Powerful firm bi-component impermeable waterproof building adhesive and preparation method thereof

Abstract

The invention relates to the field of building adhesive materials, and provides a powerful firm two-component anti-seepage waterproof building adhesive which comprises a component A and a component B, the component A is prepared from epoxy resin E-51, a reactive diluent BGE, a flexibilizer CTBN, a dispersing agent and a defoaming agent; the component B is composed of perfluoroalkyl silane modified boron nitride, dicyandiamide, an imidazole curing agent, fumed silica HL-200, a fluorine-containing silane coupling agent modified titanium dioxide nanowire and the like, and the component A and the component B are mixed according to the mass ratio of (2.0-4.0): 1. The perfluoroalkyl silane modified boron nitride is prepared through surface polymerization of dopamine hydrochloride and grafting modification of perfluorooctyltrimethoxysilane, and the fluorine-containing silane coupling agent modified titanium dioxide nanowire is obtained through surface treatment of perfluorooctyltriethoxysilane. After the colloid is cured, a high-strength waterproof layer is formed, the waterproof performance, the impermeability and the ultraviolet aging resistance are excellent, and the waterproof colloid is suitable for building waterproof engineering.

Description

Technical Field

[0001] The present invention relates to the field of building adhesive materials, and particularly to a highly effective and firm two-component anti-seepage and waterproof building adhesive and a preparation method thereof. Background Art

[0002] In the fields of building engineering, waterproof construction and underground structure protection, the performance of waterproof materials directly affects the durability and safety of building structures. Especially in underground spaces, high-humidity environments and building components that are long-term exposed to external climatic conditions, the reliability of the waterproof layer is crucial. Traditional single-component or ordinary waterproof adhesives often face problems such as water seepage, aging, and interlayer peeling during application, and it is difficult to meet the long-term use requirements in harsh environments. Therefore, a two-component building adhesive with high anti-seepage, waterproof, and ultraviolet-resistant properties has become the focus of the industry. Such materials need to maintain stable physical and chemical properties in complex environments such as high humidity, high temperature, and ultraviolet radiation. It not only requires excellent bonding strength and aging resistance, but also needs to maintain low water absorption and high anti-seepage ability in long-term water immersion or high-temperature and humid environments. In addition, in the face of the dual requirements of construction efficiency and durability in the building industry, such waterproof building adhesives also need to have a reasonable operation time, fast curing characteristics, and excellent interfacial adaptability to ensure construction convenience and long-term use stability. With the promotion of the concepts of green building and sustainable development, the environmental protection, low VOC emissions, and material durability of waterproof materials have gradually become important evaluation indicators. Therefore, developing a two-component waterproof building adhesive with high waterproofness, strong anti-seepage ability, and excellent ultraviolet-resistant properties can not only effectively improve the overall durability of building structures, but also significantly reduce maintenance costs, broaden the application scope of waterproof materials, and promote the further development of waterproof engineering technology.

[0003] At present, a variety of waterproof building glues have been proposed on the market, but there are still many technical bottlenecks. For example, the Chinese patent with publication number CN111334231A discloses a high elasticity anti-aging waterproof glue and its preparation method. Although it has waterproof function, it has certain limitations in anti-seepage and anti-ultraviolet. In addition, another patent with publication number CN104946187A discloses an anti-ultraviolet rubber glue, which uses ultraviolet absorbers to improve weather resistance, but after long-term exposure to high ultraviolet areas, there is still a certain degradation phenomenon, which affects the protective effect. The existing two-component waterproof building glue also has shortcomings in terms of anti-seepage, such as some materials are prone to microcracks under high water pressure environments, leading to hidden dangers of water seepage. The main reason for these problems is that the optimization of material components is still limited, especially in the interface compatibility between polymer matrix and inorganic filler, the durability of curing system and the long-term stability of anti-aging components. A systematic breakthrough has not yet been achieved. Therefore, how to achieve better waterproof, anti-seepage and UV resistance through reasonable material design and system optimization is still a key technical problem that needs to be solved in the current field of waterproof building glue. Summary of the invention

[0004] (1) Technical problem to be solved: The purpose of the present invention is to provide a strong and firm two-component anti-seepage and waterproof building adhesive to solve the problem that the current anti-seepage and waterproof building adhesive has insufficient anti-seepage, waterproof and UV resistance properties.

[0005] (2) Technical solution: In order to achieve the above-mentioned object, the present invention provides the following technical solution: A strong and firm two-component anti-seepage and waterproof building adhesive, comprising component A and component B; The component A comprises the following raw materials in parts by weight: 1100 parts of epoxy resin E-51, 10-12 parts of active diluent BGE, 6-8 parts of toughening agent CTBN, 0.8-1.2 parts of dispersant, and 0.3-0.5 parts of defoaming agent; The component B comprises the following raw materials in parts by weight: 2.5-4.5 parts of perfluoroalkylsilane-modified boron nitride, 4.5-5.5 parts of dicyandiamide, 1.2-1.8 parts of 2-methylimidazole, 1.0-1.5 parts of 1,2-dimethylimidazole, 3.0-4.0 parts of fumed silica HL-200, 12-15 parts of titanium dioxide nanowires surface-modified with a fluorine-containing silane coupling agent, 1.0-1.5 parts of ultraviolet absorber UV-360, and 0.5-0.8 parts of antioxidant 3114; The mass ratio of component A to component B is (2.0-4.0):1.

[0006] The perfluoroalkylsilane-modified boron nitride is first pre-modified by surface polymerization of dopamine hydrochloride salt to prepare boron nitride nanosheets, then grafted with tridecafluorooctyltrimethoxysilane, and finally filtered, washed and freeze-dried to obtain; The fluorosilane coupling agent surface-modified titanium dioxide nanowires described above are obtained by surface-modifying titanium dioxide nanowires with perfluorooctyltriethoxysilane.

[0007] Furthermore, the preparation method of the perfluoroalkylsilane-modified boron nitride is as follows: 1.0 - 1.2 g of polydopamine-modified boron nitride nanosheets are dispersed in 120 - 130 mL of toluene. After ultrasonic treatment at a frequency of 40 - 60 kHz for 15 - 25 min to form a uniform suspension, a mixed solution of 0.95 - 1.05 g of tridecafluorooctyltrimethoxysilane and 18 - 22 mL of toluene is added dropwise to the reaction system at a rate of 0.5 - 1.0 mL / min. Subsequently, the temperature is raised to 75 - 85 °C under nitrogen protection and magnetic stirring is carried out at 300 - 500 rpm for 5 - 7 h to complete the grafting reaction. After the reaction, it is naturally cooled to 20 - 25 °C, and the solid product is separated by vacuum filtration through a 0.22 μm polytetrafluoroethylene filter membrane. The filter cake is washed 3 times successively with 50 - 80 mL of acetone, 50 - 80 mL of ethanol, and 50 - 80 mL of deionized water to remove unreacted monomers and solvent residues. Finally, the product is placed in a freeze dryer at -50 - -40 °C for 70 - 74 h to obtain dark gray perfluoroalkylsilane-modified boron nitride.

[0008] Furthermore, for the polydopamine-modified boron nitride nanosheets: 2.8 - 3.2 g of boron nitride nanosheets are dispersed in 580 - 620 mL of tris(hydroxymethyl)aminomethane buffer solution with a pH of 8.3 - 8.7. After ultrasonic treatment at a power of 200 - 300 W for 25 - 35 min, 1.15 - 1.25 g of dopamine hydrochloride is slowly added at a stirring speed of 400 - 600 rpm at 20 - 25 °C and the reaction continues for 1.8 - 2.2 h to achieve surface polymerization coating. After vacuum filtration, it is washed with deionized water until the conductivity of the filtrate < 5 μS / cm, and freeze-dried for 62 - 74 h to obtain polydopamine-modified boron nitride nanosheets.

[0009] Further, the preparation method of the boron nitride nanosheets is as follows: Prepared by mechanical ball milling-liquid phase exfoliation method, specifically: hexagonal boron nitride bulk with a particle size of 0.5-5.0 mm and zirconia grinding balls with a diameter of 1.0-3.0 mm are loaded into a silicon nitride ball milling jar with a volume of 500-1000 mL according to a mass ratio of 1:(30-50), and planetary ball milled at a rotation speed of 300-400 rpm for 4-6 h under the protection of an argon flow rate of 5-10 L / min. After ball milling, the product is mixed with N-methylpyrrolidone according to a solid-liquid ratio of 1:(100-150), and subjected to pulsed ultrasonic treatment with a power of 500-800 W and a working cycle of 2 s on / 1 s off for 2-4 h. During the treatment, the temperature of the suspension is controlled at 20-40 °C. Subsequently, centrifuged at 8000-12000 rpm for 10-30 min and the operation is repeated 2-3 times to remove the unexfoliated particles. The supernatant after centrifugation is collected and vacuum filtered through a 0.22 μm polytetrafluoroethylene filter membrane. The obtained filter cake is washed 3-5 times with 50-80 mL of anhydrous ethanol and 50-80 mL of deionized water respectively to thoroughly remove the solvent residue. Finally, the product is placed in a vacuum drying oven and dried at a constant temperature of 50-60 °C for 12-24 h to obtain boron nitride nanosheets.

