CN113980559B - Water-based insulating paint and preparation method and application thereof - Google Patents
Water-based insulating paint and preparation method and application thereof Download PDFInfo
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- CN113980559B CN113980559B CN202111310600.4A CN202111310600A CN113980559B CN 113980559 B CN113980559 B CN 113980559B CN 202111310600 A CN202111310600 A CN 202111310600A CN 113980559 B CN113980559 B CN 113980559B
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- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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Abstract
The invention discloses a water-based insulating paint and a preparation method and application thereof, wherein the water-based insulating paint comprises the following raw materials: the water-based resin comprises a water-based resin matrix, a curing agent, a cosolvent, a neutralizer and water, wherein the water-based resin matrix comprises: waterborne epoxy resins and waterborne polyester resins; the raw materials of the aqueous polyester resin comprise polyhydric alcohol, soybean oil and/or linseed oil, and polybasic acid and/or polybasic acid anhydride, wherein the aqueous polyester resin is prepared by mixing part of the polyhydric alcohol, the soybean oil and/or linseed oil for alcoholysis reaction to obtain a mixture of ester containing terminal hydroxyl, and then carrying out polycondensation reaction with the rest of the polyhydric alcohol and the polybasic acid and/or polybasic acid anhydride; preparation: mixing the raw materials according to a formula; and the application of the water-based insulating paint in motors and electronic transformers; the insulating paint has excellent water resistance, stability, temperature resistance and the like on the basis of water solubility.
Description
Technical Field
The invention relates to the field of insulating materials, in particular to environment-friendly insulating paint, and specifically relates to water-based insulating paint and a preparation method and application thereof.
Background
At present, insulating paint on the market mainly comprises a solvent type insulating paint and a water-based insulating paint, wherein the solvent type insulating paint has excellent comprehensive performance and good insulating performance, but the solvent type insulating paint needs to use a volatile toxic and harmful organic solvent in the manufacturing and using processes and is difficult to adapt to stricter and stricter environmental protection requirements; the water-based insulating paint generally uses water-based acrylic resin, water-based epoxy resin and water-based polyester resin as film forming substances, and uses water as a main solvent, although a good environment-friendly effect can be obtained, the problems of insufficient water resistance, stability, temperature resistance and the like still exist in some existing water-based insulating paints, and further obvious potential safety hazards exist in the industries of applying the insulating paints as insulating paints to medium and small motors, electronic transformers and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an improved water-based insulating paint which has excellent water resistance, stability, temperature resistance and the like on the basis of water solubility.
The invention also provides a preparation method of the water-based insulating paint.
The invention also provides application of the water-based insulating paint in motors and electronic transformers.
In order to achieve the purpose, the invention adopts a technical scheme that:
an aqueous insulating paint comprises the following raw materials: the water-based resin comprises a water-based resin matrix, a curing agent, a cosolvent, a neutralizer and water, wherein the water-based resin matrix comprises: the water-based epoxy resin and the water-based polyester resin are added in a mass ratio of 1: 1-2;
the raw materials of the aqueous polyester resin comprise polyol, soybean oil and/or linseed oil, and polybasic acid and/or polybasic acid anhydride, wherein the aqueous polyester resin is prepared by mixing part of polyol, soybean oil and/or linseed oil to perform alcoholysis reaction to obtain a mixture of ester containing terminal hydroxyl groups, and then performing polycondensation reaction with the rest of polyol and polybasic acid and/or polybasic acid anhydride.
According to some preferred aspects of the present invention, the acid value of the aqueous polyester resin is 20 to 40mgKOH/g.
According to some preferred aspects of the present invention, the aqueous epoxy resin has an acid value of 20 to 30mgKOH/g.
According to some preferred aspects of the present invention, the feed equivalent ratio of the polyol, the soybean oil and/or linseed oil, the polybasic acid and/or polybasic acid anhydride is 1: 0.5-1: 1.3-1.8.
According to some preferred aspects of the present invention, the polyol is a combination of one or more selected from pentaerythritol, neopentyl glycol, propylene glycol, glycerol.
According to some preferred aspects of the invention, the polyacid and/or polyanhydride is a combination of one or more selected from phthalic anhydride, trimellitic anhydride, isophthalic anhydride, maleic anhydride, adipic acid.
