CN113174050B - Elastic epoxy resin and application thereof - Google Patents
Elastic epoxy resin and application thereof Download PDFInfo
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- CN113174050B CN113174050B CN202110500481.2A CN202110500481A CN113174050B CN 113174050 B CN113174050 B CN 113174050B CN 202110500481 A CN202110500481 A CN 202110500481A CN 113174050 B CN113174050 B CN 113174050B
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Abstract
The invention discloses an elastic epoxy resin, which is prepared by the following steps: mixing adipic acid, hexachloroendomethylene phthalic anhydride, propylene glycol and dibromoneopentyl glycol for reaction to obtain a hydroxyl-terminated flame-retardant elastic polyester prepolymer; and reacting the hydroxyl-terminated flame-retardant elastic polyester prepolymer with bisphenol A epoxy resin under the action of a catalyst to obtain the elastic epoxy resin. The resin provided by the invention has a plurality of active groups, so that the adhesion force of the prepared coating on amorphous alloy, silicon steel and mould pressing composite materials (slot wedges) can reach more than 10MPa, and the adhesion force on the surface of the fluorine silicon pouring sealant can also reach 5 MPa. The oxygen index of the water-based flame-retardant surface insulating paint provided by the invention is more than or equal to 40, and the water-based flame-retardant surface insulating paint has good wear resistance.
Description
Technical Field
The invention relates to an elastic epoxy resin and a preparation method thereof, and also relates to a water-based insulating paint prepared from the elastic epoxy resin.
Background
The iron core is the core equipment in electrical components such as motor, mutual-inductor, pump and air condition compressor, and its operating condition and life directly relate to the state and the life-span of electrical component. The iron core is mostly made of silicon steel or iron-based amorphous alloy, the surface property of the material is active, the iron core is used in a severe environment, and the surface is easy to generate defects such as corrosion and the like. The indexes of the iron loss, the magnetic conductivity, the coercive force and the like of the whole iron core are influenced, and the working efficiency of the electric part is reduced. Which can lead to failure of the electrical components in severe cases. The iron core is high in temperature in the operation process, and after the insulating material is aged, flashover discharge can be generated to cause fire. The core surface flame retardancy is therefore also an important property.
The application environment of motors in special industries such as wind power motors, coal mine motors and the like is severe, and the surfaces of iron cores are often subjected to impact friction of crushed sand, coal ash and the like, so that an insulating paint film is abraded and fails in advance. Therefore, the wear resistance of the surface insulating varnish is also an important index.
The surface insulating paint is an indispensable material in the electrical industry of motors, a large amount of solvent paint is used at present, and the organic solvent-rich surface insulating paint has high VOC content and serious environmental pollution, and is easy to cause safety accidents due to improper disposal. Therefore, how to reduce VOC and develop an environment-friendly high-performance water-based surface insulating paint become a hotspot and a focus in the field.
At present, most of the surface insulating paints used in the electrical industry of motors are high-molecular epoxy modified polyurethane or fluorocarbon modified polyurethane series, and the defects of the surface insulating paints are low solid content, low one-time film forming thickness, poor adhesion to special surfaces such as slot wedges, fluorine-silicon pouring sealant and the like, poor flame retardance of paint films and the like.
CN 101486870B discloses a solvent-free epoxy surface insulating paint which has good mechanical properties and electrical properties. However, the paint liquid has high viscosity, so that the paint liquid cannot be used in conventional construction methods such as air spraying and the like, and is difficult to use on large-scale electric parts.
Disclosure of Invention
One object of the present invention is to provide an elastic epoxy resin.
In order to solve the technical problems, the technical scheme of the invention is as follows:
an elastic epoxy resin, which is prepared by the following steps: mixing adipic acid, hexachloroendomethylene phthalic anhydride, propylene glycol and dibromoneopentyl glycol for reaction to obtain a hydroxyl-terminated flame-retardant elastic polyester prepolymer; and reacting the hydroxyl-terminated flame-retardant elastic polyester prepolymer with bisphenol A epoxy resin under the action of a catalyst to obtain the elastic epoxy resin.
Preferably, the raw materials of the elastic epoxy resin comprise: 90-150 parts of adipic acid, 80-120 parts of hexachloroendomethylene phthalic anhydride, 60-130 parts of propylene glycol, 100 parts of dibromoneopentyl glycol, 160 parts of bisphenol A epoxy resin and 2-5 parts of a catalyst.
