Inorganic modified core-shell structure water-based outdoor wood paint, preparation method and film forming method

Abstract

The invention discloses inorganic modified core-shell structure water-based outdoor wood paint, a preparation method and a film forming method. The preparation method comprises the following steps: S1, pre-dispersing a GO-TiO2-ZnO composite material modified by a silane coupling agent KH570; s2, uniformly stirring the GO-TiO2-ZnO composite material modified by KH570, an acrylic acid core-shell emulsion, dipropylene glycol monomethyl ether, bentonite and an organic silicon flatting agent, and adjusting the pH (Potential of Hydrogen) of the materials to 8.0 to 8.5; and filtering to obtain the target inorganic modified core-shell structure water-based outdoor wood paint. A GO-TiO2-ZnO composite material modified by a silane coupling agent KH570 is dispersed in a self-crosslinking acrylic core-shell emulsion, an alkaline material effectively enhances formation of a high-bond-energy bidentate chelate ([R-COO] 2Zn < 2 + >) with resin carboxyl through ZnO loaded on GO, water molecule permeation channels are reduced, ultraviolet light is shielded in situ in cooperation with TiO2, and the water-resistant service life of an obtained film layer is long.

Description

Technical Field

[0001] The present invention relates to the technical field of water-based wood paints, in particular to an inorganic modified core-shell structure water-based outdoor wood paint, a preparation method and a film-forming method. Background Art

[0002] Outdoor water-based wood paint boasts low VOC and non-toxic environmental performance as its core advantages. However, when exposed to rain for long periods of time, single-component water-based wood paint tends to absorb water and swell, causing the paint film to whiten, reduce hardness, and even cause wood ribs to swell and deform, especially in softwoods such as pine. Existing technology can improve water resistance with two-component water-based PU paint, but this increases costs by 30%. Water-based acrylic resin paint is a type of coating based on polyacrylate as the primary film-forming substance. Conventional polyacrylates struggle to achieve both a minimum film-forming temperature and mechanical strength. Summary of the Invention

[0003] The first object of the present invention is to provide an inorganic modified core-shell structure water-based outdoor wood paint. The present invention comprises a GO-TiO2-ZnO composite material modified with a silane coupling agent KH570 and dispersed in a self-crosslinking acrylic core-shell emulsion. The alkaline material effectively enhances the ZnO loaded on the GO to form a high bond energy bidentate chelate ([R-COO]2ZnO) with the carboxyl group of the resin. 2+ ), which increases the formation of ionic cross-linking points between resin chains, similar to "ionic bond cross-linking", reducing water molecule penetration channels. At the same time, it cooperates with TiO2 to in-situ shield ultraviolet light, reduce resin photooxidation, protect the durability of the complex bond, and the resulting film layer has a long-lasting water resistance life.

[0004] To solve this technical problem, the technical solution of the present invention is: an inorganic modified core-shell structure water-based outdoor wood paint, comprising the following substances in parts by mass: 40 to 45 parts of self-crosslinking acrylic core-shell emulsion; KH570 modified GO-TiO2-ZnO composite material 8 to 12 parts; 30 to 35 parts deionized water; 4 to 5 parts of dipropylene glycol methyl ether; 0.5 to 0.8 parts of bentonite; 0.1 to 0.2 parts of silicone leveling agent.

[0005] Preferably, the solid content of the self-crosslinking acrylic core-shell emulsion is 40%, wherein the mass ratio of the core monomer mixture to the shell monomer mixture is 70:30; The core monomer mixture includes the following substances in parts by mass: Butyl acrylate (BA) 182 parts; 84 parts of methyl methacrylate (MMA); Acrylic acid (AA) 14 parts; polymerizable emulsifier (DNS-86) 3.36 parts; 280 parts of deionized water; The shell monomer mixture includes the following substances in parts by mass: Methyl methacrylate (MMA) 72 parts; Glycidyl methacrylate (GMA) 6 parts; 3.6 parts of diacetone acrylamide (DAAM); 1.2 parts of polymerizable emulsifier (DNS-86); 120 parts of deionized water; 4 parts of ammonium persulfate (APS); Adipic acid dihydrazide (ADH) 1.8 parts.

