A waterproof and stain-resistant tile grout and its preparation method

Abstract

The present invention discloses a waterproof and stain-resistant tile grout and its preparation method, which relates to the technical field of building materials; the waterproof and stain-resistant tile grout is composed of a boron-silicon resin and cobalt-based MOF composite modified alkyd resin, a superhydrophobic carbon nanotube@silica dispersion, cement, lithium mica lithium slag powder, nylon and silicone oil; by blending the boron-silicon resin and cobalt-based MOF composite modified alkyd resin, the superhydrophobic carbon nanotube@silica dispersion with cement, lithium mica lithium slag powder, nylon and silicone oil, the prepared tile grout has a rough surface structure and is hydrophobic, and the extremely dense internal structure further reduces the penetration of moisture and dirt, significantly enhancing the waterproof and stain-resistant performance. At the same time, it also has excellent tensile bond strength, ensuring the firm stability of the grout and effectively extending the service life.

Description

Technical Field

[0001] The present invention belongs to the technical field of building materials, and specifically refers to a waterproof and stain-resistant tile grout and a preparation method thereof. Background Art

[0002] After the tiles are laid, the existence of gaps will damage the overall aesthetics. Using grout to fill these gaps can make the decorative surface smoother and more even, enhancing the overall beauty. At the same time, the grout can also be formulated into a color similar to that of building materials according to requirements, further enhancing the decorative effect.

[0003] The grout is mainly composed of cement, fillers, polymers, and a small amount of additives. To ensure good wear resistance and compressive and flexural strength, the proportion of cement in the grout raw materials is usually high. However, cement has strong hydrophilicity and poor hydrophobicity, and its surface is easily wetted. At the same time, during the hydration process of cement, microcracks, various macropores, and capillary pores and other defects will be generated. This heterogeneous multiphase system composed of pores has a high water absorption rate and is easily penetrated by the aqueous solutions formed by various stains, resulting in pollution.

[0004] Currently, the following main problems exist in the prior art:

[0005] Common tile grouts have poor water resistance and stain resistance, cannot meet the use requirements, and also shorten the service life. Summary of the Invention

[0006] In view of the above situation, to overcome the defects of the prior art, the present invention provides a waterproof and stain-resistant tile grout, which comprises the following components in parts by weight: 10-15 parts of boron-silicon resin and cobalt-based MOF composite modified alkyd resin, 15-20 parts of superhydrophobic carbon nanotube@silica dispersion, 30-40 parts of cement, 20-30 parts of lithium mica lithium slag powder, 2-3 parts of nylon, and 2-3 parts of silicone oil.

[0007] The boron-silicon resin and cobalt-based MOF composite modified alkyd resin comprises the following components in parts by weight: 15-20 parts of boron-silicon resin, 15-20 parts of cobalt-based MOF, and 60-70 parts of alkyd resin.

[0008] The superhydrophobic carbon nanotube@silica dispersion comprises the following components in parts by weight: 8-10 parts of carboxyl carbon nanotubes, 10-20 parts of tetraethyl orthosilicate, and 10-20 parts of γ-aminopropyltriethoxysilane.

[0009] The preparation method of the boron-silicon resin and cobalt-based MOF composite modified alkyd resin specifically comprises the following steps:

[0010] (1) 0.8 g of phenyltriethoxysilane, 3.0 g of methyltriethoxysilane, and 0.8 g of dimethyldiethoxysilane were added to a 100 mL three-necked round-bottom flask. The stirring speed was 180 - 200 rpm. After heating to 70 - 80 °C, 30 mL of a 4% hydrochloric acid solution was slowly added dropwise. After the addition was completed, the mixture was kept at 70 - 80 °C for 1 - 2 h for reaction. Then, 50 mL of a mixed solution of boric acid and absolute ethanol was added dropwise, and the reaction was carried out for 2 - 3 h. Then, it was subjected to vacuum distillation to remove small molecule compounds such as water and ethanol. After discharging, boron element was introduced into the silicone resin. It contains a large number of hydrophobic groups such as methyl groups and a cross-linked network structure, which blocks the dissolution and penetration of water molecules and also reduces the infiltration of the aqueous solution formed by dirt, improving the waterproof and anti-fouling properties. The addition of boron element can also reduce the shrinkage of cement during the curing process and reduce the risk of crack occurrence, obtaining a boron-containing silicone resin;

[0011] (2) Cobalt nitrate hexahydrate was added to 25 mL of N,N-dimethylformamide liquid and stirred until completely dissolved. Then, 0.05 g of trimesic acid was added and stirred for 1 - 2 h. The solution was transferred to a stainless-steel autoclave with a 50 mL polytetrafluoroethylene inner liner. The autoclave lid was sealed tightly and reacted at 220 - 240 °C for 1 - 2 h. After cooling to room temperature, the product was washed 3 - 5 times with N,N-dimethylformamide liquid and absolute ethanol, and then vacuum dried. The metal-organic framework MOF has excellent superhydrophobic properties, self-cleaning properties, and a dense structure that blocks moisture and dirt. The cobalt-based MOF synthesized with cobalt element as the metal source is wrapped by abundant small particles on the surface, increasing the specific surface area, which is beneficial to its fusion with the resin. And its dense structure effectively isolates the entry of moisture, thus improving the waterproof and anti-fouling effect, obtaining a cobalt-based MOF;

[0012] (3) The boron-containing silicone resin described in step (1), the cobalt-based MOF described in step (2), and alkyd resin were added to a 250 mL four-necked round-bottom flask equipped with a distillation device and a thermometer. Then, 10 mL of propylene glycol methyl ether acetate and tetrabutyl titanate liquid were added respectively, and stirred evenly. The temperature was raised to 100 - 110 °C for dehydration reaction for 0.5 - 1 h, and then the temperature was raised to 115 - 125 °C for reaction for 2 - 3 h. Then, it was subjected to vacuum distillation. The cobalt-based MOF promoted the cross-linking of the boron-containing silicone resin and the alkyd resin, increasing the density and complexity of the structure. It can not only significantly enhance the water resistance and stain resistance, but also improve the tensile bond strength of the alkyd resin, effectively adhere to the substrate surface, reduce the risk of cracking or peeling, and has excellent durability and stability, obtaining a boron-containing silicone resin and cobalt-based MOF composite modified alkyd resin;

[0013] Preferably, in step (1), the mass fraction of boric acid in the mixed solution of boric acid and anhydrous ethanol is 10-20%. Boric acid greatly improves the strength of the resin through cross-linking, enhances cohesion and adhesion, and can be better adhered to the substrate when used in the caulking agent, enhances tensile bonding strength, and improves firmness and durability.

[0014] Preferably, in step (2), the amount of cobalt nitrate hexahydrate added is 0.06-0.08 g. Cobalt, as a catalyst, can accelerate the cross-linking reaction between resins, form a strong chemical bond, and improve the bonding strength. Cobalt can increase the hardness and flexibility of alkyd resin, prevent it from cracking and falling off. Cobalt can also act as an antioxidant to inhibit the oxidation reaction of the resin and extend the service life.

