Hybrid nano material dispersion liquid and preparation method thereof

Abstract

The invention discloses a hybrid nano material dispersion liquid and a preparation method thereof. The preparation method comprises the following steps: mixing the following components and materials in parts by weight, and dispersing paste solid generated by hydrolysis reaction after mixing into 30-40 parts by weight of deionized water to prepare a hybrid nano material dispersion liquid: 1-4 parts by weight of lithium hydroxide; 1-4 parts of a silane coupling agent; 15-25 parts of a first hydrolytic monomer; 3-8 parts of a second hydrolyzed monomer; 4-8 parts of lower alcohol; and 30-40 parts of deionized water for hydrolysis. The hybrid nano-material dispersion liquid can replace a traditional plasma or nonionic emulsifier such as nonylphenol polyoxyethylene ether, is used as a surface active material in polyacrylic emulsion polymerization, and is uniformly distributed on the interface of water-polymer colloidal particles by utilizing the special water-oil balance effect of the nano-material; therefore, the polymer is uniformly and stably dispersed in water, and the adhesive force, the water resistance, the chemical medium resistance and the salt fog resistance of a paint film are improved.

Description

Technical Field

[0001] The present invention relates to the field of nanomaterials, and particularly to a hybrid nanomaterial dispersion liquid and a preparation method thereof. Background Art

[0002] Ionic or non-ionic emulsifiers such as alkylphenol polyoxyethylene ether, sorbitan polyoxyethylene fatty acid ester, sodium dodecyl sulfonate, sodium dodecyl sulfate, etc. are commonly used as emulsifiers for the emulsion polymerization of polyacrylate. The emulsifier dissolves in water to form micelles, and the monomer and initiator enter the micelles for free radical polymerization reaction, thereby obtaining a uniformly dispersed polyacrylate latex resin. The amount of emulsifier used is generally 1%-5% of the total amount of monomers. After the paint film is formed, the emulsifier remains and is free in the paint film. Due to its water solubility, it will cause a decrease in water resistance and chemical resistance.

[0003] Some nanomaterials with special structures have certain surface active effects and can replace emulsifiers to disperse oil-based substances in water to form emulsions. Such emulsions are often called Pickering emulsions. CN 109498486A discloses an amphiphilic titanium dioxide emulsifier, a Pickering emulsion and a preparation method and use thereof, and can use the prepared amphiphilic titanium dioxide emulsifier to prepare emulsions from animal and vegetable oils, synthetic esters, waxes, silicone oils or silicone oil derivatives, etc., but does not study its application in acrylate emulsion polymerization. CN 108129604A discloses a preparation method of a polyacrylate Pickering emulsion, and uses a modified hollow SiO2 nanoparticle to obtain a polyacrylate Pickering emulsion through emulsion polymerization; however, the preparation of hollow SiO2 nanoparticles requires a large amount of ethanol, which undoubtedly causes resource consumption and environmental pollution; and the solid content of the emulsion obtained by this SiO2 nanoparticle is only 30%, so the solid content of the prepared waterborne coating is low and the paint film is thin, and it is difficult to become a commercial resin. CN 104892828 A discloses a method for preparing a polyacrylate / nano-ZnO composite leather finishing agent by Pickering emulsion polymerization. A large amount of ethanol is also required in the process of preparing the nano-ZnO aqueous dispersion. At the same time, the solid content of the synthesized polyacrylate emulsion is low, only about 10%, and it is difficult to meet the standard of commercial resin.

[0004] Therefore, it is urgent to synthesize polyacrylate latex resin by Pickering emulsion method to improve the defects of the traditional emulsifier method and obtain products with good performance, simple process and high solid content. Summary of the Invention

[0005] The purpose of the present invention is to provide a hybrid nanomaterial dispersion liquid and a preparation method thereof in order to solve the above problems.

