Organic-inorganic hybrid water-borne epoxy resin and preparation method thereof

Abstract

The invention discloses organic-inorganic hybrid water-borne epoxy resin and a preparation method thereof.The preparation method comprises the following steps that S21, epoxy resin, an active diluent, a solvent and an emulsifier are mixed and then heated to 80-85 DEG C, and even dissolution is conducted till no solid particles exist; s22, dropwise adding a hybrid nano material dispersion liquid into the mixed liquid obtained in S21, and simultaneously performing high-speed dispersion; and S23, adding deionized water into the high-speed dispersion liquid obtained in the step S22, cooling and filtering to obtain the organic-inorganic hybrid water-borne epoxy resin. According to the organic-inorganic hybrid water-borne epoxy resin, in the phase inversion process, nano-material dispersion liquid is added, so that nano-materials are uniformly distributed on the surfaces of latex particles, the stable organic-inorganic hybrid water-borne epoxy resin is formed, the stability, film-forming property, water resistance and weather resistance of the water-borne epoxy resin can be improved, and the water-borne epoxy resin can be applied to the field of organic-inorganic hybrid water-borne epoxy resin. The water-based anticorrosive paint can be widely applied to steel structures.

Description

Technical Field

[0001] This application relates to the technical field of waterborne epoxy resins. Specifically, it relates to an organic-inorganic hybrid waterborne epoxy resin and a preparation method thereof. Background Art

[0002] Solvent-based epoxy resins are widely used in anti-corrosion coatings. Waterborne epoxy resins are a technical route for low-VOCs epoxy anti-corrosion coatings. Since waterborne epoxy resins need to introduce hydrophilic segments through chemical modification to disperse the epoxy resin in water, this results in a slow drying speed, poor chemical resistance and salt spray resistance, and cannot reach the level of solvent-based epoxy resins. Usually, inorganic modification can well improve the drying speed and crosslinking density of waterborne epoxy resins, and reduce VOCs without reducing the anti-corrosion performance. However, the poor dispersion uniformity and interfacial bonding force between inorganic materials and organic materials are a major difficulty restricting this technology.

[0003] Therefore, it is urgent to synthesize an organic-inorganic hybrid waterborne epoxy resin to modify waterborne epoxy resins to obtain products with good performance, simple process, good water resistance, good film-forming property and stability. Summary of the Invention

[0004] The main purpose of this application is to provide a hybrid nanomaterial dispersion liquid, and by adding the hybrid nanomaterial dispersion liquid dropwise during the phase inversion process, the hybrid nanomaterials are uniformly dispersed on the surface of latex particles to improve the stability, adhesion, chemical resistance and weather resistance of waterborne epoxy resins, so as to solve the current problems.

[0005] To achieve the above purpose, this application provides the following technology:

[0006] A preparation method of a hybrid nanomaterial dispersion liquid includes the following steps: Mix the following components and materials in parts by weight, and then disperse the paste-like solid generated by the hydrolysis reaction after mixing in 30-40 parts by weight of deionized water to obtain the hybrid nanomaterial dispersion liquid:

[0007]

[0008] The lower alcohol is at least one of C1-C5 alcohols;

[0009] The first hydrolysis monomer is selected from at least one of titanium tetrachloride, aluminum trichloride, ferric trichloride, strontium chloride, barium chloride, nickel chloride, vanadium chloride, gallium chloride;

[0010] The second hydrolysis monomer is selected from at least one of sodium hydrogen phosphate, sodium dihydrogen phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate.

[0011] The C1-C5 alcohols are selected from at least one of ethanol, isopropanol, butanol, isobutanol.

[0012] The silane coupling agent is selected from at least one of γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane.

[0013] Specifically, a method for preparing a hybrid nanomaterial dispersion of the present invention includes the following preparation steps:

[0014] (1) Hydrolysis: Mix 8-11 parts by weight of deionized water, 1-4 parts by weight of lithium hydroxide, 1-4 parts by weight of silane coupling agent, and 4-8 parts by weight of lower alcohol to form a mixed solution A; under stirring conditions, add 15-25 parts by weight of the first hydrolysis monomer, 3-8 parts by weight of the second hydrolysis monomer, and 21-29 parts by weight of deionized water to the mixed solution A for hydrolysis reaction to obtain a hybrid nanomaterial sol.

