Inorganic-organic composite grouting material and preparation method thereof

Abstract

The present application relates to the technical field of grouting material, in particular to an inorganic-organic composite grouting material and a preparation method thereof, which comprises component A and component R, the component A and the component R are prepared according to a weight ratio of 1:1, and the component A is MDI semi-prepolymer.The grouting material is prepared by using the component A and the component R, the MDI semi-prepolymer of the component A reacts with the terminal amino polyether and the liquid amine chain extender of the component R to form a polyurea elastomer main chain structure, and the modified functional agent and the uniforming agent added in the component R are harmonized and synergized, so that the mechanical strength, the elongation at break, the adhesion and the temperature resistance of the prepared grouting material are improved in coordination, and the weather resistance and the corrosion resistance of the product are significantly improved.

Description

Technical Field

[0001] This invention relates to the field of grouting materials technology, specifically to inorganic-organic composite grouting materials and their preparation methods. Background Technology

[0002] Sprayed polyurea elastomer is an environmentally friendly and green material with excellent performance and construction effect. It is not affected by the environment and is increasingly widely used in construction, transportation and other fields. Existing polyurea uses pure organic materials, resulting in poor product performance. When combined with inorganic materials, poor interfacial properties can easily occur, which can also affect the product performance. Therefore, the challenge of this invention lies in the combination of inorganic and organic materials to improve the product's mechanical strength, elongation at break, adhesion and temperature resistance, as well as weather resistance and corrosion resistance, thus solving the problem of overall product coordination. Summary of the Invention

[0003] In view of the deficiencies of the prior art, the purpose of this invention is to provide an inorganic-organic composite grouting material and its preparation method, so as to solve the problems mentioned in the background art.

[0004] The present invention solves the technical problem by adopting the following technical solution: This invention provides an inorganic-organic composite grouting material, comprising component A and component R, which are formulated in a weight ratio of 1:1, and component A is an MDI semi-prepolymer. Component R includes the following raw materials in parts by weight: 60-80 parts of amino-terminated polyether, 15-30 parts of liquid amine chain extender, 7-11 parts of modified functional agent, 5-8 parts of homogenizing agent, 0.5-2 parts of dispersant, and 0.3-1 parts of defoamer.

[0005] Preferably, the MDI semi-prepolymer is obtained by reacting MDI and polyether polyol at a weight ratio of 5.5:4.5 at 70-80°C for 2-3 hours to obtain an MDI semi-prepolymer with an NCO content of 15-20%. The MDI is a carbodiimide-modified liquefied MDI, which is liquid at room temperature, has an NCO content of 28-30%, and a functionality of 2.0-2.2. The molecular weight of polyether polyols is 2000-3000, and the OH value is 50-56.

[0006] Preferably, the terminal amino polyether has a molecular weight of 2000-5000 and an amine value of 0.5-1.5 meq / g; the liquid amine chain extender is diethyltoluenediamine; The dispersant is BYK-163 dispersant; the defoamer is BYK-A530 defoamer.

[0007] Preferably, the method for preparing the modified functional agent is as follows: S01: First, disperse 2-5 parts of silicon carbide whiskers and 4-7 parts of sodium lignosulfonate solution evenly, then add 3-5 parts of nanocellulose and continue to mix thoroughly. Then add 5-10% ammonia water to adjust the pH value to 8.5, and then add 2-4 parts of lanthanum sulfate solution and mix evenly to obtain the first modifier. S02: 2-3 parts of β-cyclodextrin, 1-3 parts of 75-85% ethanol aqueous solution, 5-8 parts of kaolin and 3-5 parts of nano-alumina are thoroughly mixed to obtain the second modifier; Carbon nanotubes are stirred thoroughly in a sufficient amount of sulfuric acid solution with a mass fraction of 10-15%, then washed with water, filtered, and dried. The dried carbon nanotubes are then stirred and modified in a first modifier that is 5-8 times the total amount of dried carbon nanotubes. After stirring, the first modified carbon nanotube solution is obtained. S03: The first modified carbon nanotube liquid and the second modifier are mixed thoroughly at a weight ratio of (8-11):5, and then ball-milled at a speed of 50-100 r / min for 20 min. After ball milling, the mixture is filtered and dried to obtain the modified carbon nanotube agent. S04: The modified carbon nanotube agent and functional liquid are stirred thoroughly at a weight ratio of (6-10):4, and then ball-milled at a speed of 50-100 r / min for 30 min. After ball milling, the mixture is filtered and dried to obtain the modified functional agent.

[0008] Preferably, the lanthanum sulfate solution has a mass fraction of 2-5%; and the sodium lignosulfonate solution has a mass fraction of 8-12%.