[0006] The object of the present invention is achieved as follows:

[0007] A method for preparing a hybrid nanomaterial dispersion, comprising the following steps: mixing the following components and materials in parts by weight, and then dispersing the paste-like solid formed by hydrolysis reaction after mixing in 30-40 parts by weight of deionized water to obtain the hybrid nanomaterial dispersion:

[0008]

[0009] The lower alcohol is at least one of C1-C5 alcohols;

[0010] 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, and gallium chloride;

[0011] The second hydrolysis monomer is selected from at least one of sodium hydrogen phosphate, sodium dihydrogen phosphate, potassium hydrogen phosphate, and potassium dihydrogen phosphate.

[0012] The C1-C5 alcohols are selected from at least one of ethanol, isopropanol, butanol, and isobutanol.

[0013] The silane coupling agent is selected from at least one of γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane.

[0014] Specifically, a method for preparing a hybrid nanomaterial dispersion of the present invention comprises the following preparation steps:

[0015] (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;

[0016] (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;

[0017] (3) Dispersion: Disperse the paste-like solid in deionized water to obtain a hybrid nanomaterial dispersion.

[0018] 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;

[0019] Or the order of adding the first hydrolysis monomer, the second hydrolysis monomer and deionized water to the mixed solution A is as follows: adding the titanium tetrachloride dropwise to the mixed solution A, then adding 10-13 parts by weight of deionized water, and then adding dropwise the solution C obtained by mixing the second hydrolysis monomer and 11-16 parts by weight of deionized water thereto;

[0020] Or the order of adding the first hydrolysis monomer, the second hydrolysis monomer and deionized water to the mixed solution A is as follows: adding the titanium tetrachloride dropwise to the mixed solution A, then adding the 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, and then adding dropwise the solution C obtained by mixing the second hydrolysis monomer and 11-16 parts by weight of deionized water thereto.

[0021] More specifically, the dropping time of the solution B or the titanium tetrachloride or the solution E dropped into the solution A is 2-5 h. After the dropping is completed, continue to react for 1-5 h, and then dropwise add the solution C; the dropping time of the solution C is 1-2 h. After the dropping is completed, continue to react for 1-2 h to obtain the solution D.

[0022] More specifically, the solution D is heated to 80-120 °C, reacted for 2-8 h, and then cooled to room temperature to prepare the hybrid nanomaterial sol.

[0023] The standing is carried out at room temperature, and the standing time is at least 24 h.

[0024] The method for removing the alcohol solvent is vacuum filtration after standing and / or centrifugation.

[0025] The method for removing water is filtration.

[0026] The paste-like solid is dispersed in deionized water by ultrasonic dispersion.

[0027] The present application further provides a hybrid nanomaterial dispersion prepared according to the above method.

[0028] The present application further provides a method for preparing a polyacrylic acid latex resin, which includes the preparation steps of the above hybrid nanomaterial dispersion, and further includes the following steps:

[0029] S1, adding the hybrid nanomaterial dispersion, ammonia water, styrene and acrylate to deionized water, heating to 80-85 °C, and then adding the mixed solution of ammonium persulfate dissolved in water, and reacting for 10-20 minutes:

[0030] S2. While simultaneously dropping a solution formed by mixing (meth)acrylic acid and its esters or other derivatives and styrene, and a mixture of ammonium persulfate dissolved in water into the reaction solution obtained in S1, after the dropping is completed, keep warm for 1 - 3 h;

[0031] S3. Add deionized water to the reaction solution obtained in S2, cool down and filter to obtain polyacrylic acid latex resin.

[0032] The present application further provides a polyacrylic acid latex resin prepared according to the above method.

[0033] The hybrid nanomaterial dispersion of the present invention can replace traditional ionic or non-ionic emulsifiers such as nonylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, sodium dodecyl sulfate, and sodium dodecyl sulfonate for emulsion polymerization of acrylate to obtain a polyacrylic acid latex resin with high solid content and good stability, and a paint film with outstanding mechanical properties, excellent water resistance and chemical resistance can be prepared by using this polyacrylic acid latex resin; the hybrid nanocrystals formed by the present invention have a strong penetration and catalytic curing effect on the concrete surface, so the polyacrylic acid latex resin prepared by using the hybrid nanomaterial dispersion can penetrate and cure the concrete surface, and is suitable for preparing a concrete interface agent with excellent performance;

