Aqueous epoxy resin and method for its preparation

Abstract

The application discloses a kind of water-based epoxy resin and preparation method thereof, the raw materials of the water-based epoxy resin, by weight parts, include: epoxy resin 15-28 parts, contain unsaturated long carbon chain phenolic compound 6-20 parts, emulsifier 5-15 parts, initiator 2-8 parts, alcohol compound 2-10 parts, alcohol ether compound 2-10 parts, water 20-50 parts;A kind of water-based epoxy resin prepared in the application, so that the water resistance of paint film is good, strong adhesion, short drying time when film forming, and high gloss, at the same time, the impact resistance and hardness of the paint film prepared using water-based epoxy resin also have certain improvement, and good corrosion resistance such as salt fog resistance, chemical resistance, good storage stability, can be applied to large steel structure, such as bridge, ship, tower crane, storage tank and the like.

Description

Technical Field

[0001] This invention relates to the field of waterborne coatings technology, classified as C08G59 / 18, and specifically to a novel waterborne epoxy ester and its preparation method. Background Technology

[0002] Epoxy resins are widely used in various fields such as chemical engineering, machinery, electronics, electrical engineering, aerospace, transportation, and construction due to their excellent mechanical properties, electrical insulation, adhesion, and chemical resistance. However, epoxy resins are generally difficult to dissolve in water and require the use of ketone or aromatic organic solvents for dissolution. During use, the volatilization of large amounts of organic solvents can cause varying degrees of personal injury and air pollution. Therefore, the water-based application of epoxy resins has become the mainstream direction for epoxy resin applications.

[0003] Steel structure construction is a commonly used construction method. In order to reduce corrosion of steel structures in rain, it is necessary to spray paint on the surface of the steel structure to isolate the steel from the outside world. Water-based epoxy resin coatings are often used as topcoats for steel structures due to their environmental advantages.

[0004] However, the current technology for making epoxy resin water-based involves esterifying vegetable oleic acid in the early stage, adding trimellitic anhydride or acrylic monomer to modify and introduce carboxyl groups in the later stage, and finally adding amine to neutralize and form salt for water-based conversion. The main problems are that due to the poor water resistance of ester bonds and carboxyl groups, the paint film is easy to hydrolyze, the curing method is singular, it cannot achieve the anti-corrosion effect that epoxy should have, and the shelf life is short, which limits its use in steel structure topcoats.

[0005] Patent CN104262587B discloses an epoxy resin containing unsaturated long carbon chain phenolic compounds and epoxy resin materials. The epoxy resin material obtained by mixing graphene, cashew phenolamine and epoxy resin improves its wear resistance and corrosion resistance, but the problems of its impact strength and salt spray resistance are not solved. Summary of the Invention

[0006] To address the aforementioned problems, a first aspect of the present invention provides a novel waterborne epoxy ester, comprising, by weight, the following raw materials: 15-28 parts epoxy resin, 6-20 parts phenolic compounds containing unsaturated long carbon chains, 5-15 parts emulsifier, 2-8 parts initiator, 2-10 parts alcohol compounds, 2-10 parts alcohol ether compounds, and 20-50 parts water.

[0007] More preferably, the novel waterborne epoxy ester, by weight, comprises the following raw materials: 15-20 parts epoxy resin, 10-20 parts phenolic compound containing unsaturated long carbon chains, 5-10 parts emulsifier, 2-5 parts initiator, 3-6 parts alcohol compound, 3-6 parts alcohol ether compound, and 30-50 parts water.

[0008] More preferably, the novel waterborne epoxy ester, by weight, comprises the following raw materials: 18 parts epoxy resin, 15 parts phenolic compound containing unsaturated long carbon chains, 7 parts emulsifier, 3 parts initiator, 5 parts alcohol compound, 5 parts alcohol ether compound, and 47 parts water.

[0009] More preferably, the phenolic compound containing an unsaturated long carbon chain is cashew phenol, the emulsifier includes at least one of polyethylene glycol, sodium dodecylbenzenesulfonate, propylene glycol block copolymer, sodium polyoxyethylene alkylphenol ether sulfate, OP-10, and allyl polyoxyethylene ether, and the initiator includes at least one of benzoyl peroxide, benzoic acid peroxide, and tert-butyl peroxide.

[0010] More preferably, the emulsifier is allyl polyoxyethylene ether, and the initiator is benzoyl peroxide.

[0011] Preferably, the epoxy resin is a first epoxy resin and a second epoxy resin.

[0012] More preferably, both the first epoxy resin and the second epoxy resin are bisphenol A type epoxy resins.

[0013] Preferably, the epoxy equivalent of the first epoxy resin is 200-800 g / mol, and the epoxy equivalent of the second epoxy resin is 200-400 g / mol.

[0014] More preferably, the epoxy equivalent of the first epoxy resin is 400-600 g / mol, and the epoxy equivalent of the second epoxy resin is 200-300 g / mol.

[0015] More preferably, the epoxy equivalent of the first epoxy resin is 500 g / mol, and the epoxy equivalent of the second epoxy resin is 227 g / mol.

[0016] Preferably, the mass ratio between the first epoxy resin and the second epoxy resin is (1-3):1.

[0017] More preferably, the mass ratio between the first epoxy resin and the second epoxy resin is (1-2):1.

[0018] More preferably, the mass ratio between the first epoxy resin and the second epoxy resin is 1:1.

[0019] Preferably, the mass ratio between the epoxy resin and the phenolic compound containing unsaturated long carbon chains is (15-20):(10-20).