[0015] The present invention also provides a method for preparing a waterproof and anti-fouling tile caulking agent, which specifically comprises the following steps:

[0016] S1. Dissolve the carboxyl carbon nanotubes in 100 mL of 60-70% ethanol solution, crush the cells and perform ultrasonic dispersion for 1-2 h, add 6 mL of 6-8% sodium hydroxide solution, stir magnetically for 5-10 min, mix thoroughly, slowly add 10-20 mL of ethyl orthosilicate, react for 10-12 h, and then age for 120 h to obtain silica sol, then add 10-20 mL of γ-aminopropyltriethoxysilane, and continue magnetic stirring for 3-4 h. Silica is evenly distributed in the network structure of the carboxyl carbon nanotubes, and the carboxymethyl carbon nanotubes are intertwined and stacked to form a flaky rough structure. The composite material is endowed with excellent superhydrophobicity and dispersibility through modification with γ-aminopropyltriethoxysilane, and has extremely low surface energy, thereby significantly improving the water resistance of the material, effectively reducing the contact and entry of water and dirt, and obtaining a superhydrophobic carbon nanotube@silica dispersion;

[0017] S2. Put cement, lithium mica lithium slag powder, nylon, and silicone oil into a colloid mill and grind and mix them at a rotation speed of 800 - 900 rpm for 30 - 50 min. The lithium mica lithium slag powder is used as a mineral admixture in cement, which improves the problems of poor cement bonding strength, poor deformation ability, and easy cracking. The addition of nylon is beneficial to the formation of pores, providing a framework for the rough structure of the superhydrophobic carbon nanotube@silica dispersion. Silicone oil has lubricating, waterproof, and mildew-proof effects. Then add the boron-silicon resin and cobalt-based MOF composite modified alkyd resin, and the superhydrophobic carbon nanotube@silica dispersion described in step S1, and continue to grind and mix for 1 - 2 h, then discharge. The boron-silicon resin and cobalt-based MOF composite modified alkyd resin have excellent bonding strength, can provide a high-strength bonding effect between different materials, ensure the firmness of the caulking agent, and the polymer film formed after drying has good waterproof and anti-fouling properties, can effectively prevent the penetration of moisture and dirt, and avoid problems such as the caulking agent getting damp and mildewing. The superhydrophobic carbon nanotube@silica dispersion and the resin are blended to form a large number of pores and holes, endowing a lower surface energy and a rough surface structure, further enhancing the waterproof and anti-fouling properties, and significantly prolonging the service effect and durability of the caulking agent, obtaining a waterproof and anti-fouling type ceramic tile caulking agent;

[0018] Preferably, in step S1, the addition amount of carboxyl carbon nanotubes is 8.0 - 10.0 g. The tubular structure of the carboxyl carbon nanotubes further enhances the density, is beneficial to reducing the penetration of moisture and dirt, and the carboxyl carbon nanotubes can reduce the adverse effects of structural defects and disorder on the mechanical properties, thereby improving the tensile bond strength.

[0019] The beneficial effects obtained by the present invention are as follows:

[0020] The present invention prepares a tile grout by blending a boron-silicon resin and cobalt-based MOF composite-modified alkyd resin, a superhydrophobic carbon nanotube@silica dispersion, cement, lithium mica lithium slag powder, nylon, and silicone oil. The surface of the prepared tile grout presents a rough structure and has hydrophobicity, and the extremely dense internal structure further reduces the penetration of moisture and dirt, significantly enhancing the waterproof and stain-resistant properties. At the same time, it also has excellent tensile bond strength, ensuring the firm stability of the grout and effectively extending the service life. In the boron-silicon resin and cobalt-based MOF composite-modified alkyd resin, boron element, silicon resin, cobalt element, and metal-organic framework MOF are introduced into the alkyd resin, which not only increases the density of the structure, effectively reducing the infiltration of moisture and dirt, but also improves the tensile bond strength of the alkyd resin, enabling it to stably adhere to the substrate surface. Among them, cobalt-based MOF can also promote the cross-linking reaction between the boron-silicon resin and the alkyd resin, further increasing the density and complexity of the structure, significantly enhancing the waterproof and stain-resistant properties and the tensile bond strength, reducing the risk of cracking or peeling, and having excellent durability and stability. In the superhydrophobic carbon nanotube@silica dispersion, silica is filled and distributed in the network structure of carboxyl carbon nanotubes, reducing the aggregation of silica particles. And under the interweaving and stacking of carboxymethyl carbon nanotubes, a flaky rough structure is formed. Through the modification treatment of γ-aminopropyltriethoxysilane, the composite material is given excellent superhydrophobicity and dispersibility, with extremely low surface energy, exerting excellent waterproof and stain-resistant properties. Among them, the addition of silica particles can improve the interfacial bonding effect, reduce the occurrence of cracking or peeling phenomena, and increase the durability of use. The present invention uses a boron-silicon resin and cobalt-based MOF composite-modified alkyd resin, a superhydrophobic carbon nanotube@silica dispersion, cement, lithium mica lithium slag powder, nylon, and silicone oil to make a waterproof and stain-resistant tile grout, which has excellent tensile bond strength and waterproof and stain-resistant properties, improves the firm stability of the grout, and effectively extends the service life. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 It is a scanning electron micrograph of the waterproof and stain-resistant tile grout prepared in Example 1 of the present invention;

[0022] Figure 2 It is a graph of the tensile bond strength results of Examples 1-4 and Comparative Examples 1-3 of the present invention;

[0023] Figure 3 It is a graph of the water absorption results of Examples 1-4 and Comparative Examples 1-3 of the present invention;

[0024] Figure 4 It is a graph of the stain resistance grade results of Examples 1-4 and Comparative Examples 1-3 of the present invention;

[0025] Figure 5SEM image of the boron-silicon resin and cobalt-based MOF composite modified alkyd resin prepared in Example 1 of the present invention. Detailed implementation mode

[0026] The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments; based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0027] Unless otherwise defined, all professional and scientific terms used herein have the same meaning as those familiar to those skilled in the art. In addition, any methods and materials similar or equivalent to the described content can be applied to the present invention. The preferred implementation methods and materials described herein are only for illustrative purposes and do not limit the content of this application.

[0028] The experimental methods in the following embodiments are all conventional methods unless otherwise specified; the test materials used in the following embodiments are all obtained from commercial channels unless otherwise specified.

[0029] The sources of the reagents used in the examples are as follows:

[0030] Nylon CAS No: 25038-54-4, brand Yuanye, product number S27531-100g;

[0031] Silicone oil brand Macklin, product number V909619-100g;

[0032] Carboxylated carbon nanotubes CAS No: 308068-56-6, brand Aladdin, product number C139822-1g;

[0033] Alkyd resin brand Kayin Chemical Industry, product number 7344XP 60.

[0034] Example 1

[0035] This example presents a waterproof and anti-fouling type tile grout, which includes the following components in parts by weight: 15 parts of boron-silicon resin and cobalt-based MOF composite modified alkyd resin, 15 parts of superhydrophobic carbon nanotube @ silica dispersion, 40 parts of cement, 30 parts of lithium mica lithium slag powder, 3 parts of nylon, and 3 parts of silicone oil.

[0036] The boron-silicon resin and cobalt-based MOF composite modified alkyd resin includes the following components in parts by weight: 20 parts of boron-silicon resin, 20 parts of cobalt-based MOF, and 70 parts of alkyd resin.

[0037] Superhydrophobic carbon nanotube@silica dispersion, comprising the following components in parts by weight: 10 parts of carboxyl carbon nanotubes, 20 parts of tetraethyl orthosilicate, and 20 parts of γ-aminopropyltriethoxysilane.