According to some preferred aspects of the invention, the alcoholysis reaction is carried out in the presence of a catalyst which is calcium isooctanoate or lithium hydroxide.
According to some preferred aspects of the invention, the alcoholysis reaction is carried out at a temperature of 240 to 260 ℃.
According to some preferred aspects of the present invention, the polycondensation reaction is performed at 180 to 220 ℃ in the preparation of the aqueous polyester resin.
According to some preferred aspects of the present invention, the portion of the polyol that is mixed with the soybean oil and/or linseed oil for the alcoholysis reaction comprises 10-40% of the total charge of polyol.
According to some preferred aspects of the present invention, the aqueous epoxy resin is obtained by condensation-polymerizing an epoxy resin containing a terminal hydroxyl group with an organic acid.
According to some preferred aspects of the present invention, the organic acid is composed of linoleic acid and maleic anhydride, and the feeding molar ratio of the linoleic acid to the maleic anhydride is 1: 0.5-1.
According to some preferred aspects of the present invention, the epoxy resin containing terminal hydroxyl groups is a combination of one or more selected from the group consisting of E-12 epoxy resin, E-20 epoxy resin, and E-44 epoxy resin.
The waterborne epoxy resin can further improve the comprehensive performance of the insulating paint film.
According to some preferred aspects of the present invention, the polycondensation reaction is performed at 180 to 200 ℃ during the preparation of the aqueous epoxy resin.
In some embodiments of the present invention, the aqueous epoxy resin is added to the aqueous insulating paint in the form of an aqueous epoxy resin solution, the aqueous polyester resin is added to the aqueous insulating paint in the form of an aqueous polyester resin solution, the aqueous epoxy resin solution is obtained by dispersing an aqueous epoxy resin in a part of co-solvents, and the aqueous polyester resin solution is obtained by dispersing an aqueous polyester resin in the remaining co-solvents.
According to some specific aspects of the present invention, the aqueous epoxy resin solution contains 75-85% by mass of the aqueous epoxy resin, and the aqueous polyester resin solution contains 75-85% by mass of the aqueous polyester resin.
According to some preferred aspects of the present invention, the raw materials of the water-based insulating paint comprise, in parts by mass: 50-140 parts of aqueous epoxy resin solution, 100-250 parts of aqueous polyester resin solution, 20-50 parts of curing agent, 5-15 parts of neutralizing agent and 80-160 parts of water.
Further, the raw materials of the water-based insulating paint comprise, by mass: 80-130 parts of a water-based epoxy resin solution, 200-250 parts of a water-based polyester resin solution, 20-50 parts of a curing agent, 5-15 parts of a neutralizer and 80-160 parts of water, wherein the mass percentage of the water-based epoxy resin in the water-based epoxy resin solution is 75-85%, and the mass percentage of the water-based polyester resin in the water-based polyester resin solution is 75-85%.
According to some preferred aspects of the present invention, the curing agent is a water-based amino resin, and the water-based amino resin is one or more selected from the group consisting of methylated amino resin, butanol-etherified amino resin, and isobutanol-etherified amino resin.
According to some preferred aspects of the present invention, the neutralizing agent is an ammonia neutralizing agent, and the ammonia neutralizing agent is dimethylethanolamine and/or aqueous ammonia.
According to some preferred aspects of the invention, the co-solvent is ethylene glycol butyl ether and/or propylene glycol methyl ether.
The invention provides another technical scheme that: the preparation method of the water-based insulating paint comprises the following steps:
(1) Preparation of aqueous epoxy resin solution: mixing epoxy resin containing terminal hydroxyl with organic acid to perform polycondensation reaction until the acid value is 20-30mgKOH/g, adding part of cosolvent, mixing and stirring to prepare aqueous epoxy resin solution;
(2) Preparation of aqueous polyester resin solution: mixing part of polyol, soybean oil and/or linseed oil for alcoholysis reaction to obtain a mixture of ester containing terminal hydroxyl, mixing with the rest polyol and polybasic acid for polycondensation reaction until the acid value is 20-40mgKOH/g, adding the rest cosolvent, mixing and stirring to prepare an aqueous polyester resin solution;
(3) And (3) mixing the aqueous epoxy resin solution prepared in the step (1), the aqueous polyester resin solution prepared in the step (2) and the rest raw materials according to the formula amount to prepare the aqueous insulating paint.
