CN112552462A - Water-based acrylic epoxy resin emulsion and preparation method and application thereof - Google Patents
Water-based acrylic epoxy resin emulsion and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a water-based acrylic acid epoxy resin emulsion and a preparation method and application thereof, wherein a nonionic surfactant is reacted with epoxy resin to generate the nonionic surfactant containing an epoxy structure; mixing an acrylic acid monomer, a nonionic surfactant containing an epoxy structure and a cosolvent to obtain a first dispersion liquid; dispersing an anionic surfactant in water to obtain a second dispersion; adding the first dispersion into the second dispersion under stirring, optionally adding water, and dispersing to obtain a pre-emulsion; respectively dripping the pre-emulsion and the initiator solution into the reactor under the stirring condition to carry out miniemulsion polymerization reaction of the acrylic monomer; the initiator solution is prepared by dispersing an initiator in water; the aqueous acrylic acid epoxy resin emulsion prepared by the method has good stability, and the prepared insulating paint has good electrical property, bonding force, paint film state and other properties after being cured, thereby realizing the improvement of the overall performance of the aqueous insulating paint.
Description
Technical Field
The invention belongs to the technical field of water-based surface paint, and particularly relates to a water-based acrylic epoxy resin emulsion as well as a preparation method and application thereof.
Background
The insulating paint is mainly used for coils of electric machines and electric appliances and other insulating parts, the gaps of the insulating paint are filled, and the dipped objects become a compact whole after curing, so that the insulating property, the mechanical property and the weather resistance of the dipped objects are improved. The insulating paint is generally divided into solvent paint and solvent-free paint, but the solvent paint and the solvent-free paint sold in the market at present contain certain volatile harmful substances, cause harm to people and environment, are inflammable and explosive, and have potential safety hazards in transportation and storage.
The water-based insulating paint takes water as a diluent, has low comprehensive cost, low toxicity, safe use and storage, excellent dielectric property, convenient use, good permeability and high bonding strength, and is the first choice of the future insulating paint. The epoxy resin is high in strength, strong in binding power, good in electrical property, poor in weather resistance and easy to age, and is an excellent insulating material; the acrylic resin has good weather resistance, but the electrical property is general, and the organic combination of the acrylic resin and the electrical property is a way for preparing the insulating paint with excellent comprehensive properties. However, if two resins are directly mixed, the two resins are severely separated after curing, and the electrical properties are greatly reduced, so that how to combine the two resins is a problem to be solved.
At present, the two methods are mainly combined by one method, namely, the epoxy resin and the acrylic monomer are firstly reacted to generate epoxy ester, and then emulsion polymerization is carried out to introduce the epoxy resin into the acrylic polymer, but the method destroys the epoxy group and changes the original excellent performance of the epoxy resin; the other method is to mix epoxy resin and acrylic monomer in advance and then add emulsifier to carry out emulsion polymerization reaction, which keeps the characteristics of epoxy resin, but the mixing amount of epoxy resin is low and can only reach about 10 percent, and a large amount of epoxy resin is separated out from the emulsion when the mixing amount exceeds 10 percent, so that the stability is poor.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an improved method for preparing the acrylic epoxy resin emulsion, the acrylic epoxy resin emulsion prepared by the method has good stability, and the prepared insulating paint has good performances such as electrical property, bonding force, paint film state and the like after being cured, so that the acrylic resin and the epoxy resin are organically integrated into a whole, and the respective performance advantages can be fully utilized.
The invention also provides the acrylic epoxy resin emulsion prepared by the method.
The invention also provides application of the acrylic epoxy resin emulsion prepared by the method in water-based insulating paint.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a water-based acrylic epoxy resin emulsion comprises the following steps:
(1) reacting a nonionic surfactant with an epoxy resin to generate a nonionic surfactant containing an epoxy structure; wherein the nonionic surfactant is polyoxyethylene sorbitan fatty acid ester and/or castor oil polyoxyethylene ether;
(2) mixing an acrylic acid monomer, the nonionic surfactant containing the epoxy structure and a cosolvent to obtain a first dispersion liquid;
dispersing an anionic surfactant in water to obtain a second dispersion;
adding the first dispersion into the second dispersion under stirring, optionally adding water, and dispersing to obtain a pre-emulsion;
(3) respectively dripping the pre-emulsion and the initiator solution into a reactor under the stirring condition to carry out miniemulsion polymerization reaction of acrylic monomers; wherein the initiator solution is prepared by dispersing an initiator in water.