[0038] Preparation method of boron-containing silicone resin and cobalt-based MOF composite modified alkyd resin, specifically comprising the following steps:

[0039] (1) Add 0.8 g of phenyltriethoxysilane, 3.0 g of methyltriethoxysilane, and 0.8 g of dimethyldiethoxysilane into a 100 mL three-necked round-bottom flask, with a stirring speed of 200 rpm. After heating to 80 °C, slowly drop 30 mL of a hydrochloric acid solution with a mass fraction of 4%. After the dropping is completed, keep the reaction at 80 °C for 2 h. Then, drop 50 mL of a mixed solution of boric acid and absolute ethanol into it. In the mixed solution of boric acid and absolute ethanol, the mass fraction of boric acid is 20%. Boric acid greatly improves the strength of the resin through cross-linking, enhances the cohesion and adhesion. When used in sealants, it can better adhere to the substrate, enhance the tensile bond strength, and improve the firmness and durability. React for 3 h, and perform vacuum distillation to remove small molecule compounds such as water and ethanol. Discharge the material. Boron element is introduced into the silicone resin, which contains a large number of hydrophobic groups such as methyl and a cross-linked network structure, blocking the dissolution and penetration of water molecules and also reducing the infiltration of the aqueous solution formed by dirt, improving the waterproof and anti-fouling properties. The addition of boron element can also reduce the shrinkage of cement during the curing process and reduce the risk of crack occurrence, obtaining a boron-containing silicone resin;

[0040] (2) Add cobalt nitrate hexahydrate into 25 mL of N,N-dimethylformamide liquid and stir until completely dissolved. The addition amount of cobalt nitrate hexahydrate is 0.08 g. Cobalt element, as a catalyst, can accelerate the cross-linking reaction between resins, form a strong chemical bond, and improve the bond strength. Cobalt element can improve the hardness and flexibility of alkyd resin, prevent its cracking and peeling. Cobalt element can also act as an antioxidant to inhibit the oxidation reaction of the resin and extend its service life. Then add 0.05 g of trimesic acid and stir for 2 h. Transfer the solution to a stainless steel reaction kettle with a 50 mL polytetrafluoroethylene inner liner, seal the kettle lid and react at 240 °C for 2 h. Cool down to room temperature. Wash the product 5 times with N,N-dimethylformamide liquid and absolute ethanol, and perform vacuum drying. Metal-organic framework MOF has excellent superhydrophobic properties, self-cleaning properties, and a dense structure that blocks moisture and dirt. Cobalt-based MOF synthesized with cobalt element as the metal source is wrapped by abundant small particles on the surface, increasing the specific surface area, which is beneficial to its fusion with the resin. And its dense structure effectively blocks the entry of moisture, thereby improving the waterproof and anti-fouling effect, obtaining cobalt-based MOF;

[0041] (3) The boron-containing silicone resin described in step (1), the cobalt-based MOF described in step (2) and the alkyd resin are added to a 250 mL four-necked round-bottom flask equipped with a distillation device and a thermometer, and then 10 mL of propylene glycol methyl ether acetate and tetrabutyl titanate liquid are added respectively, stirred evenly, heated to 110° C. for dehydration reaction for 1 hour, and then heated to 125° C. for reaction for 3 hours, and distilled under reduced pressure. The cobalt-based MOF promotes the cross-linking of the boron-containing silicone resin and the alkyd resin, increases the density and complexity of the structure, can significantly enhance the water resistance and stain resistance, and can also improve the tensile bonding strength of the alkyd resin, effectively adhere to the surface of the substrate, reduce the risk of cracking or falling off, and have excellent durability and stability, thereby obtaining a boron-containing silicone resin and cobalt-based MOF composite modified alkyd resin.

[0042] This embodiment provides a method for preparing a waterproof and anti-fouling tile caulking agent, which specifically comprises the following steps:

[0043] S1. Dissolve carboxyl carbon nanotubes in 100 mL of 70% ethanol solution, crush the cells and perform ultrasonic dispersion for 2 h. The amount of carboxyl carbon nanotubes added is 10.0 g. The tubular structure of carboxyl carbon nanotubes further enhances the compactness, which is beneficial to reduce the penetration of water and dirt. In addition, carboxyl carbon nanotubes can reduce the adverse effects of structural defects and disorder on mechanical properties, thereby improving the tensile bonding strength. Add 6 mL of 8% sodium hydroxide solution, stir magnetically for 10 min, mix thoroughly, then slowly add 20 mL of ethyl orthosilicate, and react. After aging for 12 hours, the silica sol was obtained by aging for 120 hours, and then 20 mL of γ-aminopropyltriethoxysilane was added, and the silica was continuously stirred for 4 hours. The silica was evenly distributed in the network structure of the carboxyl carbon nanotubes, and the carboxymethyl carbon nanotubes were intertwined and stacked to form a flaky rough structure. The composite material was modified by γ-aminopropyltriethoxysilane to give it excellent superhydrophobicity and dispersibility, and had extremely low surface energy, thereby significantly improving the water resistance of the material, effectively reducing the contact and entry of water and dirt, and obtaining a superhydrophobic carbon nanotube@silica dispersion;

[0044] S2. Put cement, lithium mica lithium slag powder, nylon, and silicone oil into a colloid mill and grind and mix them at a speed of 900 rpm for 50 min. The lithium mica lithium slag powder is used as a mineral admixture in cement, which improves the problems of poor cement adhesion, poor deformation ability, and easy cracking. The addition of nylon is beneficial to the formation of pores, providing a framework for the rough structure of the superhydrophobic carbon nanotube@silica dispersion. Silicone oil has lubricating, waterproof, and mildew-proof effects. Then, add the boron-silicon resin and cobalt-based MOF composite modified alkyd resin, and the superhydrophobic carbon nanotube@silica dispersion described in step S1, and continue to grind and mix for 2 h, then discharge. The boron-silicon resin and cobalt-based MOF composite modified alkyd resin have excellent adhesion strength, can provide a high-strength bonding effect between different materials, ensure the firmness of the caulking agent, and the polymer film formed after drying has good waterproof and anti-fouling properties, can effectively prevent the penetration of moisture and dirt, and avoid the caulking agent from getting damp and mildewing, etc. The superhydrophobic carbon nanotube@silica dispersion is blended with the resin to form a large number of pores and holes, endowing a low surface energy and a rough surface structure, further enhancing the waterproof and anti-fouling properties, and significantly extending the service effect and durability of the caulking agent, thus obtaining a waterproof and anti-fouling type tile caulking agent.

[0045] In this example, a scanning electron microscope was used to observe the micro-morphology of the prepared waterproof and anti-fouling type tile caulking agent. Figure 1 It is the SEM image of the waterproof and anti-fouling type tile caulking agent prepared in Example 1 magnified 50,000 times, as Figure 1 , the surface of the waterproof and anti-fouling type tile caulking agent prepared in this example presents a rough network structure.

[0046] In this example, a scanning electron microscope was used to observe the micro-morphology of the prepared boron-silicon resin and cobalt-based MOF composite modified alkyd resin. Figure 5 It is the SEM image of the boron-silicon resin and cobalt-based MOF composite modified alkyd resin prepared in Example 1 magnified 400 times, as Figure 5 , the boron-silicon resin and cobalt-based MOF composite modified alkyd resin prepared in this example presents a cross-linked dense structure.