According to some preferred aspects of the present invention, in the step (1), the reaction temperature of the polycondensation reaction is 180 to 200 ℃.
In some embodiments of the present invention, in step (1), the temperature is reduced to 80-120 ℃ before adding part of the solvent.
In some embodiments of the present invention, in step (1), the content of the aqueous epoxy resin in the aqueous epoxy resin solution is controlled to be 75-85% by mass.
According to some preferred aspects of the present invention, in step (2), the reaction temperature of the alcoholysis reaction is in the range of 220 to 260 ℃.
According to some preferred aspects of the present invention, in the step (2), the reaction temperature of the polycondensation reaction is 180 to 220 ℃.
According to some preferred aspects of the present invention, in step (2), the temperature is reduced to 80-120 ℃ before adding the residual solvent.
According to some preferred aspects of the invention, in step (2), the methanol tolerance of the reaction mixture is measured until acceptable, before the remaining polyol and polyacid are added.
In some embodiments of the present invention, in the step (2), the content of the water-based polyester resin in the water-based polyester resin solution is controlled to be 75-85% by mass.
The invention provides another technical scheme that: the application of the water-based insulating paint in motors and electronic transformers.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the invention innovatively adopts specific water-based polyester resin, the hydrophobic chain segment of soybean oil and/or linseed oil is replaced by alcoholysis in the water-based polyester resin, a mixture of ester containing terminal hydroxyl is obtained in an ester exchange mode, and then the water-based polyester resin is prepared by polycondensation, so that the water-based polyester resin and the water-based epoxy resin are compounded to be used as a film forming component of the insulating paint, the water resistance and the stability of the insulating paint are greatly improved, meanwhile, the excellent temperature resistance is also obtained, the drying speed is high, the mechanical property and the electrical property are excellent, the problems of insufficient water resistance of the water-based paint and sedimentation of epoxy emulsion are solved, and the application field of the water-based paint is widened.
Detailed Description
The above-described scheme is further illustrated below with reference to specific examples; it is to be understood that these embodiments are illustrative of the principles, essential features and advantages of the invention, and that the invention is not limited in scope by the following embodiments; the implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments.
Not specifically illustrated in the following examples, all starting materials are commercially available or prepared by methods conventional in the art.
Example 1
This example provides a water-based insulating paint and a preparation method thereof, wherein the raw material formulation is shown in table 1.
TABLE 1
Wherein the aqueous epoxy resin is obtained by condensation polymerization of an epoxy resin containing terminal hydroxyl groups, which is an E-12 epoxy resin (available from Yueyanite), and an organic acid composed of linoleic acid and maleic anhydride.
The raw materials of the aqueous polyester resin comprise polyol, linseed oil and polybasic acid anhydride, and the aqueous polyester resin is prepared by mixing part of the polyol and linseed oil (purchased from Shanghai New industry development Co., ltd.) to perform alcoholysis reaction to obtain a mixture of ester containing terminal hydroxyl groups, and then performing polycondensation reaction with the rest of the polyol and polybasic acid anhydride.
