding sodium dodecyl benzene sulfonate and liquid paraffin, ultrasonically mixing for 0.5-1h at room temperature, adding carbon disulfide, and uniformly mixing to obtain a first mixed solution;
(2) under the protection of nitrogen, weighing pyromellitic dianhydride, dividing into multiple parts, adding into the first mixed solution, and stirring at room temperature for 10-15h to obtain a second mixed solution;
(3) adding the mixed solution of acetic anhydride and pyridine into the second mixed solution, uniformly mixing, and sequentially carrying out chemical imidization treatment and thermal imidization treatment to obtain polyimide porous microspheres;
s2, preparing a copper cobaltate pretreatment solution:
weighing cobalt chloride hexahydrate and copper chloride dihydrate, mixing the cobalt chloride hexahydrate and the copper chloride dihydrate into deionized water, firstly dropwise adding an ammonium fluoride aqueous solution after completely dissolving, uniformly stirring, then dropwise adding a urea aqueous solution, and uniformly stirring again to obtain a copper cobaltate pretreatment solution;
s3, preparing copper cobaltate @ polyimide microspheres:
weighing polyimide porous microspheres, mixing the polyimide porous microspheres in a copper cobaltate pretreatment solution, stirring for 1-2h at the temperature of 45-65 ℃, pouring the mixture into a reaction kettle, placing the reaction kettle in an oven, quickly heating to 125-145 ℃, carrying out heat preservation reaction for 10-15h, filtering out solids, washing at least three times by using an ethanol solution with the mass fraction of 50%, carrying out reduced pressure drying, and then placing the product at the temperature of 225-265 ℃ for treatment for 1-3h to obtain copper cobaltate @ polyimide microspheres.
Preferably, in the S1, the mass ratio of sodium dodecyl benzene sulfonate, liquid paraffin, carbon disulfide, 4' -diaminodiphenyl ether to N, N-dimethylformamide is 0.2-0.8.
Preferably, in the S1, pyromellitic dianhydride is divided into 5 parts and added to the first mixed solution within 1h, and the mass ratio of pyromellitic dianhydride to 4,4' -diaminodiphenyl ether is 1.02-1.08.
Preferably, in S1, the mass ratio of acetic anhydride, pyridine and second mixed solution is 0.5-0.8.
Preferably, in the step S1, the chemical imidization treatment is to stir at normal temperature for 3-5 hours, add ethanol to precipitate, and then perform filtration, washing and drying treatment; the thermal imidization treatment is to subject a product obtained by chemical imidization treatment to stepped heat treatment: the first stage is carried out at 150-180 deg.C for 0.5-1h, the second stage is carried out at 200-240 deg.C for 0.5-1h, and the third stage is carried out at 260-280 deg.C for 2-4h.
Preferably, in the S2, the mass ratio of cobalt chloride hexahydrate, copper chloride dihydrate and deionized water is 1.38-1.45.
Preferably, in the S2, the mass fraction of the ammonium fluoride aqueous solution is 15%, wherein the mass ratio of ammonium fluoride to cobalt chloride hexahydrate is 1; the mass fraction of the urea aqueous solution is 25 percent, wherein the mass ratio of urea to tantalum oxalate is 1.
Preferably, in S2, the mass ratio of the polyimide porous microspheres to the copper cobaltate pretreatment liquid is 1.
In a second aspect, the invention provides an enameled wire, wherein the enameled wire is obtained by coating the high-frequency-resistant low-temperature-soldering tin H-grade insulating paint prepared in the above way on the surface layer of a conductor wire and drying the insulating paint.
Preferably, the material of the conductor wire is one of copper, aluminum or alloy.
Preferably, the coating method is spin coating on a spin coater.
Preferably, the diameter of the conductor wire is 0.5-1.5mm, and the coating thickness of the high-frequency and low-temperature soldering tin H-grade insulating paint on the conductor wire is 0.08-0.15mm.
Preferably, the drying mode is that the mixture is placed in an oven at 60-80 ℃ for 1-2 hours after being placed at room temperature for 2-4 hours.