[0010] Further, the average diameter of the boron nitride nanosheets is 0.5-2.5 μm; the average thickness is 2.5-6.5 nm.

[0011] The design of using perfluoroalkylsilane to modify boron nitride in this invention is mainly used to enhance the waterproofness, impermeability and ultraviolet resistance of two-component impermeable waterproof construction adhesives. First, boron nitride nanosheets are prepared by mechanical ball milling-liquid phase exfoliation method to endow them with a high specific surface area and lamellar structure, so as to form a uniformly dispersed reinforcing phase in the matrix, laying a foundation for subsequent interfacial modification. Subsequently, the boron nitride nanosheets are pre-modified by the method of surface polymerization of hydrochloric acid dopamine salt, and the surface is coated with a polydopamine layer, thereby improving its dispersion stability in the organic phase and enhancing the interfacial interaction with the polymer matrix. Then, a perfluoroalkylsilane structure is introduced onto the boron nitride surface through the grafting reaction of trifluorooctyltrimethoxysilane, further reducing its surface energy, making it have better compatibility in the hydrophobic system, and at the same time endowing the material with excellent hydrophobic properties and chemical stability. During the whole modification process, the synergistic effect of ultrasonic treatment and magnetic stirring ensures the uniformity and sufficiency of the grafting reaction, while steps such as vacuum filtration, gradient washing and freeze-drying ensure the high purity and structural integrity of the final product. Through this series of modification processes, perfluoroalkylsilane-modified boron nitride can not only effectively improve the impermeability and waterproof ability of two-component waterproof construction adhesives, but also improve the ultraviolet resistance of the material through its inherent optical stability. In addition, while ensuring the high efficiency of the material, this modification strategy also enhances the interfacial bonding force between the filler and the matrix, reduces the agglomeration phenomenon of the filler in the matrix, and improves the mechanical strength and long-term stability of the material. Therefore, through reasonable material design and modification path, this invention realizes the synergistic enhancement of multifunctionality, providing a new technical idea for the development of high-performance waterproof construction adhesives.

[0012] Furthermore, the preparation method of the fluorosilane coupling agent surface-modified titanium dioxide nanowires is as follows: The pre-dried titanium dioxide nanowires are mixed with anhydrous toluene at a mass-to-volume ratio of 1:(20~30), and after being ultrasonically treated at a frequency of 40~60 kHz for 10~20 min to form a uniformly dispersed system, it is transferred to a reactor equipped with a polytetrafluoroethylene stirring device, and 25~35 wt% of perfluorooctyltriethoxysilane based on the mass of titanium dioxide is added. Under a nitrogen atmosphere, it is stirred at a rate of 250~350 rpm and reacted at a constant temperature of 55~65°C for 3~5 h. After the reaction is completed, the solid product is separated by vacuum filtration through a Buchner funnel, and washed 3 times with 50~80 mL of toluene and 50~80 mL of acetone respectively to remove the free coupling agent. Finally, the washed product is treated at a constant temperature of 45~55°C in a vacuum drying oven for 10~14 h to obtain the fluorosilane coupling agent surface-modified titanium dioxide nanowires.

[0013] Furthermore, the preparation method of the titanium dioxide nanowires is as follows: by weight, 1.0 - 5.0 parts of tetrabutyl titanate and 30 - 50 parts of ethanol are mixed to form a homogeneous precursor solution, which is transferred to a high-pressure reaction kettle lined with polytetrafluoroethylene and sealed. It is heated to 120 - 250 °C at a rate of 2 - 5 °C / min for solvothermal reaction for 12 - 24 h. After the reaction, it is naturally cooled to 20 - 30 °C. The obtained suspension is centrifuged at 3000 - 5000 rpm for 5 - 10 min to remove the supernatant. The precipitate is washed 3 - 5 times with 50 - 100 mL of absolute ethanol and 50 - 100 mL of deionized water respectively to remove unreacted substances and solvent residues. Subsequently, it is treated in a vacuum drying oven at 60 - 80 °C for 6 - 12 h to obtain a titanium dioxide nanowire precursor. Optionally, the precursor is placed in a tube furnace and heated to 400 - 600 °C at a rate of 2 - 5 °C / min for calcination for 2 - 4 h to finally obtain titanium dioxide nanowires.

[0014] Furthermore, the average diameter of the titanium dioxide nanowires is 25 - 65 nm, and the average length is 2.5 - 6.0 μm.

[0015] The design of surface-modifying titanium dioxide nanowires with fluorosilane coupling agents in the present invention is mainly used to enhance the waterproofness, impermeability and ultraviolet resistance of two-component impermeable waterproof construction adhesives. First, titanium dioxide nanowires with a high aspect ratio are synthesized by solvothermal reaction and further calcined to improve their crystal integrity and chemical stability, thereby endowing the material with excellent weather resistance and enhancement effect. Subsequently, perfluorooctyltriethoxysilane is used to modify the surface of titanium dioxide nanowires. A stable hydrophobic layer is formed on the surface of titanium dioxide through the action of the fluorosilane coupling agent, thereby reducing its surface energy, making it have better dispersibility and compatibility in the organic matrix, and at the same time effectively improving the hydrophobicity and impermeability of the material. During the modification process, ultrasonic-assisted dispersion ensures the uniform distribution of titanium dioxide nanowires, and the constant-temperature stirring reaction under nitrogen protection promotes the stable grafting of the coupling agent. Finally, unreacted components are removed by vacuum filtration, solvent washing and low-temperature drying, ensuring the high purity and uniformity of the modified material. The modified titanium dioxide nanowires can not only form a stable reinforcing phase in the two-component waterproof construction adhesive to improve the mechanical strength of the material, but also effectively improve the ultraviolet aging resistance through the ultraviolet shielding effect and extend the service life of the material. In addition, the introduction of the fluorosilane coupling agent further optimizes the bonding state at the interface between the filler and the matrix, reduces the agglomeration phenomenon of the filler in the matrix, and enables the overall system to still maintain excellent stability and lasting protection effect under high humidity, high temperature and long-term water immersion environments. Therefore, through reasonable material design and surface modification strategies, the present invention realizes the synergistic enhancement of waterproofness, impermeability and ultraviolet resistance, providing a new technical path for the development of high-performance waterproof construction adhesives.

[0016] Furthermore, the active diluent BGE is butyl glycidyl ether; The toughening agent CTBN is carboxyl-terminated butadiene acrylonitrile rubber; The dispersant is BYK-163 dispersant; The defoaming agent is BYK-066N defoaming agent; The present invention also provides a preparation method of a strong and firm two-component anti-seepage waterproof building glue, comprising the following steps: S1. Preparation of component A: Add epoxy resin E-51, active diluent BGE and toughening agent CTBN into a vacuum stirring kettle, and premix at a stirring rate of 800-1000 rpm for 30-45 min under the conditions of 40-50 °C and a vacuum degree of -0.08 to -0.10 MPa to form a matrix phase; Subsequently, add the dispersant and defoaming agent in sequence, increase the stirring rate to 800-1000 rpm and maintain the temperature at 60-70 °C for high-speed dispersion for 40-60 min until the system viscosity reaches 5000-8000 mPa·s, filter through a 200-300 mesh filter screen and transfer to a sealed container for degassing at a vacuum degree of -0.1 MPa for 30-40 min to obtain the component A glue solution, which is then packaged into an oxygen-isolated aluminum-plastic packaging bag; S2. Preparation of component B: Put perfluoroalkylsilane-modified boron nitride, dicyandiamide, 2-methylimidazole, 1,2-dimethylimidazole, fluorosilane coupling agent surface-modified titanium dioxide nanowires and fumed silica HL-200 into a three-dimensional motion mixer, and dry mix at a rotation speed of 15-20 rpm for 45-60 min under nitrogen protection to form a uniform powder mixture; Subsequently, add ultraviolet absorber UV-360 and antioxidant 3114, switch to the high-speed vortex mixing mode and shear and disperse at 2000-2500 rpm for 25-35 min until the powder angle of repose ≤ 35°, and finally obtain the component B powder with a D50 particle size ≤ 10 μm by micronization treatment under a pressure of 0.4-0.6 MPa by a jet mill and store it sealed in a moisture-proof aluminum foil bag; S3. During final use, mix component A and component B according to the mass ratio, stir at 400-600 rpm for 5-10 min until a uniform colloid is formed, stand for 10-20 min to eliminate internal bubbles, apply glue and cure for 24-48 h at room temperature and a relative humidity of 50-60% to form a waterproof layer.