The waterborne epoxy resin is added into the waterborne insulating paint in the form of a waterborne epoxy resin solution, the waterborne polyester resin is added into the waterborne insulating paint in the form of a waterborne polyester resin solution, the waterborne epoxy resin solution is obtained by dispersing the waterborne epoxy resin in a cosolvent, and the waterborne polyester resin solution is obtained by dispersing the waterborne polyester resin in the cosolvent;
specifically, the preparation method of the water-based insulating paint comprises the following steps:
(1) Preparation of aqueous epoxy resin solution: adding 100g of linoleic acid, 20g of maleic anhydride and 800g of E-12 epoxy resin into a three-neck flask, controlling the temperature to be 180-200 ℃ for polycondensation reaction, controlling the acid value to be less than or equal to 30mgKOH/g, cooling to 100 ℃, adding 130g of ethylene glycol butyl ether and 100g of propylene glycol methyl ether, stirring for 30min, cooling to below 50 ℃, discharging, and preparing a water-based epoxy resin solution; the mass percentage of the aqueous epoxy resin in the aqueous epoxy resin solution is 80 percent;
(2) Preparation of aqueous polyester resin solution: heating 500g of linseed oil, 100g of pentaerythritol and 1g of calcium isooctanoate to 240 ℃, preserving heat for 2h, cooling to 180 ℃ after the methanol tolerance is qualified, adding 100g of pentaerythritol, 100g of neopentyl glycol, 100g of phthalic anhydride and 100g of trimellitic anhydride, controlling the temperature to be 200 +/-5 ℃, carrying out polycondensation reaction to obtain an acid value of 35mgKOH/g, cooling to 100 ℃, adding 150g of ethylene glycol butyl ether and 100g of propylene glycol methyl ether, stirring for 30min, cooling to below 50 ℃, discharging, and preparing into an aqueous polyester resin solution; the mass percentage of the water-based polyester resin in the water-based polyester resin solution is 79 percent;
(3) And (3) mixing the aqueous epoxy resin solution prepared in the step (1), the aqueous polyester resin solution prepared in the step (2) and the rest raw materials according to the formula amount to prepare the aqueous insulating paint.
Example 2
This example provides a water-based insulating paint and a preparation method thereof, and the raw material formula is shown in table 2.
TABLE 2
Wherein the aqueous epoxy resin is obtained by condensation polymerization of an epoxy resin containing terminal hydroxyl groups, which is an E-20 epoxy resin (available from Yueyanite), and an organic acid composed of linoleic acid and maleic anhydride. The rest is the same as example 1.
Example 3
This example provides a water-based insulating paint and a preparation method thereof, and the raw material formulation is shown in table 3.
TABLE 3
Wherein the aqueous epoxy resin is obtained by condensation polymerization of an epoxy resin containing a terminal hydroxyl group and an organic acid, the epoxy resin containing a terminal hydroxyl group is an E-20 epoxy resin (available from Yueyanite), and the organic acid is composed of linoleic acid and maleic anhydride. The rest was the same as in example 1.
Example 4
This example provides a water-based insulating paint and a preparation method thereof, and the raw material formulation is shown in table 4.
TABLE 4
Wherein the aqueous epoxy resin is obtained by condensation polymerization of an epoxy resin containing terminal hydroxyl groups, which is an E-44 epoxy resin (available from Yueyanite), and an organic acid composed of linoleic acid and maleic anhydride. The rest is the same as example 1.
Comparative example 1
Basically, the method is the same as the embodiment 1, and the differences are that: the water-based polyester resin is prepared by the following method: 200g of pentaerythritol, 100g of neopentyl glycol, 100g of phthalic anhydride and 100g of trimellitic anhydride are subjected to polycondensation reaction at the temperature of 200 +/-5 ℃ until the acid value is 35mgKOH/g, and the compound is obtained.
Performance test
The enamels obtained in examples 1 to 4 and comparative example 1 were cured at 120 ℃ for 3 hours and subjected to the following performance tests, the specific results of which are shown in Table 5.
TABLE 5
The above embodiments are only for illustrating the technical idea and features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention by this means. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
Claims (8)
1. An aqueous insulating paint comprises the following raw materials: the water-based resin comprises a water-based resin matrix, a curing agent, a cosolvent, a neutralizer and water, and is characterized in that the water-based resin matrix is composed of water-based epoxy resin and water-based polyester resin, the feeding mass ratio of the water-based epoxy resin to the water-based polyester resin is 1: 1-2, the acid value of the water-based polyester resin is 20-40mgKOH/g, and the acid value of the water-based epoxy resin is 20-30mgKOH/g;
the raw materials of the aqueous polyester resin comprise polyol, soybean oil and/or linseed oil, and polyacid and/or polybasic acid anhydride, wherein the aqueous polyester resin is prepared by mixing part of polyol, soybean oil and/or linseed oil for alcoholysis reaction to obtain a mixture containing ester with terminal hydroxyl, and then performing polycondensation reaction with the rest of polyol and polyacid and/or polybasic acid anhydride;
the charging equivalent ratio of the polyhydric alcohol, the soybean oil and/or the linseed oil and the polybasic acid and/or the polybasic acid anhydride is 1: 0.5-1: 1.3-1.8;
the alcoholysis reaction is carried out in the presence of a catalyst, wherein the catalyst is calcium isooctanoate and/or lithium hydroxide;
the alcoholysis reaction is carried out at 240-260 ℃;
in the process of preparing the waterborne polyester resin, the polycondensation reaction is carried out at 180-220 ℃;
the part of the polyol which is mixed with the soybean oil and/or the linseed oil for carrying out alcoholysis reaction accounts for 10-40% of the total input amount of the polyol.
