Waterborne epoxy ester resin composition with anti-corrosion properties and its preparation method

Abstract

This invention provides a waterborne epoxy ester resin composition with anti-corrosion properties and its preparation method. A two-step esterification method is designed to prepare epoxy ester intermediates A and B with different double bond types. The first, second, and third components are then added dropwise to a mixture of epoxy ester intermediates A and B in a segmented manner to graft and modify the two epoxy ester intermediates. Utilizing the characteristic that the conjugated double bonds in epoxy ester intermediate A readily copolymerize with vinyl monomers, the grafting rate of vinyl monomers, especially hydrophilic vinyl monomer C, onto the epoxy ester intermediate is increased, reducing the relative content of vinyl monomer self-polymers and improving the water resistance and anti-corrosion performance of the final coating. Furthermore, by introducing a functional repair monomer E, the ungrafted vinyl polymer segments are ensured to participate in the crosslinking reaction during film formation, reducing the adverse effects of ungrafted components on the water resistance and anti-corrosion performance of the waterborne epoxy ester resin.

Description

Technical Field

[0001] This invention belongs to the field of polymer technology, and in particular, relates to a waterborne epoxy ester resin composition with anti-corrosion properties and its preparation method. Background Technology

[0002] Due to their excellent comprehensive performance, waterborne epoxy ester resin coatings are widely used in light to medium-grade industrial corrosion protection. Currently, waterborne epoxy ester resins on the market are typically prepared by modifying epoxy ester intermediate resins with vinyl monomers. This method first involves esterifying epoxy resin and fatty acids to obtain an epoxy ester intermediate. Then, a hydrophilic vinyl monomer (such as acrylic acid) is used to graft copolymerize the epoxy ester intermediate, resulting in a water-dispersible vinyl-modified waterborne epoxy ester resin. During the graft modification process using vinyl monomers, a portion of the vinyl monomers grafts onto the oleic acid segments of the epoxy ester, forming a vinyl polymer-epoxy ester copolymer; a significant portion of the vinyl monomers undergoes self-polymerization, forming vinyl monomer self-polymers. Therefore, waterborne epoxy ester resins prepared using existing techniques are actually mixtures, primarily consisting of vinyl polymer-epoxy ester copolymers, ungrafted epoxy ester polymers, and vinyl monomer self-polymers. Because of the low molecular weight of vinyl monomer self-polymers, the relative content of vinyl monomer self-polymers significantly affects the water resistance and corrosion resistance of waterborne epoxy ester resins.

[0003] Currently, an effective method to reduce the relative content of vinyl monomer self-polymers in waterborne epoxy ester resin compositions is to use fatty acids with a higher content of conjugated double bonds during the preparation of epoxy ester intermediates. However, in the later stages of epoxy ester preparation, conjugated fatty acids tend to self-polymerize during the high-temperature esterification stage (reaching up to 200–230°C), leading to a rapid increase in the viscosity of the waterborne epoxy ester resin, thus making the synthesis of epoxy ester intermediates difficult to control. Furthermore, during the copolymerization of vinyl monomers and epoxy ester intermediates, the conjugated fatty acid segments are highly reactive and prone to gelation. Summary of the Invention

[0004] The purpose of this invention is to provide a waterborne epoxy ester resin composition with anti-corrosion properties, thereby solving the technical problem that the high content of vinyl monomer self-polymers in existing waterborne epoxy ester resin compositions leads to poor water resistance and anti-corrosion performance.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows: A waterborne epoxy ester resin composition with anti-corrosion properties is provided. The raw material composition of the waterborne epoxy ester resin composition with anti-corrosion properties, based on a 100% percentage of the total mass of the raw materials, comprises 18.82–74.59% of a mixed monomer component, 5–20% of epoxy ester intermediate A, 35–60% of epoxy ester intermediate B, and 2.4–5% of a neutralizing agent J. The mixed monomer component comprises a first component, a second component, and a third component. The first component comprises the following components in the following percentages:

[0006] Hydrophilic vinyl monomer C 2-4.5%;

[0007] Initiator D 0.01–0.09%;

[0008] The second component comprises the following components in the following percentages:

[0009] Functional repair monomer E 2.5–12%;

[0010] Non-hydrophilic vinyl monomer F 12-46%;

[0011] Initiator G 0.25–1.5%;

[0012] The third component comprises the following components in the following percentages:

[0013] Initiator H 0.06–0.5%;

[0014] Solvent I: 2-10%.

[0015] The waterborne epoxy ester resin composition with anti-corrosion properties as described in claim 1 is characterized in that, based on 100% of the total mass of the raw materials constituting the epoxy ester intermediate A, the epoxy ester intermediate A comprises the following components in the following percentages:

[0016]

[0017] Optionally, the molar ratio of the fatty acid L to the epoxy resin K is (1.9 to 2.1):1.

[0018] Optionally, the fatty acid L is at least one of tung oil acid and dehydrated ricinoleic acid; the epoxy resin K is a bisphenol A type epoxy resin, and the epoxy value of the bisphenol A type epoxy resin is 0.09 to 0.14 mol / 100g.

[0019] Optionally, the raw material composition of the epoxy ester intermediate B includes fatty acid P, epoxy resin Q, catalyst R, dehydrating solvent S and diluent T. Based on the total mass percentage of fatty acid P and epoxy resin Q as 100%, the mass percentage of catalyst R is 0.1-3%, the mass percentage of dehydrating solvent S is 2-10%, and the mass percentage of diluent T is 30-55%.

[0020] Optionally, the mass ratio of the fatty acid P to the epoxy resin Q is (60-122):100.

[0021] Optionally, the fatty acid P is at least one of oleic acid, linoleic acid, linolenic acid, tall oleic acid, and soybean oil, and the epoxy resin Q is a bisphenol A type epoxy resin with an epoxy value of 0.04 to 0.22 mol / 100g.

[0022] Optionally, the hydrophilic vinyl monomer C is at least one of acrylic acid and methacrylic acid, and the non-hydrophilic vinyl monomer F is at least one of methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isobornyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, isobornyl methacrylate, benzyl acrylate, and styrene.

[0023] Another objective of this invention is to provide a method for preparing a waterborne epoxy ester resin composition with anti-corrosion properties.

[0024] To achieve the above objectives, the technical solution adopted by the present invention is: to provide a method for preparing a waterborne epoxy ester resin composition with anti-corrosion properties, which can be prepared from any of the above solutions, wherein the method for preparing the waterborne epoxy ester resin composition with anti-corrosion properties includes the following steps:

[0025] Step S01: Weigh each raw material according to the components of the corrosion-resistant waterborne epoxy ester resin composition according to any one of claims 1 to 8;

[0026] Step S02: Mix epoxy ester intermediate A and epoxy ester intermediate B, and stir until homogeneous to obtain epoxy ester intermediate mixture.