[0017] The present invention adopts a two-component collaborative design, which is mainly used to enhance the waterproofness, impermeability and ultraviolet resistance of construction adhesives. Component A uses epoxy resin E-51 as the matrix, combines with the reactive diluent BGE to adjust the viscosity of the system, ensures that the colloid has good workability and infiltration ability, and at the same time introduces the toughening agent CTBN to improve the flexibility of the cured material, so that it maintains stable mechanical properties under long-term stress conditions. The addition of the dispersant helps the uniform dispersion of the filler and prevents agglomeration from affecting the performance, while the defoaming agent reduces the bubble content during the preparation process and improves the denseness and uniformity of the final cured layer. Component B optimizes the protective performance of the material through the synergistic effect of various functional fillers. Among them, perfluoroalkylsilane-modified boron nitride has excellent hydrophobicity and thermal stability, can effectively reduce water penetration, improve the impermeability of the material, and at the same time enhance the interfacial bonding force with the matrix. Dicyandiamide, as the main curing agent, together with 2-methylimidazole and 1,2-dimethylimidazole, constitutes a curing system, ensuring rapid curing of the system under suitable conditions, and at the same time providing a high crosslinking density, so that the cured construction adhesive has excellent durability and structural stability. Fumed silica HL-200, as a reinforcing filler, can improve the mechanical strength of the material and optimize the rheological properties of the colloid during the curing process. Fluorosilane coupling agent surface-modified titanium dioxide nanowires can not only enhance the weather resistance of the material, but also improve its ultraviolet aging resistance through the ultraviolet shielding effect, delay material degradation, and ensure the stability of long-term outdoor use. In addition, the synergistic effect of ultraviolet absorber UV-360 and antioxidant 3114 further improves the photoaging resistance of the material, prevents the degradation reaction caused by ultraviolet rays, and enables the waterproof layer to maintain excellent performance during long-term use. Through the reasonable ratio of Component A and Component B, the present invention realizes the comprehensive optimization of waterproof, impermeable and ultraviolet resistance performance, ensures the long-term stability of the material in complex environments, and provides a reliable technical support for the application of high-performance waterproof construction adhesives.

[0018] (3) Beneficial technical effects: 1. Through the synergistic enhancement effect of perfluoroalkylsilane-modified boron nitride, the present invention significantly improves the waterproofness, impermeability and ultraviolet resistance of the two-component impermeable waterproof construction adhesive. Compared with the traditional system, it has stronger interfacial bonding force, better dispersibility and higher long-term stability. The mechanical ball milling-liquid phase exfoliation method ensures the high specific surface area of boron nitride nanosheets, and the surface polydopamine coating enhances its dispersion stability in the matrix. The perfluoroalkylsilane grafting further optimizes the interfacial compatibility, enabling the material to maintain excellent performance under high humidity, high temperature and ultraviolet exposure conditions. Ultrasonic treatment, stirring for uniform dispersion, vacuum filtration, gradient washing and freeze-drying ensure high-purity products, thus providing a more reliable and durable solution in the waterproof construction field, broadening the application scenarios and promoting the technological upgrading of the industry.

[0019] 2. Through the synergistic effect of surface modification of titanium dioxide nanowires with fluorosilane coupling agents, the waterproofness, impermeability and UV resistance of the two-component anti-seepage waterproof building glue are significantly improved. Compared with the prior art, the modified filler has better dispersibility, stronger interfacial bonding and long-term stability, and can effectively solve the problem of performance attenuation under high humidity, high temperature and long-term UV irradiation. The solvothermal reaction ensures the high aspect ratio and chemical stability of titanium dioxide nanowires, the surface fluorosilane modification enhances the hydrophobicity and matrix compatibility, and the ultrasonic dispersion, nitrogen protection reaction and low-temperature drying ensure the uniformity and purity of the material, thus providing a more durable protection effect in waterproof building applications and promoting the industry to develop towards high performance and long life.

[0020] 3. Through the two-component synergistic optimization, the waterproofness, impermeability and UV resistance of the building glue are significantly improved. Compared with the prior art, the rheological regulation of component A and the toughening and strengthening materials improve the flexibility, the optimized interfacial bonding of the modified filler in component B, and the curing system ensures a high crosslinking density, so that the colloid remains stable in high humidity, high temperature and UV environments for a long time. The synergistic effect of perfluoroalkylsilane-modified boron nitride and fluorosilane coupling agent surface-modified titanium dioxide nanowires improves the hydrophobicity, impermeability and weather resistance, the fumed silica enhances the mechanical properties, and the UV absorber and antioxidant delay aging, ultimately achieving an efficient and durable protection effect and promoting the development of waterproof building glue towards high performance and long life. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 It is the infrared Fourier spectrum of perfluoroalkylsilane-modified boron nitride and boron nitride nanosheets prepared in Example 1 of the present invention.

[0022] Figure 2 It is the physical picture of perfluoroalkylsilane-modified boron nitride prepared in Example 1 of the present invention Figure 3 It is the morphology of titanium dioxide nanowires prepared in Example 1 of the present invention.

[0023] Figure 4 It is the XRD phase analysis diagram of titanium dioxide nanowires prepared in Example 1 of the present invention.

[0024] Figure 5 It is the surface of the anti-seepage waterproof building glue prepared in Example 2 of the present invention coated on the exterior wall of a building.

[0025] Figure 6 It is the waterproof condition of the surface of the anti-seepage waterproof building glue prepared in Example 2 of the present invention after curing. DETAILED DESCRIPTION OF THE INVENTION

[0026] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings in the embodiments of the present invention.

[0027] Example 1: A highly effective and firm two-component anti-seepage waterproof construction glue, comprising component A and component B; Component A comprises raw materials in the following weight parts: 100 parts of epoxy resin E-51, 10 parts of active diluent BGE, 6 parts of toughening agent CTBN, 0.8 part of dispersant, and 0.3 part of defoaming agent; Component B comprises raw materials in the following weight parts: 2.5 parts of perfluoroalkylsilane-modified boron nitride, 4.5 parts of dicyandiamide, 1.2 parts of 2-methylimidazole, 1.0 part of 1,2-dimethylimidazole, 3.0 parts of fumed silica HL-200, 12 parts of fluorosilane coupling agent surface-modified titanium dioxide nanowires, 1.0 part of ultraviolet absorber UV-360, and 0.5 part of antioxidant 3114; The mass ratio of component A to component B is 2.0:1.

[0028] The perfluoroalkylsilane-modified boron nitride in this embodiment is first prepared by surface polymerization of pre-modified boron nitride nanosheets with hydrochloric acid dopamine salt, then grafted with tridecafluorooctyltrimethoxysilane, and finally obtained through filtration, washing, and freeze-drying; The fluorosilane coupling agent surface-modified titanium dioxide nanowires in this embodiment are obtained by surface modification of titanium dioxide nanowires with perfluorooctyltriethoxysilane.

[0029] The preparation method of the perfluoroalkylsilane-modified boron nitride in this embodiment is as follows: 1.0 g of polydopamine-modified boron nitride nanosheets are dispersed in 120 mL of toluene. After ultrasonic treatment at a frequency of 40 kHz for 15 min to form a homogeneous suspension, a mixed solution of 0.95 g of tridecafluorooctyltrimethoxysilane and 18 mL of toluene is added dropwise to the reaction system at a rate of 0.5 mL / min. Subsequently, the temperature is raised to 75 °C under nitrogen protection and magnetic stirring is carried out at 300 rpm for 5 h to complete the grafting reaction. After the reaction is completed, it is naturally cooled to 20 °C, and the solid-phase product is separated by vacuum filtration through a 0.22 μm polytetrafluoroethylene filter membrane. The filter cake is washed three times with 50 mL of acetone, 50 mL of ethanol, and 50 mL of deionized water in sequence to remove unreacted monomers and solvent residues. Finally, the product is placed in a -50 °C freeze-dryer and processed for 70 h to obtain dark gray perfluoroalkylsilane-modified boron nitride.

[0030] Polydopamine-modified boron nitride nanosheets of this example: 2.8 g of boron nitride nanosheets were dispersed in 580 mL of tris(hydroxymethyl)aminomethane buffer solution with a pH of 8.3. After ultrasonic treatment at a power of 200 W for 25 min, 1.15 g of dopamine hydrochloride was slowly added at a stirring speed of 400 rpm under the condition of 20 °C and reacted for 1.8 h to achieve surface polymerization coating. After vacuum filtration, it was washed with deionized water until the conductivity of the filtrate < 5 μS / cm, and freeze-dried for 62 h to obtain polydopamine-modified boron nitride nanosheets.

[0031] The preparation method of boron nitride nanosheets of this example is: prepared by mechanical ball milling-liquid phase exfoliation method. Specifically: 0.5 mm hexagonal boron nitride bulk and 1.0 mm zirconia grinding balls were loaded into a 500 mL silicon nitride ball milling jar according to a mass ratio of 1:30, and planetary ball milled at a speed of 300 rpm for 4 h under the protection of an argon flow rate of 5 L / min. After ball milling, the product was mixed with N-methylpyrrolidone at a solid-liquid ratio of 1:100, and pulsed ultrasonic treatment was carried out at a power of 500 W and a working cycle of 2 s on / 1 s off for 2 h. During the treatment, the temperature of the suspension was controlled at 20 °C. Subsequently, centrifuged at 8000 rpm for 10 min and the operation was repeated 2 times to remove unexfoliated particles. The supernatant after centrifugation was collected and vacuum filtered through a 0.22 μm polytetrafluoroethylene filter membrane. The obtained filter cake was washed 3 times with 50 mL of anhydrous ethanol and 50 mL of deionized water each to thoroughly remove solvent residues. Finally, the product was placed in a vacuum drying oven and dried at a constant temperature of 50 °C for 12 h to obtain boron nitride nanosheets.

[0032] The average diameter of the boron nitride nanosheets of this example is 0.5 μm; the average thickness is 2.5 nm.