[0006] The second object of the present invention is to provide a method for preparing an inorganic modified core-shell structure water-based outdoor wood paint. The present invention uses a GO-TiO2-ZnO composite material controlled by a step-by-step process for surface modification with KH570. The resulting wood paint effectively inhibits the free migration of zinc ions and utilizes the lamellar structure of the long chain of KH570 and GO to effectively increase the steric hindrance of the wood paint. The paint is stable in storage, and the resulting film layer is dense and hydrophobic after film formation.

[0007] To solve this technical problem, the technical solution of the present invention is: a method for preparing an inorganic modified core-shell structure water-based outdoor wood paint, comprising the following steps: S1, GO-TiO2-ZnO composite modified with pre-dispersed silane coupling agent KH570; S2. Under stirring conditions, the GO-TiO2-ZnO composite material modified with the pre-dispersed silane coupling agent KH570 was added to the self-crosslinking acrylic core-shell emulsion in batches, and dipropylene glycol methyl ether, bentonite and silicone leveling agent were added; Stir evenly and adjust the pH of the material to 8.0 to 8.5; The target inorganic modified core-shell structure water-based outdoor wood paint is obtained by filtration.

[0008] The process for preparing the GO-TiO2-ZnO composite material modified with the preferred silane coupling agent KH570 comprises the following steps: S11, dispersing the GO-TiO2-ZnO composite material in an ethanol-water mixture, adding a silane coupling agent KH570, wherein the mass ratio of KH570 to the GO-TiO2-ZnO composite material is 1.5% to 2.0%; S12, reflux from 75℃ to 85℃ for 2 hours, the grafting rate exceeds 85%; S13, adding the GO-TiO2-ZnO composite material modified with silane coupling agent KH570 into deionized water dissolved with dispersant sodium polycarboxylate, and stirring at 500 rpm; S14. Place the material obtained in S13 in a sand mill and grind at a speed of 2000 rpm for 30 minutes to obtain a GO-TiO2-ZnO composite material modified with a pre-dispersed silane coupling agent KH570.

[0009] In the present invention, KH570 generates silanols by hydrolysis, and the silanols condense with the hydroxyl groups on the filler surface to form Si-OM bonds, exposing the organic end -CH=CH2 to achieve surface functionalization. In the curing stage, -CH=CH2 is further utilized to increase the ring opening of the GO-TiO2-ZnO composite material and the epoxy group of glycidyl methacrylate to form ether bonds, further improving the density of the resulting film layer.

[0010] The method for preparing the GO-TiO2-ZnO composite material preferably comprises the following steps: A1. Ultrasonic dispersion of graphene oxide aqueous dispersion (1 mg / ml) until uniform, and add Ti to the graphene oxide aqueous dispersion. 3+ The precursor solution was adjusted to pH 2.8-3.2 and the first hydrothermal reaction was performed; Ti 3+ The precursor solution contained 0.1 M TiCl 3 and 0.05 M citric acid; After the reaction, cool to room temperature; A2, adjust the pH value of the material system after the first hydrothermal reaction in A1 to 9.5-10.5, add Zn 2+ Precursor solution, Zn 2+ The concentration of the precursor solution Zn(NO3)2 was 0.1 M, and the second hydrothermal reaction was carried out; After the reaction, cool to room temperature; A3. Alternately wash with ethanol and water and dry in vacuum to obtain GO-TiO2-ZnO composite material.

[0011] The preferred process parameters of the first hydrothermal reaction are a reaction temperature of 115° C. to 125° C. and a reaction time of 50 min to 70 min. The present invention ensures that GO loads TiO2 through the first hydrothermal reaction.

[0012] The process parameters of the second hydrothermal reaction are preferably: The reaction temperature is 175° C. to 185° C., and the reaction time is 10 to 12 hours. The present invention ensures that GO loads ZnO through the first hydrothermal reaction.

[0013] Preferably, the mass ratio of GO, TiO2 and ZnO in the GO-TiO2-ZnO composite material is 1:(1 to 2):(1 to 2).