[0015] (2) Solid-liquid separation: Let the hybrid nanomaterial sol stand and / or centrifuge to remove the alcohol solvent and water to obtain a paste-like solid.

[0016] (3) Dispersion: Disperse the paste-like solid in deionized water to obtain a hybrid nanomaterial dispersion.

[0017] More specifically, the order of adding the first hydrolysis monomer, the second hydrolysis monomer, and deionized water to the mixed solution A is: Dropwise add solution B obtained by mixing the first hydrolysis monomer and 10-13 parts by weight of deionized water to the mixed solution A, and then dropwise add solution C obtained by mixing the second hydrolysis monomer and 11-16 parts by weight of deionized water thereto.

[0018] Or the order of adding the first hydrolysis monomer, the second hydrolysis monomer, and deionized water to the mixed solution A is: Dropwise add the titanium tetrachloride to the mixed solution A, then add 10-13 parts by weight of deionized water, and then dropwise add solution C obtained by mixing the second hydrolysis monomer and 11-16 parts by weight of deionized water thereto.

[0019] Or the order of adding the first hydrolysis monomer, the second hydrolysis monomer, and deionized water to the mixed solution A is: Dropwise add the titanium tetrachloride to the mixed solution A, then add solution E obtained by mixing at least one of aluminum trichloride, iron trichloride, strontium chloride, barium chloride, nickel chloride, vanadium chloride, and gallium chloride and 10-13 parts by weight of deionized water, and then dropwise add solution C obtained by mixing the second hydrolysis monomer and 11-16 parts by weight of deionized water thereto.

[0020] More specifically, the dropping time of the solution B, the titanium tetrachloride, or the solution E into the solution A is 2 to 5 hours. After the dropping is completed, the reaction continues for 1 to 5 hours, and then the solution C is dropped; the dropping time of the solution C is 1 to 2 hours. After the dropping is completed, the reaction continues for 1 to 2 hours to obtain a solution D.

[0021] More specifically, the solution D is heated to 80 to 120 °C, and after reacting for 2 to 8 hours, it is cooled to room temperature to obtain a hybrid nanomaterial sol.

[0022] The standing is carried out at room temperature, and the standing time is at least 24 hours.

[0023] The method for removing the alcohol solvent is vacuum filtration after standing and / or centrifugation.

[0024] The method for removing water is filtration.

[0025] The paste-like solid is dispersed in deionized water by ultrasonic dispersion.

[0026] The present application further provides a hybrid nanomaterial dispersion prepared according to the above method.

[0027] On the other hand, the present application also provides a method for preparing an organic-inorganic hybrid waterborne epoxy resin, including the following steps:

[0028] S21, after mixing epoxy resin, active diluent, solvent, and emulsifier, heating to 80 to 85 °C and dissolving uniformly until there are no solid particles;

[0029] S22, dropping the hybrid nanomaterial dispersion into the mixture obtained in S21 and simultaneously performing high-speed dispersion;

[0030] S23, adding deionized water to the high-speed dispersion obtained in S22, cooling and filtering to obtain the organic-inorganic hybrid waterborne epoxy resin;

[0031] The hybrid nanomaterial dispersion is prepared by the preparation method of the hybrid nanomaterial dispersion described above;

[0032] The solvent is an ether organic solvent.

[0033] The epoxy resin is at least one of E51 bisphenol A epoxy resin, E44 bisphenol A epoxy resin, E20 bisphenol A epoxy resin, E12 bisphenol A epoxy resin, E06 bisphenol A epoxy resin, E03 bisphenol A epoxy resin, F51 phenolic epoxy resin, and F44 phenolic epoxy resin.

[0034] The active diluent is at least one of 1,6 - hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, resorcinol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, 1,4 - butanediol diglycidyl ether, phenyl glycidyl ether, o - cresol glycidyl ether, cashew phenol glycidyl ether, butyl glycidyl ether, C12 - C14 glycidyl ether, octyl glycidyl ether.

[0035] The solvent is selected from at least one of propylene glycol methyl ether, ethylene glycol butyl ether, dipropylene glycol methyl ether, diethylene glycol butyl ether, ethylene glycol tert - butyl ether.