[0009] Preferably, the preparation method of the functional liquid is as follows: Hydroxyapatite and dopamine hydrochloride solution were mixed evenly at a weight ratio of 2:(4-5). Then, 10-15% of the total weight of hydroxyapatite nano-titanium dioxide, 4-7% of the total weight of hydroxyapatite yttrium oxide, and 8-11% of the total weight of hydroxyapatite boron nitride nanosheets were added. Finally, Tris buffer was added to adjust the pH to 8.5, and the mixture was thoroughly mixed to obtain the functional solution.

[0010] Preferably, the mass concentration of the dopamine hydrochloride solution is 1-2 g / L.

[0011] Preferably, the homogenizing agent comprises the following raw materials in parts by weight: Hydroxyl-terminated aliphatic hyperbranched polyester 6-10 parts, bisphenol A epoxy resin 3-6 parts, vinyltriethoxysilane 2-4 parts, polyether-modified polysiloxane 1-3 parts.

[0012] Preferably, the preparation steps of the homogenizing agent are as follows: Hydroxyl-terminated aliphatic hyperbranched polyester and bisphenol A epoxy resin were first stirred at 65-70℃ for 20-30 min at a stirring speed of 300 r / min to obtain a premix. Vinyltriethoxysilane was added to the premix and reacted at 80-85℃ for 45 min. Finally, the temperature was lowered to 45-50℃, and polyether-modified polysiloxane was added. The mixture was stirred for another 15-20 min to obtain a homogenizer.

[0013] This invention also provides a method for preparing an inorganic-organic composite grouting material, comprising the following steps: First, mix component R thoroughly at a speed of 1000-1500 r / min. Then, heat components A and R to 65-75℃ respectively, and then spray them onto the substrate surface through a high-pressure spray gun with a coating thickness of 2-4 mm to obtain an inorganic-organic composite grouting material. The pressure of the high-pressure spray gun is 2000-3500 psi, and the distance between the high-pressure spray gun and the substrate surface is 300-800 mm.

[0014] Compared with the prior art, the present invention has the following beneficial effects: This invention relates to a grouting material formulated from components A and R. The MDI semi-prepolymer in component A reacts with the terminal amino polyether and liquid amine chain extender in component R to form a polyurea elastomer main chain structure. Simultaneously, the modifiers and homogenizers added to component R provide synergistic effects, resulting in a coordinated improvement in the mechanical strength, elongation at break, adhesion, and temperature resistance of the grouting material, as well as significant improvements in weather resistance and corrosion stability. The modifier is made from carbon nanotubes activated with sulfuric acid solution, followed by a stirring modification treatment with a first modifier. The silicon carbide whiskers in the first modifier serve as the matrix, which is then blended with sodium lignosulfonate solution and nanocellulose, and finally further modified with lanthanum sulfate solution. Through multi-stage coordination of raw materials, the functional effects of the system are optimized. The second modifier, composed of β-cyclodextrin, kaolin, nano-alumina, and an ethanol aqueous solution, is added. The system's functionality is further optimized through the co-mixing and improvement of raw materials. The functional fillers introduced into the modified functional agent, such as silicon carbide whiskers, kaolin, and nano-alumina, undergo multi-step ball milling and improvement. Simultaneously, carbon nanotubes and boron nitride nanosheets are used in synergistic formulation to form a dense barrier structure, blocking the penetration of moisture and other substances, thus optimizing the system's functionality and performance stability. The functional liquid is mixed with hydroxyapatite and dopamine hydrochloride solution, using nano-titanium dioxide, yttrium oxide, and boron nitride nanosheets as additives, further enhancing the system's performance coordination and stability. The homogenizing agent incorporates hydroxyl-terminated aliphatic hyperbranched polyester, bisphenol A epoxy resin, vinyltriethoxysilane, and polyether-modified polysiloxane for blending and coordination, optimizing the organic-inorganic interface and enhancing the functionality of the grouting material. Detailed Implementation

[0015] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to specific examples. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0016] The inorganic-organic composite grouting material of this embodiment includes component A and component R, which are prepared in a weight ratio of 1:1. Component A is MDI semi-prepolymer. Component R includes the following raw materials in parts by weight: 60-80 parts of amino-terminated polyether, 15-30 parts of liquid amine chain extender, 7-11 parts of modified functional agent, 5-8 parts of homogenizing agent, 0.5-2 parts of dispersant, and 0.3-1 parts of defoamer.

[0017] In this embodiment, the MDI semi-prepolymer is obtained by reacting MDI and polyether polyol at a weight ratio of 5.5:4.5 at 70-80°C for 2-3 hours to obtain an MDI semi-prepolymer with an NCO content of 15-20%. The MDI is a carbodiimide-modified liquefied MDI, which is liquid at room temperature, has an NCO content of 28-30%, and a functionality of 2.0-2.2. The molecular weight of polyether polyols is 2000-3000, and the OH value is 50-56.