[0033] The preparation method of fluorosilane coupling agent surface-modified titanium dioxide nanowires of this example is: pre-dried titanium dioxide nanowires and anhydrous toluene were mixed at a mass-volume ratio of 1:20. After ultrasonic treatment at a frequency of 40 kHz for 10 min to form a homogeneous dispersion system, it was transferred to a reactor equipped with a polytetrafluoroethylene stirring device, and 25 wt% perfluorooctyltriethoxysilane based on the mass of titanium dioxide was added. Under a nitrogen atmosphere, it was stirred at a rate of 250 rpm and reacted at a constant temperature of 55 °C for 3 h. After the reaction was completed, the solid product was separated by vacuum filtration through a Buchner funnel, and washed 3 times with 50 mL of toluene and 50 mL of acetone each to remove free coupling agent. Finally, the washed product was treated at a constant temperature of 45 °C in a vacuum drying oven for 10 h to obtain fluorosilane coupling agent surface-modified titanium dioxide nanowires.

[0034] The preparation method of the titanium dioxide nanowires in this example is as follows: By weight, 1.0 part of tetrabutyl titanate is mixed with 30 parts of ethanol to form a homogeneous precursor solution, which is transferred to a high-pressure reaction kettle lined with polytetrafluoroethylene and sealed. It is heated to 120 °C at a rate of 2 °C / min for solvothermal reaction for 12 h. After the reaction is completed, it is naturally cooled to 20 °C. The obtained suspension is centrifuged at 3000 rpm for 5 min to remove the supernatant. The precipitate is washed 3 times with 50 mL of absolute ethanol and 50 mL of deionized water each to remove unreacted substances and solvent residues. Subsequently, it is treated in a vacuum drying oven at 60 °C for 6 h to obtain a titanium dioxide nanowire precursor. Optionally, the precursor is placed in a tube furnace and heated to 400 °C at a rate of 2 °C / min for calcination for 2 h to finally obtain titanium dioxide nanowires.

[0035] The average diameter of the titanium dioxide nanowires in this example is 25 nm, and the average length is 2.5 μm.

[0036] The active diluent BGE in this example is butyl glycidyl ether; the toughening agent CTBN is carboxyl-terminated butadiene acrylonitrile rubber; the dispersant is BYK-163 dispersant; the defoaming agent is BYK-066N defoaming agent; The preparation method of a highly effective and firm two-component anti-seepage waterproof building glue in this example includes the following steps: S1. Preparation of component A: Epoxy resin E-51, active diluent BGE and toughening agent CTBN are added to a vacuum stirring kettle and premixed at a stirring rate of 800 rpm for 30 min at 40 °C and a vacuum degree of -0.08 MPa to form a matrix phase; Subsequently, the dispersant and defoaming agent are added in sequence, the stirring rate is increased to 800 rpm and the temperature is maintained at 60 °C for high-speed dispersion for 40 min until the system viscosity reaches 5000 mPa·s. After filtering through a 200-mesh filter screen, it is transferred to a sealed container and degassed at a vacuum degree of -0.1 MPa for 30 min to obtain component A glue solution, which is then packaged into an oxygen-isolated aluminum-plastic packaging bag; S2. Preparation of component B: Perfluoroalkylsilane-modified boron nitride, dicyandiamide, 2-methylimidazole, 1,2-dimethylimidazole, fluorosilane coupling agent surface-modified titanium dioxide nanowires and fumed silica HL-200 are put into a three-dimensional motion mixer and dry-mixed at a rotation speed of 15 rpm for 45 min under nitrogen protection to form a uniform powder mixture. Subsequently, ultraviolet absorber UV-360 and antioxidant 3114 are added, and the mixing mode is switched to high-speed vortex mixing and shear-dispersed at 2000 rpm for 25 min until the powder angle of repose ≤ 35°. Finally, it is micronized by a jet mill at a pressure of 0.4 MPa to obtain component B powder with a D50 particle size ≤ 10 μm and stored in a moisture-proof aluminum foil bag in a sealed manner; S3. At the final use, mix Component A and Component B according to the mass ratio, stir at 400 rpm for 5 min until a uniform colloid is formed, let it stand for 10 min to eliminate internal bubbles, apply glue and cure for 24 h at room temperature and 50% relative humidity to form a waterproof layer.

[0037] It can be seen from Figure 1 the infrared Fourier spectrum that the perfluoroalkylsilane-modified boron nitride prepared by the present invention exhibits typical B-N stretching and bending vibration characteristic peaks of BNNS at 1352 cm⁻¹ and 812 cm⁻¹. Meanwhile, the presence of C-F and Si-O stretching vibration peaks at 1252 cm⁻¹ and 1145 cm⁻¹ further proves the successful modification of boron nitride with perfluoroalkylsilane, indicating that the chemical structure of the material has been effectively regulated. Figure 2 The physical picture of Figure 3 intuitively shows the morphology of the modified boron nitride, further verifying the successful preparation of the material. Figure 4 The morphology of the titanium dioxide nanowires shown in

[0038] Example 2: A highly effective and firm two-component anti-seepage waterproof building glue, comprising Component A and Component B; Component A comprises the following raw materials in parts by weight: 100 parts of epoxy resin E-51, 11 parts of active diluent BGE, 7 parts of toughening agent CTBN, 0.9 part of dispersant, 0.4 part of defoaming agent; Component B comprises the following raw materials in parts by weight: 3.1 parts of perfluoroalkylsilane-modified boron nitride, 4.8 parts of dicyandiamide, 1.4 parts of 2-methylimidazole, 1.2 parts of 1,2-dimethylimidazole, 3.3 parts of fumed silica HL-200, 13 parts of titanium dioxide nanowires surface-modified with fluorosilane coupling agent, 1.2 parts of ultraviolet absorber UV-360, 0.6 part of antioxidant 3114; The mass ratio of Component A to Component B is 2.6:1.

[0039] The preparation method of the perfluoroalkylsilane-modified boron nitride in this example is as follows: 1.1 g of polydopamine-modified boron nitride nanosheets are dispersed in 123 mL of toluene. After ultrasonic treatment at a frequency of 46 kHz for 18 min to form a uniform suspension, a mixed solution of 0.98 g of tridecafluorooctyltrimethoxysilane and 19 mL of toluene is added dropwise to the reaction system at a rate of 0.65 mL / min. Subsequently, under nitrogen protection, the temperature is raised to 78 °C and magnetic stirring is carried out at 360 rpm for 5.6 h to complete the grafting reaction. After the reaction is completed, it is naturally cooled to 21.5 °C, and the solid-phase product is separated by vacuum filtration through a 0.22-μm polytetrafluoroethylene filter membrane. The filter cake is washed 3 times successively with 59 mL of acetone, 59 mL of ethanol, and 59 mL of deionized water to remove unreacted monomers and solvent residues. Finally, the product is placed in a freeze dryer at -47 °C for 71 h to obtain dark gray perfluoroalkylsilane-modified boron nitride.

[0040] The polydopamine-modified boron nitride nanosheets in this example: 2.9 g of boron nitride nanosheets are dispersed in 592 mL of tris(hydroxymethyl)aminomethane buffer solution with a pH of 8.4. After ultrasonic treatment at a power of 230 W for 28 min, 1.18 g of dopamine hydrochloride is slowly added at a stirring speed of 460 rpm at 21.5 °C and the reaction continues for 1.9 h to achieve surface polymerization coating. After vacuum filtration, it is washed with deionized water until the conductivity of the filtrate < 5 μS / cm, and freeze-dried for 65 h to obtain polydopamine-modified boron nitride nanosheets.

[0041] The preparation method of the boron nitride nanosheets in this example is as follows: It is prepared by mechanical ball milling-liquid phase exfoliation method. Specifically: 1.85-mm hexagonal boron nitride bulk and 1.6-mm zirconia grinding balls are loaded into a 650-mL silicon nitride ball milling jar according to a mass ratio of 1:36. Under the protection of an argon flow rate of 6.5 L / min, planetary ball milling is carried out at a rotation speed of 330 rpm for 4.6 h. After the ball milling is completed, the product is mixed with N-methylpyrrolidone at a solid-liquid ratio of 1:115, and pulsed ultrasonic treatment is carried out at a power of 590 W and a working cycle of 2 s on / 1 s off for 2.6 h. During the treatment, the temperature of the suspension is controlled at 26 °C. Subsequently, centrifugation is carried out at 9200 rpm for 16 min and the operation is repeated 2 times to remove unexfoliated particles. The supernatant after centrifugation is collected and vacuum filtered through a 0.22-μm polytetrafluoroethylene filter membrane. The obtained filter cake is washed 4 times successively with 59 mL of absolute ethanol and 59 mL of deionized water to thoroughly remove solvent residues. Finally, the product is placed in a vacuum drying oven and dried at a constant temperature of 53 °C for 15.6 h to obtain boron nitride nanosheets.

[0042] The average diameter of the boron nitride nanosheets in this example is 1.1 μm; the average thickness is 3.7 nm.