Preferably, the preparation method of the elastic epoxy resin comprises the following steps: putting adipic acid, hexachloro-endomethylene phthalic anhydride and propylene glycol into a reaction kettle according to a formula; stirring is started, the temperature is raised to 190 ℃ and 220 ℃, and the reaction is carried out until the acid value is less than or equal to 100 mgKOH/g; adding dibromoneopentyl glycol, heating to 190-220 ℃, reacting until the acid value is less than or equal to 20mgKOH/g, and preparing a hydroxyl-terminated flame-retardant elastic polyester prepolymer; adding bisphenol A epoxy resin and a catalyst according to the formula, heating to 120 ℃ for reaction until the epoxy equivalent is 190-220g/mol, and obtaining the elastic epoxy resin.
Preferably, the bisphenol A epoxy resin is a solid bisphenol A epoxy resin with an epoxy equivalent of 450-550 g/mol.
The bisphenol A epoxy resin in the epoxy equivalent range has moderate reactivity and crosslinking degree. Too large or too small is not suitable for the present invention.
Preferably, the catalyst is boron trifluoride dimethyl ether complex, tertiary amine or triphenyl phosphate.
Further preferably, the catalyst is boron trifluoride dimethyl ether complex.
The chroma of the reaction product of the tertiary amine catalyst is darker. The triphenyl phosphate has low activity, and the temperature needs to be raised to more than 200 ℃, so that the polyester is easily degraded. The boron trifluoride ether catalyst has the advantages of low-temperature catalysis (about 100 ℃) and light color of reactants.
In the present invention, the degree of reaction is controlled by the reaction conditions. And under a proper reaction degree, the grafting degree of the elastic polyester prepolymer and the epoxy resin can be ensured to reach more than 60%, and the epoxy group is kept to react with the amine curing agent.
The elastic epoxy resin is obtained by carrying out internal toughening modification on bisphenol A resin by using flame-retardant elastic polyester. Flame retardant elastomeric segments are incorporated into epoxy resin systems. The cured product has good flame retardance and toughness. Meanwhile, due to hydroxyl and ether bonds generated in the preparation process, the resin has excellent adhesive force and toughness.
The preparation method mainly comprises three reactions, wherein one reaction is an esterification reaction of an acid monomer and an anhydride monomer with an alcohol monomer to obtain a flame-retardant elastic polyester prepolymer, and the second reaction is an electrophilic reaction of hydroxyl in the flame-retardant elastic polyester prepolymer and epoxy group in epoxy resin under the action of a catalyst to form new hydroxyl and ether bond. And the third is that the epoxy group generates self-ring-opening reaction under the action of a catalyst to form a homopolymer.
An elastic epoxy emulsion is prepared by dripping a mixture of an emulsifier and deionized water into the elastic epoxy resin under high-speed stirring.
Preferably, 550.1 parts of elastic epoxy resin is added into a reaction kettle, high-speed stirring is started, 13.2 parts of mixed solution of an emulsifier and deionized water is dropwise added, and the dropwise addition is completed within 2 hours; continuously stirring for 0.5-1 h to ensure that emulsification is completed; 425.9 parts of deionized water is added, the mixture is continuously stirred for 0.5 hour, and the discharged material is filtered to obtain the waterborne flame-retardant elastic epoxy emulsion; wherein the mixed solution of the emulsifier and the deionized water is the mixed solution of the emulsifier and the deionized water with the mass ratio of 1: 1.
An aqueous insulating paint comprises a component A and a component B; wherein the component A comprises the elastic epoxy emulsion, pigment and filler, silicon carbide dispersion liquid, flame retardant and auxiliary agent, and the component B comprises modified fatty amine, flash rust inhibitor and solvent; wherein the mass ratio of the component A to the component B is 50-80: 20-50.
Preferably, the component A comprises 35-55 parts of the elastic epoxy emulsion, 15-25 parts of pigment and filler, 5-16 parts of silicon carbide dispersion liquid, 19-33 parts of flame retardant and 1.1-3.8 parts of auxiliary agent.
Preferably, the component B comprises 60-80 parts of modified fatty amine, 1-8 parts of flash rust inhibitor and 10-40 parts of solvent.
Preferably, the pigment and filler comprises one or more of iron oxide red, carbon black, sericite and rutile type titanium dioxide.
Preferably, the flame retardant comprises one or more of zinc phosphate, nano aluminum hydroxide and antimony trioxide.
The flame retardant principle of zinc phosphate and nano aluminum hydroxide is that crystal water is lost after being heated, the process is a strong heat absorption reaction, a large amount of heat is absorbed, the effect of cooling a polymer can be achieved, meanwhile, water vapor generated by the reaction can dilute combustible gas, and the spread of combustion is inhibited.