The invention has the beneficial effects that:
the insulating paint prepared by the invention belongs to water-based environment-friendly paint, and the main raw materials comprise water-based closed polyurethane resin emulsion, copper cobaltate @ polyimide microspheres, inorganic filler and some auxiliaries. The insulating paint prepared by the invention not only keeps the direct welding property of the polyurethane paint film, but also improves the high temperature resistance and the mechanical strength, so that the insulating paint can keep the insulation grade above the H grade, and simultaneously has better wear resistance and weather resistance.
In the invention, the aqueous closed polyurethane resin emulsion is obtained by reacting polyethylene glycol adipate serving as a synthetic raw material of polyurethane with toluene diisocyanate to generate a prepolymer and then treating the prepolymer with a sealing agent dimethylglyoxime; the copper cobaltate @ polyimide microspheres are prepared by firstly preparing polyimide porous microspheres, and then generating copper cobaltate on the surfaces and in the pore diameters of the polyimide porous microspheres in situ to finally obtain composite microspheres; the inorganic filler is used in a mode of mixing mica powder and light calcium carbonate.
The closed polyurethane resin has good acid and alkali resistance, good waterproof effect and good insulating property, and the adhesive force is improved to a certain extent. And then, the mechanical property of the composite material is further improved by adding the traditional inorganic filler, but the improvement effect is limited, and the mechanical strength and the high temperature resistance of the composite material are still insufficient.
Drawings
The invention is further illustrated by means of the attached drawings, but the embodiments in the drawings do not constitute any limitation to the invention, and for a person skilled in the art, other drawings can be obtained on the basis of the following drawings without inventive effort.
FIG. 1 is a scanning electron micrograph of copper cobaltate @ polyimide microspheres prepared in example 1 of the present invention.
Detailed Description
For the purpose of more clearly illustrating the present invention and more clearly understanding the technical features, objects and advantages of the present invention, the technical solutions of the present invention will now be described in detail below, but are not to be construed as limiting the implementable scope of the present invention.
The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
The invention is further described with reference to the following examples.
Example 1
The high-frequency-resistant low-temperature soldering tin H-grade insulating paint comprises the following components in parts by weight:
73 parts of water-based closed polyurethane resin emulsion, 16 parts of copper cobaltate @ polyimide microspheres, 11 parts of inorganic filler, 1 part of dispersing agent, 0.4 part of defoaming agent, 0.6 part of neutralizing agent, 0.8 part of flatting agent and 4.8 parts of curing agent.
The water-based closed polyurethane resin emulsion is obtained by uniformly mixing closed polyurethane resin, gamma-aminopropyltriethoxysilane and deionized water; wherein the mass ratio of the blocked polyurethane resin, the gamma-aminopropyltriethoxysilane and the deionized water is 1.
The preparation method of the closed polyurethane resin comprises the following steps:
step a, weighing polyethylene glycol adipate and toluene diisocyanate, mixing the weighed polyethylene glycol adipate and the toluene diisocyanate into a container, adding dibutyltin dilaurate, introducing nitrogen as protective gas, heating to 80 ℃, and stirring for reaction for 4 hours to obtain a prepolymer product; wherein the mass ratio of the polyethylene glycol adipate to the toluene diisocyanate is 2.5; the adding amount of dibutyltin dilaurate is 0.2 percent of the mass of the polyethylene glycol adipate;
b, mixing the prepolymer product and a solvent butanone into a reaction container, adding a sealant dimethylglyoxime and a chain extender ethylenediamine while stirring, stirring at room temperature for 0.3h, heating to 80 ℃, and stirring for reaction for 3h to obtain a closed polyurethane resin; wherein the mass ratio of the prepolymer product, the dimethylglyoxime and the butanone is 1.22.
The inorganic filler comprises mica powder and light calcium carbonate; wherein the mass ratio of the mica powder to the light calcium carbonate is 2.5; the dispersant is BYK-110; the defoaming agent is TEGO-902W; the neutralizer is dimethylethanolamine; the leveling agent is BYK307; the curing agent is water-based amine curing agent, and the type is Vast EpIKURE 8536-MY-60.
The particle size of the copper cobaltate @ polyimide microspheres is 10-20 microns; the preparation method of the copper cobaltate @ polyimide microsphere comprises the following steps:
s1, preparing polyimide porous microspheres:
(1) weighing 4,4' -diaminodiphenyl ether, mixing in N, N-dimethylformamide, adding sodium dodecyl benzene sulfonate and liquid paraffin, ultrasonically mixing for 0.5h at room temperature, adding carbon disulfide, and uniformly mixing to obtain a first mixed solution; wherein, the mass ratio of the sodium dodecyl benzene sulfonate, the liquid paraffin, the carbon disulfide, the 4,4' -diaminodiphenyl ether and the N, N-dimethylformamide is 0.5.