[0020] More preferably, the mass ratio between the epoxy resin and the phenolic compound containing unsaturated long carbon chains is (18-20):(13-17).

[0021] More preferably, the mass ratio between the epoxy resin and the phenolic compound containing unsaturated long carbon chains is 18:15.

[0022] Preferably, the mass ratio between the epoxy resin and the emulsifier is (16-20):(7-15).

[0023] More preferably, the mass ratio between the epoxy resin and the emulsifier is (18-20):(7-15).

[0024] More preferably, the mass ratio of the epoxy resin to the emulsifier is 18:7.

[0025] Preferably, the hydroxyl value of the emulsifier is 50-77 mg KOH / g.

[0026] More preferably, the hydroxyl value of the emulsifier is 50-55 mg KOH / g.

[0027] More preferably, the hydroxyl value of the emulsifier is 53 mg KOH / g.

[0028] Preferably, the acid value of the phenolic compound containing the unsaturated long carbon chain is ≤10 mg KOH / g.

[0029] More preferably, the acid value of the phenolic compound containing the unsaturated long carbon chain is 2-6.5 mg KOH / g.

[0030] More preferably, the acid value of the phenolic compound containing the unsaturated long carbon chain is 3-5 mg KOH / g.

[0031] More preferably, the acid value of the phenolic compound containing the unsaturated long carbon chain is 3.6 mg KOH / g.

[0032] Preferably, the alcohol compound is n-butanol, and the alcohol ether compound includes at least one of propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, divinyl-1,4-butanediol ether, and 1,4-cyclohexanediol monovinyl ether.

[0033] More preferably, the alcohol compound is n-butanol, and the alcohol ether compound is propylene glycol methyl ether.

[0034] A second aspect of this invention provides a method for preparing a novel waterborne epoxy ester, the specific steps of which are as follows:

[0035] S1: Mix and dissolve epoxy resin, alcohol compound and alcohol ether compound by weight for 10-15 minutes to obtain epoxy resin solution, while heating to 100-120℃.

[0036] S2: Mix the phenolic compound containing unsaturated long carbon chains, emulsifier and initiator according to the weight parts, and stir at a stirring speed of 1000-2000 rpm / min for 20-25 min to obtain the first solution.

[0037] S3: Under the condition that the stirring speed and temperature remain unchanged, the first solution is added dropwise to the epoxy resin solution over a period of 1-3 hours. After that, the initiator is added continuously until the initiator is completely added. Then, after keeping the solution at 100-120℃, deionized water is added to obtain the final product.

[0038] The present invention also provides a water-based epoxy ester paint, which, by weight, comprises the following raw materials: 33 parts water-based epoxy ester, 1 part N,N-dimethylethanolamine, 35 parts deionized water, 0.3 parts water-based drier, 30 parts white paste, 0.1 parts non-silicone water-based defoamer, 0.2 parts organosilicon twin structure surfactant, 0.2 parts first thickener, and 0.2 parts second thickener.

[0039] This invention also provides a method for preparing a waterborne epoxy ester paint, the specific steps of which are as follows: First, waterborne epoxy ester, waterborne drier and N,N-dimethylethanolamine are mixed according to parts by weight to obtain a first mixed system. Then, white paste, non-silicone waterborne defoamer and organosilicon twin structure surfactant are added according to parts by weight to the first mixed system to obtain a second mixed system. Then, a first thickener, a second thickener and deionized water are added according to parts by weight to the second mixed system to obtain the final product.

[0040] In existing technologies, amine neutralization is generally used to improve the water resistance of epoxy resins. However, the applicant discovered that when the mass ratio of epoxy resin to allyl polyoxyethylene ether is limited to (15-20):(10-20), not only does the waterborne epoxy ester paint film remain free of bubbles and peeling after immersion in water for 336 hours, but it also unexpectedly shows no precipitation after storage at 50°C for 168 hours. The applicant speculates that this reaction between the allyl polyoxyethylene ether and epoxy resin introduces hydrophilic polyoxyethylene segments into the epoxy resin. Simultaneously, due to the hydrophobic components of both... With similar structure, the dipole interaction between the hydrophobic portion of allyl polyoxyethylene ether and epoxy resin is enhanced. After storage at 50°C for 7 days, no precipitation or stratification occurs. In addition, at this mass ratio, the system changes from an oil-in-water state to a water-in-oil state, so that the waterborne epoxy ester paint film remains free of bubbles and peeling after immersion in water for 336 hours. At the same time, the hydroxyl value of allyl polyoxyethylene ether is limited to 50-55 mgKOH / g to prevent the system from being too hydrophilic, which would prevent it from properly coating epoxy resin droplets and forming a dense interfacial film, thus weakening its water resistance and storage stability.

[0041] Based on this, the mass ratio of epoxy resin to cashew nut shell phenol was limited to (16-20):(7-15). Cashew nut shell phenol contains long-chain alkanes with good flexibility, which further crosslink with allyl polyoxyethylene ether and epoxy resin in the system. This not only improves the water resistance of the paint film, but also unexpectedly improves its chemical resistance to a certain extent. After a 240-hour salt spray resistance test, no bubbles or rust appeared on the test panel. However, because cashew nut shell phenol contains a certain amount of benzene rings, it may cause excessive hardness, brittleness, and weakened impact resistance. Based on this, the applicant specified the mass ratio of the first epoxy resin and the second epoxy resin as (1-2):1, which not only solved the problem of excessive hardness, but also improved its storage stability to a certain extent. It is speculated that: under the compounding of epoxy resins with this mass ratio, the viscosity of the system is improved, thus enhancing the storage stability. At the same time, the distance between benzene rings is increased, thus weakening the interaction between benzene rings. The steric hindrance in the system weakens the interaction between CH and CC and the spin electron cloud, thus making the impact resistance of the coating film as high as 40cm.