[0047] Example 2

[0048] This example proposes a waterproof and anti-fouling type tile caulking agent, which includes the following components in parts by weight: 10 parts of boron-silicon resin and cobalt-based MOF composite modified alkyd resin, 20 parts of superhydrophobic carbon nanotube@silica dispersion, 30 parts of cement, 20 parts of lithium mica lithium slag powder, 2 parts of nylon, and 2 parts of silicone oil.

[0049] The boron-silicon resin and cobalt-based MOF composite modified alkyd resin includes the following components in parts by weight: 15 parts of boron-silicon resin, 15 parts of cobalt-based MOF, and 60 parts of alkyd resin.

[0050] Superhydrophobic carbon nanotube@silica dispersion, comprising the following components in parts by weight: 8 parts of carboxyl carbon nanotubes, 10 parts of tetraethyl orthosilicate, and 10 parts of γ-aminopropyltriethoxysilane.

[0051] Preparation method of boron-containing silicone resin and cobalt-based MOF composite modified alkyd resin, specifically comprising the following steps:

[0052] (1) Add 0.8 g of phenyltriethoxysilane, 3.0 g of methyltriethoxysilane, and 0.8 g of dimethyldiethoxysilane into a 100 mL three-necked round-bottom flask, with a stirring speed of 180 rpm. After heating to 70 °C, slowly drop 30 mL of a hydrochloric acid solution with a mass fraction of 4%. After the dropping is completed, keep the reaction at 70 °C for 1 h. Then, drop 50 mL of a mixed solution of boric acid and absolute ethanol into it. In the mixed solution of boric acid and absolute ethanol, the mass fraction of boric acid is 10%. Boric acid greatly improves the strength of the resin through cross-linking, enhances the cohesion and adhesion. When used in sealants, it can better adhere to the substrate, enhance the tensile bond strength, and improve the firmness and durability. React for 2 h, and then perform vacuum distillation to remove small molecule compounds such as water and ethanol. Discharge the product. Boron element is introduced into the silicone resin, which contains a large number of hydrophobic groups such as methyl and a cross-linked network structure, blocking the dissolution and penetration of water molecules and also reducing the infiltration of the aqueous solution formed by dirt, improving the waterproof and anti-fouling properties. The addition of boron element can also reduce the shrinkage of cement during the curing process and reduce the risk of crack occurrence, obtaining boron-containing silicone resin;

[0053] (2) Add cobalt nitrate hexahydrate into 25 mL of N,N-dimethylformamide liquid and stir until completely dissolved. The addition amount of cobalt nitrate hexahydrate is 0.06 g. Cobalt element, as a catalyst, can accelerate the cross-linking reaction between resins, form a strong chemical bond, and improve the bond strength. Cobalt element can improve the hardness and flexibility of alkyd resin, prevent its cracking and peeling. Cobalt element can also act as an antioxidant to inhibit the oxidation reaction of the resin and extend its service life. Then add 0.05 g of trimesic acid and stir for 1 h. Transfer the solution to a stainless steel reaction kettle with a 50 mL polytetrafluoroethylene inner liner, seal the kettle lid, and react at 220 °C for 1 h. Cool down to room temperature. Wash the product 3 times with N,N-dimethylformamide liquid and absolute ethanol, and then perform vacuum drying. Metal-organic framework MOF has excellent superhydrophobic properties, self-cleaning properties, and a dense structure that blocks moisture and dirt. Cobalt-based MOF synthesized with cobalt element as the metal source is wrapped with abundant small particles on the surface, increasing the specific surface area, which is beneficial to its fusion with the resin. And its dense structure effectively isolates the entry of moisture, thereby improving the waterproof and anti-fouling effect, obtaining cobalt-based MOF;

[0054] (3) The boron-containing silicone resin described in step (1), the cobalt-based MOF described in step (2) and the alkyd resin are added to a 250 mL four-necked round-bottom flask equipped with a distillation device and a thermometer, and then 10 mL of propylene glycol methyl ether acetate and tetrabutyl titanate liquid are added respectively, stirred evenly, heated to 100° C. for dehydration reaction for 0.5 h, then heated to 115° C. for reaction for 2 h, and distilled under reduced pressure. The cobalt-based MOF promotes the cross-linking of the boron-containing silicone resin and the alkyd resin, increases the density and complexity of the structure, can significantly enhance the water resistance and stain resistance, and can also improve the tensile bonding strength of the alkyd resin, effectively adhere to the surface of the substrate, reduce the risk of cracking or falling off, and have excellent durability and stability, thereby obtaining a boron-containing silicone resin and cobalt-based MOF composite modified alkyd resin.

[0055] This embodiment provides a method for preparing a waterproof and anti-fouling tile caulking agent, which specifically comprises the following steps:

[0056] S1. Dissolve carboxyl carbon nanotubes in 100 mL of 60% ethanol solution, crush the cells and perform ultrasonic dispersion for 1 h. The amount of carboxyl carbon nanotubes added is 8.0 g. The tubular structure of carboxyl carbon nanotubes further enhances the compactness, which is beneficial to reduce the penetration of water and dirt. In addition, carboxyl carbon nanotubes can reduce the adverse effects of structural defects and disorder on mechanical properties, thereby improving the tensile bonding strength. Add 6 mL of 6% sodium hydroxide solution, stir magnetically for 5 min, mix thoroughly, and then slowly add 10 mL of ethyl orthosilicate to react. 10h, and then aged for 120h to obtain silica sol, then 10mL of γ-aminopropyltriethoxysilane was added, and magnetic stirring was continued for 3h, and silicon dioxide was evenly distributed in the network structure of carboxyl carbon nanotubes, and carboxymethyl carbon nanotubes were intertwined and stacked to form a flaky rough structure. The modified treatment of γ-aminopropyltriethoxysilane gave the composite material excellent superhydrophobicity and dispersibility, and had extremely low surface energy, thereby significantly improving the water resistance of the material, effectively reducing the contact and entry of water and dirt, and obtaining a superhydrophobic carbon nanotube@silica dispersion;

[0057] S2. Put cement, lithium mica lithium slag powder, nylon, and silicone oil into a colloid mill and grind and mix them at a speed of 800 rpm for 30 minutes. The lithium mica lithium slag powder is used as a mineral admixture in cement, improving the problems of poor cement bonding strength, poor deformation ability, and easy cracking. The addition of nylon is beneficial for forming pores, providing a framework for the rough structure of the superhydrophobic carbon nanotube@silica dispersion. Silicone oil has lubricating, waterproof, and mildew-proof effects. Then add the boron-silicon resin and cobalt-based MOF composite modified alkyd resin and the superhydrophobic carbon nanotube@silica dispersion described in step S1, continue to grind and mix for 1 hour, and discharge. The boron-silicon resin and cobalt-based MOF composite modified alkyd resin have excellent adhesive strength, can provide a high-strength bonding effect between different materials, ensure the firmness of the caulking agent, and the polymer film formed after drying has good waterproof and anti-fouling properties, can effectively prevent the penetration of moisture and dirt, and avoid the caulking agent from getting damp and mildewing, etc. The superhydrophobic carbon nanotube@silica dispersion and the resin are blended to form a large number of pores and holes, endowing a low surface energy and a rough surface structure, further enhancing the waterproof and anti-fouling properties, and significantly extending the service effect and durability of the caulking agent, obtaining a waterproof and anti-fouling type tile caulking agent.