According to some preferred aspects of the present invention, in the step (1), the charging mass ratio of the nonionic surfactant to the epoxy resin is 1: 10-20.
According to some preferred aspects of the present invention, in step (1), the reaction is carried out at 160-220 ℃. Further preferably, in step (1), the reaction is carried out at 180-.
According to some preferred aspects of the present invention, in the step (1), the method for preparing the nonionic surfactant containing an epoxy structure comprises the steps of: heating part of epoxy resin, heating to 160-220 ℃, adding a nonionic surfactant for reaction, then adding the rest of epoxy resin for reaction to generate the nonionic surfactant containing the epoxy structure.
According to some preferred aspects of the present invention, in step (1), the polyoxyethylene sorbitan fatty acid ester is a combination of one or more selected from tween-20, tween-60 and tween-80, and the castor oil polyoxyethylene ether is a combination of one or more selected from EL-20, EL-40, EL-60 and EL-90.
According to some preferred aspects of the present invention, in the step (1), the epoxy resin is a solid epoxy resin selected from bisphenol a type epoxy resins having an epoxy equivalent of 500 or more. Further, in the step (1), the bisphenol a type solid epoxy resin may be E20 bisphenol a type epoxy resin, E12 bisphenol a type epoxy resin, E06 bisphenol a type epoxy resin, E03 bisphenol a type epoxy resin, or the like.
According to some preferred aspects of the present invention, in the step (1), the nonionic surfactant is composed of polyoxyethylene sorbitan fatty acid ester and castor oil polyoxyethylene ether, and the feeding mass ratio of the polyoxyethylene sorbitan fatty acid ester to the castor oil polyoxyethylene ether is 0.1-2: 1, preferably 0.3-1.5: 1.
According to some preferred aspects of the present invention, in the step (2), the charging mass ratio of the nonionic surfactant containing an epoxy structure to the acrylic monomer is 1: 0.25-4.
According to some preferred aspects of the present invention, in the step (2), the mixing of the acrylic monomer, the nonionic surfactant containing an epoxy structure, and the co-solvent is controlled to be performed at a temperature of 60 ℃ or less.
According to some specific and preferred aspects of the present invention, in the step (2), the acrylic monomer is one or more selected from the group consisting of styrene, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, octyl lactone acrylate, hydroxypropyl acrylate, hydroxyethyl acrylate, methyl methacrylate, butyl methacrylate and hydroxypropyl methacrylate.
According to some specific and preferred aspects of the present invention, in the step (2), the co-solvent is one or a combination of more selected from the group consisting of alcohol ester twelve, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, ethylene glycol butyl ether, diethylene glycol propyl ether, propylene glycol butyl ether, and propylene glycol methyl ether acetate.
According to some specific and preferred aspects of the present invention, in step (2), the concentration of the anionic surfactant in the second dispersion is 0.5 to 10%, and the anionic surfactant is a fatty alcohol/nonylphenol polyoxyethylene ether sulfate salt and/or a fatty alcohol/nonylphenol polyoxyethylene ether phosphate salt. Further, the anionic surfactant may be sodium fatty alcohol/nonylphenol polyoxyethylene ether (3-24) sulfate, sodium fatty alcohol/nonylphenol polyoxyethylene ether (3-24) phosphate, potassium fatty alcohol/nonylphenol polyoxyethylene ether (3-24) sulfate, potassium fatty alcohol/nonylphenol polyoxyethylene ether (3-24) phosphate, ammonium fatty alcohol/nonylphenol polyoxyethylene ether (3-24) sulfate, ammonium fatty alcohol/nonylphenol polyoxyethylene ether (3-24) phosphate, or the like.
According to some preferred aspects of the present invention, the specific implementation manner of the step (3) is: adding water into a reactor, heating to 80-85 ℃, then respectively dropwise adding the pre-emulsion and the initiator solution into the reactor, and controlling the reaction temperature in the dropwise adding process to be 80-85 ℃ all the time; after the dropwise addition, the temperature is raised to 90-95 ℃ for reaction.