[0036] The emulsifier is selected from at least one of alkylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, Pluronic polyether, sodium dodecylbenzenesulfonate, ammonium dodecyl sulfate, polyetheramine Huntsman M - 600, polyetheramine Huntsman M - 1000, polyetheramine Huntsman M - 2070, polyetheramine Huntsman M - 3085.

[0037] The present application further provides an organic - inorganic hybrid water - borne epoxy resin prepared according to the above method.

[0038] Compared with the prior art, the present application can bring the following technical effects:

[0039] The hybrid nanomaterial dispersion liquid prepared in the present application can make the nanomaterials evenly distributed on the surface of latex particles and form a physical shielding layer, which can effectively protect the epoxy resin chain from the attack of chemical media and ultraviolet rays. The product has good stability, does not break emulsion after long - term storage, good film - forming property, excellent water resistance, chemical medium resistance and weather resistance.

[0040] When preparing the organic - inorganic hybrid water - borne epoxy resin in the present application, by adding the hybrid nanomaterial dispersion liquid during the phase inversion process, the nanomaterials are evenly distributed on the surface of latex particles, forming a stable organic - inorganic hybrid water - borne epoxy resin, which can improve the stability, film - forming property, water resistance and weather resistance of the water - borne epoxy resin, and can be widely used in water - borne anticorrosive coatings for steel structures.

[0041] The hybrid nanocrystal nuclei formed in the present invention have a strong penetration and catalytic curing effect on the surface of concrete and / or glass. Therefore, the water - borne epoxy resin made of the hybrid nanomaterial dispersion liquid can penetrate and cure the surface of concrete and / or glass, significantly improving the adhesion. Detailed implementation mode

[0042] The present invention will be further described below in conjunction with embodiments. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments in the present application without making creative efforts shall fall within the scope of protection of the present application. Unless otherwise specified, the parts in the present invention refer to parts by weight.

[0043] It should be noted that, without conflict, the embodiments in the present application and the features in the embodiments can be combined with each other.

[0044] The hybrid nanomaterial dispersion is prepared by the following steps:

[0045] (1) Hydrolysis:

[0046] 8 - 11 parts of deionized water, 1 - 4 parts of lithium hydroxide, 1 - 4 parts of silane coupling agent, and 4 - 8 parts of lower alcohol are successively added into the reaction kettle, and stirring is started to dissolve the materials evenly; 15 - 25 parts of the first hydrolysis monomer and 10 - 13 parts of deionized water are added into the 1# high-level tank and dissolved and stirred evenly (since titanium tetrachloride is a liquid and hydrolyzes directly when encountering water, if the first hydrolysis monomer is only titanium tetrachloride, then titanium tetrachloride is directly dropped into the reaction kettle, and the remaining deionized water is used for rinsing and added into the reaction kettle), the solution in the 1# high-level tank is evenly dropped into the reaction kettle, the dropping time is 2 - 5 h, after the dropping is completed, the reaction continues for 1 - 5 h. 3 - 8 parts of the second hydrolysis and 11 - 16 parts of deionized water are added into the 2# high-level tank and stirred and dissolved evenly. The solution in the 2# high-level tank is evenly dropped into the reaction kettle, the dropping time is 1 - 2 h, after the dropping is completed, the reaction continues for 1 - 2 h. The temperature is raised to 80 - 120 °C, after reacting for 2 - 8 h, it is cooled to room temperature;

[0047] (2) Static separation:

[0048] The liquid in the reaction kettle is left standing at room temperature for 24 h;

[0049] (3) Vacuum filtration:

[0050] The standing liquid is vacuum filtered under a vacuum pressure of -0.4 Mpa to -0.9 Mpa, and the filtered liquid is removed to obtain a white to light yellow paste-like solid.

[0051] The organic-hybrid waterborne epoxy resin is prepared by the following steps:

[0052] (1) Epoxy resin, active diluent, solvent, and emulsifier are added into the emulsification kettle, and the temperature is raised to 80 °C and dissolved evenly until there are no particles;

[0053] (2) The hybrid nanomaterial dispersion is pre-added into the dropping tank in advance;

[0054] (3) Add the hybrid nanomaterial dispersion in the dropping tank dropwise to the emulsifying kettle, and at the same time start high-speed dispersion for phase inversion. Finish dropping in 1 - 2 h, and continue high-speed dispersion for 30 min after dropping.