[0018] In this embodiment, the terminal amino polyether has a molecular weight of 2000-5000 and an amine value of 0.5-1.5 meq / g; the liquid amine chain extender is diethyltoluenediamine. The dispersant is BYK-163 dispersant; the defoamer is BYK-A530 defoamer.

[0019] The preparation method of the modified functional agent in this embodiment is as follows: S01: First, disperse 2-5 parts of silicon carbide whiskers and 4-7 parts of sodium lignosulfonate solution evenly, then add 3-5 parts of nanocellulose and continue to mix thoroughly. Then, add 5-10% ammonia water to adjust the pH value to 8.5, and then add 2-4 parts of lanthanum sulfate solution and mix evenly to obtain the first modifier. The average diameter of the silicon carbide whiskers is 50-100 nm; the fiber diameter of the nanocellulose is 70-100 nm. S02: 2-3 parts of β-cyclodextrin, 1-3 parts of 75-85% ethanol aqueous solution, 5-8 parts of kaolin and 3-5 parts of nano-alumina are fully mixed to obtain the second modifier. The average particle size of the nano-alumina is 50-100nm, the crystal form is α phase, and the specific surface area is 35-65m² / g. Carbon nanotubes are stirred thoroughly in a sufficient amount of sulfuric acid solution with a mass fraction of 10-15%, then washed with water, filtered, and dried. The dried carbon nanotubes are then stirred and modified in a first modifier at a mass ratio of 5-8 times the total volume of the dried carbon nanotubes. After stirring, a first modified carbon nanotube liquid is obtained. The carbon nanotubes are multi-walled carbon nanotubes with a diameter of 10-20 nm and a length of 35-45 μm. S03: The first modified carbon nanotube liquid and the second modifier are mixed thoroughly at a weight ratio of (8-11):5, and then ball-milled at a speed of 50-100 r / min for 20 min. After ball milling, the mixture is filtered and dried to obtain the modified carbon nanotube agent. S04: The modified carbon nanotube agent and functional liquid are stirred thoroughly at a weight ratio of (6-10):4, and then ball-milled at a speed of 50-100 r / min for 30 min. After ball milling, the mixture is filtered and dried to obtain the modified functional agent.

[0020] In this embodiment, the lanthanum sulfate solution has a mass fraction of 2-5%; the sodium lignosulfonate solution has a mass fraction of 8-12%.

[0021] The preparation method of the functional liquid in this embodiment is as follows: Hydroxyapatite and dopamine hydrochloride solution were mixed evenly at a weight ratio of 2:(4-5). Then, 10-15% of the total weight of hydroxyapatite nano-titanium dioxide, 4-7% of the total weight of hydroxyapatite yttrium oxide, and 8-11% of the total weight of hydroxyapatite boron nitride nanosheets were added. Finally, Tris buffer was added to adjust the pH to 8.5, and the mixture was thoroughly mixed to obtain the functional solution. The nano-titanium dioxide had a particle size of 10-20 nm and a crystal form of anatase. The boron nitride nanosheets had a sheet diameter of 1-5 μm and a thickness of 2-5 nm.

[0022] In this embodiment, the mass concentration of the dopamine hydrochloride solution is 1-2 g / L.

[0023] The homogenizing agent in this embodiment comprises the following raw materials in parts by weight: Hydroxyl-terminated aliphatic hyperbranched polyester 6-10 parts, bisphenol A epoxy resin 3-6 parts, vinyltriethoxysilane 2-4 parts, polyether-modified polysiloxane 1-3 parts.

[0024] The preparation steps of the homogenizing agent in this embodiment are as follows: Hydroxyl-terminated aliphatic hyperbranched polyester and bisphenol A epoxy resin were first stirred at 65-70℃ for 20-30 min at a stirring speed of 300 r / min to obtain a premix. Vinyltriethoxysilane was added to the premix and reacted at 80-85℃ for 45 min. Finally, the temperature was lowered to 45-50℃, polyether-modified polysiloxane was added, and stirring was continued for 15-20 min to obtain a homogenizer. The hydroxyl-terminated aliphatic hyperbranched polyester is designated Hyper H30; the bisphenol A epoxy resin is designated E-51; the polyether-modified polysiloxane is designated BYK-333; and the vinyltriethoxysilane is designated A-151 (Momentive).

[0025] The preparation method of the inorganic-organic composite grouting material in this embodiment includes the following steps: First, mix component R thoroughly at a speed of 1000-1500 r / min. Then, heat components A and R to 65-75℃ respectively, and then spray them onto the substrate surface through a high-pressure spray gun with a coating thickness of 2-4 mm to obtain an inorganic-organic composite grouting material. The pressure of the high-pressure spray gun is 2000-3500 psi, and the distance between the high-pressure spray gun and the substrate surface is 300-800 mm.

[0026] Example 1.