According to some preferred aspects of the present invention, in the specific embodiment of the step (3), the dropping speeds of the pre-emulsion and the initiator solution are controlled, and the dropping time is controlled to be 2.5 to 3 hours respectively.
According to some specific aspects of the present invention, in the step (3), the initiator is ammonium persulfate and/or potassium persulfate.
According to some particular aspects of the invention, the preparation method further comprises a step (4): and (4) cooling and filtering the material obtained after the reaction in the step (3) to obtain the water-based acrylic epoxy resin emulsion. Further, the temperature reduction in the step (4) is to be reduced to below 45 ℃.
According to some preferred aspects of the invention, the water employed in the preparation method of the invention is deionized water.
According to some preferred aspects of the present invention, in step (3), the initiator solution may be prepared in part in advance, and then the part may be prepared again during the dropping process, in batches as many as possible, so that the initiator activity may be maintained.
The invention provides another technical scheme that: the water-based acrylic epoxy resin emulsion prepared by the preparation method.
The invention also provides application of the water-based acrylic epoxy resin emulsion prepared by the preparation method in water-based insulating paint.
Due to the implementation of the technical scheme, compared with the prior art, the invention has the following advantages:
in the preparation process of the acrylic epoxy resin emulsion, a specific nonionic surfactant is innovatively used for carrying out graft modification on epoxy resin, so that a nonionic surfactant containing an epoxy structure is obtained, the nonionic surfactant can be used as an epoxy resin emulsifier with surface activity, the emulsifier can be used as a nonionic surfactant to participate in subsequent miniemulsion polymerization, and meanwhile, the emulsifier is matched with an anionic surfactant to better achieve a synergistic effect, so that the problem that epoxy resin with high content or high epoxy equivalent weight is separated out in the miniemulsion polymerization process due to the addition of the emulsifier is avoided, the stability of the prepared acrylic epoxy resin emulsion is greatly improved, the electrical property, the bonding force, the paint film state and other properties of the prepared insulating paint after curing are good, and the improvement of the overall performance is realized.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that these examples are for the purpose of illustrating the general principles, essential features and advantages of the present invention, and the present invention is not limited by the following examples. 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. The raw materials used in the examples are all commercially available commercial products.
In the following examples, all starting materials are essentially obtained commercially or prepared by conventional methods in the art, unless otherwise specified. In the examples described below, E20 bisphenol A epoxy resin was purchased from Nantong star; e12 bisphenol A epoxy resin was purchased from Nantong star; e03 bisphenol A epoxy resin was purchased from Nantong star; tween-80 was purchased from huangjiang amantadine chemical industry, tween-20 was purchased from zhejiang amantadine chemical industry, and castor oil polyoxyethylene ether EL40,60,80,90, were purchased from jiangsu haian petrochemical industry; the fatty alcohol-polyoxyethylene ether (10) potassium phosphate and the nonylphenol polyoxyethylene ether (10) potassium phosphate are purchased from Jiangsu Haian petrochemical engineering, and the acrylic monomers are purchased from Beijing Anxing Tai chemical company.
Example 1
This example provides a waterborne acrylic epoxy resin emulsion, the raw materials of which include: 20 kg of E12 bisphenol A epoxy resin, 30 kg of E20 bisphenol A epoxy resin, 15 kg of styrene, 20 kg of methyl methacrylate, 10 kg of butyl methacrylate, 5 kg of hydroxypropyl methacrylate, 2 kg of Tween-80, 2 kg of castor oil polyoxyethylene ether EL-40, 4 kg of fatty alcohol polyoxyethylene ether (10) potassium phosphate (effective component 50%), 15 kg of diethylene glycol monobutyl ether and 0.5 kg of potassium persulfate.