[0055] (4) Finally, add deionized water;

[0056] (5) Cool down to 50 °C and filter to obtain the organic-inorganic hybrid waterborne epoxy resin.

[0057] Next, the performance comparison will be carried out in combination with the following specific examples and comparative examples.

[0058] Example 1

[0059] The raw materials for each step of preparing the hybrid nanomaterial dispersion include the following components and parts by weight:

[0060]

[0061]

[0062] Take 8 parts of deionized water, 2 parts of lithium hydroxide, 2 parts of γ-aminopropyltriethoxysilane, and 6 parts of ethanol and add them to the reaction kettle, and stir to dissolve evenly. Slowly add 25 parts of titanium tetrachloride to the No. 1 high-level tank. Drop the titanium tetrachloride in the No. 1 high-level tank into the reaction kettle, and finish dropping in 3 h. After dropping, add 10 parts of deionized water and react for 2 h. Add 4 parts of sodium dihydrogen phosphate and 12 parts of deionized water to the No. 2 high-level tank, stir to dissolve evenly, and then drop it into the reaction kettle, and finish dropping in 1 h. After dropping, react for 1 h. Then raise the temperature to 90 °C and react for 3 h, and then cool down to room temperature.

[0063] Let the solution in the reaction kettle stand for 24 h. Then filter under a vacuum pressure of -0.4 Mpa to -0.9 Mpa to remove the liquid and obtain a white paste-like solid.

[0064] Mix the obtained white paste-like solid with 31 parts of deionized water for dispersion and perform ultrasonic dispersion with ultrasonic waves to obtain a hybrid nanomaterial dispersion with a solid content of 20%, a pH of 3.2, an average particle size of 35 nm, and a viscosity of 12 s for a coating - 4 cup at 25 °C.

[0065] Preparation of the organic-inorganic hybrid waterborne epoxy resin:

[0066] (1) Add 38 parts of E20 epoxy resin, 4 parts of polyethylene glycol diglycidyl ether, 8 parts of propylene glycol methyl ether, and 5 parts of polyetheramine Huntsman M-3085 to the emulsifying kettle, raise the temperature to 80 °C, and keep warm for 4 hours to dissolve evenly;

[0067] (2) Add 20 parts of the hybrid nanomaterial dispersion to the dropping tank and set aside;

[0068] (3) Add the hybrid nanomaterial dispersion in the dropping tank dropwise to the emulsification kettle, and at the same time start high-speed dispersion for phase inversion. The dropping time is 1 h, and continue high-speed dispersion for 30 min after dropping is completed.

[0069] (4) Continuously add 25 parts of deionized water.

[0070] (5) Cool down to 50 °C, filter, and obtain the organic-inorganic hybrid waterborne epoxy resin.

[0071] Example 2

[0072] The raw materials for each step of preparing the hybrid nanomaterial dispersion include the following components and parts by weight:

[0073]

[0074] Take 9 parts of deionized water, 1 part of lithium hydroxide, 1 part of γ-aminopropyltriethoxysilane, and 5 parts of isopropanol and add them to the reaction kettle, and stir to dissolve evenly. Slowly add 20 parts of ferric chloride and 10 parts of deionized water to the No. 1 high-position tank, and stir to dissolve evenly. Drop the solution in the No. 1 high-position tank into the reaction kettle, and finish dropping in 3.5 h. After dropping, react for 2 h. Add 3 parts of sodium hydrogen phosphate and 11 parts of deionized water to the No. 2 high-position tank, stir to dissolve evenly, then drop it into the reaction kettle, and finish dropping in 1.5 h. After dropping, react for 1 h. Then raise the temperature to 95 °C and react for 4 h, and then cool down to room temperature.

[0075] Let the solution in the reaction kettle stand for 24 h. Then filter under a vacuum pressure of -0.4 Mpa to -0.9 Mpa, filter off the liquid, and obtain a slightly yellow paste-like solid.