[0042] Beneficial effects: This invention prepares a novel waterborne epoxy ester, which results in a paint film with excellent water resistance, strong adhesion, short drying time during film formation, and high gloss. At the same time, the paint film prepared using the novel waterborne epoxy ester also has improved impact resistance and hardness, and good corrosion resistance such as salt spray and chemical resistance, as well as good storage stability. It can be applied to large steel structures, such as bridges, ships, tower cranes, and storage tanks.

[0043] Furthermore, the preparation method of the novel waterborne epoxy ester of the present invention is simple, low-cost, and can be applied to industrial production. Example

[0044] Example 1

[0045] A novel waterborne epoxy ester, by weight, comprises the following raw materials: 18 parts epoxy resin, 15 parts phenolic compounds containing unsaturated long carbon chains, 7 parts emulsifier, 3 parts initiator, 5 parts alcohol compounds, 5 parts alcohol ether compounds, and 47 parts water.

[0046] The epoxy resin is a first epoxy resin and a second epoxy resin.

[0047] Both the first epoxy resin and the second epoxy resin are bisphenol A type epoxy resins.

[0048] The first epoxy resin has an epoxy equivalent of 500 g / mol, was purchased from Jiangsu Sanmu, and its model is E20.

[0049] The second epoxy resin has an epoxy equivalent of 227 g / mol and was purchased from Jiangsu Sanmu, model E44.

[0050] The mass ratio of the first epoxy resin to the second epoxy resin is 1:1.

[0051] The phenolic compound containing unsaturated long carbon chains is cashew phenol, with an acid value of 3.6 mg KOH / g, and was purchased from Shandong Jiaying Chemical Technology Co., Ltd.

[0052] The mass ratio of epoxy resin to cashew phenol is 18:15.

[0053] The emulsifier is allyl polyoxyethylene ether with a hydroxyl value of 53 mgKOH / g, purchased from Jiangsu Haian Petrochemical Plant, model APEG-1000.

[0054] The mass ratio of the epoxy resin to the allyl polyoxyethylene ether is 18:7.

[0055] The initiator is benzoyl peroxide.

[0056] The alcohol compound is n-butanol, and the alcohol ether compound is propylene glycol methyl ether.

[0057] A second aspect of this invention provides a method for preparing a novel waterborne epoxy ester, the specific steps of which are as follows:

[0058] S1: Mix and dissolve epoxy resin, alcohol compound and alcohol ether compound by weight for 13 min to obtain epoxy resin solution, and heat to 110℃ at the same time.

[0059] S2: Mix the phenolic compound containing unsaturated long carbon chains, emulsifier and initiator according to the weight parts, and stir at a stirring speed of 1500 rpm / min for 22 min to obtain the first solution.

[0060] S3: Under the condition that the stirring speed and temperature remain unchanged, the first solution is added dropwise to the epoxy resin solution over a period of 2 hours. Then, the initiator is added continuously until the initiator is completely added. The solution is then kept at 100-120℃ for 2 hours, and deionized water is added to obtain the final product.

[0061] The present invention also provides a water-based epoxy ester paint, which, by weight, comprises the following raw materials: 33 parts water-based epoxy ester, 1 part N,N-dimethylethanolamine, 35 parts deionized water, 0.3 parts water-based drier, 30 parts white paste, 0.1 parts non-silicone water-based defoamer, 0.2 parts organosilicon twin structure surfactant, 0.2 parts first thickener, and 0.2 parts second thickener.

[0062] This invention also provides a method for preparing a waterborne epoxy ester paint, the specific steps of which are as follows: First, waterborne epoxy ester, waterborne drier and N,N-dimethylethanolamine are stirred at a stirring speed of 1500 rpm / min for 1 hour to obtain a first mixed system. Then, white paste, non-silicone waterborne defoamer and organosilicon twin structure surfactant are added to the first mixed system according to the weight, and stirring is continued for 30 minutes to obtain a second mixed system. Then, a first thickener, a second thickener and deionized water are added to the second mixed system according to the weight, and stirring is carried out for 1 hour to obtain the final product.

[0063] The aqueous drying agent was purchased from OMG, model Octa-So ligen421.

[0064] The white paste was purchased from Jinan Puros Building Materials Co., Ltd., and its model number is W1008-sb.

[0065] The non-silicone water-based defoamer was purchased from Tego, model number Tego 830.

[0066] The organosilicon twin structure surfactant was purchased from Tego, model number Tego 4100.

[0067] The first thickener was purchased from Hemings and its model number is WT102.

[0068] The second thickener was purchased from Hemings and is model 350D.

[0069] Example 2

[0070] A novel waterborne epoxy ester, by weight, comprises the following raw materials: 15 parts epoxy resin, 12 parts phenolic compounds containing unsaturated long carbon chains, 15 parts emulsifier, 3 parts initiator, 5 parts alcohol compounds, 5 parts alcohol ether compounds, and 45 parts water.

[0071] The epoxy resin is a first epoxy resin and a second epoxy resin.

[0072] Both the first epoxy resin and the second epoxy resin are bisphenol A type epoxy resins.