The preparation method of the water-based acrylic epoxy resin emulsion comprises the following steps:
(1) preparation of nonionic surfactant containing epoxy structure:
heating and melting 5 kg of E12 epoxy resin and 10 kg of E20 epoxy resin, heating to 190 ℃, adding 2 kg of Tween-80 and 2 kg of castor oil polyoxyethylene ether EL-40, and uniformly stirring; keeping the temperature of the system at 190 +/-5 ℃ for reacting for 60min, then adding the rest epoxy resin, and continuing to react for 60min to obtain the nonionic surfactant containing the epoxy structure;
(2) preparation of pre-emulsion:
all acrylic monomers: 15 kg of styrene, 20 kg of methyl methacrylate, 10 kg of butyl methacrylate and 5 kg of hydroxypropyl methacrylate are mixed and stirred uniformly;
slowly adding a nonionic surfactant containing an epoxy structure into the acrylic monomer, controlling the adding speed to keep the temperature of the system below 60 ℃, adding 15 kg of diethylene glycol butyl ether after the adding is finished, and uniformly stirring to obtain a first dispersion liquid;
dissolving 4 kg of fatty alcohol-polyoxyethylene ether (10) potassium phosphate in 40 kg of water, and stirring to completely dissolve the potassium phosphate to obtain a second dispersion liquid;
slowly adding the first dispersion into the second dispersion, keeping high-speed stirring in the adding process, continuously stirring for 60min after the adding is finished, and slowly adding 60 kg of water to dilute to obtain a pre-emulsion;
(3) preparation of aqueous acrylic epoxy resin emulsion:
adding 110 kg of deionized water into a reactor with a stirrer, heating to 82 +/-2 ℃, dripping the pre-emulsion and the initiator solution into a dropping funnel, controlling the stirring speed to be 100 +/-10 rpm/min, and introducing cooling water to control the reaction temperature to be 82 +/-2 ℃; controlling the dropping speed, completing the dropping of the pre-emulsion and the initiator solution in 3 hours respectively, and after the dropping is completed, heating to 92 +/-2 ℃ to continue reacting for 1 hour; the initiator solution is prepared by the following preparation method: preparing 2 kilograms of potassium persulfate solution with the concentration of 5 percent by water dispersion, preparing 2 kilograms of solution with the concentration of 5 percent by 5 batches when the potassium persulfate solution is almost dripped, and preparing in batches to keep the activity of the initiator;
(4) cooling water is introduced to reduce the temperature of the materials to below 45 ℃, and the water-based acrylic epoxy resin emulsion is obtained after filtration by a 200-mesh filter bag.
Example 2
This example provides a waterborne acrylic epoxy resin emulsion, the raw materials of which include: 10 kg of E03 bisphenol A epoxy resin, 10 kg of E12 bisphenol A epoxy resin, 30 kg of E20 bisphenol A epoxy resin, 25 kg of styrene, 10 kg of methyl methacrylate, 10 kg of butyl methacrylate, 4 kg of hydroxypropyl methacrylate, 1 kg of methacrylic acid, 2 kg of Tween-20, 2 kg of castor oil polyoxyethylene ether EL-80, 4 kg of fatty alcohol polyoxyethylene ether (10) potassium phosphate (effective component 50%), 18 kg of dipropylene glycol propyl ether and 0.5 kg of potassium persulfate.
The preparation method of the water-based acrylic epoxy resin emulsion comprises the following steps:
(1) preparation of nonionic surfactant containing epoxy structure:
heating and melting 2.5 kg of E03 epoxy resin, 2.5 kg of E12 epoxy resin and 10 kg of E20 epoxy resin, heating to 190 ℃, adding 2 kg of Tween-20 and 2 kg of castor oil polyoxyethylene ether EL-80, and uniformly stirring; keeping the temperature of the system at 190 +/-5 ℃ for reacting for 60min, then adding the rest epoxy resin, and continuing to react for 60min to obtain the nonionic surfactant containing the epoxy structure;
(2) preparation of pre-emulsion:
mixing 25 kg of styrene, 10 kg of methyl methacrylate, 10 kg of butyl methacrylate, 4 kg of hydroxypropyl methacrylate and 1 kg of methacrylic acid, and uniformly stirring;
slowly adding a nonionic surfactant containing an epoxy structure into the acrylic monomer, controlling the adding speed to keep the temperature of the system below 60 ℃, adding 18 kg of dipropylene glycol propyl ether after the adding is finished, and uniformly stirring to obtain a first dispersion liquid;
dissolving 4 kg of fatty alcohol-polyoxyethylene ether (10) potassium phosphate in 40 kg of water, and stirring to completely dissolve the potassium phosphate to obtain a second dispersion liquid;
slowly adding the first dispersion into the second dispersion, keeping high-speed stirring in the adding process, continuously stirring for 60min after the adding is finished, and slowly adding 60 kg of water to dilute to obtain a pre-emulsion;
(3) preparation of aqueous acrylic epoxy resin emulsion:
adding 110 kg of deionized water into a reactor with a stirrer, heating to 82 +/-2 ℃, dripping the pre-emulsion and the initiator solution into a dropping funnel, controlling the stirring speed to be 100 +/-10 rpm/min, and introducing cooling water to control the reaction temperature to be 82 +/-2 ℃; controlling the dropping speed, completing the dropping of the pre-emulsion and the initiator solution in 3 hours respectively, and after the dropping is completed, heating to 92 +/-2 ℃ to continue reacting for 1 hour; the initiator solution is prepared by the following preparation method: preparing 2 kilograms of potassium persulfate solution with the concentration of 5 percent by water dispersion, preparing 2 kilograms of solution with the concentration of 5 percent by 5 batches when the potassium persulfate solution is almost dripped, and preparing in batches to keep the activity of the initiator;
(4) cooling water is introduced to reduce the temperature of the materials to below 45 ℃, and the water-based acrylic epoxy resin emulsion is obtained after filtration by a 200-mesh filter bag.