[0027] Step S03: Heat the epoxy ester intermediate mixture to 110-140°C, and add the mixed monomer component dropwise to the epoxy ester intermediate mixture;

[0028] Step S04: The epoxy ester intermediate mixture containing the mixed monomer components is kept at 130-150°C for 1-2 hours, then cooled to 90-100°C, and neutralizing agent J is added to prepare a waterborne epoxy ester resin composition with anti-corrosion properties.

[0029] Optionally, in step S03, the mixed monomer component includes a first component, a second component, and a third component. During the process of adding the mixed monomer component to the epoxy ester intermediate mixed component, the first component is added dropwise over 0.5 to 1.5 hours, followed by the second component over 3 to 4 hours. Then, the temperature of the epoxy ester intermediate mixed component is adjusted to 130 to 150°C, and the third component is added dropwise over 1 to 2 hours.

[0030] Compared with the prior art, one or more technical solutions in the embodiments of the present invention have at least one of the following beneficial effects:

[0031] The corrosion-resistant waterborne epoxy ester resin composition in this embodiment of the invention, or the corrosion-resistant waterborne epoxy ester resin composition prepared by the preparation method in this embodiment of the invention, is prepared by a low-temperature ring-opening esterification reaction to obtain an epoxy ester intermediate A with a high content of conjugated double bonds. Utilizing the high copolymerization activity of the conjugated double bonds in epoxy ester intermediate A with vinyl monomers, the grafting rate of fatty acid graft polymerization in vinyl monomers and epoxy esters is effectively increased, thereby reducing the relative content of vinyl monomer self-polymers and significantly improving the water resistance and corrosion resistance of the waterborne epoxy ester resin coating. Furthermore, during the graft copolymerization of vinyl monomers and epoxy ester intermediates, a segmented dropwise addition process is adopted, with the first, second, and third components added sequentially. When there are many grafting sites in the epoxy ester intermediate, the first component containing hydrophilic vinyl monomer C is added first, effectively increasing the grafting rate of hydrophilic vinyl monomer C, thereby improving the water resistance and corrosion resistance of the waterborne epoxy ester resin composition. Secondly, the second step involves adding a second component containing the functional repair monomer E and the non-hydrophilic vinyl monomer F. As the grafting sites in the epoxy ester intermediate gradually decrease, this effectively prevents the self-polymerization of some of the non-hydrophilic vinyl monomer F in the second component. Simultaneously, by designing and introducing the functional repair monomer E to copolymerize with the non-hydrophilic vinyl monomer F, during the film formation process of the waterborne epoxy ester composition, the polymer that did not participate in the graft copolymerization contains linolenic acid segments, which can undergo oxidative crosslinking with the fatty acid segments in the waterborne epoxy ester resin. This effectively reduces the adverse effects of this ungrafted component on the performance of the waterborne epoxy ester resin, thereby further improving the water resistance and corrosion resistance of the waterborne epoxy ester resin. Detailed Implementation

[0032] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. It should be noted that the terms "first," "second," and "third" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features.

[0033] This invention provides a waterborne epoxy ester resin composition with anti-corrosion properties. The raw material composition of this waterborne epoxy ester resin composition, based on 100% of the total mass of the raw materials, includes 18.82–74.59% of a mixed monomer component, 5–20% of epoxy ester intermediate A, 35–60% of epoxy ester intermediate B, and 2.4–5% of a neutralizing agent J. The mixed monomer component includes a first component, a second component, and a third component. The first component includes the following components in the following percentages:

[0034] Hydrophilic vinyl monomer C 2-4.5%;

[0035] Initiator D 0.01–0.09%;

[0036] The second component comprises the following components in the following percentages:

[0037] Functional repair monomer E 2.5–12%;

[0038] Non-hydrophilic vinyl monomer F 12-46%;

[0039] Initiator G 0.25–1.5%;

[0040] The third component comprises the following components in the following percentages:

[0041] Initiator H 0.06–0.5%;

[0042] Solvent I: 2-10%.

[0043] In some embodiments, epoxy ester intermediate A comprises the following components in percentages based on 100% of the total mass of the raw materials constituting epoxy ester intermediate A:

[0044]

[0045] It should be noted that in some of these embodiments, the molar ratio of fatty acid L to epoxy resin K is (1.9–2.1):1.

[0046] It should be noted that in some embodiments, fatty acid L is at least one of tung oil acid and dehydrated ricinoleic acid; epoxy resin K is bisphenol A type epoxy resin, and the epoxy value of bisphenol A type epoxy resin is 0.09-0.14 mol / 100g. The polymerization inhibitor M is at least one of 2,6-di-tert-butyl-p-cresol and hydroquinone; the catalyst N is triphenylphosphine; and the solvent O is at least one of ethylene glycol butyl ether, diethylene glycol butyl ether, ethylene glycol tert-butyl ether, propylene glycol methyl ether, propylene glycol butyl ether, and dipropylene glycol butyl ether.

[0047] It should be noted that, in some embodiments, the specific preparation steps of epoxy ester intermediate A include: adding 25.99 g of fatty acid L, 77.87 g of epoxy resin K, 0.1 g of polymerization inhibitor M and 1.04 g of catalyst N to a reactor equipped with a stirrer and a thermometer; stirring and heating to 140±5℃ under nitrogen protection to carry out a ring-opening esterification reaction; maintaining the temperature for 5 hours; lowering the reaction temperature to 90-95℃; and adding 45 g of solvent O to obtain epoxy ester intermediate A.

[0048] It should be noted that, in some embodiments, the raw material composition of epoxy ester intermediate B includes fatty acid P, epoxy resin Q, catalyst R, dehydrating solvent S and diluent T. Based on the total mass percentage of fatty acid P and epoxy resin Q as 100%, the mass percentage of catalyst R is 0.1-3%, the mass percentage of dehydrating solvent S is 2-10%, and the mass percentage of diluent T is 30-55%.

[0049] It should be noted that in some embodiments, the mass ratio of fatty acid P to epoxy resin Q is (60-122):100.

[0050] It should be noted that in some embodiments, fatty acid P is at least one of oleic acid, linoleic acid, linolenic acid, tall oleic acid, and soybean oil; epoxy resin Q is bisphenol A type epoxy resin with an epoxy value of 0.04–0.22 mol / 100g; catalyst R is at least one of triphenylphosphine, dibutyltin dilaurate, and monobutyltin oxide; dehydrating solvent S is at least one of pseudotrimethylbenzene, mesitylene, C9 aromatic hydrocarbons, methyl isobutyl ketone, and solvent oil D40; and diluent T is at least one of ethylene glycol butyl ether, diethylene glycol butyl ether, ethylene glycol tert-butyl ether, propylene glycol methyl ether, propylene glycol butyl ether, and dipropylene glycol butyl ether.