[0034] The hybrid nanomaterial dispersion of the present invention can replace traditional ionic or non-ionic emulsifiers and be used as a surface active material in the emulsion polymerization of polyacrylic acid. By virtue of the special water-oil balance effect of the nanomaterial, it is evenly distributed at the interface of water-polymer colloidal particles, so as to disperse the polymer evenly and stably in water. The nanomaterial of the present invention is a material that can self-cure at room temperature. After the paint film dries, it cures to form a water-insoluble deposit, and has good compatibility with the polymer resin, and can be evenly distributed in the paint film, thereby improving the water resistance, chemical resistance and salt spray resistance of the paint film. Specific embodiments

[0035] 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. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without 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.

[0036] 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.

[0037] The hybrid nanomaterial dispersion is prepared by the following steps:

[0038] (1) Hydrolysis:

[0039] Add 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 into the reaction kettle in sequence. Start stirring to dissolve the materials evenly. Add 15 - 25 parts of the first hydrolysis monomer and 10 - 13 parts of deionized water into the No. 1 high-level tank, and dissolve and stir evenly (since titanium tetrachloride is a liquid and hydrolyzes directly when encountering water, if the first hydrolysis monomer is only titanium tetrachloride, directly drop titanium tetrachloride into the reaction kettle, and use the remaining deionized water to rinse and add it to the reaction kettle). Slowly and evenly drop the solution in the No. 1 high-level tank into the reaction kettle, and the dropping time is 2 - 5 h. After the dropping is completed, continue the reaction for 1 - 5 h. Add 3 - 8 parts of the second hydrolysis monomer and 11 - 16 parts of deionized water into the No. 2 high-level tank, and stir to dissolve evenly. Slowly and evenly drop the solution in the No. 2 high-level tank into the reaction kettle, and the dropping time is 1 - 2 h. After the dropping is completed, continue the reaction for 1 - 2 h. Raise the temperature to 80 - 120 °C, react for 2 - 8 h, and then cool down to room temperature.

[0040] (2) Static separation:

[0041] Let the liquid in the reaction kettle stand at room temperature for 24 h.

[0042] (3) Vacuum filtration:

[0043] Filter the standing liquid under a vacuum pressure of -0.4 Mpa to -0.9 Mpa to remove the filtered liquid, and obtain a white to slightly yellow paste-like solid.

[0044] (4) Dispersion:

[0045] Disperse the obtained paste-like solid under the dispersion action of ultrasonic waves in 30 - 40 parts of deionized water for dispersion to obtain a hybrid nanomaterial dispersion liquid.

[0046] Example 1

[0047] The raw materials for each step of preparing the hybrid nanomaterial dispersion liquid include the following components and weight parts:

[0048]

[0049] Take 8 parts of deionized water, 2 parts of lithium hydroxide, 2 parts of γ-aminopropyltriethoxysilane, and 6 parts of ethanol and add them into the reaction kettle, and stir to dissolve evenly. Slowly add 25 parts of titanium tetrachloride into 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 into 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, react for 3 h, and then cool down to room temperature.

[0050] Let the solution in the reactor stand still for 24 h. Then, filter it under a vacuum pressure of -0.4 Mpa to -0.9 Mpa, filter off the liquid, and obtain a white paste-like solid.

[0051] Mix 31 parts of the obtained white paste-like solid with deionized water for dispersion, and perform ultrasonic dispersion with ultrasonic waves to obtain a hybrid nanomaterial dispersion liquid with a solid content of 20%, a pH of 3.2, an average particle size of 35 nm, and a viscosity of 12 s measured by a coating - 4 cup at 25 °C.

[0052] Example 2

[0053] The raw materials for each step of preparing the hybrid nanomaterial dispersion liquid include the following components and parts by weight:

[0054]

[0055] Take 9 parts of deionized water, 1 part of lithium hydroxide, 1 part of γ-aminopropyltriethoxysilane, and 5 parts of isopropyl alcohol and add them to the reactor, and stir to dissolve evenly. Slowly add 20 parts of ferric chloride and 10 parts of deionized water to the 1# high-level tank, and stir to dissolve evenly. Drop the solution in the 1# high-level tank into the reactor, 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 2# high-level tank, stir to dissolve evenly, and then drop it into the reactor, and finish dropping in 1.5 h. After dropping, react for 1 h. Then, raise the temperature to 95 °C, react for 4 h, and then cool to room temperature.