Example 3
This example provides a waterborne acrylic epoxy resin emulsion, the raw materials of which include: 15 kg of E03 bisphenol A epoxy resin, 15 kg of E12 bisphenol A epoxy resin, 40 kg of E20 bisphenol A epoxy resin, 10 kg of styrene, 10 kg of methyl methacrylate, 8 kg of butyl methacrylate, 1.5 kg of hydroxypropyl methacrylate, 0.5 kg of methacrylic acid, 3 kg of Tween-20, 4 kg of castor oil polyoxyethylene ether EL-60, 2 kg of fatty alcohol polyoxyethylene ether (10) potassium phosphate (effective component 50%), 25 kg of dipropylene glycol propyl ether and 0.5 kg of potassium persulfate.
The preparation method of the water-based acrylic epoxy resin emulsion comprises the following steps:
(1) preparation of nonionic surfactant containing epoxy structure:
heating and melting 5 kg of E03 epoxy resin, 5 kg of E12 epoxy resin and 20 kg of E20 epoxy resin, heating to 190 ℃, adding 3 kg of Tween-20 and 4 kg of castor oil polyoxyethylene ether EL-60, and uniformly stirring; keeping the temperature of the system at 190 +/-5 ℃ for reacting for 60min, then adding the rest epoxy resin, and continuing to react for 60min to obtain the nonionic surfactant containing the epoxy structure;
(2) preparation of pre-emulsion:
mixing 10 kg of styrene, 10 kg of methyl methacrylate, 8 kg of butyl methacrylate, 1.5 kg of hydroxypropyl methacrylate and 0.5 kg of methacrylic acid, and uniformly stirring;
slowly adding a nonionic surfactant containing an epoxy structure into the acrylic monomer, controlling the adding speed to keep the temperature of the system below 60 ℃, adding 25 kg of dipropylene glycol propyl ether after the adding is finished, and uniformly stirring to obtain a first dispersion liquid;
dissolving 2 kg of fatty alcohol-polyoxyethylene ether (10) potassium phosphate in 60 kg of water, and stirring to completely dissolve the potassium phosphate to obtain a second dispersion liquid;
slowly adding the first dispersion into the second dispersion, keeping high-speed stirring in the adding process, continuously stirring for 60min after the adding is finished, and slowly adding 60 kg of water to dilute to obtain a pre-emulsion;
(3) preparation of aqueous acrylic epoxy resin emulsion:
adding 110 kg of deionized water into a reactor with a stirrer, heating to 82 +/-2 ℃, dripping the pre-emulsion and the initiator solution into a dropping funnel, controlling the stirring speed to be 100 +/-10 rpm/min, and introducing cooling water to control the reaction temperature to be 82 +/-2 ℃; controlling the dropping speed, completing the dropping of the pre-emulsion and the initiator solution in 3 hours respectively, and after the dropping is completed, heating to 92 +/-2 ℃ to continue reacting for 1 hour; the initiator solution is prepared by the following preparation method: preparing 2 kilograms of potassium persulfate solution with the concentration of 5 percent by water dispersion, preparing 2 kilograms of solution with the concentration of 5 percent by 5 batches when the potassium persulfate solution is almost dripped, and preparing in batches to keep the activity of the initiator;
(4) cooling water is introduced to reduce the temperature of the materials to below 45 ℃, and the water-based acrylic epoxy resin emulsion is obtained after filtration by a 200-mesh filter bag.