The flame retardant principle of antimony trioxide is that a glassy covering layer is formed after heating to prevent heat transfer, and meanwhile, the antimony trioxide is used as a synergistic flame retardant to generate a carbon layer and inert gas by matching with halogen flame retardant components of chlorine and bromine in flame retardant resin, so that heat insulation and oxygen and free radicals reduction are achieved, and the flame retardant effect is achieved.
Preferably, the solvent is one or more of ethylene glycol monobutyl ether, diethylene glycol butyl ether, dipropylene glycol methyl ether and dipropylene glycol butyl ether.
Preferably, the silicon carbide dispersion liquid comprises 50-70 parts of silicon carbide micro powder, 5-15 parts of silica sol, 1-2 parts of rheological agent, 5-10 parts of wetting agent and 10-30 parts of water.
More preferably, the silicon carbide dispersion liquid comprises 65 parts of silicon carbide micro powder, 10 parts of silica sol, 1.5 parts of rheological agent, 6.5 parts of wetting agent and 17 parts of water.
Preferably, the silicon carbide dispersion has a particle size distribution (D50) of 0.5 μm to 0.8 μm; the solid content is 64 to 66 percent.
Preferably, the preparation method of the silicon carbide dispersion liquid comprises the following steps: adding water into a container according to the formula amount, starting stirring, slowly adding a wetting agent and a rheological agent, and dispersing at a high speed (2500 rpm-3000 rpm) for 30min-40min to form slurry; uniformly adding silicon carbide micro powder, and stirring for 30-40 min until no obvious particles exist; dropwise adding silica sol, stirring uniformly, and grinding for 3-4 h by a ball mill to obtain the silicon carbide dispersion.
Preferably, the silicon carbide fine powder is fine powder with a particle size (D50) of 0.5-0.8 μm; the silicon carbide micro powder with larger particle size has low surface activity and is difficult to modify.
And the inventor proves through a large amount of experiments that the degree of dispersion is greatly influenced when the particle size is too large or too small. Insufficient dispersion has great influence on the performance of the later paint film.
Preferably, the silica sol is alkaline silica sol with pH value of 9-11 and particle size of 5.5-6.5 nm; at a pH of 11 or less, the higher the pH of the system, the stronger the bonding between the surface hydroxyl groups of the silica sol and the silanol bonds on the surface of the fine silicon carbide powder.
Preferably, the rheological agent is one or more of sodium bentonite, attapulgite and hydroxyethyl cellulose.
Preferably, the wetting agent is one or more of sodium polyacrylate, polyvinyl alcohol, polyethylene glycol and cetyl pyridine bromide.
Preferably, the modified fatty amine is a modified fatty amine curing agent obtained by addition reaction of ethylene oxide and triethylene tetramine. This type of fatty amine curing agent can provide a moderate degree of crosslinking and media resistance.
Preferably, the preparation method of the water-based insulating paint comprises the following steps:
preparation of component A: dispersing and grinding the pigment, the filler and the auxiliary agent according to the weight ratio; then adding the elastic epoxy emulsion, the silicon carbide dispersion liquid and the auxiliary agent, stirring and filtering to obtain a component A;
preparation of the component B: mixing the modified alicyclic amine, the flash rust inhibitor and the solvent according to the weight ratio, heating and stirring, cooling and filtering to obtain a component B;
and stirring and mixing the component A and the component B to obtain the water-based flame-retardant surface insulating paint.
The invention is further explained below:
the self-made waterborne flame-retardant elastic epoxy emulsion is used as a main film forming material and matched with a modified fatty amine curing agent, and active groups in the emulsion fully react with the curing agent to provide the adhesive force of a coating film; bromine and phosphorus flame retardant monomers in the emulsion provide flame retardancy to the coating; the elastomeric polyester component of the emulsion provides abrasion resistance to the coating film;
iron oxide red, carbon black and rutile type titanium dioxide are colorants (pigments) to provide hiding power and color of the coating film; meanwhile, the pigments of the several types are all incombustible. And the flame retardance of the system is guaranteed.
The nanometer aluminum hydroxide and the antimony trioxide are used as flame retardants to provide flame retardance of the coating film.
Sericite and zinc phosphate are used as antirust pigments, the sheet structure of sericite can provide a physical shielding effect, the time for corrosive media to enter a substrate through a coating is prolonged, and the corrosion inhibition effect of zinc phosphate is combined to provide the anticorrosion performance of the coating;
the silicon carbide powder in the silicon carbide dispersion liquid has extremely high hardness (Mohs hardness of 9.5), the hardness of a coating film can be improved, the powder is non-combustible, a large number of hydroxyl groups exist on the surface of the powder, and the hydroxyl groups are fully reacted with the elastic epoxy emulsion and the amine curing agent component to provide the wear resistance, the flame retardance and the enhanced adhesive force of the coating film.