[0058] Example 3

[0059] This example presents a waterproof and anti-fouling type tile caulking agent, which includes the following components in parts by weight: 12.5 parts of boron-silicon resin and cobalt-based MOF composite modified alkyd resin, 17.5 parts of superhydrophobic carbon nanotube@silica dispersion, 35 parts of cement, 25 parts of lithium mica lithium slag powder, 2.5 parts of nylon, and 2.5 parts of silicone oil.

[0060] The boron-silicon resin and cobalt-based MOF composite modified alkyd resin includes the following components in parts by weight: 17.5 parts of boron-silicon resin, 17.5 parts of cobalt-based MOF, and 65 parts of alkyd resin.

[0061] The superhydrophobic carbon nanotube@silica dispersion includes the following components in parts by weight: 9 parts of carboxyl carbon nanotubes, 15 parts of tetraethyl orthosilicate, and 15 parts of γ-aminopropyltriethoxysilane.

[0062] The preparation method of the boron-silicon resin and cobalt-based MOF composite modified alkyd resin specifically includes the following steps:

[0063] (1) 0.8 g of phenyltriethoxysilane, 3.0 g of methyltriethoxysilane, and 0.8 g of dimethyldiethoxysilane were added to a 100 mL three-necked round-bottom flask. The stirring speed was 190 pm. After heating to 75 °C, 30 mL of a 4% hydrochloric acid solution was slowly added dropwise. After the addition was completed, the mixture was kept at 75 °C for 1.5 h for reaction. Then, 50 mL of a mixed solution of boric acid and absolute ethanol was added dropwise. In the mixed solution of boric acid and absolute ethanol, the mass fraction of boric acid was 15%. Boric acid greatly improved the strength of the resin through cross-linking, enhanced the cohesion and adhesion. When used in caulking agents, it could better adhere to the substrate, enhance the tensile bond strength, and improve the firmness and durability. The reaction was carried out for 2.5 h, and then under reduced pressure distillation, small molecule compounds such as water and ethanol were removed. After discharging, boron element was introduced into the silicone resin. The silicone resin contained a large number of hydrophobic groups such as methyl groups and a cross-linked network structure, which blocked the dissolution and penetration of water molecules and also reduced the infiltration of the aqueous solution formed by dirt, improving the waterproof and anti-fouling properties. The addition of boron element could also reduce the shrinkage of cement during the curing process and reduce the risk of crack occurrence, obtaining a boron-containing silicone resin;

[0064] (2) Cobalt(II) nitrate hexahydrate was added to 25 mL of N,N-dimethylformamide liquid and stirred until completely dissolved. The addition amount of cobalt(II) nitrate hexahydrate was 0.07 g. Cobalt element, as a catalyst, could accelerate the cross-linking reaction between resins, form a strong chemical bond, and improve the bond strength. Cobalt element could improve the hardness and flexibility of alkyd resin, prevent its cracking and peeling. Cobalt element could also act as an antioxidant to inhibit the oxidation reaction of the resin and extend its service life. Then, 0.05 g of trimesic acid was added and stirred for 1.5 h. The solution was transferred to a stainless-steel autoclave with a 50 mL polytetrafluoroethylene inner liner. The autoclave lid was sealed and reacted at 230 °C for 1.5 h. After cooling to room temperature, the product was washed 4 times with N,N-dimethylformamide liquid and absolute ethanol and then dried under vacuum. Metal-organic framework MOF had excellent superhydrophobic properties, self-cleaning properties, and a dense structure that blocked moisture and dirt. Cobalt-based MOF synthesized with cobalt element as the metal source was wrapped with abundant small particles on the surface, increasing the specific surface area, which was beneficial to its fusion with the resin. And its dense structure effectively blocked the entry of moisture, thus improving the waterproof and anti-fouling effect, obtaining cobalt-based MOF;

[0065] (3) The boron-containing silicone resin described in step (1), the cobalt-based MOF described in step (2) and the alkyd resin are added to a 250 mL four-necked round-bottom flask equipped with a distillation device and a thermometer, and then 10 mL of propylene glycol methyl ether acetate and tetrabutyl titanate liquid are added respectively, stirred evenly, heated to 105° C. for dehydration reaction for 0.75 h, then heated to 120° C. for reaction for 2.5 h, and distilled under reduced pressure. The cobalt-based MOF promotes the cross-linking of the boron-containing silicone resin and the alkyd resin, increases the density and complexity of the structure, can significantly enhance the water resistance and stain resistance, and can also improve the tensile bonding strength of the alkyd resin, effectively adhere to the surface of the substrate, reduce the risk of cracking or falling off, and have excellent durability and stability, thereby obtaining a boron-containing silicone resin and cobalt-based MOF composite modified alkyd resin.

[0066] This embodiment provides a method for preparing a waterproof and anti-fouling tile caulking agent, which specifically comprises the following steps:

[0067] S1. Dissolve carboxyl carbon nanotubes in 100 mL of 65% ethanol solution, crush the cells and perform ultrasonic dispersion for 1.5 h. The amount of carboxyl carbon nanotubes added is 9.0 g. The tubular structure of carboxyl carbon nanotubes further enhances the compactness, which is beneficial to reduce the penetration of water and dirt. In addition, carboxyl carbon nanotubes can reduce the adverse effects of structural defects and disorder on mechanical properties, thereby improving the tensile bonding strength. Add 6 mL of 7% sodium hydroxide solution, stir magnetically for 7.5 min, mix thoroughly, then slowly add 15 mL of ethyl orthosilicate, and react. After aging for 11 hours, the silica sol was obtained by aging for 120 hours, and then 15 mL of γ-aminopropyltriethoxysilane was added, and the silica was continuously stirred for 3.5 hours. The silica was evenly distributed in the network structure of the carboxyl carbon nanotubes, and the carboxymethyl carbon nanotubes were intertwined and stacked to form a flaky rough structure. The composite material was modified by γ-aminopropyltriethoxysilane to give it excellent superhydrophobicity and dispersibility, and had extremely low surface energy, thereby significantly improving the water resistance of the material, effectively reducing the contact and entry of water and dirt, and obtaining a superhydrophobic carbon nanotube@silica dispersion;

[0068] S2. Put cement, lithium mica lithium slag powder, nylon, and silicone oil into a colloid mill and grind and mix them at a speed of 850 rpm for 40 min. The lithium mica lithium slag powder is used as a mineral admixture in cement, which improves the problems of poor cement adhesion, poor deformation ability, and easy cracking. The addition of nylon is beneficial to the formation of pores, providing a framework for the rough structure of the superhydrophobic carbon nanotube@silica dispersion. Silicone oil has lubricating, waterproof, and mildew-proof effects. Then, add the boron-silicon resin and cobalt-based MOF composite modified alkyd resin, and the superhydrophobic carbon nanotube@silica dispersion described in step S1, and continue to grind and mix for 1.5 h, then discharge. The boron-silicon resin and cobalt-based MOF composite modified alkyd resin have excellent adhesive strength, can provide a high-strength bonding effect between different materials, ensure the firmness of the caulking agent, and the polymer film formed after drying has good waterproof and anti-fouling properties, can effectively prevent the penetration of moisture and dirt, and avoid problems such as the caulking agent getting damp and mildewing. The superhydrophobic carbon nanotube@silica dispersion and the resin are blended to form a large number of pores and holes, endowing a low surface energy and a rough surface structure, further enhancing the waterproof and anti-fouling properties, and significantly extending the service effect and durability of the caulking agent, thus obtaining a waterproof and anti-fouling type tile caulking agent.

