CN116063631A - Preparation method of aqueous acrylic epoxy resin emulsion - Google Patents
Preparation method of aqueous acrylic epoxy resin emulsion Download PDFInfo
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- CN116063631A CN116063631A CN202211596681.3A CN202211596681A CN116063631A CN 116063631 A CN116063631 A CN 116063631A CN 202211596681 A CN202211596681 A CN 202211596681A CN 116063631 A CN116063631 A CN 116063631A
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Abstract
The invention discloses a preparation method of a water-based acrylic epoxy resin emulsion, which comprises the following steps: reacting a nonionic surfactant with an epoxy resin to form a nonionic surfactant having an epoxy structure; mixing a monomer, a nonionic surfactant containing an epoxy structure and a cosolvent to obtain a first dispersion; the monomer comprises styrene and an acrylic monomer; dispersing an anionic surfactant in water to obtain a second dispersion; adding the first dispersion liquid into the second dispersion liquid under the stirring condition, optionally adding water, and dispersing to prepare 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 monomers; the acrylic acid epoxy resin emulsion prepared by the method has good stability, and the prepared insulating paint has good electric property, adhesive force, paint film state and other properties after solidification, so that the acrylic acid resin and the epoxy resin are organically integrated into a whole, and the respective performance advantages can be fully utilized.
Description
The invention relates to a water-based acrylic epoxy resin emulsion, which is a divisional application of Chinese invention patent application with the application date of 2020, 12-month and 15-day, the application number of 2020114840607 and the name of 'a preparation method and application'.
Technical Field
The invention belongs to the technical field of water-based surface paint, and particularly relates to a preparation method of water-based acrylic epoxy resin emulsion.
Background
The insulating paint is mainly used for coils of electric motors and other insulating parts, fills gaps of the coils, and enables the immersed object to be a compact whole after being solidified, so that the insulating performance, the mechanical performance and the weather resistance of the coils are improved. The insulating paint is generally divided into solvent paint and solvent-free paint, but the solvent paint and solvent-free paint sold in the market at present contain certain volatile harmful substances, so that the insulating paint is harmful to human and environment, is inflammable and explosive, and has potential safety hazards in transportation and storage.
The water-based insulating paint uses 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 insulating paint in the future. The epoxy resin has high strength, strong binding power and good electrical property, is an excellent insulating material, but has poor weather resistance and is easy to age; 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 the two resins are directly mixed, the two resins are seriously phase-separated after curing, and the electrical properties are greatly compromised, so that how to organically combine the two resins becomes a problem which must be solved.
At present, two main methods for combining the two are that epoxy resin and acrylic acid monomer are firstly reacted to generate epoxy ester, then emulsion polymerization is carried out to introduce the epoxy resin into acrylic acid polymer, but the method damages epoxy groups and changes the original excellent performance of the epoxy resin; the other is to mix the epoxy resin and the acrylic monomer in advance and then add the emulsifier to carry out emulsion polymerization reaction, which maintains the characteristic of the epoxy resin, but the mixing amount of the epoxy resin is relatively low, only about 10 percent can be reached, and a large amount of epoxy resin is precipitated from the emulsion when exceeding 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 acrylic epoxy resin emulsion, the acrylic epoxy resin emulsion prepared by the method has good stability, and the prepared insulating paint has good electric property, adhesive force, paint film state and other properties after solidification, so that the acrylic resin and the epoxy resin are organically integrated into a whole, and the respective performance advantages can be fully utilized.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of an aqueous acrylic epoxy resin emulsion, which comprises the following steps:
(1) Reacting a nonionic surfactant with an epoxy resin to produce a nonionic surfactant comprising 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;
dispersing an anionic surfactant in water to obtain a second dispersion;
adding the first dispersion liquid into the second dispersion liquid under the stirring condition, optionally adding water, and dispersing to prepare 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 acid monomers; wherein the initiator solution is prepared by dispersing an initiator in water.