[0027] The inorganic-organic composite grouting material of this embodiment includes component A and component R, which are prepared in a weight ratio of 1:1. Component A is MDI semi-prepolymer. Component R includes the following raw materials in parts by weight: 60 parts of amino-terminated polyether, 15 parts of liquid amine chain extender, 7 parts of modified functional agent, 5 parts of homogenizing agent, 0.5 parts of dispersant, and 0.3 parts of defoamer.

[0028] In this embodiment, the MDI semi-prepolymer is obtained by reacting MDI and polyether polyol at a weight ratio of 5.5:4.5 at 70°C for 2 hours to obtain an MDI semi-prepolymer with an NCO content of 15%. The MDI is a carbodiimide-modified liquefied MDI, which is liquid at room temperature, has an NCO content of 28%, and a functionality of 2.0. The polyether polyol has a molecular weight of 2000 and an OH value of 50.

[0029] In this embodiment, the terminal amino polyether has a molecular weight of 2000 and an amine value of 0.5 meq / g; the liquid amine chain extender is diethyltoluenediamine. The dispersant is BYK-163 dispersant; the defoamer is BYK-A530 defoamer.

[0030] The preparation method of the modified functional agent in this embodiment is as follows: S01: First, disperse 2 parts of silicon carbide whiskers and 4 parts of sodium lignosulfonate solution evenly, then add 3 parts of nanocellulose and continue to mix thoroughly. Then, add 5% ammonia water to adjust the pH value to 8.5, and then add 2 parts of lanthanum sulfate solution and mix evenly to obtain the first modifier. The average diameter of the silicon carbide whiskers is 50nm; the fiber diameter of the nanocellulose is 70nm. S02: 2 parts β-cyclodextrin, 1 part 75% ethanol aqueous solution, 5 parts kaolin and 3 parts nano alumina are fully mixed to obtain the second modifier. The average particle size of the nano alumina is 50nm, the crystal form is α phase, and the specific surface area is 35m² / g. Carbon nanotubes were stirred thoroughly in a sufficient amount of 10% sulfuric acid solution, then washed with water, filtered, and dried. The dried carbon nanotubes were then stirred and modified in a first modifier that was 5 times the total amount of dried carbon nanotubes. After stirring, the first modified carbon nanotube liquid was obtained. The carbon nanotubes were multi-walled carbon nanotubes with a diameter of 10 nm and a length of 35 μm. S03: The first modified carbon nanotube liquid and the second modifier are mixed thoroughly at a weight ratio of 8:5, and then ball-milled at a speed of 50 r / min for 20 min. After ball milling, the mixture is filtered and dried to obtain the modified carbon nanotube agent. S04: The modified carbon nanotube agent and functional liquid are stirred thoroughly at a weight ratio of 6:4, and then ball-milled at a speed of 50 r / min for 30 min. After ball milling, the mixture is filtered and dried to obtain the modified functional agent.

[0031] In this embodiment, the lanthanum sulfate solution has a mass fraction of 2%; the sodium lignosulfonate solution has a mass fraction of 8%.

[0032] The preparation method of the functional liquid in this embodiment is as follows: Hydroxyapatite and dopamine hydrochloride solution were mixed evenly at a weight ratio of 2:4. Then, 10% of the total weight of hydroxyapatite nano-titanium dioxide, 4% of the total weight of hydroxyapatite yttrium oxide, and 8% of the total weight of hydroxyapatite boron nitride nanosheets were added. Finally, Tris buffer was added to adjust the pH to 8.5, and the mixture was thoroughly mixed to obtain the functional solution. The nano-titanium dioxide had a particle size of 10 nm and a crystal form of anatase. The boron nitride nanosheets had a sheet diameter of 1 μm and a thickness of 2 nm.

[0033] In this embodiment, the mass concentration of the dopamine hydrochloride solution is 1 g / L.

[0034] The homogenizing agent in this embodiment comprises the following raw materials in parts by weight: Six parts of hydroxyl-terminated aliphatic hyperbranched polyester, three parts of bisphenol A epoxy resin, two parts of vinyltriethoxysilane, and one part of polyether-modified polysiloxane.

[0035] The preparation steps of the homogenizing agent in this embodiment are as follows: Hydroxyl-terminated aliphatic hyperbranched polyester and bisphenol A epoxy resin were first stirred at 65°C for 20 min at a stirring speed of 300 r / min to obtain a premix. Vinyltriethoxysilane was added to the premix and reacted at 80°C for 45 min. Finally, the temperature was lowered to 45°C, polyether-modified polysiloxane was added, and stirring was continued for 15 min to obtain a homogenizer. The hydroxyl-terminated aliphatic hyperbranched polyester is designated Hyper H30; the bisphenol A epoxy resin is designated E-51; the polyether-modified polysiloxane is designated BYK-333; and the vinyltriethoxysilane is designated A-151 (Momentive).