[0014] The preferred method for curing and film-forming an inorganic modified core-shell structure water-based outdoor wood paint comprises the following steps: A1. The stage temperature is 50°C to 55°C and the maintenance time is 10min to 15min; A2. The temperature is 70°C to 75°C, the humidity is 30% to 35%, and the maintenance time is 15 minutes to 20 minutes; A3. The stage temperature is 80℃ to 85℃, the humidity is less than 10%, and the maintenance time is 20min to 30min.

[0015] The present invention balances the moisture content of the wood under the high humidity process conditions of the A1 stage, inhibits the expansion of the paint film caused by water absorption and expansion of the wood, and triggers the initial fusion of butyl acrylate in the core layer to form a continuous film base under the process conditions of the A1 stage, thereby promoting the lamination of graphene oxide. Compared with the A1 stage, the environmental humidity is reduced, and the temperature is increased in the A2 stage to promote the swelling of the latex particles. The ZnO interface dissolution is used at high temperature to tightly connect the resin and the filler, and the GO sheet structure of the filler effectively complicates the internal structure of the coating. In the process of heating and curing, TiO2 reflects heat energy to accelerate internal fusion, stabilize the interface dissolution of ZnO, ensure the stability of the film formation, and the film layer is dense and has hydrophobic properties inside. Combined with the high temperature and low humidity cross-linking curing in the A3 stage, the interface bonding in the film layer is effectively realized, such as the ring opening of the GMA epoxy group in the shell layer to form a covalent bond with the -COOH of the graphene oxide; the ZnO particles partially dissolve the Zn 2+ Forming high bond energy bidentate chelate [R-COO]2Zn with resin carboxyl group 2+ During the curing stage, the -CH=CH2 of KH570 reacts with the acrylamide group of diacetone acrylamide (DAAM) under alkaline conditions to form a cross-linked network, and the above-mentioned bonds surround the GO-TiO2-ZnO composite material, thereby effectively improving the mechanical properties and water resistance of the resulting film layer.

[0016] By adopting the above technical solution, the beneficial effects of the present invention are: The present invention uses a silane coupling agent KH570 to modify the GO-TiO2-ZnO composite material dispersed in a self-crosslinking acrylic core-shell emulsion, and uses alkaline materials to effectively enhance the ZnO loaded on the GO to form a high-bond energy bidentate chelate ([R-COO]2Zn 2+ ), which increases the formation of ionic cross-linking points between resin chains of the complex, similar to "ionic bond cross-linking", reduces the penetration channels of water molecules, and at the same time cooperates with TiO2 to shield ultraviolet light in situ, reduce resin photooxidation, protect the durability of the complex bond, and the resulting film layer has a long-lasting water resistance life.

[0017] The preparation method of the water-based outdoor wood paint proposed in the present invention utilizes GO to load TiO2 and ZnO step by step under different acid and alkaline conditions. Under the spatial limitation of GO, during the curing film formation process, TiO2 has a lower isoelectric point than ZnO and preferentially adsorbs H + , the pH value of the interface micro-region increases, which promotes the stable hydrolysis of ZnO in the area near the filler, thereby promoting a full reaction between the filler and the resin. And during the heating process, TiO2 cooperates with flaky graphene oxide to promote photothermal conversion and accelerate the penetration of thermal energy, effectively improving the completion of curing. After the wood paint proposed by the present invention is cured and formed into a film, TiO2 and ZnO are spatially confined by GO, and TiO2 is used to stabilize the hydrolysis of ZnO; after film formation, TiO2 strongly absorbs UV, reduces the generation of holes in ZnO under ultraviolet irradiation, and cooperates with GO as an electron acceptor to transfer the photogenerated electrons (e) of TiO2 - ), blocking the accumulation of ZnO holes and preventing the inhibition of Zn 2+ Excessive release improves the UV aging performance of the obtained cured film layer and also improves the water resistance life of the obtained film layer. DETAILED DESCRIPTION

[0018] In order to further explain the technical solution of the present invention, the present invention is described in detail below through specific embodiments.