According to some preferred aspects of the invention, in step (1), the ratio of the nonionic surfactant to the epoxy resin is 1:10-20 by mass.
According to some preferred aspects of the invention, in step (1), the reaction is carried out at 160-220 ℃. Further preferably, in step (1), the reaction is carried out at 180-200 ℃.
According to some preferred aspects of the present invention, in step (1), the method for preparing the nonionic surfactant having an epoxy structure comprises the steps of: heating part of epoxy resin, heating to 160-220 ℃, adding a nonionic surfactant, reacting, then adding the rest of epoxy resin, and reacting 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 one or more selected from the group consisting of tween-20, tween-60 and tween-80, and the castor oil polyoxyethylene ether is one or more selected from the group consisting of EL-20, EL-40, EL-60 and EL-90.
According to some preferred aspects of the present invention, in step (1), the epoxy resin is selected from bisphenol a type solid epoxy resins having an epoxy equivalent weight of 500 or more. Further, in the step (1), the bisphenol a type solid epoxy resin may be an E20 bisphenol a type epoxy resin, an E12 bisphenol a type epoxy resin, an E06 bisphenol a type epoxy resin, an 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 mass ratio of the two 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 ratio of the nonionic surfactant having an epoxy structure to the acrylic monomer is 1:0.25-4 by mass.
According to some preferred aspects of the present invention, in step (2), the mixing of the acrylic monomer, the nonionic surfactant having an epoxy structure, and the cosolvent is controlled to be performed at a temperature of 60 ℃ or less.
According to some specific and preferred aspects of the present invention, in step (2), the acrylic monomer is a combination of one or more selected from styrene, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, hydroxypropyl acrylate, hydroxyethyl acrylate, methyl methacrylate, butyl methacrylate, and hydroxypropyl methacrylate.
According to some specific and preferred aspects of the present invention, in step (2), the cosolvent is one or more selected from 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 fatty alcohol/nonylphenol polyoxyethylene ether sulfate and/or fatty alcohol/nonylphenol polyoxyethylene ether phosphate. 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 invention, the specific embodiments of step (3) are: 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 dripping is finished, the temperature is raised to 90-95 ℃ for reaction.
According to some preferred aspects of the invention, in the specific embodiment of the step (3), the dripping speeds of the pre-emulsion and the initiator solution are controlled and the dripping time is controlled to be 2.5-3h respectively.
According to some specific aspects of the invention, in step (3), the initiator is ammonium persulfate and/or potassium persulfate.
According to some specific aspects of the invention, the preparation method further comprises step (4): and (3) 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 in the step (4) is reduced to be lower than 45 ℃.
According to some preferred aspects of the invention, the water employed in the preparation process of the invention is deionized water.
According to some preferred aspects of the invention, in step (3), the initiator solution may be prepared in advance in portions, and then reconstituted in portions during the dropping process, as many batch-wise as possible, so that initiator activity may be maintained.
The invention provides another technical scheme that: the aqueous acrylic epoxy resin emulsion prepared by the preparation method is provided.
The invention also provides application of the aqueous acrylic epoxy resin emulsion prepared by the preparation method in aqueous 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 acid epoxy resin emulsion, a specific nonionic surfactant and epoxy resin are creatively utilized for grafting modification, so that the nonionic surfactant with 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 the nonionic surfactant to participate in the subsequent miniemulsion polymerization, meanwhile, the anionic surfactant is matched for better synergistic effect, the problem that the epoxy resin is separated out in the miniemulsion polymerization process due to the fact that the epoxy resin with high content or high epoxy equivalent is caused by the additional emulsifier is avoided, the stability of the prepared acrylic acid epoxy resin emulsion is greatly improved, the electric property, the adhesive force, the paint film state and other properties of the cured insulating paint 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 should be understood that these examples are presented to illustrate the basic principles, main features and advantages of the present invention, and that the present invention is not limited by the following examples. The implementation conditions employed in the examples may be further adjusted according to specific requirements, and the implementation conditions not specified are generally those in routine experiments. The raw materials used in the examples are all commercially available industrial products.