[0076] Mix the obtained slightly yellow paste-like solid with 40 parts of deionized water for dispersion, and perform ultrasonic dispersion with ultrasonic waves to obtain a hybrid nanomaterial dispersion with a solid content of 18%, a pH of 4, an average particle size of 48 nm, and a viscosity of 11 s for a coating-4 cup at 25 °C.

[0077] Preparation of organic-inorganic hybrid waterborne epoxy resin:

[0078] (1) Add 45 parts of E51 epoxy resin, 2 parts of polypropylene glycol diglycidyl ether, 2 parts of cashew phenol glycidyl ether, 5 parts of ethylene glycol monobutyl ether, 2 parts of alkylphenol polyoxyethylene ether, and 1 part of sodium dodecylbenzenesulfonate to the emulsification kettle, raise the temperature to 80 °C, and keep warm for 4 hours to dissolve evenly;

[0079] (2) Add 15 parts of the nanomaterial dispersion to the dropping tank and set aside;

[0080] (3) Add the hybrid nanomaterial dispersion in the dropping tank dropwise to the emulsifying kettle, and at the same time start high-speed dispersion for inversion. The dropping time is 1 h, and continue high-speed dispersion for 30 min after dropping;

[0081] (4) Continue to add 28 parts of deionized water;

[0082] (5) Cool down to 50 °C, filter to obtain the organic-inorganic hybrid waterborne epoxy resin.

[0083] Example 3

[0084] The raw materials for each step of preparing the hybrid nanomaterial dispersion include the following components and parts by weight:

[0085]

[0086] Take 8 parts of deionized water, 3 parts of lithium hydroxide, 2 parts of γ-methacryloxypropyltrimethoxysilane, and 8 parts of ethanol and add them to the reaction kettle, and stir to dissolve evenly. Slowly add 13 parts of titanium tetrachloride to the No. 1 high-level tank, and drop the titanium tetrachloride in the No. 1 high-level tank into the reaction kettle, and finish dropping in 2 h. After dropping, add 5 parts of aluminum trichloride and 10 parts of deionized water to the No. 1 high-level tank, dissolve and stir evenly, and drop it into the reaction kettle. The dropping time is 2 h, and react for 2 h after dropping. Add 6 parts of potassium dihydrogen phosphate and 12 parts of deionized water to the No. 2 high-level tank, stir to dissolve evenly, then drop it into the reaction kettle, finish dropping in 1 h, and react for 1 h after dropping. Then heat up to 90 °C, react for 3 h, and then cool down to room temperature.

[0087] Let the solution in the reaction kettle stand for 24 h. Then filter under a vacuum pressure of -0.4 Mpa to -0.9 Mpa, filter off the liquid to obtain a white paste solid.

[0088] Mix the obtained white paste solid with 33 parts of deionized water for dispersion, and perform ultrasonic dispersion with ultrasonic waves to obtain a hybrid nanomaterial dispersion with a solid content of 19%, a pH of 2.9, an average particle size of 30 nm, and a viscosity of 10 s for a coating-4 cup at 25 °C.

[0089] Preparation of organic-inorganic hybrid waterborne epoxy resin:

[0090] (1) Add 30 parts of E12 epoxy resin, 8 parts of 1,4-butanediol diglycidyl ether, 10 parts of diethylene glycol butyl ether, 8 parts of polyetheramine Huntsman M-2070, and 2 parts of Pluronic polyether Pluronic PE 6200 to the emulsifying kettle, heat up to 80 °C, and keep warm for 4 h to dissolve and mix evenly;

[0091] (2) Add 15 parts of the nanomaterial dispersion to the dropping tank and set aside;

[0092] (3) Add the hybrid nanomaterial dispersion in the dropping tank dropwise to the emulsifying kettle, and at the same time start high-speed dispersion for phase inversion. The dropping time is 1 h, and continue high-speed dispersion for 30 min after dropping is completed;

[0093] (4) Continuously add 27 parts of deionized water;

[0094] (5) Cool down to 50 °C, filter and package to obtain an organic-inorganic hybrid waterborne epoxy resin.