[0019] Example 1

[0020] This embodiment discloses an inorganic modified core-shell structure water-based outdoor wood paint, which includes the following substances in parts by mass: 40 to 45 parts of self-crosslinking acrylic core-shell emulsion; KH570 modified GO-TiO2-ZnO composite material 8 to 12 parts; 30 to 35 parts deionized water; 4 to 5 parts of dipropylene glycol methyl ether; 0.5 to 0.8 parts of bentonite; 0.1 to 0.2 parts of silicone leveling agent.

[0021] The organosilicon leveling agent used in this embodiment is BYK-349.

[0022] In this embodiment, the solid content of the self-crosslinking acrylic core-shell emulsion is 40%, wherein the mass ratio of the core monomer mixture to the shell monomer mixture is 70:30; The core monomer mixture includes the following substances in parts by mass: Butyl acrylate (BA) 182 parts; 84 parts of methyl methacrylate (MMA); Acrylic acid (AA) 14 parts; polymerizable emulsifier (DNS-86) 3.36 parts; 280 parts of deionized water; The shell monomer mixture includes the following substances in parts by mass: Methyl methacrylate (MMA) 72 parts; Glycidyl methacrylate (GMA) 6 parts; 3.6 parts of diacetone acrylamide (DAAM); 1.2 parts of polymerizable emulsifier (DNS-86); 120 parts of deionized water; 4 parts of ammonium persulfate (APS); Adipic acid dihydrazide (ADH) 1.8 parts.

[0023] This embodiment also discloses a method for preparing the inorganic modified core-shell structure water-based outdoor wood paint, comprising the following steps: S1, GO-TiO2-ZnO composite modified with pre-dispersed silane coupling agent KH570; S2. Under stirring conditions, the GO-TiO2-ZnO composite material modified with the pre-dispersed silane coupling agent KH570 was added to the self-crosslinking acrylic core-shell emulsion in batches, and dipropylene glycol methyl ether, bentonite and silicone leveling agent were added; Stir evenly and adjust the pH of the material to 8.2; The target inorganic modified core-shell structure water-based outdoor wood paint is obtained by filtration.

[0024] The process for preparing the GO-TiO2-ZnO composite material modified with the silane coupling agent KH570 in this embodiment includes the following steps: S11, dispersing the GO-TiO2-ZnO composite material in an ethanol-water mixture, adding a silane coupling agent KH570, and the mass ratio of KH570 to the GO-TiO2-ZnO composite material is 1.5%; S12, reflux at 80℃ for 2 hours, the grafting rate exceeds 85%; S13, adding the GO-TiO2-ZnO composite material modified with silane coupling agent KH570 into deionized water dissolved with dispersant sodium polycarboxylate, and stirring at 500 rpm; S14. Place the material obtained in S13 in a sand mill and grind at a speed of 2000 rpm for 30 minutes to obtain a GO-TiO2-ZnO composite material modified with a pre-dispersed silane coupling agent KH570.

[0025] In the present invention, KH570 generates silanols by hydrolysis, and the silanols condense with the hydroxyl groups on the surface of the filler to form Si-OM bonds, exposing the organic end -CH=CH2 to achieve surface functionalization. In the curing stage, -CH=CH2 is further utilized to increase the ring opening of the GO-TiO2-ZnO composite material and the epoxy group of glycidyl methacrylate to form ether bonds, thereby improving the density of the resulting film layer.

[0026] The preparation method of the GO-TiO2-ZnO composite material in this embodiment includes the following steps: A1. Ultrasonic dispersion of graphene oxide aqueous dispersion (1 mg / ml) until uniform, and add Ti to the graphene oxide aqueous dispersion. 3+ The precursor solution was adjusted to pH 3.0 and the first hydrothermal reaction was performed; Ti 3+ The precursor solution contained 0.1 M TiCl 3 and 0.05 M citric acid; After the reaction, cool to room temperature; A2, adjust the pH value of the material system after the first hydrothermal reaction in A1 to 10.0, add Zn 2+ Precursor solution, Zn 2+ The concentration of the precursor solution Zn(NO3)2 was 0.1 M, and the second hydrothermal reaction was carried out; After the reaction, cool to room temperature; A3. Alternately wash with ethanol and water and dry in vacuum to obtain GO-TiO2-ZnO composite material.