The thickening rheological additive forms a network structure by associating the micelle and emulsion particles, so that the viscosity of the system is increased, the mobility of water molecules is reduced by the micelle, and the viscosity of the water phase is increased. Viscosity matching and proper viscosity recovery under three states of low shear rate, medium shear rate and high shear rate can be formed, and good storage stability and workability are obtained;
the dispersing agent is adsorbed on the surface of the pigment and filler through hydroxyl, ether bond and other groups, so that good steric hindrance and same charge repulsion can be formed among various pigments and fillers, and meanwhile, the water-soluble chain segment of the dispersing agent has good compatibility with the emulsion. Thereby obtaining a stable suspension system;
isothiazolinone fungicides are bactericidal by breaking the bonds between bacterial and algal proteins. Isothiazolinone can rapidly and irreversibly inhibit the growth of microorganisms after contacting with them, thereby causing the death of microbial cells. Thereby providing long-acting mildew-proof effect for the coating and the film and improving the three-proofing performance (corrosion resistance, moisture resistance and mildew resistance) of the film.
In conclusion, the components interact with each other to provide excellent performance for the water-based flame-retardant surface insulating paint.
The invention has the beneficial effects that:
(1) and good adhesive force: the formula of the waterborne flame-retardant surface insulating paint provided by the invention adopts the elastic polyester modified epoxy resin which has more active groups, so that the adhesion force of the prepared coating on amorphous alloy, silicon steel and mould pressing composite materials (slot wedges) can reach more than 10MPa, and the adhesion force on the surface of the fluorine silicon pouring sealant can also reach 5 MPa.
(2) Good flame retardancy: the water-based flame-retardant surface insulating paint provided by the invention adopts bromine and chlorine composite elastic flame-retardant resin and flame retardants such as antimony trioxide, nano-alumina and silicon carbide dispersion liquid to match, so that the oxygen index of a coating film is more than or equal to 40.
(3) Good wear resistance: the water-based flame-retardant surface insulating paint provided by the invention adopts silica sol modified silicon carbide dispersion liquid and is matched with elastic polyester modified epoxy resin, so that a paint film has soft and medium hard effects, and good wear resistance (the wear is less than or equal to 15mg) is achieved.
Drawings
FIG. 1 is an electron micrograph of a silicon carbide dispersion according to the present invention;
FIG. 2 is an infrared spectrum of an aqueous elastomeric epoxy emulsion.
Detailed Description
Example 1
Preparation of elastic epoxy emulsion
The formulation is shown in table 1:
TABLE 1 flame retardant elastomeric epoxy emulsion raw materials
The preparation process comprises the following steps:
putting adipic acid, hexachloro-endomethylene phthalic anhydride and propylene glycol into a reaction kettle according to a formula, starting stirring, heating to 190-220 ℃, reacting for 3-4 h until the acid value is less than or equal to 100mgKOH/g, cooling to 140-160 ℃, putting dibromoneopentyl glycol, heating to 190-220 ℃, and reacting for 4-6 h until the acid value is less than or equal to 20 mgKOH/g. Starting a vacuum pump, vacuumizing to-0.8 MPa, and maintaining the pressure for 0.5-1 h. The vacuum pump is stopped. Quickly cooling to below 140 deg.C and discharging. Obtaining the flame-retardant elastic polyester prepolymer.
Adding CYD-011 epoxy resin and the flame-retardant elastic polyester prepolymer into a reaction kettle according to a formula, heating to 100-fold organic solvent at 120 ℃, starting stirring after the resin is melted, adding boron trifluoride dimethyl ether catalyst, reacting for 1h-2h, measuring the epoxy equivalent to 190-fold organic solvent at 220g/mol, cooling to 60-70 ℃, dropwise adding an emulsifying agent dispersion liquid according to the formula amount, and finishing dropwise adding within 2 h. Stirring is continued for 0.5h-1h to ensure that the emulsification is finished. Adding the rest deionized water into the formula, stirring for 0.5h, detecting viscosity, solid content and fineness, filtering with 200-mesh silk cloth, and discharging.
The infrared spectrum (FT-IR) of the waterborne flame-retardant elastic epoxy emulsion is shown in figure 2.