[0036] The preparation method of the inorganic-organic composite grouting material in this embodiment includes the following steps: Component R is first mixed thoroughly at a speed of 1000 r / min. Then, components A and R are heated to 65°C respectively and sprayed onto the substrate surface through a high-pressure spray gun with a coating thickness of 2 mm to obtain an inorganic-organic composite grouting material. The pressure of the high-pressure spray gun is 2000 psi and the distance between the high-pressure spray gun and the substrate surface is 300 mm.

[0037] Example 2. The inorganic-organic composite grouting material of this embodiment includes component A and component R, which are prepared in a weight ratio of 1:1. Component A is MDI semi-prepolymer. Component R includes the following raw materials in parts by weight: 80 parts of amino-terminated polyether, 30 parts of liquid amine chain extender, 11 parts of modified functional agent, 8 parts of homogenizer, 2 parts of dispersant, and 1 part of defoamer.

[0038] In this embodiment, the MDI semi-prepolymer is obtained by reacting MDI and polyether polyol at a weight ratio of 5.5:4.5 at 80°C for 3 hours to obtain an MDI semi-prepolymer with an NCO content of 20%. The MDI is a carbodiimide-modified liquefied MDI, which is liquid at room temperature, has an NCO content of 30%, and a functionality of 2.2. The polyether polyol has a molecular weight of 3000 and an OH value of 56.

[0039] In this embodiment, the terminal amino polyether has a molecular weight of 5000 and an amine value of 1.5 meq / g; the liquid amine chain extender is diethyltoluenediamine. The dispersant is BYK-163 dispersant; the defoamer is BYK-A530 defoamer.

[0040] The preparation method of the modified functional agent in this embodiment is as follows: S01: First, disperse 5 parts of silicon carbide whiskers and 7 parts of sodium lignosulfonate solution evenly, then add 5 parts of nanocellulose and continue to mix thoroughly. Then, add 10% ammonia water to adjust the pH value to 8.5, and then add 4 parts of lanthanum sulfate solution and mix evenly to obtain the first modifier. The average diameter of the silicon carbide whiskers is 100 nm; the fiber diameter of the nanocellulose is 100 nm. S02: 3 parts β-cyclodextrin, 3 parts 85% ethanol aqueous solution, 8 parts kaolin and 5 parts nano alumina are fully mixed to obtain the second modifier. The average particle size of the nano alumina is 100nm, the crystal form is α phase, and the specific surface area is 65m² / g. Carbon nanotubes were stirred thoroughly in a sufficient amount of 15% sulfuric acid solution, then washed with water, filtered, and dried. The dried carbon nanotubes were then stirred and modified in a first modifier that was 8 times the total amount of dried carbon nanotubes. After stirring, the first modified carbon nanotube liquid was obtained. The carbon nanotubes were multi-walled carbon nanotubes with a diameter of 20 nm and a length of 45 μm. S03: The first modified carbon nanotube liquid and the second modifier are mixed thoroughly at a weight ratio of 11:5, and then ball-milled at a speed of 100 r / min for 20 min. After ball milling, the mixture is filtered and dried to obtain the modified carbon nanotube agent. S04: The modified carbon nanotube agent and functional liquid are stirred thoroughly at a weight ratio of 10:4, and then ball-milled at 100 r / min for 30 min. After ball milling, the mixture is filtered and dried to obtain the modified functional agent.

[0041] In this embodiment, the lanthanum sulfate solution has a mass fraction of 5%; the sodium lignosulfonate solution has a mass fraction of 12%.

[0042] The preparation method of the functional liquid in this embodiment is as follows: Hydroxyapatite and dopamine hydrochloride solution were mixed evenly at a weight ratio of 2:5. Then, 15% of the total weight of hydroxyapatite nano-titanium dioxide, 7% of the total weight of hydroxyapatite yttrium oxide, and 11% of the total weight of hydroxyapatite boron nitride nanosheets were added. Finally, Tris buffer was added to adjust the pH to 8.5, and the mixture was thoroughly mixed to obtain the functional solution. The nano-titanium dioxide had a particle size of 20 nm and a crystal form of anatase. The boron nitride nanosheets had a sheet diameter of 5 μm and a thickness of 5 nm.

[0043] In this embodiment, the mass concentration of the dopamine hydrochloride solution is 2 g / L.

[0044] The homogenizing agent in this embodiment comprises the following raw materials in parts by weight: The mixture consists of 10 parts hydroxyl-terminated aliphatic hyperbranched polyester, 6 parts bisphenol A epoxy resin, 4 parts vinyltriethoxysilane, and 3 parts polyether-modified polysiloxane.