[0027] In this embodiment, the process parameters of the first hydrothermal reaction are a reaction temperature of 120° C. and a reaction time of 60 min. The present invention ensures that GO loads TiO 2 through the first hydrothermal reaction.

[0028] The process parameters of the second hydrothermal reaction in this embodiment are: The reaction temperature is 180° C. and the reaction time is 12 hours. The present invention ensures that GO loads ZnO through the first hydrothermal reaction.

[0029] In this embodiment, the mass ratio of GO, TiO2 and ZnO in the GO-TiO2-ZnO composite material is 1: (0.6 to 4): (0.4 to 5).

[0030] The inorganic modified core-shell structure water-based outdoor wood paint prepared in this embodiment is coated on a wood surface with a moisture content of less than 14%, with a coating thickness of 50 μm. The curing film-forming method of the inorganic modified core-shell structure water-based outdoor wood paint in this embodiment includes the following steps: A1. The stage temperature is 55°C, the humidity is 65%, and the maintenance time is 15 minutes; A2. The temperature is 75°C and the humidity is 35% for 20 minutes. A3. The stage temperature is 85℃, the humidity is 8%, and the maintenance time is 25 minutes.

[0031] Example 2

[0032] The main difference between this embodiment and embodiment 1 is that the dosage of the components of the inorganic modified core-shell structure water-based outdoor wood paint is as shown in Table 1.

[0033] Example 3

[0034] The main difference between this embodiment and embodiment 1 is that the dosage of the components of the inorganic modified core-shell structure water-based outdoor wood paint is as shown in Table 1.

[0035] Example 4

[0036] The main difference between this embodiment and embodiment 1 is that the dosage of the components of the inorganic modified core-shell structure water-based outdoor wood paint is as shown in Table 1.

[0037] Comparative Example 1 The main difference between this comparative example and Example 1 is that the GO-TiO2-ZnO composite material modified with KH570 is not added, and the process parameters for drying and curing are the same as those in Example 1.

[0038] Comparative Example 2 The main difference between this comparative example and Example 1 is that the same amount of KH570, GO, TiO2 and ZnO as in Example 1 are added respectively, without compounding or modification, and the drying and curing process parameters are the same as in Example 1.

[0039] Comparative Example 3 The main difference between this comparative example and Example 1 lies in the process parameters of drying and curing. The process parameters of curing and drying in this comparative example are drying at 80° C. for 45 minutes.

[0040] Comparative Example 4 The main difference between this comparative example and Example 1 is that the GO-TiO2-ZnO composite material is not modified with KH570, and the curing process parameters are the same as those in Example 1.

[0041] The properties of the wood paint films obtained in Examples 1 to 4 and Comparative Examples 1 and 2 are shown in Tables 2 and 3.

[0042] Table 1 Composition of wood coatings in Examples 1 to 4

[0043] Table 2 Comparison of water resistance and weather resistance of the films obtained in Examples 1 to 4 and Comparative Examples 1 to 4

[0044] Table 3 Comparison of mechanical properties of the films obtained in Examples 1 to 4 and Comparative Examples 1 to 4

[0045] Taber wear test conditions were as follows: CS-17 grinding wheel, 1000 g load, 1000 revolutions.

[0046] As shown in Tables 1, 2, and 3, the wear rate of the film obtained in Example 1 is significantly reduced compared to that of the film obtained in Comparative Example 4. This is primarily due to the following: in Example 1, the -CH=CH2 of KH570 undergoes Michael addition with DAAM under alkaline, high-temperature conditions, forming a "filler-resin" chemical bridge. The Si-OM bond anchors the GO-TiO2-ZnO, preventing filler peeling, significantly improving the wear resistance of Example 1. In Example 3, the mass ratio of GO, TiO2, and ZnO is 1:3:4. The excess TiO2 increases brittleness, and the corresponding pendulum hardness decreases to 0.62. Comparing Comparative Example 3 with Example 1, the single-stage curing in Comparative Example 3 results in the absence of the A1 and A2 stages, resulting in insufficient fusion of the latex particles. This corresponds to the change in gel content and accelerates wear.