Example 4
This example provides a waterborne acrylic epoxy resin emulsion, the raw materials of which include: 5 kg of E03 bisphenol A epoxy resin, 5 kg of E12 bisphenol A epoxy resin, 20 kg of E20 bisphenol A epoxy resin, 30 kg of styrene, 20 kg of methyl methacrylate, 15 kg of butyl methacrylate, 4 kg of hydroxypropyl methacrylate, 1 kg of methacrylic acid, 1 kg of Tween-80, 2 kg of castor oil polyoxyethylene ether EL-80, 6 kg of nonylphenol polyoxyethylene ether (10) potassium phosphate (effective component 50%), 10 kg of dipropylene glycol propyl ether and 0.6 kg of potassium persulfate.
The preparation method of the water-based acrylic epoxy resin emulsion comprises the following steps:
(1) preparation of nonionic surfactant containing epoxy structure:
heating and melting 2.5 kg of E03 epoxy resin, 2.5 kg of E12 epoxy resin and 10 kg of E20 epoxy resin, heating to 190 ℃, adding 3 kg of 1 kg of Tween-80 and 2 kg of castor oil polyoxyethylene ether EL-80, and uniformly stirring; keeping the temperature of the system at 190 +/-5 ℃ for reacting for 60min, then adding the rest epoxy resin, and continuing to react for 60min to obtain the nonionic surfactant containing the epoxy structure;
(2) preparation of pre-emulsion:
mixing and uniformly stirring 30 kg of styrene, 20 kg of methyl methacrylate, 15 kg of butyl methacrylate, 4 kg of hydroxypropyl methacrylate and 1 kg of methacrylic acid;
slowly adding a nonionic surfactant containing an epoxy structure into the acrylic monomer, controlling the adding speed to keep the temperature of the system below 60 ℃, adding 10 kg of dipropylene glycol propyl ether after the adding is finished, and uniformly stirring to obtain a first dispersion liquid;
dissolving 6 kg of potassium nonylphenol polyoxyethylene ether (10) phosphate in 100 kg of water, and stirring to completely dissolve the potassium nonylphenol polyoxyethylene ether phosphate to obtain a second dispersion solution;
slowly adding the first dispersion into the second dispersion, keeping high-speed stirring in the adding process, continuously stirring for 60min after the adding is finished, and slowly adding 60 kg of water to dilute to obtain a pre-emulsion;
(3) preparation of aqueous acrylic epoxy resin emulsion:
adding 80 kg of deionized water into a reactor with a stirrer, heating to 82 +/-2 ℃, dripping the pre-emulsion and the initiator solution into a dropping funnel, controlling the stirring speed to be 100 +/-10 rpm/min, and introducing cooling water to control the reaction temperature to be 82 +/-2 ℃; controlling the dropping speed, completing the dropping of the pre-emulsion and the initiator solution in 3 hours respectively, and after the dropping is completed, heating to 92 +/-2 ℃ to continue reacting for 1 hour; the initiator solution is prepared by the following preparation method: preparing 2 kilograms of potassium persulfate solution with the concentration of 5 percent by water dispersion, preparing 2 kilograms of solution with the concentration of 5 percent by 6 batches when the potassium persulfate solution is almost dripped, and preparing in batches to keep the activity of the initiator;
(4) cooling water is introduced to reduce the temperature of the materials to below 45 ℃, and the water-based acrylic epoxy resin emulsion is obtained after filtration by a 200-mesh filter bag.
Comparative example
Basically, the method is the same as the method of the embodiment 1, and the method only differs from the method in that: the 2 kg of Tween-80 and the 2 kg of castor oil polyoxyethylene ether EL-40 are replaced by 4 kg of alkylphenol polyoxyethylene ether (16) (which is purchased from Huangjiang aman chemical industry and has the trade name of HMNP-16) which is commonly used in the market.
Performance testing
The emulsions prepared in examples 1 to 4 and comparative example were subjected to the following performance tests, and the specific results are shown in tables 1 and 2.
TABLE 1 emulsion Performance test
Description of the detection method:
1. and (3) storage stability at normal temperature: storage at room temperature for 120 days, if there is no precipitation and separation at all, or only a small amount of precipitation or separation, but even if the dispersion is again homogeneous with slight stirring, stability is passed, otherwise no passage is observed.