[0043] The preparation method of the fluorosilane coupling agent surface-modified titanium dioxide nanowires in this example is as follows: The pre-dried titanium dioxide nanowires and anhydrous toluene are mixed at a mass-to-volume ratio of 1:23, ultrasonicated for 13 min at a frequency of 46 kHz to form a homogeneous dispersion system, and then transferred to a reactor equipped with a polytetrafluoroethylene stirring device. 28 wt% of perfluorooctyltriethoxysilane based on the mass of titanium dioxide is added, and the reaction is carried out at a constant temperature of 58 °C for 3.6 h at a stirring rate of 280 rpm under a nitrogen atmosphere. After the reaction is completed, the solid product is separated by vacuum filtration through a Buchner funnel, and washed 3 times with 59 mL of toluene and 59 mL of acetone respectively to remove the free coupling agent. Finally, the washed product is treated at a constant temperature of 48 °C for 11.2 h in a vacuum drying oven to obtain the fluorosilane coupling agent surface-modified titanium dioxide nanowires.

[0044] The preparation method of the titanium dioxide nanowires in this example is as follows: By weight, 2.2 parts of tetrabutyl titanate and 36 parts of ethanol are mixed to form a homogeneous precursor solution, which is transferred to a polytetrafluoroethylene-lined autoclave and sealed. It is heated to 159 °C at a rate of 2.9 °C / min for a solvothermal reaction for 15.6 h. After the reaction is completed, it is naturally cooled to 23 °C. The obtained suspension is centrifuged at 3600 rpm for 6.5 min to remove the supernatant, and the precipitate is washed 4 times with 65 mL of anhydrous ethanol and 65 mL of deionized water respectively to remove the unreacted substances and solvent residues. Subsequently, it is treated in a vacuum drying oven at 66 °C for 7.8 h to obtain the titanium dioxide nanowire precursor. Optionally, the precursor is placed in a tube furnace and heated to 460 °C at a rate of 2.9 °C / min for calcination for 2.6 h to finally obtain the titanium dioxide nanowires.

[0045] The average diameter of the titanium dioxide nanowires in this example is 37 nm, and the average length is 3.6 μm.

[0046] The preparation method of a highly effective and firm two-component anti-seepage waterproof construction glue in this example includes the following steps: S1. Preparation of component A: Epoxy resin E-51, reactive diluent BGE and toughening agent CTBN are added to a vacuum stirring kettle, and premixed at a stirring rate of 860 rpm for 35 min at 43 °C and a vacuum degree of -0.086 MPa to form a matrix phase; Subsequently, a dispersant and an antifoaming agent are added in sequence, the stirring rate is increased to 860 rpm and the temperature is maintained at 63 °C for high-speed dispersion for 46 min until the system viscosity reaches 5900 mPa·s, filtered through a 230-mesh filter screen, and then transferred to a sealed container for defoaming at a vacuum degree of -0.1 MPa for 33 min to obtain the component A glue solution, which is then packaged in an oxygen-isolated aluminum-plastic packaging bag; S2. Preparation of Component B: Put perfluoroalkylsilane-modified boron nitride, dicyandiamide, 2-methylimidazole, 1,2-dimethylimidazole, fluorosilane coupling agent surface-modified titanium dioxide nanowires and fumed silica HL-200 into a three-dimensional motion mixer, and dry mix at a rotation speed of 16.5 rpm for 50 min under nitrogen protection to form a uniform powder mixture. Subsequently, add ultraviolet absorber UV-360 and antioxidant 3114, switch to the high-speed vortex mixing mode, shear and disperse at 2150 rpm for 28 min until the angle of repose of the powder ≤ 35°. Finally, micronize it with a jet mill under a pressure of 0.46 MPa to obtain Component B powder with a D50 particle size ≤ 10 μm, and store it sealed in a moisture-proof aluminum foil bag; S3. During final use, mix Component A and Component B according to the mass ratio, stir at 460 rpm for 6.5 min until a uniform colloid is formed, let it stand for 13 min to eliminate internal bubbles, apply glue and cure for 31 h at room temperature and a relative humidity of 53% to form a waterproof layer.

[0047] Figure 5 The good adhesion effect of the anti-seepage and waterproof building glue prepared by the present invention on the surface of the building exterior wall is shown, indicating its excellent adhesiveness and construction adaptability. Figure 6 It further proves the waterproof performance of the surface of the waterproof building glue after curing, showing good hydrophobicity and anti-seepage ability, indicating that the waterproof system of the present invention has wide application value in the field of building protection.

[0048] Example 3: A highly effective and firm two-component anti-seepage and waterproof building glue, including Component A and Component B; Component A includes the following raw materials in parts by weight: 100 parts of epoxy resin E-51, 11 parts of active diluent BGE, 7 parts of toughening agent CTBN, 1.0 part of dispersant, and 0.4 part of defoaming agent; Component B includes the following raw materials in parts by weight: 3.7 parts of perfluoroalkylsilane-modified boron nitride, 5.1 parts of dicyandiamide, 1.6 parts of 2-methylimidazole, 1.3 parts of 1,2-dimethylimidazole, 3.6 parts of fumed silica HL-200, 14 parts of fluorosilane coupling agent surface-modified titanium dioxide nanowires, 1.3 parts of ultraviolet absorber UV-360, and 0.7 part of antioxidant 3114; The mass ratio of Component A to Component B is 3.2:1.

[0049] The preparation method of the perfluoroalkylsilane-modified boron nitride in this example is as follows: 1.1 g of polydopamine-modified boron nitride nanosheets are dispersed in 126 mL of toluene. After ultrasonic treatment at a frequency of 52 kHz for 21 min to form a uniform suspension, a mixed solution of 1.01 g of tridecafluorooctyltrimethoxysilane and 20 mL of toluene is added dropwise to the reaction system at a rate of 0.8 mL / min. Subsequently, the temperature is raised to 81 °C under nitrogen protection and magnetic stirring is carried out at 420 rpm for 6.2 h to complete the grafting reaction. After the reaction is completed, it is naturally cooled to 23 °C, and the solid-phase product is separated by vacuum filtration through a 0.22-μm polytetrafluoroethylene filter membrane. The filter cake is washed 3 times successively with 68 mL of acetone, 68 mL of ethanol, and 68 mL of deionized water to remove unreacted monomers and solvent residues. Finally, the product is placed in a freeze dryer at -44 °C for 72 h to obtain dark gray perfluoroalkylsilane-modified boron nitride.

[0050] The polydopamine-modified boron nitride nanosheets in this example: 3.0 g of boron nitride nanosheets are dispersed in 604 mL of tris(hydroxymethyl)aminomethane buffer solution with a pH of 8.5. After ultrasonic treatment at a power of 260 W for 31 min, 1.21 g of dopamine hydrochloride is slowly added at a stirring speed of 520 rpm at 23 °C and the reaction continues for 2.0 h to achieve surface polymerization coating. After vacuum filtration, it is washed with deionized water until the conductivity of the filtrate is <5 μS / cm, and freeze-dried for 69 h to obtain polydopamine-modified boron nitride nanosheets.

[0051] The preparation method of the boron nitride nanosheets in this example is as follows: It is prepared by mechanical ball milling-liquid phase exfoliation method. Specifically, hexagonal boron nitride bulk with a particle size of 3.2 mm and zirconia grinding balls with a diameter of 2.2 mm are loaded into a silicon nitride ball mill jar with a volume of 800 mL according to a mass ratio of 1:42. Planetary ball milling is carried out at a rotation speed of 360 rpm for 5.2 h under the protection of an argon flow rate of 8 L / min. After the ball milling is completed, the product is mixed with N-methylpyrrolidone at a solid-liquid ratio of 1:130, and pulsed ultrasonic treatment is carried out at a power of 680 W and a working cycle of 2 s on / 1 s off for 3.2 h. During the treatment, the temperature of the suspension is controlled at 32 °C. Subsequently, centrifugation is carried out at 10400 rpm for 22 min and the operation is repeated 3 times to remove unexfoliated particles. The supernatant after centrifugation is collected and vacuum filtered through a 0.22-μm polytetrafluoroethylene filter membrane. The obtained filter cake is washed 4 times successively with 68 mL of absolute ethanol and 68 mL of deionized water to thoroughly remove solvent residues. Finally, the product is placed in a vacuum drying oven and dried at a constant temperature of 56 °C for 19.2 h to obtain boron nitride nanosheets.

[0052] The average diameter of the boron nitride nanosheets in this example is 1.7 μm; the average thickness is 4.9 nm.

[0053] The preparation method of the fluorosilane coupling agent surface-modified titanium dioxide nanowires in this example is as follows: Mix the pre-dried titanium dioxide nanowires and anhydrous toluene at a mass-to-volume ratio of 1:26, perform ultrasonic treatment at a frequency of 52 kHz for 16 min to form a homogeneous dispersion system, then transfer it to a reactor equipped with a polytetrafluoroethylene stirring device, add 31 wt% perfluorooctyltriethoxysilane based on the mass of titanium dioxide, and react at a constant temperature of 61 °C for 4.2 h at a stirring rate of 310 rpm under a nitrogen atmosphere. After the reaction is completed, separate the solid-phase product by vacuum filtration through a Buchner funnel, wash it 3 times with 68 mL of toluene and 68 mL of acetone respectively to remove the free coupling agent, and finally treat the washed product in a vacuum drying oven at a constant temperature of 51 °C for 12.4 h to obtain the fluorosilane coupling agent surface-modified titanium dioxide nanowires.