[0051] It should be noted that, in some embodiments, the specific preparation steps of epoxy ester intermediate B include: adding fatty acid P, epoxy resin Q, catalyst R, and dehydrating solvent S into a reaction vessel equipped with a water separator, slowly raising the temperature to 100-130°C, maintaining the temperature for 1 hour to melt the epoxy resin, starting the stirrer, gradually raising the temperature to 200-230°C at a rate of 20°C / hour, maintaining the temperature for 5 hours, cooling to 160-180°C, removing the dehydrating solvent S under vacuum, cooling to 90-100°C, and adding the diluent T while stirring to obtain epoxy ester intermediate B.

[0052] It should be noted that, in some embodiments, the hydrophilic vinyl monomer C is at least one of acrylic acid and methacrylic acid, and the non-hydrophilic vinyl monomer F is at least one of methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isobornyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, isobornyl methacrylate, benzyl acrylate, and styrene.

[0053] It should be noted that, in some embodiments, the initiator D is at least one of tert-amyl peroxide-2-ethylhexanoate, tert-butyl peroxide-2-ethylhexanoate, tert-butyl peroxide acetate, 1,1-di-tert-butylperoxide-3,3,5-trimethylcyclohexane, 1,1-di-tert-butylperoxidecyclohexane, 2,2-di(tert-butylperoxide)butane, and tert-butyl peroxide.

[0054] It should be noted that, in some embodiments, the initiator G is at least one of tert-amyl peroxide-2-ethylhexanoate, tert-butyl peroxide-2-ethylhexanoate, tert-butyl peroxide acetate, 1,1-di-tert-butylperoxide-3,3,5-trimethylcyclohexane, 1,1-di-tert-butylperoxidecyclohexane, 2,2-di(tert-butylperoxide)butane, and tert-butyl peroxide.

[0055] It should be noted that, in some embodiments, the initiator H is at least one of di-tert-butyl peroxide and di-tert-pentyl peroxide.

[0056] It should be noted that, in some embodiments, solvent I is at least one of ethylene glycol butyl ether, diethylene glycol butyl ether, ethylene glycol tert-butyl ether, propylene glycol methyl ether, propylene glycol butyl ether, and dipropylene glycol butyl ether.

[0057] It should be noted that in some embodiments, the functional repair monomer E is prepared by a ring-opening esterification reaction of glycidyl methacrylate and linolenic acid. The specific preparation steps of functional repair monomer E include: adding 556 g of linolenic acid, 142 g of glycidyl methacrylate, 0.7 g of polymerization inhibitor 2,6-di-tert-butyl-p-cresol, and 7.0 g of catalyst triphenylphosphine to a reactor equipped with a stirrer and thermometer. Under nitrogen protection, the mixture is stirred and heated to 140±5℃ for a ring-opening esterification reaction. After maintaining this temperature for 5 hours, the reaction temperature is lowered to 90-95℃ to prepare functional repair monomer E.

[0058] The present invention also provides a method for preparing the corrosion-resistant waterborne epoxy ester resin composition described in the above embodiments.

[0059] In some embodiments, the method for preparing the corrosion-resistant waterborne epoxy ester resin composition provided by the present invention includes the following steps:

[0060] Step S01: Weigh each raw material according to the components contained in the corrosion-resistant waterborne epoxy ester resin composition in any of the above embodiments;

[0061] Step S02: Mix epoxy ester intermediate A and epoxy ester intermediate B, and stir until homogeneous to obtain epoxy ester intermediate mixture.

[0062] Step S03: Heat the epoxy ester intermediate mixture to 110-140°C and add the mixed monomer component dropwise to the epoxy ester intermediate mixture;

[0063] Step S04: The epoxy ester intermediate mixture containing the mixed monomer components is kept at 130-150°C for 1-2 hours, then cooled to 90-100°C, and neutralizing agent J is added to prepare a waterborne epoxy ester resin composition with anti-corrosion properties.

[0064] The waterborne epoxy ester resin composition with corrosion resistance provided by the embodiment of the present invention is prepared by a two-step esterification method to prepare epoxy ester intermediates A and B with different double bond types. The first, second, and third components are then added dropwise to the mixture of epoxy ester intermediates A and B in a segmented manner to graft and modify the two epoxy ester intermediates. Utilizing the characteristic that the conjugated double bonds in epoxy ester intermediate A are more readily copolymerized with vinyl monomers, the grafting rate of vinyl monomers, especially hydrophilic vinyl monomer C, onto the epoxy ester intermediate is increased, thereby improving the water resistance and corrosion resistance of the waterborne epoxy ester resin coating. Furthermore, by introducing a functional repair monomer E, the ungrafted vinyl polymer segments in the waterborne epoxy ester resin composition are ensured to participate in the crosslinking reaction during film formation, reducing the adverse effects of ungrafted components on resin properties, thereby further improving the initial water resistance and corrosion resistance of the coating. Furthermore, in the preparation of epoxy ester intermediate A, by introducing fatty acids with a high content of conjugated double bonds, the high content of conjugated double bonds in fatty acids is avoided from participating in the high-temperature esterification reaction, thus solving the technical problem of high viscosity and easy gelation in the preparation of epoxy ester intermediate A.

[0065] To enable those skilled in the art to clearly understand the above-described implementation details and operations of the present invention, and to demonstrate the significant improvement in the performance of the corrosion-resistant waterborne epoxy ester resin composition and its preparation method, the following examples illustrate the implementation of the present invention.

[0066] The raw materials involved in the examples and comparative examples include:

[0067] NPES-901 epoxy resin, NPES-904 epoxy resin, NPES-907 epoxy resin, industrial grade, Nan Ya Electronic Materials (Kunshan) Co., Ltd.; Ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol butyl ether, industrial grade, Nanjing Gutian Chemical Co., Ltd.; Ethylene glycol tert-butyl ether, industrial grade, Maruzen, Japan; Pseudotrimethylbenzene, methyl isobutyl ketone, chemically pure, Shanghai Aladdin Biochemical Technology Co., Ltd.; C9 aromatics, industrial grade, Nanjing Refinery Co., Ltd.; Monobutyltin oxide, industrial grade. Industrial grade, Shanghai Titan Technology Co., Ltd.; 2,6-di-tert-butyl-p-cresol, ultrapure grade, Shanghai Aladdin Biochemical Technology Co., Ltd.; Triphenylphosphine, industrial grade, Shanghai Lingfeng Chemical Reagent Co., Ltd.; Oleic acid, linoleic acid, linolenic acid, chemically pure, Shanghai Maclean Biochemical Technology Co., Ltd.; Tung oil acid, dehydrated ricinoleic acid, soybean oil acid, acrylic acid, methacrylic acid, styrene, butyl methacrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl acrylate, industrial grade, CNOOC Changzhou Environmental Protection Coatings Co., Ltd.; Di-tert-amyl peroxide (DTAP), di-tert-butyl peroxide (DTBP), 1,1-di-tert-butylperoxide-3,3,5-trimethylcyclohexane (TMCH), tert-butyl peroxide (TBPB), industrial grade, AkzoNobel; tert-amyl peroxide-2-ethylhexanoate (TAPO), industrial grade, Shandong Haijing New Materials Co., Ltd.; 2,2-di(tert-butylperoxide)butane, industrial grade, Nantong Runfeng Petrochemical Co., Ltd.; N, N-Dimethylethanolamine (DMEA), industrial grade, Eastman Chemical Company, USA; AMP-95, industrial grade, Dow Chemical Company, USA; High-efficiency composite drying agent TY-CQ-5020WD, industrial grade, Shanghai Taoyuan Cobalt Industry Co., Ltd.; BYK-190, BYK-022, BYK-346, industrial grade, BYK Corporation; Carbon black, industrial grade, Degussa; Precipitated barium sulfate, industrial grade, Nanfeng Group; Zinc phosphate, industrial grade, Guangxi Xinjing Technology Co., Ltd.; Strontium chrome yellow, industrial grade, Changzhou Deshuo Chemical Co., Ltd. Airex 901W industrial grade, DIGIC; ACRYSOL TM RM-8W, industrial grade, Dow Chemical. Unless otherwise stated, all raw materials used in the examples and comparative examples are commercially available products.