(2) Under the protection of nitrogen, dividing pyromellitic dianhydride into 5 parts, adding the 5 parts into the first mixed solution within 1h, wherein the mass ratio of the pyromellitic dianhydride to 4,4' -diaminodiphenyl ether is 1.05, and stirring at room temperature for 12h to obtain a second mixed solution;
(3) adding a mixed solution of acetic anhydride and pyridine into the second mixed solution, wherein the mass ratio of the acetic anhydride to the pyridine to the second mixed solution is 0.7: the first stage is carried out at 160 ℃ for 1h, the second stage is carried out at 220 ℃ for 1h, and the third stage is carried out at 270 ℃ for 3h, so as to obtain the polyimide porous microspheres.
S2, preparing a copper cobaltate pretreatment solution:
weighing cobalt chloride hexahydrate and copper chloride dihydrate, mixing the cobalt chloride hexahydrate and the copper chloride dihydrate into deionized water, firstly dropwise adding an ammonium fluoride aqueous solution after completely dissolving, uniformly stirring, then dropwise adding a urea aqueous solution, and uniformly stirring again to obtain a copper cobaltate pretreatment solution; wherein the mass ratio of cobalt chloride hexahydrate, copper chloride dihydrate to deionized water is 1.41; the mass fraction of the ammonium fluoride aqueous solution is 15%, wherein the mass ratio of ammonium fluoride to cobalt chloride hexahydrate is 1; the mass fraction of the urea aqueous solution is 25%, wherein the mass ratio of urea to tantalum oxalate is 1.
S3, preparing copper cobaltate @ polyimide microspheres:
weighing polyimide porous microspheres, mixing the polyimide porous microspheres in copper cobaltate pretreatment liquid, stirring for 1h at the temperature of 55 ℃, pouring the mixture into a reaction kettle, placing the reaction kettle in an oven, quickly heating to 135 ℃, carrying out heat preservation reaction for 12h, filtering out solids, washing the solids for at least three times by using an ethanol solution with the mass fraction of 50%, carrying out reduced pressure drying, and then placing the product at 245 ℃ for treatment for 2h to obtain copper cobaltate @ polyimide microspheres; wherein the mass ratio of the polyimide porous microspheres to the copper cobaltate pretreatment liquid is 1.
The preparation method of the high-frequency-resistant low-temperature soldering tin H-grade insulating paint comprises the following steps:
sequentially weighing the water-based closed polyurethane resin emulsion, the copper cobaltate @ polyimide microspheres, the inorganic filler and the dispersing agent, mixing and stirring for 1h, then weighing and adding the defoaming agent, the neutralizing agent and the flatting agent, mixing for 0.5h, then adding the weighed curing agent, and mixing for 0.2 h.
In this embodiment, the high-frequency-resistant low-temperature-soldering-tin H-level insulating varnish prepared by the method is coated on the surface layer of an aluminum conductor wire rod with the diameter of 1mm in a rotating manner through a spin coater, the coating thickness is 0.1mm, and then the aluminum conductor wire rod is placed in a 70 ℃ oven for 1H and dried after being placed at room temperature for 3H, so that an enameled wire is obtained.
Example 2
The high-frequency-resistant low-temperature soldering tin H-grade insulating paint comprises the following components in parts by weight:
67 parts of water-based closed polyurethane resin emulsion, 12 parts of copper cobaltate @ polyimide microspheres, 8 parts of inorganic filler, 0.8 part of dispersing agent, 0.3 part of defoaming agent, 0.4 part of neutralizing agent, 0.5 part of flatting agent and 4.2 parts of curing agent.
The water-based closed polyurethane resin emulsion is obtained by uniformly mixing closed polyurethane resin, gamma-methacryloxypropyltrimethoxysilane and deionized water; wherein the mass ratio of the blocked polyurethane resin, the gamma-methacryloxypropyltrimethoxysilane and the deionized water is 1.