As can be seen from FIG. 2, the position 1509cm-1 is the characteristic absorption peak of para-substitution of benzene ring in the structure of epoxy bisphenol A; the absorption peak at 1247cm-1 is the stretching vibration absorption peak of aromatic aliphatic ether (Ar-O-R); the absorption peak at 828cm-1 is the absorption peak of para-substitution of benzene ring; the absorption peak at 2929cm-1 is the absorption peak of carboxyl (-COOH); the absorption peak at 1106cm-1 is the absorption peak of an ester group (-C-O-C); the spectrum shows that the epoxy resin has the characteristic peak of the epoxy resin and the characteristic peak of the polyester resin, and the epoxy resin can be identified as the elastic polyester modified epoxy resin.
The performance indexes of the waterborne flame-retardant elastic epoxy emulsion are shown in the table
TABLE 2 aqueous flame retardant elastomeric epoxy emulsion Property Table
Example 2
The water-base fire-retardant surface insulating paint is prepared with A, B components; the component A is a mixture of a self-made water-based flame-retardant elastic epoxy emulsion of a formula 1, Langshan 4110 iron oxide red, Kbabai ZPA zinc phosphate, nano aluminum hydroxide, a self-made silicon carbide dispersion liquid, Grignard GA-5 mica powder, antimony trioxide, a Tego-755W dispersant, a Hamming 105A thickening rheological agent, a methylisothiazolinone mildew preventive and deionized water, wherein the weight ratio of each substance is respectively 40%, 8%, 4%, 15%, 8%, 10%, 0.9%, 0.6%, 0.8% and 12%; the component B is a mixture of Hansen EPIKURE6870-W-53 modified alicyclic amine, heroin X-150 antiscratch agent, ethylene glycol monobutyl ether and dipropylene glycol methyl ether, and the weight ratio of each substance is 80%, 2%, 10% and 5% respectively. The weight ratio of the two components is 80% and 20%.
The preparation method of the self-prepared silicon carbide dispersion liquid comprises the following steps: adding water into a container according to the formula amount of 65 parts of silicon carbide micro powder, 10 parts of silica sol, 1.5 parts of rheological agent, 6.5 parts of wetting agent and 17 parts of water, starting stirring, slowly adding the wetting agent and the rheological agent, and dispersing at a high speed (2500 rpm-3000 rpm) for 30-40 min to form slurry; uniformly adding silicon carbide micro powder, and stirring for 30-40 min until no obvious particles exist; dropwise adding silica sol, stirring uniformly, and grinding for 3-4 h by a ball mill to obtain the silicon carbide dispersion. The particle size distribution (D50) of the fine silicon carbide powder was 0.5. mu.m. The particle size distribution (D50) of the prepared silicon carbide dispersion liquid is 0.5-0.6 μm; the solid content is 64 percent.
The dispersion of the self-prepared silicon carbide dispersion liquid is controlled by parameters, and the performance of a paint film is adversely affected by insufficient dispersion degree or excessively small particle size.
Preparing a component A, namely putting deionized water, a dispersing agent, iron oxide red, zinc phosphate, nano aluminum hydroxide, sericite and antimony trioxide in a weight ratio into a reaction kettle, stirring at the stirring speed of 500 revolutions per minute at the temperature of 40 ℃ for 1 hour; putting the dispersed materials into a horizontal sand mill to be ground until the fineness is less than or equal to 20 mu m; and then adding the self-made aqueous flame-retardant elastic epoxy emulsion, the silicon carbide dispersion liquid, the thickening rheological agent and the mildew preventive into a reaction kettle according to the weight ratio, stirring at the stirring speed of 500 revolutions per minute and at the temperature of 40 ℃ for 1 hour, cooling and filtering to obtain the component A.
Preparation of the component B: adding EPIKURE6870-W-53 modified alicyclic amine, X-150 anti-flash rust agent, ethylene glycol monobutyl ether and dipropylene glycol methyl ether into a reaction kettle according to the weight ratio, stirring, heating to 40 ℃, stirring for 0.5h, cooling and filtering to obtain a component B.
And stirring and mixing the component A and the component B to obtain the water-based flame-retardant surface insulating paint.
The detection results of the water-based flame-retardant surface insulating paint in the using process are shown in the following table:
table 3 test results of the surface insulating paint of example 2
Example 3:
1. preparation of aqueous flame-retardant elastic epoxy emulsion: same as in example 1.