2. Storage stability at 40 ℃: and (3) storing in an oven at 40 ℃ for 30 days, and if no precipitation and delamination exist at all or only a small amount of precipitation or delamination exists, uniformly dispersing again by slight stirring, wherein the stability is passed, and otherwise, the stability is not passed.
3. Centrifugal stability: the centrifuge at 3000r/min, 30min, if there is no precipitation and delamination at all, or only a small amount of precipitation or delamination, but even if it is slightly stirred, it is again uniformly dispersed, and the stability is passed, otherwise it is not passed.
4. Calcium ion stability (GB/T20623-2006): 0.5g of calcium chloride is added into 100g of distilled water, then 25g of emulsion is added, after shaking and standing for 24 hours, if demulsification, delamination and gelation do not exist, the stability is passed.
5. Freeze-thaw stability (GB/T20623-: freezing at-15 deg.C for 16 hr, thawing at normal temperature for 8 hr, and repeating five times for five times, if not demulsifying, considering stability as passing.
6. Pigment and filler mixing stability: the emulsion is ground in a sand mill with conventional color fillers, and stability is passed if the emulsion is not broken.
TABLE 2 post cure Performance test
Curing method of cured product and specification of performance index
The curing agent is a composition of amino resin and DMP-30(2,4, 6-tri (dimethylaminomethyl) phenol), wherein the amount of the amino resin is 10% of that of the emulsion resin, and the amount of the DMP-30 is 20% of that of the amino resin.
Mixing amino resin and DPM-30 with the emulsion, stirring, and adding 0.1% defoaming agent (specifically: field chemical AT-720B).
And (3) immersing the copper sheet into the emulsion for 30s, taking out the copper sheet, putting the copper sheet into an oven at 130 ℃, and baking the copper sheet for 3 hours for observing the state of a paint film, detecting the volume resistance (the test national standard is GB/T1981.2-2009) and the breakdown strength (the test national standard is GB/T1981.2-2009).
The spiral coil is immersed in the emulsion for 30s, and then taken out and put into an oven at 130 ℃ for baking for 3 hours for testing the adhesive force of the resin (the test national standard is GB/T1981.2-2009).
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (10)
1. The preparation method of the water-based acrylic epoxy resin emulsion is characterized by comprising the following steps:
(1) reacting a nonionic surfactant with an epoxy resin to generate a nonionic surfactant containing an epoxy structure; wherein the nonionic surfactant is polyoxyethylene sorbitan fatty acid ester and/or castor oil polyoxyethylene ether;
(2) mixing an acrylic acid monomer, the nonionic surfactant containing the epoxy structure and a cosolvent to obtain a first dispersion liquid;
dispersing an anionic surfactant in water to obtain a second dispersion;
adding the first dispersion into the second dispersion under stirring, optionally adding water, and dispersing to obtain a pre-emulsion;
(3) respectively dripping the pre-emulsion and the initiator solution into a reactor under the stirring condition to carry out miniemulsion polymerization reaction of acrylic monomers; wherein the initiator solution is prepared by dispersing an initiator in water.
2. The method for preparing the aqueous acrylic epoxy resin emulsion according to claim 1, wherein in the step (1), the charging mass ratio of the nonionic surfactant to the epoxy resin is 1: 10-20.
3. The method for preparing aqueous acrylic epoxy resin emulsion according to claim 1, wherein the reaction is carried out at 220 ℃ and 160 ℃ in step (1).
4. The method for preparing the aqueous acrylic epoxy resin emulsion according to claim 1, wherein the method for preparing the nonionic surfactant containing an epoxy structure in the step (1) comprises the following steps: heating part of epoxy resin, heating to 160-220 ℃, adding a nonionic surfactant for reaction, then adding the rest of epoxy resin for reaction to generate the nonionic surfactant containing the epoxy structure.
5. The method for preparing an aqueous acrylic epoxy resin emulsion according to claim 1, wherein in the step (1), the polyoxyethylene sorbitan fatty acid ester is one or more selected from tween-20, tween-60 and tween-80, and the castor oil polyoxyethylene ether is one or more selected from EL-20, EL-40, EL-60 and EL-90; and/or in the step (1), the epoxy resin is bisphenol A type solid epoxy resin with an epoxy equivalent of more than or equal to 500.