[0095] Example 4

[0096] The raw materials for each step of preparing the hybrid nanomaterial dispersion include the following components and parts by weight:

[0097]

[0098] Take 11 parts of deionized water, 4 parts of lithium hydroxide, 2 parts of γ-glycidoxypropyltrimethoxysilane, and 4 parts of butanol and add them to the reaction kettle, and stir to dissolve evenly. Slowly add 15 parts of ferric chloride and 10 parts of deionized water to the No. 1 high-position tank, and stir to dissolve evenly. Drop the solution in the No. 1 high-position tank into the reaction kettle, and finish dropping in 3.5 h. After dropping, react for 2 h. Add 8 parts of potassium hydrogen phosphate and 16 parts of deionized water to the No. 2 high-position tank, stir to dissolve evenly, and then drop it into the reaction kettle, and finish dropping in 1.5 h. After dropping, react for 1 h. Then raise the temperature to 95 °C and react for 4 h, and then cool to room temperature.

[0099] Let the solution in the reaction kettle stand for 24 h. Then filter under a vacuum pressure of -0.4 Mpa to -0.9 Mpa, filter off the liquid, and obtain a slightly yellow paste-like solid.

[0100] Mix the obtained slightly yellow paste-like solid with 30 parts of deionized water for dispersion, and perform ultrasonic dispersion with ultrasonic waves to obtain a hybrid nanomaterial dispersion with a solid content of 19%, a pH of 3.5, an average particle size of 48 nm, and a viscosity of 10 s for a coating-4 cup at 25 °C.

[0101] Preparation of organic-inorganic hybrid waterborne epoxy resin:

[0102] (1) Add 50 parts of F51 type phenolic epoxy resin, 3 parts of octyl glycidyl ether, 5 parts of dipropylene glycol methyl ether, and 3 parts of fatty alcohol polyoxyethylene ether to the emulsifying kettle, raise the temperature to 80 °C, and keep warm for 4 hours to dissolve evenly;

[0103] (2) Add 15 parts of the nanomaterial dispersion to the dropping tank and set aside;

[0104] (3) Add the hybrid nanomaterial dispersion in the dropping tank dropwise to the emulsifying kettle, and at the same time start high-speed dispersion for inversion. The dropping time is 1 h, and continue high-speed dispersion for 30 min after dropping;

[0105] (4) Continuously add 24 parts of deionized water;

[0106] (5) Cool down to 50 °C, filter and package to obtain an organic-inorganic hybrid waterborne epoxy resin.

[0107] Example 5

[0108] The raw materials for each step of preparing the hybrid nanomaterial dispersion include the following components and parts by weight:

[0109]

[0110] Take 8 parts of deionized water, 2 parts of lithium hydroxide, 4 parts of γ-aminopropyltriethoxysilane, and 6 parts of isobutanol and add them to the reaction kettle, stir and dissolve evenly. Slowly add 12 parts of titanium tetrachloride to the No. 1 high-position tank, and drop the titanium tetrachloride in the No. 1 high-position tank into the reaction kettle, and finish dropping in 2 h. After dropping, add 8 parts of nickel chloride and 13 parts of deionized water to the No. 1 high-position tank, dissolve and stir evenly, and drop it into the reaction kettle. The dropping time is 2 h, and react for 2 h after dropping. Add 4 parts of potassium dihydrogen phosphate and 12 parts of deionized water to the No. 2 high-position tank, stir and dissolve evenly, then drop it into the reaction kettle, and finish dropping in 1 h. After dropping, react for 1 h. Then raise the temperature to 90 °C, react for 3 h, and then cool down to room temperature.

[0111] Let the solution in the reaction kettle stand for 24 h. Then filter under a vacuum pressure of -0.4 Mpa to -0.9 Mpa, filter off the liquid to obtain a white paste solid.

[0112] Disperse the obtained white paste solid in 31 parts of deionized water, and perform ultrasonic dispersion with ultrasonic waves to obtain a hybrid nanomaterial dispersion with a solid content of 20%, a pH of 3.2, an average particle size of 43 nm, and a viscosity of 11 s for a Ford 4 cup at 25 °C.