The preparation method of the closed polyurethane resin comprises the following steps:
step a, weighing polyethylene glycol adipate and toluene diisocyanate, mixing the weighed polyethylene glycol adipate and the toluene diisocyanate into a container, adding dibutyltin dilaurate, introducing nitrogen as protective gas, heating to 75 ℃, and stirring for reaction for 3 hours to obtain a prepolymer product; wherein the mass ratio of the polyethylene glycol adipate to the toluene diisocyanate is 2.1; the adding amount of dibutyltin dilaurate is 0.1 percent of the mass of the polyethylene glycol adipate;
b, mixing the prepolymer product and a solvent butanone into a reaction container, adding a sealant dimethylglyoxime and a chain extender ethylenediamine while stirring, stirring at room temperature for 0.2h, heating to 75 ℃, and stirring for reaction for 2h to obtain a closed polyurethane resin; wherein the mass ratio of the prepolymer product, the dimethylglyoxime and the butanone is 1.15.
The inorganic filler comprises mica powder and light calcium carbonate; wherein the mass ratio of the mica powder to the light calcium carbonate is 2.2; the dispersant is BYK-108; the defoaming agent is TEGO-901W; the neutralizer is triethylamine; the leveling agent is BYK310; the curing agent is water-based amine curing agent with the type of Vast EpIKURE 8545-W-52.
The particle size of the copper cobaltate @ polyimide microspheres is 10-20 microns; the preparation method of the copper cobaltate @ polyimide microsphere comprises the following steps:
s1, preparing polyimide porous microspheres:
(1) weighing 4,4' -diaminodiphenyl ether, mixing in N, N-dimethylformamide, adding sodium dodecyl benzene sulfonate and liquid paraffin, ultrasonically mixing for 0.5h at room temperature, adding carbon disulfide, and uniformly mixing to obtain a first mixed solution; wherein the mass ratio of the sodium dodecyl benzene sulfonate, the liquid paraffin, the carbon disulfide, the 4,4' -diaminodiphenyl ether to the N, N-dimethylformamide is 0.2.
(2) Under the protection of nitrogen, dividing pyromellitic dianhydride into 5 parts, adding the 5 parts into the first mixed solution within 1 hour, wherein the mass ratio of the pyromellitic dianhydride to 4,4' -diaminodiphenyl ether is 1.02;
(3) adding a mixed solution of acetic anhydride and pyridine into the second mixed solution, wherein the mass ratio of the acetic anhydride to the pyridine to the second mixed solution is 0.5: the first stage is carried out at 150 ℃ for 0.5h, the second stage is carried out at 200 ℃ for 0.5h, and the third stage is carried out at 260 ℃ for 2h, thus obtaining the polyimide porous microspheres.
S2, preparing a copper cobaltate pretreatment solution:
weighing cobalt chloride hexahydrate and copper chloride dihydrate, mixing the cobalt chloride hexahydrate and the copper chloride dihydrate into deionized water, firstly dropwise adding an ammonium fluoride aqueous solution after completely dissolving, uniformly stirring, then dropwise adding a urea aqueous solution, and uniformly stirring again to obtain a copper cobaltate pretreatment solution; wherein the mass ratio of the cobalt chloride hexahydrate to the copper chloride dihydrate to the deionized water is 1.38; the mass fraction of the ammonium fluoride aqueous solution is 15%, wherein the mass ratio of ammonium fluoride to cobalt chloride hexahydrate is 1; the mass fraction of the urea aqueous solution is 25%, wherein the mass ratio of urea to tantalum oxalate is 1.
S3, preparing copper cobaltate @ polyimide microspheres:
weighing polyimide porous microspheres, mixing the polyimide porous microspheres in a copper cobaltate pretreatment solution, stirring for 1h at the temperature of 45 ℃, pouring the mixture into a reaction kettle, placing the reaction kettle in an oven, quickly heating to 125 ℃, carrying out heat preservation reaction for 10h, filtering out solids, washing the solids for at least three times by using an ethanol solution with the mass fraction of 50%, drying the solids under reduced pressure, and then placing the product at 225 ℃ for treatment for 1h to obtain copper cobaltate @ polyimide microspheres; wherein the mass ratio of the polyimide porous microspheres to the copper cobaltate pretreatment liquid is 1.