2. The water-based flame-retardant surface insulating paint is prepared by blending A, B components, wherein the weight ratio of A, B to A, B is 50: 50; the component A is a mixture of self-made water-based flame-retardant elastic epoxy emulsion of a formula 2, Dupont R706 rutile type titanium dioxide, Eupatorium fortunei U carbon black, Kbai ZPO zinc phosphate, nano aluminum hydroxide, silicon carbide dispersion liquid, Grignard GA-5 mica powder, antimony trioxide, Zhanxin 6208 dispersant, Haiming 105A thickening rheological agent, methylisothiazolinone mildew preventive and deionized water, wherein the weight ratio of each substance is 35%, 14.26%, 0.04%, 5%, 10%, 8%, 10%, 1.2%, 0.5% and 10%; the component B is a mixture of Dutch QR chemical QR-RIT1071 modified fatty amine, FA179 anti-flash rust agent, diethylene glycol butyl ether and dipropylene glycol butyl ether, and the weight ratio of each substance is 85%, 2%, 5% and 8% respectively. The weight ratio of the two components is 50% and 50%.
The preparation of the self-prepared silicon carbide dispersion was as in example 2.
Preparing a component A, namely putting deionized water, a dispersing agent, rutile titanium dioxide, carbon black, zinc phosphate, nano aluminum hydroxide and sericite into a reaction kettle according to the weight ratio, stirring at the stirring speed of 130 r/min at the temperature of 40 ℃ for 1 h; putting the dispersed material into a horizontal sand mill to be ground until the fineness is less than or equal to 20 mu m; and then adding the self-made aqueous flame-retardant elastic epoxy emulsion, the silicon carbide dispersion liquid, the thickening rheological agent and the mildew preventive into a reaction kettle according to the weight ratio, stirring at the stirring speed of 130 revolutions per minute and at the temperature of 40 ℃ for 1 hour, cooling and filtering to obtain the component A.
Preparation of the component B: adding QR-RIT1071 modified fatty amine, FA179 anti-flash rust agent, diethylene glycol butyl ether and dipropylene glycol butyl ether into a reaction kettle according to the weight ratio, stirring, heating to 40 ℃, stirring for 0.5h, cooling and filtering to obtain the component B.
And stirring and mixing the component A and the component B to obtain the water-based flame-retardant surface insulating paint.
The detection results of the water-based flame-retardant surface insulating paint for the iron core in the using process are shown in the following table:
table 4 test results of the surface insulating varnish of example 3
Comparative example 1:
the water-based flame-retardant surface insulating paint is prepared by mixing A, B components, wherein the weight ratio of A, B to 3550; the component A is a mixture of Zhanxin EP384/53WAMP epoxy emulsion (with an epoxy equivalent of 920g/mol-1040g/mol), Dupont R706 rutile type titanium dioxide, Eupatorium U carbon black, Kbabai ZPO zinc phosphate, nano aluminum hydroxide, silicon carbide dispersion, Grignard GA-5 mica powder, antimony trioxide, Zhanxin 6208 dispersant, Hamming 105A thickening rheological agent, methylisothiazolinone mildew preventive and deionized water, wherein the weight ratio of the components is 45%, 14.26%, 0.04%, 5%, 10%, 8%, 10%, 1.2%, 0.5% and 10% respectively; the component B is a mixture of Dutch QR chemical QR-RIT1071 modified fatty amine, FA179 anti-flash rust agent, diethylene glycol butyl ether and dipropylene glycol butyl ether, and the weight ratio of each substance is 85%, 2%, 5% and 8% respectively. The weight ratio of the two components is 50% and 50%.
The silicon carbide dispersion was prepared as in example 2.
Preparing a component A, namely putting deionized water, a dispersing agent, rutile titanium dioxide, carbon black, zinc phosphate, nano aluminum hydroxide and sericite into a reaction kettle according to the weight ratio, stirring at the stirring speed of 130 r/min at the temperature of 40 ℃ for 1 h; putting the dispersed material into a horizontal sand mill to be ground until the fineness is less than or equal to 20 mu m; and then adding the EP384/53WAMP epoxy emulsion, the silicon carbide dispersion liquid, the thickening rheological agent and the mildew preventive into a reaction kettle according to the weight ratio, stirring at the stirring speed of 130 revolutions per minute at the temperature of 40 ℃ for 1 hour, cooling and filtering to obtain the component A.
Preparation of the component B: adding QR-RIT1071 modified fatty amine, FA179 anti-flash rust agent, diethylene glycol butyl ether and dipropylene glycol butyl ether into a reaction kettle according to the weight ratio, stirring, heating to 40 ℃, stirring for 0.5h, cooling and filtering to obtain the component B.
And stirring and mixing the component A and the component B to obtain the water-based flame-retardant surface insulating paint.