[0056] Let the solution in the reactor stand still for 24 h. Then, filter it under a vacuum pressure of -0.4 Mpa to -0.9 Mpa, filter off the liquid, and obtain a slightly yellow paste-like solid.

[0057] Mix 40 parts of the obtained slightly yellow paste-like solid with deionized water for dispersion, and perform ultrasonic dispersion with ultrasonic waves to obtain a hybrid nanomaterial dispersion liquid with a solid content of 18%, a pH of 4, an average particle size of 48 nm, and a viscosity of 11 s measured by a coating - 4 cup at 25 °C.

[0058] Example 3

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

[0060]

[0061] Take 8 parts of deionized water, 3 parts of lithium hydroxide, 2 parts of γ-methacryloyloxypropyltrimethoxysilane, and 8 parts of ethanol and add them to a reaction kettle, then stir to dissolve evenly. Slowly add 13 parts of titanium tetrachloride to the 1# high-level tank, and dropwise add the titanium tetrachloride in the 1# high-level tank into the reaction kettle, and finish dropping in 2 hours. After dropping, add 5 parts of aluminum trichloride and 10 parts of deionized water to the 1# high-level tank, dissolve and stir evenly, then dropwise add to the reaction kettle, and the dropping time is 2 hours. After dropping, react for 2 hours. Add 6 parts of potassium dihydrogen phosphate and 12 parts of deionized water to the 2# high-level tank, stir to dissolve evenly, then dropwise add to the reaction kettle, and finish dropping in 1 hour. After dropping, react for 1 hour. Then raise the temperature to 90 °C and react for 3 hours, and then cool to room temperature.

[0062] Let the solution in the reaction kettle stand for 24 hours. Then filter under a vacuum pressure of -0.4 Mpa to -0.9 Mpa, filter off the liquid, and obtain a white paste-like solid.

[0063] Mix the obtained white paste-like solid with 33 parts of deionized water for dispersion, and perform ultrasonic dispersion with ultrasonic waves to obtain a hybrid nanomaterial dispersion liquid 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 coat-4 cup at 25 °C.

[0064] Example 4

[0065] Example 4 is an example of preparing polyacrylic acid latex resin by polyacrylic acid emulsion polymerization using the hybrid nanomaterial dispersion liquid of Example 1.

[0066] Add 200 parts of styrene, 100 parts of butyl acrylate, 10 parts of acrylic acid, 100 parts of methyl methacrylate, and 30 parts of glycidyl methacrylate to the 1# dropping kettle, stir evenly, and set aside.

[0067] Add 2.5 parts of ammonium persulfate and 30 parts of deionized water to the 2# dropping kettle, stir to dissolve evenly, and set aside.

[0068] Add 400 parts of deionized water, 10 parts of the hybrid nanomaterial of Example 1, 1 part of ammonia water, 10 parts of styrene, and 10 parts of methyl methacrylate to the reaction kettle, start stirring, and raise the temperature to 80 °C. Add a solution of 0.2 part of ammonium persulfate and 3 parts of deionized water to the reaction kettle and react for 15 minutes.

[0069] At the same time, start dropping the liquids in the 1# dropping kettle and the 2# dropping kettle into the reaction kettle, drop for 3 hours, and keep warm for 1 hour after dropping.

[0070] Add 94.2 parts of deionized water, then cool to 40 °C, and filter to obtain a polyacrylic acid latex resin prepared from a hybrid nanomaterial with a solid content of 46%.

[0071] Example 5

[0072] Example 5 is an example of preparing polyacrylic acid latex resin by emulsion polymerization of polyacrylic acid using the hybrid nanomaterial dispersion liquid of Example 2.

[0073] Add 210 parts of styrene, 90 parts of butyl acrylate, 8 parts of methacrylic acid, 90 parts of methyl methacrylate, 10 parts of glycidyl methacrylate, 20 parts of isooctyl acrylate and 10 parts of diacetone acrylamide into the 1# dropping kettle, stir evenly and set aside.