[0054] The preparation method of the titanium dioxide nanowires in this example is as follows: By weight, mix 3.4 parts of tetrabutyl titanate and 42 parts of ethanol to form a homogeneous precursor solution, transfer it to a high-pressure reaction kettle lined with polytetrafluoroethylene and seal it, heat it to 198 °C at a rate of 3.8 °C / min for a solvothermal reaction for 19.2 h. After the reaction is completed, cool it naturally to 26 °C. After centrifuging the obtained suspension at 4200 rpm for 8 min to remove the supernatant, wash the precipitate 4 times with 80 mL of anhydrous ethanol and 80 mL of deionized water respectively to remove the unreacted substances and solvent residues, and then treat it in a vacuum drying oven at 72 °C for 9.6 h to obtain the titanium dioxide nanowire precursor. Optionally, place the precursor in a tubular furnace and heat it to 520 °C at a rate of 3.8 °C / min for calcination for 3.2 h to finally obtain the titanium dioxide nanowires.

[0055] The average diameter of the titanium dioxide nanowires in this example is 49 nm, and the average length is 4.6 μm.

[0056] The preparation method of a highly effective and firm two-component anti-seepage and waterproof building glue in this example includes the following steps: S1. Preparation of component A: Add epoxy resin E-51, reactive diluent BGE and toughening agent CTBN to a vacuum stirring kettle, premix at a stirring rate of 1000 rpm for 45 min at 50 °C and a vacuum degree of -0.10 MPa to form a matrix phase; then add a dispersant and an antifoaming agent in sequence, increase the stirring rate to 1000 rpm and maintain the temperature at 70 °C for high-speed dispersion for 60 min until the system viscosity reaches 8000 mPa·s, filter it through a 300-mesh filter screen and transfer it to a sealed container for defoaming at a vacuum degree of -0.1 MPa for 40 min to obtain the component A glue solution, which is then packaged in an oxygen-isolated aluminum-plastic packaging bag; S2. Preparation of Component B: Put perfluoroalkylsilane-modified boron nitride, dicyandiamide, 2-methylimidazole, 1,2-dimethylimidazole, fluorosilane coupling agent surface-modified titanium dioxide nanowires, and fumed silica HL-200 into a three-dimensional motion mixer. Under nitrogen protection, dry mix at a speed of 20 rpm for 60 min to form a uniform powder mixture. Subsequently, add ultraviolet absorber UV-360 and antioxidant 3114, switch to the high-speed vortex mixing mode, and shear disperse at 2500 rpm for 35 min until the powder angle of repose ≤ 35°. Finally, micronize under a pressure of 0.6 MPa by a jet mill to obtain Component B powder with a D50 particle size ≤ 10 μm, and store it sealed in a moisture-proof aluminum foil bag; S3. During final use, mix Component A and Component B according to the mass ratio, stir at 600 rpm for 10 min until a uniform colloid is formed, let it stand for 20 min to eliminate internal bubbles, apply glue and cure for 48 h at room temperature and 60% relative humidity to form a waterproof layer.

[0057] Example 4: A highly effective and firm two-component anti-seepage waterproof building glue, including Component A and Component B; Component A includes the following raw materials in parts by weight: 100 parts of epoxy resin E-51, 12 parts of active diluent BGE, 8 parts of toughening agent CTBN, 1.2 parts of dispersant, and 0.5 parts of defoaming agent; Component B includes the following raw materials in parts by weight: 4.5 parts of perfluoroalkylsilane-modified boron nitride, 5.5 parts of dicyandiamide, 1.8 parts of 2-methylimidazole, 1.5 parts of 1,2-dimethylimidazole, 4.0 parts of fumed silica HL-200, 15 parts of fluorosilane coupling agent surface-modified titanium dioxide nanowires, 1.5 parts of ultraviolet absorber UV-360, and 0.8 parts of antioxidant 3114; The mass ratio of Component A to Component B is 4.0:1.

[0058] The preparation method of the perfluoroalkylsilane-modified boron nitride in this example is as follows: Disperse 1.2 g of polydopamine-modified boron nitride nanosheets in 130 mL of toluene. After ultrasonic treatment at a frequency of 60 kHz for 25 min to form a uniform suspension, gradually add a mixed solution of 1.05 g of tridecafluorooctyltrimethoxysilane and 22 mL of toluene to the reaction system at a rate of 1.0 mL / min. Subsequently, under nitrogen protection, heat up to 85 °C and maintain magnetic stirring at 500 rpm for 7 h to complete the grafting reaction. After the reaction, naturally cool to 25 °C, separate the solid-phase product by vacuum filtration through a 0.22 μm polytetrafluoroethylene filter membrane, wash the filter cake 3 times successively with 80 mL of acetone, 80 mL of ethanol, and 80 mL of deionized water to remove unreacted monomers and solvent residues. Finally, place the product in a -40 °C freeze dryer for 74 h to obtain dark gray perfluoroalkylsilane-modified boron nitride.

[0059] Polydopamine-modified boron nitride nanosheets of this example: 3.2 g of boron nitride nanosheets were dispersed in 620 mL of tris(hydroxymethyl)aminomethane buffer solution with a pH of 8.7. After ultrasonic treatment at a power of 300 W for 35 min, 1.25 g of dopamine hydrochloride was slowly added at a stirring speed of 600 rpm at 25 °C and reacted for 2.2 h to achieve surface polymerization coating. After vacuum filtration, it was washed with deionized water until the conductivity of the filtrate was <5 μS / cm, and freeze-dried for 74 h to obtain polydopamine-modified boron nitride nanosheets.

[0060] The preparation method of the boron nitride nanosheets of this example is: prepared by mechanical ball milling-liquid phase exfoliation method. Specifically: 5.0 mm hexagonal boron nitride bulk and 3.0 mm zirconia grinding balls were loaded into a 1000 mL silicon nitride ball milling tank according to a mass ratio of 1:50, and planetary ball milled at a rotation speed of 400 rpm for 6 h under the protection of an argon flow rate of 10 L / min. After the ball milling was completed, the product was mixed with N-methylpyrrolidone at a solid-liquid ratio of 1:150, and pulsed ultrasonic treatment was carried out at a power of 800 W and a working cycle of 2 s on / 1 s off for 4 h. During the treatment, the temperature of the suspension was controlled at 40 °C. Subsequently, it was centrifuged at 12000 rpm for 30 min and the operation was repeated 3 times to remove the unexfoliated particles. The supernatant after centrifugation was collected and vacuum filtered through a 0.22 μm polytetrafluoroethylene filter membrane. The obtained filter cake was washed 5 times with 80 mL of absolute ethanol and 80 mL of deionized water each to completely remove the solvent residue. Finally, the product was placed in a vacuum drying oven and dried at a constant temperature of 60 °C for 24 h to obtain boron nitride nanosheets.

[0061] The average diameter of the boron nitride nanosheets of this example is 2.5 μm; the average thickness is 6.5 nm.

[0062] The preparation method of the fluorosilane coupling agent surface-modified titanium dioxide nanowires of this example is: The pre-dried titanium dioxide nanowires and anhydrous toluene were mixed at a mass-volume ratio of 1:30. After ultrasonic treatment at a frequency of 60 kHz for 20 min to form a uniform dispersion system, it was transferred to a reactor equipped with a polytetrafluoroethylene stirring device, and 35 wt% perfluorooctyltriethoxysilane based on the mass of titanium dioxide was added. Under a nitrogen atmosphere, it was stirred at a rate of 350 rpm and reacted at a constant temperature of 65 °C for 5 h. After the reaction was completed, the solid product was separated by vacuum filtration through a Buchner funnel, and washed 3 times with 80 mL of toluene and 80 mL of acetone each to remove the free coupling agent. Finally, the washed product was treated at a constant temperature of 55 °C in a vacuum drying oven for 14 h to obtain fluorosilane coupling agent surface-modified titanium dioxide nanowires.

[0063] The preparation method of the titanium dioxide nanowires in this embodiment is as follows: by weight, 5.0 parts of tetrabutyl titanate and 50 parts of ethanol are mixed to form a homogeneous precursor solution, which is transferred to a high-pressure reaction kettle lined with polytetrafluoroethylene and sealed. It is heated to 250 °C at a rate of 5 °C / min for a solvothermal reaction for 24 h. After the reaction is completed, it is naturally cooled to 30 °C. The obtained suspension is centrifuged at 5000 rpm for 10 min to remove the supernatant. The precipitate is washed 5 times with 100 mL of absolute ethanol and 100 mL of deionized water respectively to remove unreacted substances and solvent residues. Subsequently, it is treated in a vacuum drying oven at 80 °C for 12 h to obtain a titanium dioxide nanowire precursor. Optionally, the precursor is placed in a tube furnace and heated to 600 °C at a rate of 5 °C / min for calcination for 4 h to finally obtain titanium dioxide nanowires.

[0064] The average diameter of the titanium dioxide nanowires in this embodiment is 65 nm, and the average length is 6.0 μm.