The detection results of the water-based flame-retardant surface insulating paint for the iron core in the using process are shown in the following table:
TABLE 5 test results of the surface insulating paint of comparative example 1
The difference between comparative example 1 and examples 2-3 is mainly the difference in epoxy emulsions, which results in a clear difference in properties, due to the following reasons:
(1) the commonly used EP384 epoxy emulsion in the market is emulsion formed by emulsifying E-20 solid epoxy resin. The structure has no flexible chain segment, and the toughness of the paint film is poor. Under the friction of the grinding wheel, the energy absorption effect of the paint film is poor. The abrasion resistance value of comparative example 1 was made significantly higher than that of each example (the larger the abrasion resistance value, the worse the abrasion resistance).
(2) The hydroxyl and ether bonds in the structure of the EP384 epoxy emulsion are less than those of the self-made waterborne elastic epoxy emulsion. After neutral salt spray corrosion, the adhesion of the paint film is greatly reduced, so that the neutral salt spray performance of the prepared comparative example 1 is poorer than that of each example.
Comparative example 2:
1. preparation of aqueous flame-retardant elastic epoxy emulsion: same as in example 1.
2. The water-based flame-retardant surface insulating paint is prepared by blending A, B components, wherein the weight ratio of A, B to A, B is 50: 50; the component A is a mixture of self-made water-based flame-retardant elastic epoxy emulsion, Dupont R706 rutile type titanium dioxide, Eupatorium fortunei U carbon black, zinc Kbebaizpo phosphate, nano aluminum hydroxide, 1250-mesh talcum powder, Grignard GA-5 mica powder, antimony trioxide, Zhanxin 6208 dispersant, Hamming 105A thickening rheological agent, methylisothiazolinone mildew preventive and deionized water, wherein the weight ratio of each substance is 35%, 14.26%, 0.04%, 5%, 10%, 8%, 10%, 1.2%, 0.5% and 10% respectively; the component B is a mixture of Dutch QR chemical QR-RIT1071 modified fatty amine, FA179 anti-flash rust agent, diethylene glycol butyl ether and dipropylene glycol butyl ether, and the weight ratio of each substance is 85%, 2%, 5% and 8% respectively. The weight ratio of the two components is 50% and 50%.
Preparing a component A, namely putting deionized water, a dispersing agent, rutile titanium dioxide, carbon black, zinc phosphate, nano aluminum hydroxide, 1250-mesh talcum powder and sericite into a reaction kettle according to the weight ratio, stirring at the stirring speed of 130 r/min at the temperature of 40 ℃ for 1 h; putting the dispersed material into a horizontal sand mill to be ground until the fineness is less than or equal to 20 mu m; and then adding the self-made waterborne flame-retardant elastic epoxy emulsion, the thickening rheological agent and the mildew preventive into a reaction kettle according to the weight ratio, stirring at the stirring speed of 130 r/min at the temperature of 40 ℃ for 1h, cooling and filtering to obtain the component A.
Preparation of the component B: adding QR-RIT1071 modified fatty amine, FA179 anti-flash rust agent, diethylene glycol butyl ether and dipropylene glycol butyl ether into a reaction kettle according to the weight ratio, stirring, heating to 40 ℃, stirring for 0.5h, cooling and filtering to obtain the component B.
And stirring and mixing the component A and the component B to obtain the water-based flame-retardant surface insulating paint.
The detection results of the water-based flame-retardant surface insulating paint for the iron core in the using process are shown in the following table:
TABLE 6 test results of the surface insulating paint of comparative example 2
The difference between the comparative example 2 and the examples 2-3 is that the common talcum powder is added instead of the self-made silicon carbide dispersion liquid, so that the performance difference is obvious, and the specific reason is as follows:
(1) the Mohs hardness of silicon carbide is 9.5, and that of talc is 1.5. The talcum powder is used for replacing silicon carbide, so that the hardness of a paint film is obviously reduced (the pencil hardness is reduced from 3H to HB). The paint film cannot resist abrasion under the friction of the grinding wheel. The abrasion resistance value of comparative example 2 was made significantly higher than that of each example (the larger the abrasion resistance value, the worse the abrasion resistance).
(2) The modified silicon carbide dispersion liquid has excellent medium resistance (acid-base resistance and the like), and the nano-particle size state of the dispersion liquid can effectively fill the defects of gaps and the like of a paint film, so that the density of the paint film is improved. Thereby improving the salt spray resistance of the paint film. The talcum powder is amorphous powder, so that the porosity of a paint film is increased; in addition, the talcum powder generates hydration after meeting water, so that the volume of a paint film expands, the stress is increased, and the wet adhesion force is reduced. Therefore, after the talcum powder is used for replacement, the neutral salt spray resistance of the paint film is obviously reduced. The resulting neutral salt spray performance of comparative example 2 was inferior to that of each example.