[0074] Add 2 parts of ammonium persulfate and 30 parts of deionized water into the 2# dropping kettle, stir and dissolve evenly, and set aside.

[0075] Add 420 parts of deionized water, 8 parts of the hybrid nanomaterial of Example 2, 0.8 part of ammonia water, 20 parts of styrene and 5 parts of butyl methacrylate into the reaction kettle, start stirring, and heat up to 85 °C. Add a solution of 0.3 part of ammonium persulfate and 3 parts of deionized water into the reaction kettle and react for 15 minutes.

[0076] At the same time, start dropping the liquids in the 1# dropping kettle and the 2# dropping kettle into the reaction kettle, drop for 3 h, and keep warm for 2 h after dropping.

[0077] Add 72.9 parts of deionized water, then cool down to 40 °C, and filter to obtain a polyacrylic acid latex resin prepared from a hybrid nanomaterial with a solid content of 46%.

[0078] Example 6

[0079] The raw materials for each step of preparing the hybrid nanomaterial dispersion liquid include the following components and parts by weight:

[0080]

[0081]

[0082] Take 11 parts of deionized water, 4 parts of lithium hydroxide, 2 parts of γ-glycidyl etheroxypropyltrimethoxysilane, and 4 parts of butanol and add them into the reaction kettle, stir and dissolve evenly. Slowly add 15 parts of ferric chloride and 10 parts of deionized water into the 1# high-level tank, stir and dissolve evenly. Drop the solution in the 1# high-level 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 into the 2# high-level tank, stir and dissolve evenly, then drop it into the reaction kettle, and finish dropping in 1.5 h. After dropping, react for 1 h. Then heat up to 95 °C, react for 4 h, and then cool down to room temperature.

[0083] Let the solution in the reaction kettle stand for 24 h. Then filter it under a vacuum pressure of -0.4 Mpa to -0.9 Mpa, filter off the liquid, and obtain a slightly yellow paste-like solid.

[0084] Mix the obtained slightly yellowish paste-like solid with 30 parts of deionized water for dispersion, and perform ultrasonic dispersion using ultrasonic waves to obtain a hybrid nanomaterial dispersion liquid 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.

[0085] Example 7

[0086] The raw materials for each step of preparing the hybrid nanomaterial dispersion liquid include the following components and parts by weight:

[0087]

[0088]

[0089] 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 a reaction kettle, and stir to dissolve evenly. Slowly add 12 parts of titanium tetrachloride to the 1# high-level tank, and drip the titanium tetrachloride in the 1# high-level tank into the reaction kettle, and finish dripping in 2 h. After dripping, add 8 parts of nickel chloride and 13 parts of deionized water to the 1# high-level tank, dissolve and stir evenly, and drip into the reaction kettle. The dripping time is 2 h, and after dripping, react for 2 h. Add 4 parts of potassium dihydrogen phosphate and 12 parts of deionized water to the 2# high-level tank, stir to dissolve evenly, then drip into the reaction kettle, and finish dripping in 1 h. After dripping, react for 1 h. Then raise the temperature to 90 °C, react for 3 h, and then cool to room temperature.

[0090] 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 white paste-like solid.

[0091] Disperse the obtained white paste-like solid in 31 parts of deionized water, and perform ultrasonic dispersion using ultrasonic waves to obtain a hybrid nanomaterial dispersion liquid 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 coating-4 cup at 25 °C.

[0092] Example 8

[0093] Example 8 is an example of preparing a polyacrylic acid latex resin by polyacrylic acid emulsion polymerization using the hybrid nanomaterial dispersion liquid of Example 3.

[0094] The preparation method is the same as that of Example 4, except that the hybrid nanomaterial dispersion liquid of Example 1 is replaced with the hybrid nanomaterial dispersion liquid of Example 3. As a result, a polyacrylic acid latex resin prepared from a hybrid nanomaterial with a solid content of 46% is obtained.