[0047] Comparing Example 1 and Example 4, when the mass ratio of GO, TiO2, and ZnO is lower than 1:1:1, the loading of GO on TiO2 and ZnO is insufficient and the grafted KH570 is insufficient, resulting in weak interface bonding. Corresponding to the gel content, it can be seen that the crosslinking density of the film layer obtained in Example 4 decreases, and the Taber wear value exceeds 200 mg, which is not conducive to practical use. In Comparative Example 1, the GO-TiO2-ZnO composite material that is not modified with KH570 improves the crosslinking density and chemical bond connection of the internal structure of the obtained film layer, that is, the pure resin has poor wear resistance. In Comparative Example 2, KH570, GO, TiO2, and ZnO are physically mixed and dispersed unevenly, and the wear path is easily expanded. In Comparative Example 4, the GO-TiO2-ZnO composite material that is not modified with KH570 has no chemical bonding at the interface with the film-forming material, so the adhesion level 2 wear value is higher than that of Example 1. The wood lacquer obtained by the present invention is applied to the surface of pine wood. As a typical softwood, pine wood has a loose and porous tubular structure, which results in a significantly higher moisture absorption rate than hardwood. When the water-based outdoor wood lacquer of the present invention is applied to the surface of pine wood, moisture flows along the wood ducts. To ensure uniform moisture distribution after the water-based outdoor wood lacquer obtained by the present invention is applied to the surface of pine wood, the moisture content of the wood surface is slightly higher than that of the interior of the substrate through the A1 stage (55°C, 65% humidity), forming a reverse humidity gradient. The wood ducts are filled with the water-based outdoor wood lacquer. The rib height of Example 1 is ≤0.1mm, and the rib height of the film obtained in Comparative Example 3 after curing is 0.5mm. Combined with Examples 1 to 4, it can be seen that the present invention balances the moisture content of the wood under the process conditions of high humidity in the A1 stage, suppressing the rib expansion of the paint film caused by water absorption and expansion of the wood. Under the process conditions of the A1 stage, the butyl acrylate in the core layer is triggered to initially fuse to form a continuous film base, promoting the lamination of graphene oxide. Compared with the A1 stage, the environmental humidity is The degree of curing is reduced, and the temperature is increased in the A2 stage to promote the swelling of the latex particles. At high temperature, the ZnO interface dissolution is used to tightly connect the resin and the filler, and the GO sheet structure of the filler effectively complicates the internal structure of the coating. In the process of heating and curing, TiO2 reflects heat energy to accelerate internal fusion, stabilize the interface dissolution of ZnO, ensure the stability of the film, and the film is dense and has hydrophobic properties inside. Combined with the high temperature and low humidity cross-linking curing in the A3 stage, the interface bonding in the film is effectively achieved, such as the ring opening of the GMA epoxy group in the shell and the formation of a covalent bond with the -COOH of graphene oxide; the partially dissolved ZnO particles 2+ Forming high bond energy bidentate chelate [R-COO]2Zn with resin carboxyl group 2+ KH570 is anchored on the GO-TiO2-ZnO surface through Si-OM bonds. The vinyl reacts with the polymer to form a "filler-resin" chemical bridge, which improves adhesion. At the same time, the cross-linked network reduces the water molecule penetration channel and reduces the water absorption rate. The above-mentioned bonds surround the GO-TiO2-ZnO composite material, thereby effectively improving the mechanical properties and water resistance of the resulting film layer.

Claims

1. An inorganic modified core-shell structure water-based outdoor wood paint, characterized by: The following substances are included in parts by mass: 40 to 45 parts of self-crosslinking acrylic core-shell emulsion; KH570 modified GO-TiO2-ZnO composite material 8 to 12 parts; 30 to 35 parts deionized water; 4 to 5 parts of dipropylene glycol methyl ether; 0.5 to 0.8 parts of bentonite; 0.1 to 0.2 parts of silicone leveling agent.