[0068] Example 1

[0069] Preparation of epoxy ester intermediate A1: In a reactor equipped with a stirrer and thermometer, 25.99 g of tung oil acid, 77.87 g of NPES-904 epoxy resin, 0.1 g of polymerization inhibitor 2,6-di-tert-butyl-p-cresol, and 1.04 g of catalyst triphenylphosphine were added. Under nitrogen protection, the mixture was stirred and heated to 140±5℃ for ring-opening esterification reaction. After holding at this temperature for 5 hours, the reaction temperature was lowered to 90℃, and 45 g of ethylene glycol tert-butyl ether was added to obtain epoxy ester intermediate A1.

[0070] Example 2

[0071] Preparation of epoxy ester intermediate A2: In a reactor equipped with a stirrer and thermometer, 25.99 g of dehydrated ricinoleic acid, 77.87 g of NPES-904 epoxy resin, 0.1 g of polymerization inhibitor 2,6-di-tert-butyl-p-cresol, and 1.04 g of catalyst triphenylphosphine were added. Under nitrogen protection, the mixture was stirred and heated to 140±5℃ for ring-opening esterification reaction. After holding at this temperature for 5 hours, the reaction temperature was lowered to 90℃, and 45 g of ethylene glycol butyl ether was added to obtain epoxy ester intermediate A2.

[0072] Example 3

[0073] Preparation of epoxy ester intermediate B1: 163.82 g of soybean oil acid, 148.99 g of NPES-901 epoxy resin, 3.13 g of triphenylphosphine, and 15.64 g of mesitylene were added to a reaction vessel equipped with a water separator. The temperature was slowly increased to 100–130 °C and kept at this temperature for 1 hour to melt the epoxy resin. Stirring was started, and the temperature was gradually increased to 210 °C at a rate of 20 °C / hour. After holding at 210 ± 5 °C for 5 hours, the temperature was lowered to 160–180 °C, and the mesitylene was removed by vacuuming. The temperature was then lowered to 90–100 °C, and 134.06 g of ethylene glycol tert-butyl ether was added while stirring to obtain epoxy ester intermediate B1.

[0074] Example 4

[0075] Preparation of epoxy ester intermediate B2: 69.7 g of linolenic acid, 140.1 g of linoleic acid, 139.41 g of NPES-901 epoxy resin, 34.85 g of NPES-907 epoxy resin, 7.68 g of triphenylphosphine, and 19.2 g of C9 aromatic hydrocarbon were added to a reaction vessel equipped with a water separator. The temperature was slowly increased to 100–130 °C and held at this temperature for 1 hour to melt the epoxy resin. Stirring was started, and the temperature was gradually increased to 220 °C at a rate of 20 °C / hour. After holding at 220 ± 5 °C for 5 hours, the temperature was lowered to 160–180 °C, and the C9 aromatic hydrocarbon was removed by vacuum. The temperature was then lowered to 90–100 °C, and 69.70 g of ethylene glycol butyl ether and 58.55 g of ethylene glycol tert-butyl ether were added while stirring to obtain epoxy ester intermediate B2.

[0076] Example 5

[0077] Preparation of epoxy ester intermediate B3: 175.85 g of linolenic acid, 100.91 g of NPES-904 epoxy resin, 43.24 g of NPES-907 epoxy resin, 9.6 g of monobutyltin oxide, and 25.6 g of methyl isobutyl ketone were added to a reaction vessel equipped with a water separator. The temperature was slowly increased to 100–130 °C and held at this temperature for 1 hour to melt the epoxy resin. Stirring was started, and the temperature was gradually increased to 220 °C at a rate of 20 °C / hour. After holding at 220 ± 5 °C for 5 hours, the temperature was lowered to 160–180 °C, and methyl isobutyl ketone was removed by vacuum. The temperature was then lowered to 90–100 °C, and 92.73 g of propylene glycol butyl ether and 72.07 g of propylene glycol methyl ether were added while stirring to obtain epoxy ester intermediate B3.

[0078] Example 6

[0079] Preparation of functional repair monomer E: In a reactor equipped with a stirrer and thermometer, 556 g of linolenic acid, 142 g of glycidyl methacrylate, 0.7 g of polymerization inhibitor 2,6-di-tert-butyl-p-cresol, and 7 g of catalyst triphenylphosphine were added. Under nitrogen protection, the mixture was stirred and heated to 140±5℃ for ring-opening esterification reaction. After holding at this temperature for 5 hours, the reaction temperature was lowered to 90℃ and the mixture was discharged to obtain functional repair monomer E.

[0080] Examples 7-11 and Comparative Examples 1-7, based on the synthesis in Examples 1-6, describe the preparation of waterborne epoxy ester resin compositions with anti-corrosion properties. It should be noted that before synthesizing the waterborne epoxy ester resin compositions with anti-corrosion properties, a mixed monomer component was prepared according to the formulation in any of the above examples. The mixed monomer component includes a first component, a second component, and a third component. The first component includes a hydrophilic vinyl monomer C and an initiator D; the second component includes a functional repair monomer E, a non-hydrophilic vinyl monomer F, and an initiator G; and the third component includes an initiator H and a solvent I.