[0065] The preparation method of a highly effective and firm two-component anti-seepage waterproof building glue in this embodiment includes the following steps: S1. Preparation of component A: Epoxy resin E-51, reactive diluent BGE and toughening agent CTBN are added to a vacuum stirring kettle and premixed at a stirring rate of 920 rpm for 39 min at 46 °C and a vacuum degree of -0.092 MPa to form a matrix phase; Subsequently, a dispersant and an antifoaming agent are added in sequence, the stirring rate is increased to 920 rpm and the temperature is maintained at 66 °C for high-speed dispersion for 52 min until the system viscosity reaches 6800 mPa·s. After filtering through a 260-mesh filter screen, it is transferred to a sealed container and degassed at a vacuum degree of -0.1 MPa for 36 min to obtain component A glue solution, which is then packaged into an aluminum-plastic packaging bag that isolates oxygen; S2. Preparation of component B: Perfluoroalkylsilane-modified boron nitride, dicyandiamide, 2-methylimidazole, 1,2-dimethylimidazole, fluorosilane coupling agent surface-modified titanium dioxide nanowires and fumed silica HL-200 are put into a three-dimensional motion mixer and dry-mixed at a rotation speed of 18 rpm for 54 min under nitrogen protection to form a uniform powder mixture. Subsequently, an ultraviolet absorber UV-360 and an antioxidant 3114 are added, and the mixing mode is switched to high-speed vortex mixing and sheared and dispersed at 2300 rpm for 31 min until the angle of repose of the powder ≤ 35°. Finally, it is micronized by a jet mill at a pressure of 0.52 MPa to obtain component B powder with a D50 particle size ≤ 10 μm, which is then sealed and stored in a moisture-proof aluminum foil bag; S3. When finally used, component A and component B are mixed according to the mass ratio and stirred at 520 rpm for 8 min until a uniform colloid is formed, and left standing for 16 min to eliminate internal bubbles. The glue is applied and cured at room temperature and a relative humidity of 56% for 39 h to form a waterproof layer.

[0066] Comparative Example 1: It is basically the same as Example 1, except that boron nitride nanosheets are directly used in the preparation process of perfluoroalkylsilane-modified boron nitride, so the boron nitride nanosheets are not treated with polydopamine modification.

[0067] Comparative Example 2: It is basically the same as Example 1, except that an equal amount of boron nitride nanosheets are used to replace perfluoroalkylsilane-modified boron nitride, so the boron nitride nanosheets are not treated with 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13-tridecafluorooctyltrimethoxysilane modification.

[0068] Comparative Example 3: It is basically the same as Example 1, except that titanium dioxide nanowires are not treated with perfluorooctyltriethoxysilane.

[0069] Comparative Example 4: It is basically the same as Example 1, except that component B does not contain perfluoroalkylsilane-modified boron nitride.

[0070] Comparative Example 5: It is basically the same as Example 1, except that component B does not contain fluorosilane coupling agent surface-modified titanium dioxide nanowires.

[0071] Comparative Example 6: It is basically the same as Example 1, except that the raw material is added during the preparation process of perfluoroalkylsilane-modified boron nitride.

[0072] Comparative Example 7: It is basically the same as Example 1, except that hexagonal boron nitride bulk is used to prepare polydopamine-modified boron nitride nanosheets, so hexagonal boron nitride is not treated with mechanical ball milling-liquid phase exfoliation method.

[0073] Comparative Example 8: It is basically the same as Example 1, except that an equal amount of commercial titanium dioxide particles are used to replace titanium dioxide nanowires.

[0074] Comparative Example 9: It is basically the same as Example 1, except that toughening agent CTBN is not added, and the other components remain unchanged.

[0075] Comparative Example 10: It is basically the same as Example 1, except that BYK-163 dispersant is not added.

[0076] Performance Test: Impermeability Performance Test (Pressure Penetration Method): This experiment aims to evaluate the impermeability ability of the waterproof glue under pressure, and the test is carried out according to GB / T 23445-2009 "Polymer Cement Waterproof Coating" and GB / T 50108-2008 "Technical Code for Waterproofing of Underground Engineering". The experimental method is as follows: The mortar specimens coated with waterproof glue (size 150mm × 150mm × 30mm) are cured for 7 days under standard curing conditions, and then the water pressure penetration test is carried out using an HSP-300 type concrete impermeability tester (Beijing Zhongjian Luye). The water pressure is applied step by step (starting from 0.5 MPa, increasing by 0.1 MPa every 2h), and the maximum non-permeable pressure is recorded to evaluate its impermeability performance.

[0077] Bond strength test (tensile shear method): This experiment is used to measure the bonding performance of the waterproof adhesive to substrates (such as concrete, bricks), and the test is carried out according to GB / T 5210-2006 "Determination of Tensile Shear Strength of Adhesives". The experimental method is as follows: Uniformly coat the waterproof adhesive on the surface of a standard concrete test block (100mm × 100mm × 50mm), bond another concrete test block of the same size, and after curing for 7 days, conduct a tensile shear test using a WDW-100 type electronic universal testing machine (Jinan Times Test Gold), and record the bond strength (MPa) to evaluate the bonding firmness of the waterproof adhesive.

[0078] Aging resistance test (UV aging test): This experiment is used to evaluate the aging of the waterproof adhesive under long-term ultraviolet exposure, and the test is carried out according to GB / T 14522-2008 "Artificial Climate Accelerated Test Methods for Plastics, Coatings, and Rubber Materials for Mechanical Industry Products". The experimental method is as follows: Coat the waterproof adhesive on a glass or concrete plate, place it in a QUV / spray ultraviolet aging test chamber (Q-Lab Corporation, USA), set the UVB-313 lamp tube, temperature 50°C, humidity 50%, and conduct a 1000-hour aging test. After aging, detect color change, cracks, adhesion, and impermeability to evaluate its weather resistance.

[0079] Water resistance test (long-term immersion method): This experiment is used to evaluate the stability of the waterproof adhesive in a long-term water immersion environment, and the test is carried out according to JC / T 864-2008 "Test Methods for Building Waterproof Coatings". The experimental method is as follows: Take the prepared waterproof adhesive coating specimen (150mm × 150mm × 5mm), place it in a DHG-9140A type constant temperature water bath (Shanghai Yiheng), set the temperature at 50°C, and soak for 30 days. Regularly observe the peeling, blistering, and quality change of the coating, and finally measure the mass loss rate of the coating to evaluate its water resistance.

[0080] The performance of the impermeable waterproof building adhesives in Examples 1 to 4 and Comparative Examples 1 to 10 is summarized in Table 1.

[0081]

[0082] Since the boron nitride nanosheets were not modified with polydopamine, their dispersibility and interfacial compatibility in the matrix were reduced, thereby decreasing the anti-permeation performance and aging resistance, but having a relatively small impact on the bonding strength. The lack of modification of the boron nitride nanosheets with 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexyltrimethoxysilane led to a decrease in hydrophobicity, significantly reducing the anti-permeation performance and aging resistance. The lack of modification of the titanium dioxide nanowires with perfluorooctyltriethoxysilane resulted in a decrease in aging resistance, but having a relatively small impact on the anti-permeation performance and bonding strength. Component B without perfluoroalkylsilane-modified boron nitride significantly reduced the anti-permeation performance and aging resistance, and at the same time, the water resistance also decreased. Component B without fluorosilane coupling agent surface-modified titanium dioxide nanowires led to a decrease in bonding strength and a reduction in aging resistance. In the preparation of perfluoroalkylsilane-modified boron nitride, the lack of a modification method made its hydrophobicity insufficient, resulting in a decrease in anti-permeation performance and water resistance, and a reduction in aging resistance. Hexagonal boron nitride bulk was used instead of being treated by mechanical ball milling-liquid phase exfoliation method, resulting in poor dispersibility in the matrix, thereby affecting the anti-permeation performance, bonding strength and aging resistance. The use of commercial titanium dioxide particles instead of titanium dioxide nanowires reduced the denseness and stability of the coating, resulting in a decrease in anti-permeation performance, bonding strength and water resistance, and a reduction in aging resistance. The lack of addition of toughening agent CTBN led to a decrease in bonding strength, but having a relatively small impact on other properties. The lack of addition of BYK-163 dispersant made the material dispersibility poor, thereby reducing the anti-permeation performance, bonding strength and water resistance. At the same time, due to uneven dispersion, the aging resistance decreased significantly.

[0083] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit them. Although the present invention has been described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that any equivalent structural transformation made under the concept of the present invention using the content of the specification and drawings of the present invention should be covered within the protection scope of the claims of the present invention.

Claims

1. A strong and firm two-component anti-seepage and waterproof building adhesive, characterized in that: It includes component A and component B; The component A comprises the following raw materials in parts by weight: 1100 parts of epoxy resin E-51, 10-12 parts of active diluent BGE, 6-8 parts of toughening agent CTBN, 0.8-1.2 parts of dispersant, and 0.3-0.5 parts of defoaming agent; The B component comprises the following raw materials in parts by weight: 2.5-4.5 parts of perfluoroalkylsilane-modified boron nitride, 4.5-5.5 parts of dicyandiamide, 1.2-1.8 parts of 2-methylimidazole, 1.0-1.5 parts of 1,2-dimethylimidazole, 3.0-4.0 parts of fumed silica HL-200, 12-15 parts of titanium dioxide nanowires surface-modified with a fluorine-containing silane coupling agent, 1.0-1.5 parts of ultraviolet absorber UV-360, and 0.5-0.8 parts of antioxidant 3114; The mass ratio of component A to component B is (2.0-4.0):1; The perfluoroalkylsilane-modified boron nitride is first pre-modified by surface polymerization of dopamine hydrochloride salt to prepare boron nitride nanosheets, then grafted with tridecafluorooctyltrimethoxysilane, and finally filtered, washed and freeze-dried to obtain; The fluorinated silane coupling agent surface-modified titanium dioxide nanowires are obtained by surface-modifying the titanium dioxide nanowires with perfluorooctyltriethoxysilane.