2. The inorganic modified core-shell structure water-based outdoor wood paint according to claim 1, characterized in that: The solid content of the self-crosslinking acrylic core-shell emulsion is 40%, wherein the mass ratio of the core monomer mixture to the shell monomer mixture is 70:30; The core monomer mixture includes the following substances in parts by mass: 182 parts of butyl acrylate; 84 parts of methyl methacrylate; 14 parts of acrylic acid; 3.36 parts of polymerizable emulsifier; 280 parts of deionized water; The shell monomer mixture includes the following substances in parts by mass: 72 parts of methyl methacrylate; 6 parts of glycidyl methacrylate; 3.6 parts of diacetone acrylamide; 1.2 parts of polymerizable emulsifier; 120 parts of deionized water; Ammonium persulfate 4g; Adipic acid dihydrazide 1.8g.

3. A method for preparing the inorganic modified core-shell structure water-based outdoor wood paint according to claim 1 or 2, characterized in that: The following steps are involved: S1, GO-TiO2-ZnO composite modified with pre-dispersed silane coupling agent KH570; S2. Under stirring conditions, the GO-TiO2-ZnO composite material modified with the pre-dispersed silane coupling agent KH570 was added to the self-crosslinking acrylic core-shell emulsion in batches, and dipropylene glycol methyl ether, bentonite and silicone leveling agent were added; Stir evenly and adjust the pH of the material to 8.0 to 8.5; The target inorganic modified core-shell structure water-based outdoor wood paint is obtained by filtration.

4. The method according to claim 3, wherein: The process of preparing the GO-TiO2-ZnO composite material modified with silane coupling agent KH570 comprises the following steps: S11, dispersing the GO-TiO2-ZnO composite material in an ethanol-water mixture, adding a silane coupling agent KH570, wherein the mass ratio of KH570 to the GO-TiO2-ZnO composite material is 1.5% to 2.0%; S12, reflux from 75°C to 85°C for 2 hours; S13, adding the GO-TiO2-ZnO composite material modified with silane coupling agent KH570 into deionized water dissolved with dispersant sodium polycarboxylate, and stirring; S14. The material obtained in S13 is placed in a sand mill and ground to obtain a GO-TiO2-ZnO composite material modified with a pre-dispersed silane coupling agent KH570.

5. The method according to claim 3, wherein: The preparation method of the GO-TiO2-ZnO composite material comprises the following steps: A1. Ultrasonic dispersion of graphene oxide aqueous dispersion system until uniform, adding Ti to the graphene oxide aqueous dispersion system. 3+ The precursor solution was adjusted to pH 2.8-3.2 and the first hydrothermal reaction was performed; Ti 3+ The precursor solution contained 0.1 M TiCl 3 and 0.05 M citric acid; After the reaction, cool to room temperature; A2, adjust the pH value of the material system after the first hydrothermal reaction in A1 to 9.5-10.5, add Zn 2+ Precursor solution, Zn 2+ The concentration of the precursor solution Zn(NO3)2 was 0.1 M, and the second hydrothermal reaction was carried out; After the reaction, cool to room temperature; A3. Alternately wash with ethanol and water and dry in vacuum to obtain GO-TiO2-ZnO composite material.

6. The method according to claim 5, characterized in that: The process parameters of the first hydrothermal reaction are a reaction temperature of 115° C. to 125° C. and a reaction time of 50 min to 70 min.

7. The method according to claim 5, characterized in that: The process parameters of the second hydrothermal reaction are: The reaction temperature is 175°C to 185°C, and the reaction time is 10 to 12 hours.

8. The method according to claim 3, wherein: The mass ratio of GO, TiO2 and ZnO in the GO-TiO2-ZnO composite material is 1:(1 to 2):(1 to 2).

9. The method for curing and forming a film of an inorganic modified core-shell structure water-based outdoor wood paint according to any one of claims 1 to 6, characterized in that: The following steps are involved: A1. The stage temperature is 50°C to 55°C and the maintenance time is 10min to 15min; A2. The temperature is 70°C to 75°C, the humidity is 30% to 35%, and the maintenance time is 15 minutes to 20 minutes; A3. The stage temperature is 80℃ to 85℃, the humidity is less than 10%, and the maintenance time is 20min to 30min.

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