[0073] The first epoxy resin has an epoxy equivalent of 500 g / mol, was purchased from Jiangsu Sanmu, and its model is E20.

[0074] The second epoxy resin has an epoxy equivalent of 227 g / mol and was purchased from Jiangsu Sanmu, model E44.

[0075] The mass ratio of the first epoxy resin to the second epoxy resin is 1:1.

[0076] The phenolic compound containing unsaturated long carbon chains is cashew phenol, with an acid value of 3.6 mg KOH / g, and was purchased from Shandong Jiaying Chemical Technology Co., Ltd.

[0077] The mass ratio of epoxy resin to cashew phenol is 15:12.

[0078] The emulsifier is allyl polyoxyethylene ether with a hydroxyl value of 53 mgKOH / g, purchased from Jiangsu Haian Petrochemical Plant, model APEG-1000.

[0079] The mass ratio of the epoxy resin to the allyl polyoxyethylene ether is 15:15.

[0080] The initiator is benzoyl peroxide.

[0081] The alcohol compound is n-butanol, and the alcohol ether compound is propylene glycol methyl ether.

[0082] A second aspect of this invention provides a method for preparing a novel waterborne epoxy ester, the specific steps of which are as follows:

[0083] S1: Mix and dissolve epoxy resin, alcohol compound and alcohol ether compound by weight for 13 min to obtain epoxy resin solution, and heat to 110℃ at the same time.

[0084] S2: Mix the phenolic compound containing unsaturated long carbon chains, emulsifier and initiator according to the weight parts, and stir at a stirring speed of 1500 rpm / min for 22 min to obtain the first solution.

[0085] S3: Under the condition that the stirring speed and temperature remain unchanged, the first solution is added dropwise to the epoxy resin solution over a period of 2 hours. Then, the initiator is added continuously until the initiator is completely added. The solution is then kept at 100-120℃ for 2 hours, and deionized water is added to obtain the final product.

[0086] The present invention also provides a water-based epoxy ester paint, which, by weight, comprises the following raw materials: 33 parts water-based epoxy ester, 1 part N,N-dimethylethanolamine, 35 parts deionized water, 0.3 parts water-based drier, 30 parts white paste, 0.1 parts non-silicone water-based defoamer, 0.2 parts organosilicon twin structure surfactant, 0.2 parts first thickener, and 0.2 parts second thickener.

[0087] This invention also provides a method for preparing a waterborne epoxy ester paint, the specific steps of which are as follows: First, waterborne epoxy ester, waterborne drier and N,N-dimethylethanolamine are stirred at a stirring speed of 1500 rpm / min for 1 hour to obtain a first mixed system. Then, white paste, non-silicone waterborne defoamer and organosilicon twin structure surfactant are added to the first mixed system according to the weight, and stirring is continued for 30 minutes to obtain a second mixed system. Then, a first thickener, a second thickener and deionized water are added to the second mixed system according to the weight, and stirring is carried out for 1 hour to obtain the final product.

[0088] The aqueous drying agent was purchased from OMG, model Octa-So ligen421.

[0089] The white paste was purchased from Jinan Puros Building Materials Co., Ltd., and its model number is W1008-sb.

[0090] The non-silicone water-based defoamer was purchased from Tego, model number Tego 830.

[0091] The organosilicon twin structure surfactant was purchased from Tego, model number Tego 4100.

[0092] The first thickener was purchased from Hemings and its model number is WT102.

[0093] The second thickener was purchased from Hemings and is model 350D.

[0094] Example 3

[0095] A novel waterborne epoxy ester, by weight, comprises the following raw materials: 20 parts epoxy resin, 13 parts phenolic compounds containing unsaturated long carbon chains, 7 parts emulsifier, 3 parts initiator, 5 parts alcohol compounds, 5 parts alcohol ether compounds, and 47 parts water.

[0096] The epoxy resin is a first epoxy resin and a second epoxy resin.

[0097] Both the first epoxy resin and the second epoxy resin are bisphenol A type epoxy resins.

[0098] The first epoxy resin has an epoxy equivalent of 500 g / mol, was purchased from Jiangsu Sanmu, and its model is E20.

[0099] The second epoxy resin has an epoxy equivalent of 227 g / mol and was purchased from Jiangsu Sanmu, model E44.

[0100] The mass ratio of the first epoxy resin to the second epoxy resin is 1:1.

[0101] The phenolic compound containing unsaturated long carbon chains is cashew phenol, with an acid value of 3.6 mg KOH / g, and was purchased from Shandong Jiaying Chemical Technology Co., Ltd.

[0102] The mass ratio of epoxy resin to cashew phenol is 20:13.

[0103] The emulsifier is allyl polyoxyethylene ether with a hydroxyl value of 53 mgKOH / g, purchased from Jiangsu Haian Petrochemical Plant, model APEG-1000.

[0104] The mass ratio of the epoxy resin to the allyl polyoxyethylene ether is 20:7.

[0105] The initiator is benzoyl peroxide.

[0106] The alcohol compound is n-butanol, and the alcohol ether compound is propylene glycol methyl ether.

[0107] A second aspect of this invention provides a method for preparing a novel waterborne epoxy ester, the specific steps of which are as follows:

[0108] S1: Mix and dissolve epoxy resin, alcohol compound and alcohol ether compound by weight for 13 min to obtain epoxy resin solution, and heat to 110℃ at the same time.

[0109] S2: Mix the phenolic compound containing unsaturated long carbon chains, emulsifier and initiator according to the weight parts, and stir at a stirring speed of 1500 rpm / min for 22 min to obtain the first solution.