[0045] The preparation steps of the homogenizing agent in this embodiment are as follows: Hydroxyl-terminated aliphatic hyperbranched polyester and bisphenol A epoxy resin were first stirred at 70°C for 30 min at a stirring speed of 300 r / min to obtain a premix. Vinyltriethoxysilane was added to the premix and reacted at 85°C for 45 min. Finally, the temperature was lowered to 50°C, polyether-modified polysiloxane was added, and stirring was continued for 15-20 min to obtain a homogenizer. The hydroxyl-terminated aliphatic hyperbranched polyester is designated Hyper H30; the bisphenol A epoxy resin is designated E-51; the polyether-modified polysiloxane is designated BYK-333; and the vinyltriethoxysilane is designated A-151 (Momentive).

[0046] The preparation method of the inorganic-organic composite grouting material in this embodiment includes the following steps: Component R is first mixed thoroughly at a speed of 1500 r / min. Then, components A and R are heated to 75°C respectively and sprayed onto the substrate surface through a high-pressure spray gun with a coating thickness of 4 mm to obtain an inorganic-organic composite grouting material. The pressure of the high-pressure spray gun is 3500 psi and the distance between the high-pressure spray gun and the substrate surface is 800 mm.

[0047] Example 3. The inorganic-organic composite grouting material of this embodiment includes component A and component R, which are prepared in a weight ratio of 1:1. Component A is MDI semi-prepolymer. Component R includes the following raw materials in parts by weight: 70 parts of amino-terminated polyether, 22.5 parts of liquid amine chain extender, 9 parts of modified functional agent, 6.5 parts of homogenizer, 1 part of dispersant, and 0.6 parts of defoamer.

[0048] In this embodiment, the MDI semi-prepolymer was obtained by reacting MDI and polyether polyol at a weight ratio of 5.5:4.5 at 75°C for 2.5 hours to obtain an MDI semi-prepolymer with an NCO content of 17.5%. The MDI is a carbodiimide-modified liquefied MDI, which is liquid at room temperature, has an NCO content of 29%, and a functionality of 2.1. The polyether polyol has a molecular weight of 2500 and an OH value of 53.

[0049] In this embodiment, the terminal amino polyether has a molecular weight of 3500 and an amine value of 1.0 meq / g; the liquid amine chain extender is diethyltoluene diamine. The dispersant is BYK-163 dispersant; the defoamer is BYK-A530 defoamer.

[0050] The preparation method of the modified functional agent in this embodiment is as follows: S01: First, disperse 3.5 parts of silicon carbide whiskers and 5.5 parts of sodium lignosulfonate solution evenly, then add 4 parts of nanocellulose and continue to mix thoroughly. Then, add 7.5% ammonia water to adjust the pH value to 8.5, and then add 3 parts of lanthanum sulfate solution and mix evenly to obtain the first modifier. The average diameter of the silicon carbide whiskers is 75nm; the fiber diameter of the nanocellulose is 80nm. S02: 2.5 parts of β-cyclodextrin, 2 parts of 80% ethanol aqueous solution, 6.5 parts of kaolin and 4 parts of nano-alumina are fully mixed to obtain the second modifier. The average particle size of the nano-alumina is 75nm, the crystal form is α phase, and the specific surface area is 45m² / g. Carbon nanotubes were stirred thoroughly in a sufficient amount of 12.5% ​​sulfuric acid solution, then washed with water, filtered, and dried. The dried carbon nanotubes were then stirred and modified in a first modifier at a volume of 6.5 times the total volume of the dried carbon nanotubes. After stirring, the first modified carbon nanotube liquid was obtained. The carbon nanotubes were multi-walled carbon nanotubes with a diameter of 15 nm and a length of 40 μm. S03: The first modified carbon nanotube liquid and the second modifier are mixed thoroughly at a weight ratio of 9:5, and then ball-milled at a speed of 75 r / min for 20 min. After ball milling, the mixture is filtered and dried to obtain the modified carbon nanotube agent. S04: The modified carbon nanotube agent and functional liquid are stirred thoroughly at a weight ratio of 8:4, and then ball-milled at a speed of 75 r / min for 30 min. After ball milling, the mixture is filtered and dried to obtain the modified functional agent.

[0051] In this embodiment, the lanthanum sulfate solution has a mass fraction of 3.5%; the sodium lignosulfonate solution has a mass fraction of 10%.

[0052] The preparation method of the functional liquid in this embodiment is as follows: Hydroxyapatite and dopamine hydrochloride solution were mixed evenly at a weight ratio of 2:4.5. Then, 12.5% ​​of the total weight of hydroxyapatite nano-titanium dioxide, 5.5% of the total weight of hydroxyapatite yttrium oxide, and 9% of the total weight of hydroxyapatite boron nitride nanosheets were added. Finally, Tris buffer was added to adjust the pH to 8.5, and the mixture was thoroughly mixed to obtain the functional solution. The nano-titanium dioxide had a particle size of 15 nm and a crystal form of anatase. The boron nitride nanosheets had a sheet diameter of 3 μm and a thickness of 3.5 nm.

[0053] In this embodiment, the mass concentration of the dopamine hydrochloride solution is 1.5 g / L.