[0113] Preparation of organic-inorganic hybrid waterborne epoxy resin:

[0114] (1) Add 31 parts of E06 type bisphenol A epoxy resin, 5 parts of 1,6-hexanediol diglycidyl ether, 8 parts of ethylene glycol tert-butyl ether, and 5 parts of ammonium dodecyl sulfate to the emulsifying kettle, heat up to 80 °C, and keep warm for 4 h to dissolve and mix evenly;

[0115] (2) Add 16 parts of the nanomaterial dispersion to the dropping tank and set aside;

[0116] (3) Add the hybrid nanomaterial dispersion in the dropping tank dropwise into the emulsifying kettle, and at the same time start high-speed dispersion for phase inversion. The dropping time is 1 h, and after dropping, continue high-speed dispersion for 30 min;

[0117] (4) Continue to add 35 parts of deionized water;

[0118] (5) Cool down to 50 °C, filter and package to obtain an organic-inorganic hybrid waterborne epoxy resin.

[0119] Comparative Example 3: According to the formulation and preparation process of Example 1, replace the nano-dispersion liquid with the nano-dispersion liquid in CN11261876A.

[0120] Comparative Example 4: According to the formulation and preparation process of Example 2, replace the nano-dispersion liquid with the nano-dispersion liquid in CN11261876A.

[0121] Using the waterborne epoxy resins of Examples 1-5 and Comparative Examples 1 and 2, with polyetheramine Huntsman D230 as the curing agent, prepare according to the ratio of 20% excess epoxy, coat with an 80 μm wire bar on the polished Q235 steel plate, and test the performance after drying for 7 d. Compare the performance with Comparative Examples 1 and 2. The results are shown in Table 1. Epikote5520-W-60A waterborne epoxy resin is selected for Comparative Example 1, and Epikote3520-WY-55A waterborne epoxy resin is selected for Comparative Example 2.

[0122] Table 1

[0123]

[0124]

[0125] Table 2

[0126]

[0127] It can be clearly seen from Table 1 that for the organic-inorganic hybrid waterborne epoxy resin prepared by this application, in terms of salt spray resistance, resistance to sulfuric acid and sodium hydroxide, and comparison of artificial accelerated aging resistance performance, the products obtained by this application have higher performance than the waterborne epoxy resins of the comparative examples.

[0128] It can be seen from Table 2 that Examples 1-5 have better adhesion on glass and concrete than Comparative Examples 3-4.

Claims

1. A preparation method of an organic-inorganic hybrid waterborne epoxy resin, characterized in that It includes the following steps: S21. After mixing epoxy resin, reactive diluent, solvent and emulsifier, heat up to 80 - 85 °C and dissolve evenly until there are no solid particles. S22. Dropwise add the hybrid nanomaterial dispersion into the mixture obtained in S21, and at the same time perform high-speed dispersion. S23. Add deionized water to the high-speed dispersion obtained in S22, cool down and filter to obtain the organic-inorganic hybrid waterborne epoxy resin. The hybrid nanomaterial dispersion is prepared by the following method: Mix the following components and materials in parts by weight, and then disperse the paste-like solid generated by the hydrolysis reaction after mixing in 30 - 40 parts by weight of deionized water to obtain the hybrid nanomaterial dispersion. The lower alcohol is at least one of C1 - C5 alcohols. The first hydrolysis monomer is selected from at least one of titanium tetrachloride, aluminum trichloride, iron trichloride, strontium chloride, barium chloride, nickel chloride, vanadium chloride, gallium chloride. The second hydrolysis monomer is selected from at least one of sodium hydrogen phosphate, sodium dihydrogen phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate. The solvent is an ether organic solvent.

2. The preparation method according to claim 1, wherein The C1 - C5 alcohol is selected from at least one of ethanol, isopropanol, butanol, isobutanol; the silane coupling agent is selected from at least one of γ-aminopropyltriethoxysilane, γ-glycidyletheroxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane.

3. The preparation method according to claim 1, characterized in that, The preparation of the hybrid nanomaterial dispersion includes the following specific steps: (1) Hydrolysis: Mix 8 - 11 parts by weight of deionized water, 1 - 4 parts by weight of lithium hydroxide, 1 - 4 parts by weight of silane coupling agent and 4 - 8 parts by weight of lower alcohol to form a mixed solution A; Under stirring conditions, add 15 - 25 parts by weight of the first hydrolysis monomer, 3 - 8 parts by weight of the second hydrolysis monomer and 21 - 29 parts by weight of deionized water to the mixed solution A for hydrolysis reaction to obtain the hybrid nanomaterial sol. (2) Solid-liquid separation: Let the hybrid nanomaterial sol stand still and / or centrifuge to remove the alcohol solvent and water to obtain a paste-like solid. (3) Dispersion: Disperse the paste-like solid in deionized water to obtain a hybrid nanomaterial dispersion.