6. The method for preparing the aqueous acrylic epoxy resin emulsion according to claim 1, wherein in the step (2), the charging mass ratio of the nonionic surfactant containing the epoxy structure to the acrylic monomer is 1: 0.25-4; and/or in the step (2), the acrylic monomer, the nonionic surfactant containing the epoxy structure and the cosolvent are controlled to be mixed at the temperature of below 60 ℃; and/or, in the step (2), the acrylic monomer is one or more of styrene, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, hydroxypropyl acrylate, hydroxyethyl acrylate, methyl methacrylate, butyl methacrylate and hydroxypropyl methacrylate.
7. The method for preparing an aqueous acrylic epoxy resin emulsion according to claim 1, wherein in the step (2), the concentration of the anionic surfactant in the second dispersion is 0.5 to 10%, and the anionic surfactant is fatty alcohol/nonylphenol polyoxyethylene ether sulfate and/or fatty alcohol/nonylphenol polyoxyethylene ether phosphate; and/or in the step (2), the cosolvent is one or more of alcohol ester twelve, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, ethylene glycol butyl ether, diethylene glycol propyl ether, propylene glycol butyl ether and propylene glycol methyl ether acetate.
8. The method for preparing the aqueous acrylic epoxy resin emulsion according to claim 1, wherein the step (3) is specifically carried out by: adding water into a reactor, heating to 80-85 ℃, then respectively dropwise adding the pre-emulsion and the initiator solution into the reactor, and controlling the reaction temperature in the dropwise adding process to be 80-85 ℃ all the time; after the dropwise adding is finished, heating to 90-95 ℃ for reaction; and/or, in the step (3), the initiator is ammonium persulfate and/or potassium persulfate; and/or, the preparation method further comprises a step (4): and (4) cooling and filtering the material obtained after the reaction in the step (3) to obtain the water-based acrylic epoxy resin emulsion.
9. An aqueous acrylic epoxy resin emulsion prepared by the method of any one of claims 1 to 9.
10. Use of the aqueous acrylic epoxy resin emulsion according to claim 9 in aqueous insulating paints.
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| CN115011077A (en) * | 2022-07-27 | 2022-09-06 | 苏州太湖电工新材料股份有限公司 | Two-component high-thermal-conductivity epoxy potting resin and preparation method and application thereof |
| CN115260484A (en) * | 2022-07-25 | 2022-11-01 | 万华化学集团股份有限公司 | Preparation method of modified tween-20 and application of modified tween-20 in preparation process of vitamin E emulsion |
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| CN101037564A (en) * | 2006-03-17 | 2007-09-19 | 浙江安邦新材料发展有限公司 | Self-emulsification crylic acid epoxy emulsification agent and its aqueous crylic acid epoxy resin latex |
| CN101117390A (en) * | 2007-09-18 | 2008-02-06 | 天津大学 | Method for preparing aqueous epoxy emulsion |
| CN101921373A (en) * | 2010-08-17 | 2010-12-22 | 华南理工大学 | Acrylic modified epoxy resin emulsion and preparation method thereof |
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| CN101037564A (en) * | 2006-03-17 | 2007-09-19 | 浙江安邦新材料发展有限公司 | Self-emulsification crylic acid epoxy emulsification agent and its aqueous crylic acid epoxy resin latex |
| CN101117390A (en) * | 2007-09-18 | 2008-02-06 | 天津大学 | Method for preparing aqueous epoxy emulsion |
| CN101921373A (en) * | 2010-08-17 | 2010-12-22 | 华南理工大学 | Acrylic modified epoxy resin emulsion and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115260484A (en) * | 2022-07-25 | 2022-11-01 | 万华化学集团股份有限公司 | Preparation method of modified tween-20 and application of modified tween-20 in preparation process of vitamin E emulsion |
| CN115260484B (en) * | 2022-07-25 | 2023-05-30 | 万华化学集团股份有限公司 | Preparation method of modified Tween-20 and application of modified Tween-20 in preparation process of vitamin E emulsion |
| CN115011077A (en) * | 2022-07-27 | 2022-09-06 | 苏州太湖电工新材料股份有限公司 | Two-component high-thermal-conductivity epoxy potting resin and preparation method and application thereof |
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