[0081] Example 7

[0082] The preparation method of waterborne epoxy ester resin composition a includes the following steps: According to the formulation in Table 1, 150 g of epoxy ester intermediate A1 and 450 g of epoxy ester intermediate B1 are mixed and stirred evenly. The mixture is then heated to 115-125°C, and the mixed monomer components are added dropwise. First, the first component containing hydrophilic vinyl monomer C is added dropwise, and the addition is completed within 0.5-1.5 hours at 115-125°C. After the first component is added, the second component containing functional repair monomer E and non-hydrophilic vinyl monomer F is added dropwise at 115-125°C, and the addition is completed within 3-4 hours. Then, the temperature is adjusted to 130-140°C, and the third component is added dropwise, and the addition is completed within 1-2 hours. After the addition is completed, the temperature is maintained at 130-140°C for 1-2 hours, then cooled to 90-100°C, and neutralizing agent J is added to prepare waterborne epoxy ester resin composition a.

[0083] Example 8

[0084] The preparation method of waterborne epoxy ester resin composition b includes the following steps: According to the formulation in Table 1, 200 g of epoxy ester intermediate A2 and 350 g of epoxy ester intermediate B2 are mixed and stirred evenly. The mixture is then heated to 110-120°C, and the mixed monomer components are added dropwise. First, the first component containing hydrophilic vinyl monomer C is added dropwise, and the addition is completed within 0.5-1.5 hours at 110-120°C. After the first component is added, the second component containing functional repair monomer E and non-hydrophilic vinyl monomer F is added dropwise at 110-120°C, and the addition is completed within 3-4 hours. Then, the temperature is adjusted to 145-150°C, and the third component is added dropwise, and the addition is completed within 1-2 hours. After the addition is completed, the temperature is maintained at 145-150°C for 1-2 hours, then cooled to 90-100°C, and neutralizing agent J is added to prepare waterborne epoxy ester resin composition b.

[0085] Example 9

[0086] The preparation method of waterborne epoxy ester resin composition c includes the following steps: According to the formulation in Table 1, 50 grams of epoxy ester intermediate A1 and 380 grams of epoxy ester intermediate B3 are mixed and stirred evenly. The mixture is then heated to 125-135°C, and the mixed monomer components are added dropwise. First, the first component containing hydrophilic vinyl monomer C is added dropwise, and the addition is completed within 0.5-1.5 hours at 125-135°C. After the first component is added, the second component containing functional repair monomer E and non-hydrophilic vinyl monomer F is added dropwise at 125-135°C, and the addition is completed within 3-4 hours. Then, the temperature is adjusted to 140-145°C, and the third component is added dropwise, and the addition is completed within 1-2 hours. After the addition is completed, the temperature is maintained at 140-145°C for 1-2 hours, then cooled to 90-100°C, and neutralizing agent J is added to prepare waterborne epoxy ester resin composition c.

[0087] Example 10

[0088] The preparation method of waterborne epoxy ester resin composition d includes the following steps: According to the formulation in Table 1, 80 grams of epoxy ester intermediate A2 and 600 grams of epoxy ester intermediate B2 are mixed and stirred evenly. The mixture is then heated to 125-135°C, and the mixed monomer components are added dropwise. First, the first component containing hydrophilic vinyl monomer C is added dropwise, and the addition is completed within 0.5-1.5 hours at 125-135°C. After the first component is added, the second component containing functional repair monomer E and non-hydrophilic vinyl monomer F is added dropwise at 125-135°C, and the addition is completed within 3-4 hours. Then, the temperature is adjusted to 130-140°C, and the third component is added dropwise, and the addition is completed within 1-2 hours. After the addition is completed, the temperature is maintained at 130-140°C for 1-2 hours, then cooled to 90-100°C, and neutralizing agent J is added to prepare waterborne epoxy ester resin composition d.

[0089] Example 11

[0090] The preparation method of the waterborne epoxy ester resin composition e includes the following steps: According to the formulation in Table 1, 180 g of epoxy ester intermediate A2 and 500 g of epoxy ester intermediate B3 are mixed and stirred evenly. The mixture is then heated to 130–140 °C, and the mixed monomer components are added dropwise. First, the first component containing hydrophilic vinyl monomer C is added dropwise, and the addition is completed within 0.5–1.5 hours at 130–140 °C. After the first component is added, the second component containing functional repair monomer E and non-hydrophilic vinyl monomer F is added dropwise at 130–140 °C, and the addition is completed within 3–4 hours. Then, the temperature is adjusted to 140–150 °C, and the third component is added dropwise, and the addition is completed within 1–2 hours. After the addition is completed, the mixture is kept at 140–150 °C for 1–2 hours, cooled to 90–100 °C, and a neutralizing agent J is added to prepare the waterborne epoxy ester resin composition e.

[0091] Comparative Example 1

[0092] Preparation of waterborne epoxy ester resin composition f: According to the formulation in Table 2, 600g of epoxy ester intermediate A1 was stirred evenly, and the temperature was raised to 115-125℃. The mixed monomer components were then added dropwise. First, the first component, containing the hydrophilic vinyl monomer C, was added dropwise over 0.5-1.5 hours at 115-125℃. After the first component was added, the second component, containing the functional repair monomer E and the non-hydrophilic vinyl monomer F, was added dropwise over 3-4 hours at 115-125℃. Then, the temperature was adjusted to 130-140℃, and the third component was added dropwise over 1-2 hours. After the addition, the temperature was maintained at 130-140℃ for 1-2 hours, then lowered to 90-100℃, and neutralizing agent J was added. During the dropwise addition of the mixed monomer components, the resin viscosity became too high, causing gelation, and the reaction was stopped, failing to prepare the waterborne epoxy ester resin composition f.

[0093] Table 1. Raw material composition and formulation of the corrosion-resistant waterborne epoxy ester resin compositions in Examples 7 to 11.

[0094]

[0095] Comparative Example 2

[0096] Preparation of waterborne epoxy ester resin composition h: According to the formulation in Table 2, 600g of epoxy ester intermediate B1 was stirred evenly, and the temperature was raised to 115-125℃. The mixed monomer components were then added dropwise. First, the first component containing hydrophilic vinyl monomer C was added dropwise, and the addition was completed within 0.5-1.5 hours at 115-125℃. After the first component was added, the second component containing functional repair monomer E and non-hydrophilic vinyl monomer F was added dropwise at 115-125℃, and the addition was completed within 3-4 hours. Then, the temperature was adjusted to 130-140℃ and the third component was added dropwise, and the addition was completed within 1-2 hours. After the addition was completed, the temperature was maintained at 130-140℃ for 1-2 hours, and then the temperature was lowered to 90-100℃. Neutralizing agent J was added to prepare the waterborne epoxy ester resin composition h.

[0097] Comparative Example 3

[0098] Preparation of waterborne epoxy ester resin composition i: According to the formulation in Table 2, 600 g of epoxy ester intermediate X was stirred evenly, and the temperature was raised to 115-125℃. The mixed monomer components were then added dropwise. First, the first component containing hydrophilic vinyl monomer C was added dropwise over 0.5-1.5 hours at 115-125℃. After the first component was added, the second component containing functional repair monomer E and non-hydrophilic vinyl monomer F was added dropwise over 3-4 hours at 115-125℃. Then, the temperature was adjusted to 130-140℃ and the third component was added dropwise over 1-2 hours. After the addition was completed, the temperature was maintained at 130-140℃ for 1-2 hours, then cooled to 90-100℃, and neutralizing agent J was added to prepare waterborne epoxy ester resin composition i.