4. The preparation method according to claim 3, wherein The order of adding the first hydrolysis monomer, the second hydrolysis monomer and deionized water to the mixed solution A is: Dropwise add solution B obtained by mixing the first hydrolysis monomer and 10 - 13 parts by weight of deionized water into the mixed solution A, and then dropwise add solution C obtained by mixing the second hydrolysis monomer and 11 - 16 parts by weight of deionized water into it. Or the order of adding the first hydrolysis monomer, the second hydrolysis monomer and deionized water to the mixed solution A is: Dropwise add the titanium tetrachloride into the mixed solution A, then add 10 - 13 parts by weight of deionized water, and then dropwise add solution C obtained by mixing the second hydrolysis monomer and 11 - 16 parts by weight of deionized water into it. Alternatively, the order of adding the first hydrolyzable monomer, the second hydrolyzable monomer and deionized water to the mixed solution A is as follows: titanium tetrachloride is added dropwise to the mixed solution A, and then a solution E obtained by mixing at least one of aluminum trichloride, iron trichloride, strontium chloride, barium chloride, nickel chloride, vanadium chloride, gallium chloride and 10-13 parts by weight of deionized water is added, and then a solution C obtained by mixing the second hydrolyzable monomer and 11-16 parts by weight of deionized water is added dropwise thereto.

5. The preparation method according to claim 4, wherein The dropping time for dropping the solution B or the titanium tetrachloride or the solution E into the solution A is 2-5 h. After the dropping is completed, the reaction is continued for 1-5 h, and then the solution C is added dropwise; the dropping time for the solution C is 1-2 h. After the dropping is completed, the reaction is continued for 1-2 h to obtain a solution D. The solution D is heated to 80-120 °C, reacted for 2-8 h, and then cooled to room temperature to obtain a hybrid nanomaterial sol.

6. The preparation method according to claim 3, characterized in that The standing is carried out at room temperature, and the standing time is at least 24 h; the method for removing the alcohol solvent is vacuum filtration after standing and / or centrifugation; the method for removing water is filtration.

7. The preparation method according to claim 1, characterized in that The epoxy resin is at least one of E51 type bisphenol A epoxy resin, E44 type bisphenol A epoxy resin, E20 type bisphenol A epoxy resin, E12 type bisphenol A epoxy resin, E06 type bisphenol A epoxy resin, E03 type bisphenol A epoxy resin, F51 type phenolic epoxy resin, F44 type phenolic epoxy resin.

8. The preparation method according to claim 1, characterized in that, The active diluent is at least one of 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, resorcinol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, phenyl glycidyl ether, o-cresol glycidyl ether, cashew phenol glycidyl ether, butyl glycidyl ether, C12-C14 glycidyl ether, octyl glycidyl ether. The solvent is selected from at least one of propylene glycol methyl ether, ethylene glycol butyl ether, dipropylene glycol methyl ether, diethylene glycol butyl ether, ethylene glycol tert-butyl ether. The emulsifier is selected from at least one of alkylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, Pluronic polyether, sodium dodecylbenzenesulfonate, ammonium dodecyl sulfate, polyetheramine Huntsman M-600, polyetheramine Huntsman M-1000, polyetheramine Huntsman M-2070, polyetheramine Huntsman M-3085.

9. The preparation method according to claim 1, characterized in that, In the preparation step of the organic-inorganic hybrid waterborne epoxy resin, based on the total addition amount of 100 parts by weight of each component, the addition amounts of each component are: 30-50 parts by weight of epoxy resin, 3-8 parts by weight of active diluent, 5-10 parts by weight of solvent, 3-10 parts by weight of emulsifier, 15-25 parts by weight of hybrid nanomaterial dispersion liquid and 24-35 parts by weight of deionized water.

10. An organic-inorganic hybrid waterborne epoxy resin prepared by the method according to any one of claims 1-9.

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