[0069] Example 4

[0070] This example presents a waterproof and anti-fouling type tile caulking agent, which includes the following components in parts by weight: 15 parts of boron-silicon resin and cobalt-based MOF composite modified alkyd resin, 20 parts of superhydrophobic carbon nanotube@silica dispersion, 40 parts of cement, 20 parts of lithium mica lithium slag powder, 2 parts of nylon, and 2 parts of silicone oil.

[0071] The boron-silicon resin and cobalt-based MOF composite modified alkyd resin includes the following components in parts by weight: 20 parts of boron-silicon resin, 20 parts of cobalt-based MOF, and 70 parts of alkyd resin.

[0072] The superhydrophobic carbon nanotube@silica dispersion includes the following components in parts by weight: 10 parts of carboxyl carbon nanotubes, 20 parts of tetraethyl orthosilicate, and 20 parts of γ-aminopropyltriethoxysilane.

[0073] The preparation method of the boron-silicon resin and cobalt-based MOF composite modified alkyd resin specifically includes the following steps:

[0074] (1) 0.8 g of phenyltriethoxysilane, 3.0 g of methyltriethoxysilane, and 0.8 g of dimethyldiethoxysilane were added to a 100 mL three-necked round-bottom flask, with a stirring speed of 200 rpm. After heating to 80 °C, 30 mL of a 4% hydrochloric acid solution was slowly added dropwise. After the addition was complete, the mixture was kept at 80 °C for 1 h of reaction. Then, 50 mL of a mixed solution of boric acid and absolute ethanol was added dropwise. In the mixed solution of boric acid and absolute ethanol, the mass fraction of boric acid was 20%. Boric acid greatly improved the strength of the resin through cross-linking, enhanced the cohesion and adhesion. When used in sealants, it could better adhere to the substrate, enhance the tensile bond strength, and improve the firmness and durability. The reaction was carried out for 2 h, followed by vacuum distillation to remove small molecule compounds such as water and ethanol. After discharging, boron element was introduced into the silicone resin. The silicone resin contained a large number of hydrophobic groups such as methyl groups and a cross-linked network structure, which blocked the dissolution and penetration of water molecules and also reduced the infiltration of the aqueous solution formed by dirt, improving the waterproof and anti-fouling properties. The addition of boron element could also reduce the shrinkage of cement during the curing process and lower the risk of crack occurrence, obtaining a boron-containing silicone resin;

[0075] (2) Cobalt(II) nitrate hexahydrate was added to 25 mL of N,N-dimethylformamide liquid and stirred until completely dissolved. The addition amount of cobalt(II) nitrate hexahydrate was 0.08 g. Cobalt element, as a catalyst, could accelerate the cross-linking reaction between resins, form a strong chemical bond, and improve the bond strength. Cobalt element could increase the hardness and flexibility of alkyd resin, prevent its cracking and peeling. Cobalt element could also act as an antioxidant to inhibit the oxidation reaction of the resin and extend its service life. Then, 0.05 g of trimesic acid was added and stirred for 1 h. The solution was transferred to a stainless-steel autoclave with a 50 mL polytetrafluoroethylene inner liner, and the autoclave lid was sealed tightly and reacted at 240 °C for 1 h. After cooling to room temperature, the product was washed 5 times with N,N-dimethylformamide liquid and absolute ethanol and then dried under vacuum. Metal-organic framework MOF had excellent superhydrophobic properties, self-cleaning properties, and a dense structure that blocked moisture and dirt. Cobalt-based MOF synthesized with cobalt element as the metal source was wrapped with abundant small particles on the surface, increasing the specific surface area, which was beneficial to its integration with the resin. And its dense structure effectively blocked the entry of moisture, thus improving the waterproof and anti-fouling effect, obtaining cobalt-based MOF;

[0076] (3) The boron-containing silicone resin described in step (1), the cobalt-based MOF described in step (2) and the alkyd resin are added to a 250 mL four-necked round-bottom flask equipped with a distillation device and a thermometer, and then 10 mL of propylene glycol methyl ether acetate and tetrabutyl titanate liquid are added respectively, stirred evenly, heated to 110° C. for dehydration reaction for 0.5 h, then heated to 125° C. for reaction for 2 h, and distilled under reduced pressure. The cobalt-based MOF promotes the cross-linking of the boron-containing silicone resin and the alkyd resin, increases the density and complexity of the structure, can significantly enhance the water resistance and stain resistance, and can also improve the tensile bonding strength of the alkyd resin, effectively adhere to the surface of the substrate, reduce the risk of cracking or falling off, and have excellent durability and stability, thereby obtaining a boron-containing silicone resin and cobalt-based MOF composite modified alkyd resin.

[0077] This embodiment provides a method for preparing a waterproof and anti-fouling tile caulking agent, which specifically comprises the following steps:

[0078] S1. Dissolve carboxyl carbon nanotubes in 100 mL of 70% ethanol solution, crush the cells and perform ultrasonic dispersion for 1 h. The amount of carboxyl carbon nanotubes added is 10.0 g. The tubular structure of carboxyl carbon nanotubes further enhances the compactness, which is beneficial to reduce the penetration of water and dirt. In addition, carboxyl carbon nanotubes can reduce the adverse effects of structural defects and disorder on mechanical properties, thereby improving the tensile bonding strength. Add 6 mL of 8% sodium hydroxide solution, stir magnetically for 5 min, mix thoroughly, and then slowly add 20 mL of ethyl orthosilicate to react. 10h, and then aged for 120h to obtain silica sol, then 20mL of γ-aminopropyltriethoxysilane was added, and magnetic stirring was continued for 3h, and silicon dioxide was evenly distributed in the network structure of carboxyl carbon nanotubes, and carboxymethyl carbon nanotubes were intertwined and stacked to form a flaky rough structure. The composite material was modified by γ-aminopropyltriethoxysilane to give it excellent superhydrophobicity and dispersibility, and had extremely low surface energy, thereby significantly improving the water resistance of the material, effectively reducing the contact and entry of water and dirt, and obtaining a superhydrophobic carbon nanotube@silica dispersion;

[0079] S2. Put cement, lithium mica lithium slag powder, nylon, and silicone oil into a colloid mill and grind and mix them at a speed of 900 rpm for 30 minutes. The lithium mica lithium slag powder is used as a mineral admixture in cement, improving the problems of poor cement bonding strength, poor deformation ability, and easy cracking. The addition of nylon is beneficial to the formation of pores, providing a framework for the rough structure of the superhydrophobic carbon nanotube@silica dispersion. Silicone oil has lubricating, waterproof, and mildew-proof effects. Then, add the boron-silicon resin and cobalt-based MOF composite modified alkyd resin, and the superhydrophobic carbon nanotube@silica dispersion described in step S1, and continue to grind and mix for 1 hour, and then discharge. The boron-silicon resin and cobalt-based MOF composite modified alkyd resin have excellent adhesive strength, can provide a high-strength bonding effect between different materials, ensuring the firmness of the caulking agent. The polymer film formed after drying has good waterproof and anti-fouling properties, can effectively prevent the penetration of moisture and dirt, and avoid the caulking agent from getting damp and mildewing, etc. The superhydrophobic carbon nanotube@silica dispersion and the resin are blended to form a large number of pores and holes, endowing a low surface energy and a rough surface structure, further enhancing the waterproof and anti-fouling properties, and significantly extending the service effect and durability of the caulking agent, obtaining a waterproof and anti-fouling type tile caulking agent.