[0099] The preparation process of epoxy ester intermediate X is as follows: 25.99 g of tung oil acid, 163.82 g of soybean oil acid, 148.99 g of NPES-901 epoxy resin, 77.87 g of NPES-904 epoxy resin, 4.17 g of triphenylphosphine catalyst, 0.1 g of 2,6-di-tert-butyl-p-cresol polymerization inhibitor, and 15.64 g of mesitylene are added to a reaction vessel equipped with a water separator, and the temperature is slowly increased to 100-130°C. The epoxy resin was melted at 0℃ and held for 1 hour. The temperature was then slowly increased to 100-130℃ and held for 1 hour to melt the epoxy resin. Stirring was started, and the temperature was gradually increased to 220℃ at a rate of 20℃ / hour. After holding at 220±5℃ for 5 hours, the temperature was lowered to 160-180℃. Trimethylbenzene was removed by vacuuming, and the temperature was lowered to 90-100℃. 179.09 g of ethylene glycol tert-butyl ether was added while stirring to prepare epoxy ester intermediate X.

[0100] Comparative Example 4

[0101] Preparation of waterborne epoxy ester resin composition j: According to the formulation in Table 1, 150 g of epoxy ester intermediate A1 and 450 g of epoxy ester intermediate B1 were mixed and stirred evenly. The mixture was then heated to 115–125 °C, and the mixed monomer components were added dropwise. The first and second components were mixed and added dropwise simultaneously, with the addition temperature maintained at 115–125 °C and the addition time controlled at 4–5 hours. Then, the temperature was adjusted to 130–140 °C, and the third component was added dropwise. The addition was completed within 1–2 hours. After the addition was completed, the temperature was maintained at 130–140 °C for 1–2 hours, then cooled to 90–100 °C, and neutralizing agent J was added to prepare waterborne epoxy ester resin composition j.

[0102] Comparative Example 5

[0103] Preparation of waterborne epoxy ester resin composition k: According to the formulation in Table 2, 150 g of epoxy ester intermediate A1 and 450 g of epoxy ester intermediate B1 were mixed and stirred evenly. The mixture was then heated to 115–125 °C, and the mixed monomer components were added dropwise. First, the first component containing hydrophilic vinyl monomer C was added dropwise over 0.5–1.5 hours at 115–125 °C. After the first component was added, the second component containing non-hydrophilic vinyl monomer F was added dropwise over 3–4 hours at 115–125 °C. Then, the temperature was adjusted to 130–140 °C, and the third component was added dropwise over 1–2 hours. After the addition was completed, the mixture was kept at 130–140 °C for 1–2 hours, then cooled to 90–100 °C, and neutralizing agent J was added to prepare the waterborne epoxy ester resin composition k.

[0104] Comparative Example 6

[0105] The preparation method of waterborne epoxy ester resin composition 1 includes the following steps: According to the formulation in Table 2, 150 g of epoxy ester intermediate A1 and 450 g of epoxy ester intermediate B1 are mixed and stirred evenly. The mixture is then heated to 125-135°C, and the mixed monomer components are added dropwise. First, the first component containing hydrophilic vinyl monomer C is added dropwise, and the addition is completed within 0.5-1.5 hours at 125-135°C. After the first component is added, the second component containing functional repair monomer E and non-hydrophilic vinyl monomer F is added dropwise at 125-135°C, and the addition is completed within 3-4 hours. Then, the temperature is adjusted to 140-145°C, and the third component is added dropwise, and the addition is completed within 1-2 hours. After the addition is completed, the mixture is kept at 130-140°C for 1-2 hours, cooled to 90-100°C, and neutralizing agent J is added to prepare waterborne epoxy ester resin composition 1.

[0106] Comparative Example 7

[0107] The preparation method of the waterborne epoxy ester resin composition m includes the following steps: According to the formulation in Table 2, 150 g of epoxy ester intermediate A1 and 450 g of epoxy ester intermediate B1 are mixed and stirred evenly. The mixture is then heated to 115-125°C, and the mixed monomer components are added dropwise. First, the first component containing hydrophilic vinyl monomer C is added dropwise, and the addition is completed within 0.5-1.5 hours at 115-125°C. After the first component is added, the second component containing functional repair monomer E and non-hydrophilic vinyl monomer F is added dropwise at 115-125°C, and the addition is completed within 3-4 hours. Then, the temperature is adjusted to 130-140°C, and the third component is added dropwise, and the addition is completed within 1-2 hours. After the addition is completed, the mixture is kept at 120-130°C for 1-2 hours, cooled to 90-100°C, and a neutralizing agent J is added to prepare the waterborne epoxy ester resin composition m.

[0108] Table 2. Raw material composition and formulation of the corrosion-resistant waterborne epoxy ester resin compositions in Comparative Examples 1 to 7.

[0109]

[0110] Preparation of waterborne epoxy ester resin coatings and performance testing of waterborne epoxy ester resin coatings:

[0111] Using the aqueous epoxy ester resin compositions prepared in Examples 7-11 and Comparative Examples 2-7 above as film-forming resins, aqueous epoxy ester resin coatings were prepared. The formulations of the aqueous epoxy ester resin coatings are shown in Table 3, and the preparation process of the aqueous epoxy ester resin coatings is as follows:

[0112] (1) According to the formulation in Table 3, the film-forming resin (a, b, c, d, e in the examples and h, i, j, k, l, m in the comparative examples), the drying agent (TY-CQ-5020WD), and the pH adjuster (N,N-dimethylethanolamine) are first stirred and mixed evenly at a stirring speed of 1000 rpm. Deionized water is added while stirring, and after stirring for 30 min, an aqueous epoxy ester dispersion is obtained.

[0113] (2) Add materials 5 to 12 of Table 3 to the reaction vessel in sequence, then add them to the stirring tank, mix and stir for 40 to 60 minutes, then start grinding until the fineness is <30μm;

[0114] (3) While stirring, add material 13, adjust the viscosity, filter and discharge to obtain waterborne epoxy ester coating, filter, discharge and package. According to the waterborne epoxy ester resin composition used, the prepared coatings are successively named Ca, Cb, Cc, Cd, Ce, and the comparative coatings Ch, Ci, Cj, Ck, Cl, Cm.