[0110] S3: Under the condition that the stirring speed and temperature remain unchanged, the first solution is added dropwise to the epoxy resin solution over a period of 2 hours. Then, the initiator is added continuously until the initiator is completely added. The solution is then kept at 100-120℃ for 2 hours, and deionized water is added to obtain the final product.

[0111] The present invention also provides a water-based epoxy ester paint, which, by weight, comprises the following raw materials: 33 parts water-based epoxy ester, 1 part N,N-dimethylethanolamine, 35 parts deionized water, 0.3 parts water-based drier, 30 parts white paste, 0.1 parts non-silicone water-based defoamer, 0.2 parts organosilicon twin structure surfactant, 0.2 parts first thickener, and 0.2 parts second thickener.

[0112] This invention also provides a method for preparing a waterborne epoxy ester paint, the specific steps of which are as follows: First, waterborne epoxy ester, waterborne drier and N,N-dimethylethanolamine are stirred at a stirring speed of 1500 rpm / min for 1 hour to obtain a first mixed system. Then, white paste, non-silicone waterborne defoamer and organosilicon twin structure surfactant are added to the first mixed system according to the weight, and stirring is continued for 30 minutes to obtain a second mixed system. Then, a first thickener, a second thickener and deionized water are added to the second mixed system according to the weight, and stirring is carried out for 1 hour to obtain the final product.

[0113] The aqueous drying agent was purchased from OMG, model Octa-So ligen421.

[0114] The white paste was purchased from Jinan Puros Building Materials Co., Ltd., and its model number is W1008-sb.

[0115] The non-silicone water-based defoamer was purchased from Tego, model number Tego 830.

[0116] The organosilicon twin structure surfactant was purchased from Tego, model number Tego 4100.

[0117] The first thickener was purchased from Hemings and its model number is WT102.

[0118] The second thickener was purchased from Hemings and is model 350D.

[0119] Example 4

[0120] A novel waterborne epoxy ester, by weight, comprises the following raw materials: 23 parts epoxy resin, 10 parts phenolic compounds containing unsaturated long carbon chains, 7 parts emulsifier, 3 parts initiator, 5 parts alcohol compounds, 5 parts alcohol ether compounds, and 47 parts water.

[0121] The epoxy resin is a first epoxy resin and a second epoxy resin.

[0122] Both the first epoxy resin and the second epoxy resin are bisphenol A type epoxy resins.

[0123] The first epoxy resin has an epoxy equivalent of 500 g / mol, was purchased from Jiangsu Sanmu, and its model is E20.

[0124] The second epoxy resin has an epoxy equivalent of 227 g / mol and was purchased from Jiangsu Sanmu, model E44.

[0125] The mass ratio of the first epoxy resin to the second epoxy resin is 1:1.

[0126] The phenolic compound containing unsaturated long carbon chains is cashew phenol, with an acid value of 3.6 mg KOH / g, and was purchased from Shandong Jiaying Chemical Technology Co., Ltd.

[0127] The mass ratio of epoxy resin to cashew phenol is 23:10.

[0128] The emulsifier is allyl polyoxyethylene ether with a hydroxyl value of 53 mgKOH / g, purchased from Jiangsu Haian Petrochemical Plant, model APEG-1000.

[0129] The mass ratio of the epoxy resin to the allyl polyoxyethylene ether is 23:7.

[0130] The initiator is benzoyl peroxide.

[0131] The alcohol compound is n-butanol, and the alcohol ether compound is propylene glycol methyl ether.

[0132] A second aspect of this invention provides a method for preparing a novel waterborne epoxy ester, the specific steps of which are as follows:

[0133] S1: Mix and dissolve epoxy resin, alcohol compound and alcohol ether compound by weight for 13 min to obtain epoxy resin solution, and heat to 110℃ at the same time.

[0134] S2: Mix the phenolic compound containing unsaturated long carbon chains, emulsifier and initiator according to the weight parts, and stir at a stirring speed of 1500 rpm / min for 22 min to obtain the first solution.

[0135] S3: Under the condition that the stirring speed and temperature remain unchanged, the first solution is added dropwise to the epoxy resin solution over a period of 2 hours. Then, the initiator is added continuously until the initiator is completely added. The solution is then kept at 100-120℃ for 2 hours, and deionized water is added to obtain the final product.

[0136] The present invention also provides a water-based epoxy ester paint, which, by weight, comprises the following raw materials: 33 parts water-based epoxy ester, 1 part N,N-dimethylethanolamine, 35 parts deionized water, 0.3 parts water-based drier, 30 parts white paste, 0.1 parts non-silicone water-based defoamer, 0.2 parts organosilicon twin structure surfactant, 0.2 parts first thickener, and 0.2 parts second thickener.

[0137] This invention also provides a method for preparing a waterborne epoxy ester paint, the specific steps of which are as follows: First, waterborne epoxy ester, waterborne drier and N,N-dimethylethanolamine are stirred at a stirring speed of 1500 rpm / min for 1 hour to obtain a first mixed system. Then, white paste, non-silicone waterborne defoamer and organosilicon twin structure surfactant are added to the first mixed system according to the weight, and stirring is continued for 30 minutes to obtain a second mixed system. Then, a first thickener, a second thickener and deionized water are added to the second mixed system according to the weight, and stirring is carried out for 1 hour to obtain the final product.

[0138] The aqueous drying agent was purchased from OMG, model Octa-So ligen421.

[0139] The white paste was purchased from Jinan Puros Building Materials Co., Ltd., and its model number is W1008-sb.