[0080] Comparative Example 1

[0081] This comparative example provides a waterproof and anti-fouling type tile caulking agent, which is different from Example 1 in that the boron-silicon resin and cobalt-based MOF composite modified alkyd resin do not contain boron-silicon resin; the preparation method of the boron-silicon resin and cobalt-based MOF composite modified alkyd resin does not include step (1); the preparation method of the waterproof and anti-fouling type tile caulking agent is the same as that of Example 1.

[0082] Comparative Example 2

[0083] This comparative example provides a waterproof and anti-fouling type tile caulking agent, which is different from Example 1 in that the boron-silicon resin and cobalt-based MOF composite modified alkyd resin do not contain cobalt-based MOF; the preparation method of the boron-silicon resin and cobalt-based MOF composite modified alkyd resin does not include step (2); the preparation method of the waterproof and anti-fouling type tile caulking agent is the same as that of Example 1.

[0084] Comparative Example 3

[0085] This comparative example provides a waterproof and anti-fouling type tile caulking agent, which is different from Example 1 in that the superhydrophobic carbon nanotube@silica dispersion does not contain carboxyl carbon nanotubes and γ-aminopropyltriethoxysilane; the preparation method of the boron-silicon resin and cobalt-based MOF composite modified alkyd resin is the same as that of Example 1; in step S1 of the preparation method of the waterproof and anti-fouling type tile caulking agent, carboxyl carbon nanotubes and γ-aminopropyltriethoxysilane are not added.

[0086] Experimental Example 1

[0087] Firm Stability Experiment

[0088] Test Samples: Waterproof and Stain-Resistant Tile Grouts prepared in Examples 1-4 and Comparative Examples 1-3.

[0089] Test Method: The test samples were made into specimens with dimensions of 40mm×40mm×160mm, and the shaped specimens were cured using plastic film. After 7 days, the demoulding treatment was carried out, and then they were covered with polyethylene film for another 7 days of curing. According to (JG158-2004), the specimens for testing the tensile bond strength were cured. The test steps were as follows: A 40mm×40mm×15mm iron head was glued to the specimen with AB glue, and the iron head was controlled to measure the tensile bond strength (MPa) of the sample at a speed of 5 millimeters per minute.

[0090] Figure 2 Figure for the tensile bond strength results of Examples 1-4 and Comparative Examples 1-3; as shown in the figure, the tensile bond strength of Examples 1-4 was 1.46 - 1.65 MPa, indicating a relatively strong tensile bond strength, which was beneficial to firm stability; the tensile bond strength of Comparative Examples 1-3 was 0.72 - 0.98 MPa, indicating a relatively weak tensile bond strength, which was not conducive to firm stability; in the boron-silicon resin and cobalt-based MOF composite modified alkyd resin of Comparative Example 1, there was no boron-silicon resin, and it was unable to exert the improvement effect of the silicon-oxygen bond in the silicone resin and the boron-oxygen bond formed by the introduction of boron elements on the tensile bond performance of the material, resulting in a relatively weak tensile bond strength and being not conducive to firm stability; in the boron-silicon resin and cobalt-based MOF composite modified alkyd resin of Comparative Example 2, there was no cobalt-based MOF, which was not conducive to promoting the cross-linking reaction between the boron-silicon resin and the alkyd resin, resulting in a relatively weak tensile bond strength and being not conducive to firm stability; in the superhydrophobic carbon nanotube@silica dispersion of Comparative Example 3, there were no carboxyl carbon nanotubes and γ-aminopropyltriethoxysilane, which increased the adverse effects of structural defects and disorder on the mechanical properties and was also not conducive to the uniform dispersion of silica particles, resulting in a relatively weak tensile bond strength and being not conducive to firm stability.

[0091] Experimental Example 2

[0092] Waterproof Experiment

[0093] Test Samples: Waterproof and Stain-Resistant Tile Grouts prepared in Examples 1-4 and Comparative Examples 1-3.

[0094] Test Method: Referring to the method in DL / T5126-2001 "Test Procedures for Polymer Cement Mortar", the test samples were prepared into specimens with dimensions of 40mm×40mm×10mm and cured for 28 days, and the water absorption rate (%) was measured.

[0095] Figure 3The water absorption results of Examples 1-4 and Comparative Examples 1-3 are shown in the figure; as shown in the figure, the water absorption of Examples 1-4 is 0.3-1.5%, indicating good water resistance; the water absorption of Comparative Examples 1-3 is 8.7-14.5%, indicating poor water resistance; the boron-containing silicone resin and cobalt-based MOF composite modified alkyd resin of Comparative Example 1 does not contain boron-containing silicone resin, lacks hydrophobic groups and cross-linked network structures, is not conducive to blocking the dissolution and penetration of water molecules, resulting in poor water resistance; the boron-containing silicone resin and cobalt-based MOF composite modified alkyd resin of Comparative Example 2 The alkyd resin does not contain cobalt-based MOF, which can neither provide MOF with excellent hydrophobic properties nor further promote the cross-linking reaction between the boron silicone resin and the alkyd resin, which is not conducive to the compactness and complexity of the structure, resulting in poor waterproofness; the super-hydrophobic carbon nanotube@silica dispersion of Comparative Example 3 does not contain carboxyl carbon nanotubes and γ-aminopropyltriethoxysilane, and cannot exert the barrier effect of the tubular structure on moisture, nor can it be modified with γ-aminopropyltriethoxysilane to impart super-hydrophobicity and dispersibility, resulting in poor waterproofness.

[0096] Experimental Example 3

[0097] Antifouling test

[0098] Test sample: the waterproof and anti-fouling tile grout prepared in Examples 1-4 and Comparative Examples 1-3.

[0099] Test method: Referring to the specimen preparation method of JG / T298-2010 "Architectural Interior Putty", the test sample is molded onto a 155mm×85mm tinplate with a thickness of 3mm. It is cured for 28 days under standard test conditions. Three drops of 1:1 diluted soy sauce are added to the surface of the specimen, and it is retained for 30 minutes. It is then wiped and cleaned, and the stain resistance level is visually inspected. The stain resistance level is divided into five levels:

[0100] Level 1 means it can be cleaned by gently wiping with a hot water sponge;

[0101] Level 2 means it can be cleaned by gently wiping with a mild detergent and a sponge;

[0102] Level 3 means it can be cleaned by wiping vigorously with a general detergent and a sponge;

[0103] Level 4 means it can be cleaned with a solvent-based or acidic cleaner and vigorous wiping with a sponge;

[0104] Level 5 means that it cannot be cleaned using any of the above methods.