[0095] Example 9

[0096] Example 9 is an example of preparing a polyacrylic acid latex resin by emulsion polymerization of polyacrylic acid using the hybrid nanomaterial dispersion of Example 6.

[0097] The preparation method is the same as that of Example 4, except that the hybrid nanomaterial dispersion of Example 1 is replaced with the hybrid nanomaterial dispersion of Example 6. As a result, a polyacrylic acid latex resin prepared from hybrid nanomaterials with a solid content of 46% is obtained.

[0098] Example 10

[0099] Example 10 is an example of preparing a polyacrylic acid latex resin by emulsion polymerization of polyacrylic acid using the hybrid nanomaterial dispersion of Example 7.

[0100] The preparation method is the same as that of Example 5, except that the hybrid nanomaterial dispersion of Example 2 is replaced with the hybrid nanomaterial dispersion of Example 7. As a result, a polyacrylic acid latex resin prepared from hybrid nanomaterials with a solid content of 46% is obtained.

[0101] Comparative Example 3

[0102] Using the nano-dispersion formulation for emulsion polymerization in Example 4 of CN112661876A, a paste-like solid was prepared according to the preparation method of the present invention, and then the paste-like solid was compounded to obtain a nano-dispersion M;

[0103] Take 8 parts of deionized water, 4.8 parts of diethanolamine, 5.8 parts of cetyl carboxylic acid, and 9.2 parts of n-butanol and add them to the reaction kettle, stir and dissolve evenly. Slowly add 15 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 13 parts of nickel chloride 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 after dropping, react for 2 h. Add 3.1 parts of potassium nitrate and 12 parts of deionized water to the No. 2 high-level 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 and react for 3 h, and then cool to room temperature.

[0104] 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 white paste-like solid.

[0105] Disperse the obtained 22 parts of white paste-like solid in deionized water according to the weight ratio of 22 parts of white paste-like solid to 78 parts of deionized water, and perform ultrasonic dispersion with ultrasonic waves to obtain a hybrid nanomaterial dispersion with a solid content of 22%, a pH of 3.5, an average particle size of 44 nm, and a viscosity of 11 s for a coating -4 cup at 25 °C, that is, nano-dispersion M.

[0106] Comparative Example 4

[0107] Comparative Example 4 is a comparative example in which a polyacrylic acid latex resin is prepared by emulsion polymerization of polyacrylic acid using the nano-dispersion for emulsion polymerization in Example 4 of CN112661876A.

[0108] Add 210 parts of styrene, 90 parts of butyl acrylate, 8 parts of methacrylic acid, 90 parts of methyl methacrylate, 10 parts of glycidyl methacrylate, 20 parts of isooctyl acrylate and 10 parts of diacetone acrylamide to the 1# dropping kettle, stir evenly, and set aside.

[0109] Add 2 parts of ammonium persulfate and 30 parts of deionized water to the 2# dropping kettle, stir and dissolve evenly, and set aside.

[0110] Add 420 parts of deionized water, 8 parts of the nano-dispersion for emulsion polymerization in Example 4 of CN112661876A, 0.8 part of ammonia water, 20 parts of styrene, and 5 parts of butyl methacrylate to the reaction kettle, start stirring, and heat up to 85 °C. Add a solution of 0.3 part of ammonium persulfate and 3 parts of deionized water to the reaction kettle, and react for 15 minutes.

[0111] At the same time, start dropping the liquids in the 1# dropping kettle and the 2# dropping kettle into the reaction kettle, drop for 3 h, and keep warm for 2 h after dropping.

[0112] Add 72.9 parts of deionized water, then cool down to 40 °C, and filter to obtain a polyacrylic acid latex resin prepared from a hybrid nano-material with a solid content of 47%.

[0113] Comparative Example 5

[0114] Comparative Example 5 is a comparative example in which a polyacrylic acid latex resin is prepared by emulsion polymerization of polyacrylic acid using the nano-dispersion M prepared in Comparative Example 3.

[0115] Add 210 parts of styrene, 90 parts of butyl acrylate, 8 parts of methacrylic acid, 90 parts of methyl methacrylate, 10 parts of glycidyl methacrylate, 20 parts of isooctyl acrylate and 10 parts of diacetone acrylamide to the 1# dropping kettle, stir evenly, and set aside.