2. The aqueous insulating paint according to claim 1,
the polyalcohol is one or more of pentaerythritol, neopentyl glycol, propylene glycol and glycerol;
the polybasic acid and/or polybasic acid anhydride is one or a combination of more selected from phthalic anhydride, trimellitic anhydride, isophthalic anhydride, maleic anhydride and adipic acid.
3. The aqueous insulating varnish according to claim 1, wherein the aqueous epoxy resin is obtained by polycondensation reaction of an epoxy resin containing a terminal hydroxyl group with an organic acid.
4. The water-based insulating paint according to claim 3, characterized in that the organic acid is composed of linoleic acid and maleic anhydride, and the feeding molar ratio of the linoleic acid to the maleic anhydride is 1: 0.5-1; the epoxy resin containing the terminal hydroxyl is one or a combination of more of E-12 epoxy resin, E-20 epoxy resin and E-44 epoxy resin;
in the process of preparing the waterborne epoxy resin, the polycondensation reaction is carried out at 180-200 ℃.
5. The aqueous insulating varnish according to claim 1, wherein the aqueous epoxy resin is added to the aqueous insulating varnish in the form of an aqueous epoxy resin solution, the aqueous polyester resin is added to the aqueous insulating varnish in the form of an aqueous polyester resin solution, the aqueous epoxy resin solution is obtained by dispersing an aqueous epoxy resin in a part of co-solvents, and the aqueous polyester resin solution is obtained by dispersing an aqueous polyester resin in the remaining co-solvents; the mass percentage of the water-based epoxy resin in the water-based epoxy resin solution is 75-85%, and the mass percentage of the water-based polyester resin in the water-based polyester resin solution is 75-85%;
the water-based insulating paint comprises the following raw materials in parts by mass: 50-140 parts of aqueous epoxy resin solution, 100-250 parts of aqueous polyester resin solution, 20-50 parts of curing agent, 5-15 parts of neutralizing agent and 80-160 parts of water.
6. The water-based insulating paint according to claim 1 or 5, wherein the curing agent is a water-based amino resin, and the water-based amino resin is a combination of one or more selected from methylated amino resins, butanol-etherified amino resins, and isobutanol-etherified amino resins;
the neutralizer is an ammonia neutralizer which is dimethylethanolamine and/or ammonia water;
the cosolvent is ethylene glycol butyl ether and/or propylene glycol methyl ether.
7. A method for preparing the water-based insulating paint according to any one of claims 1 to 6, characterized in that the preparation method comprises the following steps:
(1) Preparation of aqueous epoxy resin solution: mixing epoxy resin containing terminal hydroxyl with organic acid to perform polycondensation reaction until the acid value is 20-30mgKOH/g, adding part of cosolvent, mixing and stirring to prepare aqueous epoxy resin solution;
(2) Preparation of aqueous polyester resin solution: mixing part of polyol, soybean oil and/or linseed oil for alcoholysis reaction to obtain a mixture of ester containing terminal hydroxyl, then mixing the mixture with the rest of polyol and polybasic acid and/or polybasic acid anhydride for polycondensation reaction until the acid value is 20-40mgKOH/g, adding the rest of cosolvent, mixing and stirring to prepare an aqueous polyester resin solution;
(3) And (3) mixing the aqueous epoxy resin solution prepared in the step (1), the aqueous polyester resin solution prepared in the step (2) and the rest raw materials according to the formula amount to prepare the aqueous insulating paint.
8. Use of the aqueous insulating varnish according to any one of claims 1 to 6 in electrical machines, electronic transformers.
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| CN202211596674.3A CN115820087B (en) | 2021-11-08 | 2021-11-08 | Water-based insulating paint |
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| CN115820087A (en) | 2023-03-21 |
| CN113980559A (en) | 2022-01-28 |
| CN115820087B (en) | 2023-12-29 |
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