[0105] Figure 4Graph of stain resistance levels for Examples 1-4 and Comparative Examples 1-3; as shown in the figure, the stain resistance levels of Examples 1-4 are 1-2, indicating better stain resistance; the stain resistance levels of Comparative Examples 1-3 are 3-4, indicating poor stain resistance; the boron-silicate resin and cobalt-based MOF composite modified alkyd resin in Comparative Example 1 does not contain boron-silicate resin, which is not conducive to increasing the compactness of the structure and increases the infiltration of the aqueous solution formed by dirt, resulting in poor stain resistance; the boron-silicate resin and cobalt-based MOF composite modified alkyd resin in Comparative Example 2 does not contain cobalt-based MOF, which can neither provide MOF that can block the entry of moisture and dirt nor further promote the cross-linking reaction between boron-silicate resin and alkyd resin, is not conducive to the compact complexity of the structure, and thus is not conducive to blocking the infiltration of dirt, resulting in poor stain resistance; the superhydrophobic carbon nanotube@silica dispersion in Comparative Example 3 does not contain carboxyl carbon nanotubes and γ-aminopropyltriethoxysilane, cannot exert the blocking effect of the tubular structure on dirt, and cannot be modified by γ-aminopropyltriethoxysilane, thus being not conducive to dispersion compatibility, restricting the function of the superhydrophobic carbon nanotube@silica dispersion, and resulting in poor stain resistance.

[0106] The above experimental results show that the firm stability, water resistance, and stain resistance of Examples 1-4 of the present invention are significantly better than those of the samples in Comparative Examples 1-3. Among them, Example 1 using boron-silicate resin and cobalt-based MOF composite modified alkyd resin and superhydrophobic carbon nanotube@silica dispersion has stronger tensile bond strength, better water resistance, and better stain resistance. In the boron-silicate resin and cobalt-based MOF composite modified alkyd resin, boron element, silicone resin, cobalt element, and metal-organic framework MOF are introduced, which not only increases the compactness of the structure, effectively reduces the infiltration of moisture and dirt, but also improves the tensile bond strength of the alkyd resin. Among them, cobalt-based MOF can also promote the cross-linking reaction between boron-silicate resin and alkyd resin, further increasing the compact complexity of the structure, significantly enhancing the waterproof and stain resistance performance and the tensile bond strength, and reducing the risk of cracking or peeling. In the superhydrophobic carbon nanotube@silica dispersion, silica is filled and distributed in the network structure of carboxyl carbon nanotubes, reducing the aggregation of silica particles, and under the interweaving and stacking of carboxymethyl carbon nanotubes, a flaky rough structure is formed, and through the modification treatment of γ-aminopropyltriethoxysilane, the composite material is given excellent superhydrophobicity and dispersibility, with extremely low surface energy, and excellent waterproof and stain resistance is exerted.

[0107] Although the embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention.

[0108] The above describes the present invention and its embodiments. Such description is not restrictive. What is shown in the drawings is only one of the embodiments of the present invention, and the actual application is not limited thereto. In summary, if those of ordinary skill in the art are inspired by it and, without departing from the spirit of the present invention, design similar methods and embodiments to this technical solution without creative efforts, they shall fall within the protection scope of the present invention.

Claims

1. A waterproof and anti-fouling tile caulking agent, characterized in that: The waterproof and anti-fouling tile caulking agent comprises the following components in parts by weight: 10-15 parts of boron-containing silicone resin and cobalt-based MOF composite modified alkyd resin, 15-20 parts of super-hydrophobic carbon nanotube@silica dispersion, 30-40 parts of cement, 20-30 parts of lithium mica lithium slag powder, 2-3 parts of nylon, and 2-3 parts of silicone oil; the boron-containing silicone resin and cobalt-based MOF composite modified alkyd resin comprises the following components in parts by weight: 15-20 parts of boron-containing silicone resin, 15-20 parts of cobalt-based MOF, and 60-70 parts of alkyd resin; the super-hydrophobic carbon nanotube@silica dispersion comprises the following components in parts by weight: 8-10 parts of carboxyl carbon nanotubes, 10-20 parts of tetraethyl orthosilicate, and 10-20 parts of γ-aminopropyltriethoxysilane.

2. A method for preparing the waterproof and anti-fouling tile caulking agent according to claim 1, characterized in that: The specific steps include: S1. Dissolve the carboxyl carbon nanotubes in 100 mL of 60-70% ethanol solution, crush the cells and perform ultrasonic dispersion for 1-2 h, add 6 mL of 6-8% sodium hydroxide solution, stir magnetically for 5-10 min, mix thoroughly, slowly add 10-20 mL of ethyl orthosilicate, react for 10-12 h, and age for 120 h to obtain silica sol, then add 10-20 mL of γ-aminopropyltriethoxysilane, continue magnetic stirring for 3-4 h, and obtain superhydrophobic carbon nanotube@silica dispersion; S2. Put cement, lithium mica lithium slag powder, nylon and silicone oil into a colloid mill, grind and mix at a speed of 800-900 rpm for 30-50 minutes, then add boron silicone resin and cobalt-based MOF composite modified alkyd resin, and the super hydrophobic carbon nanotube @silica dispersion described in step S1, continue grinding and mixing for 1-2 hours, and discharge the material to obtain a waterproof and anti-fouling tile caulking agent.

3. The method for preparing the waterproof and anti-fouling tile caulking agent according to claim 2, characterized in that: In step S1, the amount of carboxyl carbon nanotubes added is 8.0-10.0 g.

4. The method for preparing the waterproof and anti-fouling tile caulking agent according to claim 3, characterized in that: The preparation method of the boron-containing silicone resin and cobalt-based MOF composite modified alkyd resin specifically comprises the following steps: (1) 0.8 g of phenyltriethoxysilane, 3.0 g of methyltriethoxysilane and 0.8 g of dimethyldiethoxysilane were added to a 100 mL three-necked round-bottom flask, stirred at 180-200 rpm, heated to 70-80°C, and then slowly dripped with 30 mL of a 4% hydrochloric acid solution. After the addition was completed, the mixture was kept at 70-80°C for 1-2 h, and then 50 mL of a mixed solution of boric acid and anhydrous ethanol was dripped into the mixture, and the mixture was reacted for 2-3 h. The mixture was distilled under reduced pressure to remove water and ethanol small molecular compounds, and the material was discharged to obtain a boron-containing silicone resin; (2) Add cobalt nitrate hexahydrate to 25 mL of N,N-dimethylformamide liquid and stir until completely dissolved. Then add 0.05 g of trimesic acid and stir for 1-2 h. Transfer the solution to a 50 mL stainless steel reactor with a polytetrafluoroethylene liner. Seal the reactor lid and react at 220-240 °C for 1-2 h. Cool to room temperature. Wash the product with N,N-dimethylformamide liquid and anhydrous ethanol for 3-5 times and vacuum dry to obtain a cobalt-based MOF. (3) The boron-containing silicone resin described in step (1), the cobalt-based MOF described in step (2) and the alkyd resin are added to a 250 mL four-necked round-bottom flask equipped with a distillation device and a thermometer, and then 10 mL of propylene glycol methyl ether acetate and tetrabutyl titanate liquid are added respectively, stirred evenly, heated to 100-110° C. for dehydration reaction for 0.5-1 h, then heated to 115-125° C. for reaction for 2-3 h, and distilled under reduced pressure to obtain a boron-containing silicone resin and cobalt-based MOF composite modified alkyd resin.

5. The method for preparing the waterproof and anti-fouling tile caulking agent according to claim 4, characterized in that: In step (1), in the mixed solution of boric acid and anhydrous ethanol, the mass fraction of boric acid is 10-20%.

6. The method for preparing the waterproof and anti-fouling tile caulking agent according to claim 5, characterized in that: In step (2), the amount of cobalt nitrate hexahydrate added is 0.06-0.08 g.

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