[0054] The homogenizing agent in this embodiment comprises the following raw materials in parts by weight: The mixture consists of 8 parts hydroxyl-terminated aliphatic hyperbranched polyester, 4.5 parts bisphenol A epoxy resin, 3 parts vinyltriethoxysilane, and 2 parts polyether-modified polysiloxane.

[0055] The preparation steps of the homogenizing agent in this embodiment are as follows: Hydroxyl-terminated aliphatic hyperbranched polyester and bisphenol A epoxy resin were first stirred at 68°C for 25 min at a stirring speed of 300 r / min to obtain a premix. Vinyltriethoxysilane was added to the premix and reacted at 82°C for 45 min. Finally, the temperature was lowered to 47.5°C, polyether-modified polysiloxane was added, and stirring was continued for 17 min to obtain a homogenizer. The hydroxyl-terminated aliphatic hyperbranched polyester is designated Hyper H30; the bisphenol A epoxy resin is designated E-51; the polyether-modified polysiloxane is designated BYK-333; and the vinyltriethoxysilane is designated A-151 (Momentive).

[0056] The preparation method of the inorganic-organic composite grouting material in this embodiment includes the following steps: Component R is first mixed thoroughly at a speed of 1250 r / min. Then, components A and R are heated to 70°C respectively and sprayed onto the substrate surface through a high-pressure spray gun with a coating thickness of 3 mm to obtain an inorganic-organic composite grouting material. The pressure of the high-pressure spray gun is 3000 psi and the distance between the high-pressure spray gun and the substrate surface is 500 mm.

[0057] Comparative Example 1. Unlike Example 3, no modifying functional agent was added to component R.

[0058] Comparative Example 2. Unlike Example 3, no second modifier was added in the preparation of the modified carbon nanotube agent.

[0059] Comparative Example 3. Unlike Example 3, kaolin and nano-alumina were not added in the preparation of the second modifier.

[0060] Comparative Example 4. Unlike Example 3, silicon carbide whiskers were not added in the preparation of the first modifier.

[0061] Comparative Example 5. Unlike Example 3, nanocellulose and lanthanum sulfate solution were not added in the preparation of the first modifier.

[0062] Comparative Example 6. Unlike Example 3, no functional liquid was added during the preparation of the modified functional agent.

[0063] Comparative Example 7. Unlike Example 3, boron nitride nanosheets and nano-titanium dioxide were not added in the preparation of the functional liquid.

[0064] Comparative Example 8. Unlike Example 3, hydroxyapatite was not added during the preparation of the functional liquid.

[0065] Comparative Example 9. Unlike Example 3, no homogenizing agent was added to component R.

[0066] The products of Examples 1-3 and Comparative Examples 1-9 were subjected to performance tests, including mechanical strength, elongation at break, and adhesion. The test results are as follows:

[0067] Test the temperature resistance, weather resistance, and corrosion resistance stability (place the product at 75℃ for 12 hours, place it under 5% hydrochloric acid mist for 12 hours, and then age it under a xenon lamp for 12 hours. This is one cycle, and the cycle is repeated 10 times).

[0068] As can be seen from Comparative Examples 1-9 and Examples 1-3, the product of Example 3 has excellent mechanical strength, elongation at break and adhesion. The performance of the product can be improved in a coordinated manner. In addition, the product has excellent performance stability under temperature resistance, weather resistance and corrosion resistance. In this invention, no modifying functional agent is added to component R, no second modifying agent is added in the preparation of the modified carbon nanotube agent, no functional liquid is added in the preparation of the modified functional agent, and no homogenizing agent is added to component R. The performance of the products in these cases shows a significant downward trend. Furthermore, the absence of kaolin and nano-alumina in the preparation of the second modifying agent, the absence of silicon carbide whiskers in the preparation of the first modifying agent, the absence of nano-cellulose and lanthanum sulfate solution in the preparation of the first modifying agent, the absence of boron nitride nanosheets and nano-titanium dioxide in the preparation of the functional liquid, and the absence of hydroxyapatite in the preparation of the functional liquid all contribute to varying degrees of performance degradation. Only the modified functional agent prepared using the specific method and the specific series of process steps of this invention exhibits the most significant performance improvement. Moreover, the preparation methods of the functional liquid, the second modifying agent, and the first modifying agent of this invention are all unique; only by using the technology and raw materials of this invention can the product's performance be most significantly improved.

[0069] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

[0070] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. An inorganic-organic composite grouting material, characterized in that, It includes component A and component R, which are formulated in a weight ratio of 1:

1. Component A is an MDI semi-prepolymer. Component R includes the following raw materials in parts by weight: 60-80 parts of amino-terminated polyether, 15-30 parts of liquid amine chain extender, 7-11 parts of modified functional agent, 5-8 parts of homogenizing agent, 0.5-2 parts of dispersant, and 0.3-1 parts of defoamer.