In the examples which follow, all starting materials are essentially obtained commercially or are prepared by methods conventional in the art, unless otherwise specified. In the examples below, E20 bisphenol A epoxy resin was purchased from Nantong stars; e12 bisphenol A epoxy resin is purchased from Nantong stars; e03 bisphenol A epoxy resin is purchased from Nantong stars; tween-80 is purchased from the chemical industry of Zhejiang Royal, tween-20 is purchased from the chemical industry of Zhejiang Royal, and castor oil polyoxyethylene ether EL40,60,80,90 is purchased from the petrochemical industry of Jiangsu sea-An; the fatty alcohol polyoxyethylene ether (10) potassium phosphate and the nonylphenol polyoxyethylene ether (10) potassium phosphate are all purchased from Jiangsu sea-ampere petrochemical industry, and the acrylic acid monomer is all purchased from Beijing Anxing Tai chemical industry Co.
Example 1
The example provides an aqueous acrylic epoxy resin emulsion, which comprises the following raw materials: 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 (active ingredient 50%), 15 kg of diethylene glycol butyl ether and 0.5 kg of potassium persulfate.
The preparation method of the aqueous acrylic epoxy resin emulsion comprises the following steps:
(1) Preparation of nonionic surfactant containing epoxy structure:
melting 5 kg of E12 epoxy resin and 10 kg of E20 epoxy resin by heating, heating to 190 ℃, adding 2 kg of Tween-80,2 kg of castor oil polyoxyethylene ether EL-40, and uniformly stirring; keeping the system temperature at 190+/-5 ℃ for reaction for 60min, then adding the rest epoxy resin, and continuing the reaction for 60min to obtain the nonionic surfactant containing the epoxy structure;
(2) Preparation of the 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 system temperature below 60 ℃, adding 15 kg of diethylene glycol butyl ether after the adding is finished, and uniformly stirring to obtain a first dispersion;
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;
slowly adding the first dispersion liquid into the second dispersion liquid, 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 by using a dropping funnel, controlling the stirring speed to be 100+/-10 rpm/min, and controlling the reaction temperature to be 82+/-2 ℃ by introducing cooling water; controlling the dropping speed, respectively dropping the pre-emulsion and the initiator solution for 3 hours, and heating to 92+/-2 ℃ to continue to react for 1 hour after the dropping is finished; wherein, the initiator solution adopts the following preparation method: dispersing with water, firstly preparing 2 kg of 5% concentration potassium persulfate solution, and then preparing 2 kg of 5% concentration solution when the solution is just dripped, and preparing the solution in 5 batches, wherein the aim of the batch preparation is to keep the activity of an initiator;
(4) Cooling water is introduced to reduce the temperature of the materials to below 45 ℃, and a 200-mesh filter bag is used for filtering to obtain the water-based acrylic epoxy resin emulsion.
Example 2
The example provides an aqueous acrylic epoxy resin emulsion, which comprises the following raw materials: 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 (active ingredient 50%), 18 kg of dipropylene glycol propyl ether and 0.5 kg of potassium persulfate.
The preparation method of the aqueous acrylic epoxy resin emulsion comprises the following steps:
(1) Preparation of nonionic surfactant containing epoxy structure:
2.5 kg of E03 epoxy resin, 2.5 kg of E12 epoxy resin and 10 kg of E20 epoxy resin are heated to be melted, the temperature is raised to 190 ℃, then 2 kg of Tween-20 and 2 kg of castor oil polyoxyethylene ether EL-80 are added and stirred uniformly; keeping the system temperature at 190+/-5 ℃ for reaction for 60min, then adding the rest epoxy resin, and continuing the reaction for 60min to obtain the nonionic surfactant containing the epoxy structure;
(2) Preparation of the pre-emulsion:
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 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 system temperature below 60 ℃, adding 18 kg of dipropylene glycol propyl ether after the adding is finished, and uniformly stirring to obtain a first dispersion;
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;
slowly adding the first dispersion liquid into the second dispersion liquid, 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 by using a dropping funnel, controlling the stirring speed to be 100+/-10 rpm/min, and controlling the reaction temperature to be 82+/-2 ℃ by introducing cooling water; controlling the dropping speed, respectively dropping the pre-emulsion and the initiator solution for 3 hours, and heating to 92+/-2 ℃ to continue to react for 1 hour after the dropping is finished; wherein, the initiator solution adopts the following preparation method: dispersing with water, firstly preparing 2 kg of 5% concentration potassium persulfate solution, and then preparing 2 kg of 5% concentration solution when the solution is just dripped, and preparing the solution in 5 batches, wherein the aim of the batch preparation is to keep the activity of an initiator;
(4) Cooling water is introduced to reduce the temperature of the materials to below 45 ℃, and a 200-mesh filter bag is used for filtering to obtain the water-based acrylic epoxy resin emulsion.