The preparation method of the high-frequency-resistant low-temperature soldering tin H-grade insulating paint comprises the following steps:
sequentially weighing the water-based closed polyurethane resin emulsion, the copper cobaltate @ polyimide microspheres, the inorganic filler and the dispersing agent, mixing and stirring for 0.5h, then weighing and adding the defoaming agent, the neutralizing agent and the flatting agent, mixing for 0.5h, then adding the weighed curing agent, and mixing for 0.2 h.
In this embodiment, the high-frequency-resistant low-temperature-soldering-tin H-level insulating varnish prepared by the method is coated on the surface layer of an aluminum conductor wire with the diameter of 0.5mm in a rotating manner by a spin coater, the coating thickness is 0.08mm, and then the aluminum conductor wire is placed in an oven at 60 ℃ for 1H and dried after being placed at room temperature for 2H, so as to obtain an enameled wire.
Example 3
The high-frequency-resistant low-temperature soldering tin H-grade insulating paint comprises the following components in parts by weight:
78 parts of water-based closed polyurethane resin emulsion, 20 parts of copper cobaltate @ polyimide microspheres, 14 parts of inorganic filler, 1.2 parts of dispersing agent, 0.6 part of defoaming agent, 0.8 part of neutralizing agent, 1 part of flatting agent and 5.6 parts of curing agent.
The water-based closed polyurethane resin emulsion is obtained by uniformly mixing closed polyurethane resin, gamma-aminopropyltriethoxysilane and deionized water; wherein the mass ratio of the blocked polyurethane resin, the gamma-aminopropyltriethoxysilane and the deionized water is 1.
The preparation method of the closed polyurethane resin comprises the following steps:
step a, weighing polyethylene glycol adipate and toluene diisocyanate, mixing the weighed polyethylene glycol adipate and the toluene diisocyanate into a container, adding dibutyltin dilaurate, introducing nitrogen as protective gas, heating to 85 ℃, and stirring for reaction for 5 hours to obtain a prepolymer product; wherein the mass ratio of the polyethylene glycol adipate to the toluene diisocyanate is 2.8; the adding amount of dibutyltin dilaurate is 0.3 percent of the mass of the polyethylene glycol adipate;
b, mixing the prepolymer product and a solvent butanone into a reaction container, adding a sealant dimethylglyoxime and a chain extender ethylenediamine while stirring, stirring at room temperature for 0.5h, heating to 85 ℃, and stirring for reacting for 4h to obtain a closed polyurethane resin; wherein the mass ratio of the prepolymer product, the dimethylglyoxime and the butanone is 1.24.
The inorganic filler comprises mica powder and light calcium carbonate; wherein the mass ratio of the mica powder to the light calcium carbonate is 2.8; the dispersant is BYK-192; the defoaming agent is TEGO-902W; the neutralizer is ethylenediamine; the leveling agent is BYK307; the curing agent is water-based amine curing agent, and the type is Vast EpIKURE 8536-MY-60.
The particle size of the copper cobaltate @ polyimide microspheres is 10-20 microns; the preparation method of the copper cobaltate @ polyimide microsphere comprises the following steps:
s1, preparing polyimide porous microspheres:
(1) weighing 4,4' -diaminodiphenyl ether, mixing in N, N-dimethylformamide, adding sodium dodecyl benzene sulfonate and liquid paraffin, ultrasonically mixing for 1h at room temperature, adding carbon disulfide, and uniformly mixing to obtain a first mixed solution; wherein the mass ratio of the sodium dodecyl benzene sulfonate, the liquid paraffin, the carbon disulfide, the 4,4' -diaminodiphenyl ether to the N, N-dimethylformamide is 0.8.
(2) Under the protection of nitrogen, dividing pyromellitic dianhydride into 5 parts, adding the 5 parts into the first mixed solution within 1h, wherein the mass ratio of the pyromellitic dianhydride to 4,4' -diaminodiphenyl ether is 1.08, and stirring at room temperature for 15h to obtain a second mixed solution;
(3) adding a mixed solution of acetic anhydride and pyridine into the second mixed solution, wherein the mass ratio of the acetic anhydride to the pyridine to the second mixed solution is 0.8: the first stage is carried out at 180 ℃ for 1h, the second stage is carried out at 240 ℃ for 1h, and the third stage is carried out at 280 ℃ for 4h, so as to obtain the polyimide porous microspheres.