[0115] Table 3 Formulations of Waterborne Epoxy Ester Resin Coatings

[0116] Serial Number raw materials Function Dosage / gram 1 Waterborne epoxy ester resin composition Film-forming resin 380.0 2 TY-CQ-5020WD drying agent 10.0 3 DMEA pH adjuster 4.0 4 Deionized water Deionized water 250.0 5 BYK-190 dispersant 6.5 6 TEGO Airex 901W Defoamer 0.5 7 BYK-346 wetting agent 2.8 8 PU carbon black pigment 18.5 9 Precipitated barium sulfate pigment 255.0 10 Zinc phosphate Rust-preventive pigments 50.0 11 Strontium chrome yellow Rust-preventive pigments 2.5 12 Deionized water Deionized water 15.0 13 <![CDATA[ACRYSOL TM RM-8W]]> Thickener 5.2

[0117] The prepared waterborne epoxy ester resin coating was diluted with water to adjust to an appropriate viscosity. The coating was then sprayed onto a polished cold-rolled steel plate with a film thickness of 50–60 μm. After surface drying at room temperature, the sample was placed in an oven at 80±2℃ for 30 minutes and left at room temperature for 7 days. The coating properties were then tested according to the national standard test method for coatings.

[0118] In addition, the waterborne epoxy ester resins prepared in the above examples and comparative examples were characterized, and the rotational viscosity, gel content, and monomer conversion rate of the resin compositions were tested. For the coatings, the main tests included appearance, surface drying time, adhesion, water resistance, initial water resistance, and neutral salt spray resistance time.

[0119] Rotational viscosity: The rotational viscosity of the resin was tested using an NDJ-8S rotational viscometer.

[0120] Gel content: The resin grafting rate is characterized by gel content. The specific test method is as follows: Weigh the waterborne epoxy ester resin composition, add 5 wt% of TY-CQ-5020WD drying agent (total resin mass), stir evenly, form a film on a tetrafluoroethylene plate, and after surface drying, bake at 80℃ for 2 hours. After standing at 25±2℃ for 7 days, collect the solid resin and weigh it, recording the mass as M0 grams. Perform Soxhlet extraction, dry the extracted sample and weigh it, recording the weight as M1. Gel content = (M0-M1) / M0×100%.

[0121] Residual monomer content: The residual monomer content was determined using an Agilent 8890 gas chromatograph.

[0122] Initial water resistance: After spraying the sample, dry it in a standard constant temperature and humidity room at 25±2℃ for 24 hours. After edge sealing, place the sample in deionized water in a constant temperature room at 25±2℃, with about 2 / 3 of the sample immersed in water. Observe the coating condition every 2 hours within 24 hours, and observe it every 12 hours after 24 hours, until the coating blister, wrinkle or the substrate rusts. The initial water resistance is judged by the time it takes for the coating to be damaged.

[0123] Neutral salt spray resistance test: The corrosion resistance performance of the coating is determined by the neutral salt spray resistance test, in accordance with GB / T1771-2007. The test is conducted every 24 hours until the coating blisteres, rusts or peels off.

[0124] Other properties of the coating were tested in accordance with the relevant national standards, and the relevant test results are listed in Tables 4 and 5.

[0125] Table 4 shows the test results of the corrosion-resistant waterborne epoxy resin compositions in Examples 7 to 11 and Comparative Examples 1 to 7.

[0126] Test Project Rotational viscosity (mPa·s) Gel content (%) Residual monomer content (%) Example 7 32480 78.36 0.49 Example 8 40850 80.84 0.63 Example 9 63120 71.43 0.79 Example 10 37150 86.12 0.33 Example 11 32540 74.54 0.59 Comparative Example 1 gel / / Comparative Example 2 29835 53.22 1.45 Comparative Example 3 131720 67.28 0.96 Comparative Example 4 37460 77.91 0.58 Comparative Example 5 29420 63.84 0.83 Comparative Example 6 92260 82.85 0.29 Comparative Example 7 30850 76.53 1.23

[0127] As can be seen from the data in Table 4, the rotational viscosity of the waterborne epoxy ester resin compositions prepared using the technical solution of the present invention is all below 70000 mPa·s, the gel content is all above 70%, and the residual monomer content is all below 0.8%.

[0128] Table 5 shows the test results of the performance of the waterborne epoxy ester coatings in Examples 7 to 11 and Comparative Examples 2 to 7.

[0129]

[0130] As shown in Table 5, the waterborne epoxy ester resin composition prepared in the embodiments of the present invention, used as a film-forming agent, produces waterborne epoxy ester resin coatings with excellent performance. Specifically, the coating has a smooth and even appearance, and the pencil hardness of the coating exceeds HB, meeting the requirements of industrial coating primers. It is particularly noteworthy that, through polymer segment molecular design and process innovation, the waterborne epoxy ester coating prepared in the embodiments of the present invention achieves a neutral salt spray resistance time of 360 hours, exhibiting excellent corrosion resistance. Initial water resistance reaches 120 hours, and overall water resistance reaches 240 hours, meeting the latest requirements for water resistance and corrosion resistance in the automotive parts industry.

[0131] Comparing Example 7 with Comparative Example 1, Comparative Example 1 used only epoxy ester intermediate A1 containing conjugated double bonds to prepare the waterborne epoxy ester. Due to the high reactivity of the conjugated double bonds, Comparative Example 1 experienced gelation due to excessive viscosity during the preparation of the waterborne epoxy ester resin, making it impossible to obtain the waterborne epoxy ester resin. Comparing Example 7 with Comparative Example 2, Comparative Example 2 used only epoxy ester intermediate B1 without conjugated double bonds, resulting in a reduction in gel content from 78.36% in Example 7 to 53.22% in Comparative Example 2. The initial water resistance of the corresponding coating in Comparative Example 2's waterborne epoxy ester resin composition h also decreased to 48 hours, and the neutral salt spray resistance time decreased to 240 hours.

[0132] Comparing Example 7 with Comparative Example 3, Example 7 used a two-step esterification method to prepare epoxy ester intermediates A1 and B1, respectively, and used a mixture of epoxy ester intermediates A1 and B1 to prepare an aqueous epoxy ester resin composition a, which had a rotational viscosity of 32480 mPa·s. In contrast, Comparative Example 3 used a one-step esterification method to prepare epoxy ester intermediate X to synthesize an aqueous epoxy ester resin composition i. Although the preparation process, raw materials, and amounts were exactly the same in Example 6 and Comparative Example 3, the rotational viscosity of the aqueous epoxy ester resin composition i in Comparative Example 3 reached 131720 mPa·s, far exceeding the viscosity of the aqueous epoxy ester resin composition a in Example 7, which is unfavorable for the application of the aqueous epoxy ester resin. Furthermore, the gel content of the aqueous epoxy ester resin i prepared in Comparative Example 3 was also reduced to below 67.28%, possibly due to the loss of conjugated double bonds during the high-temperature esterification process. Correspondingly, in Comparative Example 3, the initial water resistance and neutral salt spray resistance time of the waterborne epoxy ester coating corresponding to waterborne epoxy ester resin composition i both decreased significantly.