[0140] The non-silicone water-based defoamer was purchased from Tego, model number Tego 830.

[0141] The organosilicon twin structure surfactant was purchased from Tego, model number Tego 4100.

[0142] The first thickener was purchased from Hemings and its model number is WT102.

[0143] The second thickener was purchased from Hemings and is model 350D.

[0144] Example 5

[0145] A novel waterborne epoxy ester, by weight, comprises the following raw materials: 25 parts epoxy resin, 8 parts phenolic compounds containing unsaturated long carbon chains, 7 parts emulsifier, 3 parts initiator, 5 parts alcohol compounds, 5 parts alcohol ether compounds, and 47 parts water.

[0146] The epoxy resin is a first epoxy resin and a second epoxy resin.

[0147] Both the first epoxy resin and the second epoxy resin are bisphenol A type epoxy resins.

[0148] The first epoxy resin has an epoxy equivalent of 500 g / mol, was purchased from Jiangsu Sanmu, and its model is E20.

[0149] The second epoxy resin has an epoxy equivalent of 227 g / mol and was purchased from Jiangsu Sanmu, model E44.

[0150] The mass ratio of the first epoxy resin to the second epoxy resin is 1:1.

[0151] The phenolic compound containing unsaturated long carbon chains is cashew phenol, with an acid value of 3.6 mg KOH / g, and was purchased from Shandong Jiaying Chemical Technology Co., Ltd.

[0152] The mass ratio of epoxy resin to cashew phenol is 25:8.

[0153] The emulsifier is allyl polyoxyethylene ether with a hydroxyl value of 53 mgKOH / g, purchased from Jiangsu Haian Petrochemical Plant, model APEG-1000.

[0154] The mass ratio of the epoxy resin to the allyl polyoxyethylene ether is 25:7.

[0155] The initiator is benzoyl peroxide.

[0156] The alcohol compound is n-butanol, and the alcohol ether compound is propylene glycol methyl ether.

[0157] A second aspect of this invention provides a method for preparing a novel waterborne epoxy ester, the specific steps of which are as follows:

[0158] S1: Mix and dissolve epoxy resin, alcohol compound and alcohol ether compound by weight for 13 min to obtain epoxy resin solution, and heat to 110℃ at the same time.

[0159] S2: Mix the phenolic compound containing unsaturated long carbon chains, emulsifier and initiator according to the weight parts, and stir at a stirring speed of 1500 rpm / min for 22 min to obtain the first solution.

[0160] S3: Under the condition that the stirring speed and temperature remain unchanged, the first solution is added dropwise to the epoxy resin solution over a period of 2 hours. Then, the initiator is added continuously until the initiator is completely added. The solution is then kept at 100-120℃ for 2 hours, and deionized water is added to obtain the final product.

[0161] The present invention also provides a water-based epoxy ester paint, which, by weight, comprises the following raw materials: 33 parts water-based epoxy ester, 1 part N,N-dimethylethanolamine, 35 parts deionized water, 0.3 parts water-based drier, 30 parts white paste, 0.1 parts non-silicone water-based defoamer, 0.2 parts organosilicon twin structure surfactant, 0.2 parts first thickener, and 0.2 parts second thickener.

[0162] This invention also provides a method for preparing a waterborne epoxy ester paint, the specific steps of which are as follows: First, waterborne epoxy ester, waterborne drier and N,N-dimethylethanolamine are stirred at a stirring speed of 1500 rpm / min for 1 hour to obtain a first mixed system. Then, white paste, non-silicone waterborne defoamer and organosilicon twin structure surfactant are added to the first mixed system according to the weight, and stirring is continued for 30 minutes to obtain a second mixed system. Then, a first thickener, a second thickener and deionized water are added to the second mixed system according to the weight, and stirring is carried out for 1 hour to obtain the final product.

[0163] The aqueous drying agent was purchased from OMG, model Octa-So ligen421.

[0164] The white paste was purchased from Jinan Puros Building Materials Co., Ltd., and its model number is W1008-sb.

[0165] The non-silicone water-based defoamer was purchased from Tego, model number Tego 830.

[0166] The organosilicon twin structure surfactant was purchased from Tego, model number Tego 4100.

[0167] The first thickener was purchased from Hemings and its model number is WT102.

[0168] The second thickener was purchased from Hemings and is model 350D.

[0169] Example 6

[0170] A novel waterborne epoxy ester, by weight, comprises the following raw materials: 26 parts epoxy resin, 8 parts phenolic compounds containing unsaturated long carbon chains, 6 parts emulsifier, 3 parts initiator, 5 parts alcohol compounds, 5 parts alcohol ether compounds, and 47 parts water.

[0171] The epoxy resin is a first epoxy resin and a second epoxy resin.

[0172] Both the first epoxy resin and the second epoxy resin are bisphenol A type epoxy resins.

[0173] The first epoxy resin has an epoxy equivalent of 500 g / mol, was purchased from Jiangsu Sanmu, and its model is E20.

[0174] The second epoxy resin has an epoxy equivalent of 227 g / mol and was purchased from Jiangsu Sanmu, model E44.

[0175] The mass ratio of the first epoxy resin to the second epoxy resin is 1:1.

[0176] The phenolic compound containing unsaturated long carbon chains is cashew phenol, with an acid value of 3.6 mg KOH / g, and was purchased from Shandong Jiaying Chemical Technology Co., Ltd.

[0177] The mass ratio of epoxy resin to cashew phenol is 26:8.