Example 3
The example provides an aqueous acrylic epoxy resin emulsion, which comprises the following raw materials: 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 (active ingredient 50%), 25 kg of dipropylene glycol propyl ether and 0.5 kg of potassium persulfate.
The preparation method of the aqueous 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 system temperature at 190+/-5 ℃ for reaction for 60min, then adding the rest epoxy resin, and continuing the reaction for 60min to obtain the nonionic surfactant containing the epoxy structure;
(2) Preparation of the pre-emulsion:
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 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 system temperature below 60 ℃, adding 25 kg of dipropylene glycol propyl ether after the adding is finished, and uniformly stirring to obtain a first dispersion;
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;
slowly adding the first dispersion liquid into the second dispersion liquid, 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 by using a dropping funnel, controlling the stirring speed to be 100+/-10 rpm/min, and controlling the reaction temperature to be 82+/-2 ℃ by introducing cooling water; controlling the dropping speed, respectively dropping the pre-emulsion and the initiator solution for 3 hours, and heating to 92+/-2 ℃ to continue to react for 1 hour after the dropping is finished; wherein, the initiator solution adopts the following preparation method: dispersing with water, firstly preparing 2 kg of 5% concentration potassium persulfate solution, and then preparing 2 kg of 5% concentration solution when the solution is just dripped, and preparing the solution in 5 batches, wherein the aim of the batch preparation is to keep the activity of an initiator;
(4) Cooling water is introduced to reduce the temperature of the materials to below 45 ℃, and a 200-mesh filter bag is used for filtering to obtain the water-based acrylic epoxy resin emulsion.
Example 4
The example provides an aqueous acrylic epoxy resin emulsion, which comprises the following raw materials: 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 (active ingredient 50%), 10 kg of dipropylene glycol propyl ether and 0.6 kg of potassium persulfate.
The preparation method of the aqueous acrylic epoxy resin emulsion comprises the following steps:
(1) Preparation of nonionic surfactant containing epoxy structure:
2.5 kg of E03 epoxy resin, 2.5 kg of E12 epoxy resin and 10 kg of E20 epoxy resin are heated to be melted, the temperature is raised to 190 ℃, then 3 kg of 1 kg of Tween-80,2 kg of castor oil polyoxyethylene ether EL-80 is added, and the mixture is stirred uniformly; keeping the system temperature at 190+/-5 ℃ for reaction for 60min, then adding the rest epoxy resin, and continuing the reaction for 60min to obtain the nonionic surfactant containing the epoxy structure;
(2) Preparation of the pre-emulsion:
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 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 system temperature below 60 ℃, adding 10 kg of dipropylene glycol propyl ether after the adding is finished, and uniformly stirring to obtain a first dispersion;
dissolving 6 kg of polyoxyethylene nonylphenol ether (10) potassium phosphate in 100 kg of water, and stirring to completely dissolve the potassium nonylphenol ether and the potassium nonylphenol ether to obtain a second dispersion;
slowly adding the first dispersion liquid into the second dispersion liquid, 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 by using a dropping funnel, controlling the stirring speed to be 100+/-10 rpm/min, and controlling the reaction temperature to be 82+/-2 ℃ by introducing cooling water; controlling the dropping speed, respectively dropping the pre-emulsion and the initiator solution for 3 hours, and heating to 92+/-2 ℃ to continue to react for 1 hour after the dropping is finished; wherein, the initiator solution adopts the following preparation method: dispersing with water, firstly preparing 2 kg of 5% concentration potassium persulfate solution, and then preparing 2 kg of 5% concentration solution in 6 batches when the solution is just about to be dripped, wherein the aim of batch preparation is to keep the activity of an initiator;
(4) Cooling water is introduced to reduce the temperature of the materials to below 45 ℃, and a 200-mesh filter bag is used for filtering to obtain the water-based acrylic epoxy resin emulsion.