2. The inorganic-organic composite grouting material according to claim 1, characterized in that, The MDI semi-prepolymer is obtained by reacting MDI and polyether polyol at a weight ratio of 5.5:4.5 at 70-80℃ for 2-3 hours to obtain an MDI semi-prepolymer with an NCO content of 15-20%. The MDI is a carbodiimide-modified liquefied MDI, which is liquid at room temperature, has an NCO content of 28-30%, and a functionality of 2.0-2.

2. The molecular weight of polyether polyols is 2000-3000, and the OH value is 50-56.

3. The inorganic-organic composite grouting material according to claim 1, characterized in that, The terminal amino polyether has a molecular weight of 2000-5000 and an amine value of 0.5-1.5 meq / g; the liquid amine chain extender is diethyltoluenediamine. The dispersant is BYK-163 dispersant; the defoamer is BYK-A530 defoamer.

4. The inorganic-organic composite grouting material according to claim 1, characterized in that, The preparation method of the modified functional agent is as follows: S01: First, disperse 2-5 parts of silicon carbide whiskers and 4-7 parts of sodium lignosulfonate solution evenly, then add 3-5 parts of nanocellulose and continue to mix thoroughly. Then add 5-10% ammonia water to adjust the pH value to 8.5, and then add 2-4 parts of lanthanum sulfate solution and mix evenly to obtain the first modifier. S02: 2-3 parts of β-cyclodextrin, 1-3 parts of 75-85% ethanol aqueous solution, 5-8 parts of kaolin and 3-5 parts of nano-alumina are thoroughly mixed to obtain the second modifier; Carbon nanotubes are stirred thoroughly in a sufficient amount of sulfuric acid solution with a mass fraction of 10-15%, then washed with water, filtered, and dried. The dried carbon nanotubes are then stirred and modified in a first modifier that is 5-8 times the total amount of dried carbon nanotubes. After stirring, the first modified carbon nanotube solution is obtained. S03: The first modified carbon nanotube liquid and the second modifier are mixed thoroughly at a weight ratio of (8-11):5, and then ball-milled at a speed of 50-100 r / min for 20 min. After ball milling, the mixture is filtered and dried to obtain the modified carbon nanotube agent. S04: The modified carbon nanotube agent and functional liquid are stirred thoroughly at a weight ratio of (6-10):4, and then ball-milled at a speed of 50-100 r / min for 30 min. After ball milling, the mixture is filtered and dried to obtain the modified functional agent.

5. The inorganic-organic composite grouting material according to claim 4, characterized in that, The lanthanum sulfate solution has a mass fraction of 2-5%; the sodium lignosulfonate solution has a mass fraction of 8-12%.

6. The inorganic-organic composite grouting material according to claim 4, characterized in that, The preparation method of the functional liquid is as follows: Hydroxyapatite and dopamine hydrochloride solution were mixed evenly at a weight ratio of 2:(4-5). Then, 10-15% of the total weight of hydroxyapatite nano-titanium dioxide, 4-7% of the total weight of hydroxyapatite yttrium oxide, and 8-11% of the total weight of hydroxyapatite boron nitride nanosheets were added. Finally, Tris buffer was added to adjust the pH to 8.5, and the mixture was thoroughly mixed to obtain the functional solution.

7. The inorganic-organic composite grouting material according to claim 6, characterized in that, The mass concentration of the dopamine hydrochloride solution is 1-2 g / L.

8. The inorganic-organic composite grouting material according to claim 1, characterized in that, The homogenizing agent comprises the following raw materials in parts by weight: Hydroxyl-terminated aliphatic hyperbranched polyester 6-10 parts, bisphenol A epoxy resin 3-6 parts, vinyltriethoxysilane 2-4 parts, polyether-modified polysiloxane 1-3 parts.

9. The inorganic-organic composite grouting material according to claim 1, characterized in that, The preparation steps of the homogenizing agent are as follows: Hydroxyl-terminated aliphatic hyperbranched polyester and bisphenol A epoxy resin were first stirred at 65-70℃ for 20-30 min at a stirring speed of 300 r / min to obtain a premix. Vinyltriethoxysilane was added to the premix and reacted at 80-85℃ for 45 min. Finally, the temperature was lowered to 45-50℃, and polyether-modified polysiloxane was added. The mixture was stirred for another 15-20 min to obtain a homogenizer.

10. The method for preparing the inorganic-organic composite grouting material according to any one of claims 1 to 9, characterized in that, Includes the following steps: First, mix component R thoroughly at a speed of 1000-1500 r / min. Then, heat components A and R to 65-75℃ respectively, and then spray them onto the substrate surface through a high-pressure spray gun with a coating thickness of 2-4 mm to obtain an inorganic-organic composite grouting material. The pressure of the high-pressure spray gun is 2000-3500 psi, and the distance between the high-pressure spray gun and the substrate surface is 300-800 mm.

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