2. A strong and firm two-component anti-seepage and waterproof building adhesive as claimed in claim 1, characterized in that: The preparation method of the perfluoroalkylsilane-modified boron nitride is as follows: 1.0-1.2 g of polydopamine-modified boron nitride nanosheets are dispersed in 120-130 mL of toluene, and a uniform suspension is formed by ultrasonic treatment at a frequency of 40-60 kHz for 15-25 min, and a mixed solution of 0.95-1.05 g of tridecafluorooctyltrimethoxysilane and 18-22 mL of toluene is dropwise added to the reaction system at a rate of 0.5-1.0 mL / min, and then the temperature is raised to 75-85°C under nitrogen protection and magnetic stirring is maintained at 300-500 rpm for 5-7 h to complete the grafting reaction. After the reaction is completed, the temperature is naturally cooled to 20-25°C, and the solid phase product is separated by vacuum filtration through a 0.22 μm polytetrafluoroethylene filter membrane, and 50-80 mL of acetone, 50-80 mL of ethanol and 50-80 mL of deionized water are used in sequence. The filter cake was washed three times with a mL gradient to remove unreacted monomers and solvent residues, and finally the product was placed in a -50~-40°C freeze dryer for 70~74 h to obtain dark gray perfluoroalkylsilane-modified boron nitride.

3. A strong and firm two-component anti-seepage and waterproof building adhesive as claimed in claim 2, characterized in that: The polydopamine-modified boron nitride nanosheets are prepared by dispersing 2.8-3.2 g of the boron nitride nanosheets in 580-620 mL of a tris(hydroxymethyl)aminomethane buffer solution with a pH value of 8.3-8.7, subjecting the solution to ultrasonic treatment at a power of 200-300 W for 25-35 min, slowly adding 1.15-1.25 g of dopamine hydrochloride salt at a stirring speed of 400-600 rpm at 20-25° C. and continuing the reaction for 1.8-2.2 h to achieve surface polymerization coating, vacuum filtering, washing with deionized water until the filtrate conductivity is less than 5 μS / cm, and freeze-drying for 62-74 h to obtain the polydopamine-modified boron nitride nanosheets.

4. A strong and firm two-component anti-seepage and waterproof building adhesive as claimed in claim 3, characterized in that: The preparation method of the boron nitride nanosheets is as follows: the boron nitride nanosheets are prepared by mechanical ball milling-liquid phase exfoliation method, specifically: a hexagonal boron nitride block with a particle size of 0.5-5.0 mm and a zirconium oxide grinding ball with a diameter of 1.0-3.0 mm are loaded into a silicon nitride ball mill with a volume of 500-1000 mL in a mass ratio of 1: (30-50), and the planetary ball milling is performed at a speed of 300-400 rpm for 4-6 h under the protection of an argon flow rate of 5-10 L / min. After the ball milling, the product is mixed with N-methylpyrrolidone at a solid-liquid ratio of 1: (100-150), and the product is subjected to a pulse ultrasonic treatment with a power of 500-800 W and a working cycle of 2 s on / 1s off for 2-4 h. During the treatment, the suspension temperature is controlled at 20-40°C, and then centrifuged at 8000-12000 rpm for 10-30 The supernatant was collected after centrifugation and filtered through a 0.22 μm polytetrafluoroethylene filter membrane under vacuum. The filter cake was washed with 50-80 mL of anhydrous ethanol and 50-80 mL of deionized water for 3-5 times respectively to completely remove the residual solvent. Finally, the product was placed in a vacuum drying oven and dried at a constant temperature of 50-60°C for 12-24 h to obtain boron nitride nanosheets.

5. A strong and firm two-component anti-seepage and waterproof building adhesive as claimed in claim 4, characterized in that: The average diameter of the boron nitride nanosheets is 0.5-2.5 μm, and the average thickness is 2.5-6.5 nm.

6. A strong and firm two-component anti-seepage and waterproof building adhesive as claimed in claim 1, characterized in that: The preparation method of the fluorinated silane coupling agent surface-modified titanium dioxide nanowires is as follows: pre-dried titanium dioxide nanowires and anhydrous toluene are mixed at a mass volume ratio of 1: (20-30), ultrasonically treated at a frequency of 40-60 kHz for 10-20 min to form a uniformly dispersed system, and then transferred to a reactor equipped with a polytetrafluoroethylene stirring device, 25-35 wt% perfluorooctyltriethoxysilane based on the mass of titanium dioxide is added, and the mixture is stirred at a rate of 250-350 rpm under a nitrogen atmosphere at a constant temperature of 55-65°C for 3-5 h. After the reaction is completed, the solid phase product is separated by vacuum filtration with a Buchner funnel, and washed three times with 50-80 mL of toluene and 50-80 mL of acetone in turn to remove free coupling agent, and finally the washed product is treated at a constant temperature of 45-55°C for 10-14 h in a vacuum drying oven to obtain fluorinated silane coupling agent surface-modified titanium dioxide nanowires.

7. A strong and firm two-component anti-seepage and waterproof building adhesive as claimed in claim 1, characterized in that: The preparation method of the titanium dioxide nanowires is as follows: by weight, 1.0-5.0 parts of tetrabutyl titanate and 30-50 parts of ethanol are mixed to form a homogeneous precursor solution, which is transferred to a polytetrafluoroethylene-lined autoclave and sealed, and the temperature is raised to 120-250°C at 2-5°C / min for a solvent thermal reaction for 12-24 hours. After the reaction is completed, the suspension is naturally cooled to 20-30°C, and the obtained suspension is centrifuged at 3000-5000 rpm for 5-10 minutes to remove the supernatant. The precipitate is washed with 50-100 mL of anhydrous ethanol and 50-100 mL of deionized water for 3-5 times to remove unreacted products and solvent residues, and then treated in a vacuum drying oven at 60-80°C for 6-12 hours to obtain a titanium dioxide nanowire precursor, and the precursor is optionally placed in a tubular furnace and heated to 400-600°C at 2-5°C / min for calcination for 2-4 hours. h, finally titanium dioxide nanowires were obtained.

8. A strong and firm two-component anti-seepage and waterproof building adhesive as claimed in claim 1, characterized in that: The average diameter of the titanium dioxide nanowires is 25-65 nm, and the average length is 2.5-6.0 μm.

9. A strong and firm two-component anti-seepage and waterproof building adhesive as claimed in claim 1, characterized in that: The active diluent BGE is butyl glycidyl ether; The toughening agent CTBN is carboxyl-terminated nitrile rubber; The dispersant is BYK-163 dispersant; The defoamer is BYK-066N defoamer.

10. A method for preparing a strong and firm two-component anti-seepage and waterproof building adhesive as claimed in any one of claims 1 to 9, characterized in that: The following steps are involved: S1. Preparation of component A: Add epoxy resin E-51, active diluent BGE and toughening agent CTBN into a vacuum stirring kettle, premix at a stirring rate of 800-1000 rpm for 30-45 min at 40-50°C and a vacuum degree of -0.08-0.10 MPa to form a matrix phase; then add dispersant and defoamer in sequence, increase the stirring rate to 800-1000 rpm and maintain the temperature at 60-70°C for high-speed dispersion for 40-60 min until the system viscosity reaches 5000-8000 mPa·s, filter through a 200-300 mesh filter, transfer to a closed container and degas at a vacuum degree of -0.1 MPa for 30-40 min to obtain component A glue and dispense into oxygen-isolated aluminum-plastic packaging bags; S2. Preparation of component B: perfluoroalkyl silane-modified boron nitride, dicyandiamide, 2-methylimidazole, 1,2-dimethylimidazole, fluorinated silane coupling agent surface-modified titanium dioxide nanowires and fumed silica HL-200 are placed in a three-dimensional motion mixer, and dry mixed at a speed of 15-20 rpm for 45-60 min under nitrogen protection to form a uniform powder mixture, and then ultraviolet absorber UV-360 and antioxidant 3114 are added, and the mixture is switched to a high-speed vortex mixing mode and sheared and dispersed at 2000-2500 rpm for 25-35 min until the powder repose angle is ≤35°, and finally, the powder of component B with a D50 particle size of ≤10 μm is obtained by micronization treatment with a jet mill at a pressure of 0.4-0.6 MPa and sealed and stored in a moisture-proof aluminum foil bag; S3. When finally used, mix component A and component B according to the mass ratio, stir at 400-600 rpm for 5-10 minutes until a uniform colloid is formed, let it stand for 10-20 minutes to eliminate internal bubbles, apply the glue at room temperature and 50-60% relative humidity and cure for 24-48 hours to form a waterproof layer.

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