The present invention has been described in detail with reference to the embodiments, which are illustrative and not restrictive, and several embodiments may be mentioned within the scope of the composition defined by the components, so that variations and modifications may be effected without departing from the general inventive concept and the scope of the present invention is thus protected.
Claims (9)
1. The water-based insulating paint is characterized by comprising a component A and a component B; the component A comprises elastic epoxy emulsion, pigment and filler, silicon carbide dispersion liquid, flame retardant and auxiliary agent, and the component B comprises modified fatty amine, flash rust inhibitor and solvent; wherein the mass ratio of the component A to the component B is 50-80: 20-50;
the elastic epoxy emulsion is obtained by dropwise adding a mixture of an emulsifier and deionized water into elastic epoxy resin under high-speed stirring;
the preparation method of the elastic epoxy resin comprises the following steps: mixing adipic acid, hexachloroendomethylene phthalic anhydride, propylene glycol and dibromoneopentyl glycol for reaction to obtain a hydroxyl-terminated flame-retardant elastic polyester prepolymer; and reacting the hydroxyl-terminated flame-retardant elastic polyester prepolymer with bisphenol A epoxy resin under the action of a catalyst to obtain the elastic epoxy resin.
2. The water-based insulating paint according to claim 1, wherein the component A comprises 35-55 parts of elastic epoxy emulsion, 15-25 parts of pigment and filler, 5-16 parts of silicon carbide dispersion, 19-33 parts of flame retardant and 1.1-3.8 parts of auxiliary agent; the component B comprises 60-80 parts of modified fatty amine, 1-8 parts of anti-flash rust agent and 10-40 parts of solvent.
3. The water-based insulating paint according to claim 1 or 2, characterized in that the silicon carbide dispersion comprises 50-70 parts of silicon carbide micro powder, 5-15 parts of silica sol, 1-2 parts of rheological agent, 5-10 parts of wetting agent and 10-30 parts of water.
4. The water-based insulating paint according to claim 3, wherein the silicon carbide dispersion is prepared by a method comprising: adding water into a container according to the formula amount, starting stirring, slowly adding a wetting agent and a rheological agent, and dispersing at 2500-3000 rpm for 30-40 min to form slurry; uniformly adding silicon carbide micro powder, and stirring for 30-40 min until no obvious particles exist; dropwise adding silica sol, stirring uniformly, and grinding for 3-4 h by a ball mill to obtain the silicon carbide dispersion.
5. The water-based insulating varnish according to claim 3, wherein the D50 of the silicon carbide micropowder is a micropowder having a particle size of 0.5 to 0.8 μm; the silica sol is alkaline silica sol with the pH value of 9-11 and the particle size of 5.5 nm-6.5 nm; the rheological agent is one or more of sodium bentonite, attapulgite and hydroxyethyl cellulose; the wetting agent is one or more of sodium polyacrylate, polyvinyl alcohol, polyethylene glycol and cetyl pyridine bromide.
6. The water-based insulating paint according to claim 1, wherein the raw material of the elastic epoxy resin comprises: 90-150 parts of adipic acid, 80-120 parts of hexachloroendomethylene phthalic anhydride, 60-130 parts of propylene glycol, 100 parts of dibromoneopentyl glycol, 160 parts of bisphenol A epoxy resin and 2-5 parts of a catalyst.
7. The aqueous insulating paint according to claim 6, wherein the elastic epoxy resin is prepared by a method comprising: putting adipic acid, hexachloro-endomethylene phthalic anhydride and propylene glycol into a reaction kettle according to a formula; starting stirring, heating to 190-220 ℃, and reacting until the acid value is less than or equal to 100mg KOH/g; adding dibromoneopentyl glycol, heating to 190-220 ℃, reacting until the acid value is less than or equal to 20mg KOH/g, and preparing a hydroxyl-terminated flame-retardant elastic polyester prepolymer; adding bisphenol A epoxy resin and a catalyst according to the formula, heating to the temperature of 100-120 ℃, and reacting until the epoxy equivalent is 190-220g/mol to obtain the elastic epoxy resin.
8. The aqueous enamel paint according to claim 6 or 7, wherein the catalyst is boron trifluoride dimethyl ether complex, tertiary amine or triphenyl phosphate.
9. The aqueous insulating varnish according to claim 8, wherein the catalyst is a boron trifluoride dimethyl ether complex.
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