[0133] Example 7 was compared with Comparative Example 4. The raw materials, formulation, and process of Comparative Example 4 were similar to those of Example 7. The only difference was the change in the dropwise addition process in Example 7; instead of the segmented dropwise addition of the "first component and the second component" in Example 7, the process was changed to "simultaneous dropwise addition" in Comparative Example 4. All other process conditions were identical to those of Example 7. The rotational viscosity, gel content, and residual monomer content of the waterborne epoxy ester resin compositions prepared in Example 7 and Comparative Example 4 were similar. However, it is noteworthy that the initial water resistance of the coating corresponding to the waterborne epoxy ester resin composition j in Comparative Example 4 decreased from 120 h to 48 h, and the neutral salt spray resistance time decreased from 360 h to 240 h.

[0134] Example 7 was compared with Comparative Example 5. The raw materials, formulations, and processes of Comparative Example 5 and Example 7 were similar. The only difference was that "functional repair monomer E" was not used in Comparative Example 5. The viscosity of the resin prepared in Comparative Example 5 was reduced to 29420 mPa·s, and the gel content was reduced to 63.84%. Correspondingly, the initial water resistance of the coating of the waterborne epoxy ester resin composition k in Comparative Example 5 was reduced to 48 hours, and the neutral salt spray resistance time was reduced to 300 hours.

[0135] Example 7 was compared with Comparative Example 6. The raw materials, formulation, and process of Comparative Example 6 were similar to those of Example 7. The only difference was that the temperature during the copolymerization of the vinyl monomers in Comparative Example 6 exceeded the range of "110-140°C" specified in the technical solution of this invention, and the reaction temperature was adjusted to "140-145°C". The viscosity of the waterborne epoxy ester resin composition prepared in Comparative Example 6 increased to 92260 mPa·s, which is detrimental to product application and construction.

[0136] Example 7 was compared with Comparative Example 7. The raw materials, formulation, and process of Comparative Example 7 were similar to those of Example 7. The only difference was that the third component was added and the holding temperature during the copolymerization of the vinyl monomers in Comparative Example 6 was adjusted from "140-150°C" to "120-130°C". In Comparative Example 7, the gel content of the aqueous epoxy ester resin composition m was slightly reduced to 76.53%, and the residual monomer content increased to 1.23%. Correspondingly, the neutral salt spray resistance time of the coating of the aqueous epoxy ester resin composition m in Comparative Example 7 was reduced to 300 hours.

[0137] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A waterborne epoxy ester resin composition with anti-corrosion properties, characterized in that, The raw material composition of the corrosion-resistant waterborne epoxy ester resin composition, based on 100% of the total mass of the raw materials, includes 18.82–74.59% of a mixed monomer component, 5–20% of epoxy ester intermediate A, 35–60% of epoxy ester intermediate B, and 2.4–5% of a neutralizing agent J. The mixed monomer component comprises a first component, a second component, and a third component. The first component comprises the following components in the following percentages: Hydrophilic vinyl monomer C 2-4.5%; Initiator D 0.01–0.09%; The second component comprises the following components in the following percentages: Functional repair monomer E 2.5–12%; Non-hydrophilic vinyl monomers F12–46%; Initiator G 0.25–1.5%; The third component comprises the following components in the following percentages: Initiator H 0.06–0.5%; Solvent I 2-10%, Wherein, based on a percentage of 100% of the total mass of the raw materials constituting the epoxy ester intermediate A, the epoxy ester intermediate A comprises the following components in the following percentages: The raw material composition of the epoxy ester intermediate B includes fatty acid P, epoxy resin Q, catalyst R, dehydrating solvent S, and diluent T. Based on the total mass percentage of fatty acid P and epoxy resin Q (100%), the mass percentage of catalyst R is 0.1–3%, the mass percentage of dehydrating solvent S is 2–10%, and the mass percentage of diluent T is 30–55%. The fatty acid L is at least one of tung oil acid and dehydrated ricinoleic acid; the epoxy resin K is a bisphenol A type epoxy resin, and the epoxy value of the bisphenol A type epoxy resin is 0.09-0.14 mol / 100g. The functional repair monomer E is prepared by ring-opening esterification of glycidyl methacrylate and linolenic acid.

2. The waterborne epoxy ester resin composition with anti-corrosion properties as described in claim 1, characterized in that, The molar ratio of fatty acid L to epoxy resin K is (1.9~2.1):

1.

3. The waterborne epoxy ester resin composition with anti-corrosion properties as described in claim 1, characterized in that, The mass ratio of fatty acid P to epoxy resin Q is (60-122):

100.

4. The waterborne epoxy ester resin composition with anti-corrosion properties as described in claim 1, characterized in that, The fatty acid P is at least one of oleic acid, linoleic acid, linolenic acid, tall oleic acid, and soybean oil acid; the epoxy resin Q is a bisphenol A type epoxy resin; and the epoxy value of the bisphenol A type epoxy resin is 0.04 to 0.22 mol / 100g.

5. The waterborne epoxy ester resin composition with anti-corrosion properties as described in claim 1, characterized in that, The hydrophilic vinyl monomer C is at least one of acrylic acid and methacrylic acid, and the non-hydrophilic vinyl monomer F is at least one of methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isobornyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, isobornyl methacrylate, benzyl acrylate, and styrene.

6. A method for preparing a waterborne epoxy ester resin composition with anti-corrosion properties, characterized in that, Includes the following steps: Step S01: Weigh each raw material according to the components of the corrosion-resistant waterborne epoxy ester resin composition according to any one of claims 1 to 5; Step S02: Mix epoxy ester intermediate A and epoxy ester intermediate B, and stir until homogeneous to obtain epoxy ester intermediate mixture. Step S03: Heat the epoxy ester intermediate mixture to 110-140°C, and add the mixed monomer components dropwise to the epoxy ester intermediate mixture. Specifically, the dropwise addition operation is carried out by adopting a segmented dropwise addition process, in which the first component, the second component, and the third component are added sequentially as three components. Step S04: The epoxy ester intermediate mixture containing the mixed monomer components is kept at 130-150°C for 1-2 hours, then cooled to 90-100°C, and neutralizing agent J is added to prepare a waterborne epoxy ester resin composition with anti-corrosion properties.

7. The method for preparing the corrosion-resistant waterborne epoxy ester resin composition as described in claim 6, characterized in that, In step S03, the mixed monomer components include a first component, a second component, and a third component. During the process of adding the mixed monomer components to the epoxy ester intermediate mixed components, the first component is added dropwise over 0.5 to 1.5 hours, followed by the second component over 3 to 4 hours. Then, the temperature of the epoxy ester intermediate mixed components is adjusted to 130 to 150°C, and the third component is added dropwise over 1 to 2 hours.

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