S2, preparing a copper cobaltate pretreatment solution:
weighing cobalt chloride hexahydrate and copper chloride dihydrate, mixing the cobalt chloride hexahydrate and the copper chloride dihydrate into deionized water, firstly dropwise adding an ammonium fluoride aqueous solution after completely dissolving, uniformly stirring, then dropwise adding a urea aqueous solution, and uniformly stirring again to obtain a copper cobaltate pretreatment solution; wherein the mass ratio of the cobalt chloride hexahydrate to the copper chloride dihydrate to the deionized water is 1.45; the mass fraction of the ammonium fluoride aqueous solution is 15%, wherein the mass ratio of ammonium fluoride to cobalt chloride hexahydrate is 1; the mass fraction of the urea aqueous solution is 25%, wherein the mass ratio of urea to tantalum oxalate is 1.
S3, preparing copper cobaltate @ polyimide microspheres:
weighing polyimide porous microspheres, mixing the polyimide porous microspheres in copper cobaltate pretreatment liquid, stirring for 2 hours at the temperature of 65 ℃, pouring the mixture into a reaction kettle, placing the reaction kettle in an oven, quickly heating to 145 ℃, carrying out heat preservation reaction for 15 hours, filtering out solids, washing the solids for at least three times by using an ethanol solution with the mass fraction of 50%, carrying out reduced pressure drying, and then placing the product at 265 ℃ for treatment for 3 hours to obtain copper cobaltate @ polyimide microspheres; wherein the mass ratio of the polyimide porous microspheres to the copper cobaltate pretreatment liquid is 1.
The preparation method of the high-frequency-resistant low-temperature soldering tin H-grade insulating paint comprises the following steps:
sequentially weighing the water-based closed polyurethane resin emulsion, the copper cobaltate @ polyimide microspheres, the inorganic filler and the dispersing agent, mixing and stirring for 1h, then weighing and adding the defoaming agent, the neutralizing agent and the flatting agent, mixing for 0.5h, then adding the weighed curing agent, and mixing for 0.2 h.
In the embodiment, the high-frequency-resistant low-temperature-soldering-tin H-level insulating varnish prepared by the method is coated on the surface layer of an aluminum alloy conductor wire with the diameter of 1.5mm in a rotating manner through a spin coater, the coating thickness is 0.15mm, and then the aluminum alloy conductor wire is placed in an oven at 80 ℃ for 1H and dried to obtain an enameled wire.
Comparative example 1
The high-frequency-resistant low-temperature-solder-resistant H-grade insulating varnish has the same components as those in example 1, except that the copper cobaltate @ polyimide microspheres in example 1 are replaced by polyimide microspheres.
The coating comprises the following components in parts by weight:
73 parts of water-based closed polyurethane resin emulsion, 16 parts of polyimide microspheres, 11 parts of inorganic filler, 1 part of dispersing agent, 0.4 part of defoaming agent, 0.6 part of neutralizing agent, 0.8 part of flatting agent and 4.8 parts of curing agent.
The particle size of the polyimide microsphere is 10-20 μm; the preparation method of the polyimide microsphere comprises the following steps:
(1) weighing 4,4' -diaminodiphenyl ether, mixing in N, N-dimethylformamide, adding sodium dodecyl benzene sulfonate and liquid paraffin, ultrasonically mixing for 0.5h at room temperature, adding carbon disulfide, and uniformly mixing to obtain a first mixed solution; wherein, the mass ratio of the sodium dodecyl benzene sulfonate, the liquid paraffin, the carbon disulfide, the 4,4' -diaminodiphenyl ether and the N, N-dimethylformamide is 0.5.
(2) Under the protection of nitrogen, dividing pyromellitic dianhydride into 5 parts, adding the 5 parts into the first mixed solution within 1h, wherein the mass ratio of the pyromellitic dianhydride to 4,4' -diaminodiphenyl ether is 1.05, and stirring at room temperature for 12h to obtain a second mixed solution;
(3) adding a mixed solution of acetic anhydride and pyridine into the second mixed solution, wherein the mass ratio of the acetic anhydride to the pyridine to the second mixed solution is 0.7: the first stage is carried out at 160 ℃ for 1h, the second stage is carried out at 220 ℃ for 1h, and the third stage is carried out at 270 ℃ for 3h, so as to obtain the polyimide porous microspheres.