[0178] The emulsifier is allyl polyoxyethylene ether with a hydroxyl value of 53 mgKOH / g, purchased from Jiangsu Haian Petrochemical Plant, model APEG-1000.

[0179] The mass ratio of the epoxy resin to the allyl polyoxyethylene ether is 26:6.

[0180] The initiator is benzoyl peroxide.

[0181] The alcohol compound is n-butanol, and the alcohol ether compound is propylene glycol methyl ether.

[0182] A second aspect of this invention provides a method for preparing a novel waterborne epoxy ester, the specific steps of which are as follows:

[0183] S1: Mix and dissolve epoxy resin, alcohol compound and alcohol ether compound by weight for 13 min to obtain epoxy resin solution, and heat to 110℃ at the same time.

[0184] S2: Mix the phenolic compound containing unsaturated long carbon chains, emulsifier and initiator according to the weight parts, and stir at a stirring speed of 1500 rpm / min for 22 min to obtain the first solution.

[0185] S3: Under the condition that the stirring speed and temperature remain unchanged, the first solution is added dropwise to the epoxy resin solution over a period of 2 hours. Then, the initiator is added continuously until the initiator is completely added. The solution is then kept at 100-120℃ for 2 hours, and deionized water is added to obtain the final product.

[0186] The present invention also provides a water-based epoxy ester paint, which, by weight, comprises the following raw materials: 33 parts water-based epoxy ester, 1 part N,N-dimethylethanolamine, 35 parts deionized water, 0.3 parts water-based drier, 30 parts white paste, 0.1 parts non-silicone water-based defoamer, 0.2 parts organosilicon twin structure surfactant, 0.2 parts first thickener, and 0.2 parts second thickener.

[0187] This invention also provides a method for preparing a waterborne epoxy ester paint, the specific steps of which are as follows: First, waterborne epoxy ester, waterborne drier and N,N-dimethylethanolamine are stirred at a stirring speed of 1500 rpm / min for 1 hour to obtain a first mixed system. Then, white paste, non-silicone waterborne defoamer and organosilicon twin structure surfactant are added to the first mixed system according to the weight, and stirring is continued for 30 minutes to obtain a second mixed system. Then, a first thickener, a second thickener and deionized water are added to the second mixed system according to the weight, and stirring is carried out for 1 hour to obtain the final product.

[0188] The aqueous drying agent was purchased from OMG, model Octa-So ligen421.

[0189] The white paste was purchased from Jinan Puros Building Materials Co., Ltd., and its model number is W1008-sb.

[0190] The non-silicone water-based defoamer was purchased from Tego, model number Tego 830.

[0191] The organosilicon twin structure surfactant was purchased from Tego, model number Tego 4100.

[0192] The first thickener was purchased from Hemings and its model number is WT102.

[0193] The second thickener was purchased from Hemings and is model 350D.

[0194] Example 7

[0195] A novel waterborne epoxy ester, by weight, comprises the following raw materials: 15 parts epoxy resin, 15 parts phenolic compounds containing unsaturated long carbon chains, 7 parts emulsifier, 3 parts initiator, 5 parts alcohol compounds, 5 parts alcohol ether compounds, and 47 parts water.

[0196] The epoxy resin is a first epoxy resin and a second epoxy resin.

[0197] Both the first epoxy resin and the second epoxy resin are bisphenol A type epoxy resins.

[0198] The first epoxy resin has an epoxy equivalent of 500 g / mol, was purchased from Jiangsu Sanmu, and its model is E20.

[0199] The second epoxy resin has an epoxy equivalent of 227 g / mol and was purchased from Jiangsu Sanmu, model E44.

[0200] The mass ratio of the first epoxy resin to the second epoxy resin is 4:1.

[0201] The phenolic compound containing unsaturated long carbon chains is cashew phenol, with an acid value of 3.6 mg KOH / g, and was purchased from Shandong Jiaying Chemical Technology Co., Ltd.

[0202] The mass ratio of epoxy resin to cashew phenol is 18:15.

[0203] The emulsifier is allyl polyoxyethylene ether with a hydroxyl value of 53 mgKOH / g, purchased from Jiangsu Haian Petrochemical Plant, model APEG-1000.

[0204] The mass ratio of the epoxy resin to the allyl polyoxyethylene ether is 18:7.

[0205] The initiator is benzoyl peroxide.

[0206] The alcohol compound is n-butanol, and the alcohol ether compound is propylene glycol methyl ether.

[0207] A second aspect of this invention provides a method for preparing a novel waterborne epoxy ester, the specific steps of which are as follows:

[0208] S1: Mix and dissolve epoxy resin, alcohol compound and alcohol ether compound by weight for 13 min to obtain epoxy resin solution, and heat to 110℃ at the same time.

[0209] S2: Mix the phenolic compound containing unsaturated long carbon chains, emulsifier and initiator according to the weight parts, and stir at a stirring speed of 1500 rpm / min for 22 min to obtain the first solution.

[0210] S3: Under the condition that the stirring speed and temperature remain unchanged, the first solution is added dropwise to the epoxy resin solution over a period of 2 hours. Then, the initiator is added continuously until the initiator is completely added. The solution is then kept at 100-120℃ for 2 hours, and deionized water is added to obtain the final product.

[0211] The present invention also provides a water-based epoxy ester paint, which, by weight, comprises the following raw materials: 33 parts water-based epoxy ester, 1 part N,N-dimethylethanolamine, 35 parts deionized water, 0.3 parts water-based drier, 30 parts white paste, 0.1 parts non-silicone water-based defoamer, 0.2 parts organosilicon twin structure surfactant, 0.2 parts first thickener, and 0.2 parts second thickener.