Comparative example
Substantially the same as in example 1, the only difference is that: "2 kg Tween-80,2 kg castor oil polyoxyethylene ether EL-40" was replaced with 4 kg alkylphenol polyoxyethylene ether (16) (commercially available from Zhejiang Royal horse chemical, trade name HMNP-16).
Performance testing
The emulsions prepared in examples 1-4 and comparative examples above were subjected to the following performance tests, with specific results shown in tables 1 and 2.
Table 1 emulsion performance test
The detection method comprises the following steps:
1. the storage stability at normal temperature is stable: storage at room temperature for 120 days is considered to be stable if there is no precipitation and delamination at all, or only a small amount of precipitation or delamination, but again even dispersion with gentle stirring is considered to be stable or else not.
2. Storage stability at 40 ℃): storage in an oven at 40 ℃ for 30 days is considered stability passing if there is no precipitation and delamination at all, or only a small amount of precipitation or delamination, but again even dispersion with gentle stirring is considered stability passing, otherwise not passing.
3. Centrifugal stability: centrifuge 3000r/min,30min, if there is no precipitation and delamination at all, or there is only a small amount of precipitation or delamination, but even dispersion again with gentle stirring is considered to be a stable pass, otherwise not pass.
4. Calcium ion stability (GB/T20623-2006): 100g of distilled water is added with 0.5g of calcium chloride, then 25g of emulsion is added, and after shaking up and standing for 24 hours, if demulsification, delamination and gel are not carried out, the stability is passed.
5. Freeze-thaw stability (GB/T20623-2006): freezing at-15deg.C for 16 hr, thawing at normal temperature for 8 hr, and circulating for five times, and if no demulsification is performed, the stability is considered to pass.
6. Pigment and filler mixing stability: the emulsion is ground with the usual pigments and fillers in a sand mill, if no demulsification is considered as a stability pass.
TABLE 2 Performance test after curing
Method for curing cured product and performance index specification
The curing agent is selected from amino resin and DMP-30 (2, 4, 6-tri (dimethylaminomethyl) phenol) composition, the amount of the amino resin is 10% of the amount of the emulsion resin, and the amount of the DMP-30 is 20% of the amount of the amino resin.
The amino resin and DPM-30 were mixed with the emulsion and stirred well and 0.1% defoamer (specifically: field chemical AT-720B) was added.
Immersing the copper sheet into the emulsion for 30s, taking out the copper sheet, putting the copper sheet into a baking oven at 130 ℃ for baking for 3 hours, and observing the state of a paint film, detecting volume resistance (the testing national standard is GB/T1981.2-2009) and breakdown strength (the testing national standard is GB/T1981.2-2009).
The spiral coil was immersed in the emulsion for 30s, and then the spiral coil was taken out and put in an oven at 130 ℃ for baking for 3 hours for testing the adhesive force of the resin (test national standard is GB/T1981.2-2009).