[0116] Add 2 parts of ammonium persulfate and 30 parts of deionized water to the 2# dropping kettle, stir and dissolve evenly, and set aside.

[0117] Add 420 parts of deionized water, 8 parts of nano-dispersion M, 0.8 part of ammonia water, 20 parts of styrene, and 5 parts of butyl methacrylate to the reaction kettle, start stirring, and heat up to 85 °C. Add a solution of 0.3 part of ammonium persulfate and 3 parts of deionized water to the reaction kettle, and react for 15 minutes.

[0118] Start dropping the liquids in the 1# dropping kettle and the 2# dropping kettle into the reaction kettle simultaneously, for 3 hours, and keep warm for 2 hours after dropping is completed.

[0119] Add 72.9 parts of deionized water, then cool down to 40°C, and filter to obtain a polyacrylic acid latex resin prepared from a hybrid nanomaterial with a solid content of 48%.

[0120] Comparative Example 6

[0121] Use the acrylic emulsion for heavy-duty anti-corrosion coatings prepared in Example 3 of CN112625169A as a comparison.

[0122] Comparative Example 7

[0123] Use the nano-modified acrylic resin prepared in Example 3 of CN112662256A as a comparison.

[0124] Use the polyacrylic acid latex resin prepared in Examples 4 - 5 and Examples 8 - 10, mix it with additives to make an aqueous concrete interface adhesive, and brush it on the concrete surface, and compare the performance with the aqueous concrete interface adhesive made with the same additives in the comparative examples. The formula of the aqueous concrete interface adhesive is shown in Table 1, and the performance comparison is shown in Table 2.

[0125] Table 1

[0126]

[0127]

[0128] Table 2

[0129]

Claims

1. A preparation method of a hybrid nanomaterial dispersion liquid, characterized in that, It includes the following steps: Mix the following components and materials in parts by weight, and then disperse the paste-like solid formed by the hydrolysis reaction after mixing in 30-40 parts by weight of deionized water to obtain a 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, ferric trichloride, strontium chloride, barium chloride, nickel chloride, vanadium chloride, and gallium chloride; The second hydrolysis monomer is selected from at least one of sodium hydrogen phosphate, sodium dihydrogen phosphate, potassium hydrogen phosphate, and potassium dihydrogen phosphate.

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

3. The preparation method according to claim 1, characterized in that, It includes the following preparation 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 a hybrid nanomaterial sol; (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; (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 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 to 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 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 to 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 to the mixed solution A, then add solution E obtained by mixing at least one of aluminum trichloride, ferric 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 to it.

5. The preparation method according to claim 4, characterized in that, The dropping time of solution B or the titanium tetrachloride or solution E into solution A is 2-5 h. After the dropping is completed, continue to react for 1-5 h, and then dropwise add solution C; the dropping time of solution C is 1-2 h. After the dropping is completed, continue to react for 1-2 h to obtain solution D; Heat solution D to 80-120 °C, react for 2-8 h, and then cool 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 for 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 3, characterized in that, In the step (3), ultrasonic dispersion is adopted.

8. A method for preparing a polyacrylic acid latex resin, comprising the steps of preparing the hybrid nanomaterial dispersion liquid according to any one of claims 1 to 7, and further comprising the following steps: S1. Add the hybrid nanomaterial dispersion liquid, ammonia water, styrene and acrylate to deionized water, heat up to 80-85 °C, and then add the mixed solution of ammonium persulfate dissolved in water, and react for 10-20 minutes: S2. While dropping the solution mixed by (meth)acrylic acid and its esters or other derivatives and styrene and the mixed solution of ammonium persulfate dissolved in water into the reaction solution obtained in S1, after the dropping is completed, keep the temperature for 1-3 h; S3. Add deionized water to the reaction solution obtained in S2, cool down and filter to obtain the polyacrylic acid latex resin.

9. A hybrid nanomaterial dispersion liquid prepared by the method according to any one of claims 1 to 7.

10. A polyacrylic acid latex resin prepared by the method according to claim 8.

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