[0212] This invention also provides a method for preparing a waterborne epoxy ester paint, the specific steps of which are as follows: First, waterborne epoxy ester, waterborne drier and N,N-dimethylethanolamine are stirred at a stirring speed of 1500 rpm / min for 1 hour to obtain a first mixed system. Then, white paste, non-silicone waterborne defoamer and organosilicon twin structure surfactant are added to the first mixed system according to the weight, and stirring is continued for 30 minutes to obtain a second mixed system. Then, a first thickener, a second thickener and deionized water are added to the second mixed system according to the weight, and stirring is carried out for 1 hour to obtain the final product.

[0213] The aqueous drying agent was purchased from OMG, model Octa-So ligen421.

[0214] The white paste was purchased from Jinan Puros Building Materials Co., Ltd., and its model number is W1008-sb.

[0215] The non-silicone water-based defoamer was purchased from Tego, model number Tego 830.

[0216] The organosilicon twin structure surfactant was purchased from Tego, model number Tego 4100.

[0217] The first thickener was purchased from Hemings and its model number is WT102.

[0218] The second thickener was purchased from Hemings and is model 350D.

[0219] Performance Evaluation

[0220] (1) Test of surface drying time and actual drying time: The test was conducted according to the test standard GB / T 1728-2020, and the test results are shown in Table 1 below.

[0221] (2) Test of pendulum stiffness: The test was conducted according to the test standard GB / T 1730-2006, and the test results are shown in Table 1 below.

[0222] (3) Gloss performance test: The test was conducted according to the test standard GB / T 9754-2007, and the test results are shown in Table 1 below.

[0223] (4) Adhesion test: The test was conducted according to the test standard GB / T 9286-2021, and the test results are shown in Table 1 below.

[0224] (5) Impact resistance test: The test was conducted according to the test standard GB / T 1732-2020, and the test results are shown in Table 1 below.

[0225] (6) Water resistance test: The test was conducted according to the test standard GB / T 1733-1993, and the test results are shown in Table 1 below. (7) Salt water resistance test: The test was conducted according to the test standard GB / T 9274-1988, and the test results are shown in Table 1 below.

[0226] (8) Salt spray resistance test: The test was conducted according to the test standard GB / T 1771-2007, and the test results are shown in Table 1 below.

[0227] (9) Viscosity test: The test was conducted according to the test standard GB / T 9269-2009, and the test results are shown in Table 1 below. (10) Storage stability test: The test was conducted according to the test standard GB / T 6753.3-1986, and the test results are shown in Table 1 below.

[0228] Table 1

[0229]

Claims

1. A waterborne epoxy resin, characterized in that, By weight, its raw materials include: 15-28 parts epoxy resin, 6-20 parts phenolic compounds containing unsaturated long carbon chains, 5-15 parts emulsifier, 2-8 parts initiator, 2-10 parts alcohol compounds, 2-10 parts alcohol ether compounds, and 20-50 parts water. The phenolic compound containing unsaturated long carbon chains is cashew phenol; the mass ratio between the epoxy resin and the phenolic compound containing unsaturated long carbon chains is (15-20):(10-20); the epoxy resin is a first epoxy resin and a second epoxy resin; the epoxy equivalent of the first epoxy resin is 500-800 g / mol, and the epoxy equivalent of the second epoxy resin is 200-300 g / mol; the mass ratio between the first epoxy resin and the second epoxy resin is (1-2):

1. The mass ratio of the epoxy resin to the emulsifier is (16-20):(7-15); the emulsifier is APEG-1000 with a hydroxyl value of 53 mgKOH / g. The acid value of the phenolic compound containing an unsaturated long carbon chain is ≤10 mgKOH / g; The alcohol compound is n-butanol, and the alcohol ether compound includes at least one of propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, ethylene glycol propyl ether, and ethylene glycol butyl ether. The specific steps for preparing the waterborne epoxy resin are as follows: S1: Mix and dissolve epoxy resin, alcohol compound and alcohol ether compound by weight for 10-15 minutes to obtain epoxy resin solution, while heating to 100-120℃. S2: Mix the phenolic compound containing unsaturated long carbon chains, emulsifier and initiator according to the weight parts, and stir at a stirring speed of 1000-2000 rpm / min for 20-25 min to obtain the first solution; S3: Under the condition that the stirring speed and temperature remain unchanged, the first solution is added dropwise to the epoxy resin solution over a period of 1-3 hours. After that, the initiator is added continuously until the initiator is completely added. Then, after keeping the solution at 100-120℃, deionized water is added to obtain the final product.

2. A method for preparing the waterborne epoxy resin according to claim 1, characterized in that, The specific steps are as follows: S1: Mix and dissolve epoxy resin, alcohol compound and alcohol ether compound by weight for 10-15 minutes to obtain epoxy resin solution, while heating to 100-120℃. S2: Mix the phenolic compound containing unsaturated long carbon chains, emulsifier and initiator according to the weight parts, and stir at a stirring speed of 1000-2000 rpm / min for 20-25 min to obtain the first solution; S3: Under the condition that the stirring speed and temperature remain unchanged, the first solution is added dropwise to the epoxy resin solution over a period of 1-3 hours. After that, the initiator is added continuously until the initiator is completely added. Then, after keeping the solution at 100-120℃, deionized water is added to obtain the final product.

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