The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement the same, but are not intended to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (10)
1. The preparation method of the aqueous acrylic epoxy resin emulsion is characterized by comprising the following steps of:
(1) Reacting the nonionic surfactant with epoxy resin at 160-220 ℃ to generate the nonionic surfactant containing an epoxy structure; the nonionic surfactant is composed of polyoxyethylene sorbitan fatty acid ester and castor oil polyoxyethylene ether, the feeding mass ratio of the polyoxyethylene sorbitan fatty acid ester to the castor oil polyoxyethylene ether is 0.1-2:1, the epoxy resin is bisphenol A type solid epoxy resin with the epoxy equivalent of more than or equal to 500, and the feeding mass ratio of the nonionic surfactant to the epoxy resin is 1:10-20;
(2) Mixing a monomer, the nonionic surfactant containing the epoxy structure and a cosolvent to obtain a first dispersion;
the monomer comprises styrene, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, hydroxypropyl acrylate, hydroxyethyl acrylate, methyl methacrylate, butyl methacrylate and hydroxypropyl methacrylate;
dispersing an anionic surfactant in water to obtain a second dispersion;
adding the first dispersion liquid into the second dispersion liquid under the stirring condition, optionally adding water, and dispersing to prepare 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 the monomers; wherein the initiator solution is prepared by dispersing an initiator in water.
2. The method for producing an aqueous acrylic epoxy resin emulsion according to claim 1, wherein in the step (1), the epoxy resin is an E20 bisphenol a type epoxy resin, an E12 bisphenol a type epoxy resin, an E06 bisphenol a type epoxy resin or an E03 bisphenol a type epoxy resin, 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.
3. The method for preparing an aqueous acrylic epoxy resin emulsion according to claim 1, wherein in the step (1), the method for preparing the nonionic surfactant having an epoxy structure comprises the steps of: heating part of epoxy resin, heating to 160-220 ℃, adding a nonionic surfactant, reacting, then adding the rest of epoxy resin, and reacting to generate the nonionic surfactant containing the epoxy structure.
4. The method for producing an aqueous acrylic epoxy resin emulsion according to claim 1 or 3, wherein in the step (1), the reaction is carried out at 180 to 200 ℃, and the mass ratio of the polyoxyethylene sorbitan fatty acid ester to the castor oil polyoxyethylene ether is 0.3 to 1.5:1.
5. The method for producing an aqueous acrylic epoxy resin emulsion according to claim 1, wherein in the step (2), the mass ratio of the nonionic surfactant having an epoxy structure to the monomer is 1:0.25-4.
6. The method for producing an aqueous acrylic epoxy resin emulsion according to claim 1, wherein in the step (2), the mixing of the monomer, the nonionic surfactant having an epoxy structure and the cosolvent is controlled to be performed at a temperature of 60 ℃ or lower, and the cosolvent 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.
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 liquid is 0.5-10%, and the anionic surfactant is fatty alcohol/nonylphenol polyoxyethylene ether sulfate and/or fatty alcohol/nonylphenol polyoxyethylene ether phosphate.
8. The method for preparing an aqueous acrylic epoxy resin emulsion according to claim 7, wherein the anionic surfactant is sodium fatty alcohol/polyoxyethylene nonylphenol ether (3-24) sulfate, sodium fatty alcohol/polyoxyethylene nonylphenol ether (3-24) phosphate, potassium fatty alcohol/polyoxyethylene nonylphenol ether (3-24) sulfate, potassium fatty alcohol/polyoxyethylene nonylphenol ether (3-24) phosphate, ammonium fatty alcohol/polyoxyethylene nonylphenol ether (3-24) sulfate, or ammonium fatty alcohol/polyoxyethylene nonylphenol ether (3-24) phosphate.
9. The method for preparing an aqueous acrylic epoxy resin emulsion according to claim 1, wherein the specific embodiment of the step (3) is as follows: 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 dripping is finished, heating to 90-95 ℃ for reaction; wherein the drop time of the pre-emulsion and the initiator solution is controlled to be 2.5-3h respectively.
10. The method of preparing an aqueous acrylic epoxy resin emulsion according to claim 1, wherein the water is deionized water;
the initiator is potassium persulfate, the initiator solution is prepared in batches, a part is prepared in advance, and then the part is prepared in the dripping process.
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