Comparative example 2
The high-frequency-resistant low-temperature-solder H-grade insulating paint has the same components as those in example 1, except that the aqueous blocked polyurethane resin emulsion in example 1 is replaced by a polyurethane resin emulsion.
The coating comprises the following components in parts by weight:
73 parts of water-based closed polyurethane resin emulsion, 16 parts of copper cobaltate @ polyimide microspheres, 11 parts of inorganic filler, 1 part of dispersing agent, 0.4 part of defoaming agent, 0.6 part of neutralizing agent, 0.8 part of flatting agent and 4.8 parts of curing agent.
The water-based closed polyurethane resin emulsion is obtained by uniformly mixing polyurethane resin, gamma-aminopropyltriethoxysilane and deionized water; wherein the mass ratio of the polyurethane resin, the gamma-aminopropyltriethoxysilane and the deionized water is 1.
The preparation method of the polyurethane resin comprises the following steps:
step a, weighing polyethylene glycol adipate and toluene diisocyanate, mixing the weighed polyethylene glycol adipate and the toluene diisocyanate into a container, adding dibutyltin dilaurate, introducing nitrogen as protective gas, heating to 80 ℃, and stirring for reaction for 4 hours to obtain a prepolymer product; wherein the mass ratio of the polyethylene glycol adipate to the toluene diisocyanate is 2.5; the adding amount of dibutyltin dilaurate is 0.2 percent of the mass of the polyethylene glycol adipate;
b, mixing the prepolymer product and a solvent butanone into a reaction container, adding chain extender ethylenediamine while stirring, stirring at room temperature for 0.3h, heating to 80 ℃, and stirring for reaction for 3h to obtain polyurethane resin; wherein the mass ratio of the prepolymer product to the butanone is 1.
Comparative example 3
The high-frequency-resistant low-temperature-soldering tin H-grade insulating varnish has the same components as those in example 1, except that the acid copper @ polyimide microspheres in example 1 are replaced by inorganic fillers in equal proportion.
The coating comprises the following components in parts by weight:
73 parts of water-based closed polyurethane resin emulsion, 27 parts of inorganic filler, 1 part of dispersing agent, 0.4 part of defoaming agent, 0.6 part of neutralizing agent, 0.8 part of flatting agent and 4.8 parts of curing agent.
In order to more clearly illustrate the content of the invention, the high-frequency and low-temperature solder H-grade insulating varnish prepared in the example 1 and the comparative examples 1 to 3 of the invention is subjected to drying treatment (in the same way as the example 1) and then is subjected to performance detection and comparison. Wherein the detection standard is that the surface hardness is in accordance with GB/T6739-2006; the adhesive force is in accordance with GB/T1720-2020; the impact resistance is in accordance with GB/T1732-2020; the water resistance is according to GB/T1733-1993; volume resistivity measurements were as SJ/T11294-2003; the wear rate was measured according to GB/T4893.8-1985 (40W, 500g, 500r); the salt spray resistance detection is in accordance with GB/T1771-2007; acid corrosion resistance detection is to soak the film in 0.1mol/L sulfuric acid for 7d, and then to take out and observe the condition of the paint film; the alkali-resistant corrosion detection is to soak the film in 0.1mol/L sodium hydroxide for 7d, and then to take out the film to observe the condition of the paint film; the results are shown in table 1 below:
TABLE 1 comparison of the Properties of different insulating lacquers
Figure BDA0003657002880000111
As can be seen from Table 1, the insulating paint prepared in example 1 of the present invention has better mechanical properties, wear resistance, high temperature resistance, water resistance and corrosion resistance.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (8)

1. The high-frequency-resistant low-temperature soldering tin H-grade insulating paint is characterized by comprising the following components in parts by weight:
67-78 parts of water-based closed polyurethane resin emulsion, 12-20 parts of copper cobaltate @ polyimide microspheres, 8-14 parts of inorganic filler, 0.8-1.2 parts of dispersant, 0.3-0.6 part of defoaming agent, 0.4-0.8 part of neutralizer, 0.5-1 part of flatting agent and 4.2-5.6 parts of curing agent;
the preparation method of the closed polyurethane resin comprises the following steps:
step a, weighing polyethylene glycol adipate and toluene diisocyanate, mixing the weighed polyethylene glycol adipate and the toluene diisocyanate into a container, adding a catalyst dibutyltin dilaurate, introducing nitrogen as a protective gas, heating to 75-85 ℃, and stirring for reaction for 3-5 hours to obtain a prepolymer product;
b, mixing the prepolymer product and a solvent butanone into a reaction container, adding a sealant dimethylglyoxime and a chain extender ethylenediamine while stirring, stirring at room temperature for 0.2-0.5h, heating to 75-85 ℃, and stirring for reaction for 2-4h to obtain a sealed polyurethane resin;
the preparation method of the copper cobaltate @ polyimide microsphere comprises the following steps:
s1, preparing polyimide porous microspheres:
(1) weighing 4,4' -diaminodiphenyl ether, mixing in N, N-dimethylformamide, adding sodium dodecyl benzene sulfonate and liquid paraffin, ultrasonically mixing for 0.5-1h at room temperature, adding carbon disulfide, and uniformly mixing to obtain a first mixed solution;
(2) under the protection of nitrogen, weighing pyromellitic dianhydride, dividing into multiple parts, adding into the first mixed solution, and stirring at room temperature for 10-15h to obtain a second mixed solution;
(3) adding the mixed solution of acetic anhydride and pyridine into the second mixed solution, uniformly mixing, and sequentially carrying out chemical imidization treatment and thermal imidization treatment to obtain polyimide porous microspheres;
s2, preparing a copper cobaltate pretreatment solution:
weighing cobalt chloride hexahydrate and copper chloride dihydrate, mixing the cobalt chloride hexahydrate and the copper chloride dihydrate into deionized water, firstly dropwise adding an ammonium fluoride aqueous solution after completely dissolving, uniformly stirring, then dropwise adding a urea aqueous solution, and uniformly stirring again to obtain a copper cobaltate pretreatment solution;
s3, preparing copper cobaltate @ polyimide microspheres:
weighing polyimide porous microspheres, mixing the polyimide porous microspheres with copper cobaltate pretreatment liquid, stirring for 1-2 hours at the temperature of 45-65 ℃, pouring the mixture into a reaction kettle, placing the reaction kettle in an oven, rapidly heating to 125-145 ℃, keeping the temperature for reaction for 10-15 hours, filtering out solids, washing the solids with an ethanol solution with the mass fraction of 50% for at least three times, drying under reduced pressure, and then placing the product at the temperature of 225-265 ℃ for treatment for 1-3 hours to obtain copper cobaltate @ polyimide microspheres.
2. The high-frequency-resistant low-temperature-solder H-grade insulating paint as claimed in claim 1, wherein the water-based blocked polyurethane resin emulsion is obtained by uniformly mixing blocked polyurethane resin, a surfactant and deionized water; wherein the mass ratio of the blocked polyurethane resin to the surfactant to the deionized water is 1.2-0.4.
3. The high frequency and low temperature solder H-level insulating varnish according to claim 2, wherein the surfactant is γ -aminopropyltriethoxysilane or γ -methacryloxypropyltrimethoxysilane.
4. The high frequency and low temperature soldering tin H-grade insulating paint as claimed in claim 1, wherein the inorganic filler comprises mica powder and light calcium carbonate; wherein the mass ratio of the mica powder to the light calcium carbonate is 2.2-2.8.
5. The high-frequency-resistant low-temperature soldering tin H-grade insulating paint as claimed in claim 1, wherein the dispersant is one of BYK-110, BYK-108 and BYK-192; the defoaming agent is TEGO-902W or TEGO-901W; the neutralizing agent is one of dimethylethanolamine, triethylamine and ethylenediamine; the leveling agent is BYK307 or BYK310.
6. The high frequency and low temperature soldering tin H-grade insulating paint as claimed in claim 1, wherein the curing agent is water amine curing agent of type Vansen EPIKURE 8536-MY-60 or Vansen EPIKURE 8545-W-52.
7. An enameled wire, wherein the enameled wire is obtained by coating the high-frequency and low-temperature soldering resistant H-grade insulating varnish according to any one of claims 1 to 6 on the surface layer of a conductor wire and drying the enamel.
8. The enameled wire according to claim 7, wherein the drying is performed by placing the enameled wire in an oven at 60-80 ℃ for 1-2 hours after 2-4 hours at room temperature.
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